Anti-corrosion composition

Abstract

This application relates to photoresist compositions. Specifically, it relates to photoresists that can be used in photolithography, particularly in the manufacture of integrated circuits and derivative products. The photoresist compositions of this application include anti-scattering components with a significant amount of porosity and therefore fewer scattering centers, thereby further limiting radiation scattering events during exposure. This anti-scattering effect can improve resolution by reducing common proximity effects associated with photolithography, thus allowing the fabrication of smaller, higher-resolution microchips. Furthermore, some embodiments include anti-scattering components directly linked to the photoresist components, which can improve overall photolithography chemistry, thus providing benefits in both resolution and photoresist sensitivity.

Description

[0001] This application is a divisional application of the application filed on September 29, 2016, with application number 201680062388.5 and invention title "Resistant Composition". Technical Field

[0002] This invention relates to a photoresist composition, and more particularly to a photoresist composition. The invention also relates to methods for preparing and using such a photoresist composition, as well as several related aspects. background

[0003] For a variety of reasons well known to those skilled in the art, there is a persistent motivation in the electronics industry to miniaturize integrated circuits (ICs). Significant advancements in the semiconductor industry have been made possible by progress in lithography from the micrometer to the nanometer scale, but the physical resolution limits of optical lithography have now been largely reached, thus restricting further development. However, the continued growth of the semiconductor industry depends on improving the performance of integrated circuits on silicon substrates.

[0004] Recent advancements in far-ultraviolet (EUV) lithography at 13.5nm have enabled some further scaling / miniaturization of integrated circuits, but significant challenges still hinder its full implementation in the semiconductor industry.

[0005] Immersion 193nm lithography has extended patterning resolution by utilizing subwavelength techniques such as surface plasmon resonance and phase-shift masks. Unfortunately, these resist materials require longer patterning times, leading to reduced yields.

[0006] One object of the present invention is to develop a novel photoresist composition that addresses at least one problem left over from the prior art. Photoresists are already widely used in the IC manufacturing industry, so a new photoresist composition that is compatible with existing technologies and hardware (which may be expensive) (i.e., can be “modified”) is particularly desirable to reduce the burden of any technology migration.

[0007] Photoresists are divided into two main categories: positive photoresists and negative photoresists. Positive photoresists (or +ve photoresists) react to exposure radiation by becoming more soluble in the photoresist developer, allowing the removal of radiation-exposed areas during development without disturbing unexposed areas. Conversely, negative photoresists (or -ve photoresists) react to exposure radiation by becoming less soluble in the photoresist developer, allowing the removal of unexposed areas during development while retaining exposed areas. While both types of photoresists are useful, negative photoresists are particularly suitable for IC manufacturing.

[0008] Typically, ultraviolet (UV) and deep ultraviolet (DUV) wavelengths are used for exposure in existing photoresist processes, but the wavelength parameter is usually chosen based on the thickness of the applied photoresist layer. Thinner layers can be advantageously exposed with shorter wavelengths, allowing for lower aspect ratios and higher resolution. However, current photoresist techniques suffer from a trade-off between resolution and exposure speed / sensitivity (i.e., throughput).

[0009] The key to high-resolution lithography is the control of photoresist exposure (good control allows the exposed photoresist to exhibit maximum developer-solubility contrast over short distances), while the key to high-speed lithography is a large supply of available energy. Although shorter UV wavelengths offer better exposure control and tend to provide higher-resolution lithographic patterns (due to their ability to interact with smaller scale features), they are generally better absorbed (by the photoresist) than longer wavelengths because shorter wavelengths allow for a higher rate of spin-based electronic transitions (within absorbing molecules and atoms), thus limiting the supply of available energy. Since this absorption event tends to “lock” the energy of photons, and because the eventual vibrational energy dissipation is often futile from a lithographic perspective, this photon energy can no longer be used in a lithographically efficient manner (e.g., by triggering chemical reactions that selectively alter the solubility of the exposed and unexposed portions of the photoresist by promoting appropriate bond formation or breaking, depending on the resist’s anode or cathode). Therefore, resolution gain often comes at the expense of lithographic dynamics.

[0010] Nevertheless, photons with sufficient energy to ionize the photoresist can cause electron ejection (typically from the ionization of the valence band, valence orbitals, and / or the highest occupied molecular orbital HOMO), which can then effectively participate in further exposure of the photoresist material. In the context of this application, such "ejected" electrons are referred to as secondary electrons, but it should be understood that incident primary electrons are not actually required in its production (contrary to the technical requirements). Although photon energy is absorbed during this ionization process, the energy (or at least a portion thereof) is effectively released (rather than futilely trapped) for further exposure events, but this naturally leads to exposure control issues, particularly considering the electron ejection angle (~80°C) that causes the similarity effect.

[0011] Photons with energies as low as 5 eV (i.e., ~248 nm) can induce this ionization (leading to the emission of a corresponding secondary electron), but photon energies above 20 eV (~62 nm) tend to produce more internal electron ionization and Auger transitions (which are generally less efficient from a lithographic perspective). Therefore, the useful photon and / or corresponding secondary electron energy range is 5–20 eV. This electron energy (actually photon energy) is sufficient to induce localized chemical reactions (“localized” because the electron’s energy is typically completely consumed in a single collision event), for example, by inducing:

[0012] • Bond breaking (e.g., bond dissociation energy: CC (~3.60 eV), CH (~4.5 eV));

[0013] • Another electron ionization event in a neighboring molecule / atom (e.g., leading to the formation of an active substance, such as a free radical, that can then react with neighboring molecules);

[0014] • Electronic excitation that puts molecules in a more active state.

[0015] Commonly used photoresist materials such as polymethyl methacrylate (PMMA), polymethyl glutarimide (PMGI), phenolic resins (e.g., DNQ / Novolac), and epoxy polymers (e.g., SU-8) can all be applied as liquids to the substrate surface (e.g., silicon) via spin coating (which preferably ensures a uniform thickness across the entire surface).

[0016] Sometimes, chemical enhancer compounds (such as photoacid generators) are incorporated into resist compositions to improve sensitivity. During exposure, these chemical enhancers typically release acidic compounds, which then diffuse during post-exposure baking, making the surrounding / nearby polymers soluble in the developer. Therefore, the post-exposure diffusion of the acid generated during exposure is crucial to the acid-catalyzed reaction that ultimately produces the difference in photoresist solubility required for successful development. Even very small amounts of acid can have a significant effect (e.g., by deprotecting the resist polymer to make it more soluble in the developer), thus requiring fewer effective photon collisions for development, thereby increasing sensitivity. The dependence of successful exposure / development on post-exposure acid diffusion (typically during post-exposure baking) can impose certain limitations, particularly in terms of the resolution and contrast of the final pattern.

[0017] Therefore, the object of the present invention is to solve at least one problem in the prior art.

[0018] Another object of the present invention is to provide a photoresist composition, preferably a photoresist composition, which has a good balance between resolution and sensitivity. Summary of the Invention

[0019] According to a first aspect of the invention, a resist composition comprising an antiscattering component and a resist component is provided. The antiscattering component is locally used to reduce scattering (one or both of primary / incident radiation and / or secondary radiation), thereby providing better exposure control and minimizing proximity effects. The resist component suitably imparts resist quality to the composition, thereby selectively converting the "developer solubility" of the radiation-exposed (wavelength / radiation-appropriate) portions of the composition (or its coating) in contrast to the unexposed portions, such that the exposed and unexposed portions exhibit different developer solubility. The antiscattering component and the resist component can be separate compounds, or they can be combined with each other or connected in some way (whether chemically or physically, suitably by bonding). Such combination can facilitate the interaction or synergy between exposure control functions and sensitivity control functions, thereby providing a resist composition that produces good resolution and good sensitivity.

[0020] According to another aspect of the invention, a photoresist composition is provided, comprising an antiscattering component and a secondary electron generator (suitably as defined herein). The antiscattering component is suitably or comprises a photoresist component. The antiscattering component and the secondary electron generator are suitably covalently or coordinately bonded to each other.

[0021] According to another aspect of the invention, an anti-scattering-secondary electron hybrid compound (or complex) (AS-SEG mixture) is provided, comprising a multi-metal cage compound covalently or coordinately bonded to a secondary electron generator. The AS-SEG mixture may comprise a secondary electron generator (suitably a metal-centric compound or group, suitably having one or more properties as defined herein) covalently bonded to a multi-metal cage via one or more ligands bound to the multi-metal cage—for example, the secondary electron generator acting as an electron pair acceptor (or Lewis acid).

[0022] According to another aspect of the invention, a method for preparing a substrate coated with a resist material is provided, the method comprising coating the substrate with a resist coating; wherein the resist coating comprises a resist composition optionally dried and / or cured as defined herein.

[0023] According to another aspect of the invention, a material / substrate coated with a resist is provided, which can be obtained, acquired, or directly obtained by a method for preparing a material / substrate coated with a resist as defined herein.

[0024] According to another aspect of the invention, a material / substrate coated with a resist is provided, comprising a substrate coated with a resist coating; wherein the resist coating comprises a resist composition that is optionally dried and / or cured as defined herein.

[0025] According to another aspect of the present invention, a method for preparing a patterned substrate is provided, the method comprising:

[0026] i) Provide a substrate coated with resist as defined herein or apply a resist coating to the substrate;

[0027] ii) Exposing the resist coating to electromagnetic radiation to provide exposure;

[0028] iii) Develop the exposed resist coating to produce a resist pattern layer, the resist pattern layer comprising: a portion of the resist coating that is insoluble in the developer (i.e., ridges); and an array of grooves extending through the resist pattern layer;

[0029] The resist coating comprises a resist composition that is optionally dried and / or cured as defined herein.

[0030] According to another aspect of the present invention, a patterned substrate is provided, which can be obtained, acquired, or directly obtained by a method for preparing a patterned substrate as defined herein.

[0031] According to another aspect of the present invention, an imaging method is provided, the method comprising:

[0032] i) Provide a substrate coated with resist as defined herein or apply a resist coating to the substrate;

[0033] ii) Exposing the resist coating to electromagnetic radiation to provide exposure;

[0034] iii) Develop the exposed resist coating to produce a resist pattern layer, the resist pattern layer comprising: a portion of the resist coating that is insoluble in the developer (i.e., ridges); and an array of grooves extending through the resist pattern layer;

[0035] The resist coating comprises a resist composition that is optionally dried and / or cured as defined herein.

[0036] According to another aspect of the present invention, a method for performing photolithography is provided, the method comprising:

[0037] i) Provide a substrate coated with resist as defined herein or apply a resist coating to the substrate;

[0038] ii) Exposing the resist coating partially to radiation to provide exposure to the resist coating;

[0039] iii) Develop the exposed resist coating to produce a resist pattern layer, the resist pattern layer comprising: a portion of the resist coating that is insoluble in the developer (i.e., ridges); and an array of grooves extending through the resist pattern layer;

[0040] iv) Optionally, the substrate, substrate surface, or a portion thereof under the resist pattern layer may be modified;

[0041] v) Optionally remove the resist pattern layer to provide a modified substrate;

[0042] vi) Optionally, steps iv) and / or i)-v) may be repeated once or multiple times on the modified substrate (optionally replacing the photoresist coating with an alternative photoresist coating, such as a standard photoresist; and optionally using alternative radiation during exposure);

[0043] Optionally, steps (i) to (vi) (i.e., preliminary steps (i)-(vi)) are performed before step (i) of the method, and optionally they are repeated once or multiple times, using a resist coating or alternative resist coating and using electromagnetic radiation or alternative radiation during exposure.

[0044] The resist coating comprises a resist composition that is optionally dried and / or cured as defined herein.

[0045] According to another aspect of the invention, an imaging substrate is provided, which can be obtained, acquired, or directly obtained by a photolithography method as defined herein.

[0046] According to another aspect of the present invention, a method for manufacturing a photolithographic mask (e.g., a photomask) is provided, the method comprising:

[0047] i) Provide a substrate coated with resist as defined herein or apply a resist coating to a substrate (suitably for photolithography);

[0048] ii) Exposing the resist coating to electromagnetic radiation to provide exposure;

[0049] iii) Develop the exposed resist coating to produce a resist pattern layer, the resist pattern layer comprising: a portion of the resist coating that is insoluble in the developer (i.e., ridges); and an array of grooves extending through the resist pattern layer;

[0050] iv) Optionally selectively modify the substrate, substrate surface or portion thereof beneath the resist pattern layer (appropriately such that the modified portion of the substrate or substrate surface has increased or decreased transparency to a predetermined type of radiation (e.g., radiation used in photolithography) relative to the original substrate or unmodified portion of the substrate or substrate surface).

[0051] v) Optionally, the resist pattern layer is removed to provide a modified substrate;

[0052] The resist coating comprises a resist composition that is optionally dried and / or cured as defined herein.

[0053] According to another aspect of the invention, a photomask (e.g., a photomask) is provided that can be obtained, acquired, or directly obtained by a method for manufacturing a photomask (e.g., a photomask) as defined herein.

[0054] According to another aspect of the present invention, a method for performing photolithography is provided, the method comprising:

[0055] i) Provide a substrate coated with resist or apply a resist coating to the substrate (the resist coating can be any resist coating suitable for exposure by a photomask, such as a photoresist);

[0056] ii) A resist coating that provides exposure by partially exposing the resist coating to radiation (e.g., UV or visible light) through a photomask (e.g., a photomask) as defined herein;

[0057] iii) Develop the exposed resist coating to produce a resist pattern layer, the resist pattern layer comprising: a portion of the resist coating that is insoluble in the developer (i.e., ridges); and an array of grooves extending through the resist pattern layer;

[0058] iv) Optionally, the substrate, substrate surface, or a portion thereof under the resist pattern layer may be modified;

[0059] v) Optionally, the resist pattern layer is removed to provide a modified substrate;

[0060] vi) Optionally, steps iv) and / or i)-v) may be repeated once or multiple times on the modified substrate (with the resist coating of the present invention or an alternative resist coating, such as a standard photoresist; and electromagnetic radiation or alternative radiation may be used during exposure with or without a photomask).

[0061] Optionally, steps (i) to (vi) of the method and / or the photolithography method (i) are performed before step (i) of the method (i) (i) and can be repeated once or multiple times, using a resist coating or alternative resist coating and using electromagnetic radiation or alternative radiation during exposure.

[0062] According to another aspect of the invention, an imaging substrate is provided, which can be obtained, acquired, or directly obtained by a photolithography method as defined herein.

[0063] According to another aspect of the present invention, a method for manufacturing an integrated circuit die or an integrated circuit wafer comprising a plurality of integrated circuit dies is provided, wherein each die comprises a plurality of electronic components, wherein the method comprises:

[0064] i) Providing a substrate coated with resist as defined herein, or applying a resist coating to a substrate; and

[0065] ii) Expose the resist coating partially to radiation (e.g., UV) to provide exposure to the resist coating;

[0066] or

[0067] i) Providing a substrate coated with resist or applying a resist coating to a substrate (the resist coating can be any resist coating suitable for exposure through a photomask, such as a photoresist); and

[0068] ii) A resist coating that exposes a portion of the resist coating to radiation (e.g., UV or visible light) by means of a photomask (e.g., a photomask) as defined herein (or available by means of means defined herein);

[0069] and

[0070] iii) Develop the exposed resist coating to produce a resist pattern layer, the resist pattern layer comprising: a portion of the resist coating that is insoluble in the developer (i.e., ridges); and an array of grooves extending through the resist pattern layer;

[0071] iv) Modifying the substrate, substrate surface, or portion thereof beneath the resist pattern layer (this may include interconnecting the electronic components of the die or each die with conductive conductors).

[0072] v) Remove the resist pattern layer to provide a modified substrate;

[0073] vi) Optionally repeat steps iv) and / or i)-v) once or more on the modified substrate (with the resist coating of the present invention or an alternative resist coating; and optionally use alternative radiation during exposure);

[0074] vii) Optionally, the electronic components of the said or each die are interconnected with the conductor conductivity (if not performed during one or more substrate / substrate surface modification steps) to provide an integrated circuit with external contact terminals.

[0075] viii) Optionally, one or more further finishing steps may be performed;

[0076] ix) Optionally, the integrated circuit die can be separated from a wafer that includes multiple integrated circuit dies;

[0077] Optionally, steps (i) to (vi) of the method (i) (i.e., preliminary steps (i)-(vi), optionally using one of the two steps (i) / (ii)) combination) and / or steps (i) to (vi) of the photolithography method are performed before step (i) of the method, optionally repeated once or multiple times, using the resist coating of the present invention or an alternative resist coating;

[0078] The resist coating comprises a resist composition that is optionally dried and / or cured as defined herein.

[0079] According to another aspect of the invention, an integrated circuit die is provided, which can be obtained, acquired, or directly obtained by a method for manufacturing an integrated circuit die as defined herein.

[0080] According to another aspect of the invention, an integrated circuit wafer comprising a plurality of integrated circuit dies is provided, which can be obtained, acquired, or directly obtained by a method for manufacturing integrated circuit wafers as defined herein. This integrated circuit and wafer exhibit very high resistance and high dry etching selectivity (typically greater than 20:1, i.e., resist etching is 20 times or more slower than the silicon substrate on the lower facet). This, in turn, provides a high aspect ratio.

[0081] According to another aspect of the present invention, a method for manufacturing an integrated circuit package is provided, the integrated circuit package including a plurality of pins and an integrated circuit die, the integrated circuit die having external contact terminals electrically connected to the respective plurality of pins, wherein the method includes:

[0082] i) Provide an integrated circuit die as defined herein or manufacture an integrated circuit die by means of manufacturing an integrated circuit die as defined herein;

[0083] ii) Attaching an integrated circuit die to a package substrate, wherein the package substrate includes electrical contacts, each of which is optionally connected to or can be connected to a corresponding pin;

[0084] iii) Conductively connect each external contact terminal of the integrated circuit die to the corresponding electrical contact on the package substrate;

[0085] iv) Optionally (and if necessary) the electrical contacts of the package substrate can be connected to the corresponding pins;

[0086] v) Package integrated circuit die.

[0087] According to another aspect of the invention, an integrated circuit package is provided, which can be obtained, acquired, or directly obtained by a method of manufacturing an integrated circuit package as defined herein.

[0088] According to another aspect of the invention, a method for manufacturing a circuit board is provided, the circuit board comprising an integrated circuit package (appropriately defined herein) including a plurality of pins, wherein the method comprises:

[0089] i) Provide an integrated circuit package as defined herein or manufacture an integrated circuit package by means of manufacturing an integrated circuit package as defined herein;

[0090] ii) Connect the integrated circuit package to the circuit board.

[0091] According to another aspect of the invention, a circuit board is provided that can be obtained, acquired, or directly obtained by a method of manufacturing a circuit board as defined herein.

[0092] According to another aspect of the present invention, a method of manufacturing an electronic device or system is provided, the electronic device or system including or connectable to a power source and including a circuit board electrically connected to or connectable to the power source, wherein the method includes:

[0093] i) Provide a circuit board as defined herein or manufacture a circuit board by means of manufacturing a circuit board as defined herein;

[0094] ii) Integrating the circuit board into the electronic device or system.

[0095] According to another aspect of the invention, an electronic device or system is provided that is obtainable, acquired, or directly obtained by means of manufacturing an electronic device or system as defined herein.

[0096] According to another aspect of the invention, the use of the resist composition is provided for: coating a substrate with a resist coating; patterning a substrate; imaging; as a resist coating in photolithography; selectively modifying the surface of a substrate; manufacturing photolithographic masks (e.g., those used in photolithography or integrated circuit manufacturing); manufacturing multilayer substrates; manufacturing integrated circuit dies; manufacturing integrated circuit wafers; manufacturing integrated circuit packages; manufacturing circuit boards; or manufacturing electronic devices or systems.

[0097] While the resist compositions of the present invention can be applied to various radiation sources, including UV, eBeam, etc., most suitably, the resist compositions are resist compositions for use in photolithography, and any resist component is suitably a photoresist component.

[0098] However, the present invention also provides other aspects of the invention, such as “compositions”, wherein the composition is suitably defined or suitably has any component, property, or parameter of any resist composition as defined herein. Such “compositions” can be used in applications other than resists or lithography, for example, the composition can be used as a self-healing composition, for example, alone or in combination with one or more polymers as needed for self-healing. Self-healing can then be induced using electromagnetic radiation as defined herein.

[0099] In another aspect of the invention, anti-scattering components or compounds as defined herein are provided.

[0100] In another aspect of the invention, an anti-scattering-resist mixture or compound as defined herein is provided.

[0101] Any feature described with respect to any particular aspect of the invention (including optional, suitable, and preferred features) may also be a feature of any other aspect of the invention (including optional, suitable, and preferred features). Attached Figure Description

[0102] To better understand the present invention, and to illustrate how to implement embodiments of the invention, reference is now made to the following schematic diagrams by way of example, wherein:

[0103] Figure 1 The graphs shown illustrate how radiation absorption varies with incident wavelength for each of formulation A(i) (i.e., Cr7Ni metal complex only) and formulation A(ii) (Cr7Ni complex + photoacid-producing agent).

[0104] Figure 2 SEM images of the resist coatings after development based on the resist compositions of Examples 2A(i) and 2A(ii) are shown: (a) a 250 nm nanostructure with a 600 nm pitch produced at a wavelength of 248 nm using formulation A(i); (b) a nanostructure indicated by a closed black box in a, manufactured using formulation A(i); (c) a 250 nm nanostructure manufactured using PAG with formulation A(ii); and (d) a nanostructure indicated by a closed black box in c, manufactured using formulation A(ii).

[0105] Figure 3SEM images of the resist coatings after development based on the resist compositions of Examples 2A(i) and 2A(ii) are shown: (a) SEM image of a 200 nm nanostructure produced at a wavelength of 193 nm using formulation A(i); (b) nanostructures fabricated using formulation A(i) and indicated by closed black boxes in a; (c) 200 nm nanostructures fabricated using PAG (i.e., formulation A(ii)); (d) nanostructures fabricated using formulation A(ii) and indicated by closed black boxes in c.

[0106] Figure 4 The comparison curves of Cr7Ni ring molecules after exposure at a wavelength of 248 nm are shown.

[0107] Figure 5 The contrast curve of Cr7Ni ring molecules after exposure at a wavelength of 193 nm is shown.

[0108] Figure 6 It shows 396mJ / cm 2 An enlarged view of a substrate coated with a post-development / drying resist, based on compound 3 (HgCl2-derived), exposed to EUV at an exposure dose to produce a feature width of approximately 22 nm and a pitch of approximately 44 nm.

[0109] Figure 7 It shows 322mJ / cm 2 An enlarged view of a substrate coated with a post-development / drying resist, based on compound 3 (HgCl2-derived), exposed to eUV at an exposure dose to produce a feature width of approximately 16 nm and a pitch of approximately 32 nm.

[0110] Figure 8 It shows 357mJ / cm 2 An enlarged view of a substrate coated with a post-development / drying resist, based on compound 5 (HgI2 derivative), exposed to eUV at an exposure dose to produce a feature width of approximately 22 nm and a pitch of approximately 44 nm.

[0111] Figure 9 It shows 268mJ / cm 2 An enlarged view of a substrate coated with a post-development / drying resist, based on compound 5 (HgI2 derivative), exposed to eUV at an exposure dose to produce a feature width of approximately 16 nm and a pitch of approximately 32 nm.

[0112] Figure 10 It shows 244 mJ / cm 2 Exposure to eUV at a dose of approximately 13 nm in feature width and approximately 32 nm in pitch produces magnified images of a substrate coated with post-development / drying resist based on compound 5 (HgI2 derivative). This exposure yielded optimal results under these conditions.

[0113] Figure 11 It shows 222mJ / cm 2 Exposure to eUV at a dose of approximately 13 nm in feature width and approximately 32 nm in pitch produces magnified images of a substrate coated with post-development / drying resist based on compound 5 (HgI2 derivative). This exposure yielded optimal results under these conditions.

[0114] Figure 12 The figure illustrates the reduced exposure dose required (and therefore increased sensitivity) in the six generations of improvements to the photoresist coating. Detailed Implementation

[0115] definition

[0116] Unless otherwise stated, the following terms used in the specification and claims have the following meanings as stated in the following statements.

[0117] Here, unless otherwise stated, the terms "radiation" and "irradiation" refer to the exposure of a resist composition or its coating to radiation that causes a physical or chemical change in the resist composition, thereby allowing it to be "developed". The radiation can be any suitable type of radiation. In the case of electron beam lithography, the radiation is electron beam radiation; where lithography is performed, electromagnetic radiation (typically UV) is used.

[0118] "Resist component" is a component that changes upon exposure to relevant radiation (e.g., electron beam radiation, ionizing radiation, ultraviolet radiation). In some embodiments, the antiscattering component is a resist component, particularly one that reacts under exposure (or shortly after exposure) to produce varying solubility. However, suitably, the resist component itself is not an antiscattering component, although in some embodiments it may be part of (or otherwise associated with) an antiscattering component. For example, an antiscattering component may be incorporated into a resist component (or in fact multiple resist components, each being the same or different in each case) such that they together form a single compound or component, which may be referred to as a resist / antiscattering mixture. In some embodiments, the resist composition may include one or more additional resist components, such as standard resist polymers like PMMA. When using resist compositions excluded from the scope of this invention, such compositions may include other resist components, including polymer components, and may optionally (substantially) contain no antiscattering compound.

[0119] In this document, non-limiting references to "resist composition," "resist coating," "resist material," "material coated with resist," etc., may refer to the resist compositions, coatings, materials, or coating materials of the present invention, or may refer to alternative resist compositions, coatings, materials, or coating materials. Most preferably, non-limiting references to resist compositions, coatings, materials, or coating materials refer to alternative resists.

[0120] The alternative resist compositions and coatings can be produced and used according to standard workshop techniques known to those skilled in the art. They can also be used in the same manner as defined herein with respect to the resist compositions and coatings of the present invention (including methods of coating, exposure, development, removal, etc.), but those skilled in the art can readily apply the methods defined herein to the alternative resists in question.

[0121] In this document, an "antiscattering compound" in a resist composition (which in some cases may be the resist component itself or may otherwise be associated with or combined with the resist component) is used to modulate and control the effects of incident radiation, scattered radiation, and / or secondary electrons during resist patterning. By minimizing scattering events, the antiscattering compound is considered to help focus and guide this radiation to the desired exposure location, thereby minimizing any undesirable exposure. This, in turn, allows for the formation of a sharper, higher-resolution image within the resist. Furthermore, the antiscattering compound can prevent or reduce overexposure of certain vulnerable components within the resist that could otherwise affect subsequent development of the resist after exposure. Thus, the antiscattering compound allows for reduced blurring; reduced proximity effects (i.e., energy spilling over to other unexposed portions of the resist); increased resolution; and increased aspect ratio (where aspect ratio is the depth divided by the width of the associated pattern lines (whether grooves or ridges)). When an antiscattering compound is described as containing one or more complexes whose charges do not cancel each other out (to produce a neutral compound), the actual antiscattering compound is a suitable salt of a non-neutral combination of complexes (thus generally given as a neutral compound). Those skilled in the art will readily understand that any remaining charge will generally be offset by a suitable anti-cation. Therefore, throughout the specification, anti-scattering compounds, and virtually any complex, can be defined without the stated anti-ion.

[0122] Here, the term "insoluble in developer" is intended to indicate that a given portion of the coating has relatively lower solubility in the developer than a corresponding "soluble in developer" portion. This does not necessarily exclude the possibility that a "insoluble in developer" portion of the coating may have partial or even complete solubility in the developer (if the development time is sufficiently long). As those skilled in the art will understand, the distinction between "soluble in developer" and "insoluble in developer" for a portion of the coating indicates that a part of the coating (e.g., the portion exposed to radiation) has different solubility properties than other parts of the coating (e.g., the portion not exposed to radiation), and therefore generally different chemical properties. The nature of the developer is irrelevant, as a developer can be reasonably selected based on the different solubility properties of the individual coating portions, depending on which portions of the coating are to be removed. Generally, the term "solubility," as used in the context of development, refers to kinetic solubility rather than thermodynamic solubility, because the rate of dissolution is critical, although thermodynamic solubility may be related to kinetic solubility, as those skilled in the art should understand.

[0123] Generally, in the methods of the present invention, the terms "photoresist coating" and "electromagnetic radiation" are used to indicate that the photoresist coating and electromagnetic radiation (typically UV) of the present invention are used at least once in the method. However, alternative photoresist coatings and alternative radiation may be optionally used in one, some, or all of any other steps (e.g., repeating steps and / or pre-steps). In some methods of the present invention, reference is made to optional repeating or pre-steps including "steps (i) to (vi) of the method of performing photolithography," in which case the method of performing photolithography may optionally include only alternative photoresist coatings and alternative radiation, rather than the photoresist coating and electromagnetic radiation of the present invention—that is, in this case, the mentioned method of performing photolithography is merely a shorthand for repeating or pre-steps involving the photoresist or alternative photoresist of the present invention.

[0124] Unless otherwise stated, any reference to the term "average" in this document is intended to refer to the average value.

[0125] In this document, unless otherwise stated, the term "parts by weight" (pbw) used when referring to multiple components / components refers to the relative proportions between the multiple components / components. Although in many embodiments the amount of a single component in the composition may be given as a "% by weight" value, in alternative embodiments any or all of these % by weight values ​​may be converted to parts by weight to define a multi-component composition. This is because the relative proportions between components are generally more important than their absolute concentrations. When a composition comprising multiple components is described only in parts by weight (i.e., only indicating the relative proportions of the components), it is not necessary to specify the absolute amount or concentration of the components (whether all or individually), because these advantages of the invention arise from the relative proportions of the individual components rather than their absolute amounts or concentrations. However, suitably, a resist composition comprises a combination of at least 1% by weight, suitably at least 5% by weight, suitably at least 10% by weight, suitably at least 15% by weight of all specified components (excluding any diluents / solvents). Suitably, a resist composition comprises a combination of at most 50% by weight, suitably at most 30% by weight, suitably at most 20% by weight of all specified components (excluding any diluents / solvents). The balance (i.e. the remaining portion of the resist composition consisting of the specified components excluding the diluent / solvent) may consist primarily of the diluent / solvent.

[0126] In this document, those skilled in the art (particularly in inorganic chemistry) will readily understand the reference to “complex” as to metal complexes (e.g., host metal complexes) or coordination complexes. Herein, a complex generally refers to one or more metallic substances (typically metal ions) coordinated to one or more ligands. Where a particular complex is defined by reference to a formulation and / or a series of components, unless otherwise stated, a suitable complex may include any salt, solvate, or hydrate thereof, and may additionally or alternatively include one or more optional additional / terminal ligands and / or one or more additional metallic substances. In most embodiments, any defined complex may suitably include its salt (particularly where the complex has a net charge). However, suitably, such a complex may (substantially) as specifically defined (albeit in the optional salt form) exclude solvates, hydrates, or complexes having one or more optional additional / terminal ligands, and / or one or more additional metallic substances. Furthermore, where a particular complex is defined by a formulation and / or a series of components and the absolute or relative amounts of the individual substances in the complex are given (e.g., by reference to stoichiometry or the number of moles of the substance per mole of the complex), unless otherwise stated, this may suitably include any variation in which the absolute or relative amounts of the individual substances are within + / - 10% of those specified, more suitably within + / - 5%, more suitably within + / - 1%, more suitably within + / - 0.1%, but in a preferred embodiment, the complex (including the absolute or relative amounts of the individual substances in the complex) is substantially as defined.

[0127] Here, the unspecified number of multiple substances of class X (e.g., it can be a metallic substance, a ligand substance, etc.) can be referred to as X1, X2, ..., X n Alternatively, in the context, the complex can be defined as [X1X2…X… n ], where X1 is the first type of X, X2 is the second type of X, and X n It is the nth type of X (e.g., X3, X4, ...).

[0128] In this document, unless otherwise stated, all chemical nomenclature shall be defined in accordance with the IUPAC definition.

[0129] In this specification, the term "alkyl" includes both straight-chain alkyl and branched-chain alkyl. Individual alkyl groups, such as "propyl," refer only to the straight-chain form, and individual branched alkyl groups, such as "isopropyl," refer only to the branched form. For example, "(1-6C)alkyl" includes (1-4C)alkyl, (1-3C)alkyl, propyl, isopropyl, and tert-butyl. Similar convention applies to other radicals; for example, "phenyl(1-6C)alkyl" includes phenyl(1-4C)alkyl, benzyl, 1-phenylethyl, and 2-phenylethyl.

[0130] The term "(m-nC)" or "(m-nC) group" used alone or as a prefix refers to any group having m to n carbon atoms. In embodiments where the value of n is greater than or equal to 6, n may optionally be a smaller number, such as 2, 4, or 5.

[0131] "alkylene", "alkenylene", or "alkynylene" groups are alkyl, alkenyl, or alkynyl groups located between two other chemical groups and used to connect the two other chemical groups. Therefore, "(1-6C)alkylene" refers to a straight-chain saturated divalent hydrocarbon group with 1-6 carbon atoms or a branched saturated divalent hydrocarbon group with 3-6 carbon atoms, such as methylene, ethylene, propylene, 2-methylpropylene, pentylene, etc.

[0132] "(2-6C)-enylene" refers to a straight-chain divalent hydrocarbon group with 2-6 carbon atoms containing at least one double bond, or a branched divalent hydrocarbon group with 3-6 carbon atoms, such as vinylene, 2,4-pentadienylene, etc.

[0133] "(2-6C)-ynylene" refers to a straight-chain divalent hydrocarbon group with 2-6 carbon atoms containing at least one triple bond, or a branched divalent hydrocarbon group with 3-6 carbon atoms, such as ethynylene, propynylene, and butynylene.

[0134] “(3-8C)cycloalkyl” refers to a hydrocarbon ring containing 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or bicyclic [2.2.1]heptyl.

[0135] "(3-8C)cycloalkenyl" refers to a hydrocarbon ring containing at least one double bond, such as cyclobutenyl, cyclopentenyl, cyclohexenyl, or cycloheptenyl, for example, 3-cyclohexen-1-yl or cyclooctenyl.

[0136] "(3-8C)cycloalkyl-(1-6C)alkylene" means a (3-8C)cycloalkyl group covalently linked to a (1-6C)alkylene group, both of which are defined herein.

[0137] The term "halogenated" refers to fluorinated, chlorinated, brominated, and iodinated compounds.

[0138] The terms "heterocyclic group," "heterocyclic," or "heterocyclic" refer to a non-aromatic, saturated, or partially saturated monocyclic, fused, bridged, or spirobicyclic heterocyclic system. The term heterocyclic group includes both monovalent and divalent substances. Monocyclic heterocycles contain about 3 to 12 (suitably 3 to 7) ring atoms, with 1 to 5 (suitably 1, 2, or 3) heteroatoms selected from nitrogen, oxygen, or sulfur. Bicyclic heterocycles contain 7 to 17 member atoms, suitably 7 to 12 member atoms. Bicyclic heterocycles can be fused, spirocyclic, or bridged ring systems. Examples of heterocyclic groups include cyclic ethers such as ethylene oxide, oxetyl, tetrahydrofuranyl, dioxyl, and substituted cyclic ethers. Nitrogen-containing heterocycles include, for example, nitrogen-containing heterocyclic butyl, pyrrolyl, piperidinyl, piperazine, tetrahydrotriazine, and tetrahydropyrazolyl. Typical sulfur-containing heterocycles include tetrahydrothiophene, dihydro-1,3-dimercapto, tetrahydro-2H-thiaran, and hexahydrothiazolinyl. Other heterocycles include dihydrooxazolyl, tetrahydrooxadiazolyl, tetrahydrodioxazolyl, tetrahydrooxazolyl, hexahydrotriazine, tetrahydrooxazine, morpholinyl, thiomorpholinyl, tetrahydropyrimidinyl, dioxacyclopentenyl, octahydrobenzofuranyl, octahydrobenzimidazolyl, and octahydrobenzothiazolinyl. For sulfur-containing heterocycles, sulfur oxide heterocycles containing SO or SO2 groups are also included. Examples include the sulfoxide and sulfone forms of tetrahydrothiophene and thiomorpholinyl, such as tetrahydrothiophene 1,1-dioxide and thiomorpholinyl 1,1-dioxide. Suitable examples of heterocyclic groups with one or two oxo (=O) or thio (=S) substituents are, for example, 2-oxopyrrolyl, 2-thiopyrrolyl, 2-oxoimidazoyl, 2-thioimidazoyl, 2-oxopyridinyl, 2,5-dioxopyrrolyl, 2,5-dioxoimidazoyl, or 2,6-dioxopyridinyl. Particularly desirable heterocyclic groups are saturated monocyclic 3- to 7-membered heterocyclic groups containing one, two, or three heteroatoms selected from nitrogen, oxygen, or sulfur, such as azobutyric, tetrahydrofuranyl, tetrahydropyranyl, pyrrolyl, morpholinyl, tetrahydrothiophenyl, tetrahydrothiophenyl 1,1-dioxide, thiomorpholinyl, thiomorpholinyl 1,1-dioxide, piperidinyl, homopiperidinyl, piperazinyl, or homopiperazinyl. As those skilled in the art will understand, any heterocycle can be linked to another group via any suitable atom, for example, via a carbon or nitrogen atom. However, the piperidine- or morpholino- referred to in this article are piperidine-1-yl or morpholino-4-yl rings linked by a cyclic nitrogen ring.

[0139] A "bridged ring system" refers to a ring system in which two rings share more than two atoms. See, for example, Advanced Organic Chemistry, by Jerry March, 4. thEdition, Wiley Interscience, pages 131-133, 1992. Bridged heterocyclic ring systems include azabicyclo[2.2.1]heptane, 2-oxa-5-azabicyclo[2.2.1]heptane, azabicyclo[2.2.2]octane, azabicyclo[3.2.1]octane, and quinine ring.

[0140] "Heterocyclic (1-6C)alkyl" refers to a heterocyclic group covalently linked to a (1-6C)alkylene group, both of which are defined herein.

[0141] The term "heteroaryl" or "heteroaromatic" refers to an aromatic monocyclic, bicyclic, or polycyclic group that incorporates one or more (e.g., 1-4, particularly 1, 2, or 3) heteroatoms selected from nitrogen, oxygen, or sulfur. The term heteroaryl includes both monovalent and divalent substances. Examples of heteroaryls are monocyclic and bicyclic groups containing 5 to 12 ring members, more typically 5 to 10 ring members. A heteroaryl can be, for example, a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic, such as a bicyclic structure formed by fused five-membered and six-membered rings or by two fused six-membered rings. Each ring may contain up to about four heteroatoms, typically selected from nitrogen, sulfur, and oxygen. Typically, a heteroaryl ring will include up to 3 heteroatoms, more typically up to 2 heteroatoms, such as a single heteroatom. In one embodiment, the heteroaryl ring contains at least one cyclic nitrogen atom. The nitrogen atom in a heteroaryl ring can be basic, as in the case of imidazole or pyridine, or substantially non-basic, as in the case of indole or pyrrole nitrogen. Typically, the number of basic nitrogen atoms present in a heteroaryl ring (including any amino substituents in the ring) will be less than five.

[0142] Examples of heteroaryl groups include furanyl, pyrroloyl, thiophene, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, 1,3,5-triazenoyl, benzofuranyl, indolyl, isoindolyl, benzothiophene, benzooxazolyl, benzoimidazolyl, benzothiazolyl, benzothiazolyl, indolyl, purinyl, benzofuranyl, quinolinyl, isoquinolinyl, quinazolinyl, and quinolineyl. Oxalinyl, cyclolinyl, pteridinyl, naphridinyl, carbazolyl, phenazinyl, benzisoquinolinyl, pyridopyrazinyl, thieno[2,3-b]furanyl, 2Hfurano[3,2-b]pyranyl, 5Hpyrido[2,3-d]oxazinyl, 1Hpyrazolo[4,3-d]oxazolyl, 4H imidazo[4,5-d]thiazolyl, pyrazolo[2,3-d]pyridazinyl, imidazo[2,1-b]thiazolyl, imidazo[1,2-b][1,2,4]triazinyl. "Heteroaryl" also includes some aromatic bicyclic or polycyclic systems, wherein at least one ring is an aromatic ring and one or more other rings are non-aromatic saturated or partially saturated rings, provided that at least one ring contains one or more heteroatoms selected from nitrogen, oxygen, or sulfur. Examples of some aromatic heteroaryl groups include, for example, tetrahydroisoquinolinyl, tetrahydroquinolinyl, 2-oxo-1,2,3,4-tetrahydroquinolinyl, dihydrobenzothiophene, dihydrobenzofuranyl, 2,3-dihydrobenzo[1,4]dioxacyclohexenyl, benzo[1,3]dioxacyclopentenyl, 2,2-dioxo-1,3-dihydro-2-benzothiophene, 4,5,6,7-tetrahydrobenzofuranyl, indololinyl, 1,2,3,4-tetrahydro-1,8-naphthidyl, 1,2,3-tetrahydropyrido[2,3-b]pyrazinyl, and 3,4-dihydro-2H-pyrido[3,2-b][1,4]oxazinyl.

[0143] Examples of five-membered heteroaryl groups include, but are not limited to, pyrrole, furanyl, thiophene, imidazolyl, furazolidone, oxazolyl, oxadiazolyl, oxtriazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, triazolyl, and tetrazolyl.

[0144] Examples of six-membered heteroaryl groups include, but are not limited to, pyridyl, pyrazinyl, pyridinyl, pyrimidinyl, and triazinyl.

[0145] The bicyclic heteroaryl group can be, for example, selected from the following groups:

[0146] A benzene ring fused with a 5- or 6-membered ring containing 1, 2, or 3 heteroatoms;

[0147] A pyridine ring fused with a 5- or 6-membered ring containing 1, 2, or 3 heteroatoms;

[0148] A pyrimidine ring fused with a 5- or 6-membered ring containing 1 or 2 heteroatoms;

[0149] Pyrrole rings fused with 5- or 6-membered rings containing 1, 2, or 3 heteroatoms;

[0150] A pyrazole ring fused with a 5- or 6-membered ring containing one or two heteroatoms;

[0151] Pyrazine rings fused with 5- or 6-membered rings containing 1 or 2 heteroatoms;

[0152] An imidazole ring fused with a 5- or 6-membered ring containing one or two heteroatoms;

[0153] An oxazole ring fused with a 5- or 6-membered ring containing one or two heteroatoms;

[0154] An isoxazole ring fused with a 5- or 6-membered ring containing one or two heteroatoms;

[0155] A thiazole ring fused with a 5- or 6-membered ring containing one or two heteroatoms;

[0156] An isothiazole ring fused with a 5- or 6-membered ring containing one or two heteroatoms;

[0157] Thiophene rings fused with 5- or 6-membered rings containing 1, 2, or 3 heteroatoms;

[0158] Furan rings fused with 5- or 6-membered rings containing 1, 2, or 3 heteroatoms;

[0159] Cyclohexyl rings fused with 5- or 6-membered heteroaromatic rings containing 1, 2, or 3 cyclic heteroatoms; and

[0160] A cyclopentyl ring fused with a 5- or 6-membered heteroaromatic ring containing 1, 2, or 3 cyclic heteroatoms.

[0161] Specific examples of bicyclic heteroaryl groups containing a six-membered ring fused with a five-membered ring include, but are not limited to, benzofuranyl, benzothiophenyl, benzimidazolyl, benzoxazolyl, benzoisoxazolyl, benzothiazolyl, benzoisothiazolyl, isobenzofuranyl, indolyl, isoindolyl, indololinyl, isoindololinyl, purine (e.g., adenine, guanine), indazole, benzodioxanepentenyl, and pyrazolopyridyl.

[0162] Specific examples of bicyclic heteroaryl groups containing two fused six-membered rings include, but are not limited to, quinolinyl, isoquinolinyl, benzodihydropyranyl, thiobenzodihydropyranyl, chromenyl, isochromenyl, benzodioxane, benzoxazinyl, benzodiazinyl, quinoxolinyl, quinazolinyl, cyclolinyl, phthalazinyl, naphthidyl, and pteridylyl.

[0163] "Heteroaryl(1-6C)alkyl" refers to a heteroaryl group covalently linked to a (1-6C) alkylene group, both of which are defined herein. Examples of heteroaryl groups include pyridin-3-ylmethyl, 3(benzofuran-2-yl)propyl, etc.

[0164] The term "aryl" refers to a cyclic or polycyclic aromatic ring having 5 to 12 carbon atoms. The term aryl includes both monovalent and divalent substances. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, and naphthyl. In a specific embodiment, the aryl group is phenyl.

[0165] The term "aryl(1-6C)alkyl" refers to an aryl group covalently linked to a (1-6C)alkylene group, both of which are defined herein. Examples of aryl-(1-6C)alkyl groups include benzyl, phenethyl, etc.

[0166] This specification also uses multiple composite terms to describe groups that include more than one function. These terms should be understood by those skilled in the art. For example, heterocyclic (m-nC) alkyl includes (m-nC) alkyl groups substituted with heterocyclic groups.

[0167] The term "optionally substituted" refers to both substituted and unsubstituted groups, structural or molecular groups.

[0168] When the optional substituents are selected from "one or more" groups, it should be understood that the definition includes all substituents selected from one of the specified groups or two or more substituents selected from the specified groups. Suitable examples of optional substituents include, but are not limited to, halides, amino, cyano, imino, enamino, (1-6C)alkylamino, di-[(1-6C)alkyl]amino, tri-[(1-6C)alkyl]amino, oxo, oxide, hydroxide (OH-), (1-6C) alkoxide, (2-6C) alkenoxy, (2-6C) alkynoxy, formyl, carboxyl, (1-6C) alkoxycarbonyl, (2-6C) alkanoyl, (2-6C) alkanoyloxy, sulfonyl, sulfide, hydrosulfide, (1-6C) alkylthio, (2-6C) alkenthio, (2-6C) alkynthio, thiocarbonyl, heterocyclic group containing at least one internal heteroatom selected from nitrogen, oxygen or sulfur, heteroaryl group (e.g., pyridyl) containing at least one internal heteroatom selected from nitrogen, oxygen or sulfur, or (where appropriate); wherein any CH, CH2 or CH3 may optionally be substituted.

[0169] Unless otherwise stated, “pKa” as used herein should be interpreted as the pKa value in water at standard ambient temperature and pressure (SATP), and appropriately as the pKa value of the conjugate acid of the relevant substance.

[0170] In this document, the terms "carbocyclic group," "carbocyclic," or "carbocyclic group" refer to a non-aromatic cyclic hydrocarbon group that typically has 3 to 10 cyclic carbon atoms (i.e., (3-10C) carbocyclic group) and zero heteroatoms in a non-aromatic ring system. Suitably, carbocyclic groups include (3-nC) cycloalkyl and (3-nC) cycloalkenyl groups. Exemplary embodiments include: cyclobutyl, cyclobutenyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptenyl, cycloheptadienyl, cyclohepttrienyl, cyclooctyl, cyclooctenyl, bicyclo[2.2.1]heptyl, and bicyclo[2.2.2]octyl.

[0171] In this document, the terms "macrocyclic group," "macrocycle," or "macrocycle family" refer to macrocycles well known in the art. Such macrocyclic compounds are suitable cyclic macromolecules or macrocyclic portions of molecules. Suitably, the macrocycle contains nine or more atoms. Suitably, the macrocycle has three or more internal electron pair donor atoms. The macrocycle is suitably capable of reacting with a central metallic substance (e.g., Mg). 2+ Coordinated cyclic molecules. Examples include porphyrins.

[0172] In this article, the term "hydrocarbon group" generally refers to any aliphatic, acyclic, or cyclic (including aryl) hydrocarbon group that appropriately lacks heteroatoms.

[0173] In this text, "coordinating moiety" suitably refers to an atom or moiety capable of coordinating with other independent atoms, molecules, ions, or complexes by means of coordination, or suitably by means of bonding. Suitably, the coordinating moiety can accept or donate one or more lone pairs of electrons, but suitably, the coordinating moiety cannot accept and donate simultaneously.

[0174] In this paper, a "multimetallic" system (e.g., a multimetal cage) simply refers to a system (or complex) containing more than one metal atom / ion (which can be the same or different (in terms of metal element, oxidation state, etc.)). For example, a metal complex containing eight Cr(III) ions and a metal complex containing seven Cr(III) ions and one Ni(II) ion are multimetallic. Multimetallic systems such as multimetal cages can be of the same metal (e.g., where all metallic substances originate from the same metal element, even if some metallic substances have a different oxidation state than another metal) or of different metals (e.g., where the metallic substances are a mixture of different metallic substances originating from different metal elements, regardless of whether the different metallic substances have the same or different oxidation states). Most preferably, all metallic substances in a homometallic complex have the same oxidation state, but they can also have different oxidation states. Most preferably, the different metallic substances in a heterometallic complex have different oxidation states, but they can also have the same oxidation state.

[0175] Here, a "secondary electron generator" is a component that appropriately releases secondary electrons using electromagnetic radiation after irradiation. In a particular embodiment, the secondary electron generator releases electrons upon exposure to ultraviolet radiation of an appropriate wavelength (typically above 5 eV).

[0176] In this article, the "effective atomic number (Z)" of a compound is used. eff ")" is the average atomic number obtained from the weighted sum of the atomic components of a compound.

[0177] Although those skilled in the art will know that calculating and / or measuring Z eff Various methods (e.g., FWSpiers, Effective Atomic Number and Energy Absorption in Tissues, Br. J. radiool., 19, 52, 1946), but for the purposes of this invention, "effective atomic number (Z)" is used. eff The following formula is used appropriately to calculate a simple mass-weighted average:

[0178] Z eff =Σα i Z i

[0179] Z i α is the atomic number of the i-th element in the compound. i It is the fraction of the total atomic numbers of all atoms in the compound (i.e., the total number of protons in the compound) that is composed of the i-th element. For a compound containing n elements, this formula can be expressed as:

[0180] Z eff =α1Z1+α2Z2+…(+α n Z n ).

[0181] This is similar to the Spiers equation (FWSpiers, Effective Atomic Number and Energy Absorption in Tissues, Br. J. radiool., 19, 52, 1946), but without the exponents used by Spiers. The Spiers equation represents Z... eff as follows:

[0182] Z eff p =Σα i Z i p

[0183] The exponent p is appropriately approximately 3 (e.g., p = 2.94). Although in some implementations, Z can be used eff This Spiers definition (especially at p = 2.94), and the Z disclosed in this paper eff Any preferred, optional, and appropriate value can be applied to Spiers' definition, but the Z value described above should preferably be used. eff The simple quality-weighted average is defined.

[0184] Secondary electron generating agents may suitably be or include those having an effective atomic number (Z) greater than or equal to 15. eff Compounds of the metal compound / complex HAuCl4·4H2O (tetrachloroauric acid tetrahydrate) (optionally, when the effective atomic number calculation does not include any solvates having a boiling point less than or equal to 150°C at 100 kPa pressure). For example, although the effective atomic number (Z) of the metal compound / complex HAuCl4·4H2O (tetrachloroauric acid tetrahydrate) is included in the calculation when the solvate (4×H2O) is included. eff The effective atomic number (Z) of HAuCl4·4H2O is 40.76, but when water (boiling point below 150℃) is not included in the calculation, HAuCl4·4H2O has an effective atomic number (Z). eff The value is 49.99 because:

[0185] First, the 4H2O portion of the compound is excluded from the calculation because water is a solvate (or hydrate) with a boiling point of less than or equal to 150° at 100 kPa pressure (its boiling point is 150° at 100 kPa pressure).

[0186] Therefore, the relevant atomic number of HAuCl4·4H2O is:

[0187] Z H =1

[0188] Z Au =79

[0189] Z Cl =17

[0190] • Except for 4H2O, the sum of the atomic numbers of all atoms in HAuCl4·4H2O (i.e., HAuCl4) is:

[0191] Z H +Z Au +(4x Z Cl ) = 1 + 79 + (4 x 17) = 148

[0192] The relevant atomic number fractions of ·HAuCl4·4H2O are:

[0193] α H =1 / 148=0.00676

[0194] α Au =79 / 148=0.53378

[0195] α Cl = (4 x 17) / 148 = 0.45946

[0196] Using equation Z eff =α H Z H +α Au Z Au +α Cl Z Cl Calculated Z eff for:

[0197] Z eff =(0.00676x 1)+(0.53378x 79)+(0.45946x 17)

[0198] Z eff =0.00676 + 42.168 + 7.81082 = 49.99

[0199] The effective atomic number of organic compounds can be calculated in exactly the same way—usually in this case, it is not necessary to exclude solvate molecules, as solvates are more often bound to metal complexes. The effective atomic number of polymers can also be calculated in the same way, but it is simplest to perform this calculation only on monomers, as this will produce the same result. Therefore, the Z of PMMA (or methyl methacrylate) eff Approximately 5.85. The effective atomic number of the copolymer can be calculated in the same manner, although this time-weighted average of the individual monomers should be incorporated into the equation. Similarly, although generally unrelated to this invention, the effective atomic number of a mixture or composition of compounds can also be calculated by including a weighted average of its respective components. Those skilled in the art are fully capable of calculating the effective atomic number (Z) of all compounds and compositions. eff ).

[0200] When a group having a large carbon chain (e.g., (1-12C)alkyl, (1-8C)alkenyl, etc.) is disclosed, such a group may optionally be shortened, for example, containing 1 to 5 carbons (e.g., (1-5C)alkyl or (1-5C)alkenyl), or containing 1 to 3 carbons (e.g., (1-3C)alkyl or (1-3C)alkenyl instead of (1-12C)alkyl or (1-8C)alkenyl).

[0201] In this document, unless otherwise stated, the weight percentage (wt%) of any given component in the composition properly refers to the weight percentage of said component based on the total weight of the composition.

[0202] In this document, the term "mainly composed of" when used to describe the proportion of a given component within a material appropriately means that the material comprises at least 70% by weight, more appropriately at least 80% by weight, more appropriately at least 90% by weight, more appropriately at least 95% by weight, and most appropriately at least 99% by weight of the given component.

[0203] In this article, the term "hydrocarbon group" refers to any hydrocarbon group, including but not limited to alkyl, alkenyl, alkynyl, and aryl groups.

[0204] When specified herein (generally relating to Lewis acidic substances), the metal atom, substance, complex, or compound referred to may include boron and / or silicon metal atoms, substances, complexes, or compounds, even if boron and silicon are not strictly metallic substances themselves. However, such metal atom, substance, complex, or compound may not include the corresponding boron and / or silicon atoms, substances, complexes, or compounds.

[0205] General methods and advantages of the present invention

[0206] This invention provides resist compositions, such as photoresist compositions (whether positive or negative resists), that offer the use of enhanced-quality resist patterns deployable in the production of high-precision, high-specification electronic components (e.g., those present in integrated circuits). Specifically, the quality and resolution of the imaged resist patterns facilitate the production of extremely high-quality, high-resolution electronic components and integrated circuits, which in turn allows for further reduction in the size of integrated circuits. This, in turn, paves the way for faster microprocessors and microprocessors capable of operating in low-power mobile devices.

[0207] Intentionally including antiscattering components within the resist composition prevents, suppresses, or reduces unwanted radiation scattering, radiation absorption, and the generation of secondary electrons. This minimizes proximity effects and blurring, allowing for higher resolution patterning. It also allows for the use of very thin resist films.

[0208] This disclosure enables those skilled in the art to rationally select appropriate resist compositions and methods to optimize the final product. The examples and data provided herein provide highly reliable evidence of the broad applicability of the invention to a range of resist compositions.

[0209] Anti-corrosion composition

[0210] This invention provides a photoresist composition, most preferably a photoresist composition. Suitably, the photoresist composition or its corresponding coating responds to electromagnetic radiation at least some wavelengths between 10 nm and 1000 nm, suitably between 50 nm and 700 nm, suitably between 100 nm and 400 nm, suitably between 150 nm and 300 nm, and suitably between 170 nm and 280 nm. Suitably exposing the photoresist composition or its coating to specific electromagnetic radiation having wavelengths falling within this range causes a change in the developer solubility of the exposed portion of the photoresist composition or its coating relative to its unexposed portion.

[0211] The resist composition suitably includes an antiscattering component (also referred to herein as an antiscattering compound). While the antiscattering component / compound may be used as the resist material itself, or even the only resist material (e.g., it may crosslink during exposure and / or post-exposure baking, or it may break down during exposure and / or baking, thus exhibiting significantly different developer solubility between exposed and unexposed areas), the resist composition suitably also includes a resist component. The resist component may be different from the antiscattering component and may be a completely different and separate compound. However, the antiscattering component itself may include or otherwise combine with the resist component or a portion of the resist component (e.g., it may be associated with or otherwise combined with it, and may be, for example, a group or portion). Where the antiscattering component includes or is otherwise combined with the resist component (e.g., if the resist component is combined with it, for example, via a coordinate bond), the two combined components may be collectively referred to as an "antiscattering-resist mixture".

[0212] A photoresist composition may include one or more antiscattering compounds as defined herein. A photoresist composition may include one or more photoresist components as defined herein.

[0213] Including an antiscattering compound within the resist composition (and any resist coating produced therefrom) appropriately limits scattering (e.g., primary and / or secondary radiation) during exposure to radiation, thereby better focusing the incident radiation onto the intended target site. This, in turn, increases lithographic resolution and minimizes proximity effects and / or blurring. Appropriately, the antiscattering compound induces minimal forward or backscattering of electrons.

[0214] As is known in the art, resist components are adapted to provide the typical function of a resist, resulting in significant differences in developer solubility between the irradiated and unexposed portions of the resist composition (or its coating). Typically, relevant portions of a resist composition (or its coating) deform upon exposure to radiation (including incident radiation, scattered radiation, and / or secondary radiation such as secondary electrons) to cause the irradiated and unexposed portions of the resist composition to exhibit different developer solubility. This difference in developer solubility can be directly induced by exposure to radiation and / or promoted by subsequent processing (e.g., post-exposure baking). Subsequent processing may affect the developer solubility of the irradiated, unexposed, or both portions, thus providing contrast between them. For example, if a photoacid generator is used within the resist composition, post-exposure baking typically causes the acid selectively generated in the irradiated portions of the resist composition / coating to diffuse slightly and ultimately trigger a reaction in which the resist components alter local developer solubility (e.g., through acid deprotection). (For example, a positive resist becomes more soluble in the developer, or a negative resist becomes less soluble in the developer.) Regardless of the resist component itself and / or other components of the resist composition, this exposure-induced transformation can maintain molecular fragmentation; and / or can maintain bond formation, whether between the resist component and / or other components. In specific embodiments, particularly where the resist composition includes an antiscattering component associated with or bound to one or more resist components, exposure to radiation promotes chemical reactivity between adjacent resist components (or between resist components suitably bound to adjacent (but different) antiscattering components) (e.g., via high-energy intermediates such as groups).

[0215] The resist composition may also include a photosensitizing component, such as a photoinitiator, photoacid generator, or photosensitizer. In the context of this invention, the photosensitizing component is suitably a component that is activated upon exposure to radiation / photons to initiate or otherwise trigger a chemical reaction. In some embodiments, the resist component may be or otherwise comprise or include a photosensitizing component. However, the photosensitizing component may be a separate photoinitiator or photoelectron generator. Such an additional photosensitizing component can promote exposure-induced chemical reactions that result in significant differences in developer solubility between exposed and unexposed portions. However, in certain embodiments, the resist composition is (substantially) free of photoacid generators or photoinitiators.

[0216] In a preferred embodiment, exposure to radiation causes the resist components to react in situ (during exposure, even without additional photosensitive components), resulting in the exposed portions of the resist composition / coating depositing to the corresponding unexposed portions with different developer solubility. Although post-exposure baking and / or other post-exposure treatment steps may be used prior to the development of the exposed resist composition / coating, such additional treatment steps are suitably unnecessary to trigger the chemical reactions involved in providing contrasting developer solubility between the exposed and unexposed portions.

[0217] The resist composition may also suitably include a resist crosslinking agent, which is suitably a crosslinking component that reacts with the resist components (e.g., during exposure or post-exposure treatment) to promote crosslinking between resist components or between a resist component and another component. In cases where a resist component is allegedly capable of reacting with another resist component, such reaction may be indirect and may involve the intervention of the resist crosslinking agent. Suitable crosslinking agents are known in the art.

[0218] The resist composition may suitably further include a plasmon component as defined herein.

[0219] Suitably, the resist composition (e.g., a pre-coating) includes a diluent or solvent. Suitably, the resist composition includes 20-99.5% by weight of solvent, suitably 50-99% by weight of solvent, more suitably 80-98.5% by weight of solvent, and more suitably 95-99% by weight of solvent. Thus, the resist composition suitably includes 0.5-80% by weight of non-solvent component, suitably 1-50% by weight of non-solvent component, more suitably 1.5-20% by weight of non-solvent component, and more suitably 1-5% by weight of non-solvent component. Suitably, the resist composition is a solution that suitably does not contain any dispersed or suspended particulate matter. Suitably, the resist composition is suitable for spin-coating onto a surface (e.g., spin coating) to provide a (substantially) uniform coating on said surface. Suitably, the resist composition does not contain any particulate matter. Appropriately, the resist composition is (substantially) free of any nanoparticles, particularly free of any metal (O) nanoparticles or metal-containing nanoparticles.

[0220] The resist composition may include one or more optional additional components.

[0221] In a particular embodiment, the resist composition includes:

[0222] -100pbw antiscattering compound / component; and

[0223] -0-10000pbw resist components.

[0224] The resist composition can be a negative resist composition or a positive resist composition. Most preferably, the resist composition is a negative resist composition.

[0225] Anti-corrosion components

[0226] In addition to the anti-scattering component, the resist composition or the corresponding resist coating suitably includes a resist component. The resist composition may also include a resist crosslinking agent, which is capable of reacting with the resist components or with another substance to form crosslinks between the resist components or with another substance.

[0227] Technicians can easily select an appropriate developer based on the resist components used. Appropriately, the developer is selected based on the properties of the relevant resist components and / or other ingredients present in the resist composition / coating, and on the developer's ability to selectively dissolve the radiated portions (e.g., in the case of positive resists) or non-radiated portions (e.g., in the case of negative resists).

[0228] The resist component can be a positive resist component (which reacts appropriately to make the resist composition / coating more soluble in the developer in the irradiated area) or a negative resist component (which reacts appropriately to make the resist composition / coating less soluble in the developer in the irradiated area). Typically, the positive resist component may break down upon exposure to radiation (e.g., via photodegradation) or post-exposure treatment, or may otherwise react (under exposure to radiation or post-exposure treatment) to make the resist composition / coating more soluble in the developer. Conversely, the negative resist component is typically optionally reacted and bonded with other components (e.g., other resist components) via a crosslinking agent.

[0229] The resist component suitably includes one or more π systems, which are suitably crosslinkable or otherwise susceptible to photodecoupling.

[0230] In one embodiment, the resist component is distinct from and separate from the antiscattering component (at least in terms of its molecular structure). Any suitable resist component can be suitably used in combination with a suitable developer (i.e., a solvent that selectively dissolves the exposed or unexposed portions of the resist component). Suitably, the resist component reacts directly (e.g., where exposure radiation causes a chemical transformation of the resist component and may lead to further chemical reactions) or indirectly (e.g., where exposure radiation causes a chemical transformation of a component of the resist composition, such as a photoinitiator or photoacid generator, which may ultimately lead to a chemical transformation of the resist component during post-exposure processing and may lead to further chemical reactions) with exposure radiation. Various resist components (e.g., resist polymers), including positive and negative resists, are known in the art, any of which are suitable for the context of this invention, wherein the antiscattering combined with the component can provide beneficial results. Typically, during exposure to radiation or post-exposure treatment (e.g., post-exposure baking), negative resist components are polymerized and / or crosslinked (directly or indirectly, e.g., through intervening crosslinking agents or intervening molecules attached to the resist components).

[0231] Therefore, the resist component may be or includes polymerizable monomers / comonomers or pyrolytic polymers.

[0232] Examples of suitable resist components for use in this invention include, in particular: polymethyl methacrylate (PMMA); poly(methyl methacrylate-co-methacrylic acid) (PMMA co-MA); poly(α-methylstyrene-co-methyl methacrylate) (PMS co-Cl-MMA); polystyrene (PS); polyimide (PI); polyhydroxystyrene (PSOH); poly(hydroxystyrene-co-methyl methacrylate) (PSOH co-MMA); (long-chain) hydrocarbons; phenolic varnishes (i.e., phenolic resins comprising a formaldehyde-phenol ratio of less than 1:1); poly(1-naphthyl methacrylate), poly(1-vinylnaphthalene), poly(2,6-naphthylenevinylene), poly(2-chlorostyrene), poly(2,6-dichlorostyrene), poly(2-vinylthiophene), poly(N-vinylphenyl o-dicarboximide), poly(vinylphenyl sulfide), polyhydroxystyrene, or any suitable mixture or copolymer thereof.

[0233] Although the resist compositions of the present invention may include different resist components (e.g., resist polymers or resins, such as those described above), in other embodiments, the resist component may alternatively or additionally be combined with an antiscattering component. For example, the resist component may be combined with or otherwise combined with the antiscattering component, and may be, for example, a group or portion (e.g., a ligand or portion thereof) of the antiscattering component. Where the antiscattering component includes or is otherwise combined with the resist component (e.g., via coordinate bonds), the two combined components may be collectively referred to as an "antiscattering-resist mixture." Further details regarding this embodiment are provided below with respect to the antiscattering component.

[0234] Anti-scattering components / compounds

[0235] Anti-scattering components function appropriately within the resist composition / coating to limit scattering events (or scattering probabilities) within the resist composition / coating during exposure to radiation. This scattering suppression is considered a result of a lower density of scattering centers and / or a lower scattering cross-section of the scattering centers.

[0236] Because radiative scattering (especially primary radiation / incident radiation) exposes non-targeted portions of the resist composition / coating to scattered radiation (due to the primary radiation being "off-tracked"), incorporating an anti-scattering component into the resist composition according to the invention can significantly improve lithographic resolution, aspect ratio, and / or reduce blurring. In this case, with the presence of the anti-scattering component, the primary radiation can be considered to be more "focused" on the target site (whether the target is determined by a mask such as a photomask or a directional beam).

[0237] Antiscattering components or compounds may themselves include one or more subcomponents. Suitablely, one or more components of an antiscattering compound (especially complexes, such as multimetal cage systems and / or multimetal ring systems) have a molecular structure comprising a large amount of free internal space. Suitablely, the antiscattering compound as a whole (considering the arrangement of its individual components—e.g., a combination of multiple metal cages or rings optionally arranged around a common center or one or more connecting subcomponents) has a structure comprising a large amount of free internal space. Without wishing to be bound by theory, it is considered that this free space is a key factor in the advantageous properties of antiscattering compounds and helps to minimize primary radiation scattering. Therefore, antiscattering compounds suitablely have a high mean free path (λ)—i.e., a large distance between successive electron collisions. Suitablely, antiscattering compounds have a small scattering cross section (σ)—i.e., a low collision probability.

[0238] While porous, open (suitably three-dimensional) crystalline metal-organic frameworks (MOFs) well-known in the art can provide compounds and complexes with ample free space (often used practically for gas absorption), antiscattering compounds, especially when part of a resist coating (i.e., pre-exposure), are most suitably (substantially) amorphous and / or do not form three-dimensional crystalline / lattice structures. This lack of tendency to form three-dimensional crystalline structures may indicate that antiscattering compounds have more suitable solubility, resulting in more uniform coatings of the resist composition (e.g., spin coating). Therefore, most suitably, antiscattering compounds are not metal-organic frameworks (MOFs). Suitablely, antiscattering compounds are (substantially) non-porous.

[0239] Suitablely, the antiscattering compound has a relatively low density. Where the antiscattering compound actually comprises one or more resist components (e.g., therein coordinating bonds), the antiscattering compound may include locally high-density regions where the resist components are present, and other low-density regions (i.e., distant from the resist components). This configuration maximizes the overall antiscattering effect of the resist composition while increasing the radiation sensitivity to critical target sites (i.e., the resist components). Thus, the resist composition appropriately includes relatively low-density regions (for limiting scattering) and relatively high-density regions where needed (i.e., at the locations of the resist components).

[0240] Appropriately, the density of the antiscattering compound is less than or equal to 2.5 g / cm³. 3 Appropriately less than or equal to 2.0 g / cm³ 3 Appropriately less than or equal to 1.6 g / cm³ 3 When the antiscattering compound and the resist component are different entities, the antiscattering compound can appropriately have a concentration of less than or equal to 1.5 g / cm³. 3 Its density is appropriately less than 1.3 g / cm³. 3 Appropriately less than or equal to 1.2 g / cm³ 3 Appropriately less than or equal to 0.95 g / cm³ 3 Appropriately less than or equal to 0.9 g / cm³ 3 Appropriately less than or equal to 0.85 g / cm³ 3 Appropriately less than or equal to 0.8 g / cm³ 3 Appropriately less than or equal to 0.7 g / cm³ 3 Appropriately, the density of the antiscattering compound is greater than or equal to 0.4 g / cm³. 3 Appropriately greater than or equal to 0.5 g / cm 3 Appropriately greater than or equal to 0.55 g / cm³ 3 Appropriately greater than or equal to 0.6 g / cm³ 3In one specific embodiment, the anti-scattering compound has a concentration of 0.6 g / cm³. 3 and 0.85g / cm 3 The density is between [specific values]. In one specific embodiment, the antiscattering compound has a density less than or equal to 1.2 g / cm³. 3 The density. When the resist component is combined with the antiscattering compound, the density of the antiscattering compound is appropriately greater than or equal to 0.9 g / cm³. 3 Appropriately greater than or equal to 1.2 g / cm³ 3 .

[0241] Suitablely, the molecular weight of the antiscattering compound is greater than or equal to 1000 g / mol, suitablely greater than 2000 g / mol, suitablely greater than or equal to 5000 g / mol, suitablely greater than or equal to 10,000 g / mol, suitablely greater than or equal to 15,000 g / mol. Suitablely, the molecular weight of the antiscattering compound is less than or equal to 300,000 g / mol, suitablely less than or equal to 200,000 g / mol, suitablely less than or equal to 100,000 g / mol, suitablely less than or equal to 50,000 g / mol, suitablely less than or equal to 20,000 g / mol, suitablely less than or equal to 5000 g / mol.

[0242] Appropriately, in response to exposure to primary radiation, particularly when the primary radiation is greater than 150 nm, and appropriately when the primary radiation is 180 nm, the antiscattering compound (substantially) does not produce secondary electrons as ionization products (at least in the absence of any attached secondary electron generating agent).

[0243] Antiscattering compounds are suitably organometallic complexes. Suitably, antiscattering compounds are polymetallic compounds. Antiscattering compounds suitably do not contain elemental metals (i.e., metal(0)). Suitably, any metallic component of the antiscattering compound is a metal ion.

[0244] Antiscattering compounds suitably include host metal complexes (PMCs). Suitably, host metal complexes are defined as described herein and are suitably metal cages, most suitably multimetal cages (suitably having at least one trivalent metal and at least one divalent metal, but in some embodiments, all metals may be trivalent, regardless of whether all trivalent metals are from the same metal element or different metal elements). Metal cages may include those disclosed in GFS Whitehead, F. Moro, GATimco, W. Wernsdorfer, SJTeat and REP Winpenny, “A Ring of Rings and Other Multicomponent Assemblies of Clusters”, Angew. Chem. Int. Ed., 2013, 52, 9932-9935. In some embodiments, the multimetal cage is a homogeneous metal. In a preferred embodiment, the multimetal cage is a heterogeneous metal (i.e., having two or more, most suitably exactly two different metal elements).

[0245] The host metal complex can be neutral or charged (either positive or negative). Antiscattering compounds, especially when the host metal complex is charged, can include one or more counterions suitably defined herein (e.g., C2). 1 C 2 C c ), appropriately combined with a host metal complex that is part of a host metal complex salt. Thus, the antiscattering compound can be defined by a host metal complex salt of formula A or can include units defined by a host metal complex salt of formula A:

[0246] (C 1 i1 C 2 i2 …C c ic (PMC) p

[0247] Wherein PMC is a main metal complex, suitably as defined herein, and p is the relative stoichiometry of PMC in formula A or p is the number of moles of PMC per mole of formula A; and

[0248] Where C 1 It is the first counterion, C 2 It is the second counterion, and C c It is the c-th counterion, appropriately defined as herein, where i1, i2, and ic are C in formula A. 1 C 2 ... and C cThe relative stoichiometry of each of them, or i1, i2 and ic, are the C per mole of formula A. 1 C 2 ... and C c The number of moles for each.

[0249] p can have any suitable value, but is preferably a non-zero integer. p can suitably be a value between 1 and 6 (suitably an integer).

[0250] In a preferred embodiment, there is no counterion bound to the host metal complex (i.e., i1, i2, and ic are all zero), or the host metal complex is bound to only a single (type) of counterion (i.e., the host metal complex salt comprises only a single (type) of counterion) (i.e., i1 is non-zero but i2 and ic are zero). Appropriately, the stoichiometry or relative molar number of the PMC and the counterion is such that the resulting host metal complex salt is neutral. However, the presence of additional charged components (e.g., linker components – see below) within the antiscattering compound may mean that the host metal complex salt does not necessarily have to be neutral.

[0251] Antiscattering compounds suitably include linker components (or one or more linker components) that are adapted to combine with one or more, preferably two or more, host metal complexes (e.g., electrostatically and / or covalently, most suitably at least partially covalently). Suitably, the linker component is defined as described herein and is suitably a complex or compound capable of coordinating (i.e. forming valence bonds) with one or more (preferably two or more) host metal complexes. Complexes resulting from one or more linker components combined with one or more host metal complexes may be referred to as “hybrid complexes”.

[0252] Antiscattering compounds can be defined by hybrid complexes of formula B or can include units defined by hybrid complexes of formula B:

[0253] (PMC) p (LINK) l

[0254] Wherein PMC is a main metal complex, suitably as defined herein, and p is the relative stoichiometry of PMC in formula B or p is the number of moles of PMC per mole of formula B; and

[0255] Wherein LINK is the linker component, appropriately as defined herein, and l is the relative stoichiometry of LINK in formula B or l is the number of moles of LINK per mole of formula B.

[0256] p can have any suitable value, and is preferably a non-zero integer. p can suitably be a value from 1 to 120 (where 120 is the theoretical limit) (suitably an integer), preferably between 1 and 48. p can suitably be a value between 1 and 30 (suitably an integer), preferably between 2 and 24, more preferably between 2 and 8, and preferably between 4 and 6. Most preferably, p is an even number (especially 2, 4, or 6).

[0257] l can have any suitable value (including 0), and is suitable to be zero or a non-zero integer, most suitable to be a non-zero integer. l can be a value between 0 and 10 (suitable to be an integer), suitable to be between 0 and 2, more suitable to be 0 or 1, and most suitable to be 1.

[0258] The host metal complex (e.g., PMC) and / or linker component (e.g., LINK) can be neutral or charged (whether positive or negative). In the presence of both the host metal complex and the linker component, both can be charged, and in some embodiments, each can have opposite charges (i.e., one is negatively charged and the other is positively charged, and thus may electrostatically bind to each other in addition to their valence / covalent interactions). If the host metal complex and the linker component have opposite charges, the total charge of these substances within the antiscattering compound can be zero (i.e., the charges can neutralize each other to produce a compound or unit of formula A with no net charge). Alternatively, the antiscattering compound, especially when the hybrid complex has a net charge (i.e., non-neutral), can include, suitably as defined herein, one or more counterions (e.g., C10) appropriately combined with the hybrid complex (and / or suitably combined with either or both of the host metal complex and / or the linker component). 1 C 2 C c As part of a mixed complex salt, the antiscattering compound can be defined by a mixed complex salt of formula C or can include units defined by a mixed complex salt of formula C.

[0259] (C 1 i1 C 2 i2 …C c ic (PMC) p (LINK) l

[0260] Wherein PMC is the main metal complex, appropriately as defined herein, and p is the relative stoichiometry of PMC in formula C or p is the number of moles of PMC per mole of formula C;

[0261] Wherein LINK is the linker component, suitably as defined herein, and l is the relative stoichiometry of LINK in formula C or l is the number of moles of LINK per mole of formula C; and

[0262] Where C 1 It is the first counterion, C 2 It is the second counterion, and C c It is the c-th counterion, appropriately defined as herein, where i1, i2, and ic are C in formula C. 1 C 2 ... and C c The relative stoichiometry of each of them, or i1, i2 and ic, are C per mole of the formula C. 1 C 2 ... and C c The number of moles for each.

[0263] p can have any suitable value, and is preferably a non-zero integer. p can suitably be a value from 1 to 120 (where 120 is the theoretical limit) (suitably an integer), preferably between 1 and 48. p can suitably be a value between 1 and 30 (suitably an integer), preferably between 2 and 24, more preferably between 2 and 8, and preferably between 4 and 6. Most preferably, p is an even number (especially 2, 4, or 6).

[0264] l can have any suitable value (including 0), and is suitable to be zero or a non-zero integer, most suitable to be a non-zero integer. l can be a value between 0 and 10 (suitable to be an integer), suitable to be between 0 and 2, more suitable to be 0 or 1, and most suitable to be 1.

[0265] Any one or both of the main metal complex and linker components within the hybrid complex (or its salt) can independently bind to any counterion, and / or the counterion can bind to the hybrid complex as a whole.

[0266] Appropriately, hybrid complexes are generally neutral.

[0267] Antiscattering agents may include one or more additional metal complexes (AMCs) (or salts thereof), optionally bound to one or more counterions and / or one or more linker components as defined herein with respect to a host metal complex. Any additional metal complex differs from the host metal complex (e.g., in terms of the metallic substance and / or ligands or their relative stoichiometry). However, while differing from the host metal complex, any, some, or all of the additional metal complexes may be defined as described herein with respect to any host metal complex. Thus, any additional metal complex may be a metal cage, such as a multimetal cage, suitably wherein all the metallic substances are divalent or wherein the metal sites are in different oxidation states. Such a multimetal cage may be of the same metal. However, the metal cage of an AMC may be any of those metal cages as defined herein with respect to a host metal complex. In the presence of one or more additional metal complexes in addition to the host metal complex, suitably, at least one, preferably two, additional metal complexes have metallic substances different from those of the host metal complex.

[0268] Therefore, antiscattering agents can be defined by hybrid complexes or hybrid salts of formula D, or can include units defined by hybrid complexes or hybrid salts of formula D:

[0269] (C 1 i1 C 2 i2 …C c ic (PMC) p-a (AMC) a (LINK) l

[0270] Wherein PMC is the main metal complex, appropriately as defined herein, and pa is the relative stoichiometry of PMC in formula D or pa is the number of moles of PMC per mole of formula D;

[0271] Wherein AMC is one or more other metal complexes, suitably as defined herein (optionally in the same manner as PMC, provided that AMC is different from PMC), and a is the relative stoichiometry of AMC in formula D or a is the number of moles of AMC per mole of formula D;

[0272] Wherein LINK is the linker component, suitably as defined herein, and l is the relative stoichiometry of LINK in formula C or l is the number of moles of LINK per mole of formula C; and

[0273] Where C 1 It is the first counterion, C 2 It is the second counterion, and C cIt is the c-th counterion, appropriately defined as herein, where i1, i2, and ic are C in formula C. 1 C 2 ... and C c The relative stoichiometry of each of them, or i1, i2 and ic, are C per mole of the formula C. 1 C 2 ... and C c The number of moles for each.

[0274] p can have any suitable value, and is preferably a non-zero integer. p can suitably be a value from 1 to 120 (where 120 is the theoretical limit) (suitably an integer), preferably between 1 and 48. p can suitably be a value between 1 and 30 (suitably an integer), preferably between 2 and 24, more preferably between 2 and 8, and preferably between 4 and 6. Most preferably, p is an even number (especially 2, 4, or 6).

[0275] a can have any suitable value, and is preferably zero or a non-zero integer. a can suitably be a value between 1 and 30 (suitably an integer), suitably between 2 and 24, more suitably between 2 and 8, and suitably between 4 and 6. Most suitably, a is an even number (especially 2, 4, or 6). However, suitably, a is greater than zero.

[0276] l can have any suitable value (including 0), and is suitable to be zero or a non-zero integer, most suitable to be a non-zero integer. l can be a value between 0 and 10 (suitable to be an integer), suitable to be between 0 and 2, more suitable to be 0 or 1, and most suitable to be 1.

[0277] Optionally, the hybrid complex of formula D may be free of counterions—that is, all i1, i2, ..., ic are zero.

[0278] Appropriately, antiscattering agents comprise a host metal complex but (substantially) contain no other metal complexes. However, in the presence of other metal complexes, they may be considered as substitutes for a portion of the host metal complex, and the parameters and values ​​may optionally be as defined herein, as if the other metal complex were actually replacing the host metal complex.

[0279] Any metal salt and / or complex of the mentioned antiscattering compound generally refers to a pre-mixed form of such salt / complex (i.e., in terms of cation-anion binding) (i.e., before mixing with other components of the resist composition), and suitably also to its pre-coated, pre-cured, pre-exposed, pre-baked, or pre-developed form. Those skilled in the art will understand that, upon mixing with other components of the resist composition (and / or after coating, curing, exposure, baking, and / or developing), the associated cations, anions, and ligands of the metal salt and / or complex of the antiscattering compound may dissociate and bind with other counterions and / or ligands in some embodiments (but not all). Therefore, the mention of a resist composition (or actually a coating, or its cured, exposed, or developed product) suitably indicates that the resist composition (or coating, or its cured, exposed, or developed product) is "formed" (or obtained) by mixing the antiscattering compound with any other components of the resist composition. Those skilled in the art can directly determine inputs regarding anti-scattering compounds derived from resist compositions or their coated, cured, exposed, baked, or developed products using standard techniques.

[0280] Appropriately, any metal salt and / or complex of an antiscattering compound comprises two or more metal substances.

[0281] The anti-scattering compound is suitably soluble in any diluent or solvent or diluent / solvent system of the resist composition (i.e., soluble in the coating solvent system, which can be considered as the diluent / solvent within the pre-coated resist composition). Suitably, at standard ambient temperature and pressure (SATP), the solubility of the anti-scattering compound in the coating solvent system is at least 1 mg / g, suitably at least 2 mg / g, suitably at least 10 mg / g, and suitably at least 20 mg / g. Suitably, the coating solvent system to which these solubility ranges apply comprises or is primarily composed of (1-10C) hydrocarbon-based solvent systems (most preferably hexane).

[0282] The anti-scattering compound is suitably soluble in any diluent or solvent or diluent / solvent system of the predetermined developing medium (especially when the resist composition is a negative resist composition). Suitably, at standard ambient temperature and pressure (SATP), the solubility of the anti-scattering compound in the developing medium is at least 1 mg / g, suitably at least 2 mg / g, suitably at least 10 mg / g, and suitably at least 20 mg / g. Suitably, the coating solvent system to which these solubility ranges apply comprises or is primarily composed of (1-10C) hydrocarbon-based solvent systems (most preferably hexane).

[0283] Ideally, the anti-scattering agent is soluble in the coating solvent system and the intended developing medium, preferably to at least the extent defined herein.

[0284] Suitably, the antiscattering component / compound is a resist component (i.e., used for dual function) and / or includes a resist component, suitably including one or more resist components. Suitably, such resist component is cleavable (e.g., according to a positive resist) or crosslinkable (e.g., according to a negative resist). Suitably, the resist component is combined with one or more host metal complexes or a portion thereof. An antiscattering component that is or includes said resist component may be referred to as an antiscattering-resist hybrid component.

[0285] Main metal complex (and / or additional metal complex)

[0286] Antiscattering compounds suitably include host metal complexes. In some embodiments, the antiscattering compound may consist of or be primarily composed of a host metal complex (and optionally one or more counterions). Suitably, the host metal complex is a metal cage, preferably a metal cage without (direct) metal-metal bonds.

[0287] The host metal complex suitably comprises at least two types of metal ions, wherein the at least two types of metal ions comprise the same or different metals. When the metal ions are based on the same metal, it is suitable that the corresponding metal ions have different oxidation states.

[0288] The host metal complex is suitably a polymetallic complex. The host metal complex is suitably a polymetallic cage complex comprising multiple metal ions of at least one type interconnected via one or more bridging ligands (i.e., unlike direct metal-metal bonds). Any suitable bridging ligand can be used, but typically it can be a monodentate (e.g., fluorine) or bidentate (e.g., carboxylate) ligand.

[0289] Polymetallic complexes can be of the same metal type (e.g., composed of metallic substances derived from the same element, regardless of whether they have the same oxidation state, but most preferably all metallic substances of the same metal PMC have the same oxidation state, preferably metal (III)). Or, most preferably, polymetallic complexes are of different metal types (e.g., composed of metallic substances derived from different metal elements, regardless of whether they have the same oxidation state, but most preferably the relevant metallic substances of the different metal PMC have different oxidation states, most preferably metal (II) and metal (III)).

[0290] The host metal complex suitably comprises one or more metallic substances, each of which may suitably be represented as M. 1 M 2 M n (See below). Thus, the host metal compound suitably includes at least one metallic substance M. 1 Appropriately, only one metallic substance M exists within the PMC.1 In this case, the metallic substance has an oxidation state of III (i.e., +3) (but for AMC, II (+2) is preferred). In one specific embodiment, the main metal complex comprises Cr(III) as the sole metallic substance, wherein each complex most suitably comprises 8 Cr(III) units.

[0291] Suitablely, the main metal complex comprises two or more (different / different types) metallic substances, each of which may suitably be represented as M. 1 M 2 M n Thus, appropriately, the host metal complex includes metallic substance M. 1 Metallic substance M 2 and optionally one or more other metallic substances (e.g., M) 3 M n Suitable, the main metal complex consists of two or more (different) metallic substances (suitably at least M). 1 and M 2 ) is two or more (different) metal ions. M 1 and M 2 Suitablely derived from the same metallic element and having different valences, or suitablely derived from different metallic elements and having the same or different valences. Suitablely, two or more (different) metal ions (suitably at least M 1 and M 2 The metal ions have different oxidation states, and appropriately, the oxidation states differ by one valence, most appropriately one of the metal ions (appropriately M) 1 One metal ion is trivalent (i.e., oxidation state III or +3), and the other metal ion is divalent (i.e., oxidation state II or +2). When two or more metal substances are present, both or all of them can be derived from the same metal element but have different oxidation states. For example, this can include PMC containing both Fe(II) and Fe(III).

[0292] Suitable, two or more (different) metallic substances (suitably at least M 1 and M 2 Derived from two or more different metals. Therefore, appropriately, an antiscattering compound is a heterometallic polymetallic compound (i.e., containing two or more different metallic substances). Appropriately, at least one of the two or more (different) metallic substances (or M... 1 and M 2 At least one of them) is a transition metal (d-block) substance, more preferably at least two of two or more (different) metal substances (or M) 1 and M 2Both are transition metal (d-block) materials. In one embodiment, M 1 and M 2 All are transition metal ions, making the host metal complex a transition metal complex. Suitablely, at least one (or M) of the two or more (different) metallic substances... 1 and M 2 At least one of the following is a transition metal of the 3d-block of the periodic table, more appropriately at least two of the two or more (different) metallic substances (or M) 1 and M 2 Both are transition metals in the 3d-block of the periodic table.

[0293] Suitable, at least one of two or more (different) metallic substances (or M 1 and M 2 At least one of them, most appropriately M 1 () is a trivalent metallic substance, appropriately selected from substances including Cr III Fe III V III Ga III Al III or In III The group, but the most suitable trivalent metal (suitably M1) is Cr. III Suitable, at least one of two or more (different) metallic substances (preferably one other than the aforementioned trivalent metallic substances) (or M 1 and M 2 At least one of them, most appropriately M 2 () is a divalent metallic substance, appropriately selected from substances including Ni II Co II Zn II Cd II Mn II Mg II Ca II 、Sr II Ba II Cu II or Fe II The group, but most suitable is a divalent metal substance (suitable M 2 ) for Ni II .

[0294] In one specific embodiment, the host metal complex (and therefore the antiscattering compound) comprises at least one trivalent metal (suitably, M... 1 Appropriately selected from Cr III Fe III V III Ga III AlIII or In III The group; most appropriately sized as Cr III ) and at least one divalent metal substance (appropriate M) 2 Appropriately selected from Ni II Co II Zn II Cd II Mn II Mg II Ca II 、Sr II Ba II Cu II or Fe II The group; most appropriately Ni II ).

[0295] Appropriately, each mole of the host metal complex comprises two or more moles of the metal substance (i.e., a combination) (e.g., two or more moles of M). 1 and / or M 2 Appropriately, two or more moles of M 1 and M 2 Combinations - for example [M] 1 x M 2 y [where x + y ≥ 2], suitably each mole of the main metal complex comprises three or more moles of metallic substance, suitably four or more moles, suitably five or more moles, suitably six or more moles, suitably seven or more moles, and most suitably each mole of the main metal complex comprises about eight moles of metallic substance. Suitably, each mole of the main metal complex comprises twelve or fewer moles of metallic substance (i.e., the combination), suitably ten or fewer moles.

[0296] Suitablely, at least one metallic substance (suitably two or more metallic substances) of the main metal complex is magnetic, and suitablely paramagnetic.

[0297] Appropriately, the host metal complex includes substances with a higher valence than divalent metals (e.g., M). 2 More (appropriately by molar or stoichiometric ratio) of trivalent metals (e.g., M) 1 ), suitably at least two times, suitably at least three times, suitably at least four times, suitably at least seven times. Suitably, in the main metal complex, M 1 (It is appropriately trivalent) and M 2The molar ratio (which is suitably divalent) is between 12:1 and 1:1, suitably between 10:1 and 2:1, suitably between 9:1 and 3:1, more suitably between 8:1 and 6:1, and most suitably around 7:1.

[0298] Suitablely, the antiscattering component / compound includes (particularly when it includes a resist component or a portion of an antiscattering compound combined with a resist component) one or more host metal complexes, wherein:

[0299] • One or more host metal complexes are interconnected (or cross-linked) via one or more interconnecting groups (which may suitably represent the resist component or a portion thereof) – this configuration is particularly suitable for applications including positive antiscattering.

[0300] A positive resist composition with mixed resist components;

[0301] • The main metal complex includes one or more crosslinkable or polymerizable components (which may suitably represent a resist component or a portion thereof) - this configuration is particularly suitable for negative resist compositions that include a negative antiscattering-resist mixture.

[0302] In cases where the resist composition comprises an antiscattering-resist mixture, suitably, the antiscattering-resist mixture has the dual function of both an antiscattering component and a resist component, but the resist component can be separated into portions of the antiscattering-resist mixture subjected to radiation-induced transformation. Suitably, the negative antiscattering-resist mixture is suitably prone to crosslinking upon exposure to radiation (suitably, multiple negative antiscattering-resist mixtures, particularly their host metal complexes, crosslink with each other). Suitably, the positive antiscattering-resist mixture is suitably prone to fragmentation upon exposure to radiation (suitably, the relevant resist component portions of the positive antiscattering-resist mixture are cleaved, thereby releasing multiple host metal complexes).

[0303] Most suitably, the resist composition comprises a negative antiscattering-resist mixture, wherein the antiscattering-resist mixture comprises a host metal complex, said host metal complex comprising one or more resist components (suitably bonded or coupled thereto, e.g., via coordinate bonds). Thus, the resist component may be a ligand of the corresponding host metal complex.

[0304] Suitablely (especially in combination with antiscattering components / compounds), the resist component comprises one or more π-systems. Suitablely, the resist component comprises one or more organic (i.e., carbon-containing) moieties comprising π-systems. Suitablely, the host metal complex comprises such a resist component. Suitable π-systems may, for example, include:

[0305] • π-systems characterized by carbon-carbon double or triple bonds;

[0306] • Carbon-heteroatom double or triple bonds;

[0307] • Aromatic or hybrid aromatic ring system;

[0308] • Conjugated π systems including carbon and optional heteroatoms.

[0309] Suitablely, this π system can or can be made to interconnect (or crosslink) across multiple host metal complex units, thereby achieving a polymeric and / or crosslinked form between the host metal complex units. Suitablely, such crosslinking between host metal complex units can be induced by exposure to radiation (suitably as described herein) or by chemicals generated by exposure of the resist composition / coating to radiation (e.g., photoacid-producing agents—e.g., trifluoromethanesulfonic acid). Most suitably, such crosslinking is caused directly by exposure to radiation (e.g., by photolysis). An illustrative example of such crosslinking chemistry is described in Scheme 1 below.

[0310]

[0311] Scheme 1 - Schematic diagram of the cross-linking chemistry between the π-systems of two adjacent anti-scattering and photoresist mixtures.

[0312] Suitably, one or more ligands that are bonded to or linked (or preferably via valence bonds) to the host metal complex of the antiscattering-resist mixture are or comprise the resist component. Such ligands may be referred to as “resist ligands.” Resist ligands thus suitably comprise crosslinkable atoms or groups (e.g., π-systems) and coordination donor atoms or groups. One or more of these resist ligands, or other ligands, may be incorporated into the host metal complex as a substitute for any other ligands as defined herein with respect to antiscattering compounds. For example, the host metal complex may comprise a mixture of resist ligands and other ligands described elsewhere herein (e.g., non-resist ligands, such as alkanoates).

[0313] Suitably, the donor atom or group includes a heteroatom with a lone pair charge (e.g., suitably nitrogen and / or oxygen atoms), or a heteroatom having two or more lone pairs of electrons (thereby promoting polydentate coordination of the ligand via the donor atom or group). For example, the resist ligand may include a carboxylate, a carboxyl group, or a carboxylic acid group—which includes two oxygen atoms, each having a lone pair of electrons capable of coordinating with the metal center of the host metal complex.

[0314] Suitablely, crosslinkable atoms or groups include π-systems, preferably terminal π-systems, and most preferably terminal olefin groups. For example, resist ligands may include terminal olefin groups.

[0315] Appropriately, especially when the host metal complex is a polymetallic cage or other polymetallic material, at least one or more resist ligands (appropriately all) are coordinated inside and outside the corresponding host metal complex (i.e., located on the outer part of the cage opposite to the inner part or cleavage within the cage). This juxtaposition of the ligands is beneficial for crosslinking chemistry, which would otherwise hinder the retention of resist ligands within the metal cage structure.

[0316] Particularly suitable resist ligands may be independently selected from the group consisting of optionally substituted acrylates, acrylates, acrylate radicals, acrylate amides, alkynates, alkynates, alkynates, alkynates, or mixtures thereof. In one embodiment, the resist ligand is selected from the group consisting of (optionally substituted) acrylates, acrylates, acrylate radicals, acrylate amides, or mixtures thereof. In one embodiment, the resist ligand is selected from the group consisting of (optionally substituted) (2-20C) acrylates, (2-20C) acrylates, (2-20C) acrylate radicals, (2-20C) acrylate amides, or mixtures thereof. In one embodiment, the resist ligand is selected from the group consisting of (optionally substituted) (2-12C) acrylates, (2-12C) acrylates, (2-12C) acrylate radicals, (2-12C) acrylate amides, or mixtures thereof. In one specific embodiment, the resist ligand is selected from the group consisting of (optionally substituted) (2-6C) acrylate, (2-6C) acrylate, (2-6C) acrylate ion, (2-6C) acrylate amide, or mixtures thereof. Any of the foregoing optional substituents suitably prevents coordination or cross-linking within the host metal complex (under relevant conditions). Suitably, any or all of the foregoing groups comprise at least one terminal olefin or alkyne moiety.

[0317] In one embodiment, the resist ligand comprises one or more heteroatoms with lone pair charges (e.g., N and / or O) and one or more terminal olefin groups. In a particular embodiment, the resist ligand comprises (2-20C) olefins optionally substituted with one or more heteroatoms.

[0318] In one specific embodiment, the resist ligand is selected from 2-methyl-4-pentenoic acid, diallylamine, N,N-methylenebisacrylamide (bis-AMD), or pentaerythritol tetraacrylate.

[0319] The host metal complex suitably comprises 1-16 resist ligands (or resist components), suitably 2-12, or suitably 4-10. Suitably, the host metal complex comprises 1-16 olefin groups (suitably, crosslinkable olefin groups), suitably 2-12, or suitably 4-10.

[0320] The host metal complex suitably includes one or more ligands, which suitably interact with one, more, or all (or two) metals of the host metal complex (e.g., M). 1 and / or M 2 Coordination. The host metal complex suitably includes a sufficient type and a sufficient number of ligands (including mixtures of ligands) to bond all the metallic substances within the host metal complex together (suitably indirectly, suitably through valence bonds), suitably forming a metal cage, and suitably without any metal-metal bonds. Thus, the host metal complex suitably includes one or more bridging ligands that are suitably capable of providing bridging between two or more metallic substances—such bridging ligands can be multidentate, for example, bidentate, but can also be monodentate, such as fluorinated or oxygen-based ligands, if they are capable of providing more than one lone pair of electrons. Most suitably, the host metal complex includes a mixture of two or more different types of ligands, wherein suitably one type of ligand is bidentate and the other is monodentate. Most suitably, all ligands within the host metal complex have coordinating atoms capable of providing more than one lone pair of electrons. Suitable, the host metal complex comprises a sufficient type and number of ligands (which may be a mixture of monodentate ligands such as fluorine and bidentate ligands such as carboxylate) to provide each individual metal substance within the complex with an average of at least 3 covalent bonds (e.g., each individual M within the complex) 1 and M 2 The ligands associated with the substance and the complex form at least 3 valence bonds on average, preferably at least 4 valence bonds, and most preferably about 6 valence bonds. Suitablely, the coordination sites of all metal substances can be completely filled / saturated by ligands within the complex (e.g., especially where the host metal complex is intended to function as a Lewis base throughout the antiscattering compound), or one or more empty coordination sites may exist between the metal substances (e.g., especially where the host metal complex is intended to function as a Lewis acid throughout the antiscattering compound).

[0321] Suitablely, at least some of the ligands are negatively charged, most preferably with a single negative charge. Suitablely, the conjugate acid of the ligands of the host metal complex has a pKa value greater than or equal to 2, and suitablely greater than or equal to 3 (in water at standard ambient temperature and pressure).

[0322] Suitablely, the ligands of the host metal complex are selected from monodentate ligands, bidentate ligands, or mixtures thereof. Most suitablely, the ligands of the host metal complex include mixtures of monodentate and bidentate ligands.

[0323] Monodentate ligands appropriately have coordinating atoms with more than one pair of electrons (atoms that form coordinate bonds with metallic substances), most appropriately fluorides.

[0324] The bidentate ligand suitably has at least one, more preferably two, coordinating atoms having more than one pair of electron pairs, most preferably a carboxyl group (e.g., an optionally substituted organic carboxyl group, such as an optionally substituted hydrocarbon carboxyl group, such as acetate, neopentanoate, 3,3-dimethylbutyrate, benzoate, 4-tert-butylbenzoate, isonicotinic acid). In some embodiments (particularly where the host metal complex is intended to be used as a Lewis base), the ligand of the host metal complex comprises at least two different types of bidentate ligands (e.g., including a first bidentate ligand and a second bidentate ligand) or carboxyl ligands. In such embodiments, suitably, at least one bidentate ligand (e.g., a second one) comprises a coordinating atom capable of forming an internal covalent bond with a metal within the host metal complex and one or more additional coordinating atoms capable of forming an external covalent bond with a metal of another (different) complex or cage. Suitablely, such bifunctional ligands (e.g., second bidentate ligands) may comprise a carboxylate group and an additional oxygen- or nitrogen-containing moiety, preferably a nitrogen-containing moiety, examples of which include isonicotinic acid and 4-aminobenzoate. However, in some embodiments (particularly where the host metal complex is intended to be used as a Lewis acid), the ligands of the host metal complex do not contain any additional coordinating atoms capable of forming external covalent bonds with another (different) complex or cage metal, and may suitably comprise a type of bidentate ligand or carboxylate ligand.

[0325] In one specific embodiment, the host metal complex is defined by formula I or includes units defined by formula I:

[0326] [M 1 x M 2 y… M n zn (monoLIG 1 ) m1 (monoLIG 2 ) m2… (monoLIG q ) mq (biLIG 1 ) b1 (biLIG 2 ) b2… (biLIG r ) br (optLIG s (optLIG) 1 ) o1 (optLIG 2 ) o2… (optLIG s ) os ];

[0327] or

[0328] Defined as comprising, being primarily composed of, or formed by mixing, reacting, or otherwise combining the following (per mole of the main metal complex):

[0329] -x moles of the first metallic substance (M) 1 );

[0330] -y moles of the second metallic substance (M) 2 );

[0331] -Optional zn moles for each additional nth metal (M n );

[0332] -m1 molar first monodentate ligand (monoLIG) 1 )

[0333] -Optional m2 moles of the second monodentate ligand (monoLIG) 2 )

[0334] -Optionally, each additional qth monodentate ligand (monoLIG) of mq moles q )

[0335] -b1 moles of the first bidentate ligand (biLIG) 1 )

[0336] -Optional b2 molar second bidentate ligand (biLIG) 2 )

[0337] -Optionally, each additional r-th bidentate ligand (biLIG) of br molar r )

[0338] -o1 moles of the first optional additional / terminal ligand (optLIG) 1 )

[0339] -o2 moles of the second optional additional / terminal ligand (optLIG) 2 )

[0340] -os mole for each additional optional s-terminal ligand (optLIG) s )

[0341] in:

[0342] M 1 It is a first-metallic substance, appropriately as defined herein (most appropriately a trivalent metal ion, such as Cr). 3 + );

[0343] M 2It is a second metallic substance, suitably as defined herein (most suitably a divalent metal ion, such as Ni). 2 + );

[0344] M n It is the nth metallic substance, appropriately as defined herein (most appropriately it does not exist);

[0345] monoLIG 1 It is the first monodentate ligand, appropriately as defined herein (most appropriately its conjugate acid has a pKa ≥ 2, and appropriately a fluorine monoanion);

[0346] monoLIG 2 It is the second monodentate ligand, appropriately as defined herein (most appropriately it does not exist);

[0347] monoLIG q It is the qth monodentate ligand, appropriately as defined herein (most appropriately it does not exist);

[0348] biLIG 1 It is the first bidentate ligand, suitably as defined herein (most suitably carboxylate, suitably, suitably without any other heteroatoms);

[0349] biLIG 2 It is a second bidentate ligand, suitably as defined herein (most suitably absent or a carboxylate having an additional oxygen- or nitrogen-containing moiety, most preferably an additional nitrogen-containing moiety);

[0350] biLIG r It is the second bidentate ligand, appropriately as defined herein (most appropriately it does not exist);

[0351] optLIG 1 It is the first optional additional ligand (suitably having d-coordination), suitable as defined herein (most suitable not present, or a polydentate ligand having d-coordination, such as N-methyl-D-glucosamine, solvent or carboxylic acid in the case of d=6);

[0352] optLIG 2 It is a second optional additional / terminal ligand, suitably as defined herein (most suitably absent or a solvent or carboxylic acid);

[0353] optLIG s It is the s-th optional additional / terminal ligand, suitably as defined herein (most suitably absent or a solvent or carboxylic acid);

[0354] Most appropriately, x, y, zn, m1, m2, mq, b1, b2, br, o1, o2, os are zero or integers, but in some instances, any, some, or all of these may have intermediate values ​​between 0 and 1 or between any two integers.

[0355] x is appropriately a number between 1 and 16 (most appropriately an integer), appropriately between 4 and 10; more appropriately between 2 and 8; appropriately 7.

[0356] y is appropriately a number between 0 and 15 (most appropriately an integer), appropriately between 0 and 7; appropriately between 0 and 2, appropriately 0 or 1, and most appropriately 1.

[0357] zn is appropriately a number between 0 and 14 (most appropriately an integer), appropriately between 0 and 6; appropriately between 0 and 2; appropriately 0.

[0358] m1 is appropriately a number between 0 and 40 (most appropriately an integer); appropriately between 0 and 20 or between 0 and 10; appropriately between 1 and 20; appropriately between 2 and 12; appropriately between 4 and 10; appropriately 8.

[0359] m2 is appropriately a number between 0 and 39 (most appropriately an integer); appropriately between 0 and 18; appropriately between 0 and 10; appropriately between 0 and 2; appropriately 0.

[0360] mq is appropriately a number between 0 and 38 (most appropriately an integer); appropriately between 0 and 17; appropriately between 0 and 9; appropriately between 0 and 2; appropriately 0.

[0361] b1 is appropriately a number between 0 and 20 (most appropriately an integer); appropriately between 1 and 20; appropriately between 1 and 16; appropriately between 12 and 16; appropriately between 12 and 15; appropriately 15 or 16.

[0362] b2 is a number between 0 and 20 (most appropriate integer); between 0 and 16; between 0 and 8; between 0 and 3; between 1 and 4; or 0 or 1.

[0363] br is appropriately a number between 0 and 19 (most appropriately an integer); appropriately between 0 and 15; appropriately between 0 and 7; appropriately between 0 and 2; appropriately 0.

[0364] o1 is appropriately a number between 0 and 8 (appropriately an integer), appropriately between 0 and 4, appropriately 0 or 1, and most appropriately 0.

[0365] o2 is appropriately a number between 0 and 7 (appropriately an integer), appropriately between 0 and 3, appropriately 0 or 1, and most appropriately 0.

[0366] os is appropriately a number between 0 and 6 (appropriately an integer), appropriately between 0 and 2, appropriately 0 or 1, and most appropriately 0.

[0367] In one embodiment, the host metal complex is defined by formula I or comprises units defined by formula I:

[0368] [M 1 x M 2 y… M n zn (monoLIG 1 ) m1 (monoLIG 2 ) m2… (monoLIG q ) mq (biLIG 1 ) b1 (biLIG 2 ) b2… (biLIG r ) br (optLIG s (optLIG) 1 ) o1 (optLIG 2 ) o2… (optLIG s ) os ];

[0369] in:

[0370] M 1 It is the first metallic substance, and x is the amount of M per mole of the main metal complex. 1 The number of moles, where x is a number between 1 and 16;

[0371] M 2 It is the second metallic substance, and y is the amount of M per mole of the main metal complex. 2 The number of moles, where y is a number between 0 and 7;

[0372] M n It is the nth metallic substance, and zn is the amount of each M per mole of the main metal complex. n The number of moles, where zn is a number between 0 and 6; appropriately between 0 and 2; appropriately 0;

[0373] monoLIG 1It is the first monodentate ligand, and m1 is the monoligand in the host metal complex per mole of monoLIG. 1 The number of moles, where m1 is a number between 0 and 20;

[0374] monoLIG 2 It is the second monodentate ligand, and m2 is the monoLIG per mole of the host metal complex. 2 The number of moles, where m2 is a number between 0 and 10;

[0375] monoLIG q It is the qth monodentate ligand, and mq is the number of monoligands per mole of the host metal complex. q The number of moles, where mq is a number between 0 and 2;

[0376] biLIG 1 It is the first bidentate ligand, b1 is the biLIG per mole of the host metal complex. 1 The number of moles, where b1 is a number between 1 and 20;

[0377] biLIG 2 It is the second bidentate ligand, b2 is the biLIG per mole of the host metal complex. 2 The number of moles, where b2 is a number between 0 and 16;

[0378] biLIG r It is the r-th bidentate ligand, and br is the additional biLIG per mole of the host metal complex. r The number of moles,

[0379] Where br is a number between 0 and 2;

[0380] optLIG 1 It is the first optional additional ligand, o1 is the optLIG per mole of the host metal complex. 1 The number of moles, where o1 is a number between 0 and 4;

[0381] optLIG 2 It is the second optional additional / terminal ligand, and o2 is the optLIG per mole of the host metal complex. 2 The number of moles, where o2 is a number between 0 and 3;

[0382] optLIG s It is the s-th optional additional / terminal ligand, os is each additional optional optLIG per mole of host metal complex. s The number of moles; where os is a number between 0 and 2.

[0383] In one embodiment, the host metal complex is defined by formula Ia or comprises units defined by formula I:

[0384] [M 1 x M 2 y (monoLIG 1 ) m1 (biLIG 1 ) b1 (biLIG 2 ) b2 ];

[0385] in:

[0386] M 1 It is the first metallic substance, and x is the amount of M per mole of the main metal complex. 1 The number of moles, where x is a number between 4 and 10;

[0387] M 2 It is the second metallic substance, and y is the amount of M per mole of the main metal complex. 2 The number of moles, where y is a number between 0 and 2;

[0388] monoLIG 1 It is the first monodentate ligand, and m1 is the monoligand in the host metal complex per mole of monoLIG. 1 The number of moles, where m1 is a number between 4 and 10;

[0389] biLIG 1 It is the first bidentate ligand, b1 is the biLIG per mole of the host metal complex. 1 The number of moles, where b1 is a number between 12 and 16;

[0390] biLIG 2 It is the second bidentate ligand, b2 is the biLIG per mole of the host metal complex. 2 The number of moles, where b2 is a number between 0 and 3.

[0391] Suitablely, the sum of x and y is at least 2, more suitablely at least 3, suitablely at least 4, suitablely at least 5, suitablely at least 6, suitablely at least 7, suitablely about 8. Suitablely, the sum of x and y is at most 16, suitablely at most 12, suitablely at most 10. Suitablely, x is at least 4, suitablely at least 6, suitablely at most 10, and most suitablely about 7. In a particular embodiment, y is 0 (i.e., there is no second metallic substance at all), but preferably y is not zero, suitablely at least 1, most suitablely about 1. Most suitablely, x is 7 + / - δ (i.e., δ = at most 10% of x, suitablely at most 1% of x) and y is 1 - / + δ. In one specific embodiment, M 1 It is Cr 3+ M 2 It's Ni 2+ The sum of x and y is between 7 and 10; x is between 6 and 10. In one specific implementation, M 1 It is Cr3+, M 2 It is Cr 3+ x is approximately 7, and y is approximately 1.

[0392] Most appropriately, the main metal complex, except for the first metal substance (M) 1 ) and optional second metal material (M 2 The main metal complex contains no other metallic substances besides z3, z4, ..., zn, and therefore zn is zero. However, in some instances, the main metal complex may be doped, for example, with a small amount of alternative metallic substances to reasonably alter the properties of the antiscattering compound. In such embodiments, the sum of any or all zn values ​​(z3 + z4 + ... + zn) is suitably less than the sum of x and y, suitably at least a factor of 5 (i.e., at most one-fifth of the sum of x and y), suitably at least a factor of 10, and suitably at least a factor of 100.

[0393] Appropriately, the sum of the following:

[0394] -(m1+m2+…+mq); (i.e., the sum of the number of moles of monodentate ligands per mole of the complex)

[0395] -2×(b1+b2+…+bq); (i.e., twice the sum of the number of bidentate ligands per mole of the complex)

[0396] -o1×d (i.e., d times the number of optional additional ligands per mole of the complex)

[0397] Less than or equal to 50, appropriately less than or equal to 42, appropriately less than or equal to 40, appropriately greater than or equal to 30, appropriately greater than or equal to 38, appropriately approximately 40.

[0398] Suitablely, the sum of m1, m2, ..., and mq is at least 1, suitablely at least 2, suitablely at least 3, suitablely at least 6, suitablely at most 7, suitablely at most 16, suitablely at most 12, suitablely at most 10, and most suitablely about 8. In a preferred embodiment, there are no monodentate ligands other than the first monodentate ligand (i.e., m2 and mq are both 0). In one specific embodiment, monoLIG 1 It is a fluoride (F). In one specific embodiment, monoLIG 1 It is a fluoride (F), m1 is between 2 and 9, and m2 and mq are both 0, where appropriately, M 1 It is Cr 3+ M 2 It's Ni 2+ The sum of x and y is between 7 and 10; x is between 6 and 10. In one specific implementation, monoLIG 1 It is a fluoride (F), m1 is 3, and m2 and mq are both 0 (i.e., there are no other monodentate ligands). In one specific embodiment, monoLIG 1 It is a fluoride (F), m1 is 8, and m2 and mq are both 0 (i.e., there are no other monodentate ligands).

[0399] Appropriately, the sum of b1, b2, ..., and br is at least 6, appropriately at least 10, appropriately at least 14, appropriately at most 22, appropriately at most 20, appropriately at most 18, and most appropriately about 16. In some embodiments, there are no bidentate ligands other than the first and second bidentate ligands (i.e., all br are 0), and in some embodiments, there are no bidentate ligands other than the first bidentate ligand (i.e., both b2 and br are 0). In one embodiment, biLIG 1 It is composed of formula -O2CR B1 (or R) B1 CO2 - The carboxylate group is defined as R. B1 Suitablely, it is a (optionally substituted) group, such as a hydrocarbon moiety (suitably, a hydrocarbon moiety without a basic or chelating group), and suitably selected from: (1-12C)alkyl, (1-12C)alkenyl, (1-12C)ynyl, (3-8C)cycloalkyl, (3-8C)cycloalkenyl, (1-3C)alkyl(3-8C)cycloalkyl, (1-3C)alkyl(3-8C)cycloalkenyl, aryl, (1-3C)alkylaryl, aryl(1-3C)alkyl. Suitably, R B1 It is (1-12C)alkenyl, (1-12C)ynyl, (3-8C)cycloalkenyl, aryl, (1-3C)alkylaryl, or aryl(1-3C)alkyl. Most preferably, R B1It is (1-5C)alkenyl. In one embodiment, biLIG 2 It is composed of formula -O2CR B2 (or R) B2 CO2 - The carboxylate group is defined as R. B2 Suitablely, it is a group comprising a basic or chelating group (e.g., a portion with a lone pair of electrons, which freely coordinate to form a coordinate bond), and suitably selected from optionally substituted heterocyclic, heteroaryl, heterocyclic (1-6C)alkyl, heteroaryl (1-6C)alkyl, or selected from (1-12C)alkyl, (1-12C)alkenyl, (1-12C)ynyl, (3-8C)cycloalkyl, (3-8C)cycloalkenyl, (1-3C)alkyl(3-8C)cycloalkyl, (1-3C)alkyl(3-8C)cycloalkenyl, aryl, (1-3C)alkylaryl, or aryl(1-3C)alkyl, substituted with one or more basic or chelating groups (e.g., amino, alkylamino, dialkylamino, hydroxyl, (1-6C)alkoxy, carbonyl, imino, mercapto, thiocarbonyl, etc.). Most suitably, R B2 It is pyridyl, aminophenyl, N-(1-3C)alkylaminophenyl, N,N-bis(1-3C)alkylaminophenyl, most preferably pyridyl, most preferably 4-pyridyl, most preferably, biLIG 2 It is isonicotinic acid. In one specific implementation, biLIG 1 It is an optional substituted hydrocarbon carboxylate (e.g., (1-6C) alkyl carboxylate, such as neopentanoate), biLIG 2 It is an organic or optionally substituted hydrocarbon carboxylate group with at least one additional heteroatom (e.g., the kind that can be used as a Lewis base or as a ligand for externally chelating a metal to a complex, such as isonicotinic acid), b1 is between 12 and 20 (most suitable 14-18, most suitable 15-16), b2 is between 0 and 4 (most suitable 0 or 1-3), wherein suitably, M 1 It is Cr 3+ M 2 It's Ni 2+ The sum of x and y is between 7 and 10; x is between 6 and 10, and the appropriate monolig is given. 1 It is a fluoride (F), m1 is between 2 and 9, and m2 and mq are both 0.

[0400] Suitablely, the sum of o1, o2, ..., and os is between 0 and 4, suitablely between 0 and 2, and most suitablely between 0 and 1. In some embodiments, there are no optional additional / terminal ligands other than the first optional additional / terminal ligand (i.e., both o2 and os are 0). In one specific embodiment, the sum of o1, o2, ..., and os is zero (i.e., there are substantially no optional additional / terminal ligands). In the presence of one or more optional additional / terminal ligands, these ligands may include solvent molecules (which are monodentate, bidentate, or multidentate), such as H2O, tetrahydrofuran, pyridine, etc. In some embodiments, the host metal complex includes an additional / terminal ligand that is a multidentate ligand with a degree of congruence greater than or equal to 3, suitablely greater than or equal to 4, but suitablely at most 6. Such a multidentate compound may, for example, include N-(1-6C)alkyl-D-glucosamine (e.g., N-methyl-D-glucosamine). In one specific embodiment, optLIG 1 From the formula Gluc-NH-R O1 Definition, where Gluc-NH-R O1 It is N-(1-8C)alkyl-D-glucosamine or its deprotonated form, and wherein, suitably, R O1 It is a (1-8C) alkyl, more preferably a (1-2C) alkyl (e.g., methyl or ethyl). In this embodiment, o1 is suitably 1 while o2 and os are both zero.

[0401] In certain embodiments, the host metal complex is defined by Formula II or comprises units defined by Formula II:

[0402] [M 1 x M 2 y (monoLIG 1 ) m1 (O2CR B1 ) 16-b2 (O2CR B2 ) b2 ]

[0403] in:

[0404] M 1 It is a trivalent metal ion as defined in this article, most appropriately Cr. 3+ ;

[0405] M 2 It is a divalent metal ion as defined in this article, most appropriately Ni. 2+ ;

[0406] x is defined as in this paper (appropriately, x is 6, 7, 8 or 9, most appropriately x is 7);

[0407] y is as defined herein (appropriately y is 1 or 2, most appropriately y is 1, but it can be a polymetallic complex of the same metal in the form of 0 with the same metal oxidation state, such as Cr(III));

[0408] monoLIG 1 As defined in this article (most appropriately monoLIG) 1 It is fluorine (F);

[0409] m1 is as defined in this paper (most appropriately m1 is 8);

[0410] R B1 As defined herein, but suitably free of basic groups or chelating groups, and suitably selected from (1-12C)alkyl, (1-12C)alkenyl, (1-12C)ynyl, (3-8C)cycloalkyl, (3-8C)cycloalkenyl, (1-3C)alkyl(3-8C)cycloalkyl, (1-3C)alkyl(3-8C)cycloalkenyl, aryl, (1-3C)alkylaryl, aryl(1-3C)alkyl;

[0411] R B2 As defined in this article, but R B2 Suitablely, it is a group comprising a basic group or a chelating group (e.g., a portion having lone pairs of electrons that are freely coordinated to form a coordinate bond), and suitably selected from optionally substituted heterocyclic groups, heteroaryl groups, heterocyclic (1-6C)alkyl groups, heteroaryl (1-6C)alkyl groups, or selected from (1-12C)alkyl groups, (1-12C)alkenyl groups, (1-12C)ynyl groups, (3-8C)cycloalkyl groups, (3-8C)cycloalkenyl groups, (1-3C)alkyl(3-8C)cycloalkyl groups, (1-3C)alkyl(3-8C)cycloalkenyl groups, aryl groups, (1-3C)alkylaryl groups, or aryl(1-3C)alkyl groups, substituted with one or more basic groups or chelating groups (e.g., amino, alkylamino, dialkylamino, hydroxyl, (1-6C)alkoxy, carbonyl, imino, mercapto, thiocarbonyl, etc.).

[0412] b2 is defined as in this article, but b2 is suitable to be 0, 1, 2 or 3;

[0413] Where appropriate, the sum of x and y is as defined in this paper, but most appropriately the sum of x and y is 7, 8, 9 or 10 (most appropriately 8).

[0414] In one specific embodiment, the host metal complex is defined by formula IIa or includes units defined by formula IIa:

[0415] [M 1 8-y M 2 y F8(O2CRB1 ) 16-b2 (O2CR B2 ) b2 ]

[0416] in:

[0417] M 1 It is a trivalent metal ion as defined in this article, most appropriately Cr. 3+ ;

[0418] M 2 It is a divalent metal ion as defined in this article, most appropriately Ni. 2+ ;

[0419] y is 0 or 1;

[0420] R B1 It is a group that does not contain a basic group or a chelating group, and is suitably selected from (1-12C) alkyl,

[0421] (1-12C)alkenyl, (1-12C)alkynyl, (3-8C)cycloalkyl, (3-8C)cycloalkenyl, (1-3C)alkyl(3-8C)cycloalkyl, (1-3C)alkyl(3-8C)cycloalkenyl, aryl, (1-3C)alkylaryl, aryl(1-3C)alkyl;

[0422] R B2 It is a group that includes a basic group or a chelating group (e.g., a portion having lone pairs of electrons that are freely coordinated to form a coordinate bond), and suitably selected from optionally substituted heterocyclic groups, heteroaryl groups, heterocyclic (1-6C)alkyl groups, heteroaryl (1-6C)alkyl groups, or selected from (1-12C)alkyl groups, (1-12C)alkenyl groups,

[0423] (1-12C) alkynyl, (3-8C) cycloalkyl, (3-8C) cycloalkenyl, (1-3C) alkyl(3-8C) cycloalkyl, (1-3C) alkyl(3-8C) cycloalkenyl, aryl, (1-3C) alkylaryl or aryl(1-3C) alkyl, substituted by one or more basic groups or chelating groups (e.g., amino, alkylamino, dialkylamino, hydroxyl, (1-6C) alkoxy, carbonyl, imino, mercapto, thiocarbonyl, etc.);

[0424] b2 is 0, 1, 2, or 3.

[0425] In one specific embodiment, the host metal complex is defined by formula IIb or includes units defined by formula IIb:

[0426] [Cr7NiF8(O2CR B1 ) 16-b2 (O2CR B2 ) b2 ]

[0427] Where R B1 R B2 and b2 as defined in this paper, but most appropriately R B1 It is tert-butyl and R B2 If present, it is 4-pyridyl.

[0428] In one specific embodiment, the host metal complex is defined by formula IIc or comprises units defined by formula IIc:

[0429] [Cr7NiF8(O2CR B1 ) 16 ];

[0430] Where R B1 As defined in this article, but most appropriately R B1 It is tert-butyl.

[0431] In one specific embodiment, the host metal complex is defined by formula IId or includes units defined by formula IId:

[0432] [Cr8F8(O2CR B1 ) 16-b2 (O2CR B2 ) b2 ]

[0433] Where R B1 R B2 and b2 as defined in this paper, but most appropriately R B1 It is tert-butyl and R B2 If present, it is 4-pyridyl.

[0434] In one specific embodiment, the host metal complex is defined by formula IIe or comprises units defined by formula IIe:

[0435] [Cr8F8(O2CR B1 ) 16 ];

[0436] Where R B1 As defined in this article, but most appropriately R B1 It is tert-butyl.

[0437] In another embodiment, the host metal complex is defined by Formula III or comprises units defined by Formula III:

[0438] [M 1 8-y M 2 y F3(O2CR B1 ) 15 (Gluc-NH-RO1 )]

[0439] in:

[0440] M 1 It is a trivalent metal ion as defined in this article, most appropriately Cr. 3+ ;

[0441] M 2 It is a divalent metal ion as defined in this article, most appropriately Ni. 2+ ;

[0442] y is 0 or 1;

[0443] R B1 It is a group that does not contain a basic group or a chelating group, and is suitably selected from (1-12C) alkyl,

[0444] (1-12C)alkenyl, (1-12C)alkynyl, (3-8C)cycloalkyl, (3-8C)cycloalkenyl, (1-3C)alkyl(3-8C)cycloalkyl, (1-3C)alkyl(3-8C)cycloalkenyl, aryl, (1-3C)alkylaryl, aryl(1-3C)alkyl;

[0445] Gluc-NH-R O1 It is N-(1-8C)alkyl-D-glucosamine (i.e., R) O1 It is (1-8C)alkyl, more appropriately (1-2C)alkyl, or its deprotonated form.

[0446] In another embodiment, the host metal complex is defined by formula IIIa or comprises units defined by formula IIIa:

[0447] [Cr7NiF3(O2CR B1 ) 15 (Gluc-NH-R O1 )]

[0448] Where R B1 and Gluc-NH-R O1 As defined in this article, but most appropriately R B1 It is tert-butyl and R O1 It is a methyl group.

[0449] As mentioned earlier, the host metal complex of the antiscattering compound comprises one or more resist ligands (i.e., ligands that can be induced to crosslink with other such ligands in the host metal complex, which may be in adjacent host metal complexes and / or adjacent antiscattering compounds). Any of the aforementioned ligands, whether monodentate, bidentate, or other forms, can be replaced by any of the aforementioned resist components. However, regardless of the amount of resist ligands in each host metal complex, suitably, the entire coordination sphere of the host metal complex is adequately filled by alternative ligands as defined herein (e.g., not electron-deficient, or otherwise thermodynamically stable). Thus, host metal complexes comprising resist ligands and mixtures of any of the aforementioned ligands are conceivable, but some of the aforementioned ligands may also be used as resist ligands (e.g., alkenoic acid and alkenoate ligands).

[0450] In one embodiment, the host metal complex is a multimetallic cage complex comprising one or more ligands (e.g., resist ligands) with crosslinkable moieties (e.g., π-based moieties). In one embodiment, the multimetallic cage complex comprises chromium ions and nickel ions. In one embodiment, the ligands with crosslinkable moieties are suitably coupled to the metal ions of the multimetallic complex via one or more heteroatoms with lone pairs of electrons (most suitably via carboxylates, carboxylic acids, carboxyl groups, or carboxylic acid-amide moieties of the ligands). The crosslinkable moieties discussed are suitably olefin or alkyne moieties, most suitably olefin moieties, and most suitably terminal olefin moieties. The crosslinkable moieties of adjacent host metal complexes can be crosslinked directly (e.g., in the case where an olefin of one host metal complex ligand is coupled to an olefin of an adjacent host metal complex ligand) or indirectly, for example, via the intervention of a resist (e.g., in the case where olefins of two adjacent host metal complex ligands are coupled to a common resist crosslinking agent, such as a suitable diene).

[0451] In one specific embodiment, the host metal complex is defined by formula IIf or comprises units defined by IIf:

[0452] [M 1 x M 2 y (O2CR B1 ) r ];

[0453] Where M 1 It is the first metallic substance, and x is the amount of M per mole of the main metal complex. 1 The number of moles (where x is a number between 4 and 10, where appropriate); M 2 It is the second metallic substance, and y is the amount of M per mole of the main metal complex. 2 The number of moles of y (where y is a number between 0 and 2, where R B1It is an optional substituted (1-20C) hydrocarbon group including π-system (appropriately terminal π-system); wherein r is an integer having a value of 1 or greater (appropriately between 1 and 16); and wherein the unit of formula IIf optionally includes one or more other related ligands (i.e., valence-bonded within the complex).

[0454] In one specific embodiment, the host metal complex is defined by formula IIg or comprises units defined by formula IIg:

[0455] [Cr7Ni(O2CR B1 ) r ];

[0456] Where R B1 It is an optional substituted (1-20C) hydrocarbon group including π-system (appropriately terminal π-system); wherein r is an integer having a value of 1 or greater (appropriately between 1 and 16); and wherein the unit of formula IIg optionally includes one or more other related ligands (i.e., valence-bonded within the complex).

[0457] In one specific embodiment, the host metal complex is defined by formula IIh or comprises units defined by formula IIh:

[0458] [Cr7NiF8(O2CR B1 ) r ];

[0459] Where R B1 It is an optional substituted (1-10C) hydrocarbon group comprising an olefin or alkyne moiety, suitably a terminal olefin or alkyne moiety, most suitably an olefin moiety; wherein r is an integer having a value of 1 or greater (suitably between 1 and 16); and wherein the unit of formula IIh optionally comprises one or more other related ligands (i.e., coordinated within the complex).

[0460] In one specific embodiment, the host metal complex is defined by formula IIi or includes units defined by formula IIi:

[0461] [Cr7NiF8(O2CR B1 ) r ];

[0462] Where R B1 It is an optionally substituted (1-6C) hydrocarbon group comprising an olefin or alkyne moiety, suitably a terminal olefin or alkyne moiety, most suitably an olefin moiety; wherein r is an integer having a value of 1 or greater (suitably between 1 and 16); and wherein the unit of formula IIi optionally comprises one or more other related ligands (i.e., coordinated within the complex).

[0463] Generally, the more resist ligands in each host metal complex, the more sensitive the corresponding resist composition will be, because the crosslinking rate is related to the probability of effective collisions between the relevant crosslinked resist ligands.

[0464] counterions

[0465] Depending on the type of metal within the complex and the balance of the associated ligands, the host metal complex can be neutral or charged (whether positive or negative). The same applies to any other metal complex and any linker component. Furthermore, the host metal complex, any linker component, and / or any other metal complex, in combination with their associated stoichiometry, can generate a net charge. Thus, antiscattering compounds can include one or more counterions (e.g., C2). 1 C 2 C c As appropriately defined herein, such counterion is suitably combined with a host metal complex, one or more other metal complexes, a linker component, and / or a hybrid complex as a whole. The hybrid complex may be defined by formula E or may comprise units defined by formula E:

[0466] (PMC) p-a (AMC) a (LINK) l

[0467] Where PMC, AMC, LINK, p, a, and l are as defined in this paper, appropriately with respect to equation D;

[0468] Furthermore, the corresponding hybrid complex salts that bind to the aforementioned counterions are suitably defined by formula D or include units defined by formula D:

[0469] (C 1 i1 C 2 i2 …C c ic (PMC) p-a (AMC) a (LINK) l

[0470] Equation D and its components are as defined in this paper.

[0471] If the hybrid complex of formula E (or actually formula B) is neutral, the antiscattering compound may not contain the counterion as defined herein, but this does not necessarily preclude instances where the components of the complex or hybrid complex act as counterions to each other.

[0472] A counterion can be any suitable counterion, and can be positive (anti-cation) or negative (anti-anion) depending on the polarity of the charge carried on the substance to which the counterion is intended to neutralize.

[0473] In a preferred embodiment, the host metal complex has a negative net charge (i.e., produces an anionic complex), most suitably having a negative charge of about -1. Furthermore, in a preferred embodiment, the hybrid complex (whether of formula B or E) has a negative net charge. Thus, the antiscattering compound suitably further comprises one or more antications, suitably a single antication (i.e., only C). 1 But it does not contain C. 2 …C c ), to neutralize the negative charge of the related complex.

[0474] The antication can be any suitable cation. However, in a preferred embodiment, the antication comprises a monovalent cation (i.e., +1 charged) (and preferably consists mainly of monovalent cations), suitably selected from alkali metal cations or ammonium cations (including any ammonium, primary ammonium, secondary ammonium, tertiary ammonium, quaternary ammonium cations, imidazolium), most suitably selected from NH3R. cat1 + NH2R cat1 R cat2 + Cs + 、Rb + The cation, wherein R cat1 and R cat2 Each is independently selected from (1-12C) alkyl groups (most preferably (1-4C) alkyl groups, especially ethyl or propyl). Dipropylammonium salts are used in particular.

[0475] Connecting subcomponents (or central complexes)

[0476] Antiscattering compounds may suitably include a linker component, but this is not mandatory. Suitably, the linker component indirectly links (or binds) two or more host metal complexes and / or suitably links (or binds) one or more host metal complexes to one or more additional metal complexes via the linker component. Suitably, the linker component is capable of forming electrostatic and / or covalent bonds with two or more host metal complexes and / or one or more host metal complexes and one or more additional metal complexes.

[0477] Appropriately, when a linker component is defined by reference to a radical substance (e.g., a halogen), it may instead refer to its ionic form (e.g., a halide).

[0478] The linker component may include one or more, suitably two or more Lewis base moieties and / or one or more Lewis acid moieties. Thus, the linker component may include one or more, suitably two or more electron pair donors and / or one or more, suitably two or more electron pair acceptors. In a preferred embodiment, the linker component forms a bridge (or hub) between two or more host metal complexes and / or between one or more host metal complexes and one or more additional metal complexes, and therefore the linker component suitably includes at least one Lewis acid or base moiety bonded (suitably via valence bond) to one complex and at least one Lewis acid or base moiety bonded (suitably via valence bond) to another complex.

[0479] The antiscattering compound or hybrid complex (or its salt) may include one or more moles of linker component per mole of the compound or hybrid complex (whether the linker component is the same or different, suitably the same), but most suitably, the antiscattering compound or hybrid complex (or its salt) includes only one mole of linker component per mole of the compound or hybrid complex. Thus, the linker component most suitably serves as a common central hub within the hybrid complex for the main metal complex and / or additional metal complexes (but most preferably only the main metal complex) to connect (or bind). Suitably, this common central hub is surrounded by two or more main metal complexes and / or additional metal complexes, more suitably by four or more main metal complexes and / or additional metal complexes. Thus, suitably, the linker component includes a suitable number of Lewis acid or base portions so that the linker component is suitably able to bond (preferably by valence) all of its surrounding main metal complexes and / or additional metal complexes (one or more) via valence bonds. However, when the linker portion binds to only a single host metal complex without additional metal complexes, the linker component can simply be a terminal ligand, such as one selected from optLIG. 2 Those, such as solvent molecules (e.g., water, THF, pyridine, or substituted pyridine).

[0480] Antiscattering compounds suitably include hybrid complexes as defined by formula E or include units as defined by formula E:

[0481] (PMC) p-a (AMC) a (LINK) l

[0482] Where l is 1; p ≥ 2 (appropriately between 2 and 8, more appropriately 2, 4 or 6, but p can be between 23 and 49); a is between 0 and 7 (appropriately 0).

[0483] The linker component or LINK group / molecule suitably provides one or more, preferably two or more, electron-donating pair coordinating groups and / or electron-accepting pair coordinating groups. Although in some embodiments, the linker component may comprise a mixture of electron-donating pair coordinating groups and / or electron-accepting pair coordinating groups, most preferably the linker component uniquely comprises electron-donating pair coordinating groups and / or electron-accepting pair coordinating groups. Whether the linker component comprises electron-donating pair coordinating groups or electron-accepting pair coordinating groups suitably depends on the electron-donating or electron-accepting capabilities of the respective host metal complex and optionally additional metal complexes (particularly their ligands).

[0484] When the connecting sub-component, or each of the connecting sub-components, particularly when two or more PMCs or two or more PMC / AMC combinations are combined with the connecting sub-component, may be or include units independently selected from:

[0485] i) Including a single atom, molecule, ion, or complex that is capable of accepting or giving two or more lone pairs of electrons to a single coordinating part;

[0486] ii) Monomolecules, ions, or complexes (e.g., optionally substituted acyclic, cyclic, polycyclic, or macrocyclic molecules containing multiple heteroatoms; or compounds or complexes centered on a Lewis acid metal; or metal-centered compounds or complexes attached to a leaving group or a substituted ligand), comprising two or more coordinating moieties (e.g., internal heteroatoms such as nitrogen, oxygen, or sulfur; or external heteroatoms carried by optional substituents; or electron-deficient metal centers; or metal centers attached to leaving groups or substituted ligands),

[0487] Each coordination moiety can accept or donate one or more lone pairs of electrons;

[0488] iii) Molecules, ions, or complexes defined by Formula IV:

[0489] Q-[Core]-[W] w

[0490] in:

[0491] [Nucleus] The nucleus is absent or connected to the subcomponent and includes one or optionally more than one nuclear group;

[0492] Q is a group directly attached to the [nucleus] or one or more of its nuclear groups, wherein Q includes a coordination moiety (suitably a coordination moiety coordinated to a host metal complex);

[0493] Each W is a group that is independently and directly attached to the [nucleus] or one or more of its nuclear groups, and optionally further attached to one or more other W groups or Q, wherein each W independently includes a coordination moiety (appropriately, the coordination moiety that coordinates to the host metal complex and the coordination moiety that binds to Q or another metal complex are different).

[0494] Where w is an integer greater than zero.

[0495] One, more, or all of the Q and W groups may be the same or different. However, even if one, more, or all of the Q and W groups are different, they are properly selected from the same library of acceptable groups.

[0496] When the linker component is a single atom, molecule, ion, or complex comprising a single coordinating moiety capable of donating two or more lone pairs of electrons, suitably, the single coordinating moiety comprises or consists of an oxygen, sulfur, or halogen (especially fluorine or chlorine, particularly fluorine) atom. For example, the linker component may be or include a selection from halides (preferably fluorine), oxygen groups, oxides, hydroxides (OH-). - (1-6C) alkoxide, (2-6C) alkenyloxy, (2-(2-6C) alkynyloxy, formyl, carboxyl, (1-6C) alkoxycarbonyl, (2-6C) acyl, (2-6C) acyloxy, sulfonyl, sulfide, hydrosulfide, (1-6C) alkylthio, (2-6C) alkenylthio, (2-6C) alkynylthio, thiocarbonyl, heterocyclic group containing at least one internal heteroatom selected from oxygen or sulfur, or (where appropriate) its deprotonated form or a salt thereof; wherein any CH, CH2 or CH3 may optionally be substituted.

[0497] Where the linker component is a single atom, molecule, ion, or complex comprising a single coordinating portion capable of accepting two or more lone pairs of electrons, suitably, the single coordinating portion comprises or is composed of a Lewis acid metal atom (which may include boron or silicon) or a metal atom attached to or consisting of a leaving group or a substituted ligand. For example, the linker component may be or comprise a group selected from metal cations (e.g., divalent metal cations), Lewis acid metal compounds (suitably, Lewis acid metal compounds, such as AlCl3, FeCl3, ZnCl2, etc.), Lewis acid metal complexes (suitably Lewis acids or complexes having one or more free coordination sites, e.g., in the case of a metal center having fewer than 18 electrons in its valence electron shell), and / or metal compounds or complexes comprising leaving groups or substituted ligands (suitably, the conjugate acid of said leaving group or substituted ligand has a pKa less than or equal to 1, suitably less than or equal to 0, suitably less than or equal to -1, more suitably less than or equal to -5 in water at standard ambient temperature and pressure). Suitable metal cations can include divalent cations (e.g., alkaline earth metals, transition metals (II) or Sn). 2+ cations), trivalents (e.g., Al) 3+ Transition metal (III) or f-block metal (III) cations) or tetravalent (Sn) 4+ Pb 4+ The cations are transition metal (IV) or f-block metal (IV) cations, most preferably divalent cations. Suitable Lewis acid metal compounds may include boron compounds (e.g., boron halides, alkoxides, etc.), silicon compounds (e.g., silanes, siloxanes, silicon halides, etc.), and Lewis acid metal compounds (e.g., AlCl3, FeCl3, ZnCl2, etc.). Suitable Lewis acid metal complexes or complexes including leaving groups or substituted ligands may include carboxylate complexes, such as bimetallic carboxylate complexes (e.g., [M2(O2C-R)4], where M may be Cu). 2+ Ru 2+ ,Rh 2+ Trimetallic carboxylate complexes (e.g., [M2M'O(O2CR)6], where M can be a trivalent metal ion and M' can be a divalent metal ion), and hexametallic carboxylate complexes (e.g., [M'4M2O2(O2CR)6]). 12 ], where M can be a trivalent metal ion and M' can be a divalent metal ion), a dodecyl metal complex (e.g., [Ni 12 (chp) 12[(O2CMe)6(H2O)6], where chp = 6-chloro-2-pyridone ester), metal compounds (e.g. halides such as chlorides, such as AlCl3) with the metal center bonded to the leaving group, and metal complexes with the metal center coordinated to substituted ligands (e.g. halides, water, solvents such as THF, pyridine, or even carboxylate groups).

[0498] When the linker component is a single molecule, ion, or complex comprising two or more coordination moieties, each coordination moiety is capable of donating one or more lone pairs of electrons. Suitably, each of the two or more coordination moieties comprises or is composed of an oxygen, nitrogen, sulfur, or halogen (particularly fluorine or chlorine, especially fluorine) atom. For example, the linker component may be or comprise a group selected from halides (preferably fluorine), amino, cyano, imino, enamino, (1-6C)alkylamino, di-[(1-6C)alkyl]amino, tri-[(1-6C)alkyl]amino, oxy, oxide, hydroxide (OH-), (1-6C) alkoxide, (2-6C) alkenoxy, (2-6C) alkynoxy, formyl, carboxyl, (1-6C) alkoxycarbonyl, (2-6C) acyl, (2-6C) acyloxy One or more, preferably two or more, of the group consisting of alkyl, sulfonyl, sulfide, hydrosulfide, (1-6C) alkylthio, (2-6C) alkynylthio, (2-6C) alkynylthio, thiocarbonyl, heterocyclic group containing at least one internal heteroatom selected from nitrogen, oxygen or sulfur, heteroaryl (e.g., pyridyl) containing at least one internal heteroatom selected from nitrogen, oxygen or sulfur, or (where appropriate) their deprotonated form or salt; wherein any CH, CH2 or CH3 may optionally be substituted. Any of the foregoing groups may be directly linked to each other or indirectly linked via a [nucleus] as defined herein to form a linker component.

[0499] When the linker component is a single molecule, ion, or complex comprising two or more coordination moieties, each coordination moiety is capable of accepting one or more lone pairs of electrons. Suitably, each of the two or more coordination moieties comprises or consists of a Lewis acid metal atom (which may include boron or silicon) or a metal atom attached to a leaving group or a substituted ligand. For example, the linker component may be or comprise a Lewis acid metal atom (which may include boron or silicon) or a metal atom attached to a leaving group or a substituted ligand, or consists of. For example, the linker component may be or include the group selected from metal cations (e.g., divalent metal cations), Lewis acid metal compounds (suitably, Lewis acid metal compounds, such as AlCl3, FeCl3, ZnCl2, etc., or complex derivatives thereof), Lewis acid metal complexes (suitably Lewis acids or complexes having one or more free coordination sites, e.g., in the case of metal centers having fewer than 18 electrons in their valence electron shell), and / or metal compounds or complexes including leaving groups or substituted ligands (suitably, the conjugate acid of said leaving group or substituted ligand has a pKa less than or equal to 1, suitably less than or equal to 0, suitably less than or equal to -1, more suitably less than or equal to -5 in water at standard ambient temperature and pressure). Suitable metal cations may include divalent (e.g., alkaline earth metals, transition metals (II), or Sn). 2+ cations), trivalents (e.g., Al) 3+ Transition metal (III) or f-block metal (III) cations) or tetravalent (Sn) 4+ Pb 4+ The cations are transition metal (IV) or f-block metal (IV) cations, most preferably divalent cations. Suitable Lewis acid metal compounds may include boron compounds (e.g., boron halides, alkoxides, etc.), silicon compounds (e.g., silanes, siloxanes, silicon halides, etc.), and Lewis acid metal compounds (e.g., AlCl3, FeCl3, ZnCl2, etc.). Suitable Lewis acid metal complexes or complexes including leaving groups or substituted ligands may include carboxylate complexes, such as bimetallic carboxylate complexes (e.g., [M2(O2C-R)4], where M may be Cu). 2+ Ru 2+ ,Rh 2+ Trimetallic carboxylate complexes (e.g., [M2M'O(O2CR)6], where M can be a trivalent metal ion and M' can be a divalent metal ion), and hexametallic carboxylate complexes (e.g., [M'4M2O2(O2CR)6]). 12 ], where M can be a trivalent metal ion and M' can be a divalent metal ion), a dodecyl metal complex (e.g., [Ni 12 (chp) 12[(O2CMe)6(H2O)6], where chp = 6-chloro-2-pyridone ester), metal compounds (e.g., halides such as chlorides, e.g., AlCl3) with a metal center bonded to a leaving group, and metal complexes with a metal center coordinated to substituted ligands (e.g., halides, water, solvents such as THF, pyridine, or even carboxylate groups). Any of the aforementioned groups may be directly interconnected or indirectly connected via a [nucleus] as defined herein to form a linker component.

[0500] Suitablely, two or more coordination moieties can coordinate with two different electron-donating or electron-accepting substances or complexes—for example, the coordination moieties are suitably far enough apart to allow each to independently bond to a separate substance or complex. The coordination moieties may be able to coordinate directly with one of the metal centers of a host metal complex and / or another metal complex and / or may be able to coordinate with one of the ligands that binds to the host metal complex and / or another metal complex.

[0501] When the linker component is a molecule, ion, or complex as defined by Formula IV, the [core] may include one or more coordinating groups, but suitably, any coordinating groups present in the [core] are (substantially) unusable for coordination with any substance or complex other than the linker component. In some embodiments, the [core] may be completely absent, and Q and one or more W groups may be directly linked to each other.

[0502] The [nucleus] can be any suitable nucleus that allows the Q group to coordinate with the host metal complex while simultaneously allowing the W group or each W group to coordinate with another host metal complex or with another metal complex.

[0503] The [nucleus] can include a single nuclear group consisting of a Q group and a W group, or each W group linked together. Similarly, the [nucleus] can be a divalent or polyvalent nuclear group (its valence state depends on the value of w). Such a single nuclear group (particularly suitable for linker components with electron-donating capabilities) can be selected from:

[0504] a) A divalent or polyvalent optionally substituted acyclic core group, (e.g., optionally comprising one or more intervening heteroatoms or an optionally substituted (1-nC) alkylene, (1-nC) alkenylene, etc.)

[0505] (1-nC) ynyne group, i.e., heteroatoms or heteroatoms are scattered throughout the carbon chain;

[0506] b) Divalent or polyvalent cyclic or polycyclic nuclei, such as optionally substituted cyclic hydrocarbons (e.g., cycloalkanes), heterocycles (e.g., morpholine), aromatic hydrocarbons (benzene, naphthalene), or heteroaromatic hydrocarbons (pyridine, imidazole, indole);

[0507] c) A divalent or polyvalent core group, comprising at least one cyclic or polycyclic group (e.g., optionally substituted cyclocarbon, heterocycle, aromatic or heteroaromatic) connected to one or more acyclic and / or cyclic or polycyclic moieties;

[0508] d) A divalent or polyvalent macrocyclic nucleus group (which itself may include one or more optional substituted cyclocarbyl, heterocyclic, aryl and / or heteroaryl groups) (e.g. porphyrin or phthalocyanine).

[0509] A single nuclear group may be or include a nuclear metal complex or a complex centered on a nuclear cation. Where the single nuclear group is or includes a nuclear metal complex, suitably, the nuclear metal complex comprises a nuclear ligand and at least one nuclear metal substance (suitably a central metal ion, such as Mg). 2+ Appropriately, nucleoli include those that interact with one or more metal ions, such as a central metal ion (e.g., Mg). 2+ One or more atoms or groups (particularly electron pair donor atoms, such as nitrogen, oxygen, and / or sulfur) are coordinated. For example, macrocyclic mononuclear groups can be or include divalent or polyvalent groups:

[0510] or its salt;

[0511] It may be a divalent or polyvalent complex or its salt, for example:

[0512] Where M x+ It can be any suitable metal cation, especially a divalent metal cation such as Mg. 2+ .

[0513] The linker component may include a single nucleus and may be selected from the group consisting of bridged diimines (e.g., 4,4'-bipyridine, 1,2-dipyridylethylene, 1,4-dipyridyltetraazine) and macrocycles substituted with two or more pyridyl groups (i.e., polypyridyl compounds) (e.g., porphyrins or phthalocyanines).

[0514] When the [nucleus] comprises a single nuclear group as defined above, the linker component suitably comprises Q and W groups having electron-donating coordination moieties, such as those containing one or more heteroatoms (e.g., nitrogen, oxygen, and / or sulfur). However, those skilled in the art will understand that the single nuclear group itself may comprise one or more, suitably two or more coordination moieties (e.g., containing one or more heteroatoms, such as nitrogen, oxygen, and / or sulfur), which may themselves be linked to Q and / or W groups including electron-accepting moieties.

[0515] Suitablely, the Q group and / or W group for each electron-donating pair is selected from any suitable group including internal or external heteroatoms having lone pairs of electrons. Most suitably, the electron-donating group or each electron-donating Q group and / or W group is independently selected from optionally substituted heterocyclic groups, heteroaryl groups, heterocyclic (1-6C)alkyl groups, heteroaryl (1-6C)alkyl groups, or selected from (1-12C)alkyl groups, (1-12C)alkenyl groups, (1-12C)ynyl groups, (3-8C)cycloalkyl groups, (3-8C)cycloalkenyl groups, (1-3C)alkyl(3-8C)cycloalkyl groups, (1-3C)alkyl(3-8C)cycloalkenyl groups, aryl groups, (1-3C)alkylaryl groups, or aryl(1-3C)alkyl groups, which are substituted with one or more basic groups or chelating groups (e.g., amino, alkylamino, dialkylamino, hydroxyl, (1-6C)alkoxy, carbonyl, imino, mercapto, thiocarbonyl, etc.). In one embodiment, the or each electron-donating pair Q group and / or W group is independently selected from pyridinyl, aminophenyl, N-(1-3C)alkylaminophenyl, N,N-bis(1-3C)alkylaminophenyl, most preferably pyridinyl, and most preferably 4-pyridinyl. For example, in a particular embodiment, the linker is:

[0516]

[0517] Appropriately, each pyridyl moiety can coordinate with the host metal complex.

[0518] The [nucleus] may comprise multiple nucleogroups indirectly linked together via one or more Q groups and / or W groups to form the [nucleus]. This [nucleus] is particularly meaningful when one or more of the Q groups and / or W groups are centered on a metal (which in this case includes centered on boron, silicon, and standard metals; for example, to provide Lewis acid / electron-accepting pair coordinating groups). Each such nucleogroup may be independently selected from:

[0519] a) Contains a single coordinating moiety capable of donating two or more lone pairs of electrons (e.g., O). 2- Individual atoms, molecules, ions, or complexes of (oxygen groups);

[0520] b) A single molecule, ion, or complex (e.g., an optional substituted acyclic, cyclic, polycyclic, or macrocyclic molecule containing multiple heteroatoms) comprising two or more coordination motifs (e.g., internal heteroatoms, such as nitrogen, oxygen, or sulfur, or external heteroatoms carried by optional substituents) capable of independently donating lone pairs of electrons, each coordination motif.

[0521] For example, each nucleus group can be independently selected from single atoms, molecules, ions, or complexes comprising oxygen, sulfur, or halogen (especially fluorine or chlorine, especially fluorine) atoms or those thereof; particularly suitable are halogens (preferably fluorine), oxygen groups, oxides, hydroxides (OH-). - (1-6C) alkoxide, (2-6C) alkenyloxy, (2-6C) alkynyloxy, formyl, carboxyl, (1-6C) alkoxycarbonyl, (2-6C) acyl, (2-6C) acyloxy, sulfonyl, sulfide, hydrosulfide, (1-6C) alkylthio, (2-6C) alkenylthio, (2-6C) alkynylthio, thiocarbonyl, heterocyclic group containing at least one internal heteroatom selected from oxygen or sulfur, or (where appropriate) its deprotonated form or a salt thereof; wherein any CH, CH2 or CH3 may optionally be substituted.

[0522] For example, each nucleogroup may be independently selected from a single molecule, ion, or complex comprising two or more coordination moieties, said coordination moieties comprising or consisting of oxygen, nitrogen, sulfur, or halogen (especially fluorine or chlorine, especially fluorine) atoms; more suitably, it may include those selected from halogens (preferably fluorine), amino, cyano, imino, enamine, (1-6C)alkylamino, di-[(1-6C)alkyl]amino, tri-[(1-6C)alkyl]amino, oxygen, oxide, hydroxide (OH) - (1-6C) alkoxide, (2-6C) alkenoxy, (2-6C) alkynoxy, formyl, carboxyl, (1-6C) alkoxycarbonyl, (2-6C) acyl, (2-6C) acyloxy, sulfonyl, sulfide, hydrosulfide, (1-6C) alkylthio, (2-6C) alkenthio, (2-6C) alkynthio, thiocarbonyl, heterocyclic group containing at least one internal heteroatom selected from nitrogen, oxygen or sulfur, heteroaryl group (e.g., pyridyl) containing at least one internal heteroatom selected from nitrogen, oxygen or sulfur, or (where appropriate) its deprotonated form or salt thereof, or the group consisting of or composed of such groups; wherein any CH, CH2 or CH3 may optionally be substituted.

[0523] In one specific implementation, each nuclear group may be independently selected from biLIG as defined herein. 1 Groups, such as biLIG as defined in this paper 2 Groups or as defined herein, optLIG 1 In one specific embodiment, each nuclear group is independently selected from biLIG as defined herein. 1 Groups or biLIG as defined herein 2 The most suitable group is biLIG. 1 Group. Most preferably, each or all of the nuclear groups are carboxyl groups or carboxylic acids, most preferably of the formula -O2CR B1 Defined or derived from formula -O2CR B2(or R) B2 CO2 - The carboxylate group or carboxylic acid defined as R is a carboxyl group or carboxylic acid. B1 and R B2 Appropriately as defined herein, but most appropriately, R B1 It is (1-5C) alkyl, most appropriately R B2 It is pyridyl, aminophenyl, N-(1-3C)alkylaminophenyl, or N,N-bis(1-3C)alkylaminophenyl.

[0524] Appropriately, in cases where the [nucleus] comprises multiple nuclear groups, the nuclear groups are identical.

[0525] For example, a linker comprising multiple nuclear groups can be defined as follows:

[0526]

[0527] Each [nucleus] is a nucleus group as defined herein independently; and W and Q are electron-accepting Q groups and / or W groups as defined herein, and w is as defined herein.

[0528] Suitably, the Q group and / or W group of each electron-accepting pair is a single atom, molecule, ion, or complex containing a coordination moiety capable of accepting one or more, suitably two or more lone pairs of electrons. Suitable associated coordination moieties include or consist of a Lewis acid metal atom (which may include boron or silicon) or a metal atom attached to a leaving group or a substituted ligand. For example, the coordination moieties may be or include a Lewis acid metal atom (which may include boron or silicon) or a metal atom attached to a leaving group or a substituted ligand, or consist of or consist of such a moieties. For example, the linker component may be or include the group selected from metal cations (e.g., divalent metal cations), Lewis acid metal compounds (suitably, Lewis acid metal compounds, such as AlCl3, FeCl3, ZnCl2, etc.), Lewis acid metal complexes (suitably Lewis acids or complexes having one or more free coordination sites, e.g., in the case of metal centers having fewer than 18 electrons in their valence electron shell), and / or metal compounds or complexes including leaving groups or substituted ligands (suitably, the conjugate acid of said leaving group or substituted ligand has a pKa less than or equal to 1, suitably less than or equal to 0, suitably less than or equal to -1, more suitably less than or equal to -5 in water at standard ambient temperature and pressure). Suitable metal cations may include divalent (e.g., alkaline earth metals, transition metals (II), or Sn). 2+ cations), trivalents (e.g., Al) 3+ Transition metal (III) or f-block metal (III) cations) or tetravalent (Sn) 4+ Pb 4+The cations are transition metal (IV) or f-block metal (IV) cations, most preferably divalent cations. Suitable Lewis acid metal compounds may include boron compounds (e.g., boron halides, alkoxides, etc.), silicon compounds (e.g., silanes, siloxanes, silicon halides, etc.), and Lewis acid metal compounds (e.g., AlCl3, FeCl3, ZnCl2, etc.). Suitable Lewis acid metal complexes or complexes including leaving groups or substituted ligands may include carboxylate complexes, such as bimetallic carboxylate complexes (e.g., [M2(O2C-R)4], where M may be Cu). 2 + Ru 2+ ,Rh 2+ Trimetallic carboxylate complexes (e.g., [M2M'O(O2CR)6], where M can be a trivalent metal ion and M' can be a divalent metal ion), and hexametallic carboxylate complexes (e.g., [M'4M2O2(O2CR)6]). 12 ], where M can be a trivalent metal ion and M' can be a divalent metal ion), a dodecyl metal complex (e.g., [Ni 12 (chp) 12 [(O2CMe)6(H2O)6], where chp = 6-chloro-2-pyridone ester), metal compounds (e.g., halides such as chlorides, e.g., AlCl3) with the metal center bonded to the leaving group, and metal complexes with the metal center coordinated to substituted ligands (e.g., halides, water, solvents such as THF, pyridine, or even carboxyl groups). However, in a preferred embodiment, the Q group and / or W group of each electron-accepting pair are independently metal cations, suitably independently divalent or trivalent metal cations as defined herein. Suitably, Q may be different from at least one W group. Suitably, all Q groups and W groups may be the same.

[0529] In a particular implementation, the connector is selected from:

[0530] - Bimetallic carboxylic acid complexes (e.g., [M2(O2C)] R )4], where M = Cu, Ru, Rh).

[0531] - Trimetallic carboxylic acid complexes (e.g., [M2M'O(O2CR)6], where M = trivalent metal ion and M' = divalent metal ion);

[0532] - Hexametallic carboxylic acid complexes (e.g., [M'4M2O2(O2CR)]) 12 ], where M = trivalent metal ion, M' is divalent metal ion;

[0533] -Twelve-metal complexes, such as [Ni 12 (chp) 12[(O2CMe)6(H2O)6], where chp = 6-chloro-2-pyridone ester.

[0534] The linker components can be independently selected from:

[0535] -MonoLIG as defined in this article 1 Group;

[0536] -as defined in this article, biLIG 2 Group;

[0537] -optLIG as defined in this article 1 Group;

[0538] -Metal complexes;

[0539] -Optional macrorings coordinated with metals;

[0540] - Bimetallic carboxylic acid complexes (e.g., [M2(O2C)] R )4], where M=Cu、Ru、Rh);

[0541] - Trimetallic carboxylic acid complexes (e.g., [M2M'O(O2CR)6], where M = trivalent metal ion; M' = divalent metal ion;

[0542] - Hexametallic carboxylic acid complexes (e.g., [M'4M2O2(O2CR)]) 12 ], where M = trivalent metal ion, M' is divalent metal ion;

[0543] - Dodecyl metal complexes, such as [Ni 12 (chp) 12 [(O2CMe)6(H2O)6], where chp = 6-chloro-2-pyridone ester;

[0544] -Terminal ligands, such as H2O, pyridine, or substituted pyridine, where n = 1;

[0545] -Bridged diimine, such as 4,4'-bipyridine, 1,2-dipyridyl ethylene, 1,4-dipyridyl tetrazine;

[0546] - Other polypyridyl ligands, including pyridyl groups substituted around the macrocycle, such as porphyrins or phthalocyanines;

[0547] Linkers may have other solvates or ligands bound to them, or they may be salts.

[0548] Secondary electron generator (SEG)

[0549] The resist composition of the present invention may suitably include a secondary electron generator (SEG). Compared to other components of the resist composition, the SEG suitably has a relatively high Z-value. eff The compound or component can appropriately have a high density (appropriately, a high electron density). Upon exposure to radiation, particularly ultraviolet radiation (eUV or UV), the SEG appropriately promotes the generation of secondary electrons. These secondary electrons are typically scattered "laterally" (appropriately at 80° to the incident beam), thereby extending the "writing" effect, increasing the resist's sensitivity, and thus reducing the "dose" required for the primary radiation. In this way, the secondary electron generator appropriately performs the opposite effect of the antiscattering agent.

[0550] SEG can be a (substantially) separate or independent component within the resist composition (e.g., not attached to any other component within the resist composition, such as an antiscattering component); or SEG can suitably be attached to one or more other components of the resist composition by covalent and / or coordination bonding, for example, coordinateally attached to an antiscattering compound / component (this is particularly suitable when SEG is one or more metal compounds of counterions or ligands that can be replaced by the coordination bonding portion of the antiscattering compound / component).

[0551] Patent publication WO 2015 / 145144 (by the same inventor / applicant) describes a series of suitable secondary electron generators and their principles of use. Any of these SEGs can be incorporated into the resist compositions of the present invention, either as a separate / independent component or attached to one of other components (as described above). WO2015 / 145144 is incorporated herein by reference.

[0552] Secondary electron generators are suitably compounds (and SEG compounds) or groups derived from such compounds (e.g., SEG groups can be bonded to another set of partitioned valences), whose effective atomic number (Z) eff ) greater than or equal to 15 (wherein, optionally, Z) eff The calculation excludes any solvates associated with the compound that have a boiling point less than or equal to 150°C at 100 kPa, and suitably, excludes any solvates that have a boiling point less than or equal to 120°C (suitably ≤105°C at the pressure).

[0553] When SEG is in the form of a SEG group derived from a SEG compound (e.g., a -HgCl or -HgI group covalently bonded to another component, such as an antiscattering compound), Z eff (or any other properties and characteristics relating to SEG compounds as defined herein) may be suitably derived by referring to the Z of the initial compound from which the SEG group is derived. eff(or corresponding properties or characteristics) to define. However, alternatively, given the Z of the SEG group eff (or any other properties and characteristics of SEG compounds as defined herein) can be determined by referring to the Z of the SEG group itself. eff Defined by (or corresponding properties or characteristics) (by excluding the molecules to which it is attached, such as antiscattering compounds).

[0554] Appropriately, the Z eff Greater than or equal to 18, appropriately greater than or equal to 23, appropriately greater than or equal to 25, appropriately greater than or equal to 30, appropriately greater than or equal to 32, appropriately greater than or equal to 40. Appropriately, the Z eff Less than or equal to 70, appropriately less than or equal to 66, appropriately less than or equal to 61, appropriately less than or equal to 60, appropriately less than or equal to 55. The secondary electron generating agent appropriately has a higher Z than the antiscattering component. eff Appropriately higher by at least 10 units, appropriately higher by at least 20 units, appropriately higher by at least 30 units.

[0555] Appropriately, a secondary electron generator is or includes a compound or group with a molecular weight of less than or equal to 500 g / mol.

[0556] Secondary electron generating agents suitably are or include metal compounds (or metal groups, such as -HgCl or -HgI, for example, when valently or covalently bonded to another compound). They cannot be or include elemental metals (i.e., metals (O)). In practice, resist compositions are preferably (substantially) free of any metals (O). Suitably, any metallic substance in the metal compound is a metal ion.

[0557] The compound of the secondary electron generating agent (or the compound deriving the SEG group) suitably has a higher density than the base polymer component. The density of the compound of the secondary electron generating agent suitably is greater than or equal to 1.7 g / cm³. 3 Appropriately greater than or equal to 2 g / cm 3 Appropriately greater than or equal to 2.5 g / cm³ 3 Appropriately greater than or equal to 3g / cm 3 Appropriately greater than or equal to 4 g / cm 3 More appropriately, it is greater than or equal to 4.1 g / cm³. 3 Appropriately greater than or equal to 4.5 g / cm³ 3 A more appropriate value is greater than or equal to 4.7 g / cm³. 3 The most appropriate value is greater than or equal to 5 g / cm³. 3 The density of the secondary electron generating compound is suitably less than or equal to 9 g / cm³. 3Appropriately less than or equal to 8.5 g / cm³ 3 Appropriately less than or equal to 8 g / cm³ 3 In one specific embodiment, the density of the secondary electron generating agent compound is suitably 3.5 g / cm³. 3 and 8.3g / cm 3 Between. Appropriately, the density is at least twice the density of the antiscattering component, and appropriately at least three times.

[0558] Suitablely, any metal compound of a secondary electron generating agent includes a metal having an oxidation state of +1 or higher, suitablely +2 or higher, or suitablely +3 or higher. Suitablely, any metal compound of a secondary electron generating agent includes a metal having an oxidation state of +4 or lower. Suitablely, any metal compound of a secondary electron generating agent includes a metal having an oxidation state of +3.

[0559] Suitably, any metal compound of the secondary electron generating agent comprises a single metallic substance or other predominant metallic substance (i.e., at least 50% by weight, suitably at least 80% by weight, suitably at least 90% by weight, suitably at least 95% by weight of the total metallic substance). The metallic substance or metal ion (whether single or predominant) of such a metal compound of the secondary electron generating agent suitably has an oxidation state of +1 or higher, suitably has an oxidation state of +2 or higher, and suitably has an oxidation state of +3 or higher. The metallic substance or metal ion (whether single or predominant) of such a metal compound of the secondary electron generating agent suitably has an oxidation state of +4 or lower. The metallic substance or metal ion (whether single or predominant) of such a metal compound of the secondary electron generating agent suitably has an oxidation state of +3. In one embodiment, the metallic substance or metal ion of such a metal compound of the secondary electron generating agent has an oxidation state of +2.

[0560] Any metal compound of a secondary electron generating agent suitably includes a metallic substance (or a single or predominant metallic substance) with an atomic number (Z) greater than or equal to 21 (i.e., scandium or heavier). Any metal compound of a secondary electron generating agent suitably includes a metallic substance (or a single or predominant metallic substance) with an atomic number (Z) greater than or equal to 22 (i.e., titanium or heavier). Any metal compound of a secondary electron generating agent suitably includes a metallic substance (or a single or predominant metallic substance) with an atomic number (Z) greater than or equal to 39 (i.e., yttrium or heavier). Any metal compound of a secondary electron generating agent suitably includes a metallic substance (or a single or predominant metallic substance) with an atomic number (Z) greater than or equal to 49 (i.e., indium or heavier). Any metal compound of a secondary electron generating agent suitably includes a metallic substance (or a single or predominant metallic substance) with an atomic number (Z) greater than or equal to 57 (i.e., lanthanum or heavier). Any metallic compound of a secondary electron generating agent suitably comprises only metallic substances (or a single or predominant metallic substance) with an atomic number (Z) less than or equal to 82 (i.e., lead or lighter). Any metallic compound of a secondary electron generating agent suitably comprises only metallic substances (or a single or predominant metallic substance) with an atomic number (Z) less than or equal to 80 (i.e., mercury or lighter). The metallic substance of the metallic compound may suitably be d-block, p-block, or f-block metallic substances, or mixtures thereof. Suitably, the metallic compound is non-radioactive.

[0561] Suitably, the secondary electron generating agent is or includes a metal halide or its complex (e.g., HAuCl4). Suitably, the secondary electron generating agent is a metal (I), metal (II), metal (III), or metal (IV) halide or its complex. Suitably, the secondary electron generating agent is a metal (III) halide or a metal (I) halide, or its complex. Suitably, the secondary electron generating agent is a metal chloride, preferably a metal (I), metal (II), metal (III), or metal (IV) chloride. Suitably, the secondary electron generating agent is a metal chloride, preferably a metal (I) or metal (III) chloride.

[0562] The secondary electron generator can be a metal (II) halide (e.g., HgCl2) or its complex (e.g., -HgCl when valence-coordinated with an antiscattering component). In a particular embodiment, the secondary electron generator is a metal (II) chloride.

[0563] The secondary electron generating agent may suitably be selected from the group consisting of AlCl3, TiCl3, TiCl4, CrCl3, GaCl3, YCl3, MoCl3, AgCl, InCl3, SbCl3, HfCl3, TaCl3, WCl3, OsCl3, IrCl3, AuCl, AuCl3, HAuCl4, HgCl2, CeCl3, NdCl3, ErCl3, OsO4, or any suitable complex (including any suitable salt or salt complex). In one embodiment, the metal compound is chloroauric acid (hydrochloroauric acid, HAuCl4) or its hydrate (HAuCl4.4H2O). In another embodiment, the metal compound is sodium chloroaurate (NaAuCl4) or its hydrate (e.g., NaAuCl4.2H2O). In one embodiment, the metal compound is a mercury(II) halide. In one embodiment, the metal compound is mercuric dichloride. In one embodiment, the metal compound is mercuric diiodide.

[0564] The secondary electron generator is suitably non-particulate, particularly within the resist composition (where it is suitably dissolved in a solvent). The secondary electron generator is preferably dissolved in the resist composition. This allows for uniform distribution within the final resist coating and can facilitate the formation of a metal-organic nanocomposite coating.

[0565] In the context of this invention, appropriate incorporation of SEG can enhance the sensitivity of resists exposed to radiation without (substantially) adversely affecting the resolution of the beneficial properties imparted by the antiscattering compound / component. This can be achieved by not using excessive amounts of secondary electron generators. Alternatively or additionally, this can be achieved by appropriately attaching a secondary electron generator to another component of the resist composition prior to the formation of the final resist composition. In such embodiments, the secondary electron generator can be in the form of an SEG group, preferably an SEG group attached to another resist component (e.g., an antiscattering compound).

[0566] In one specific embodiment, a secondary electron generator is attached to an antiscattering compound—suitably, one or more secondary electron generators may be attached to one or more antiscattering compounds. In this embodiment, one or more secondary electron generators are suitably covalently or coordinately bonded to one or more antiscattering compounds via one or more ligands that are bound to the antiscattering compound. Suitably, the “original” antiscattering compound (i.e., without any attached SEG groups) reacts with or otherwise mixes with the secondary electron generator compound to bind the antiscattering compound to or to the secondary electron generator. The resulting secondary electron generator may therefore be an SEG group derived from the original SEG compound. This reaction may involve replacing one or more groups, counterions, or ligands of the initial secondary electron generator compound with coordinating or bonding groups within the antiscattering compound. Alternatively, the secondary electron generator compound may remain intact and form a coordinate bond with the antiscattering compound without any substitution—for example, the secondary electron compound may be used as a Lewis acid.

[0567] For example, an antiscattering compound (or its precursor) suitably comprises a multi-metal cage-based antiscattering compound (e.g., amines, imines, pyridines, etc., such as nicotinic acid) containing one or more ligands with free lone pairs of electrons, which can react with a secondary electron generating compound, such as mercuric(II) dihalide, to produce an antiscattering SEG complex comprising an antiscattering compound covalently or coordinately bonded to a secondary electron generating group (e.g., the corresponding mercuric(II) monohalide group (-HgX)) derived therefrom from the secondary electron generating compound.

[0568] In one specific embodiment, the antiscattering compound is a multimetal cage, suitably as defined herein, comprising one or more ligands with one or more lone pairs of electrons (suitably nitrogen centers with lone pairs, such as amines, imines, pyridines, amides, etc.), and a secondary electron-generating group (suitably derived from a Lewis acid or a compound comprising a substitutable counterion, ligand, or group) is covalently bonded to the antiscattering compound via the lone pairs of electrons. In an alternative embodiment, the secondary electron-generating group may be attached to the antiscattering compound in the opposite manner, for example, wherein the secondary electron-generating compound comprises one or more ligands with one or more lone pairs of electrons forming covalent bonds with the metal center of the antiscattering compound.

[0569] In one specific embodiment, the antiscattering compound is a multimetal cage comprising one or more nicotinic acid ligands per molecule, and one or more mercury(II) halide secondary electron groups (suitably mercuric monohalides) are covalently bonded to the pyridyl moiety of the nicotinic acid ligand.

[0570] Chemically bonding secondary electron generators to antiscattering compounds (e.g., via covalent or coordinate bonds) is particularly advantageous because it introduces a high-electron-density dispersion (and appropriately regular and well-defined) region that enhances local scattering to increase resist sensitivity without compromising the advantages of resist compositions with typically low density that promote high-resolution lithography.

[0571] Photosensitive components

[0572] The resist composition / coating may include a photosensitive component, such as a photoinitiator, photoacid generator, or photosensitizer, which is suitably a component that promotes the transformation reactivity of the resist component in the resist composition.

[0573] In some embodiments, the resist component may be or otherwise comprise or include a photosensitive component. For example, some resist components (e.g., those capable of photolysis without the assistance of additional photoinitiators, photocatalysts, etc.) may be inherently photolytically reactive (but this may depend on the relevant incident wavelength of the radiation source). Thus, the resist composition may suitably (substantially) be free of photoacid generators or photoinitiators.

[0574] However, the photosensitive component can be either a photoinitiator or a photoelectron generator. Such a photoinitiator can be a compound that converts absorbed UV or visible light energy into chemical energy in the form of an initiating substance (i.e., a free radical or a cation). Based on the mechanism of forming initiating free radicals, photoinitiators are generally classified into two categories:

[0575] Type I photoinitiators: They generate free radicals upon irradiation by breaking single molecular bonds;

[0576] Type II photoinitiators: They undergo a bimolecular reaction in which the excited state of the photoinitiator interacts with a second molecule (co-initiator) to generate free radicals.

[0577] Suitable photosensitive components in the resist compositions / coatings of the present invention may include: acetophenone; anthraquinone; sodium anthraquinone-2-sulfonate monohydrate; benzoyl; benzoin; benzoin ethyl ether; benzoin isobutyl ether; benzoin methyl ether; benzophenone; benzophenone / 1-hydroxycyclohexylphenyl ketone; benzophenone tetracarboxylic dianhydride; 4-benzoylbiphenyl; camphorquinone; 2-chlorothiazolium; (isopropylbenzene)cyclopentadienyl iron(II) hexafluorophosphate; 2,2-diethoxyacetophenone; 2 2-Dimethoxy-2-phenylacetophenone; 4-(dimethylamino)benzophenone; 2,5-dimethylbenzophenone; 4-ethoxyacetophenone; ferrocene; 4-hydroxyacetophenone; 3-hydroxyacetophenone; 2-methylbenzophenone; 3-methylbenzophenone; methylbenzoylcarbamate; 2-methyl-4'-(methylthio)-2-morpholinoacetophenone; phenanthrenequinone; 4'-phenoxyacetophenone; thioxanthone-9-one; triarylsulfonium hexafluoroantimonate; triarylsulfonium hexafluorophosphate.

[0578] In one specific embodiment, the photosensitive component is selected from the group consisting of 2,2-diethoxyacetophenone and tris(4-tert-butylphenyl)trifluorosulfonate sulfonate.

[0579] The decision to use a photosensitive component within the resist composition of this invention can depend on many factors, such as the incident wavelength, the required sensitivity, the required resolution, and the inherent photolytic reactivity of the relevant resist composition.

[0580] In certain embodiments, the resist composition is (substantially) free of any additional photosensitive component (although any inherent photosensitive properties of the resist component are suitably desired), or the resist composition includes more than 1 part by weight of additional photosensitive component per 100 parts by weight (pbw) of the total weight of the antiscattering component and the resist component, suitably includes no more than 1 part by weight of additional photosensitive component per 500 parts by weight of the total weight of the antiscattering component and the resist component, and suitably includes no more than 1 part by weight of additional photosensitive component per 1000 parts by weight of the total weight of the antiscattering component and the resist component.

[0581] Corrosion resist crosslinking agent

[0582] The resist composition may suitably further include a resist crosslinking agent, which is suitably a crosslinking component that reacts with the resist components (e.g., during exposure or post-exposure treatment) to promote crosslinking between resist components or between a resist component and another component. It is understood that a resist component is capable of reacting with another resist component, and this reaction may be indirect and may involve the intervention of the resist crosslinking agent. Suitable crosslinking agents are known in the art.

[0583] When properly applied, crosslinking agents can facilitate the formation of resists that are insoluble in developer after exposure to radiation.

[0584] Any crosslinking agent may be used appropriately, but most advantageously, a rational crosslinking agent should be selected for maximum compatibility with the radiation source and the resist composition and its components.

[0585] In some embodiments, the crosslinking agent is dipentaerythritol pentaacrylate (DPEPA) or pentaerythritol tetraacrylate (PET), or any other suitable miscible polyfunctional acrylate and / or mixtures thereof. Other crosslinking agents include epoxy resins (SU8), or if the copolymer used is, for example, polyhydroxystyrene, a suitable photoacid-generating agent may be used to induce a change in solubility.

[0586] Plasmon components

[0587] The resist composition / coating may include a plasmon component. The plasmon component is suitably a component or material that generates a surface plasmon resonance (SPR) effect on the surface to which the resist composition of the present invention is coated. These plasmon resonance effects can be beneficial for high-resolution lithography because surface plasmons can have very low wavelengths and the ability to confine incident radiation to extremely small sizes, as reported in the literature (e.g., Lewis S et al., “Highdensity self-assembled nanoparticle film with temperature-controllable interparticle spacing for deep sub-wavelength nanolithography using localized surface Plasmon modes on planar silver nanoparticle tunable grating”, Microelectronic Engineering 85(2008)486-491).

[0588] Surface plasmon resonance is a well-known phenomenon in the art, involving the resonant oscillation of conduction band electrons at the interface between materials with different dielectric constants (typically negative and positive dielectric constant materials) stimulated by radiation (e.g., UV or light). Resonance is induced by the restoring force oscillation of photons with frequencies matching the intrinsic frequencies of the surface electrons relative to the positive atomic nuclei.

[0589] Thus, the plasmon component is the component that causes the aforementioned SPR effect. Suitablely, the plasmon component is particulate, preferably nanoparticle-based. Thus, the resist composition can be a colloidal dispersion or suspension of this plasmon component. Therefore, the resulting coating suitably comprises a thin layer (i.e., a nanoparticle film) of the nanoparticle plasmon component.

[0590] In some embodiments, the resist composition itself may not include the plasmonic component, but the plasmonic component may be separately coated on the relevant substrate surface (as part of a separate plasmonic coating composition), preferably on its pre-resist coated surface. If desired, multiple plasmonic coatings can be applied to further improve lithographic resolution.

[0591] Any suitable plasmon component can be used. Most suitable, plasmon components include metallic nanoparticles, such as silver or gold nanoparticles.

[0592] Specific implementation methods

[0593] In one embodiment, the resist composition comprises an antiscattering compound covalently or coordinately bonded to a secondary electron generator, wherein the antiscattering compound is suitably a multimetallic cage bonded to one or more ligands with lone pairs of electrons that form coordinate bonds with the secondary electron generator, wherein the secondary electron generator is a metal compound, a metal-containing group or fragment, or has a Z-value greater than or equal to 25. eff Metallic substances.

[0594] In one specific embodiment, the resist composition includes a hybrid compound (or complex) that generates anti-scattering secondary electrons (AS-SEG hybrid), wherein the AS-SEG comprises:

[0595] -Comprising one or more metallic substances (suitably at least two metallic substances, most preferably chromium and nickel) and a set of binding ligands in a multimetallic cage, wherein at least one of the ligands comprises a valence soliton pair electron, and at least one of the ligands comprises a π-system or π-bond capable of forming crosslinks with an adjacent multimetallic cage;

[0596] - A secondary electron-generating group of a multimetal cage, which is attached to the multimetal cage by a lone pair of valence electrons carried by one of the ligands of the multimetal cage, the secondary electron-generating group comprising a metal-centered compound or group (suitably a metal different from any metal in the multimetal cage and suitably having a higher atomic number), which is suitably a metal halide.

[0597] Photolithography using the resist composition of the present invention

[0598] This invention provides a method for performing photolithography, the method comprising:

[0599] i) Provide a substrate coated with resist as defined herein or apply a resist coating to the substrate;

[0600] ii) Exposing the resist coating partially to radiation to provide exposure to the resist coating;

[0601] iii) Develop the exposed resist coating to produce a resist pattern layer, the resist pattern layer comprising: a portion of the resist coating that is insoluble in the developer (i.e., ridges); and an array of grooves extending through the resist pattern layer;

[0602] iv) Optionally modify the substrate, substrate surface, or portion thereof under the photoresist pattern layer;

[0603] v) Optionally, the resist pattern layer is removed to provide a modified substrate;

[0604] vi) Optionally repeat step iv) and / or steps i)-v) on the modified substrate (optionally replacing the resist coating with an alternative resist coating, such as a standard photoresist; and optionally using alternative radiation during exposure);

[0605] The method may optionally be performed before steps (i) to (vi) using a resist coating or an alternative resist coating (i) (i) prior to steps (i) to (vi) and may optionally be repeated once or multiple times; and electromagnetic radiation or alternative radiation may be used during the exposure process.

[0606] The resist coating comprises a resist composition that is optionally dried and / or cured as defined herein.

[0607] Suitablely, the method involves at least one photolithography cycle, appropriately using the resist coating of the present invention. Suitablely, this photolithography can be achieved using a photomask, whether a photomask produced by the method of the present invention or a standard photomask.

[0608] The method may optionally be performed before steps (i) to (vi) using a resist coating or an alternative resist coating (i) (i) prior to steps (i) to (vi)), may optionally be repeated once or multiple times, and electromagnetic radiation or alternative radiation may be used during exposure.

[0609] The resist coating suitably comprises, or optionally dries and / or cures, a resist composition as defined herein, which is primarily composed thereof. However, the resist coating may include one or more coatings, at least one of which is the resist coating of the present invention. In one embodiment, the resist coating may include one or more additional coatings (e.g., a plasmonic coating).

[0610] The present invention further provides an imaging substrate that can be obtained by the method, or obtained directly therefrom.

[0611] This method can be used for imaging, for fabricating patterned substrates, for selectively modifying the surface of substrates, and for manufacturing multilayer substrates (e.g., integrated circuits), as appropriately defined herein.

[0612] In certain embodiments, the above-described methods are used to manufacture integrated circuits (which are examples of multilayer substrates) or multiple integrated circuits (e.g., on a wafer). Those skilled in the art are well aware of the standard manufacturing processes used in integrated circuit manufacturing. The methods of the present invention can be used to manufacture one or more layers of an integrated circuit, and in some embodiments, can be used to manufacture all layers. However, since high resolution may be required only for one or some resolution-critical layers (e.g., if resolution is not important for each layer), alternative lithography methods (e.g., standard lithography) may be involved in the manufacturing of other layers. In this way, the lithography methods of the present invention can complement other forms of lithography (e.g., existing lithography techniques) in integrated circuit manufacturing.

[0613] substrate

[0614] The substrate on which photolithography is performed can be any suitable substrate.

[0615] The substrate is suitably a single solid or a portion thereof. The substrate is suitably in the form of a (basically rigid) plate, wafer, or sheet, most suitably in the form of a wafer.

[0616] Since certain processing steps (including those involving the "substrate") can be "repeated" according to the method of the invention, the term "substrate" can refer to an initial "input substrate" (i.e., prior to any method step of the invention) or a "modified substrate" (after certain method steps). Thus, in principle, the "substrate" can be any substrate suitable for photolithography (including partially manufactured products or integrated circuits).

[0617] The substrate (whether an input substrate or a modified substrate) is suitable as part of a pre-formed resist-coated substrate or as the substrate for which resist coating is applied in the methods disclosed herein (e.g., in step i). Thus, the substrate (regardless of its properties, parameters, material form, etc.) can be defined without reference to the resist coating itself. The substrate or modified substrate may be planarized before the resist coating is applied.

[0618] In some embodiments, the substrate (or a portion thereof) to which the method of the present invention is applied is integrated into a final (printed) product (e.g., an integrated circuit), but it may itself be integrated into a product (e.g., a circuit board and / or electronic device). In other words, the "imaging substrate" may be or can be a consumer product, or may otherwise be integrated into a consumer product. Such consumer products include integrated circuits, integrated circuit dies or wafers, integrated circuit packages, circuit boards, or electronic devices or systems.

[0619] However, in some embodiments, the substrate (or a portion thereof) to which the method of the present invention is applied is not integrated into the final (printed) product (e.g., an integrated circuit) but rather integrated into a tool used to manufacture such a final (printed) product, for example, a photomask (whether positive or negative) used in photolithography. In other words, the “imaging substrate” can be a tool used to manufacture consumer products. Thus, the advantages of the present invention (e.g., high resolution) can be imparted to the photolithography tool (e.g., a photomask with high-resolution detail), which can then be imparted to the final (printed) product made using said tool. Thus, ultra-high resolution photolithography (according to the present invention) can be used to manufacture a corresponding ultra-high resolution photomask (e.g., a photomask), which can then be used in ultra-high resolution photolithography, for example, to manufacture ultra-high resolution integrated circuits (or one or more ultra-high resolution layers thereof). Thus, the present invention provides a method for manufacturing a photomask and a photomask (e.g., a photomask) as defined herein; and the use of such a photomask in the manufacture of integrated circuits, integrated circuit dies or wafers, integrated circuit packages, circuit boards, or electronic devices or systems.

[0620] The substrate appropriately includes or is mainly composed of a substrate substrate.

[0621] The substrate material may comprise or consist primarily of any suitable material used in the methods of the present invention. The substrate material (and suitably as a whole substrate base layer) is suitably a single substance (element or compound) or a single composite material (a mixture of two or more elements and / or compounds). However, the substrate material may be a multilayer composite material.

[0622] When a substrate (or a portion thereof) is integrated into a tool (e.g., a photomask) rather than into a final (printed) product (e.g., an integrated circuit), the substrate substrate is suitably a material suitable for said tool. Suitably, the substrate substrate is a photomask (which may comprise one or more layers of one or more materials). When the tool is a photomask (e.g., a photomask), depending on the nature of the final mask, the substrate substrate can be (substantially) transparent or (substantially) opaque to relevant radiation (e.g., UV or visible light if it is a photomask). For example, in the case where a photomask is formed by creating opaque regions on the substrate substrate during mask manufacturing, a substrate substrate that is (substantially) transparent to relevant radiation can be used (e.g., an unremoved resist coating can provide opaque regions, or opaque regions can be generated by reasonable surface modification). Alternatively, in the case where a photomask is formed by creating transparent regions on the substrate substrate during mask manufacturing, a substrate substrate that is (substantially) opaque or opaque to relevant radiation can be used (e.g., where the process involves surface modification, for example, removing portions of the substrate substrate by etching). In other embodiments, the substrate material may be a laminated composite material comprising at least one layer of material (e.g., glass, transparent plastic) that is (substantially) transparent to relevant radiation and at least one layer of material that is opaque to relevant radiation—in which case the process of fabricating the photomask may involve removing areas of the opaque material to leave the transparent portion.

[0623] A photolithographic mask, such as a photomask, may comprise a transparent molten silicon layer covered by a pattern defined by a chromium metal absorbing film, the pattern having been generated according to the method of the invention, thereby providing a high-resolution pattern. Such a mask can then be used in the photolithography method of the invention to fabricate high-resolution products, such as integrated circuits.

[0624] When a substrate (or a portion thereof) is integrated into a final (printed) product, the substrate substrate is suitably a material suitable for said product. In a particular embodiment, the bottom substrate is an electronic component substrate. Suitable electronic component substrates may include substrates comprising or made of silicon (e.g., a silicon wafer), copper, chromium, iron, aluminum, or glass. The bottom substrate itself may include a surface coating, such as an undercoat as a resist coating to be applied thereto. In a particular embodiment, the bottom substrate is a silicon substrate. The substrate substrate may include or consist primarily of a semiconductor material (most suitably silicon, most suitably a monolithic single-crystal silicon crystal). Most suitably, the substrate base layer is a silicon wafer. Suitablely, when the resist coating and composition of the present invention are used in the manufacture of integrated circuits, the input substrate can be a partially manufactured integrated circuit, wherein some layers of the integrated circuit have already been formed (optionally with or without the resist coating or composition of the present invention – other layers can be formed using conventional IC manufacturing techniques (e.g., standard photolithography). Furthermore, after the resist coating of the present invention has been used (and suitably removed) in a portion of the manufacture of the integrated circuit, other layers of the integrated circuit can be formed (optionally with or without the resist coating or composition of the present invention – other layers can be formed using conventional IC manufacturing techniques such as standard photolithography).

[0625] The substrate may consist primarily of a substrate substrate (e.g., wherein the input substrate has not yet been modified, for example, by surface oxidation, photolithography and / or other substrate modification steps).

[0626] Alternatively, the substrate (which may include an input substrate) suitably includes a modified substrate base material (e.g., a modified substrate) (suitably composed primarily of the substrate base material). Such a modified substrate may include a substrate base material that has been modified by a pretreatment or pre-coating step (e.g., surface thermal oxidation, for example, to produce a silicon oxide insulating layer before applying a resist coating) prior to carrying out the methods of the invention; modified in other ways prior to carrying out the methods of the invention (e.g., using alternative techniques such as photolithography to partially form an integrated circuit); or modified after the substrate has been carried out by the methods of the invention (or some steps thereof). Each additional substrate layer suitably includes or is composed primarily of an additional substrate material, which may be the same as or different from the substrate base material. In certain embodiments, one or more additional substrate layers may include or be composed primarily of the substrate base material, although not necessarily part of the substrate base layer.

[0627] Appropriately, the substrate base is arranged toward the bottom of the substrate (or at the bottom of the substrate) relative to the exposed surface of its substrate (i.e. the surface on which its resist coating will be exposed to radiation - which can be considered the top of the substrate, regardless of the final orientation of the substrate coated with resist during processing).

[0628] Suitably, the method of the present invention includes: forming additional layers (including partial layers) on a substrate base layer and optionally subsequently on each other; integrating the additional layers within the substrate base layer or any other substrate layer (e.g., by doping); and / or removing portions of the substrate base layer and / or portions of additional substrate layers (e.g., by etching). Suitably, the method of the present invention produces a multilayer substrate comprising a substrate substrate facing down (or at its bottom). The substrate base layer suitably serves as the basis for constructing other layers.

[0629] In a preferred embodiment, the input substrate comprises a substrate base layer located beneath an oxide (preferably thermally oxidized) substrate substrate. In a particular embodiment, the input substrate comprises a silicon (suitably monocrystalline silicon) wafer located beneath a silicon oxide (or silicon dioxide) layer.

[0630] As those skilled in the art will understand, when using a photomask (e.g., a photomask, which is a standard photomask or a photomask formed by the method of the present invention) for subsequent photolithography (e.g., to form alternative imaging substrates, multilayer substrates, integrated circuits, etc.), the same substrate substrate (e.g., a silicon wafer) can be used. Furthermore, the same photolithography methods defined herein can be used, but alternative resist coatings, photolithography methods (e.g., exposure and development methods) can be used with the photomask, except for (e.g., in repetitive steps) the resist coating and the specific method steps of the present invention.

[0631] While the methods of this invention are particularly suitable for manufacturing silicon-based integrated circuits and their derivatives, the invention will also be applicable to future materials used in the construction of electronic components—such as graphene-based materials.

[0632] Materials coated with resist and their formation

[0633] This invention provides a material coated with a resist and a method for forming such a material, as defined herein. A material coated with a resist or a substrate is a “substrate” as defined herein, having a resist coating on its surface (or a portion thereof).

[0634] Materials coated with resist suitably include: coating an input substrate with a resist composition as defined herein, and optionally subsequently curing and / or drying the coating to form a coating of the resist composition on the substrate.

[0635] Coating an input substrate can be performed using many methods well known to those skilled in the art, which suitably includes applying a resist composition to the surface of the input substrate. Applying a resist coating to a substrate (a single body of a substrate substrate, multilayer substrate, input substrate, or modified substrate) suitably includes applying a resist composition (suitably as defined herein, but alternative resist compositions outside the scope of the invention may also be used, provided that the resist composition of the invention is used at least once in the method of the invention) to its surface (or a portion of the surface), and optionally subsequently curing and / or drying the applied resist composition to form a resist coating. The resist composition can be applied in any suitable manner, but is most suitably applied by dip coating, spraying, brushing, rolling, and / or spin coating. Most preferably, the resist composition is applied to the substrate by spin coating, which is particularly suitable during integrated circuit manufacturing. In one specific embodiment, the resist composition is applied to a bottom substrate or input substrate by spin coating (e.g., using a spin coater) to form a spin-coated input substrate. Ideally, the applied resist composition is cured and / or dried (appropriately by baking). The resist coating appropriately has a (substantially) uniform thickness. Those skilled in the art are familiar with how to apply the resist coating to the substrate prior to photolithography.

[0636] When the substrate is said to include or be coated with a coating such as a resist, the coating appropriately covers the surface of the substrate (or a portion thereof).

[0637] After the resist composition is applied to the bottom substrate or input substrate, the coating is preferably cured and / or dried. Suitably, the coating is dried at a certain temperature and pressure for a period of time to form a resist film on the bottom substrate or input substrate. The temperature (and pressure, especially when using reduced pressure) can be selected to be compatible with a particular solvent of the resist composition (e.g., for evaporating the solvent). In one specific embodiment, the coating (or the coated bottom substrate or the coated input substrate) is baked for 30 seconds to 5 seconds (suitably between 90 seconds and 150 seconds, suitably around 120 seconds) at atmospheric pressure (about 1 bar) and a temperature between 60°C and 200°C (more suitably between 80°C and 180°C). Suitably, this curing / drying can remove some, most, or all of the solvent present in the resist composition. In the case of anti-scattering compounds combined with solvates, some, most, or all of the solvates are suitably removed by said curing and / or drying.

[0638] The average thickness of the coating is suitably 10-500 nm, preferably 50-200 nm. The maximum thickness of the coating is suitably 1000 nm, preferably 500 nm. The minimum thickness of the coating is suitably 5 nm, preferably 20 nm. The technique of this invention allows for efficient, high-quality patterning of very thin resist coatings.

[0639] The resist coating of the present invention provides good adhesion to the bottom substrate and input substrate (especially those substrates suitable for electronic components).

[0640] Exposure and radiation

[0641] Expose the resist coating partially to radiation to provide exposure to the resist coating.

[0642] Exposing a portion of a coating containing a resist material to radiation appropriately includes selectively exposing that portion while selectively withholding exposure from other portions. Thus, the method appropriately excludes the exposure of the entire coating to radiation.

[0643] Selective exposure of a coating portion may include direct irradiation of the relevant portion with a focused or targeted beam (e.g., an electron beam or laser beam, such as a UV-laser beam) or exposure of the entire coating area (i.e., unfocused / unoriented) through a mask (e.g., a photomask, preferably when a photoresist is used), the mask comprising predetermined holes corresponding to the locations of the exposed portions of the coating. Specific exposure techniques may be used depending on the specific radiation employed.

[0644] Appropriately, the exposed portion of the coating undergoes a transformation (appropriate chemical transformation) to change its solubility properties (appropriately for a predetermined developing medium, such as one of the developing media described herein), appropriately before or after optional post-exposure baking, appropriately even before any such post-exposure baking.

[0645] Appropriately, the portions of the coating "exposed to radiation" have different solubility properties than the portions "not exposed to radiation". This difference in solubility is suitable for developing and selectively removing the "radiation-exposed" or "not exposed to radiation" portions of the coating (depending on whether the resist is positive or negative).

[0646] Exposure of the coating can directly produce a developable substrate (i.e., a substrate that undergoes development to produce a patterned substrate). However, additional post-processing steps can be employed. Suitablely, the coating can be post-exposure baked after exposure to radiation. Post-exposure baking can include baking at a certain temperature and pressure for a period of time suitable for forming a developable substrate. The temperature (and pressure, especially when using reduced pressure) can be selected to be compatible with a particular solvent of the resist composition (e.g., for evaporating the solvent). In one specific embodiment, the exposed coating (or exposed coated substrate or exposed coated input substrate) is baked at atmospheric pressure (about 1 bar) and at a temperature between 60°C and 200°C (more suitably between 80°C and 180°C) for 30 seconds and 5 minutes (suitably between 90 seconds and 150 seconds, suitably about 120 seconds).

[0647] Any radiation suitable for the resist composition can be used. The resist composition is suitably formulated for exposure to a specific radiation, thus the radiation can be selected based on the resist composition. Suitably, the radiation is electromagnetic radiation (especially ultraviolet light) or an electron beam. Preferably, the radiation is electromagnetic radiation.

[0648] Appropriately, electromagnetic radiation includes radiation with wavelengths between 10 nm and 1000 nm, appropriately between 50 nm and 700 nm, appropriately between 100 nm and 400 nm, appropriately between 150 nm and 300 nm, and appropriately between 170 nm and 280 nm. Most appropriately, electromagnetic radiation is ultraviolet radiation. Electromagnetic radiation may appropriately include radiation with wavelengths between 10 nm and 30 nm, appropriately between 11 nm and 20 nm, and appropriately between 12 nm and 15 nm.

[0649] Properly, where the alleged “radiation” has a specified wavelength or a specified wavelength range, the specified wavelength or wavelength range constitutes at least 20%, at least 50%, at least 80%, or substantially all of the total intensity of the “radiation”.

[0650] Developing resist coating and developing medium

[0651] This invention provides a patterned substrate and a method for preparing the same (e.g., a material coated with resist after development and exposure), as defined herein. Suitably, "development" forms grooves within the resist coating, thereby forming a patterned layer.

[0652] The photoresist coating step after development and exposure produces a photoresist pattern layer, which includes portions of the photoresist coating that are insoluble in the developer coating (i.e., ridges) and an array of grooves extending through the photoresist pattern layer. In some embodiments, the surface of the substrate beneath the photoresist pattern layer is exposed in / through the grooves, but is suitably masked by the ridges.

[0653] The exposed resist-coated material is suitably developed using a developing medium. Thus, the exposed resist-coated material, or at least its exposed coating, is suitably brought into contact with (e.g., washed and / or immersed in) a developing medium (suitably a liquid) to sufficiently remove (suitably by dissolving) the exposed portions (for positive resists) or unexposed portions (for negative resists) of the resist composition coating. Most suitably, the developing medium suitably removes the unexposed portions.

[0654] As described above, exposure of a resist-coated material typically results in different solubilities between the exposed and unexposed portions of the coating (appropriately related to the intended developing medium). This difference in solubility between the exposed and unexposed portions of the coating facilitates subsequent development of the resist-coated material after exposure. Thus, the exposed or unexposed portions of the coating can be selectively removed (preferably dissolved or otherwise eliminated) to transform the coating into a patterned layer comprising an array of grooves extending through the patterned layer (i.e., through the initial coating). The grooves of the patterned layer then correspond to the portions of the coating that have been removed, while the ridges / protrusions (i.e., non-grooves) of the patterned layer correspond to the retained portions of the coating. The patterned layer (appropriately, its non-grooves portions) therefore appropriately includes ridges or protrusions (i.e., between the grooves) of the exposed portions (for positive resists) or unexposed portions (for negative resists) of the resist composition coating.

[0655] For example, specific development conditions can be adjusted to optimize the quality of the resulting patterned substrate, or the development process can be optimized (whether for cost, speed, or final product quality). For example, development time (e.g., immersion time of the exposed coating) can be optimized to maximize the removal of portions of the coating intended to be removed and minimize the removal or damage to portions of the coating intended to be retained. Similarly, the developing medium can be adjusted to optimize either or both of the development process and the resulting product.

[0656] Appropriately, after development, the method for preparing a patterned substrate includes rinsing the patterned layer with a rinsing medium that appropriately includes an organic solvent.

[0657] Appropriately, after development and optionally after enhancement, the method further includes drying (or baking) the patterned substrate.

[0658] The developing medium itself can be any suitable developing medium known in the art. Suitablely, the developing medium is complementary to the resist composition (or its coating). Most suitably, the developing medium complements the solubility properties of the resist composition and its corresponding exposed portions, appropriately to optimize the contrast (i.e., different solubilities and / or dissolution rates) between the exposed and unexposed portions of the resist coating.

[0659] When the resist composition (or coating thereof) is a negative resist, the developing medium suitably includes a solvent in which the antiscattering component and / or resist component is (substantially) soluble, or at least more soluble than the corresponding exposed portions of the antiscattering compound and / or resist component. When the resist composition (or coating thereof) is a positive resist, the developing medium suitably includes a solvent in which the antiscattering compound and / or resist component is (substantially) insoluble, or at least less soluble than the corresponding exposed portions of the antiscattering compound and / or resist component.

[0660] The developing medium may or may not dissolve all components of the exposed or unexposed (depending on the positive or negative resist) resist composition (or its coating) intended to be removed by developing, but any insoluble (or less soluble) component may still be removed from the slurry, suspension, or dispersion after the corresponding portion of the resist component has been dissolved (or partially dissolved) or after the resist component has been mixed with the insoluble component during exposure.

[0661] The developing medium for the resist coating of the present invention suitably comprises or consists of an organic solvent (suitably a nonpolar organic solvent, suitably an organic compound). The organic solvent is suitably selected from one or more hydrocarbon solvents, and suitably from one or more (4-12) hydrocarbon solvents. For example, the organic solvent may be selected from one or more of pentane, hexane, octane, decane, 2,2,4-trimethylpentane, 2,2,3-trimethylpentane, perfluorohexane, and perfluoropentane, as well as aromatic hydrocarbon solvents such as toluene, ethylmethylpropylbenzene, dimethylbenzene, ethyldimethylbenzene, and dipropylbenzene. In one specific embodiment, the developing medium for the resist coating of the present invention is hexane. In one specific embodiment, the developing medium for the resist coating of the present invention is MTBE.

[0662] The patterned layer can be considered to include an array of grooves (i.e., grooved patterns) extending through the patterned layer and an array of ridges / protrusions (i.e., non-grooved portions of the patterned layer). The ridges appropriately correspond to coating portions that are insoluble in the developer, while the grooves appropriately correspond to coating portions that are soluble in the developer (i.e., removed during development).

[0663] The aspect ratio (i.e., width / height ratio) of the groove can be appropriately greater than or equal to 1:1, appropriately greater than or equal to 5:1, appropriately greater than or equal to 10:1, and remarkably, aspect ratios greater than or equal to 15:1 or even greater than or equal to 20:1 can be achieved. The technology upon which this invention is based can achieve extremely high aspect ratios, particularly when using anti-scattering compounds.

[0664] Further processing of patterned / developable substrates

[0665] Following the resist coating after development and exposure, the surface of the substrate beneath the patterning layer can be selectively modified in any one or more of a variety of ways. Since the steps of selectively modifying the substrate, substrate surface, or portions thereof can be repeated indefinitely (before or after removing any residual resist patterning layer, and optionally after further photolithography stages), one or more successive selective substrate / surface modification steps can be performed, which may optionally be selected from those or combinations thereof detailed herein.

[0666] Appropriately, during this selective modification, the portion of the substrate / surface being modified is either exposed by the grooves in the patterned layer or located beneath them (i.e., the lower surface to be modified may be exposed / visible or have only a thin layer of resist remaining on it).

[0667] Selective modification of a substrate / surface may include removing portions of the substrate / surface, adding or depositing material onto (or onto) the substrate / surface, and / or altering portions of the substrate / surface.

[0668] Modifying a substrate / surface by removing a portion of its surface can include, for example, etching the substrate / surface. In the case of integrated circuit manufacturing, such etching is typically performed to remove insulating material (e.g., a silicon oxide / silicon dioxide layer that appropriately protects the underlying conductive material), thereby exposing the underlying conductive material (e.g., silicon). Alternatively or additionally, etching may include etching the conductive material (e.g., silicon) – for example, a capacitor can be created by etching grooves deep into the silicon surface.

[0669] In the case of fabricating a photomask (e.g., a photomask), this etching can remove opaque material or layers to expose the transparent material underneath through which radiation can pass (e.g., during photolithographic exposure through the resulting photomask).

[0670] The etching will selectively etch the portion of the substrate / surface below the grooves of the patterned layer, rather than the portion of the substrate / surface below the ridges (which are essentially protected).

[0671] Modifying a substrate / surface by altering portions thereof can include, for example, changing the transparency of the substrate / surface (e.g., when fabricating a photomask) or changing the electrical properties of the substrate / surface (or a related portion thereof) (e.g., when fabricating an integrated circuit). Changing the electrical properties of the substrate / surface is particularly suitable when the underlying substrate / surface being modified (e.g., exposed via a groove) is a semiconductor (e.g., silicon). Changes in the electrical properties of the substrate / surface can include “doping” of the relevant portions of the substrate / surface. Doping is a well-known phenomenon in the field of semiconductor technology and contributes to the creation of electronic components within integrated circuits (e.g., diodes, logic gates, transistors, etc.). Such doping can be performed using techniques known in the art, such as diffusion (e.g., where a dopant diffuses into the substrate such that it is embedded therein) and ion implantation (e.g., in the case of ion beam implantation of ions into the substrate).

[0672] However, doping can be achieved through pre-deposition, for example, through epitaxial growth of doped deposits (e.g., epitaxial growth of Si-Ge layers).

[0673] Modifying the substrate / surface by altering a portion of the substrate / surface may optionally or additionally include forming an insulating layer (or isolation layer) or gate by appropriately transforming a portion of the substrate / surface—for example, by thermal oxidation (e.g., thermal oxidation of a conductor such as silicon to produce insulating silicon dioxide).

[0674] Modifying a substrate / surface by adding or depositing materials can include, for example, depositing insulating materials to isolate electronic components or conductive elements. Alternatively, it may include depositing conductive materials (e.g., metal plating).

[0675] Any, some, or all of the aforementioned surface modification steps (appropriately sequentially, but optionally with photolithography steps interspersed in between - such as recoating, re-exposure, and re-development) can be performed to form multilayer substrates such as integrated circuits (e.g., dies or wafers).

[0676] Suitable, at some stage (e.g., after one or more surface modifications), one or more resist pattern layers (which may or may not be resist pattern layers) are removed. This removal can be performed using various techniques known in the art (e.g., chemical removal, physical removal, thermal treatment, radiation removal, or plasma ashing or a combination thereof), but plasma ashing may be used in the case of integrated circuit manufacturing. Alternatively, residual resist pattern layers can be removed using solvents (e.g., by dissolution) or by selective etching processes.

[0677] In some implementations, once the resist pattern layer is removed, the entire modified surface can be treated / modified.

[0678] Step (vi) allows the surface modification steps to be repeated, enabling consecutive surface modification steps (before and / or after pattern layer removal). Furthermore, step (vi) allows all photolithography steps (steps i)-iii), further surface modification steps (step iv), and optional pattern layer removal steps (step v) to be repeated any number of times. Any or all repeated steps may be performed using an alternative resist coating (during exposure) instead of the resist coating of the present invention, provided the method includes at least one step involving the resist composition / coating of the present invention or at least one step involving the tooling of the present invention (e.g., a photomask). Alternatively, any or all repeated steps may use the resist coating of the present invention. Therefore, it is evident that, appropriately in the production of integrated circuits, etc., repeated steps are not limited, and multiple method steps outside the scope of the present invention are permitted.

[0679] In the manufacture of integrated circuits, selective modification of the substrate / surface (or portions thereof) may include a front-end line (FEOL) process (e.g., forming electronic components such as transistors directly in the substrate, i.e., in silicon). In practice, steps (i) through (vi) may collectively constitute a front-end line (FEOL) process. It is understood that the multilayer substrate of the integrated circuit, as an example, can be shaped through multiple repeating steps and optional pre-steps.

[0680] The above-described processing options and features are equally applicable to methods for manufacturing photomasks (but features related to integrated circuit manufacturing are obviously not particularly applicable to the fabrication of photomasks), methods for performing photolithography (using photomasks formed by the methods of the present invention), methods for manufacturing multilayer substrates, or methods for manufacturing integrated circuit dies or integrated circuit wafers comprising multiple integrated circuit dies.

[0681] Typically, step (vi) can be followed by one or more finishing steps, such as end-of-line (BEOL) processing (as used in the manufacture of integrated circuits). This may include conductively interconnecting electronic components and / or providing external contact terminals.

[0682] It is evident that any number of pre-processing steps may precede step (i) of the method. In a particular implementation, the input substrate itself is a partially constructed integrated circuit die (or wafer) that has already undergone multiple pre-processing steps.

[0683] Integrated circuit wafers and dies

[0684] This invention provides a method for manufacturing an integrated circuit die or an integrated circuit wafer comprising multiple integrated circuit dies, wherein the die or each die comprises multiple electronic components, wherein the method includes:

[0685] i) Providing a substrate coated with resist as defined herein, or applying a resist coating to a substrate; and

[0686] ii) Exposing the resist coating partially to radiation to provide exposure to the resist coating;

[0687] or

[0688] i) Providing a substrate coated with resist or applying a resist coating to a substrate (the resist coating can be any resist coating suitable for exposure through a photomask, such as a photoresist); and

[0689] ii) A resist coating that exposes a portion of the resist coating to radiation (e.g., UV or visible light) by means of a photomask (e.g., a photomask) as defined herein (or obtained by means of means defined herein);

[0690] and

[0691] iii) Develop the exposed resist coating to produce a resist pattern layer, the resist pattern layer comprising: a portion of the resist coating that is insoluble in the developer (i.e., ridges); and an array of grooves extending through the resist pattern layer;

[0692] iv) Modify the substrate, substrate surface, or portion thereof beneath the resist pattern layer (this may include interconnecting the electronic components of the die or each die with conductive materials);

[0693] v) Remove the resist pattern layer to provide a modified substrate;

[0694] vi) Optionally repeat steps iv) and / or i)-v) once or more on the modified substrate (with the resist coating of the present invention or an optional resist coating; with or without a photomask; and with radiation suitable for resisting the resist coating of the present invention or alternative radiation).

[0695] vii) Optionally, the electronic components of the said or each die are interconnected with conductive conductors (if not performed during one or more substrate / substrate surface modification steps) to provide an integrated circuit with external contact terminals;

[0696] viii) Optionally, one or more further finishing steps may be performed;

[0697] (ix) Optionally, the integrated circuit die can be separated from the wafer that includes multiple integrated circuit dies.

[0698] Optionally, steps (i) to (vi) of the method (i) (i.e., preliminary steps (i)-(vi), optionally using any one of the two steps (i) / (i) combinations) and / or steps (i) to (vi) of the photolithography method and appropriate exposure to radiation may be performed before step (i) of the method, optionally repeated once or multiple times, using the resist coating of the present invention or an alternative resist coating.

[0699] The resist coating suitably comprises a resist composition that is optionally dried and / or cured; wherein the resist composition comprises an anti-scattering compound.

[0700] In a particular implementation, steps (i) and (ii) include:

[0701] i) Providing a substrate coated with resist as defined herein, or applying a resist coating to a substrate; and

[0702] ii) Exposing the resist coating partially to radiation to provide exposure to the resist coating;

[0703] The features of the method for manufacturing integrated circuit dies or integrated circuit wafers comprising multiple integrated circuit dies described above include optional, appropriate, and preferred features.

[0704] However, it is important to understand that the manufacturing of integrated circuit dies can include many processing steps and may involve the fabrication of multilayer substrates.

[0705] As those skilled in the art will understand, manufacturing an integrated circuit (for inclusion in a circuit board) typically includes wafer processing (i.e., processing of a silicon wafer), die fabrication (e.g., dicing / separating individual dies from a processed wafer), integrated circuit packaging (whereby each die is packaged so that it can be used in a circuit board), and appropriately also includes integrated circuit testing.

[0706] While wafer processing is well understood in the art, it is noteworthy that in some embodiments, wafer processing includes wet cleaning; photolithography; ion implantation; dry etching and / or wet etching; plasma ashing; thermal treatment (e.g., annealing or thermal oxidation); chemical vapor deposition (CVD), physical vapor deposition (PVD), molecular beam epitaxy (MBE), and / or electrochemical deposition (ECD); wafer testing (e.g., to verify electrical performance); and wafer back-side grinding (to reduce wafer thickness and produce dies and chips). The methods, resist compositions / coatings, and photomasks of the present invention are suitably used at least once during wafer processing. Where a resist coating is used during wafer processing, suitably, at least one photolithography operation (which combines substrate resist coating, exposure, and development) is replaced by the use of the resist coating of the present invention instead of the conventional resist-based photolithography operation. In the case of a photomask fabricated using the resist coating of the present invention during wafer processing, at least one photolithography operation is suitably replaced by a photolithography operation utilizing the photomask during exposure (which itself includes photolithography or other types of photolithography, including eBeam, but most preferably photolithography). However, it should be understood that the benefits of the present invention can be achieved even if the resist coating or photomask of the present invention is used only once (or only a single layer or only a single electronic component or a single set of electronic components is produced), and it is conceivable that any other photolithography operation (e.g., photolithography) can employ standard techniques known in the field of integrated circuit manufacturing. Therefore, the method of the present invention provides options for any or all repetitive steps (and even any or all of any pre-steps) without requiring the coating or photomask of the present invention.

[0707] As previously described, steps (i)-(vi) of the method can constitute a front-end line (FEOL) process. Optionally, this process includes at least some extent the conductive interconnection of the electronic components of the die or each die. However, most appropriately, steps vii) to ix) constitute a back-end line (BEOL) process.

[0708] Suitable for conductive interconnection of electronic components, metallization is included. Suitable for conductive interconnection of electronic components, forming metallic interconnects isolated by one or more dielectric (i.e., insulating) layers, wherein the insulating material is typically silicon dioxide (usually formed by thermal oxidation of silicon) or silicate glass, but the material is not limited.

[0709] Metallization can include creating a metal wire mesh, such as copper or aluminum wires. This process may suitably include: a) overall coating of a modified substrate with a metal (e.g., copper or aluminum), patterning (e.g., using photolithography to create a resist pattern layer), etching the metal beneath the resist pattern layer (i.e., creating individual metal wires), and forming or depositing an insulating material on the metal wires. It should be understood that, for example, in cases where multiple layers of metal wires are required to create a usable integrated circuit, some or all of such metal wire layers may alternatively be formed during a surface modification step that may include the same process.

[0710] After the wafers are manufactured into dies, die dicing ensures that all dies are separated and ready for packaging.

[0711] The wafers and dies manufactured by the method of this invention are characterized by high performance, which is at least due to the high resolution achieved. They can also be smaller than standard IC dies.

[0712] Integrated circuit packaging

[0713] Technicians in the integrated circuit field can manufacture integrated circuit packages from integrated circuit dies using standard workshop techniques. However, this invention provides a method for manufacturing an integrated circuit package comprising a plurality of pins and an integrated circuit die having external contact terminals electrically connected to the respective plurality of pins, wherein the method comprises:

[0714] i) Provide an integrated circuit die as defined herein or manufacture an integrated circuit die by means of manufacturing an integrated circuit die as defined herein;

[0715] ii) Attaching an integrated circuit die to a package substrate, wherein the package substrate includes electrical contacts, each of which is optionally connected to or can be connected to a corresponding pin;

[0716] iii) Conductively connect each external contact terminal of the integrated circuit die to the corresponding electrical contact of the package substrate;

[0717] iv) Optionally (and if necessary) the electrical contacts of the package substrate can be connected to the corresponding pins;

[0718] v) Package integrated circuit die.

[0719] Conductive connection die and packaging substrate

[0720] Typically, this method involves electrically connecting a die to a package substrate using one of a variety of methods known in the art, such as wire bonding, thermo-ultrasonic bonding, flip chip bonding, wafer bonding, or tab bonding.

[0721] Connecting pins makes it easy and convenient to integrate an IC onto a circuit board. Therefore, this method appropriately includes electrically connecting the IC package pins to the die via suitable contacts. Typically, connecting pins is part of the package assembly, so this step can be combined with the packaging process.

[0722] Dies can be air / moisture sensitive, so they are typically encapsulated. The encapsulated IC packages are then properly baked, electroplated, laser-marked, and trimmed. Finally, the IC packages undergo appropriate electronic testing to ensure quality.

[0723] Circuit board, electronic device or system

[0724] Appropriately, a circuit board integrating the integrated circuit package (with multiple pins) of the present invention can be easily manufactured by simply conductively connecting the integrated circuit package to the circuit board.

[0725] Furthermore, the circuit board can be easily integrated into electronic devices or systems as defined herein. Thus, consumer products of the electronic devices or systems of the present invention, or consumer products including the electronic devices or systems of the present invention, benefit from the high-resolution (and other significant advantages) integrated circuits provided by the method of the present invention, as well as the novel resist coating described herein.

[0726] Example

[0727] Materials and equipment

[0728] Unless otherwise specified, all reagents and solvents are commercially available and used as is. Elemental analysis was performed by the Departmental Services of the University of Manchester. Carbon, nitrogen, and hydrogen analysis was performed using a Flash 200 elemental analyzer. Metal analysis was performed using a Thermo iCap 6300 inductively coupled plasma optical emission spectrometer (ICP-OES).

[0729] The silicon wafer substrate (500μm thick wafer) 10mm×10mm was purchased from University wafer.com and used as is.

[0730] Spin coating equipment includes the SCS G3P-8 spin coater, which has 8-inch rollers and a rotation speed of 100 rpm to 10,000 rpm.

[0731] The patterned substrate after development was examined and analyzed using a Leica optical microscope with a 10x objective lens.

[0732] UV exposure was performed using a UV crosslinking agent AH lamp box with five 254nm bulbs. These bulbs had an exposure band of 11nm covering the 248nm radiation. Exposure at 193nm was performed using a pulsed laser with a wavelength of 193nm. The gas used was a mixture of argon and fluorine. The pulse duration was 100ms, with 193nm photons being irradiated for 10ns in each pulse. The measured laser power was 18.8mW.

[0733] Example 1 - Preparation of Anti-scattering Compound

[0734] Typically, the resist compositions of the present invention (e.g., photoresists) can be manufactured by forming compositions comprising antiscattering compounds as defined herein. Suitably, the compositions also include a coating solvent to enable the antiscattering compounds to be applied as a resist coating.

[0735] Because antiscattering compounds suitably include low-density, high-molecular-weight multimetallic cages (which produce less scattering due to the amount of free space within such cage structures), any multimetallic cage can be used to obtain the relevant advantageous effects. With guidance to those skilled in the art, suitable structures can include any multimetallic cage complexes that are the same as or similar to those disclosed in GFS Whitehead, F. Moro, GATimco, W. Wernsdorfer, SJTeat and REP Winpenny, “ARing of Rings and Other Multicomponent Assemblies of Clusters”, Angew. Chem. Int. Ed., 2013, 52, 9932-9935. This document describes the synthesis of such multimetallic cages, and those skilled in the art can directly adapt the processes disclosed therein to prepare a wide variety of possible antiscattering compounds.

[0736] Typically, multimetallic cages are formed by mixing the relevant inorganic salt (including a metal intended to be integrated into the cage) with relevant ligands (usually carboxylic acids and fluoride salts) (e.g., by adapting to the process disclosed in GATimco et al., Nat. Nanotechnol. 2009, 4, 173-178). In some cases, the multimetallic cage can act as a Lewis acid (i.e., capable of coordinately accepting one or more electron pairs) and can be mixed with a suitable complementary Lewis base linker (e.g., a pyridyl-substituted porphyrin) to produce a total complex, wherein multiple metal cages surround the linker. Alternatively, the multimetallic cage can act as a Lewis base (i.e., capable of cocoordinately donating one or more electron pairs), suitably by means of a basic moiety present in one or more relevant ligands within the cage, and can be mixed with a suitable complementary Lewis acid linker (e.g., optionally another metal-centric cage structure that is Lewis acidic or has substituted ligands). Suitably, the Lewis acid and Lewis base components of the antiscattering compound can be mixed in a stoichiometric ratio to produce a linker surrounded by a desired number of host metal complexes.

[0737] In addition, various suitable multimetal cage compounds are disclosed by reference to pending international patent application number PCT / GB2015 / 052204 (filed on July 30, 2015), which is incorporated herein by reference.

[0738] For example, [H2NR2][Cr7NiF8(2-methyl-4-pentenoate)] is prepared by mixing 28 molar equivalents of chromium(III) fluoride with 2.7 molar equivalents of nickel(II) inorganic salt and 137 molar equivalents of 2-methyl-4-pentenoic acid in the presence of 11 molar equivalents of a secondary amine (suitably dipropylamine). 16 Metal complexes. A modified version of this process is disclosed in FK Larsen et al., Synthesis and Characterisation of Heterometallic {Cr7M}Wheels, Angew. Chem. Int. Ed. 42, 101-105 (2003).

[0739] Example 1A - Metal complex [H2NPr2][Cr7NiF8(2-methyl-4-pentenoate)] 16 ] Preparation

[0740] The host metal complex, [H2NR2][Cr7NiF8(2-methyl-4-pentenoate), can be prepared by mixing 28 molar equivalents of chromium(III) fluoride with 2.7 molar equivalents of nickel(II) inorganic salt and 137 molar equivalents of 2-methyl-4-pentenoic acid in the presence of 11 molar equivalents of a secondary amine (suitably dipropylamine). 16[H₂NR₂][Cr₇NiF₈(2-methyl-4-pentenoate)] A modified version of this process is disclosed in FK Larse et al., Synthesis and Characterisation of Heterometallic {Cr₇M}Wheels, Angew. Chem. Int. Ed. 42, 101-105 (2003). The mixture was heated and stirred at 140 °C for 5 hours, during which time chromium fluoride dissolved and formed a green crystalline product. The flask was cooled to room temperature and 50 ml of acetone was added with stirring. The crystalline product was filtered, washed with a large amount of acetone, dried in air, and recrystallized from toluene to give [H₂NR₂][Cr₇NiF₈(2-methyl-4-pentenoate)]. 16 ].

[0741] Elemental analysis (%): C 102 H 160 Cr7F8NNiO 32 Calculated values: Cr 14.63, Ni 2.36, C 49.26, H 6.48, N 0.56. Measured values: Cr 14.51, Ni 2.07, C 49.41, H 6.79, N 0.50. ESI-MS (sample dissolved in THF, run in MeOH): m / z: 2487 [M+H] + ;2509[M+Na] + .

[0742] Cr7Ni (2-methyl-4-pentenoate) can be appropriately used as a Lewis acid. 16 Metal cage complexes can optionally be mixed with various Lewis base linker components (e.g., central electron-donating hubs) to produce antiscattering compounds with different molecular weights, densities, and average ionization potentials. The mixture is then concentrated to obtain the final antiscattering compound, which comprises associated linkers (e.g., porphyrins) surrounded by multiple metal cages. However, in the present case, Lewis base linkers are not used; instead, the resist compositions tested so far are already dominated by metal complexes. Nevertheless, the principles and benefits can be readily deduced.

[0743] [(C3H7)2NH2Cr7NiF8(4-pentenoate)] 16CrF3·4H2O (3.0 g, 16.5 mmol), [2NiCO3·3Ni(OH)2·4H2O] (0.4 g, 6.8 mmol), dipropylamine (0.7 g, 6.9 mmol), and 4-pentenoic acid (15.0 g, 150.0 mmol) were heated and stirred at 120 °C for 20 hours. During this time, chromium fluoride dissolved and formed a green crystalline product. The flask was cooled to room temperature, and 50 mL of water / acetonitrile (9 / 1) was added with stirring. The crystalline product was filtered, washed with a large amount of water / acetonitrile (9 / 1), and the resulting oily product was stirred overnight with a solution of 10 g of potassium carbonate dissolved in 600 mL of water. The precipitate was collected by filtration, washed with water, dried in air, and purified by rapid chromatography using hexane:dichloromethane (1:1 to 1:4) to give the green product. Yield: 2.14 g (40%). Elemental analysis (%): C 86 H 128 Cr7F8NNiO 32 Calculated values: Cr 16.09, Ni 2.59, C 45.66, H 5.70, N 0.62. Measured values: Cr 15.81, Ni 2.29, C 45.95, H 5.99, N 0.53. ESI-MS (sample dissolved in THF, run in MeOH): m / z: 2266 [M+H] + ;2288[M+Na] + .

[0744] Example 1B - Metal complex with a central diallylamine molecule [H2NPr2][Cr7NiF8(2-methyl)

[0745] -4-pentenoate) 16 Preparation of ]

[0746] [(C3H5)2NH2Cr7NiF8(2-methyl-4-pentenoate)] 16 CrF3·4H2O (3.0 g, 16.5 mmol), [2NiCO3·3Ni(OH)2·4H2O] (0.4 g, 6.8 mmol), diallylamine (0.7 g, 7.2 mmol), and 2-methyl-4-pentenoic acid (15.0 g, 131.5 mmol) were stirred and heated at 140 °C for 14 hours. During this time, chromium fluoride dissolved and formed a green crystalline product. The flask was cooled to room temperature, and 50 mL of water / acetonitrile (1 / 1) was added with stirring. The crystalline product was filtered, washed with a large amount of acetonitrile / water (1 / 1), and the resulting oily product was stirred overnight with a solution of 15 g of potassium carbonate dissolved in 600 mL of water. The precipitate was collected by filtration, washed with water and acetonitrile, dried in air, and purified by rapid chromatography using dichloromethane:diethyl ether (Et2O) (10:1 to 5:1) to give the green product. Yield: 2.06 g (35%). Elemental analysis (%): C102 H 156 Cr7F8NNiO 32 Calculated values: Cr 14.66, Ni 2.36, C 49.34, H 6.33, N 0.56. Measured values: Cr 14.30, Ni 2.11, C 49.61, H 6.59, N 0.49. ESI-MS (sample dissolved in THF, run in MeOH): m / z: 2483 [M+H] + ;2505[M+Na] + .

[0747] Example 2 - Preparation of the resist composition

[0748] The antiscattering compounds of Examples 1A and 1B can be considered as antiscattering-resist hybrid compounds because they incorporate both an antiscattering component (i.e., a low-density metal cage compound) and a resist component (i.e., a 2-methyl-4-pentenoate resist ligand with crosslinkable terminal olefin groups).

[0749] In this way, various resist compositions are formed and their effectiveness is tested.

[0750]

[0751] Examples 2A(i) and (ii) - Formulation A (Cr7Ni / / 2-methyl-4-pentenoate complex + sulfonium trifluoromethanesulfonate)

[0752] Formulations A(i) and (ii) were prepared using the anti-scattering-resist mixed compound of Example 1A, one of which was free of sulfonium tri(4-tert-butylphenyl)trifluoromethanesulfonate (A(i)) and the other contained sulfonium tri(4-tert-butylphenyl)trifluoromethanesulfonate.

[0753] To form the resist composition, 20 mg of the anti-scattering-resist mixture of Example 1A was dissolved in 1 g of tert-butyl methyl ether (MTBE) and filtered through a 0.2 μm PTFE filter to produce formulation A(i).

[0754] To prepare formulation A(ii), 4 mg of sulfonium tris(4-tert-butylphenyl)trifluoromethanesulfonate (a common photoacid generator and photoinitiator) was dissolved in 8 g of acetone in a separate container and filtered through a 0.2 μm PTFE filter. Finally, 100 mg of the sulfonium tris(4-tert-butylphenyl)trifluoromethanesulfonate / acetone product was introduced into a Cr7Ni antiscattering-resist mixed compound solution to obtain formulation A(ii).

[0755] Example 2B - Formulation B (Cr7Ni / 2-methyl-4-pentenoate / diallylamine complex)

[0756] Formulation B was prepared using the anti-scattering-resist mixed compound of Example 1B.

[0757] To form the resist composition, 15 mg of the anti-scattering-resist mixture of Example 1B was dissolved in 1 g of tert-butyl methyl ether (MTBE) and filtered through a 0.2 μm PTFE filter.

[0758] Example 2C-Formulation C(Cr7Ni / 2-methyl-4-pentenoate / diallylamine complex + diethoxyphenethyl) Ketone photoinitiator)

[0759] Formulation C was prepared using the anti-scattering-resist mixed compound of Example 1B.

[0760] To form the resist composition, 15 mg of the anti-scattering-resist mixture of Example 1B was dissolved together with 50 μg of 2,2-diethoxyacetophenone in 1 g of tert-butyl methyl ether (MTBE) and filtered through a 0.2 μm PTFE filter.

[0761] Example 2D-Formulation D(Cr7Ni / 2-methyl-4-pentenoate / diallylamine complex + diethoxyphenethyl) Ketone photoinitiator + additional diallylamine or N,N-methylenebisacrylamide (bis-AMD)

[0762] Formulation D was prepared using the anti-scattering-resist mixed compound of Example 1B.

[0763] To form the resist composition, 15 mg of the anti-scattering-resist mixture of Example 1B was dissolved in 1 g of tert-butyl methyl ether (MTBE) along with 50 μg of 2,2-diethoxyacetophenone and 4 mg of diallylamine or N,N-methylenebisacrylamide (bis-AMD), and then filtered through a 0.2 μm PTFE filter.

[0764] Example 2 E-Formulation E (Cr7Ni / 2-methyl-4-pentenoate / diallylamine complex + diethoxyphenyl) Ketone photoinitiator + diallylamine or N,N-methylenebisacrylamide (bis-AMD)

[0765] Formulation E was prepared using the anti-scattering-resist mixed compound of Example 1B.

[0766] To form the resist composition, 15 mg of the anti-scattering-resist mixture of Example 1B was dissolved in 1 g of tert-butyl methyl ether (MTBE) along with 50 μg of 2,2-diethoxyacetophenone and 1 mg of pentaerythritol tetraacrylate (PET), and then filtered through a 0.2 μm PTFE filter.

[0767] Example 2F - Formulation F (Cr7Ni / 2-methyl-4-pentenoate / diallylamine complex + sulfonium trifluoromethanesulfonate)

[0768] Formulation F was prepared using the anti-scattering-resist mixed compound of Example 1B.

[0769] To form the resist composition, 15 mg of the anti-scattering-resist mixture of Example 1A was dissolved together with 50 μg of tris(4-tert-butylphenyl)trifluoromethanesulfonate in 1 g of tert-butyl methyl ether (MTBE) and then passed through a 0.2 μm PTFE filter.

[0770] Example 2 G-Formulation G (Cr7Ni / 2-methyl-4-pentenoate / diallylamine complex + sulfonium trifluoromethanesulfonate)

[0771] Formulation G was prepared using the anti-scattering-resist mixed compound of Example 1B.

[0772] To form the resist composition, 15 mg of the anti-scattering-resist mixture of Example 1B was dissolved in 1 g of tert-butyl methyl ether (MTBE) along with 50 μg of tris(4-tert-butylphenyl)trifluoromethanesulfonate and 4 mg of diallylamine or N,N-methylenebisacrylamide (bis-AMD), and then filtered through a 0.2 μm PTFE filter.

[0773] Example 2H - Formulation H (Cr7Ni / 2-methyl-4-pentenoate / diallylamine complex + sulfonium trifluoromethanesulfonate)

[0774] Formulation H was prepared using the anti-scattering-resist mixed compound of Example 1B.

[0775] To form the resist composition, 15 mg of the anti-scattering-resist mixture of Example 1B was dissolved in 1 g of tert-butyl methyl ether (MTBE) along with 50 μg of tris(4-tert-butylphenyl)trifluoromethanesulfonate and 1 mg of pentaerythritol tetraacrylate, and then filtered through a 0.2 μm PTFE filter.

[0776] Example 3 - Preparation of a substrate coated with resist

[0777] Each of the above-described resist compositions 2A-2H was spin-coated onto a 10mm × 10mm silicon substrate. Each resist composition was spin-coated for 60 seconds using a spin cycle of 8000 rpm, followed by soft baking at 100°C for 2 minutes to evaporate the casting solvent. The resulting resist film had a thickness of 100 nm. The resist film was exposed to radiation at 248 nm and 193 nm using silver optical masks with features of 250 nm and 200 nm, respectively. Each material was developed using a hexane solution for 30 seconds, followed by drying with N2.

[0778] Results and Discussion

[0779] Figure 1 The diagram illustrates how radiation absorption varies with incident wavelength for each of formulations A(i) (i.e., Cr7Ni metal complex only) and formulation A(ii) (Cr7Ni complex + photoacid-producing agent).

[0780] from Figure 1 It is evident that at a wavelength of 248 nm (suitable for photolithography), a single Cr7Ni ring molecule absorbs approximately 0.5% of the total available radiation, while when combined with a photoacid generator, it absorbs approximately 2% of the available radiation. Thus, even at ultra-low concentrations of the photoacid generator used (i.e., 400 times less than the weight of the Cr7Ni ring molecule), the photoacid generator appears to impart a 4-fold increase in efficiency based on its absorption spectrum. This is considered promising because using very low concentrations of PAG or photoinitiator can improve the resulting resolution by reducing proximity effects.

[0781] Figure 2 SEM images of the resist coatings after development based on the resist compositions of Examples 2A(i) and 2A(ii) are shown: (a) a 250 nm nanostructure with a 600 nm pitch produced at a wavelength of 248 nm using formulation A(i); (b) a nanostructure indicated by a closed black box in a, manufactured using formulation A(i); (c) a 250 nm nanostructure manufactured using PAG with formulation A(ii); and (d) a nanostructure indicated by a closed black box in c, manufactured using formulation A(ii).

[0782] These nanostructures were created using very low exposure doses (3.29 mJ / cm² for formulation A(i)). 2 This suggests a highly sensitive resist composition. It is believed that such high sensitivity is due to the periphery of the metal cage compound being essentially saturated with 16 crosslinkable olefin groups. Therefore, the probability of effective photon collisions is high, as it accounts for 45.6% of the total molecule, thus providing conditions for the crosslinking of Cr7Ni ring molecules with each other, leading to the polymerization process.

[0783] Similarly, formulation A(ii) (with PAG-2.4 mJ / cm) 2 The photosensitivity of PAG is also significantly high. Therefore, adding PAG obviously reduces the exposure time by 1.37 times (thus increasing photosensitivity). However, considering... Figure 1 The absorption coefficient shown is lower than expected. Therefore, it is concluded that the resist composition of the present invention provides high sensitivity and high resolution even without a photoinitiator or photoacid generator.

[0784] Figure 3SEM images of the resist coatings after development based on the resist compositions of Examples 2A(i) and 2A(ii) are shown: (a) SEM image of a 200 nm nanostructure produced at a wavelength of 193 nm using formulation A(i); (b) nanostructures manufactured using formulation A(i) and indicated by closed black boxes in a; (c) 200 nm nanostructures manufactured using PAG (i.e., formulation A(ii)); (d) nanostructures manufactured using formulation A(ii) and indicated by closed black boxes in c.

[0785] Figure 3 (a) and Figure 3 (b) The nanostructure (i.e., without PAG) is produced using 4.6 mJ / cm². 2 It was manufactured using high exposure doses, and it exhibits extremely impressive sensitivity.

[0786] Figure 3 Figures (c) and (d) (i.e., those with PAG) are using 3.4 mJ / cm 2 Produced with high exposure doses, it exhibits extremely impressive sensitivity.

[0787] Furthermore, the resist composition of formulation A(ii) (with PAG) exhibited 1.35 times greater sensitivity than that without PAG (i.e., formulation A(i)). Therefore, by comparison, the CrNi ring itself appears to be more sensitive at a radiation wavelength of 248 nm.

[0788] Because 193nm photons are larger than molecules, the interactions are small, but there are approximately 10 per unit volume. 14 There are only a few molecules, so they can scatter light in any direction (this is called Mie scattering). It is this mechanism that limits the sensitivity and resolution. This is because the molecular density is 1.6 g / cm³. 3 (From the perspective of photon scattering, it is low, and the high-density part of the molecule is actually composed of groups that should absorb photons) and its molecular weight is large (2501 g / mol). Therefore, most of the film is in free space, and due to the small scattering interactions, photons are confined, thus prohibiting transverse scattering. Therefore, higher resolution can be achieved.

[0789] Figure 4 The contrast curves of the Cr7Ni ring molecules after exposure at 248 nm are shown. It can be seen that the material produces a contrast ratio of 5.67, which is obtained by the following equation:

[0790]

[0791] The value of D1 is 3, and the value of D0 is 2. Figure 6The value of D1 is found in the diagram. When PAG is added, the value of D1 is 2.3 and the value of D0 is 1.45. This produces a contrast ratio of 4.99. Therefore, the introduction of PAG has a minimal impact on the contrast ratio.

[0792] Figure 5 The contrast curves of the Cr7Ni ring molecules after exposure at 193 nm are shown. It can be seen that the material produces a contrast ratio of 3.15. When PAG is added to the CrNi ring molecules, this produces a contrast ratio of 2.86. Therefore, the introduction of PAG has a negligible effect on the contrast ratio.

[0793] in conclusion

[0794] A novel photoresist system based on multimetal cage compounds has been developed, such as Cr7Ni complexes containing crosslinkable or polymerizable olefin-containing ligands. This photoresist system exhibits nanostructures of 250 nm and 200 nm upon irradiation with 248 nm and 193 nm radiation, respectively. Both exposures show a yield of 3.29 mJ / cm². 2 and 4.6 mJ / cm 2 The Cr7Ni ring exhibits significant sensitivity, with contrast ratios of 4.64 and 3.15 (248 nm and 193 nm, respectively). Introducing PAG into the Cr7Ni ring molecule increased the sensitivity by 1.3-fold; however, the contrast ratios decreased to 4.99 and 2.86, respectively. This sensitivity is clearly due to the presence of numerous crosslinkable sections (i.e., 16 olefin groups attached to the molecule's exterior), which is conducive to the polymerization process. Therefore, the probability of creating crosslinking conditions for the Cr7Ni ring molecules to crosslink with each other is 45.6%. The sensitivity can be easily tuned by changing the olefin content.

[0795] To avoid being bound by theory, it is believed that an initial electronic excitation (~3.6 eV) causes the π-bond cleavage of an alkene (e.g., following the π→π bond). * A single-electron transition occurs, followed by a radical reaction with an adjacent olefin (possibly unexcited), resulting in photolysis-induced crosslinking between adjacent olefin groups. Depending on various factors (e.g., steric effects, electron transfer properties of surrounding groups, kinetics of the terminating reaction, photoemission, etc.), this π→π* transition and subsequent reaction can, in principle, lead to a cascade reaction. Although the presence of a photoinitiator or photoacid-producing agent can enhance sensitivity in some cases, the resist compositions of the present invention do not need to contain such a photosensitive compound, especially when the relevant resist components themselves already possess sufficient photolytic activity.

[0796] The fundamental principles of improved exposure control provided by anti-scattering compounds also apply to resist compositions in which the resist component itself is not bound to the anti-scattering compound. In view of the teachings given herein, those skilled in the art will be able to make reasonable adjustments and selections to enable the manufacture of resist compositions that benefit from the principles of this invention.

[0797] Example 4 - Preparation and use of another resist composition containing a secondary electron generating agent in deep ultraviolet (eUV) light. Radiation testing

[0798] [C6H 10 NH2] [ C6H 10 NH2][Cr7NiF8(O2C t Bu) 15 (O2CC5H4N)](compound 1) and [ C6H 10 NH2] [Cr7NiF8(O2C t This) 14 (O2CC5H4N)2 ] Synthesis of (Compound 2)

[0799] [C6H] 10 NH2][Cr7NiF8(O2C t Bu) 16 [4.3 g, 1.78 mmol (which can be obtained by simply modifying the process used in Example 1), isonicotinic acid (0.68 g, 5.34 mmol), and n-propanol (100 mL) were refluxed with constant stirring for 24 hours. The resulting solution was cooled to room temperature and filtered. The solvent in the filtrate was removed under reduced pressure and extracted with diethyl ether (100 mL). The resulting solution was filtered, and the diethyl ether was removed under reduced pressure, leaving a solid. Rapid chromatography with toluene / ethyl acetate (97 / 3) was used to give product 1, followed by gradient elution (up to toluene / ethyl acetate (50 / 50)) to give product 2. Both products were green solids after evaporation of the solvent mixture.]

[0800] Yield: 4.89 g (32%). Elemental analysis (%) C 87 H 151 Cr7F8N2NiO 32 Calculated values: Cr 15.72, Ni 2.53, C 45.12, H 6.75, N 1.21; Measured values: Cr 15.97, Ni 2.56, C 44.90, H 6.90, N 1.19. ES-MS (sample dissolved in THF, run in MeOH): m / z = 2334 [M+Na] + ;2312[M+H] + .

[0801] 2. Yield: 1.62 g (10%). Elemental analysis (%): C 88 H 146 Cr7F8N3NiO 32Calculated values: Cr 15.60, Ni 2.52, C 45.31, H 6.31, N 1.80. Measured values: Cr 15.56, Ni 2.39, C 45.56, H 6.77, N 1.82. ES-MS (sample dissolved in THF, run in MeOH): m / z = 2355 [M+Na] + ;2333[M+H] + .

[0802] Coordination with mercuric chloride:

[0803] [C6H 10 NH2][Cr7NiF8(O2CC2H5 ) 15 Synthesis of (O2CC5H4N).HgCl](Compound 3)

[0804] Compound 1 (100 mg, 0.04 mmol) was dissolved in hot acetone (10 mL). A solution of mercuric chloride (11.7 mg, 0.04 mmol) in acetone (2 mL) was added dropwise, and the green solution was stirred at 50 °C for 1 hour. The solution was cooled to room temperature and concentrated to obtain green microcrystalline powder 3. Elemental analysis (%): C 87 H 151 Cr7F8N2NiO 32 Calculated values ​​of HgCl: Cr 14.29, Ni 2.30, C 41.02, H 5.97, N 1.10; Measured values: Cr 14.22, Ni 2.28, C 41.10, H 5.99, N 1.16.

[0805] [C6H 10 NH2][Cr7NiF8(O2CC2H5 ) 14 Synthesis of [(O2CC5H4N)2.2HgCl] (Compound 4) Compound 2 (100 mg, 0.04 mmol) was dissolved in hot acetone (10 mL). A solution of mercuric chloride (23.1 mg, 0.08 mmol) in acetone (2 mL) was added dropwise, and the green solution was stirred at 50 °C for 1 hour. The solution was cooled to room temperature and concentrated to obtain green microcrystalline powder 4. Elemental analysis (%): C 88 H 146 Cr7F8N3NiO 32 Calculated values ​​of Hg2Cl4: Cr 12.66, Ni 2.04, C 36.76, H 5.12, N 1.46; Measured values: Cr 12.80, Ni 2.09, C 36.96, H 5.21, N 1.46.

[0806] Coordination with mercuric iodide:

[0807] [C6H 10 NH2][Cr7NiF8(O2CC2H5 ) 15 Synthesis of (O2CC5H4N).HgI](Compound 5)

[0808] Compound 1 (100 mg, 0.04 mmol) was dissolved in hot acetone (10 mL). Mercuric iodide (19.4 mg, 0.04 mmol) was added dropwise. A solution of 0.04 mmol) in acetone / tetrahydrofuran (1.5 mL / 0.5 mL) was prepared, and the green solution was stirred at 50 °C for 1 hour. The solution was then...The liquid was cooled to room temperature and concentrated. A green microcrystalline powder was obtained. Elemental analysis (%): C 87 H 151 Cr7F8N2NiO 32 Hgl calculation Cr values: Cr 13.79, Ni 2.22, C 39.59, H 5.77, N 1.06; Measured values: Cr 13.98, Ni 2.20, C 39.92, H 5.86, N 1.10。

[0809] [C6H 10 NH2][Cr7NiF8(O2CC2H5) 14 Synthesis of (O2CC5H4N)2.2Hgl](Compound 6)

[0810] Compound 2 (100 mg, 0.04 mmol) was dissolved in hot acetone (10 mL). Mercuric iodide (38.9 mg, 0.04 mmol) was added dropwise. A solution of 0.08 mmol) in acetone / tetrahydrofuran (1.5 mL / 0.5 mL) was prepared, and the green solution was stirred at 50 °C for 1 hour. The solution was then... The liquid was cooled to room temperature and concentrated. Green microcrystalline powder 6 was obtained. Elemental analysis (%): C 88 H 146 Cr7F8N3NiO 32 Calculation of Hg2l4 Values: Cr 11.23, Ni 1.81, C 32.61, H 4.54, N 1.30; Measured values: Cr 11.30, Ni 1.79, C 32.76, H 4.66, N 1.19。

[0811] Formation of the resist composition

[0812] The resist formulation was prepared by dissolving 20 mg of Cr7Ni derivatives (i.e., compounds 3, 4, 5 and 6 above) in 5 g of tert-butyl methyl ether and filtering through a 0.2 μm PTFE filter.

[0813] Spin coating, exposure and development of resist compositions

[0814] The manufacturing process is as follows: The resist formulation prepared above is a negative resist. This resist composition is spin-coated onto a 10mm × 10mm silicon substrate. The resist is spin-coated for 60 seconds using a spin cycle of 8000 rpm, and then soft-baked at 100°C for 2 minutes to evaporate the casting solvent. The resulting resist film has a thickness of 25 nm. The resist film is exposed to 13.4 nm radiation (deep ultraviolet-eUV) through a photomask comprising 22 nm features with a pitch of 44 nm and 16 nm features with a pitch of 32 nm. Each material is developed using a hexane solution for 30 seconds, and then dried with N2.

[0815] The experiments discussed below used a resist composition of compound 3 (mercuric chloride derivative) and compound 5 (mercuric iodide derivative), and the exposure dose was varied.

[0816] Figure 6 It shows 396mJ / cm 2 An enlarged view of a substrate coated with a developed / dried resist, based on compound 3 (HgCl2 derivative), exposed to EUV at an exposure dose to produce a feature width of approximately 22 nm and a pitch of approximately 44 nm.

[0817] Figure 7 It shows 322mJ / cm 2 An enlarged view of a substrate coated with a post-development / drying resist, based on compound 3 (HgCl2-derived), exposed to eUV at an exposure dose to produce a feature width of approximately 16 nm and a pitch of approximately 32 nm.

[0818] Figure 8 It shows 357mJ / cm 2An enlarged view of a substrate coated with a post-development / drying resist, based on compound 5 (HgI2 derivative), exposed to eUV at an exposure dose to produce a feature width of approximately 22 nm and a pitch of approximately 44 nm.

[0819] Figure 9 It shows 268mJ / cm 2 An enlarged view of a substrate coated with a post-development / drying resist, based on compound 5 (HgI2 derivative), exposed to eUV at an exposure dose to produce a feature width of approximately 16 nm and a pitch of approximately 32 nm.

[0820] Figure 10 It shows 244 mJ / cm 2 Exposure to eUV at a dose of approximately 13 nm in feature width and approximately 32 nm in pitch produces magnified images of a substrate coated with post-development / drying resist based on compound 5 (HgI2 derivative). This exposure yielded optimal results under these conditions.

[0821] Figure 11 It shows 222mJ / cm 2 Exposure to eUV at a dose of approximately 13 nm in feature width and approximately 32 nm in pitch produces magnified images of a substrate coated with post-development / drying resist based on compound 5 (HgI2 derivative). This exposure yielded optimal results under these conditions.

[0822] Results and Discussion

[0823] Table 1 below summarizes the results of eUV experiments conducted using the synthetic resist composition.

[0824] Table 1 - Summary of eUV Exposure Experiment Results

[0825]

[0826] Experiment 5 was conducted under the main test conditions (i.e., at 244 mJ / cm). 2 Optimal results were achieved under exposure to mercuric iodide derivatives. Some line edge roughness (LER) in exposures is due to quality limitations caused by the photomask.

[0827] The introduction of secondary electron generating agents such as HgCl2 and / or HgI2 improves the sensitivity of the resist without affecting resolution. For example, the inventors have found that using HgI2 improves sensitivity by at least ×1.32 compared to equivalent formulations without HgI2. This is reflected in the lower exposure dose required during exposure.

[0828] Figure 12The figure illustrates the reduced exposure dose required (and therefore increased sensitivity) for the currently available 6th generation resist coatings, the corresponding 6th generation coatings being:

[0829] First-generation - 60nm thick resist coating of compound 1 (without secondary electron generator)

[0830] Second-generation - 60nm thick compound 3 resist coating

[0831] 3rd generation - 60nm thick Compound 5 resist coating

[0832] 4th generation - 50nm thick compound 3 resist coating

[0833] 5th generation - 20nm thick compound 3 resist coating

[0834] 6th generation - 20nm thick Compound 5 resist coating

[0835] The inventors have exposed the aforementioned sixth-generation photoresist to EUV radiation (energy = 92 eV).

[0836] The first-generation corrosion resist material has a higher efficiency of 990 mJ / cm than required. 2 The exposure dose. Because the chemical principles of secondary electron generators and their incorporation into the resist compositions of this invention are better understood, the inventors have been able to make significant improvements in resist sensitivity. The sixth-generation resist shows a reduction to 244 mJ / cm². 2 The exposure dose of the line exposure dose. Progress can be made in Figure 12 As can be seen from the chart.

[0837] Thus, including secondary electron generators (e.g., high Z-elements) eff High-density metal compounds are desirable for improving sensitivity, and it is feasible to conveniently coordinate secondary electron generators with resist compounds. This essentially provides low-density resist compositions (e.g., primarily antiscattering materials) that promote high resolution and reduce scattering, with high-density dispersed (and regular) regions that promote localized scattering to increase resist sensitivity.

[0838] Those skilled in the art will understand that the foregoing is merely an example of a broader concept applicable to other resist compounds, resist compositions, and other secondary electron generators. Regarding the secondary electron generator component, patent publication WO2015 / 145144 (by the same inventor / applicant) describes a series of suitable alternative secondary electron generators that can be incorporated into the resist compositions of the present invention in a free, dispersed form and / or coordinated with antiscattering and / or resist materials. For this purpose, WO2015 / 145144 is incorporated herein by reference.

[0839] in conclusion

[0840] The above experimental results demonstrate the feasibility of the resist compositions of the present invention across the entire ultraviolet wavelength range. Thus, these resists not only provide important benefits (e.g., high resolution, sensitivity, spin coating, etc.) outlined elsewhere herein, but also offer sufficient versatility to enable these benefits to be obtained and realized under a range of conditions, thereby expanding their industrial applicability. The resists of the present invention make a particular contribution to the field of electronic devices and integrated circuits, where the benefits of the present invention can be universally realized to produce the highest quality next-generation high-specification electronic devices.

[0841] This invention also relates to the following items:

[0842] 1) A photoresist composition comprising an antiscattering component and a photoresist component, wherein the antiscattering component comprises a multi-metal cage and / or a multi-metal ring system; wherein the photoresist component is optionally a part of the antiscattering component (e.g., together forming an antiscattering-photoresist hybrid component), wherein the photoresist composition is a photoresist composition.

[0843] 2) The resist composition according to any of the foregoing items, wherein the resist composition is a negative resist composition.

[0844] 3) The resist composition according to any of the preceding items, wherein the anti-scattering component is combined with one or more resist components such that they together form an anti-scattering-resist mixed component.

[0845] 4) The resist composition according to any of the preceding items, wherein the anti-scattering component comprises a main metal complex (PMC), wherein the main metal complex is a multi-metallic metal cage complex comprising a plurality of metal ions of at least one type interconnected by one or more bridging ligands.

[0846] 5) The resist composition according to item 4), wherein the main metal complex comprises at least two types of metal ions, wherein the at least two types of metal ions comprise the same or different metals.

[0847] 6) The corrosion resist composition according to item 5), wherein the at least two types of metal ions have different oxidation states.

[0848] 7) The resist composition according to item 6), wherein one of the metal ions is trivalent and the other of the metal ions is divalent.

[0849] 8) The corrosion resist composition according to item 7), wherein the trivalent metal ion is selected from CrIII ,

[0850] Fe III V III Ga III Al III or In III or a mixture thereof, wherein the divalent metal ion is selected from Ni II Co II Zn II Cd II Mn II Mg II Ca II 、Sr II Ba II Cu II or Fe II A group consisting of its mixture or other combinations thereof.

[0851] 9) The corrosion resist composition according to item 8), wherein the trivalent metal ion is Cr III And wherein the divalent metal ion is Ni II .

[0852] 10) The resist composition according to item 9), wherein the main metal complex is defined by or comprises units defined by formula IIg:

[0853] [Cr7Ni(O2CR B1 ) r ];

[0854] Where R B1 It is a (1-20C) hydrocarbon group with optional substitution of π system; wherein r is an integer having a value of 1 or greater (appropriately between 1 and 16); and wherein the unit of formula IIg optionally includes one or more other binding ligands.

[0855] 11) A resist composition according to any one of items 4) to 10), wherein the main metal complex comprises one or more resist ligands covalently bonded to the metal ions of the multimetal complex, each resist ligand having a crosslinkable portion.

[0856] 12) The resist composition according to item 11), wherein each resist ligand comprises a crosslinkable π system and one or more coordination donor atoms or groups, wherein:

[0857] The π system is selected from the group consisting of: carbon-carbon double or triple bonds; carbon-heteroatom double or triple bonds; aromatic or heteroaromatic ring systems; conjugated π systems comprising carbon and optional heteroatoms; or mixtures thereof; and

[0858] The one or more coordination donor atoms or groups include one or more heteroatoms with lone pairs of electrons.

[0859] 13) The resist composition according to item 12), wherein each resist ligand is independently selected from the group consisting of optionally substituted acrylates, acrylates, acrylate ions, acrylate amides, alkynates, alkynates, alkynates, alkynates, alkynates amides or mixtures thereof.

[0860] 14) The resist composition according to item 13), wherein each resist ligand is independently (1-20C) acrylate, (1-20C) acrylate, (1-20C) acrylate or (1-20C) acrylate amide, such that the resist ligand includes at least one terminal olefin moiety.

[0861] 15) The resist composition according to item 14), wherein the main metal complex is defined by or comprises units defined by formula IIi:

[0862] [Cr7NiF8(O2CR B1 ) r ];

[0863] Where R B1 It is an optionally substituted (1-6C) hydrocarbon group comprising a terminal olefinic moiety, wherein r is an integer having a value of 1 or greater (appropriately between 1 and 16); and wherein the unit of formula IIi optionally comprises one or more other binding ligands (i.e., valence-bonded within the complex).

[0864] 16) A resist composition according to any of the preceding items, wherein the resist composition comprises an antiscattering compound covalently or coordinately bonded to a secondary electron generator, wherein the antiscattering compound is a multimetallic cage bonded to one or more ligands having lone pairs of electrons, the ligands forming coordinate bonds with the secondary electron generator, wherein the secondary electron generator is a metal compound, a metal-containing group or fragment, or has a Z-value greater than or equal to 25. eff Metallic substances.

[0865] 17) A resist composition according to any of the preceding items, wherein the resist composition further comprises a photosensitizing component, wherein the photosensitizing component is optionally a photoinitiator, a photoacid generator, or a photosensitizer.

[0866] 18) The resist composition according to any of the preceding items, wherein the resist composition further comprises a resist crosslinking agent.

[0867] 19) A method for performing photolithography, the method comprising:

[0868] i) Apply a resist coating to the substrate;

[0869] ii) Exposing a portion of the resist coating to radiation to provide exposure to the resist coating;

[0870] iii) Develop the exposed resist coating to produce a resist pattern layer, the resist pattern layer comprising: a portion of the resist coating that is insoluble in the developer (i.e., ridges); and an array of grooves extending through the resist pattern layer;

[0871] iv) Optionally, the substrate, substrate surface, or a portion thereof beneath the resist pattern layer may be modified;

[0872] v) Optionally, the resist pattern layer is removed to provide a modified substrate;

[0873] vi) Optionally, steps iv) and / or i)-v) may be repeated once or multiple times on the modified substrate (optionally replacing the photoresist coating with an alternative photoresist coating, such as a standard photoresist; and optionally using alternative radiation during exposure);

[0874] Optionally, steps (i) to (vi) (i.e., preliminary steps (i)-(vi)) are performed before step (i) of the method, and optionally repeated once or more, using a resist coating or alternative resist coating and using electromagnetic radiation or alternative radiation during exposure;

[0875] The resist coating comprises a resist composition according to any one of items 1) to 18) which is optionally dried and / or cured.

[0876] 20) A method for manufacturing an integrated circuit die or an integrated circuit wafer, the integrated circuit wafer comprising a plurality of integrated circuit dies, the dies or each die comprising a plurality of electronic components, wherein the method comprises:

[0877] i) Apply a resist coating to the substrate;

[0878] ii) Exposing a portion of the resist coating to radiation (e.g., UV) to provide exposure to the resist coating;

[0879] iii) Develop the exposed resist coating to produce a resist pattern layer, the resist pattern layer comprising: a portion of the resist coating that is insoluble in the developer (i.e., ridges); and an array of grooves extending through the resist pattern layer;

[0880] iv) Modifying the substrate, substrate surface, or portion thereof beneath the resist pattern layer (this may include electrically interconnecting the electronic components of the die or each die with conductors);

[0881] v) Remove the resist pattern layer to provide a modified substrate;

[0882] vi) Optionally repeat steps iv) and / or i)-v) once or more on the modified substrate (with the resist coating of the present invention or an alternative resist coating; and optionally use alternative radiation during exposure);

[0883] vii) Optionally, the electronic components of the said or each die are electrically interconnected with conductors (if not yet performed during one or more substrate / substrate surface modification steps) to provide an integrated circuit with external contact terminals;

[0884] viii) Optionally, one or more further finishing steps may be performed;

[0885] ix) Optionally, the integrated circuit die can be separated from a wafer that includes multiple integrated circuit dies;

[0886] Optionally, steps (i) to (vi) of the method (i) (i.e., preliminary steps (i)-(vi), optionally using one of the two steps (i) / (ii)) combination) and / or steps (i) to (vi) of the photolithography method are performed before step (i) of the method, optionally repeated once or more, using the resist coating of the present invention or an alternative resist coating;

[0887] The resist coating comprises a resist composition according to any one of items 1) to 18) which is optionally dried and / or cured.

[0888] 21) An integrated circuit die or an integrated circuit wafer comprising multiple integrated circuit dies, which can be obtained, acquired or directly obtained by the method of manufacturing an integrated circuit die or integrated circuit wafer as described in item 20).

[0889] 22) A method of manufacturing an integrated circuit package, the integrated circuit package including a plurality of pins and an integrated circuit die, the integrated circuit die having external contact terminals electrically connected to corresponding of the plurality of pins, wherein the method includes:

[0890] i) Provide an integrated circuit die according to item 21), or manufacture an integrated circuit die by means of the method according to item 20;

[0891] ii) Attaching the integrated circuit ...

Claims

1. A method for performing photolithography, the method comprising: i) Apply a photoresist coating to the substrate; ii) Expose the photoresist coating portion to radiation to provide exposure to the photoresist coating; iii) Develop the exposed photoresist coating to produce a photoresist pattern layer, the photoresist pattern layer comprising: a coating portion of the photoresist coating that is insoluble in the developer, and an array of grooves extending through the photoresist pattern layer; iv) Optionally, the substrate beneath the photoresist pattern layer may be modified; v) Optionally, the photoresist pattern layer is removed to provide a modified substrate; vi) Optionally, steps iv) and / or i)-v) can be repeated once or more on the modified substrate, optionally with the same photoresist coating or an alternative photoresist coating, and optionally with alternative radiation during exposure. Optionally, steps i) to vi) are performed before step i) of the method, i.e., preliminary steps i)-vi), which may be repeated once or multiple times, using the same photoresist coating or alternative photoresist coating and electromagnetic radiation or alternative radiation during exposure; The photoresist coating comprises a photoresist composition, which optionally is dried and / or cured; The photoresist composition includes an anti-scattering component, wherein the anti-scattering component includes a main metal complex, and the main metal complex is a boron- and silicon-free multi-metal cage and / or multi-metal ring system.

2. The method according to claim 1, wherein modifying the substrate in step iv) includes modifying the substrate surface beneath the photoresist pattern layer.

3. The method of claim 1, wherein modifying the substrate in step iv) includes modifying a portion of the substrate beneath the photoresist pattern layer.

4. The method according to claim 1, wherein the main metal complex is a metal-organic complex.

5. The method according to any of the preceding claims, wherein the main metal complex comprises one or more ligands coordinated with the metallic substance of the main metal complex.

6. The method according to any preceding claim, wherein the main metal complex comprises a plurality of metal ions of at least one type interconnected by one or more bridging ligands.

7. The method of claim 6, wherein one or more bridging ligands bond together the plurality of metal ions of at least one type within the host metal complex.

8. The method according to any one of claims 1-5, wherein the host metal complex comprises a sufficient type and number of ligands to provide an average of at least 4 valence bonds for each individual metal substance within the complex.

9. The method according to any one of claims 1-5, wherein the coordination sites of all metal substances within the host metal complex are completely saturated with ligands.

10. The method according to any one of claims 1-5, wherein all ligands within the host metal complex have coordinating atoms capable of providing more than one pair of lone electrons.

11. The method according to any one of claims 1-5, wherein all ligands are negatively charged except for any solvates.

12. The method according to any one of claims 1-5, wherein all ligands within the host metal complex are coordinated with the metal substance via donor atoms or groups comprising one or more heteroatoms with lone pairs of electrons.

13. The method according to any one of claims 1-5, wherein the main metal complex comprises a mixture of two or more different types of ligands.

14. The method of claim 13, wherein one of the ligand types is monodentate and one of the ligand types is bidentate.

15. The method of claim 5, wherein one or more ligands comprise carboxylate ligands.

16. The method of claim 15, wherein the carboxylate ligand is a bridging ligand that provides bridging between two or more metal substances.

17. The method of claim 5, wherein one or more ligands comprise fluorine ligands.

18. The method according to any one of claims 1-5, wherein the host metal complex comprises a bifunctional ligand, the bifunctional ligand comprising a coordinating atom capable of forming an internal coordination bond with a metal substance within the host metal complex and one or more other coordinating atoms capable of forming an external coordination bond.

19. The method of claim 18, wherein the bifunctional ligand comprises a carboxylate group and an additional nitrogen-containing moiety.

20. The method according to any preceding claim, wherein the main metal complex comprises at least one type of metal ion M. 1 .

21. The method of claim 20, wherein the host metal complex comprises three or more moles of the at least one type of metal ion M per mole of the host metal complex. 1 .

22. The method according to any preceding claim, wherein the main metal complex comprises two or more different types of metal ions M 1 and M 2 M 1 and M 2 Derived from the same metallic element but with different valences, or derived from different metallic elements and having the same or different valences.

23. The method according to any one of claims 20 to 22, wherein the main metal complex is defined by formula I or comprises units defined by formula I: [M 1 x M 2 y …M n zn (mono 1 ) m1 (mono 2 ) m2 …(mono q ) mq (good) 1 ) b1 (good) 2 ) b2 …(by LIG r ) br (opt.) s )(opt. 1 ) o1 (opt.) 2 ) o2… (opt.) s ) os ]; Formula I in: M 1 It is the first metal ion; M 2 It is the second metal ion; M n It is the nth metal ion; monoLIG 1 It is the first monodentate ligand; monoLIG 2 It is the second monodentate ligand; monoLIG q It is the qth monodentate ligand; biLIG 1 It is the first bidentate ligand; biLIG 2 It is the second bidentate ligand; biLIG r It is the r-th bidentate ligand; optLIG 1 It is the first optional additional ligand; optLIG 2 It is a second optional additional / terminal ligand; and optLIG s It is the s-th optional additional / terminal ligand; Each of x, y, zn, m1, m2, mq, b1, b2, br, o1, o2, and os is zero or an integer.

24. The method according to any one of claims 20 to 22, wherein the main metal complex is defined as comprising, per mole of the main metal complex, the following: -x moles of the first metal ion M 1 -y moles of the second metal ion M 2 ; -Optionally, for each additional nth metal ion M in zn moles n ; -m1 moles of the first monodentate ligand monoLIG 1 ; -Optionally, m2 moles of the second monodentate ligand monoLIG 2 ; -Optionally, each additional qth monodentate ligand monoLIG in mq moles q ; -b1 moles of the first bidentate ligand biLIG 1 ; -Optionally b2 moles of the second bidentate ligand biLIG 2 ; -Optionally, each additional r-th bidentate ligand of br molar, biLIG r ; -o1 mole of the first optional additional / terminal ligand optLIG 1 ; -o2 moles of the second optional additional / terminal ligand optLIG 2 ; -os mole for each additional optional s-terminal ligand optLIG s ; Each of x, y, zn, m1, m2, mq, b1, b2, br, o1, o2, and os is zero or an integer.

25. The method of claim 24, wherein the main metal complex is defined as consisting primarily of the following per mole of the main metal complex: -x moles of the first metal ion M 1 -y moles of the second metal ion M 2 ; -Optionally, for each additional nth metal ion M in zn moles n ; -m1 moles of the first monodentate ligand monoLIG 1 ; -Optionally, m2 moles of the second monodentate ligand monoLIG 2 ; -Optionally, each additional qth monodentate ligand monoLIG in mq moles q ; -b1 moles of the first bidentate ligand biLIG 1 ; -Optionally b2 moles of the second bidentate ligand biLIG 2 ; -Optionally, each additional r-th bidentate ligand of br molar, biLIG r ; -o1 mole of the first optional additional / terminal ligand optLIG 1 ; -o2 moles of the second optional additional / terminal ligand optLIG 2 ; -os mole for each additional optional s-terminal ligand optLIG s ; Each of x, y, zn, m1, m2, mq, b1, b2, br, o1, o2, and os is zero or an integer.

26. The method of claim 24, wherein the main metal complex is defined as formed per mole of the main metal complex by mixing, reacting, or otherwise combining the following: -x moles of the first metal ion M 1 -y moles of the second metal ion M 2 ; -Optionally, for each additional nth metal ion M in zn moles n ; -m1 moles of the first monodentate ligand monoLIG 1 ; -Optionally, m2 moles of the second monodentate ligand monoLIG 2 ; -Optionally, each additional qth monodentate ligand monoLIG in mq moles q ; -b1 moles of the first bidentate ligand biLIG 1 ; -Optionally b2 moles of the second bidentate ligand biLIG 2 ; -Optionally, each additional r-th bidentate ligand of br molar, biLIG r ; -o1 mole of the first optional additional / terminal ligand optLIG 1 ; -o2 moles of the second optional additional / terminal ligand optLIG 2 ; -os mole for each additional optional s-terminal ligand optLIG s ; Each of x, y, zn, m1, m2, mq, b1, b2, br, o1, o2, and os is zero or an integer.

27. The method according to any one of claims 23-26, wherein zn, m2, mq, br, o1, o2 and os are 0; and y or b2 is 0.

28. The method according to any one of claims 23-26, wherein zn, m2, mq, br, o1, o2 and os are 0; and y and b2 are 0.

29. The method according to any one of claims 23-26, wherein x, m1, and b1 are non-zero integers; and y or b2 is a non-zero integer.

30. The method according to any one of claims 23-26, wherein x, m1, and b1 are non-zero integers; and y and b2 are non-zero integers.

31. The method according to any one of claims 23 to 30, wherein x is an integer between 1 and 16.

32. The method of claim 31, wherein x is an integer between 4 and 10.

33. The method according to any one of claims 23-26, wherein y is an integer between 0 and 15.

34. The method of claim 33, wherein y is 0 or 1.

35. The method of claim 34, wherein y is 0.

36. The method of claim 34, wherein y is 1.

37. The method according to any one of claims 23 to 36, wherein m1 is an integer between 1 and 20.

38. The method of claim 37, wherein m1 is an integer between 4 and 10.

39. The method according to any one of claims 23 to 38, wherein b1 is an integer between 1 and 20.

40. The method according to any one of claims 23-26, wherein b2 is an integer between 0 and 20.

41. The method of claim 40, wherein b2 is an integer between 0 and 3.

42. The method of claim 41, wherein b2 is 0.

43. The method of claim 41, wherein b2 is 1.

44. The method according to any one of claims 1-21, wherein the main metal complex comprises at most one type of metal ion M. 1 .

45. The method according to any one of claims 20-44, wherein M 1 Choose free Cr III Fe III V III Ga III Al III or In III A group that is formed.

46. ​​The method of claim 22, wherein M 2 Choose freely Ni II Co II Zn II Cd II Mn II Mg II Ca II 、Sr II Ba II Cu II or Fe II A group that is formed.

47. The method according to claim 23 or 24, wherein monoLIG 1 It is a fluoride.

48. The method according to claim 23 or 24, wherein biLIG 1 It is derived from formula R B1 CO2 - Defined carboxylate anion, where R B1 It is the optional substituted hydrocarbon moiety.

49. The method of claim 48, wherein R B1 It is a hydrocarbon group that does not have a basic group or a chelating group.

50. The method of claim 49, wherein R B1 It is a hydrocarbon moiety selected from (1-12C)alkyl, (1-12C)alkenyl, (1-12C)ynyl, (3-8C)cycloalkyl, (3-8C)cycloalkenyl, (1-3C)alkyl(3-8C)cycloalkyl, (1-3C)alkyl(3-8C)cycloalkenyl, aryl, (1-3C)alkylaryl, and aryl(1-3C)alkyl.

51. The method according to claim 23 or 24, wherein biLIG 2 It is derived from formula R B2 CO2 - Defined carboxylate anion, where R B2 It includes a basic group or a chelating group, the basic group or chelating group having a lone pair of electrons, the lone pair of electrons being freely coordinated to form a coordinate bond.

52. The method of claim 51, wherein R B2 It is selected from optionally substituted heterocyclic groups, optionally substituted heteroaryl groups, optionally substituted heterocyclic (1-6C)alkyl groups or optionally substituted heteroaryl (1-6C)alkyl groups.

53. The method of claim 51, wherein R B2 It is selected from (1-12C)alkyl, (1-12C)alkenyl, (1-12C)ynyl, (3-8C)cycloalkyl, (3-8C)cycloalkenyl, (1-3C)alkyl(3-8C)cycloalkyl, (1-3C)alkyl(3-8C)cycloalkenyl, aryl, (1-3C)alkylaryl or aryl(1-3C)alkyl, which are substituted with one or more basic or chelating groups.

54. The method according to any one of claims 51 to 53, wherein the basic group or chelating group is selected from amino, alkylamino, dialkylamino, hydroxyl, (1-6C)alkoxy, carbonyl, imino, mercapto, or thiocarbonyl.

55. The method of claim 51, wherein R B2 It is pyridyl, aminophenyl, N-(1-3C)alkylaminophenyl or N,N-bis(1-3C)alkylaminophenyl.

56. The method of claim 51, wherein biLIG 2 It is an organic or optionally substituted hydrocarbon carboxylate ion with at least one additional heteroatom, said organic or optionally substituted hydrocarbon carboxylate ion being capable of serving as a Lewis base or as a ligand for externally chelating a metal substance to the host metal complex.

57. The method of claim 51, wherein biLIG 2 It is isonicotinic acid.

58. The method according to any one of claims 1-22, wherein the main metal complex is defined by formula II or comprises units defined by formula II: [M 1 x M 2 y (monoLIG 1 ) m1 (O2CR B1 ) 16-b2 (O2CR B2 ) b2 ] Formula II.

59. The method of claim 58, wherein the main metal complex is defined by formula IIa or comprises units defined by formula IIa: [M 1 8-y M 2 y F8(O2CR B1 ) 16-b2 (O2CR B2 ) b2 ] Formula IIa.

60. The method according to any preceding claim, wherein the antiscattering component comprises one or more counterions bound to the host metal complex.

61. The method of claim 60, wherein the one or more counterions comprise one or more cations selected from the group consisting of primary ammonium cations, secondary ammonium cations, tertiary ammonium cations, quaternary ammonium cations, and imidazolium cations.

62. The method according to any preceding claim, wherein the photoresist composition comprises a secondary electron generator, said secondary electron generator having a Z-value greater than or equal to 25. eff Or, a compound or component characterized by a metallic substance having an atomic number greater than or equal to 49 and an oxidation state of +1 or higher, wherein the secondary electron generating agent is: Compounds separated from the anti-scattering component; or With the aid of the attached antiscattering component, wherein the Z of the secondary electron generator eff Calculated by excluding the molecules to which it is attached; Z eff The effective atomic number is calculated as a simple mass-weighted average using the following formula: WITH eff =Σα i WITH i Z i It is the atomic number of the i-th element in the secondary electron generator, and α i It is the fraction of the total atomic number of all atoms in the secondary electron generator that is composed of the i-th element.

63. The method of claim 62, wherein the secondary electron generator is a Lewis acid or a compound derived from a Lewis acid.

64. The method according to any one of claims 62 to 63, wherein the secondary electron generating agent comprises a d-block, p-block, or f-block metallic substance having an atomic number greater than 57.

65. The method according to any one of claims 62 to 64, wherein the secondary electron generating agent is a metal (I), metal (II), metal (III) or metal (IV) halide.

66. The method according to any one of claims 62 to 65, wherein the antiscattering component forms one or more coordinate bonds with the secondary electron generator, such that the secondary electron generator is coordinated with the host metal complex.

67. The method according to any one of claims 62 to 66, wherein one or more ligands of the antiscattering component comprise one or more heteroatoms with lone pairs of electrons coordinated to the secondary electron generator.

68. The method of claim 67, wherein one or more ligands of the antiscattering component coordinated with the secondary electron generator are bifunctional ligands, said bifunctional ligands being derived from formula R B2 CO2 - Defined carboxylate anion, where R B2 It is a group that contains a basic or chelating group selected from the group consisting of: Optionally substituted heterocyclic, heteroaryl, heterocyclic (1-6C)alkyl, or heteroaryl (1-6C)alkyl groups; (1-12C)alkyl, (1-12C)alkenyl, (1-12C)ynyl, (3-8C)cycloalkyl, (3-8C)cycloalkenyl, (1-3C)alkyl(3-8C)cycloalkyl, (1-3C)alkyl(3-8C)cycloalkenyl, aryl, (1-3C)alkylaryl or aryl(1-3C)alkyl group substituted with one or more basic or chelating groups; Pyridyl, aminophenyl, N-(1-3C)alkylaminophenyl or N,N-bis(1-3C)alkylaminophenyl groups; and Isonicotinic acid radical.

69. The method of claim 68, wherein R B2 It is a group that contains a basic or chelating group selected from the group consisting of: (1-12C)alkyl, (1-12C)alkenyl, (1-12C)ynyl, (3-8C)cycloalkyl, (3-8C)cycloalkenyl, (1-3C)alkyl(3-8C)cycloalkyl, (1-3C)alkyl(3-8C)cycloalkenyl, aryl, (1-3C)alkylaryl or aryl(1-3C)alkylalkyl group substituted with amino, alkylamino, dialkylamino, hydroxyl, (1-6C)alkoxy, carbonyl, imino, mercapto or thiocarbonyl groups.

70. The method according to any preceding claim, wherein the photoresist composition comprises one or more photoresist components, wherein: a) The anti-scattering component is the photoresist component; b) The anti-scattering component includes the photoresist component, such that the photoresist component is part of the anti-scattering component, or is combined or connected to the anti-scattering component, whether chemically or physically; or c) The photoresist component is a compound separate from the antiscattering component.

71. The method of claim 70, wherein the host metal complex comprises one or more photoresist components or is otherwise combined with one or more photoresist components, because the one or more photoresist components are photoresist ligands bonded to the host metal complex via coordination donor atoms or groups carried by photoresist ligands.

72. The method of claim 71, wherein the photoresist component is a photosensitive component or otherwise includes a photosensitive component.

73. The method according to claim 72, wherein the photosensitizing component is a photoinitiator, a photoacid-producing agent, or a photosensitizer.

74. The method according to claim 72 or 73, wherein the one or more photoresist components change upon exposure to radiation and are, or otherwise include, a photosensitive component capable of photolysis without the assistance of additional photoinitiators and photocatalysts.

75. The method according to any preceding claim, wherein the antiscattering component is combined with one or more photoresist components such that they together form an antiscattering-resist hybrid component.

76. The method according to any one of claims 1 to 69, wherein the step of exposing the photoresist coating portion to radiation comprises exposing the photoresist coating portion to electromagnetic radiation with wavelengths between 10 nm and 1000 nm.

77. The method of claim 76, wherein the step of exposing the photoresist coating portion to electromagnetic radiation with wavelengths between 10 nm and 1000 nm comprises exposing the photoresist coating portion to electromagnetic radiation with wavelengths between 100 nm and 400 nm.

78. The method of claim 76, wherein the step of exposing the photoresist coating portion to electromagnetic radiation with wavelengths between 10 nm and 1000 nm comprises exposing the photoresist coating portion to electromagnetic radiation with wavelengths between 10 nm and 30 nm.

79. The method according to any preceding claim, wherein the method produces a photomask.

80. The method of claim 79, wherein the photomask is characterized by a transparent region of the surface / substrate juxtaposed with an opaque region of the surface / substrate.

81. The method according to any one of claims 79 to 80, wherein the substrate is a photomask for producing a photomask.

82. The method according to any one of claims 1 to 78, wherein the method produces an integrated circuit die or an integrated circuit wafer comprising a plurality of integrated circuit dies.

83. The method of claim 82, wherein the substrate is an electronic component substrate selected from substrates made of silicon, copper, chromium, iron, aluminum, or glass.

84. The method of claim 83, wherein the substrate is a silicon substrate.

85. A photomask that can be obtained by the method according to any one of claims 79 to 81.

86. An integrated circuit die or an integrated circuit wafer comprising a plurality of integrated circuit dies, which can be obtained by the method according to any one of claims 82 to 84.

87. A method of manufacturing an integrated circuit die or an integrated circuit wafer comprising a plurality of integrated circuit dies, wherein the die or each die comprises a plurality of electronic components, wherein the method comprises: i) Apply a photoresist coating to the substrate; and ii) Expose the photoresist coating portion to radiation to provide exposure to the photoresist coating; as well as iii) Develop the exposed photoresist coating to produce a photoresist pattern layer, the photoresist pattern layer comprising: a coating portion of the photoresist coating that is insoluble in the developer; and an array of grooves extending through the photoresist pattern layer; iv) Modifying the substrate beneath the photoresist pattern layer, which may optionally include electrically interconnecting the die or the electronic components of each die with a conductor; v) Remove the photoresist pattern layer to provide a modified substrate; vi) Optionally repeat steps iv) and / or i)-v) once or more on the modified substrate with the same photoresist coating or an alternative photoresist coating; and optionally use alternative radiation during exposure; vii) Optionally, one or more further finishing steps may be performed; viii) Optionally, the integrated circuit die can be separated from the wafer that includes multiple integrated circuit dies; The photoresist coating comprises a photoresist composition, which optionally is dried and / or cured; The photoresist composition includes an anti-scattering component, wherein the anti-scattering component includes a main metal complex, and the main metal complex is a boron- and silicon-free multi-metal cage and / or multi-metal ring system.

88. The method of claim 87, wherein modifying the substrate in step iv) includes modifying the substrate surface beneath the photoresist pattern layer.

89. The method of claim 87, wherein modifying the substrate in step iv) includes modifying a portion of the substrate beneath the photoresist pattern layer.

90. The method of claim 87, wherein the method further comprises: If this has not been done during one or more substrate modification steps, the die or the electronic components of each die are electrically interconnected with a conductor to provide an integrated circuit with external contact terminals.

91. A method of manufacturing an integrated circuit die or an integrated circuit wafer comprising a plurality of integrated circuit dies, wherein the die or each die comprises a plurality of electronic components, wherein the method comprises: i) Apply a resist coating to the substrate; And providing a photomask by performing the method according to any one of claims 79 to 81 or providing a photomask according to claim 85; and ii) Exposing the resist coating portion to radiation through the photomask to provide exposure of the resist coating; as well as iii) Develop the exposed resist coating to produce a resist pattern layer, the resist pattern layer comprising: a coating portion of the resist coating that is insoluble in the developer; and an array of grooves extending through the resist pattern layer; iv) Modifying the substrate beneath the resist pattern layer, which may optionally include electrically interconnecting the die or the electronic components of each die with a conductor; v) Remove the resist pattern layer to provide a modified substrate; vi) Optionally repeat steps iv) and / or i)-v) once or more on the modified substrate with the same or alternative resist coating, and optionally use alternative radiation during exposure. vii) Optionally, one or more further finishing steps may be performed; viii) Optionally, the integrated circuit die can be separated from the wafer that includes multiple integrated circuit dies.

92. The method of claim 91, wherein modifying the substrate in step iv) includes modifying the substrate surface beneath the resist pattern layer.

93. The method of claim 91, wherein modifying the substrate in step iv) includes modifying a portion of the substrate beneath the resist pattern layer.

94. The method of claim 91, wherein the method further comprises: If this has not been done during one or more substrate modification steps, the die or the electronic components of each die are electrically interconnected with a conductor to provide an integrated circuit with external contact terminals.

95. The method according to any one of claims 87 to 94, wherein steps (i) to (vi) of the method are performed prior to step (i) of the method, optionally repeated once or more, using the same photoresist coating or a photoresist coating or an alternative photoresist coating, and optionally using the same or different radiation.

96. A method of manufacturing an integrated circuit package, the integrated circuit package including a plurality of pins and an integrated circuit die, the integrated circuit die having external contact terminals electrically connected to corresponding of the plurality of pins, wherein the method includes: i) Manufacturing an integrated circuit die by any one of claims 82-84 or 87-95, or providing an integrated circuit die obtained by any one of claims 82-84 or 87-95; ii) Attaching the integrated circuit die to a packaging substrate, wherein the packaging substrate includes electrical contacts, each of which is optionally connected to or can be connected to a corresponding pin; iii) Conductively connect each of the external contact terminals of the integrated circuit die to the corresponding electrical contact of the packaging substrate; iv) Optionally and if necessary, the electrical contacts of the package substrate can be connected to the corresponding pins; v) Package the integrated circuit die.

97. An integrated circuit package obtained by the method of claim 96.

98. A method of manufacturing a circuit board including an integrated circuit package having multiple pins, wherein the method comprises: i) Providing an integrated circuit package as claimed in claim 97 or manufacturing an integrated circuit package by the method as claimed in claim 96; and ii) Conductively connect the integrated circuit package to the circuit board.

99. A circuit board obtained by the method according to claim 98.

100. A method of manufacturing an electronic device or system, the electronic device or system including a power source or connectable to a power source and including a circuit board electrically connected to or connectable to the power source, wherein the method includes: i) Providing a circuit board according to claim 99 or manufacturing a circuit board by the method according to claim 98; and ii) Integrating the circuit board into the electronic device or system.

101. An electronic device or system obtained by the method of claim 100.

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