Gas-releasing underlayer for photo-patternable organometallic resist

Abstract

A gas-releasing composition capable of promoting improved patterning of organometallic resists is described. The gas-releasing composition is capable of releasing water, carbon dioxide, or alcohol in response to radiation or heating. The film-forming composition comprises a fluid blend of a reactive gas-releasing portion, a matrix-forming species, an organic solvent, and an optional activating additive. The underlayer composition comprises a blend of a reactive gas-releasing portion, a polymer matrix, and an optional activating additive. A multilayer structure based on an organometallic radiation-sensitive patterning composition, such as an alkyltin oxo-hydroxo composition, is described, which is disposed to cover the gas-releasing underlayer formed on a substrate such as a semiconductor wafer. A method for patterning the multilayer structure is also described.

Description

[Technical Field]

[0001] The present invention relates to a radiation-patternable coating having a lower layer of a gas-releasing composition capable of promoting improved patterning. [Background technology]

[0002] Semiconductor fabrication generally consists of iterative processing steps including deposition, etching, photopatterning, and pattern transfer. Photopatterning is generally carried out via a lithography process, in which a photosensitive material (i.e., photoresist) is irradiated with an appropriate radiation source such as ultraviolet (UV), extreme ultraviolet (EUV), or an ion beam, inducing a change in solubility in the irradiated material compared to the unirradiated material. Generally, improvements to this photolithographic process are desired, particularly to reduce the cost of device fabrication, reduce component size, and improve pattern fidelity and device performance.

[0003] In the ongoing efforts to reduce the size of devices produced by photolithography, photolithographic systems using EUV with very short wavelengths, capable of forming extremely small images and high-resolution patterns, have been developed. Organometallic coatings have shown usefulness as suitable photoresist materials for achieving high-resolution patterning and are very promising for the commercial use of EUV lithography and even electron beam patterning. To fully utilize the advantages of organometallic resists, improvements and innovations in auxiliary materials, such as underlayers, that enable further improvements in resist pattern fidelity are desired. [Overview of the Initiative] [Means for solving the problem]

[0004] In a first aspect, a film-forming composition is described that includes a fluid blend of a reactive gas-releasing moiety, a matrix-forming species, an organic solvent, and an optional activating additive. The reactive gas-releasing moiety releases metal ligand-forming molecules in response to radiation or heat. When the gas-releasing moiety is stimulated and activated by the activating additive to release a reactive gas, the activating additive is present. The matrix-forming species includes a polymer and / or one or more polymer precursors.

[0005] In a further aspect, a composition is described that includes a blend of a reactive gas-releasing moiety, a polymer matrix, and an optional activating additive, wherein the reactive gas-releasing moiety releases metal ligand-forming molecules in response to radiation or heat. When the gas-releasing moiety is stimulated and activated by the activating additive to release a reactive gas, the activating additive is present. The reactive gas-releasing moiety is bonded to the polymer matrix or blended within the polymer matrix.

[0006] In a further aspect, a multi-layer structure is described that includes a substrate having a surface, an underlying material covering at least a portion of the substrate surface, and a radiation-sensitive organometallic patterning material covering at least a portion of the underlying material. The underlying material includes a polymer and a reactive gas-releasing moiety that may or may not be bonded to the polymer. The reactive gas-releasing moiety releases metal ligand-forming molecules in response to radiation and / or heat.

[0007] In a further aspect, a lower layer structure is formed by coating a composition comprising a reactive gas release portion onto the surface of a substrate to form a lower layer material that covers at least a portion of the surface; depositing an organometallic patterning material onto the lower layer structure to form a multi-layer structure; irradiating the multi-layer structure according to a selected pattern to form a latent image; and heating the irradiated multi-layer structure having the latent image as a post-exposure bake, wherein the lower layer material releases a metal ligand-forming molecule through the lower layer material or a portion thereof in response to irradiation or heating, and the organometallic patterning material or a portion thereof reacts with the metal ligand-forming molecule, and developing the latent image after the post-exposure bake and the reaction with the metal ligand-forming molecule, and a method for patterning a radiation-sensitive organometallic composition is described.

[0008] Another aspect of the present invention relates to a lower layer material capable of releasing a species that can react with a metal oxide photoresist.

[0009] Another aspect of the present invention relates to a lower layer material that releases CO2 upon heating and / or irradiation.

[0010] In a further aspect, a polymeric material comprising a CO2 release portion and a polymer material is described. The CO2 release portion releases CO2 in response to radiation or heat. The polymer material provides a matrix for the CO2 release portion.

[0011] Another aspect of the present invention relates to a lower layer material that releases H2O upon heating and / or irradiation.

Brief Description of the Drawings

[0012] [Figure 1] It is a side view of a multi-layer stack of a substrate, a lower layer, and an irradiated photoresist. [Figure 2A] It is a side view of the multi-layer stack of FIG. 1 in which the lower layer below the irradiated region of the photoresist releases gas. [Figure 2B]This is a side view of a multi-layer stack consisting of a substrate, a lower layer, and a photoresist, where the lower layer uniformly releases gas into the photoresist. [Figure 3] This cartoon illustrates the lower-layer mediated crosslinking of irradiated organosin materials via lower-layer emitted reactive gas species. [Figure 4] This is a plot of the relative amount of CO2 generated per sample for a set of five lower-layer formulations baked at 220°C for 1 minute. [Figure 5] This is a plot of mass percentage as a function of temperature for the lower layer formulation set. [Modes for carrying out the invention]

[0013] Novel compositions providing underlayers that may enable improved processing of organometallic photoresists are described herein. The underlayers may be useful in semiconductor lithographic processing, in which the photoresist material is typically deposited on the surface of the underlayer material to form a multilayer structure, which is then subjected to subsequent processing, such as one or more heating, radiation exposure, development, etching, etc. The objective therein is to form a pattern according to a specified design. The underlayer materials described herein are thermosensitive and / or radiation sensitive, and consequently, they are capable of releasing vapor species, such as H2O, alcohol, and / or CO2, which can react with the photoresist in the multilayer structure. Generally, the released reactive gases contain metal ligand-forming molecules that, when in contact with the irradiated area of ​​the organometallic patterning composition, can promote the stabilization of the metal oxo-hydroxo network and the release of cleaved organic ligands. Depending on the mechanism of vapor release, the timing of the release can be coordinated to a time appropriate to achieve the desired process improvement. Reactions with released species can modify patternability and facilitate / improve the patterning process. The use of the underlying layer can be woven into the overall process flow to suit appropriate commercial utility.

[0014] The lower layer contains a composition selected to release gas based on heat and / or radiation. The lower layer may also contain a matrix, such as a polymer, to be in interface with the gas-releasing composition. The released gas compound is diffusible into the upper layer of the patterning composition. If the gas is released before irradiation, such as via pre-irradiation baking, the gas can modify the patterning composition throughout the layer, and it would be intended to modify the organometallic composition to enhance radiation-based patterning through adjustments to the properties of the material. If the gas is released during or subsequently to irradiation, the gas can differentially modify the irradiated and / or unirradiated patterning composition. If the gas is released by radiation, the gas release will be concentrated beneath the irradiated organometallic composition. If the gas is released thermally following irradiation, the gas is generally released uniformly along the layer, but the gas can react differently with the irradiated and unirradiated compositions, as the patterning composition is modified between the irradiated and unirradiated regions. Interaction with the gas can improve patterning performance by increasing the development contrast.

[0015] Conventional photoresists are composed of organic materials, particularly polymers, and have found use in various applications such as lithography. Significant attention and effort have been focused on improving the performance of conventional polymer photoresists, for example, boosting their photoefficiency, resolution, and pattern fidelity (roughness) against extreme ultraviolet (EUV) radiation. Therefore, improvements have been made to the underlying materials to enhance the performance of multi-layer stacks containing conventional photoresists. However, less attention has been paid to improving the underlying materials for use in organometallic and / or metal oxide photoresists.

[0016] Metal oxides and organometallic photoresists, particularly those containing Sn, have been shown to possess many properties that make them promising for use in high-resolution lithography processes, including high EUV photon absorption, very high resolution, high pattern fidelity, and high etching resistance. For example, organometallic radiation-sensitive resists are approximately given by formula R z SnO(2-z / 2-x / 2) (OH) x (where 0 < x < 3, 0 < z ≤ 2, x + z ≤ 4, and R is a hydrocarbyl group that forms a carbon bond with a tin atom) has been developed based on alkyltin compositions such as alkyltin oxide hydroxides. A particularly effective form of such compositions is monoalkyltin oxide hydroxide where z = 1 in the above formula. Alkyltin-based photoresist materials are described further in U.S. Patent No. 9,310,684 to Meyers et al. entitled “Organometallic Solution Based High Resolution Patterning Compositions” (the ‘684 patent herein), U.S. Patent No. 10,642,153 to Meyers et al. entitled “Organometallic Solution Based High Resolution Patterning Compositions and Corresponding Methods” (the ‘153 patent herein), and U.S. Patent No. 10,228,618 to Meyers et al. entitled “Organotin Oxide Hydroxide Patterning Compositions, Precursors, and Patterning” (the ‘618 patent herein) (each of which is incorporated herein by reference). Organotin patterning compositions are described further below.

[0017] While alkyltin compositions have demonstrated particularly promising results, other organometallic resist compositions have been explored. See, for example, U.S. Patent No. 9,176,377, entitled "Patterned Inorganic Layers, Radiation Based Patterning Compositions and Corresponding Methods," U.S. Patent Publication No. 2013 / 0224652, entitled "Metal Peroxo Compounds with Organic Co-ligands for Electron Beam, Deep UV, and Extreme UV Photoresist Applications," and U.S. Patent Publication No. 2002 / 0076495, entitled "Method of Making Electronic Materials," all of which are incorporated herein by reference. Other organometallic patterning compositions based on various metals are described in U.S. Patent No. 9,372,402B2, entitled "Molecular Organometallic Resists for EUV," granted to Freedman et al. (incorporated herein by reference). Resists containing metal oxide particles with organic coatings are described in U.S. Patent Application Publication No. 2015 / 0234272A1, entitled "Metal Oxide Nanoparticles and Photoresist Compositions," granted to Sarma et al. (incorporated herein by reference). Generally, the underlying materials described herein may be generally useful for organometallic resists.

[0018] Generally, organosin photoresist materials contain radiation-sensitive organic ligands bonded to Sn atoms via Sn-C and / or Sn-carboxylate bonds. While not intended to be limited by theory, it is generally believed that irradiating organosin materials with EUV radiation can break these radiation-sensitive bonds, providing additional crosslinking sites, thereby increasing condensation between tin atoms and promoting the formation of a Sn-O-Sn bond network within the irradiated area. Therefore, the irradiated area of ​​an organosin photoresist is generally more condensed than the unirradiated area. After radiation exposure, such as EUV exposure, and subsequent processing, the unirradiated area may substantially retain Sn-C and / or Sn-carboxylate bonds to the organic ligands, while the irradiated area may have substantially fewer such bonds. Thus, the unirradiated area is generally more hydrophobic than the irradiated area, and selective development of either area can be achieved through a suitable development process.

[0019] Therefore, introducing H2O, alcohols, CO2, and / or other reactive gases capable of reacting with irradiated photoresists may be beneficial in further driving an increase in chemical contrast, i.e., developer contrast, between irradiated and unirradiated areas. Generally, reactive gases include metal ligand-forming molecules. This invention relates to an underlying layer capable of enhancing chemical contrast within an organometallic photoresist.

[0020] The effects of CO2 and other reactive gas species in the process atmosphere on the lithographic performance of organosin photoresists are described in U.S. Patent Application Publication No. 2021 / 0271170, entitled "Process Environment for Inorganic Resist Patterning" (incorporated herein by reference). Treatment with an appropriate concentration of atmospheric CO2 has been found to reduce the radiation dose required to achieve a particular feature size. In organosin photoresists, although we do not wish to be limited by theory, it is thought that the irradiated areas of the material can form hydroxides, oxides, carbonates, and / or bicarbonates, for example, which can enhance the developer contrast between irradiated and unirradiated areas of the material, through reactions with and / or incorporation of H2O, CO2, and / or other species.

[0021] By reacting the irradiated material with a reactive gas, the developer contrast between irradiated and unirradiated areas can be improved. This improved developer contrast allows for developer compositions and processes that can better remove unwanted materials such as scum and / or microbridges, potentially resulting in fewer defect patterns. Alternatively or additionally, the improved developer contrast can consequently reduce the patterning dose required for the desired pattern due to the reduced solubility of the irradiated material.

[0022] Figure 1 schematically depicts a side view of a multilayer structure 100 having a substrate 102, a lower layer 104, and an irradiated photoresist 106. The irradiated photoresist 106 has a latent image along with the irradiated photoresist regions 108 in a patterned manner. In organosin photoresists, as detailed above, irradiation causes cleavage of Sn-C bonds, resulting in a lower C:Sn ratio in the irradiated region compared to the unirradiated region. Generally, higher irradiation doses result in a lower C:Sn ratio, and after irradiation, the irradiated region can increase the Sn-OH and / or Sn-O-Sn concentration by reacting with ambient moisture to drive hydrolysis and condensation processes.

[0023] Figure 2A schematically depicts a side view of a multilayer structure 200 having a substrate 202, a lower layer 204, and an irradiated photoresist 206. The irradiated photoresist 206 has a latent image along with the irradiated photoresist regions 208 in a patterned manner. The lower layer 204 is capable of releasing a reactive gas 210 into the irradiated photoresist regions 208. The reactive gas 210 may have the ability to coordinate to, react with, and / or bind to the Sn portions within the irradiated photoresist regions 208. Figure 2B schematically depicts a side view of a multilayer structure 250 having a substrate 252, a lower layer 254, and a photoresist 206. The photoresist 206 may be irradiated or unirradiated. The lower layer 254 is capable of releasing a reactive gas 260 into the photoresist 206. In some embodiments, the lower layer may uniformly release seeds from its bulk. Bulk release is generally based on the thermal release of the reactive gas. In other embodiments, the lower layer may release seeds only upon irradiation. In some embodiments, the reactive gas may be substantially inactive with respect to the unirradiated areas of the resist.

[0024] In some embodiments, the reactive gas emitted by the underlying layer may include a gas having at least one oxygen atom. Preferred examples of emitted species are CO2, ROH, and H2O. Referring to Figure 3, the organosin photoresist material 304 contains Sn-R bonds, which form a linkage 314 between tin atoms by leaving active sites 308 capable of being cleaved by radiation and / or heating 306 and reacting 310 with the underlying layer emitted reactive gas 312; however, alternatively, the reactive gas 312 can bond to a single Sn atom, while still contributing to the stabilization and hydrophilicity of the material. The underlying materials and compositions disclosed herein are capable of emitting reactive gases that can migrate into the irradiated area of ​​the photoresist and result in increased crosslinking by coordinating and / or bonding to Sn atoms.

[0025] Compositions providing reactive vapor species may be provided in the underlying layer and combined with a matrix such as a polymer. The use of a polymer matrix can provide a processing aid and help provide a desirable surface for the deposition of organometallic patterning compositions. The reactive gas-releasing portion may or may not be bonded to the matrix material. Several suitable reactive gas-releasing compositions can be formed in the underlying layer without using separate matrix materials. As described below, the reactive portion for releasing reactive gas species can be formed in functional groups as part of a larger composition. Unless otherwise explicitly stated in the context, references to reactive gas-releasing compounds may include reactive gas-releasing portions bonded to a polymer or other matrix or matrix-forming compound.

[0026] The emission of reactive gases from the reactive gas emission portion can be incorporated into the entire patterning process. In the radiation-emitting reactive gas emission portion, this would be emitted during the irradiation step. While we do not wish to limit ourselves to theory, the reactive gases can diffuse through the organometallic patterning composition, and the C-Sn bond can be photocleaved, thus facilitating the corresponding reaction. Thermally emitted reactive gases can be emitted during the pre-exposure bake step and / or post-irradiation bake step. Since any emitted vapor species may not readily escape from the material, some reaction with the emitted reactive gas may eventually occur, potentially altering the contrast enhancement between irradiated and unirradiated areas of the patterning composition layer. In subsequent development of the radiation image, the improved contrast enhancement can be utilized to form patterned structures.

[0027] Underlayer forming composition The compositions for forming the underlying film disclosed herein are generally formed from a composition comprising a reactive gas-releasing compound (A), one or more polymers and / or polymer-forming compositions (B), and a solvent (C). In some embodiments, the underlying composition may further contain an optional component (D). The solvent (C) is used in forming the underlying film and is removed following the application of the coating. The optional component (D) may or may not be volatile and may be identified as being 10 wt% or less relative to the solvent (C). The total solvent is identified as the volatile component of the film-forming precursor liquid, which may contain the solvent (C) and any of the volatile components of the optional component (D), and is generally not limited as long as it satisfies the desired properties. The solvent (C) is generally selected based on the solubility of the polymer or polymerizable species and the reactive gas-releasing compound (if it is not bonded to component (B)). The solvent may be aqueous (at least about 10 volume percent water) or organic (non-aqueous) and may contain blends of compounds. Optional component (D) can include suitable soluble additives, such as crosslinking agents, viscosity modifiers, and surfactants. Example 2 illustrates trimethyl orthoformate as a volatile optional component (D) as a dehydrating agent. The amount of solvent is generally selected to provide the desired coating properties based on a deposition approach such as spin coating, so that the liquid has the desired viscosity and the resulting coating has the desired dry thickness after solvent removal. Once the underlayer is formed and dried, the solvent is removed along with any of the volatile optional components (D). The dried underlayer then comprises a reactive gas-releasing compound (A), a polymer-forming composition (B), and any of the non-volatile optional components (D). In some embodiments, the dried underlayer composition comprises about 0.01 wt% to about 20 wt% of the reactive gas-releasing portion, about 50 wt% to about 99 wt% of the matrix-forming component, and about 0 to about 50 wt% of the optional component, such as an activating additive. The proportion of each is carried into the dried composition from the corresponding relative amount in the underlayer-forming composition.

[0028] In some embodiments, the reactive gas-releasing compound can constitute at least about 0.001 wt.% of the total dry composition, at least about 0.01 wt.% of the total dry underlayer composition in some embodiments, at least about 0.1 wt.% of the total composition in some embodiments, and at least about 0.5 wt.% to about 10 wt% of the total dry underlayer composition in other embodiments. Within the range where the gas-releasing portion is bonded to the matrix material, generally a polymer, the weight contribution of the gas-releasing portion can be considered separately from the weight of the rest of the matrix material to evaluate the relative weight in appropriate divisions selected at the chain branching points. In some embodiments, the total solids content of the underlayer-forming solution can be less than about 15 wt%, at least about 0.1 wt% to about 12 wt% in further embodiments, and at least about 0.25 wt% to about 10 wt% in other embodiments. Optional component (D) generally constitutes about 15 wt% or less of the coating solution, at least about 0.1 wt% to about 12 wt% in some embodiments. The remainder of the dry coating is the polymer-forming composition (B). The polymer-forming composition (B) generally constitutes about 15 wt% or less of the coating solution, about 0.1 wt% to about 12 wt% in further embodiments, and about 0.25 wt% to about 10 wt% in other embodiments. Those skilled in the art will see that additional ranges of component compositions within the above express ranges are intended and are within this disclosure.

[0029] The composition for forming the matrix of the underlying film can generally include any suitable film-forming composition, such as a polymer, oligomer, F-containing composition, or Si-containing composition, while also including a reactive gas-releasing compound or a reactive gas-releasing portion bonded to the matrix-forming portion. The desirable matrix composition forms a flat layer for depositing the patterning composition on top of it and also forms good dispersion of the reactive gas-releasing composition (A). When the composition for forming the underlying film contains the reactive gas-releasing compound described herein, improved resist patterning can be achieved. Some examples of film-forming compositions used to form the underlayer composition are described in U.S. Patent Application Publication No. 2020 / 0354575A1 (hereinafter referred to as the '575 application) by Seiko et al., entitled “Film-forming composition, silicon-containing film, and resist pattern-forming method” and in U.S. Patent Application Publication No. 2021 / 0286267A1 (hereinafter referred to as the '267 application) by Abe et al., entitled “Composition, resist underlayer film, and resist pattern-forming method” (both incorporated herein by reference).

[0030] Reactive gas-releasing compounds Compounds suitable for incorporation into a sublayer for the release of metal ligand-forming molecules such as water, alcohol, and carbon dioxide are described. Preferred classes of compounds are described along with specific species that can be incorporated. The following sections describe the incorporation of such compounds into a sublayer along with matrix materials. Generally, any class of reactive gas-releasing compounds can utilize bonds capable of forming derivatives. Some derivatives may be harmless and, for example, can be treated or modified in terms of reactivity, such as the addition of alkyl chains, under appropriate circumstances, but not significantly. Other derivatives may affect solubility, for example, by adding polar groups to promote solubility in polar solvents or nonpolar groups to promote solubility in nonpolar solvents. Further derivatives may provide functional groups to be bonded to the matrix polymer before or during polymerization or crosslinking, and such functional groups can be selected based on the polymer structure. Examples of groups suitable for addition reactions include, for example, alkene, alkyne, carbonyl, or imine groups, but other groups may be suitable with appropriate reaction conditions, crosslinking agents, and / or catalysts.

[0031] water releasing compound With respect to the compounds of the first group, the reactive gas-releasing compounds have the ability to release H2O when heated and / or irradiated. In some embodiments, the reactive gas-releasing compounds capable of releasing H2O include a nitrobenzyl moiety having adjacent hydroxyl groups bonded to an aromatic ring. The basic structure is shown in the following formulas A1-1 to A1-8 and can be described as a radiation-sensitive 2-hydroxymethyl-1-nitrobenzene group or 2-nitrobenzyl alcohol group. The structure is represented by the general formula 4-(CH2OH)-3-NO2-C6H3-R (wherein R is hydrogen, COO - , bonding to polymer, or CR1R2R3 (wherein R 1~3These compounds can individually have aromatic, cyclic, and heteroatoms in their various structures, several embodiments of which are shown below. In further embodiments, the reactive gas-releasing compound capable of releasing H2O includes an onium salt compound, in which case the onium ion supplies a counterion to the H2O-releasing compound. Onium cations, such as triphenylsulfonium cations, can function as photoacid generators, while anions function to release gas species. The reactive gas-releasing compound capable of releasing H2O can be a polymer bond or simply blended with a polymer. Some non-limiting preferred examples of reactive gas-releasing compounds capable of releasing H2O upon heating and / or irradiation are represented by the following compounds (A1-1) to (A1-15). [ka] [ka]

[0032] Under acidic conditions, ethylene glycol and its derivatives can form acetaldehyde, accompanied by the release of water molecules. Photoacid generators (PAGs) can be incorporated into the undercoating, and consequently, generating acid using radiation can trigger the corresponding release of water. PAGs, further discussed below, are activating additives that cooperate in the release of reactive gases in combination with certain reactive gas-releasing compounds. This water release mechanism is related to compounds A1-9 to A1-11, which can also be added to polymers to stabilize their presence in the undercoating. [ka]

[0033] Alcohols can release water under acidic conditions upon heating. Upon water release, the organic product may be an ether or an alkene having a double bond carbon atom. Acidic conditions are achievable by the activation additive PAG in the underlying layer, resulting in acid release upon irradiation. Heat can be applied simultaneously or subsequently to aid in driving water release. Depending on the compound, sufficient heat can be approximately 40°C to 200°C. Representative compounds are shown as A1-12 and A1-13, which can be incorporated into polymers as desired. Similarly, acids generated from PAG compounds can also stimulate the dehydration of oxime (R=N-OH) to form nitriles. Representative compounds of this class are shown as A1-14 and A1-15. [ka]

[0034] The synthesis of compounds A1-2 is described in Example 1 below. Some of the compounds are readily available and can be adapted in appropriate forms or as suitable derivatives to provide incorporation into the underlying structure. The remaining compounds can be synthesized by those skilled in the art based on this example and knowledge of the art.

[0035] The reactive gas-releasing compounds described above can release H2O when the underlying coating substrate is irradiated with radiation, such as UV, EUV, or ion beams. When metal oxide resist materials such as organosin materials are irradiated, reactive sites are generated that can react with H2O to form metal hydroxide and / or metal oxide bonds, which can drive an improved solubility contrast between irradiated and unirradiated areas of the photoresist. Alternatively or additionally, the reactive gas-releasing compounds can release water during heating steps such as post-application bake (PAB) or post-exposure bake (PEB).

[0036] As described below, the lower layer may contain orthoesters. Orthoesters are generally capable of reacting with water to release alcohols. Suitable alcohols for release include, for example, low molecular weight alcohols such as volatile methanol, ethanol, and propanol. Therefore, the use of orthoesters allows for the conversion of water-releasing agents into alcohol-releasing agents in combination. This increases the range of reagent-releasing agents, and further alcohol-releasing agents may be included based on combinations of these agents.

[0037] CO2 releasing compounds In some embodiments, reactive gas-releasing compounds have the ability to release CO2 upon heating and / or irradiation. Specifically, reactive gas-releasing compounds capable of releasing CO2 may include onium salt compounds. Onium cations, such as triphenylsulfonium cations, can function as photoacid generators, while anions function to release gas species. In some embodiments, the reactive gas-releasing compound capable of releasing CO2 is a polymer-bonded moiety. Some CO2-releasing moieties include a functional group having a meldrum acid group (2,2-dimethyl-1,3-dioxane-4,6-dione) that releases carbon dioxide and acetone while forming a reactive ketene through thermal decomposition or radiation absorption. Other compounds incorporate functional groups based on propylene carbonate functional groups. Another class of compounds involves photobase generators having aromatic groups bonded to amines via carbamate linkages. In some embodiments, reactive gas-releasing compounds include more than one type of gas-releasing moiety. Compounds from all three classes are illustrated. Some non-limiting preferred examples of reactive gas-releasing compounds capable of releasing CO2 upon heating and / or irradiation are represented by the following compounds (A2-1) to (A2-14). [ka] [ka] [ka] [ka] [ka]

[0038] Meldrum acid and propylene carbonate (A2-8) are commercially available. Both meltrum acid and propylene carbonate are illustrated below and investigated with respect to CO2 release. A2-9 and A2-10 are derivatives of propylene carbonate and can be synthesized based on U.S. Patent Application Publication 2020 / 0393755A1 (incorporated herein by reference) to Nemoto et al., entitled "Radiation-sensitive resin composition, resist pattern-forming method, compound, and method of controlling acid diffusion." See compound C-1... in the '755 Nemoto application. In the synthesis of compounds A2-1 to A2-7 and A2-11, the meltrum acid functional group is incorporated into the compound. The general synthesis of meldramic acid and related compounds is described in U.S. Patent Application Publication No. 2008 / 0015365, Specification A1, entitled “Method for the production of 1,3-dioxolane-4,6-dione compounds,” to Sato et al. (incorporated herein by reference).

[0039] Photobase generators are commonly described in U.S. Patent No. 8,957,212B2 (hereinafter referred to as the '212 patent) granted to Kuramoto et al., titled "Photobase Generator" (incorporated herein by reference). The '212 patent explicitly describes a family covering compounds A2-12 and A2-13, along with closely related species. A2-12 to A2-14 are illustrated below and investigated with respect to CO2 emission. Photobase generators are also described in Arimitsu et al., “Application to Photoreactive Materials of Photochemical Generation of Superbases with High Efficiency Based on Photodecarboxylation Reactions,” Chemical Materials 2013, 25, 4461-4463 (incorporated herein by reference). The photobase generators in the Arimitsu paper also emit CO2.

[0040] The reactive gas-releasing compounds described above can release CO2 when the underlying coating substrate is irradiated with radiation, such as UV, EUV, or ion beams. When metal oxide resist materials such as organosin materials are irradiated, reactive sites are generated that can react with CO2 to form metal carbonate bonds, which can drive improved solubility contrast between irradiated and unirradiated areas of the photoresist. Alternatively or additionally, the reactive gas-releasing compounds can release CO2 during heating steps such as post-application bake (PAB) or post-exposure bake (PEB). The CO2 released during the heating steps can similarly react with the organosin material.

[0041] The underlying polymer and / or polymer-forming composition The underlying polymer and / or polymer-forming composition (referred to herein as polymer B) can generally include polymers, oligomers, and / or small molecule compositions capable of forming a film composition comprising polymeric structures having one or more desirable structural units. In some embodiments, polymer (B) may be polycondensation compounds and / or compounds obtained by reactions other than polycondensation.

[0042] Generally, the polymer forming the support matrix for the reactive gas-releasing compound (A) can be any of a wide range of polymers, but it may be desirable to utilize existing underlayer compositions that have a proven track record in photolithography. Finally, the underlayer is generally removed at a later stage of the process, where known polymer materials have established suitability in the process environment and throughout the process flow.

[0043] Polymer (B) is illustrated herein as a polymeric composition having at least two structural units, each having a side chain and a main chain. As used herein, “main chain” means the longest chain of atoms in the polymer. As used herein, “side chain” means any chain other than the longest chain of atoms in the polymer.

[0044] Polymer structural components Polymer (B) provides a matrix for reactive gas-emitting species and, more generally, offers stabilization and improved adhesion to organometallic resists. The selection of a suitable polymer can be guided by these properties and by its suitability for radiation patterning equipment and process environments. Given this perspective, it may be useful to adapt polymers with established uses in the field of photolithography technology. In this regard, several classes of polymers are described below.

[0045] In some embodiments, polymer (B) may contain structural units having aromatic rings. In some embodiments, the structural units having aromatic rings may be substituted with fluorine. Suitable structural units having aromatic ring structures include aromatic carbon rings (e.g., benzene rings, naphthalene rings, anthracene rings, indene rings, pyrene rings, fluorenylidene biphenyl rings, fluorenylidene binaphthalene rings, etc.) and aromatic heterorings (e.g., furan rings, pyrrole rings, thiophene rings, phosphole rings, pyrazole rings, oxazole rings, isoxazole rings, thiazole rings, pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, triazine rings, etc.). In some embodiments, polymer (B) contains aromatic carbon rings.

[0046] Some preferred examples of structural units containing compositions having an aromatic ring structure include novolac resins, resol resins, styrene resins, acenaphthylene resins, indene resins, arylene resins, and calixarene resins.

[0047] A preferred example of a novolac resin is a resin obtained by reacting a phenolic compound with an aldehyde compound, a divinyl compound, or the like using an acidic catalyst. Multiple phenolic compounds can be mixed and reacted with aldehyde compounds, divinyl compounds, or the like. Some preferred examples of phenolic compounds include phenols (e.g., phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(3-hydroxyphenyl)fluorene, and 4,4'-(α-methylbenzylidene)bisphenol), naphthols (e.g., α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 9,9-bis(6-hydroxynaphthyl)fluorene), antrols (e.g., 9-antrol), and pyrenols (e.g., 1-hydroxypyrene and 2-hydroxypyrene).

[0048] Some suitable examples of aldehyde compounds for reacting with phenolic compounds include aldehydes (e.g., formaldehyde, benzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, and 1-formylpyrene) and aldehyde sources (e.g., paraformaldehyde and trioxane).

[0049] Some preferred examples of divinyl compounds for reaction with phenolic compounds include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, divinylpyrene, limonene, and 5-vinylnorbornadiene.

[0050] Some preferred examples of novolac resins include: 1) resins having structural units derived from phenol and formaldehyde; 2) resins having structural units derived from cresol and formaldehyde; 3) resins having structural units derived from dihydroxynaphthalene and formaldehyde; 4) resins having structural units derived from fluorenebisphenol and formaldehyde; 5) resins having structural units derived from fluorenebisnaphthol and formaldehyde; 6) resins having structural units derived from hydroxypyrene and formaldehyde; 7) resins having structural units derived from hydroxypyrene and naphthaldehyde; 8) resins having structural units derived from 4,4'-(α-methylbenzylidene)bisphenol and formaldehyde; 9) resins having structural units derived from phenol compounds and formylpyrene; 10) resins of combinations thereof; 11) resins obtained by substituting some or all of the hydrogen atoms of the phenolic hydroxyl group of any of these resins with propargyl groups, etc.; and 12) resins of the same type.

[0051] A preferred example of a resol resin is a resin obtained by reacting a phenolic compound with an aldehyde compound using an alkaline catalyst.

[0052] A preferred example of a styrene resin is a resin having structural units derived from compounds containing aromatic rings and polymerizable carbon-carbon double bonds. In addition to the structural units described above, styrene resins may also have structural units derived from acrylic monomers, vinyl ethers, and the like.

[0053] Some suitable examples of styrene resins include polystyrene, polyvinylnaphthalene, polyhydroxystyrene, polyphenyl (meth)acrylate, and resins that are combinations thereof.

[0054] A preferred example of an acenaphthylene resin is a resin having structural units derived from a compound containing an acenaphthylene skeleton. Some examples of acenaphthylene resins include copolymers of acenaphthylene and hydroxymethylacenaphthylene.

[0055] A preferred example of an indene resin is a resin having structural units derived from a compound containing an indene skeleton.

[0056] A preferred example of an arylene resin is a resin having structural units derived from compounds containing an arylene skeleton. The arylene skeleton is exemplified by phenylene skeletons, naphthylene skeletons, biphenylene skeletons, and the like. Some preferred examples of arylene resins include polyarylene ethers, polyarylene sulfides, polyarylene ethersulfones, polyarylene ether ketones, resins having structural units containing a biphenylene skeleton, and resins having structures containing a biphenylene skeleton and structural units derived from compounds containing an acenaphthylene skeleton.

[0057] Preferred examples of triazene resins are resins having structural units derived from compounds containing a triazene skeleton, such as melamine compounds and cyanuric acid compounds.

[0058] In some embodiments, polymer (B) may contain one or more fluorine-containing structural units, for example, those described in application 267. For example, a preferred fluorine-containing structural unit is given by formula (1): [ka] It can be represented as follows, in which case the repeating unit in parentheses is repeated to provide an appropriate molecular weight or its distribution.

[0059] In equation (1) above, R 1 This represents a monovalent organic group containing fluorine atoms having 1 to 20 carbon atoms, and R 2 represents a monovalent hydrocarbon group having a hydrogen atom or 1 to 20 carbon atoms. A suitable copolymer may contain a non-fluorine-containing structural unit (2) which can have a formula equivalent to (1) except that it does not have a fluorine substituent.

[0060] As used herein, “organic group” means a group containing at least one carbon atom, and this consideration applies to any preferred organic group herein unless otherwise specifically indicated. Preferred examples of monovalent organic groups include monovalent linear or branched hydrocarbon groups having 1 to 20 carbon atoms, such as alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, and their isomers), alkenyl groups (e.g., ethenyl, propenyl, butenyl, and their isomers), alkynyl groups (e.g., ethynyl, propynyl, butynyl), alicyclic groups (e.g., cycloalkyl groups (e.g., cyclopentyl, cyclohexyl), cycloalkenyl groups (e.g., cyclopropenyl, cyclopentenyl, cyclohexenyl), bridged cyclic groups (e.g., norbornyl, adamantyl), and aromatic groups (e.g., aryl groups (e.g., phenyl, tolyl, xylyl, naphthyl), and aralkyl groups (e.g., benzyl, phenethyl, naphthylmethyl).

[0061] In some embodiments, an organic group, for example, R 1The base may include a divalent heteroatom group, such as, for example, -CO-, -CS-, -NH-, -O-, -S-, and / or combinations thereof. In that case, the divalent heteroatom group is bonded between two adjacent carbon atoms of a monovalent hydrocarbon group having 1 to 20 carbon atoms. In some embodiments, the organic group may include a monovalent heteroatom group, such as, for example, a hydroxyl group, a sulfanyl group, a cyano group, a nitro group, a primary amine, a halogen atom, etc. A tertiary amine substituent is also possible.

[0062] R 1 The fluorine atom-containing monovalent organic group having 1 to 20 carbon atoms represented by R is exemplified by a group obtained by substituting one or more hydrogens of the monovalent organic group defined above with fluorine atoms.

[0063] Some preferred examples of the fluorine atom-containing monovalent organic group having 1 to 20 carbon atoms include fluorinated hydrocarbon groups, such as, for example, fluorinated chain hydrocarbon groups (such as, for example, fluorinated alkyl groups, such as, for example, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 2,2,3,3,3-pentafluoropropan-1-yl group, 1,1,1,3,3,3-hexafluoropropan-2-yl group, heptafluoropropan-1-yl group, 2,2,3,3,4,4,4-heptafluorobutan-1-yl group, nonafluorobutan-1-yl group, 3,3,4,4,5,5,6,6,6-nonafluorohexan-1-yl group, and tridecafluorohexan-1-yl group), fluorinated alicyclic hydrocarbon groups (such as, for example, fluorinated cycloalkyl groups, such as, for example, undecafluorocyclohexan-1-yl group and undecafluorocyclohexan-1-ylmethyl group), and fluorinated aromatic hydrocarbon groups (such as, for example, fluorinated aryl groups, such as, for example, 2,4,6-trifluorophenyl group and pentafluorophenyl group, and fluorinated aralkyl groups, such as, for example, pentafluorobenzyl group).

[0064] Further preferred examples of fluorine-containing monovalent organic groups having 1 to 2 carbon atoms include groups containing an oxygen atom and a fluorine atom, for example, a group containing an oxo group and a fluorine atom (e.g., 4,4,4-trifluoro-3-oxobutan-1-yl group), a group containing an ether group and a fluorine atom (e.g., 4,4,5,5,6,6,6-heptafluoro-3-oxahexane-1-yl group), a group containing a hydroxyl group and a fluorine atom (e.g., 2-hydroxy-2-trifluoromethyl-3,3,3-trifluoropropane-1-yl group, 4-hydroxy-4-trifluoromethyl-5,5,5-trifluoropentan-2-yl group, and 3,5-di(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)cyclohexane-1-yl group).

[0065] In some embodiments, R 1 It contains a fluorinated hydrocarbon group, and in some embodiments, R 1 It contains a fluorinated chain hydrocarbon group, and in other embodiments, R 1 This includes a fluorinated alkyl group, and in further embodiments, R 1 It contains a 2,2,2-trifluoroethyl group or a 1,1,1,3,3,3-hexafluoropropan-2-yl group.

[0066] In equation (1) above, R 2 In general, it is possible to include the monovalent hydrocarbon group having 1 to 20 carbon atoms as described above. In some embodiments, R 2 It may contain a hydrogen atom or a linear hydrocarbyl group, and in other embodiments, R 2 It may contain a hydrogen atom or an alkyl group, and in other embodiments, R 2 It may contain a hydrogen atom or a methyl group. 2 Furthermore, as suggested above in relation to general organic groups, it is possible to include heteroatoms.

[0067] In some embodiments, the proportion of structural units (1) contained in polymer (B) relative to the total structural units can be about 1 mol% to about 100 mol%, in other embodiments about 10 mol% to about 90 mol%, in other embodiments about 20 mol% to about 80 mol%, and in further embodiments about 40 mol% to about 75 mol%. The remaining repeating units of polymer (B) may be structural units (2). It will be apparent to those skilled in the art that additional ranges beyond the express range above are intended and within the scope of this disclosure.

[0068] In some embodiments, polymer (B) may contain one or more silicon-containing compounds, such as polysiloxanes. Some preferred examples of silicon-containing compounds are described in the '575 application referenced above. Preferred silicon-containing compounds generally have the formula (H a R b SiO (4-a-b) / 2These can be represented by (wherein a=0, 1, 2, or 3, b=0, 1, 2, or 3, and R is a monovalent organic group, hydroxyl group, or halogen atom having 1 to 20 carbon atoms, and in the case of b=2 or 3, R can be the same or different). These parts can be organized in the polymer to form -Si-O-repeating units along the polymer chain and can form polysiloxanes. Some preferred examples of monovalent organic groups may include monovalent linear or branched hydrocarbon groups having 1 to 20 carbon atoms, such as alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, and their isomers), alkenyl groups (e.g., ethenyl, propenyl, butenyl, and their isomers), alkynyl groups (e.g., ethynyl, propynyl, butynyl), alicyclic groups (e.g., cycloalkyl groups (e.g., cyclopentyl, cyclohexyl), cycloalkenyl groups (e.g., cyclopropenyl, cyclopentenyl, cyclohexenyl), bridged cyclic groups (e.g., norbornyl, adamantyl), and aromatic groups (e.g., aryl groups (e.g., phenyl, tolyl, xylyl, naphthyl), and aralkyl groups (e.g., benzyl, phenethyl, naphthylmethyl).

[0069] In embodiments in which polymer (B) contains one or more silicon-containing moieties, the silicon-containing groups of the polymer contain Si-H bonds, for example, a=1 in the above formula and the following formula: [ka] What is represented by this may be preferable.

[0070] In equations (2) and (3) above, "a" is an integer from 1 to 3, and R 3 represents a hydroxyl group, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms, and b is an integer from 0 to 2. In the case where b is 2, there are two R 3These are either exactly the same or different, and the sum of "a" and "b" is 3 or less. As proposed above, such parts are found in polymers in which double bond oxygen is -Si-O-linked (polysiloxane) along the polymer backbone.

[0071] In the above equations (1-2), c is an integer from 1 to 3, and R 4 represents a hydroxyl group, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms, and d is an integer from 0 to 2. In the case where d is 2, there are two R 2 They are either exactly the same or different, R 5 R5 represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms bonded to 2 Si atoms, and p is an integer from 1 to 3. In cases where p is 2 or greater, multiple R5s are either exactly the same or different, and the sum of c, d, and p is 4 or less.

[0072] R 3 or R 4 A monovalent organic group having 1 to 20 carbon atoms that can be represented by the following are exemplified by: a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent group having 1 to 20 carbon atoms containing a divalent heteroatom-containing group between two adjacent carbon atoms of a monovalent hydrocarbon group; a monovalent group having 1 to 20 carbon atoms obtained by substituting some or all of the hydrogen atoms contained in a monovalent hydrocarbon group with a monovalent heteroatom-containing group or a group containing a divalent heteroatom-containing group; a monovalent group containing -O- in combination with a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent group having 1 to 20 carbon atoms containing a divalent heteroatom-containing group between two adjacent carbon atoms of a monovalent hydrocarbon group, or a monovalent group having 1 to 20 carbon atoms obtained by substituting some or all of the hydrogen atoms contained in a monovalent hydrocarbon group with a monovalent heteroatom-containing group or a group containing a divalent heteroatom-containing group; and so on.

[0073] Examples of exemplary monovalent hydrocarbon groups containing 1 to 20 carbon atoms include monovalent chain hydrocarbon groups having 1 to 20 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms.

[0074] Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms include: alkyl groups, such as methyl and ethyl groups; alkenyl groups, such as ethenyl and ethynyl groups; and alkynyl groups.

[0075] Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include: monovalent monocyclic alicyclic saturated hydrocarbon groups, such as cyclopentyl and cyclohexyl groups; monovalent monocyclic alicyclic unsaturated hydrocarbon groups, such as cyclopentenyl and cyclohexenyl groups; monovalent polycyclic alicyclic saturated hydrocarbon groups, such as norbornyl and adamantyl groups; and monovalent polycyclic alicyclic unsaturated hydrocarbon groups, such as norbornyl and tricyclodecenyl groups.

[0076] Examples of monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include: aryl groups, such as phenyl, tolyl, xylyl, naphthyl, methylnapthyl, and anthryl groups; and aralkyl groups, such as benzyl, naphthylmethyl, and anthrylmethyl groups.

[0077] Heteroatoms constituting divalent heteroatom-containing groups and monovalent heteroatom-containing groups are exemplified by oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, halogen atoms, and the like. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0078] Examples of divalent heteroatom-containing groups include -O-, -CO-, -S-, -CS-, -NR'-, and combinations thereof, where R' represents a hydrogen atom or a monovalent hydrocarbon group. In some embodiments, the divalent heteroatom-containing group is -O-, and in other embodiments, the divalent heteroatom-containing group is -S-.

[0079] Examples of monovalent heteroatom-containing groups include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, amino groups, and sulfanyl groups.

[0080] In some embodiments, R 3 or R 4 The monovalent organic group represented by has about 1 to 10 carbon atoms, and in further embodiments, about 1 to 6 carbon atoms.

[0081] In some embodiments, R 3 or R 4 It contains chlorine atoms.

[0082] In some embodiments, R 3 and R 4 R represents a monovalent group obtained by substituting a monovalent chain hydrocarbon group, a monovalent aromatic hydrocarbon group, or some or all of the hydrogen atoms contained in a monovalent hydrocarbon group with a monovalent heteroatom-containing group. In some embodiments, R 3 and R 4 is independently an alkyl group or an aryl group, and in other embodiments, R 3 and R 4 R is independently a methyl group, an ethyl group, or a phenyl group, and in further embodiments, R 3 and R 4 These are independently either a methyl group or an ethyl group.

[0083] In some embodiments, R 5 R is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms bonded to 2 Si atoms. In some embodiments, R 5These include substituted or unsubstituted divalent aliphatic cyclic hydrocarbon groups having 3 to 20 carbon atoms, and substituted or unsubstituted divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms.

[0084] Some preferred examples of unsubstituted divalent chain hydrocarbon groups having 1 to 20 carbon atoms include: chain saturated hydrocarbon groups, such as methanediyl and ethanediyl groups; and chain unsaturated hydrocarbon groups, such as ethenediyl and propenediyl groups.

[0085] Examples of unsubstituted divalent aliphatic cyclic hydrocarbon groups having 3 to 20 carbon atoms include: monocyclic saturated hydrocarbon groups, e.g., cyclobutanediyl group; monocyclic unsaturated hydrocarbon groups, e.g., cyclobutenediyl group; polycyclic saturated hydrocarbon groups, e.g., bicyclo[2.2.1]heptanediyl group; polycyclic unsaturated hydrocarbon groups, e.g., bicyclo[2.2.1]heptenediyl group, etc.

[0086] Examples of unsubstituted divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenylene groups, biphenylene groups, phenyleneethylene groups, and naphthylene groups.

[0087] R 5 Examples of substituents in a substituted divalent hydrocarbon group having 1 to 20 carbon atoms, represented by , include halogen atoms, hydroxyl groups, cyano groups, nitro groups, alkoxy groups, acyl groups, and acyloxy groups.

[0088] In some embodiments, R 5 R is an unsubstituted chain saturated hydrocarbon group or an unsubstituted aromatic hydrocarbon group. In other embodiments, R 5 This is a methanediyl group, an ethanediyl group, or a phenylene group.

[0089] In some embodiments, "a" is 1 or 2, and in specific embodiments, "a" is 1.

[0090] In some embodiments, "b" is 0 or 1, and in specific embodiments, "b" is 0.

[0091] In some embodiments, "c" is 1 or 2, and in specific embodiments, "c" is 1.

[0092] In some embodiments, "d" is 0 or 1, and in specific embodiments, "d" is 0.

[0093] In some embodiments, "p" is 2 or 3.

[0094] In embodiments in which polymer (B) comprises one or more silicon-containing compounds, the silicon-containing compounds can constitute about 1% to about 99% by mass, about 5% to about 75% by mass in some embodiments, and about 10% to about 50% by mass in further embodiments. Those skilled in the art will see that additional ranges beyond the express range above are intended and within the scope of this disclosure.

[0095] The synthesis of polymer (B) based on the copolymers of the parts shown in formulas (2) and (3) above is presented in the following examples. Further examples are described in the '247 application cited above. In the synthesis of these polymers, orthoesters are used as water scavengers to withstand hydrolysis of the polymer or its precursors, which may cause gelation and modification of the material. These orthoesters are generally removed along with the solvent during solvent removal. These polymers (B) are used in the examples in combination with CO2-releasing agents. Orthoesters are also described herein as alcohol-releasing agents that release alcohol in response to water released from the corresponding water-releasing agent. Based on the same chemical reactivity of the orthoesters, these are distinguishable paths of such compounds.

[0096] Polymer (B) may also contain one or more structural units represented by the following formulas (4) and / or (5). [ka]

[0097] In equations (4) and (5) above, R 6 and R 8 Each independently contains a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 7 and R 9 Each independently comprises a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Preferred examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms are similar to those exemplified above as monovalent hydrocarbon groups having 1 to 20 carbon atoms in Formula 1. Some preferred examples of monovalent organic groups may include monovalent linear or branched hydrocarbon groups having 1 to 20 carbon atoms, such as alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, and their isomers), alkenyl groups (e.g., ethenyl, propenyl, butenyl, and their isomers), alkynyl groups (e.g., ethynyl, propynyl, butynyl), alicyclic groups (e.g., cycloalkyl groups (e.g., cyclopentyl, cyclohexyl), cycloalkenyl groups (e.g., cyclopropenyl, cyclopentenyl, cyclohexenyl), bridged cyclic groups (e.g., norbornyl, adamantyl), and aromatic groups (e.g., aryl groups (e.g., phenyl, tolyl, xylyl, naphthyl), and aralkyl groups (e.g., benzyl, phenethyl, naphthylmethyl).

[0098] In some embodiments, R 6 and R 8 It independently comprises a chain-like hydrocarbon group, and in some embodiments, R 6 and R 8 This independently includes an alkyl group, and in other embodiments, R 6 and R 8 This independently comprises a butane-1-yl group or a 2-ethylhexane-1-yl group.

[0099] In some embodiments, the proportion of individually contained structural units (4) and (5) to the total structural units constituting polymer (B) is about 1 mol% to about 100 mol%, in other embodiments about 5 mol% to about 90 mol%, in other embodiments about 10 mol% to about 75 mol%, and in further embodiments about 20 mol% to about 60 mol%. Those skilled in the art will see that additional ranges beyond these express ranges are intended and within the scope of this disclosure.

[0100] In some embodiments, polymer (B), for example, polymers based on formulas (1), (4), and (5), may contain other structural units. Some examples of such preferred other structural units may include structural units derived from (meth)acrylic acid, acenaphthylene compounds, and the like. In embodiments in which polymer (B) contains other structural units, the upper limit of the proportion of the other structural units contained in polymer (B) to the total structural units can be 0 mol% to about 20 mol%, in other embodiments about 1 mol% to about 15 mol%, and in further embodiments about 5 mol% to about 10 mol%. In some embodiments, the proportion of other structural units contained in polymer (B) may be 0 mol%. Those skilled in the art will see that additional ranges beyond the express range above are contemplated and within the scope of this disclosure.

[0101] In some embodiments, the weight-average molecular weight (Mw) of polymer (B) can be about 1,000 to about 100,000, about 2,000 to about 50,000 in some embodiments, about 3,000 to about 30,000 in some embodiments, and about 4,000 to about 20,000 in further embodiments. It will be apparent to those skilled in the art that additional ranges beyond the express range above are intended and within the scope of this disclosure.

[0102] In embodiments where polymer (B) is a novolac resin, resol resin, styrene resin, acenaphthylene resin, indene resin, arylene resin, or triazene resin, the polystyrene equivalent weight-average molecular weight (Mw) of polymer (B) can be determined by gel permeation chromatography (GPC). In some embodiments, Mw can be about 1,000 to about 100,000, in other embodiments about 2,000 to about 60,000, in further embodiments about 3,000 to about 30,000, and in other further embodiments about 4,000 to about 15,000. It will be apparent to those skilled in the art that additional ranges beyond the express range above are intended and within the scope of this disclosure.

[0103] In some embodiments, the Mw / Mn of polymer B (where "Mn" as used herein means the polystyrene equivalent number-average molecular weight as determined by GPC) can be about 1 to about 5, about 1.1 to about 3 in some embodiments, and about 1.2 to about 2 in other embodiments. It will be apparent to those skilled in the art that additional ranges beyond the express range above are contemplated and within the scope of this disclosure.

[0104] Where referenced herein, the Mw and Mn of polymers are measured by gel permeation chromatography using a GPC column (e.g., two "G2000 HXL", one "G3000 HXL", and one "G4000 HXL" commercially available from Tosoh Corporation) with a differential refractive index detector, under analytical conditions involving monodisperse polystyrene as a standard, a flow rate of 1.0 mL / min, tetrahydrofuran as the eluent, and a column temperature of 40°C.

[0105] Preferred examples of calixarene resins are cyclic oligomers derived from multiple aromatic rings to which hydroxyl groups are bonded by linking them cyclically via hydrocarbon groups, or such cyclic oligomers in which some or all of the hydrogen atoms contained in the hydroxyl groups, aromatic rings, and hydrocarbon groups are substituted.

[0106] Further examples of suitable calixarene resins include cyclic tetramers to dodecamers formed from formaldehyde and phenolic compounds (e.g., phenol or naphthol), cyclic tetramers to dodecamers formed from benzaldehyde and phenolic compounds (e.g., phenol or naphthol), and substituted resins obtained by substituting hydrogen atoms of phenolic hydroxyl groups contained in such cyclic compounds with propargyl groups or the like.

[0107] In some embodiments, the molecular weight of the calixarene resin can be about 500 to about 5,000, in other embodiments about 700 to about 3,000, and in further embodiments about 1,000 to about 1,500. Those skilled in the art will see that additional ranges beyond the express range above are intended and within the scope of this disclosure.

[0108] In some embodiments, the proportion of polymer (B) to the total components other than the organic solvent (C) in the composition for forming the resist underlayer film is about 1% to about 70% by mass, in other embodiments about 3% to about 65% by mass, in other embodiments about 5% to about 60% by mass, in other embodiments about 10% to about 55% by mass, in other embodiments about 15% to about 50% by mass, and in further embodiments about 20% to about 40% by mass. It will be apparent to those skilled in the art that additional ranges beyond these express ranges are intended and within the scope of this disclosure.

[0109] In some embodiments, the proportion of polymer (B) in the composition for forming the resist underlayer film is about 0.01% to about 50% by mass, in other embodiments about 0.1% to about 20% by mass, and in further embodiments about 1% to about 10% by mass. Those skilled in the art will see that additional ranges beyond the express range above are intended and within the scope of this disclosure.

[0110] solvent The organic solvent is not particularly limited, as long as it has the ability to effectively disperse or dissolve the reactive gas-releasing compound (A), polymer (B), and additional optional components. Preferred examples of organic solvents include alcohols, ketones, ethers, esters, nitrogen-containing solvents, hydrocarbons, and combinations thereof. In some embodiments, the organic solvent (C) may comprise one or more solvent types.

[0111] Suitable examples of alcohol solvents include monohydric alcohols such as methanol, ethanol, n-propanol, iso-propanol, butanol, and iso-butanol, as well as polyhydric alcohols such as ethylene glycol and 1,2-propylene glycol.

[0112] Suitable examples of ketone solvents include linear ketones, such as methyl ethyl ketone and methyl isobutyl ketone, and cyclic ketones, such as cyclohexanone.

[0113] Suitable examples of ether solvents include polyhydric alcohol ether solvents (e.g., linear ether solvents, e.g., n-butyl ether), cyclic ether solvents (e.g., tetrahydrofuran, 1,4-dioxane, etc.), and polyhydric alcohol partial ether solvents (e.g., diethylene glycol monomethyl ether).

[0114] Suitable examples of ester solvents include carbonate solvents (e.g., dimethyl carbonate, diethyl carbonate, etc.), acetic acid monoester solvents (e.g., methyl acetate, ethyl acetate, etc.), lactone solvents (e.g., γ-butyrolactone, etc.), polyhydric alcohol partial ether carboxylate solvents (e.g., diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc.), and lactic acid ester solvents (e.g., methyl lactate, ethyl lactate, etc.).

[0115] Preferred examples of nitrogen-containing solvents include linear nitrogen-containing solvents (e.g., N,N-dimethylacetamide) and cyclic nitrogen-containing solvents (e.g., N-methylpyrrolidone).

[0116] Suitable examples of hydrocarbon solvents include aliphatic hydrocarbon solvents (e.g., decalin) and aromatic hydrocarbon solvents (e.g., toluene, xylene).

[0117] In some embodiments, the organic solvent (C) can constitute about 50% to about 99.9% by mass of the total composition for forming the resist underlayer film, in other embodiments about 60% to about 99% by mass of the total composition, and in further embodiments about 70% to about 95% by mass of the total composition. Those skilled in the art will see that additional ranges beyond these express ranges are intended and within the scope of this disclosure.

[0118] Optional ingredients The composition for forming the resist underlayer may further include optional components (D), such as acid generators, such as photoacid generators, orthoesters, additives, such as surfactants, adhesion promoters, or combinations thereof.

[0119] Acidifying agent An acid generator is a component capable of generating acid when exposed to radiation or heat. Examples of acid generators capable of generating acid when exposed to radiation (hereinafter sometimes referred to as "photoacid generating agents" or "photoacid generators (PAGs)") include the acid generators disclosed in paragraphs

[0077] to

[0081] of Japanese Patent Application Publication No. 2004-168748 (incorporated herein by reference), as well as triphenylsulfonium, trifluoromethanesulfonate, and the like. Triphenylsulfonium is an example of an onium ion capable of releasing acid in response to acid or heat. As described above, in certain reactive gas-releasing agents, the acid generator can react with and / or activate the reactive gas-releasing compound to trigger the release of the reactive gas. In such embodiments, the acid generator is also an activating additive. The acid-releasing additive may also be present for other purposes in the lower layers.

[0120] Examples of acid generators capable of generating acid when heated (hereinafter sometimes referred to as "thermal acid generating agents" or "thermal acid generators (TAGs)") include onium salt-type acid generators exemplified as photoacid generators in the patent documents cited above, as well as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl sulfonates. Some of the reactive gas-releasing agents described above contain onium salts, in which case the salts function in a dual role as both counterions to the reactive gas-releasing agent and as acid generators. The acid-releasing moieties, such as sulfonium sulfonates, iodonium sulfonates, N-sulfonimides, and N-sulfonimines, can also be covalently bonded to the side chains of the matrix polymer. Polymers having photoacid generators bonded by covalent bonds are further described in U.S. Patent Application Publication No. 2021 / 011383, entitled “Stabilizing Interfaces of Inorganic Radiation Patterning Compositions on Substrates,” by Cardineau et al. (incorporated herein by reference).

[0121] In cases where the composition contains an acid generator, the upper limit of the acid generator content per 100 parts by mass of compound (B) is 100 parts by mass or less, 40 parts by mass or less in one embodiment, 30 parts by mass or less in another embodiment, and about 0.5 parts by mass to about 25 parts by mass in another embodiment. Those skilled in the art will see that an additional range of acid generators within the above express range is intended and is within the scope of this disclosure.

[0122] Orthoester In some embodiments, the film-forming composition may preferably contain an orthoester. In some embodiments, the film-forming composition may include a polymer-forming composition comprising an orthoester and a silicon-containing compound, such as those described above. In the treatment of such silicon-containing polymers, the orthoester can function as a water-scavenging agent to inhibit the hydrolysis of the polymer, which may be undesirable. As a treatment aid, the orthoester is generally provided in high concentrations and removed with the solvent during solvent removal. The use of orthoesters in polymer underlayers for the treatment of organic photoresists is described in the '575 application cited above. The presence of orthoesters has been found to improve patterning and / or vapor development compared to the use of underlayers without orthoesters. Orthoesters are generally esters of orthocarboxylic acids. Although not wishing to be limited by theory, it is thought that orthoesters drive reactions with water to give carboxylic acid esters, etc. Examples of orthoesters include: orthoformate esters, such as methyl orthoformate, ethyl orthoformate, and propyl orthoformate; orthoacetate esters, such as methyl orthoacetate, ethyl orthoacetate, and propyl orthoacetate; orthopropionate esters, such as methyl orthopropionate, ethyl orthopropionate, and propyl orthopropionate; and so on. In some embodiments, the orthoester is an orthoformate ester. In some embodiments, the orthoester is trimethyl orthoformate.

[0123] Orthoesters are generally removed during the treatment of silicon-containing polymers, but by incorporating them into the polymer along with the water-releasing agents described above, the water-releasing sublayer can be converted into an alcohol-releasing sublayer, and in addition, a polymer that is adequately resistant to water-driven degradation is obtained. In such embodiments, the orthoester can be considered a reactive gas-releasing agent in relation to alcohol-reactive gases. Suitable acrylate-based polymers are described above.

[0124] In cases where the composition contains an orthoester as a dehydrating agent to assist in the processing of silicon-based polymers, the lower limit of the orthoester content per 100 parts by mass of compound (B) can be about 10 parts by mass, about 100 parts by mass in some embodiments, about 200 parts by mass in further embodiments, and about 300 parts by mass in some embodiments. The upper limit of the orthoester content per 100 parts by mass of compound (B) can be about 10,000 parts by mass, about 5,000 parts by mass in some embodiments, about 2,000 parts by mass in further embodiments, and about 1,000 parts by mass in other embodiments. When used as an alcohol-releasing agent in combination with a water-releasing agent, the amount of orthoester can be based on the molar equivalent of the water-releasing agent. The amount may depend on whether it is desired to attempt to convert almost all or effectively all of the released water into alcohol, or only a portion of the released water. In some embodiments, the amount of orthoester can be at least about 1 mol percent based on the molar equivalent of (A), and in further embodiments, it has lower limits of about 10 mol%, about 25 mol%, about 50 mol%, about 75 mol%, about 100 mol%, or about 120 mol%, with upper limits of about 5000 mol%, about 1000 mol%, about 500 mol%, about 250 mol%, or about 200 mol% for any lower limit. It will be apparent to those skilled in the art that additional ranges of orthoesters within the above express ranges are intended and within the scope of this disclosure.

[0125] Optional additives The underlayer film-forming composition may further contain other additives, generally present in amounts of 10% by weight or less each, and in further embodiments, about 5% by weight or less. Those skilled in the art will see that an additional range of additive amounts within the express range is intended and is included in this disclosure. Suitable additives include, for example, viscosity modifiers, crosslinking agents, polymerization catalysts, wetting agents, surfactants, adhesion promoters, other property modifiers, and combinations thereof.

[0126] A lower layer coating is formed. A composition for forming a resist underlayer can be prepared, for example, by mixing a reactive gas-releasing compound (A), a polymer (B), and an organic solvent (C), or any other optional component, in appropriate ratios. The compositions for forming a resist underlayer described herein can be further treated by any suitable means known in the art, such as filtration, to give a high-purity composition for forming the resist underlayer.

[0127] The underlayer can be formed from the underlayer forming composition described herein by treating the underlayer forming composition onto a selected substrate. The substrate generally presents a surface on which the coating material can be deposited, and the substrate may include multiple layers on which the surface relates to the uppermost layer. In some embodiments, the substrate surface can be treated to prepare an adhesive surface for the coating material. The surface can also be cleaned and / or smoothed as appropriate. Suitable substrate surfaces may include any reasonable material. Some substrates of particular interest include, for example, silicon wafers, silica substrates, other inorganic materials, such as ceramic materials, polymer substrates, such as organic polymers, composites thereof, and combinations thereof across the surface of the substrate and / or within layers of the substrate. Wafers, for example, relatively thin cylindrical structures, may be convenient, but any reasonable shaped structure can be used. Substrates having polymer layers on polymer substrates or non-polymer structures may be desirable in certain applications due to their low cost and flexibility, and suitable polymers can be selected based on the relatively low processing temperatures available for processing the patternable materials described herein. Suitable polymers include, for example, polycarbonates, polyimides, polyesters, polyalkenes, copolymers thereof, and mixtures thereof. Generally, especially in high-resolution applications, it is desirable for the substrate to have a flat surface.

[0128] Generally, any suitable solution coating process can be used to deliver the underlayer-forming composition to the substrate. Suitable coating approaches include, for example, spin coating, spray coating, dip coating, knife-edge coating, and printing approaches such as inkjet printing and screen printing. In some embodiments, spin coating is used to deliver the underlayer-forming composition to the substrate.

[0129] After the formation of the underlayer film on the substrate, the underlayer film can be subjected to heating. Heating can complete the removal of volatile components if they were not removed during deposition and during standing before heating. Drying and, optionally, the application of heat can help drive any further polymerization and / or crosslinking of the polymer-forming components. In any heating step involved in underlayer film formation, attention should be paid to the potential thermal reactivity of reactive gas-releasing compounds, and heat may be applied intentionally to partially induce the release of reactive gases. Heating may be useful for more rapidly removing the solvent or for curing or stabilizing the polymer matrix. Heating of the underlayer film can generally be carried out under ambient conditions, but heating can also be carried out in an inert environment, for example, in N2, Ar, which may be desirable in embodiments where the underlayer components are sensitive to ambient gases. In some embodiments, heating can be performed at temperatures of approximately 70°C to 600°C, approximately 100°C to 500°C, approximately 150°C to 400°C, and approximately 200°C to 300°C. In some embodiments, heating can be performed for a duration of approximately 15 seconds to 1,200 seconds, approximately 30 seconds to 600 seconds, and in further embodiments, approximately 45 seconds to 300 seconds. Those skilled in the art will see that additional ranges beyond these express limits are intended and within the scope of this disclosure.

[0130] The thickness of the underlayer film is generally controllable by the deposition conditions and the concentration of the precursor solution. For example, in a spin-coating deposition process, the wafer spin speed is generally tunable to give the desired film thickness. The initial wet film thickness determines the dry film thickness following the removal of volatile components. In some embodiments, the dry underlayer film thickness can be about 5 nanometers (nm) to about 1000 nm, in other embodiments about 10 nm to about 500 nm, and in still other embodiments about 15 nm to about 250 nm. It will be apparent to those skilled in the art that additional ranges beyond these express ranges are intended and within the scope of this disclosure.

[0131] Formation of a resist coating The underlayer materials described herein are particularly useful as underlayer films in the lithographic processing of organometallic photoresists. As described above, some preferred examples of organometallic photoresists include the organotin materials disclosed in the '684, '153, and '618 patents referenced herein. Generally, any preferred deposition method can be used to form a resist coating on the underlayer surface. In some embodiments, a solution deposition method can be used to form the resist coating. Some preferred coating approaches include, for example, spin coating, spray coating, dip coating, knife-edge coating, and printing approaches, such as inkjet printing and screen printing. Some of these coating approaches form a pattern of the coating material during the coating process, but the resolution currently available from printing and the like is significantly lower than the resolution available from radiation-based patterning described herein.

[0132] In some embodiments, vapor-based deposition methods can be used to form a resist coating on the underlying surface. Preferred vapor-based deposition methods are described in the '618 patent referenced above and in U.S. Patent Application Publication 2022 / 0308454 by Weidman et al., entitled "Bake Strategy for Enhancing the Lithographic Performance of Metal-Containing Resists" (incorporated herein by reference). Potential deposition methods include, for example, physical vapor deposition (PVD), chemical vapor deposition (CVD), atomic layer deposition (ALD), or modified forms thereof. For example, one or more gaseous hydrolysis-sensitive organosin compounds can be introduced into a reaction chamber and reacted with a coprecursor or associated decomposition product, such as H2O, either in the gas phase or on the substrate surface, thereby producing a radiation-sensitive organosin oxide hydroxide coating. When hydrolyzable compounds are deposited on the surface by a subsequent hydrolysis reaction, this process can be considered a PVD deposition with in situ hydrolysis; however, if hydrolysis occurs during a continuous deposition process, it can be considered a CVD process. Similarly, when a hydrolyzable precursor is sequentially adsorbed, chemisorbed, or decomposed on the substrate surface, and the corresponding organostin oxide hydroxide is deposited by reacting the residual film with a second reactive precursor via a multiple deposition / reaction cycle, this can be considered an ALD process. In some embodiments, the process may involve combinations of these PVD, CVD, and ALD processes, so the precise terminology may not be as simple as suggested by individual acronyms. Advantages of vapor deposition methods include reduced resist film defect density, improved thickness, and compositional uniformity, as well as conformal and sidewall coating of the substrate topography. Disadvantages of vapor deposition include deposition on chamber components other than the substrate, limitations on the formation of more complex layer compositions, the need for more specialized process equipment, and limitations on sufficiently volatile precursors.

[0133] In some embodiments, the wafer can be spun at speeds of approximately 500 rpm to approximately 10,000 rpm, in further embodiments approximately 1,000 rpm to approximately 7,500 rpm, and in other embodiments approximately 2,000 rpm to approximately 6,000 rpm. The spinning speed can be adjusted to obtain the desired coating thickness. Spin coating can be performed for approximately 5 seconds to approximately 5 minutes, and in further embodiments approximately 15 seconds to approximately 2 minutes. Initial bulk spreading of the composition across the substrate can be performed using an initial low-speed spin, for example, 50 rpm to 250 rpm. To remove any edge beads, back-side rinsing, edge bead removal steps, etc., can be performed with water or other suitable solvents. Those skilled in the art will see that additional ranges of spin coating parameters within the express ranges described above are intended and are within the scope of this disclosure.

[0134] The thickness of a resist coating can generally be a function of the deposition process parameters. For example, in spin coating, the resist coating thickness may depend on the precursor solution concentration, viscosity, and the spin speed used for spin coating. In other coating processes, the thickness can also generally be adjusted through the selection of coating parameters. In some embodiments, it may be desirable to use a thin coating to facilitate the formation of small, high-resolution features in subsequent patterning processes. For example, the dried coating material can have an average thickness of about 1 micron or less, about 250 nanometers or less (nm) in other embodiments, about 50 nm or less in further embodiments, about 1 nm to about 40 nm in other embodiments, a monolayer to about 50 nm in other embodiments, and about 2 nm to about 25 nm in some embodiments. It will be apparent to those skilled in the art that an additional range of thicknesses beyond the above express ranges is intended and is within this disclosure.

[0135] The thickness can be evaluated using non-contact X-ray reflectivity and / or ellipsometry methods based on the optical properties of the film. Generally, the coating is relatively uniform to facilitate processing. In some embodiments, the variation in coating thickness is less than or equal to ±50% from the average coating thickness, less than or equal to ±40% in further embodiments, and less than or equal to about ±25% compared to the average coating thickness in other embodiments. In some embodiments, for example, in highly uniform coatings on larger substrates, the evaluation of coating uniformity can be evaluated with a 1-centimeter edge exclusion, i.e., coating uniformity is not evaluated for portions of the coating within 1 centimeter from the edge. Those skilled in the art will see that any additional range beyond the express range above is intended and within the scope of this disclosure.

[0136] After the initial formation of the coating, the coated substrate can be heated in a post-application bake (PAB) process to drive densification of the resist coating. In embodiments in which heat is applied, the coating material can be heated to temperatures of about 45°C to about 300°C, about 55°C to about 255°C in other embodiments, and about 65°C to about 225°C in further embodiments. PAB can generally be carried out for at least about 0.1 minutes, about 0.5 minutes to about 30 minutes in further embodiments, and about 0.75 minutes to about 10 minutes in other embodiments. It will be apparent to those skilled in the art that additional ranges of heating temperatures and times within the express range above are intended and within the scope of this disclosure.

[0137] Exposure and patterning Following hydrolysis, condensation, and drying, the coating material can be finely patterned using radiation. Radiation absorption causes energy absorption capable of breaking the Sn-C bonds between the metal and organic ligands, rendering at least some of the organic ligands no longer available for stabilizing the material. Radiolysis products, including organic ligands or their fragments, may or may not diffuse from the film, depending on the process variables and the identity of such products. With sufficient radiation absorption, the exposed coating material condenses, i.e., forms an enhanced metal oxo-hydroxo network, which may involve additional water absorbed from the process atmosphere. Radiation can generally be delivered according to a selective pattern. The radiation pattern can be transformed into a corresponding pattern or latent image in the coating material, which has irradiated and unirradiated regions. The irradiated region includes the chemically modified coating material, while the unirradiated region generally includes the as-formed coating material. When the coating material is developed, either with the removal of the unirradiated coating material or, alternatively, with the selective removal of the irradiated coating material, as described below, very smooth edges can be formed.

[0138] Radiation is generally directional to a coated substrate via a mask, or the radiation beam is scannable so as to be controlled across the substrate. Generally, the radiation may include electromagnetic radiation, electron beams (beta rays), or other suitable radiation. Generally, electromagnetic radiation may have a desired wavelength or wavelength range, such as visible radiation, ultraviolet radiation, or X-ray radiation. The achievable resolution of the radiation pattern generally depends on the radiation wavelength, and higher resolution patterns are generally achievable with shorter wavelength radiation. For this reason, it may be desirable to use ultraviolet light, X-ray radiation, or electron beams, especially to achieve high resolution patterns.

[0139] In accordance with the international standard ISO 21348 (2007) (incorporated herein by reference), ultraviolet light spans wavelengths from 100 nm to less than 400 nm. Krypton fluoride lasers can be used as 248 nm ultraviolet light sources. The ultraviolet range can be subdivided in several ways under recognized standards, including extreme ultraviolet (EUV) from 10 nm to less than 121 nm and far ultraviolet (FUV) from 122 nm to less than 200 nm. The 193 nm line from argon fluoride lasers can be used as an FUV radiation source. EUV light has been used in 13.5 nm lithography, and this light is generated from Xe or Sn plasma sources excited with high-energy lasers or discharge pulses. Soft X-rays can be defined from 0.1 nm to less than 10 nm.

[0140] Electromagnetic radiation dose can be characterized by the fluence or dose obtained from the integrated radiation flux with respect to exposure time. A suitable radiation fluence is approximately 1 mJ / cm². 2 ~Approx. 150mJ / cm 2 In further embodiments, approximately 2 mJ / cm² 2 ~Approx. 100mJ / cm 2 In further embodiments, approximately 3 mJ / cm² 2 ~about 50mJ / cm 2 It is possible. A person skilled in the art will see that an additional range of radiation fluence within the express range described above is intended and falls within the scope of this disclosure.

[0141] In electron beam lithography, the electron beam generally induces secondary electrons that modify the irradiated material as a whole. Resolution can be a function, at least in part, of the range of secondary electrons in the material, and higher resolution is generally thought to result from a narrower range of secondary electrons. Based on the high resolution that can be achieved in electron beam lithography using the inorganic coating materials described herein, the range of secondary electrons in inorganic materials is limited. The electron beam can be characterized by its energy, and preferred energies can be in the range of about 5 V to about 200 kV (kilovolts), and in further embodiments, about 7.5 V to about 100 kV. The proximity-corrected beam dose at 30 kV is about 0.1 microcoulombs / cm² to about 5 millicoulombs / cm² (mC / cm²). 2 In further embodiments, approximately 0.5 μC / cm² 2 ~about 1mC / cm 2 In other embodiments, approximately 1 μC / cm² 2 ~100 μC / cm 2 It is possible to be within this range. Those skilled in the art will be able to calculate the corresponding doses at other beam energies based on the teachings herein, and will see that an additional range of electron beam properties within the above express range is intended and is also within this disclosure.

[0142] During irradiation, some radiation can penetrate the resist coating and enter the underlying coating, driving the release of reactive gases such as H2O and / or CO2. These reactive gases can then migrate into the resist coating and react with reactive metal centers created as a result of the irradiation. For example, released water can react with metal centers to create metal oxide and hydroxide moieties, and released CO2 can react with metal centers to drive the formation of metal carbonate and bicarbonate moieties. In some embodiments, the underlying layer can release unstable reactive gases capable of reacting with and / or coordinating with the organosin photoresist during or after irradiation. For example, certain reactive gases can be released thermally, for example, during a post-exposure baking step, to promote condensation of the irradiated material following irradiation. In some embodiments, irradiation can be carried out with an EUV source, in other embodiments, with an ultraviolet source, and in other embodiments, with an ion source. In some embodiments, a second irradiation with an ultraviolet or visible radiation source can be carried out after the initial EUV irradiation step. A second irradiation with an ultraviolet or visible radiation source may be performed before or after the post-exposure bake step described below. In such a secondary irradiation step, the underlying layer can release reactive gases into the resist layer to drive beneficial reactions that can boost the development contrast. For example, the release of water into the irradiated patterning material after EUV irradiation can enhance hydrolysis in the irradiated area, i.e., increase the Sn-OH concentration. In some embodiments, the substrate can be heated during the second irradiation step using an ultraviolet or visible radiation source. In embodiments where the substrate is heated with ultraviolet or visible radiation, the substrate can be heated to about 45°C to about 300°C, in other embodiments about 50°C to about 250°C, in further embodiments about 60°C to about 220°C, and in other embodiments about 100°C to about 200°C. With respect to these ranges, preferred ranges explicitly include any combination of these upper and lower temperature limits, such as about 100°C to about 300°C. Those skilled in the art will see that an additional range of heating temperatures within the express range described above is intended and is also included in this disclosure.

[0143] Based on the design of the coating material, a significant contrast in material properties can exist between the irradiated region with the condensed coating material and the unirradiated coating material containing substantially intact organic ligands. While the contrast at a given dose can be improved by post-irradiation heat treatment, it has been found that in some embodiments, satisfactory results can be achieved without post-irradiation heat treatment. Post-exposure baking (PEB) may be desirable to anneal the irradiated coating material and increase its condensation without significantly condensing the unirradiated region of the coating material based on the thermal breakdown of organic ligand-metal bonds. In suitable embodiments, reactive gases in the underlying layer can be thermally released during post-exposure baking. In such embodiments, suitable temperatures for reactive gas release may influence the selectable temperature for post-exposure baking, although these temperatures are generally still within the following ranges. In embodiments where a PEB is used, the post-irradiation heat treatment can be carried out at temperatures of approximately 45°C to approximately 300°C, approximately 50°C to approximately 250°C in other embodiments, approximately 60°C to approximately 220°C in further embodiments, and approximately 100°C to approximately 200°C in other embodiments. With respect to these ranges, preferred ranges explicitly include any combination of these upper and lower temperature limits, such as approximately 100°C to approximately 300°C. Post-exposure heating can generally be carried out for at least approximately 0.1 minutes, approximately 0.5 minutes to approximately 30 minutes in further embodiments, and approximately 0.75 minutes to approximately 10 minutes in other embodiments. It will be apparent to those skilled in the art that additional ranges of post-irradiation heating temperatures and times within the express ranges above are intended and within the scope of this disclosure. In embodiments in which the second irradiation step is carried out with ultraviolet or visible light after the PEB, the second PEB can be carried out after the second irradiation step under conditions similar to those described above. The high contrast properties of the material further promote the formation of high-resolution lines with smooth edges in the developed pattern, as described in the following sections.

[0144] In some embodiments, the reactive gas-releasing compound in the resist layer can release reactive gases when heated, such as during the PEB step. As described above, irradiation of the resist coating can induce the formation of polymeric metal oxide / hydroxyl species and / or metal carbonate / bicarbonate species that are resistant to subsequent development steps by inducing the formation of reactive metal centers that readily react with water and / or CO2.

[0145] developing After patterning the resist coating with a suitable radiation source, the resist can then be developed with a suitable developer solution. Several developer compositions useful for such organostin oxide photoresists are described in U.S. Patent Application Publication 2020 / 0326627A1 (Application 627) by Jiang et al. (incorporated herein by reference). These compositions, containing both metal oxide hydroxides and organic ligands, have been shown to achieve both positive and negative tone patterning in organostin oxide hydroxide systems. For example, when an organic solvent is used as the developer, unexposed material is dissolved and removed, while exposed material remains, resulting in negative tone patterning. In contrast, when an aqueous acid or base solution, for example containing tetraalkylammonium hydroxide, is used as the developer, exposed material is dissolved and removed, while unexposed material remains, resulting in positive tone patterning.

[0146] In negative tone imaging, the developer may contain organic solvents, such as the solvent used to form the precursor solution. The developer solvent can also contain one or more solvents in the blend composition. Generally, the selection of a suitable developer solvent composition may be influenced by solubility parameters for both irradiated and unirradiated coating materials, as well as the volatility, flammability, toxicity, viscosity, and potential chemical interactions of the developer with other process materials. Specifically, suitable developer solvents include, for example, aromatic compounds (e.g., benzene, xylene, toluene), esters (e.g., propylene glycol monomethyl acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone), alcohols (e.g., 4-methyl-2-pentanol, 1-butanol, isopropanol, 1-propanol, methanol), ketones (e.g., methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, 2-octanone), and ethers (e.g., tetrahydrofuran, dioxane, anisole). The developer composition may further include one or more organic acids, such as carboxylic acids (e.g., formic acid, acetic acid, pivalic acid, oxalic acid, etc.), as described in the '627 application referenced above. Development may be carried out for about 5 seconds to about 30 minutes, in further embodiments for about 8 seconds to about several minutes, and in other embodiments for about 10 seconds to about 10 minutes. It will be apparent to those skilled in the art that any additional range beyond the express range above is contemplated and falls within the scope of this disclosure.

[0147] In positive tone imaging, the developer can generally contain an aqueous acid or a base. In some embodiments, an aqueous base can be used to obtain a sharper image. To reduce developer contamination, it is sometimes desirable to use a developer that does not contain metal atoms. For this reason, quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof are preferred as developers. Generally, quaternary ammonium hydroxides of particular interest can be represented by the formula R4NOH (wherein R = methyl group, ethyl group, propyl group, butyl group, or combination thereof). The coating materials described herein can generally be developed with the same developers currently commonly used for polymer resists, specifically tetramethylammonium hydroxide (TMAH). Commercially available TMAH is available at 2.38 weight percent, and this concentration is suitable for use in the processes described herein. Furthermore, mixed quaternary tetraalkyl-ammonium hydroxides can be used. Generally, the developer may contain about 0.5 to about 30 weight percent of tetraalkylammonium hydroxide or similar quaternary ammonium hydroxide in a further embodiment of about 30 to about 25 weight percent, and in other embodiments of about 1.25 to about 20 weight percent of tetraalkylammonium hydroxide. It will be apparent to those skilled in the art that an additional range of developer concentrations within the express range above is intended and within the scope of this disclosure.

[0148] Furthermore, it has been discovered that solvent-free development, also known as dry development, can be used with organosin materials. Examples of dry development include the selective removal of irradiated or unirradiated areas of a photoresist by exposing the material to a suitable plasma or a suitable flowing gas. Dry development of organosin resists is described in the international publication 2020 / 132281A1 by Volosskiy et al., titled "Dry Development of Resists," and in the pending U.S. Provisional Patent Application No. 63 / 247,885 by Cardineau et al., titled "High-Resolution Latent Image Processing and Thermal Development" (both incorporated herein by reference). In such dry development processes, development can be achieved by subjecting the irradiated substrate to a plasma process or thermal process while flowing a gas containing a suitable developer composition, such as a halid composition (e.g., containing F, Cl, Br, I), alcohol, carboxylic acid, amine, etc.

[0149] Following development, the developed structure can generally be dried by heating the structure at a suitable temperature for a desired amount of time. The temperature of this final drying step is not particularly limited. In some embodiments, annealing can be 100°C to 500°C, in other embodiments 200°C to 500°C, and in further embodiments 300°C to 400°C. Those skilled in the art will see that additional ranges beyond the express range above are intended and within the scope of this disclosure. [Examples]

[0150] Example 1: Synthesis of reactive gas-releasing compounds This example demonstrates the synthesis of compound A1-2.

[0151] Methyl 4-formyl-3-nitrobenozate (nitrobenozate) (3.9 g) was dissolved in EtOH (100 mL). The solution was cooled to 0°C. Then, sodium boride (0.2 g) was added while stirring, and the contents were warmed to room temperature. After stirring the contents at room temperature for 6 hours, the solvent was removed under vacuum, and the mixture was further purified by Et2O extraction. After ether removal, the crude product compound was obtained as a colorless liquid. The crude material was further purified by silica column chromatography using a solvent blend of 50 vol% hexane and 50 vol% ethyl acetate. The collected fraction was dissolved in a mixture of MeOH (50 mL) and tetrahydrofuran (THF) (50 mL), and then aqueous KOH (100 g) was added. The mixture was refluxed for 5 hours, and then the solvent was removed under vacuum. Then, 2 M aqueous HCl was added and the mixture was stirred at room temperature for 30 minutes. The HCl solution was extracted with dichloromethane, and the solvent was removed under vacuum. Next, the obtained material was dissolved in dichloromethane (20 mL), triphenylsulfonium chloride (1.0 g), and aqueous NaHCO3 (1.0 M, 20 mL). The mixture was stirred for 3 hours. Then, 50 mL of dichloromethane was added. The product was extracted, and the solvent was removed again under vacuum. The product compound was characterized by 1H NMR.

[0152] Example 2: Synthesis of polymer composition This example illustrates the two-part synthesis of a polymer composition for use in a lower layer composition.

[0153] Part A: Synthesis of polycarbosilane (compound b-1) precursor polymer This synthesis followed the procedure in the '575 application' cited above. 5.83 g of magnesium powder and 11 g of tetrahydrofuran were charged into a nitrogen-purged first reaction vessel. The mixture was kept at 20°C and stirred until well blended. In separate vessels, monomer solutions were prepared by dissolving 17.38 g of dibromomethane (0.10 mol) and 13.54 g of trichlorosilane (0.10 mol) in 111 g of tetrahydrofuran. The monomer solutions were added dropwise to the first reaction vessel while stirring and maintaining a nitrogen-purged environment. The dropwise addition took approximately 1 hour to complete. Subsequently, the mixture was heated to 40°C and reacted for 1 hour. Then, the mixture was heated to 60°C and reacted for another 3 hours. Next, 67 g of tetrahydrofuran was added to the reaction mixture, and then the mixture was cooled to approximately 0-10°C to obtain the polymerization reaction solution. While stirring, 30.36 g of triethylamine aliquots were added to the polymerization reaction solution, followed by the dropwise addition of 9.61 g of methanol. The dropwise addition took approximately 10 minutes to complete. Subsequently, the mixture was heated to 20°C and reacted for 1 hour. The reaction solution was poured into 220 g of diisopropyl ether to form a crude product as a precipitate. The crude product was collected by filtration, and the solvent was removed from the crude product using an evaporator. The obtained material was mixed with 50 g of diisopropyl ether. The solid material was collected by filtration, and the residual solvent was removed using an evaporator to obtain 63 g of polycarbosilane (compound B-1) as a white solid with a weight-average molecular weight of 900 as measured by gel permeation chromatography (GPC). A polycarbosilane solution was prepared by adding 900 ml of methyl isobutyl ketone to 63 g of compound B-1. [ka]

[0154] Part B: Synthesis of polymer composition (compound B-1) 100 g of the polycarbosilane solution in diisopropyl ether obtained in Part A and 90 g of methanol were charged into the reaction vessel. The contents were heated to 30°C, and then 8 g of 3.2% by mass aqueous oxalic acid solution was added dropwise to the reaction vessel with stirring. The dropwise addition required approximately 20 minutes to complete. Subsequently, the mixture was heated to 40°C and reacted for 4 hours. The mixture was then cooled to approximately 20-30°C. Next, 99 g of diisopropyl ether and 198 g of water were added to the reaction vessel and liquid separation extraction was performed. 0.26 g of oxalic acid dihydrate and 396 g of propylene glycol monomethyl ether acetate were added to the resulting organic layer with stirring. The volume of the solution was reduced by approximately half using an evaporator to remove the water, diisopropyl ether, alcohol, and excess propylene glycol monomethyl ether acetate (PGMEA) produced by the reaction. To the resulting solution, which is thought to retain approximately half the volume of PGMEA, 19.82 g of trimethyl orthoformate was added. Trimethyl orthoformate was used as a dehydrating agent. The mixture was heated to 40°C and reacted for 1 hour. The mixture was then cooled to approximately 20-30°C, and 99 g of propylene glycol monomethyl ether acetate was added while stirring. To remove the ester and alcohol produced by the reaction, unreacted trimethyl orthoformate, and excess propylene glycol monomethyl ether acetate, the volume of the solution was reduced to approximately half using an evaporator to give a 5% by mass solution of the polymer composition (compound B-1) in propylene glycol monomethyl ether acetate. 0.5 g of the compound B-1 solution was baked at 250°C for 30 min, and the mass of the resulting residue was measured. The concentration (by mass) of the solution was determined by dividing the mass of the residue by the mass of the solution used (0.5 g). Compound B-1 is represented by formula (B-1), where the subscript "w" represents the relative ratio of repeating units cross-linked via Si-O-Si bonds, with w+x=1. The weight-average molecular weight of compound B-1 was 2,500 when measured by gel permeation chromatography. [ka]

[0155] Example 3: Lower layer composition This example describes the preparation of a set of lower-layer formulations utilizing the polymer prepared according to Example 2.

[0156] Lower formulations J-1 to J-3 were prepared by mixing the reactive gas-releasing compound (A), polymer compound (B), solvent (C), and orthoester (D) according to Table 1. Lower formulation J-0 was prepared by mixing the polymer compound (B), solvent (C), and orthoester (D) according to Table 1. Polymer compound (B) is provided as a 5% by mass solution by the preparation described in Example 2. In each formulation, the amount of component (B) refers to the mass of neat polymer, and the mass of component (C) refers to the total mass of propylene glycol methyl ether acetate (PGMEA) solvent, including the PGMEA solvent contained in the solution of compound (B). Each formulation was filtered through a 0.2 μm syringe filter.

[0157] [Table 1]

[0158] Example 4: Lithographic performance This example describes the lithographic performance of a photoresist deposited on a set of underlayer films prepared using the underlayer formulation described in Example 3.

[0159] Each of the formulations shown in Table 3 was individually spin-coated onto one of four 300mm Si wafers using the TEL CLEAN wafer track and baked at 220°C for 1 minute to provide a set of undercoated wafers. Each undercoat had a thickness of approximately 10 nm. Next, Inpria YATU1011 photoresist was deposited onto each undercoated wafer by spin-coating. The wafers were baked at 100°C for 1 minute. Each resist film had a thickness of approximately 22 nm. The films were EUV-exposed using an ASML NXE Twin Scan 3400 exposure tool with a dose meander exposure scheme of 50 mJ to 142 mJ, a target critical dimension (CD) of 22 nm, and a Hex Pillar mask with an xy pitch of 66 nm to 38 nm (Px66y38). The underlayers were expected to emit H2O as a result of irradiation. After EUV exposure, each wafer was baked at 180°C for 1 minute. Each wafer was developed with 5 vol.% acetic acid in PGMEA, followed by a final hard bake at 250°C for 1 minute. The exposure field was measured by CD-SEM. Capture images of target 22 nm CD pillars of the Px66y38y pattern were analyzed using LCDU, and the results are shown in Table 2 below. LCDU is local critical dimension uniformity, which is used in EUV patterning to evaluate arrays of features, such as variations in critical dimensions between adjacent holes or pillars in the array. LCDU evaluation is described, for example, in Kong et al., “Measuring Local CD Uniformity in EUV vias with scatterometry and machine learning,” 2020, Proc. of SPIE Vol.11325 113251I-1 (incorporated herein by reference).

[0160] [Table 2]

[0161] The data in Table 2 shows that samples prepared with an additive-containing underlayer (samples S-1 to S-3) achieved a 22 nm CD of the selected pattern at a lower dose than the sample prepared without an additive-containing underlayer (S-0). The results suggest that additives in the underlayer can improve the sensitivity of the resist without increasing the LCDDU. The data also shows that the LCDDU of samples with higher additive-loaded underlayers (S-2 and S-3) was lower than that of the unadditive-loaded underlayer (S-0). These results suggest that additives in the underlayer can enhance lithographic performance by promoting both increased resist sensitivity and lower patterned feature roughness.

[0162] Example 5: Formulation study This example illustrates the effects of additive composition and treatment temperature on the amount of reactive gas generated from the underlying coating during heat treatment, in this case, carbon dioxide.

[0163] General coating step and processing step The base layer formulations were prepared by mixing the reactive gas-releasing compound (A) and polymer compound (B) in the amounts specified in Table 3, dissolving the compounds in PGMEA, and forming a solution with a solute concentration of approximately 0.5% by mass. Similarly, the formulations for the control samples (Samples 5-6) were prepared by dissolving polymer compound (B) in PGMEA to form a solution with a polymer concentration of approximately 0.5% by mass. Each of the formulations was individually spin-coated onto a 300 mm Si wafer using a TEL CLEAN wafer track to provide each of the sets of samples 5-1 to 5-6. Each base layer film had a thickness of approximately 50 nm. The additive amounts shown in Table 3 were provided so that the selected additives in the base layers of samples 5-1 to 5-5 were equimolar.

[0164] [Table 3]

[0165] Evaluation method Each of the first set of Samples 5-1 to 5-6 was deposited into the sealed test chamber of a headspace gas chromatography-mass spectrometry (HS-GC-MS) analyzer (JTD-505III / J<S-Q1500GC (JEOL)(JAI)). The test chamber was equipped with an air environment. The samples were baked at 220 °C for 1 minute, and the amount of CO2 generated was measured. Figure 4 shows the results of GC-MS analysis by plotting the relative amounts of CO2 generated in each of Samples 5-1 to 5-6. For samples with reactive gas-releasing compound (A), the relative amount of CO2 generated was calculated by normalizing the measured amount of CO2 by the mass % of each additive shown in Table 3. Figure 4 shows that Sample 5-5 generated the highest relative amount of CO2, followed by Sample 5-3.

[0166] Each of the second set of Samples 5-1 to 5-6 was deposited into the sealed test chamber for thermogravimetry-differential thermal analysis (TG-DTA) testing (TG-DTA2000SR (NETZSCH)). The test chamber was equipped with a nitrogen environment. Each sample was subjected to a gradual chamber temperature increase from room temperature to 280 °C. Figure 5 shows the thermogravimetry results by plotting the mass percentages of Samples 5-1 and 5-3 to 5-5 as a function of chamber temperature. Sample 5-1 showed the onset of mass loss at approximately 120 °C. Sample 5-4 showed the onset of mass loss at approximately 190 °C, and Samples 5-3 and 5-5 showed the onset of mass loss at approximately 220 °C. The results indicate that the thermal stability of the additives is a function of temperature.

[0167] The results suggest that it is possible to control the concentration of reactive gases such as CO2 in the treatment environment using the additive type and treatment conditions, thereby resulting in improved patterning performance compared to standard treatments.

[0168] The embodiments described herein are illustrative and not limiting. Additional embodiments are within the claims. While the invention has been described with reference to specific embodiments, it will be apparent to those skilled in the art that modifications in form and detail are possible without departing from the spirit and scope of the invention. Any incorporation by reference of the above documents is limited so as not to incorporate subject matter contrary to the express disclosure herein. Unless otherwise specifically indicated, to the extent that specific structures, compositions, and / or processes are described herein together with components, elements, components, or other parts, it should be understood that the disclosure herein covers embodiments that essentially consist of specific components, components, or other parts, or combinations thereof, including specific embodiments, specific components, elements, components, other parts, or combinations thereof, and further include additional features that do not alter the fundamental nature of the subject matter proposed in the discussion. The use of the term “about” herein means, unless otherwise explicitly indicated, any inaccuracies resulting from measurements of specific parameters that can be understood by those skilled in the art.

Claims

1. A film-forming composition comprising a fluid blend of a reactive gas-releasing portion, a matrix-forming species, an organic solvent, and an optional activating additive, wherein the reactive gas-releasing portion releases metal ligand-forming molecules in response to radiation or heat, the activating additive is present such that the gas-releasing portion releases the reactive gas when stimulated and activated by the activating additive, and the matrix-forming species comprises a polymer and / or one or more polymer precursors.

2. The aforementioned metal ligand-forming molecule is H ２ O, CO ２ The composition according to claim 1, comprising alcohol, or a combination thereof.

3. The composition according to claim 1 or claim 2, wherein the reactive gas-releasing portion comprises a nitrobenzyl functional group, a nitrobenzyl alcohol functional group, a meldrum acid group, a propylene carbonate functional group, nitrobenzyl alcohol or a derivative thereof, ethylene glycol or a derivative thereof, an alcohol, a photobase generator having an aromatic group bonded to an amine via carbamate linkage, or a mixture thereof.

4. The composition according to any one of claims 1 to 3, wherein the reactive gas emission portion is covalently bonded to the matrix-forming species.

5. The composition according to any one of claims 1 to 4, further comprising an orthoester, a photoacid generator, or a combination thereof.

6. The composition according to any one of claims 1 to 5, wherein the matrix-forming species comprises precursors of novolac resin, resol resin, styrene resin, acenaphthylene resin, indene resin, arylene resin, or calixarene resin, copolymers thereof, fluorinated derivatives thereof, polysiloxane, polycarbosilane, polyethylene-polyester copolymer, or mixtures thereof.

7. The composition according to any one of claims 1 to 6, wherein the organic solvent comprises an alcohol, a ketone, an ether, an ester, or a combination thereof.

8. The composition according to any one of claims 1 to 7, wherein the activating additive comprises a photoacid generator (PAG), a thermoacid generator (TAG), or a combination thereof.

9. The composition according to claim 8, wherein the photoacid generator comprises 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, alkyl sulfonate, onium salt, or a combination thereof.

10. The composition according to any one of claims 1 to 7, wherein the activating additive comprises a sulfonium sulfonate, iodonium sulfonate, N-sulfonimide, and / or N-sulfonimine, covalently bonded to the matrix-forming species.

11. The composition according to any one of claims 1 to 10, wherein the composition comprises about 0.001 wt% to about 5 wt% of the reactive gas-releasing portion, about 0.1 wt% to about 20 wt% of the matrix-forming species, about 60 wt% to about 99.9 wt% of the organic solvent, and about 0 to about 15 wt% of the activating additive.

12. A composition comprising a blend of a reactive gas-releasing portion, a polymer matrix, and an optional activating additive, wherein the reactive gas-releasing portion releases metal ligand-forming molecules in response to radiation or heat, the activating additive is present such that the gas-releasing portion releases the reactive gas when stimulated and activated by the activating additive, and the reactive gas-releasing portion is bonded to or blended into the polymer matrix.

13. The aforementioned metal ligand-forming molecule is H ２ O, CO ２ The composition according to claim 12, comprising alcohol, or a combination thereof.

14. The composition according to claim 12 or claim 13, wherein the reactive gas-releasing portion comprises a nitrobenzyl functional group, a nitrobenzyl alcohol functional group, a meldrum acid group, a propylene carbonate functional group, nitrobenzyl alcohol or a derivative thereof, ethylene glycol or a derivative thereof, an alcohol, a photobase generator having an aromatic group bonded to an amine via carbamate linkage, or a mixture thereof.

15. The composition according to any one of claims 12 to 14, wherein the reactive gas-releasing portion is covalently bonded to the polymer matrix.

16. The composition according to any one of claims 12 to 15, further comprising an orthoester, a photoacid generator, or a combination thereof.

17. The composition according to any one of claims 12 to 16, wherein the polymer matrix comprises a novolac resin, a resol resin, a styrene resin, an acenaphthylene resin, an indene resin, an arylene resin, a calixarene resin, copolymers thereof, fluorinated derivatives thereof, a polysiloxane, a polycarbosilane, a polyethylene-polyester copolymer, or a mixture thereof.

18. The composition according to any one of claims 12 to 17, wherein the activating additive comprises a photoacid generator (PAG), a thermoacid generator (TAG), or a combination thereof.

19. The composition according to claim 18, wherein the photoacid generator comprises 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, alkyl sulfonate, onium salt, or a combination thereof.

20. The composition according to any one of claims 12 to 19, wherein the activating additive comprises a sulfonium sulfonate, iodonium sulfonate, N-sulfonimide, and / or N-sulfonimine, covalently bonded to the polymer matrix.

21. The composition according to any one of claims 12 to 20, wherein the reactive gas emission portion emits metal ligand-forming molecules in response to EUV radiation.

22. The composition according to any one of claims 12 to 21, wherein the reactive gas emission portion emits metal ligand-forming molecules in response to ultraviolet or visible radiation.

23. The composition according to any one of claims 12 to 21, wherein the reactive gas release portion releases metal ligand-forming molecules in response to heat.

24. The composition according to any one of claims 12 to 23, wherein the composition is in a layer on a substrate, and the composition comprises about 0.01 wt% to about 20 wt% of the reactive gas emission portion, about 50 wt% to about 99 wt% of the matrix-forming species, and about 0 to about 50 wt% of the activating additive.

25. A substrate having a surface, a lower layer material covering at least a portion of the surface of the substrate, and a radiation-sensitive organometallic patterning material covering at least a portion of the lower layer material, A multilayer structure comprising a polymer and a reactive gas-emitting portion which may or may not be bonded to the polymer, wherein the reactive gas-emitting portion emits metal ligand-forming molecules in response to radiation and / or heat.

26. The aforementioned metal ligand-forming molecule is H ２ O, CO ２ The multilayer structure according to claim 25, comprising alcohol, or a combination thereof.

27. The multilayer structure according to claim 25 or claim 26, wherein the lower layer material releases the metal ligand-forming molecule in response to EUV radiation.

28. The multilayer structure according to claim 25 or claim 26, wherein the lower layer material releases the metal ligand-forming molecules in response to ultraviolet or visible radiation.

29. The multilayer structure according to any one of claims 25 to 28, wherein the reactive gas emission portion comprises a nitrobenzyl functional group, a nitrobenzyl alcohol, an ethylene glycol portion, an alcohol, a meldramic acid group, a propylene carbonate functional group, a photobase generator having an aromatic group bonded to an amine via carbamate linkage, or a mixture thereof.

30. The multi-layer structure according to any one of claims 25 to 29, wherein the lower layer material further comprises an acid generator.

31. The multilayer structure according to any one of claims 25 to 30, wherein the lower layer material has an average thickness of about 5 nm to about 500 nm and comprises at least about 0.001 wt% of a gas-releasing compound including the reactive gas-releasing portion, and a polymer selected from novolac resin, resol resin, styrene resin, acenaphthylene resin, indene resin, arylene resin, calixarene resin, copolymers thereof, fluorinated derivatives thereof, polysiloxane, polyethylene-polyester copolymer, or mixtures thereof.

32. The multilayer structure according to any one of claims 25 to 31, wherein the organometallic patterning material includes radiation-sensitive metal-carbon bonds and / or metal carboxylate bonds.

33. The organometallic patterning material is of the formula R ｚ SnO （２－ｚ／２－ｘ／２） (OH) ｘ (where 0 < x < 3, 0 < z ≤ 2, x + z ≤ 4, and R is a hydrocarbyl group forming a carbon bond with the tin atom), the multilayer structure according to any one of claims 25 to 32, which contains an alkyltin oxide hydroxide approximately represented by the formula.

34. The multilayer structure according to claim 33, wherein R comprises a hydrocarbyl group having 1 to 31 carbon atoms or a blend of identifiable hydrocarbyl groups each having 1 to 31 carbon atoms, and z is about 1.

35. The multilayer structure according to claim 33, wherein R comprises a branched alkyl, cycloalkyl, alkenyl, aryl, aryl, or alkynyl, or a combination thereof.

36. The multilayer structure according to claim 33, wherein R comprises t-butyl, t-amyl, i-propyl, n-butyl, methyl, or a combination thereof.

37. The multilayer structure according to any one of claims 33 to 36, wherein R comprises a hydrocarbyl group substituted with a heteroatom functional group.

38. The multilayer structure according to claim 37, wherein the heteroatom functional group comprises a cyano, thio, silyl, ether, keto, ester, or halogenated group, or a combination thereof.

39. The multilayer structure according to any one of claims 25 to 38, wherein the substrate is a semiconductor wafer.

40. A method for patterning a radiation-sensitive organometallic composition, the method being as follows: A composition containing a reactive gas emission portion is coated onto the surface of a substrate, forming a lower layer material that covers at least a portion of the surface, thereby forming a lower layer structure. The process involves depositing organometallic patterning material onto the aforementioned lower structure to form a multi-layer structure, Irradiating the multi-layer structure according to a selected pattern to form a latent image, Heating the irradiated multilayer structure having the latent image as a post-exposure bake, wherein the lower layer material releases metal ligand-forming molecules via the lower layer material or a portion thereof in response to irradiation or heating, and the organometallic patterning material or a portion thereof reacts with the metal ligand-forming molecules. After the post-exposure baking and the reaction with the metal ligand-forming molecule, the latent image is developed. Methods that include...

41. The composition further comprises a matrix-forming species and an organic solvent, wherein the matrix-forming species comprises a polymer and / or one or more polymer precursors, and the metal ligand-forming molecule is H ２ O, CO ２ The method according to claim 40, comprising alcohol, or a combination thereof.

42. The method according to claim 40 or claim 41, wherein the reactive gas-releasing portion comprises a photobase generator having a nitrobenzyl functional group, nitrobenzyl alcohol, an ethylene glycol portion, an alcohol, a meldramic acid group, a propylene carbonate functional group, an aromatic group bonded to an amine via carbamate linkage, or a mixture thereof.

43. The method according to any one of claims 40 to 42, wherein the coating and / or deposition includes spin coating, spray coating, dip coating, knife edge coating, and / or printing approaches.

44. The method according to any one of claims 40 to 42, wherein the deposition includes gas phase deposition and / or the development is a dry development process carried out with a reactive gas or plasma for development.

45. The method according to any one of claims 40 to 44, wherein the heating is carried out at a temperature of about 45°C to about 300°C for at least about 0.1 minutes.

46. The method according to any one of claims 40 to 45, wherein the irradiation is carried out with EUV radiation, UV radiation, electron beam radiation, or a combination thereof.

47. The irradiation was 100 mJ / cm². ２ The method according to any one of claims 40 to 46, wherein the electromagnetic radiation is of the following doses.

48. The method according to any one of claims 40 to 47, wherein the irradiation is carried out with EUV radiation, and the method further comprises irradiation of the multilayer structure with ultraviolet or visible light following the irradiation with EUV radiation.

49. The method according to claim 48, wherein irradiation with ultraviolet or visible light is performed before heating the irradiated multilayer structure having the latent image as a post-exposure bake.

50. The method according to claim 48, wherein irradiation with ultraviolet or visible light is performed after heating the irradiated multilayer structure having the latent image as a post-exposure bake and before development.

51. The method according to claim 48, further comprising heating the irradiated multilayer structure at approximately 45°C to approximately 300°C after irradiation with ultraviolet light or visible light and before development.

52. The method according to any one of claims 40 to 51, further comprising heating the irradiated multilayer structure to about 45°C to about 300°C when irradiated with ultraviolet light or visible light.

53. The method according to any one of claims 40 to 50, wherein the substrate includes a semiconductor wafer.

54. CO ２ A polymeric material comprising an emission portion and a polymer material, wherein the CO ２ The emission portion reacts to radiation or heat by emitting CO ２ The polymer material releases CO ２ A polymeric material that provides a matrix for the release portion.

55. The polymeric material according to claim 54, wherein the polymer material comprises novolac resin, resol resin, styrene resin, acenaphthylene resin, indene resin, arylene resin, calixarene resin, copolymers thereof, fluorinated derivatives thereof, polysiloxane, polycarbosilane, polyethylene-polyester copolymer, or mixtures thereof.

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