Method for making hard mask useful in next-generation lithography

Abstract

To provide a method for making imaging layers on the surface of a substrate.SOLUTION: A method of making an imaging layer on a substrate, involves providing a substrate having a surface comprising exposed hydroxyl groups, and forming a hydrocarbyl-terminated SnOx film as the imaging layer on the surface of the substrate, the hydrocarbyl-terminated SnOx film having a tin-carbon bond cleavable by irradiating the imaging layer.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] Incorporation by Reference As part of this application, a PCT application is filed simultaneously with this specification. As confirmed in the simultaneously filed PCT application, each application for which this application claims benefit or priority is hereby incorporated by reference in its entirety for all purposes.

[0002] The present disclosure relates to systems and methods for creating an imaging layer on a substrate surface. Such an imaging layer may be patterned using next-generation lithography techniques, and the resulting patterned film may be used, for example, as a lithography mask for the production of semiconductor devices.

Background Art

[0003] The description of "Background Art" provided herein presents a general outline of the context of this technology. The achievements of the inventors named herein, within the scope described in the "Background Art" of this specification, as well as aspects of this specification that may not be considered prior art at the time of filing, are not recognized as prior art to this technology.

[0004] The manufacture of semiconductor devices such as integrated circuits is a multi-step process involving photolithography. Generally, this process includes depositing materials on a wafer and then patterning the materials using lithography techniques to form the structural features of the semiconductor device (e.g., transistors, conductors, and other circuit features). The steps of a typical photolithography process known in the art include preparing a substrate; applying a photoresist by spin coating or the like; exposing the photoresist in a desired pattern to render the exposed areas of the photoresist, to some extent, soluble in a developer; developing by applying the developer to remove either the exposed or unexposed areas of the photoresist; and subsequent processing, such as by etching or material deposition, to form features in the areas of the substrate where the photoresist has been removed.

[0005] The evolution of semiconductor design has created a need to fabricate ever finer features on semiconductor substrate materials, and has been driven by the ability to do so. Such progress in technology is characterized by "Moore's Law," which states that the transistor density in high-density integrated circuits doubles every two years. In fact, chip design and manufacturing have advanced to the point where the latest microprocessors may include billions of transistors and other circuit functions on a single chip. The individual features on such chips may be on the order of 22 nanometers (nm) or less, and in some cases less than 10 nm.

[0006] One of the challenges in manufacturing devices with such small features is the ability to reliably and reproducibly create photolithography masks with sufficient resolution. Current photolithography processes typically use ultraviolet (UV) light at 193 nm to expose photoresist. The fact that light has a wavelength significantly larger than the desired size of the features formed on the semiconductor substrate creates inherent problems. Achieving feature sizes smaller than the wavelength of light requires the use of complex resolution enhancement techniques such as multipatterning. Therefore, significant interest and research effort have been directed towards the development of so-called "next-generation lithography" techniques, which use electron beam radiation or light with shorter wavelengths such as extreme ultraviolet (EUV) radiation having a wavelength of less than 20 nm, for example 13.5 nm.

[0007] However, next-generation lithography techniques can present challenges. For example, the effectiveness of EUV photolithography processes can be limited by the low output of the light source and the loss of light during pattern formation. Conventional organic chemically amplified resists (CARs) similar to those used in 193 nm UV lithography have potential drawbacks when used in EUV lithography. In particular, they have low absorption coefficients in the EUV region, and the diffusion of photoactivated species can cause blurring or line edge roughness. Furthermore, the required thickness of conventional CAR materials to provide the etching resistance necessary to pattern the underlying device layer can result in high aspect ratios that carry a risk of pattern collapse. Therefore, there remains a need for improved EUV photoresist materials having properties such as reduced thickness, greater absorbance, and greater etching resistance. SUMMARY OF THE INVENTION

[0008] The present disclosure provides a method for fabricating an imaging layer on a substrate surface. Such an imaging layer may generally be patterned into chemically distinct regions (i.e., surface imaging) using next-generation lithography techniques such as DUV, EUV, X-rays, and electron beams. The resulting patterned film may be used, for example, as a lithography mask for producing semiconductor devices.

[0009] In some embodiments, the method according to the present disclosure may include fabricating an imaging layer of a SnOx thin film terminated with an alkyl group selected to undergo tin-carbon bond cleavage, such as beta-hydrogen elimination, upon irradiation with EUV light. In the EUV patterning process, the alkyl group can be cleaved while leaving regions of Sn-H bonds and leaving the unexposed surface alkyl-terminated.

[0010] In one embodiment, a method of fabricating an imaging layer on a substrate includes providing a substrate having a surface with exposed hydroxyl groups, and forming, on the substrate surface, a hydrocarbyl-terminated SnO x film as the imaging layer, and the hydrocarbyl-terminated SnO x film has tin-carbon bonds that can be cleaved by irradiating the imaging layer.

[0011] In some embodiments, the substrate surface may include a SnOx underlayer for the hydrocarbyl-terminated SnO x film imaging layer. The hydroxy Ru terminated SnO x underlayer on the surface of the substrate material is irradiated to improve radiation absorption, generate secondary electrons from the substrate, collect additional EUV photons, make the EUV patterning process more sensitive, and reduce the EUV dose required for exposure of the imaging layer.

[0012] In various embodiments, the imaging layer may be deposited by an atomic layer deposition process that exhibits self-limiting characteristics. In other embodiments, the imaging layer is a thin film deposited by a (non-self-limiting) chemical vapor deposition process.

[0013] For example, an alkyl-substituted Suzuki capping agent may have a general formula of R n SnX 4-n where R is a C2-C 10 alkyl or substituted alkyl substituent. X may be any suitable leaving group that is readily substituted by water to form a hydroxyl intermediate product, which in turn reacts with other Sn-X functional groups to form Sn-O-Sn bridges. In various embodiments, R is branched and has a plurality of beta hydrogen atoms (the largest corresponding to the tert-butyl substituent). For example, R may be t-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n-pentyl, or n-hexyl, or derivatives thereof, as well as similar materials containing one or more heteroatoms such as fluorine, chlorine, bromine, iodine, nitrogen, oxygen.

[0014] The present technology also provides a method for forming a pattern on the surface of a coated substrate produced by the method of the present technology using EUV or other radiation. Further processing of the coated substrate may utilize chemical differences in the exposed and unexposed regions, particularly the conversion of hydrocarbyl-terminated SnO x to hydrogen-terminated SnO x in the exposed regions of the imaging layer. The difference in properties between the exposed and unexposed regions may be utilized in subsequent processing, for example, by reacting the irradiated region, the non-irradiated region, or both with one or more reagents to selectively add material to or remove material from the imaging layer.

[0015] In various embodiments, the present technology provides a method of patterning a thin hard mask layer having etch resistance on a substrate surface, the method comprising: providing a substrate comprising a substrate material having a surface comprising exposed hydroxyl groups; hydrocarbyl-terminated SnO x depositing an imaging layer comprising on the surface; selectively irradiating the imaging layer, wherein hydrocarbyl substitution is removed in the SnO x portion of the hydrocarbyl-terminated imaging layer and / or converted to hydrogen-terminated SnO group and an irradiated region in which the imaging layer comprises an unirradiated region comprising hydrocarbyl-terminated SnO x x x comprising the imaging layer; reacting the irradiated region, the unirradiated region, or both with one or more reagents to selectively deposit material on or remove material from the imaging layer to process the imaging layer.

[0016] The irradiation may include the use of DUV, EUV, X-rays, or electron beam radiation. In some embodiments, the processing step further comprises oxidizing hydrogen-terminated (Sn-H) functional groups in the irradiated region to form Sn-OH hydroxy Ru terminated SnO x forming.

[0017] Further applicable areas of the present technology will become apparent from the "Description of Embodiments for Carrying Out the Invention", "Claims", and the drawings. The "Description of Embodiments for Carrying Out the Invention" and the specific examples are for illustrative purposes only and are not intended to limit the scope of the technology. The present technology will be more fully understood from the detailed description and the accompanying drawings.

Brief Description of the Drawings

[0018]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7A

Figure 7B

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

DETAILED DESCRIPTION OF THE INVENTION

[0019] In this specification, specific embodiments of the present disclosure are referred to in detail. Examples of specific embodiments are shown in the accompanying drawings. Although the present disclosure is described in connection with these specific embodiments, it will be understood that the present disclosure is not intended to be limited to such specific embodiments. Rather, it is intended to cover alternatives, modifications, and equivalents that may be included within the spirit and scope of the present disclosure. Numerous specific details are set forth in the following description in order to provide a thorough understanding of the present disclosure. The present disclosure may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the present disclosure.

[0020] As discussed above, the present disclosure provides a method for fabricating an imaging layer on a semiconductor substrate, and the imaging layer may be patterned using EUV or other next-generation lithography techniques. In addition to EUV including the currently used and developed standard 13.5 nm EUV wavelength, the radiation sources most relevant to such lithography generally refer to DUV (deep-UV) which uses an excimer laser light source of 248 nm or 193 nm, X-rays including EUV within the low-energy range of the formal X-ray range, and an electron beam that can cover a wide energy range. Such methods include a method of contacting a substrate having exposed hydroxyl groups with a hydrocarbyl-substituted tin capping agent to form a hydrocarbyl-terminated SnO x film on the substrate surface. In various embodiments, the imaging layer is a thin layer that functions as an adhesion layer on the substrate and may facilitate the selective deposition of additional materials onto the substrate, for example, when forming a hard mask for a lithography process. The specific method may depend on the specific materials and applications used in the semiconductor substrate and the final semiconductor device. Accordingly, the methods described in this application are merely examples of methods and materials that may be used in this technology.

[0021] substrate Substrates useful in the methods of the present technology may include any material structure suitable for lithographic processing, particularly for the production of integrated circuits and other semiconductor devices. In some embodiments, the substrate is a silicon wafer. The substrate may be a silicon wafer on which features having an irregular surface topography ("underlying topographical features") are fabricated. (As referred to herein, "surface" is the surface on which the film of the present technology is to be deposited or the surface to be exposed to EUV during processing.) Such underlying topographical features may include regions from which material has been removed (e.g., by etching) or regions to which material has been added (e.g., by deposition) during processing prior to implementing the methods of the present technology. Such preprocessing may include the methods of the present technology or other processing methods in an iterative process in which two or more layers of features are formed on the substrate.

[0022] In some embodiments, the substrate is a hard mask used in lithographic etching of underlying semiconductor material. The hard mask may include any of a variety of materials including amorphous carbon (a-C), SnO x , SiO2, SiO x N y , SiO x C, Si3N4, TiO2, TiN, W, W-doped carbon, WO x , HfO2, ZrO2, and Al2O3. For example, the substrate may preferably include SnO x such as SnO2. In various embodiments, the layer may have a thickness of 1 nm to 100 nm, or a thickness of 2 nm to 10 nm.

[0023] In various embodiments, the substrate includes hydroxyl groups exposed on its surface. Generally, the surface may be any surface that includes or has been treated to produce an exposed hydroxyl surface. (As referred to herein, "surface" means a portion of the substrate that defines a boundary between the substrate and another material, or the absence of such a boundary (e.g., gas, coating, or vacuum), and in various embodiments may be available for exposure to radiation or reaction with components in other materials.) Thus, the method may include a step of "providing such a substrate", in which, apart from the method of the present technology, a substrate having exposed hydroxyl groups is obtained as a starting material, or, as described above and further described below, hydroxyl groups are formed on the substrate and then produced as part of a single process that includes contacting the surface with a hydroxyl-substituted Suzuki capping agent. For example, such hydroxyl groups may be formed on the substrate surface by surface treatment of the substrate using oxygen plasma, water plasma, or ozone.

[0024] In some embodiments, the substrate including the exposed hydroxyl groups includes a surface layer or film including hydroxyl-terminated SnO x For example, the substrate may include amorphous carbon having a surface of hydroxyl-terminated SnO x Without limiting the mechanism, function, or usefulness of the present technology, the hydroxyl-terminated SnO x layer may provide advantages such as improved adhesion of the deposited material on the substrate surface and improved absorption of EUV (or other radiation) during patterning. The sensitivity and resolution to EUV or other irradiation may depend on the properties of the SnO x layer, such as thickness, density, and short-range charge transfer properties. In various embodiments, the SnO x layer has a thickness of 0.1 nm to 20 nm, or 0.2 nm to 10 nm, or 0.5 nm to 5 nm.

[0025] In some embodiments, the hydroxyl-terminated SnO xThe layer is deposited on the substrate surface by vapor deposition. In such a method, the deposition involves reacting Sn-X n with an oxygen-containing counter-reactant, where X is a ligand such as a dialkylamide (e.g., dimethylamide, methylethylamide, and diethylamide), an alcohol (e.g., t-butoxy, and isopropoxy), a halogen (e.g., F, Cl, Br, and I), or another organic substituent (e.g., acetylacetone, N2,N3-di-tert-butyl-butane-2,3-diamide). For example, Sn-X n may be SnCl4, SnI4, or Sn(NR2)4, where R is methyl or ethyl, or Sn(t-BuO)4. In some embodiments, there are multiple types of ligands. The oxygen-containing counter-reactant may be selected from the group consisting of water, hydrogen peroxide, formic acid, alcohol, oxygen, ozone, and combinations thereof.

[0026] Suitable vapor deposition processes include chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma-enhanced chemical vapor deposition (PECVD), or plasma-enhanced atomic layer deposition (PEALD). In some embodiments, the deposition is ALD in a cyclic process where Sn-X n is deposited and then the oxygen-containing counter-reactant is deposited. In some embodiments, the deposition is CVD by flowing Sn-X n and the oxygen-containing counter-reactant simultaneously. The materials and processes useful herein for depositing the SnO x layer are described in Atomic Layer Deposition of Tin Dioxide Nanofilms: A Review, 40 Rev. Adv. Mater. Sci 262 (2015) by Nazarov et al.

[0027] In an exemplary continuous CVD process, two or more gas streams of sources of Sn-X n and the oxygen-containing counter-reactant are introduced into the deposition chamber of the CVD apparatus through separate inlet paths, and they are mixed and reacted in the gas phase to deposit SnO xA coating is formed. The stream may be introduced, for example, using a dual-plenum showerhead. The apparatus is Sn-X n and a stream of a source of an oxygen-containing counter-reactant are mixed within the chamber, and Sn-X n and the source of the oxygen-containing counter-reactant react to enable the formation of an SnO x layer. The CVD process is generally carried out at a reduced pressure such as 0.1 Torr to 10 Torr. In some embodiments, the process is carried out at 1 to 2 Torr. The temperature of the substrate is preferably lower than the temperature of the reactant stream. For example, the substrate temperature may be from 0 °C to 250 °C, or from ambient temperature (e.g., 23 °C) to 150 °C.

[0028] SnO x The substrate can also be deposited by an ALD process. For example, Sn-X n and the oxygen-containing counter-reactant are introduced at separate times. The precursors react on the surface to form, at most, a monolayer of material per pulse. This may enable excellent control over the film thickness uniformity across the entire surface. The ALD process is generally carried out at a reduced pressure such as 0.1 Torr to 10 Torr. In some embodiments, the process is carried out at 1 to 2 Torr. The substrate temperature may be from 0 °C to 250 °C, or from ambient temperature (e.g., 23 °C) to 150 °C. This process may be a thermal process or, preferably, plasma-assisted deposition.

[0029] Tin capping agent Useful hydrocarbyl-substituted tin capping agents herein contain substituents that undergo tin-carbon bond cleavage upon irradiation of the imaging layer. Such cleavage may be homolytic. In some embodiments, the cleavage may occur by beta-hydrogen elimination that releases an alkene fragment and leaves a hydrogen atom bonded to the tin atom that originally had an alkyl substituent.

[0030] The specific Suzuki capping agent may be selected according to the intended lithography process, i.e., the specific irradiation used. Further, the hydrocarbyl-substituted Suzuki capping agent may be selected to function as a barrier to subsequent deposition of materials onto the substrate. Thus, in some embodiments, the hydrocarbyl-substituted Suzuki capping agent is an atomic layer deposition blocking agent for preventing the attachment or growth of soluble metal oxide precursors from a solution in contact with the surface.

[0031] In various embodiments, the hydrocarbyl-substituted Suzuki capping agent is alkyl-substituted and has, for example, the following general formula: R n SnX m wherein the agent has R which is C2-C having beta hydrogen 10 alkyl or substituted alkyl, X is a suitable leaving group by reaction with the hydroxyl group of the exposed hydroxyl group, and in various embodiments, n = 1 to 3, and m = 4 to n. For example, R may be t-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n-pentyl, or n-hexyl, or derivatives thereof having a heteroatom substituent at the beta position. Suitable heteroatoms include halogen (F, Cl, Br, or I), or oxygen (-OH or -OR). X may be a dialkylamide (e.g., dimethylamide, methylethylamide, or diethylamide), an alcohol (e.g., t-butoxy, isopropoxy), a halogen (e.g., F, Cl, Br, or I), or another organic ligand. Examples of hydrocarbyl-substituted Suzuki capping agents include t-butyltris(dimethylamino)tin, n-butyltris(dimethylamino)tin, t-butyltris(diethylamino)tin, di(t-butyl)di(dimethylamino)tin, sec-butyltris(dimethylamino)tin, n-pentyltris(dimethylamino)tin, isobutyltris(dimethylamino)tin, isopropyltris(dimethylamino)tin, t-butyltris(t-butoxy)tin, n-butyl(tris(t-butoxy)tin )or isopropyltris(t-butoxy)tin.

[0032] Method for producing an imaging layer In various embodiments, the method of the present technology comprises providing a substrate having a surface containing exposed hydroxyl groups; contacting the surface with a hydrocarbyl-substituted tin capping agent to form a hydrocarbyl-terminated SnO x film on the substrate surface.

[0033] Generally, contacting the surface with a hydrocarbyl-substituted tin capping agent may be carried out using any suitable technique, preferably to create a uniform distribution of the capping agent on the surface. Such methods include deposition techniques such as ALD and CVD. Water may also be added to assist the reaction between the capping agent and the exposed hydroxyl groups of the substrate. In such methods, the capping agent and water are repeatedly applied to form a hydrocarbyl-substituted tin capping is sufficiently saturated function surface. Exposure to additional alkyl-based reagents such as alkanethiols may form a surface having an increased level of hydrocarbyl substituents on the substrate surface. Ru

[0034] In an exemplary continuous CVD process, two or more gas streams of R n Sn-X m and a source of an oxygen-containing counter-reactant are introduced into the deposition chamber of a CVD apparatus through separate inlet paths, where they are mixed and reacted in the gas phase and condensed to form an SnO x coating on the substrate. The streams may be introduced, for example, using a dual-plenum showerhead. The apparatus has a stream of R n Sn-X m and a source of an oxygen-containing counter-reactant mixed within the chamber, and R n Sn-X m and a source of an oxygen-containing counter-reactant react to form SnO xIt is configured to enable the formation of a layer. The CVD process is generally carried out under reduced pressure, such as 0.1 Torr to 10 Torr. In some embodiments, the process is carried out at 1 to 2 Torr. The temperature of the substrate is preferably lower than the temperature of the reactant stream. For example, the substrate temperature may be from 0 °C to 250 °C, or from ambient temperature (e.g., 23 °C) to 150 °C.

[0035] SnO x The imaging layer can also be deposited by an ALD process. In this case, R n Sn-X m The oxygen-containing counter-reactant is introduced at separate times representing an ALD cycle. The precursor reacts on the surface to form a maximum of a monolayer of material per ALD cycle. This enables excellent control over the film thickness uniformity across the wafer. The ALD process is generally carried out under reduced pressure, such as 0.1 Torr to 10 Torr. In some embodiments, the process is carried out at 1 to 2 Torr. The substrate temperature may be from 0 °C to 250 °C, or from ambient temperature (e.g., 23 °C) to 150 °C. This process is a thermally driven process. The film is not expected to grow significantly after the first cycle, and subsequent cycles are designed to further saturate the surface with R-terminated Sn.

[0036] Pattern formation The present technology also provides a method of patterning an imaging layer by exposing an area of the imaging layer to irradiation such as EUV, DUV, or an electron beam. In such patterning, the radiation is focused onto one or more areas of the imaging layer. The exposure is typically performed such that it includes one or more areas where the film of the imaging layer is not exposed to the radiation. The resulting imaging layer includes a plurality of exposed and unexposed areas and is patterned to be consistent with the fabrication of transistors or other features of semiconductor devices formed by the addition or removal of material from the substrate in subsequent substrate processing. Among those useful herein, EUV, DUV, and electron beam radiation methods and apparatuses include methods and apparatuses known in the art.

[0037] In particular, the areas of the imaging layer are created by patterning where the physical or chemical properties are changed compared to the unexposed areas. In particular, in various embodiments, the hydrocarbyl-terminated SnO present on the surface x is converted to hydrogen-terminated SnO in the exposed areas of the imaging layer, especially when the exposure is performed in a vacuum using EUV. x However, by removing the exposed imaging layer from the vacuum and introducing it into the air, or by controlling the introduction of oxygen, ozone, H2O2, or water, the surface Sn-H may be oxidized to Sn-OH. The difference in properties between the exposed and unexposed areas can be utilized in subsequent processing, for example, by reacting the irradiated area, the non-irradiated area, or both with one or more reagents to selectively add material to or remove material from the imaging layer.

[0038] Accordingly, in various embodiments, the present technology provides a method of fabricating a lithography hard mask on a substrate surface, the method comprising: providing a substrate comprising a substrate material having a surface with exposed hydroxyl groups; hydrocarbyl-terminated SnO xDepositing an imaging layer containing on a surface; Selectively irradiating the imaging layer, wherein the hydrocarbyl-terminated SnO of the imaging layer x is converted to hydrogen-terminated SnO x in the irradiated region, and the imaging layer has hydrocarbyl-terminated SnO x in the non-irradiated region, and the imaging layer contains the steps; Reacting the irradiated region, the non-irradiated region, or both with one or more reagents to selectively add material to or remove material from the imaging layer to process the imaging layer. In various embodiments, the substrate material is amorphous carbon or SnO x including.

[0039] Optionally, the imaging layer is heated or "baked" to remove excess moisture and promote Sn-O-Sn crosslinking. For example, the sample can be baked at 50 °C to 200 °C for 5 minutes or at 70 °C to 150 °C for 2 minutes under conditions where the R-Sn bonds are not significantly cleaved.

[0040] Lithography process As described above, the subsequent processing of the imaging layer following irradiation will depend on the substrate material and the desired features of the semiconductor device fabricated using the substrate. For example, the features may be fabricated on the substrate by various lithography techniques using, for example, spin-coating of a film that is selectively soluble in a liquid developer in either the exposed (positive-type) or unexposed (negative-type) regions defined by an exposure tool involving patterning.

[0041] The lithography method of the present technology is generally shown in the process flow of FIG. 1. As shown, the substrate is formed by depositing a hydroxy Ru terminated SnO x "lower layer" on the substrate material (110). Hydroxy on the substrate surface Ru terminated SnOx The lower layer is irradiated to the imaging layer, improving the absorption of radiation, generating secondary electrons from the substrate, further collecting additional EUV photons, making the EUV patterning process more sensitive, and reducing the EUV dose required for the exposure of the imaging layer.

[0042] Next, a hydrocarbyl-substituted Suzuki capping agent is deposited on the surface to form a hydrocarbyl-terminated SnO x film on the substrate surface, thereby forming an imaging layer (120). Next, the substrate is exposed to radiation (e.g., using EUV) (130) and optionally baked (140). Next, the surface of the imaging layer is processed (150). FIG. 2 schematically shows the general architecture of a substrate formed by such a process along with an exemplary chemical structure. FIG. 3 shows a specific example of such a process, where the imaging layer is formed from the hydrocarbyl-substituted Suzuki capping agent t-butylSn(N(CH3)2)3. FIG. 4 shows an alternative of an activated (EUV release) PR adhesion imaging layer formed from the Suzuki capping agent n-BuSn(OtBu)3.

[0043] In some methods, the processing step includes oxidizing hydrogen-terminated SnO in the irradiated region x to form hydroxy Ru terminated SnO x The oxidizing step may include exposing the irradiated region to oxygen or water. In some methods, the subsequent processing step includes removing hydroxy Ru terminated SnO x in the irradiated region to expose and etch the underlying substrate material. The etching may be performed by treating the patterned film with a dilute hydrofluoric acid aqueous solution or alternatively a dilute tetramethylammonium hydroxide aqueous solution (TMAH). The processing step may further include etching the underlying substrate layer using an oxygen plasma.

[0044] In some embodiments, the processing step further includes depositing a metal oxide that may act as a hard mask over the hydroxylated irradiated region. Such hard mask materials may include metal oxides selected from the group consisting of SnO2, SiO2, TiO2, WO Ru terminal SnO x , HfO2, ZrO2, Ta2O5, Nb2O5, B2O3, GeO2, ZnO, V2O5, and Al2O3. The deposition may be performed, for example, by ALD. x

[0045] In some methods of the present technology, the hydrocarbyl-terminated SnO in the non-irradiated region is removed by hydrogen or methane plasma, exposing the underlying amorphous carbon layer. The processing step may further include etching the underlying substrate material using oxygen plasma. x

[0046] Without limiting the mechanism, function, or utility of the present technology, in some embodiments, the lithography method of the present technology is believed to offer advantages over methods known in the art. The advantages include, for example, avoiding the need to apply and remove wet resist formulations (e.g., avoiding scum and pattern distortion), simplifying processes such as developing a substrate exposed under vacuum in a continuous process after EUV or other irradiation, reducing pattern collapse by using very thin metal oxide structures, improving line edge roughness, and providing the ability to tailor the chemical properties of the hard mask to specific substrate and semiconductor device designs.

[0047] Additional embodiments As described above, the specific post-imaging method and application of the present technology may involve any of a variety of materials and processes, depending on the substrate and the desired device design. The processing of the imaging layer may depend on the substrate material and the desired features of the semiconductor device fabricated using the substrate. For example, the features may typically involve the application of a film that becomes selectively soluble in a developer in either exposed (positive-type) or unexposed (negative-type) regions defined by an exposure tool involving patterning, and may be fabricated on the substrate by various standard lithography techniques. The processing may include the fabrication of a lithography mask, including directed self-assembly (DSA) block copolymer (BCP), self-organization of sol-gel, and selective deposition of materials (such as metals or metal oxides) by atomic layer deposition or chemical vapor deposition.

[0048] For example, in some embodiments, a positive-type mask is fabricated by processing the imaging layer and the substrate. Such a method includes selectively irradiating regions of the imaging layer of the substrate fabricated by the method of the present technology; for example, reacting the irradiated regions with air or water to oxidize hydrogen-terminated SnO x to form hydroxy Ru terminated SnO x ; contacting the irradiated regions with a dilute hydrofluoric acid aqueous solution (HF) or a dilute tetramethylammonium hydroxide aqueous solution (TMAH) to etch the exposed hydroxyl-terminated surface and expose the underlying substrate material (such as amorphous carbon); and etching the exposed underlying layer with an oxygen plasma.

[0049] In some embodiments, the processing of the imaging layer and the substrate fabricates a negative-type resist. For example, such a method includes selectively irradiating regions of the imaging layer of the substrate fabricated by the method of the present technology; For example, reacting the irradiated region with air or water to oxidize the hydrogen-terminated SnO x to form hydroxyl Ru -terminated SnO x ; and a step of forming; selectively depositing a metal oxide hard mask on the hydroxyl-terminated region, for example, by ALD; removing, for example, using H2, CH4, or BCl3-based plasma, the non-exposed region of the substrate (i.e., the region having hydrocarbyl-terminated SnO x ) to expose the underlying substrate (e.g., amorphous carbon); etching the exposed underlying substrate with oxygen plasma, may be included.

[0050] Elements of one such process are shown in the process flow of FIG. 5. FIGS. 6 and 7A, 7B show, respectively, a general schematic architecture of a mask formed in one such negative resist process (starting from hydroxylation of the exposed surface) and an exemplary chemical structure.

[0051] Elements of an alternative negative resist process are shown in FIG. 8. In this process, the hydrogen-terminated SnO in the irradiated region x is not oxidized. Rather, a hard mask of metal or metal oxide is deposited on the Sn-H surface of the irradiated region, for example, by ALD. General methods and conditions for ALD deposition of metals on hydride surfaces are described by Kwon et al., Substrate Selectivity of ( t(Bu-Allyl)Co(CO)3 during Thermal Atomic Layer Deposition of Cobalt, 24 Chem. Mater. 1025 (2012), and Understanding inherent substrate selectivity during atomic layer deposition: Effect of surface preparation, hydroxyl density, and metal oxide composition on nucleation mechanisms during tungsten ALD, 146 J. Chem. Phys. 052811 (2017), by Lemaire et al., are included. In such processes, the substrate may be maintained under vacuum from irradiation to ALD deposition, which can simplify the material handling procedures during the process and result in increased efficiency in manufacturing. Figure 9 shows a general architecture of a mask when formed in an alternative negative resist process.

[0052] In some embodiments, the imaging layer and substrate are processed using negative patterning. For example, such a method comprises selectively irradiating regions of the imaging layer of the substrate produced by the method of the present technology; for example, reacting the irradiated regions with air or water to oxidize hydrogen-terminated SnO x to form hydroxy Ru terminated SnO x ; selectively depositing a solution of a metal sol-gel oxide (e.g., spin-coated tetraethyl orthosilicate at pH 2 containing nitric acid) onto the hydroxyl-terminated regions to form a metal oxide etch mask on the irradiated regions; removing the unreacted sol-gel solution (e.g., by rinsing); etching the exposed regions of the substrate (i.e., hydrocarbyl-terminated SnO xremoving the region having it (e.g., using hydrogen or methane plasma) to expose the underlying substrate (e.g., amorphous carbon); etching the exposed underlying substrate with oxygen plasma, may be included.

[0053] Materials and methods for making sol-gels are described in Hench et al., The Sol-Gel Process, 90 Chem. Rev. 33 (1990), and Lu et al., Continuous formation of supported cubic and hexagonal mesoporous films by sol-gel dip-coating, 389 Nature 364 (1997). Elements of such processes are shown in the process flow of FIG. 10.

[0054] In some embodiments, the step of treating the imaging layer and the substrate includes depositing and self-organizing a block copolymer to pattern hydrophilic and hydrophobic regions of the imaging surface to create a hard mask. For example, such a method for creating a hard mask is selectively irradiating regions of the imaging layer of the substrate made by the method of the present technology; for example, reacting the irradiated regions with air or water to oxidize hydrogen-terminated SnO x to form hydroxy Ru terminated SnO x forming; coating the surface with a block copolymer reactant; annealing the surface to create an organized block copolymer; selectively removing substituents of the block copolymer to form a mask; etching the exposed underlying layer with oxygen plasma, may be included.

[0055] In some embodiments, prior to coating with the block copolymer reactant, a hydrophilic metal oxide may be deposited on the hydrophilic regions of the imaging surface (i.e., the irradiated regions) to create a topography that induces self-organization of the block copolymer. Materials and methods for making self-assembled block copolymers are described in Hamley, Nanostructure fabrication using block copolymers, 14 Nanotechnology R39 (2003). Elements of such a process are shown in the process flow of FIG. 11. By this approach, the feature size can be reduced and defects associated with the self-organization of the BCP can be reduced.

[0056] The present technology also provides a method for the selective growth of electroless metal device structures, such as hard masks, on a substrate. For the subsequent selective growth of conductive cobalt, nickel, or copper features by electroless deposition (ELD), for example, the surface may be exposed to an aqueous solution of a metal oxide ion (such as Pd +2 salts) to selectively deposit a catalytic Pd "seed" atomic layer. In other embodiments, exposed "deprotected" regions of a thin tin-based imaging layer that are no longer hydrophobic may be selectively etched away by short exposure to an acidic aqueous etchant such as concentrated HF or oxalic acid solution.

[0057] For example, such a method includes selectively irradiating a region of the imaging layer of a substrate fabricated by the method of the present technology; selectively depositing a palladium (Pd) activation layer on the exposed regions of the substrate (i.e., the regions having the Sn-H surface portion); depositing a metal, such as cobalt, on the Pd activation layer by electroless deposition.

[0058] In various embodiments, the deposited metal is a late transition metal such as cobalt, nickel, copper, or mixtures thereof. Without limiting the mechanisms, functions, or utilities of the present technology, in some embodiments, such a method may provide a simple additive patterning technique for depositing metal features on a substrate only when such features are needed, as opposed to subtractive techniques known in the art that involve blanket deposition of a metal followed by removal with subsequent patterning. Elements of such a process are shown in the process flow of FIG. 12 and illustrated in FIG. 13.

[0059] Conclusion A method for creating an imaging layer on a substrate surface that may be patterned into chemically distinct regions using next-generation lithography techniques (i.e., surface imaging) is provided The resulting patterned film may be used, for example, as a lithography mask for producing semiconductor devices.

[0060] The examples and embodiments described herein are for illustrative purposes only, and it is understood that various modifications or changes will be proposed to those skilled in the art in light of them. Although various details have been omitted for clarity, various design alternatives may be realized. Accordingly, the present examples should be considered illustrative and not limiting, and the present disclosure is not limited to the details described herein and may be modified within the scope of the present disclosure and the appended claims. The present invention can also be realized, for example, in the following aspects. Application Example 1: A method of forming an imaging layer on a substrate, the method comprising: providing a substrate having a surface containing exposed hydroxyl groups; forming a hydrocarbyl-terminated SnO film as the imaging layer on the surface of the substrate, x wherein the hydrocarbyl-terminated SnO film has a tin-carbon bond cleavable by irradiating the imaging layer. x A method. Application Example 2: The method of Application Example 1, wherein the step of forming the imaging layer of the hydrocarbyl-terminated SnO film includes contacting the surface of the substrate with a hydrocarbyl-substituted tin capping agent, and the hydrocarbyl-substituted tin capping agent undergoes tin-carbon bond cleavage upon irradiation of the imaging layer. x A method. Application Example 3: The method of Application Example 1, wherein the hydrocarbyl-substituted tin capping agent functions as a blocking agent for preventing the adhesion or growth of a soluble metal oxide precursor from a solution in contact with the surface. A method. Application Example 4: R n The method of any one of Application Examples 1 to 3, wherein the chemical formula of the hydrocarbyl-substituted tin capping agent is 4-n SnX, where R is a C alkyl or substituted alkyl containing beta hydrogen, X is a leaving group by reaction with the hydroxyl group of the exposed hydroxyl group, and n = 1 to 3. 2 -C 10 A method. Application Example 5: The method of Application Example 4, wherein R is selected from the group consisting of t-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n-pentyl, or n-hexyl, and derivatives thereof having a heteroatom substituent at the beta position. A method. Application Example 6: The method of Application Example 4 or 5, wherein X is selected from the group consisting of dialkylamides (e.g., dimethylamide, methylethylamide, or diethylamide), alcohols (e.g., t-butoxy, isopropoxy), and halogens (e.g., F, Cl, Br, or I). A method. The method of Application Example 2, wherein the hydrocarbyl-substituted Suzuki capping agent is selected from the group consisting of t-butyltris(dimethylamino)tin, n-butyltris(dimethylamino)tin, t-butyltris(diethylamino)tin, isopropyltris(dimethylamino)tin, t-butyltris(t-butoxy)tin, n-butyl(tris(t-butoxy)tin, di(t-butyl)di(dimethylamino)tin, sec-butyltris(dimethylamino)tin, n-pentyltris(dimethylamino)tin, isobutyltris(dimethylamino)tin, isopropyltris(dimethylamino)tin, t-butyltris(t-butoxy)tin, n-butyl(tris(t-butoxy)tin, and isopropyltris(t-butoxy)tin). Application Example 8: The method according to any one of Application Examples 1 to 7, wherein the substrate comprises amorphous carbon (a-C), SnO x , SiO 2 , SiO x N y , SiO x C, Si 3 N 4 , TiO 2 , TiN, W, W-doped carbon, WO x , HfO 2 , ZrO 2 、Al 2 O 3 , or Bi 2 O 3 . Application Example 9: The method according to any one of Application Examples 1 to 8, wherein the providing step includes forming a hydroxyl-terminated SnO x layer on the surface of the substrate material. Application Example 10: The method of Application Example 9, wherein the forming step includes depositing a hydroxyl-terminated SnO x layer on the surface by vapor deposition. Application Example 11: The method of Application Example 10, wherein the depositing step includes a reaction of Sn-X n with an oxygen-containing counter-reactant, and X is a dialkylamide (e.g., dimethylamide, methylethylamide, diethylamide), an alcohol (t-butoxy, isopropoxy), or a halogen (e.g., F, Cl, Br, and I). Application Example 12: The method of Application Example 11, wherein Sn-X n is SnCl 4 , SnI 4 , or Sn(NR 2 ) 4 ), where R is methyl or ethyl, or Sn(t-BuO) 4 . Application Example 13: The method according to Application Example 11 or 12, wherein the oxygen-containing counter-reactant is selected from the group consisting of water, hydrogen peroxide, formic acid, alcohol, oxygen, ozone, oxygen plasma, water plasma, and combinations thereof. Application Example 14: The method according to any one of Application Examples 10 to 13, wherein the vapor deposition is chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma-enhanced chemical vapor deposition (PECVD), or plasma-enhanced atomic layer deposition (PEALD). Application Example 15: The method according to any one of Application Examples 10 to 14, wherein the depositing step is an ALD cyclic process including a step of depositing the Sn-X n and a step of depositing the oxygen-containing counter reactant. Application Example 16: The method according to any one of Application Examples 10 to 14, wherein the depositing step is a CVD process including a step of simultaneously depositing the Sn-X n and the oxygen-containing counter reactant. Application Example 17: The method according to any one of Application Examples 1 to 16, wherein the imaging layer has a thickness of 0.5 nm to 5 nm. Application Example 18: The method according to any one of Application Examples 1 to 17, wherein the substrate comprises a topographical feature thereunder. Application Example 19: The method according to any one of Application Examples 1 to 18, further comprising a step of irradiating the imaging layer to form at least one exposed region, wherein the hydrocarbyl-terminated SnO x is converted to hydrogen-terminated SnO x in the exposed region. Application Example 20: The method according to Application Example 19, wherein the irradiating step includes the use of DUV, EUV, X-ray, or electron beam radiation. Application Example 21: The method according to Application Example 19, wherein the irradiation of the imaging layer improves the radiation absorption of the hydroxyl-terminated SnO x layer on the surface of the substrate material. Application Example 22: The method according to any one of Application Examples 1 to 21, wherein the irradiating step includes the use of EUV radiation. Application Example 23: A method of fabricating a lithography hard mask on a surface of a substrate, comprising providing a substrate including a substrate material having a surface with exposed hydroxyl groups; depositing an imaging layer including hydrocarbyl-terminated SnO x on the surface; selectively irradiating the imaging layer, wherein the irradiated region has hydrocarbyl substitution removed in the SnO x portion of the hydrocarbyl-terminated imaging layer and / or is converted to hydrogen-terminated SnO x , and the imaging layer includes the irradiated region and the unirradiated region where the imaging layer includes the hydrocarbyl-terminated SnO x . reacting the irradiated area, the non-irradiated area, or both with one or more reagents to selectively add material to or remove material from the imaging layer, thereby processing the imaging layer; Application Example 24: The method of Application Example 23, wherein the providing step includes depositing a hydroxyl-terminated SnO layer on the surface of the substrate material by vapor deposition; x A method comprising the step of depositing a layer. Application Example 25: The method of Application Example 23, wherein the step of depositing the imaging layer of the hydrocarbyl-terminated SnO film includes contacting the surface of the substrate with a hydrocarbyl-substituted tin capping agent, and the hydrocarbyl-substituted tin capping agent undergoes tin-carbon bond cleavage upon irradiation of the imaging layer; x A method. Application Example 26: The method of Application Example 25, wherein the chemical formula of the hydrocarbyl-substituted tin capping agent is SnX, where R is C alkyl or substituted alkyl having beta hydrogen, X is a suitable leaving group by reaction with the hydroxyl group of the exposed hydroxyl group, and n = 1 to 3; R n SnX 4-n where R is C alkyl or substituted alkyl having beta hydrogen, X is a suitable leaving group by reaction with the hydroxyl group of the exposed hydroxyl group, and n = 1 to 3; 2 -C 10 A method. Application Example 27: The method of Application Example 26, wherein the hydrocarbyl-substituted tin capping agent is t-butyltris(dimethylamino)tin, n-butyltris(dimethylamino)tin, t-butyltris(diethylamino)tin, isopropyltris(dimethylamino)tin, and t-butyltris(t-butoxy)tin, or n-butyl(tris(t-butoxy)tin; Application Example 28: The method of any one of Application Examples 23 to 27, wherein the irradiation includes the use of DUV, EUV, X-ray, or electron beam radiation; Application Example 29: The method of Application Example 28, wherein the irradiation includes the use of EUV radiation; Application Example 30: The method of Application Example 23, wherein the hydrocarbyl substitution in the SnO portion of the hydrocarbyl-terminated imaging layer is converted to hydrogen-terminated SnO by beta hydrogen elimination; x by beta hydrogen elimination to hydrogen-terminated SnO; x A method. Application Example 31: The method of any one of Application Examples 23 to 30, wherein the processing step includes oxidizing the hydrogen-terminated SnO in the irradiated area to form hydroxyl-terminated SnO; x oxidizing the hydrogen-terminated SnO in the irradiated area to form hydroxyl-terminated SnO; x A method comprising the step of forming. Application Example 32: The method of Application Example 31, wherein the oxidizing step includes the step of exposing the irradiated area to oxygen or water. Application Example 33: The method of Application Example 31, wherein the processing step includes the step of removing the hydroxy-terminated SnO of the irradiated area to expose the underlying substrate material, and the underlying substrate material contains amorphous carbon. x A method. Application Example 34: The method of Application Example 33, wherein the removing step includes the step of treating the irradiated area with dilute hydrofluoric acid or an aqueous solution of dilute tetramethylammonium hydroxide (TMAH). Application Example 35: The method of Application Example 33, wherein the processing step further includes the step of etching the underlying amorphous carbon substrate material using oxygen plasma. Application Example 36: The method of Application Example 31, wherein the processing step further includes the step of depositing a metal oxide hard mask on the hydroxy-terminated SnO of the irradiated area. xA method. Application Example 37: The method of Application Example 36, wherein the metal oxide hard mask contains a metal oxide selected from the group consisting of SnO, SiO, SiO, SiO, SiC, TiO, WO, HfO, ZrO, and Bi. x A method. 2 A method. x N y A method. x A method. 2 A method. x A method. 2 A method. 2 、Al 2 O 3 A method. 2 O 3 A method. Application Example 38: The method of Application Example 23, further including the step of selectively depositing a metal layer by atomic layer deposition only on the hydrogen-terminated SnO generated by selectively irradiating the imaging layer. x A method. Application Example 39: The method of Application Example 23, wherein the hydrocarbyl-terminated SnO of the non-irradiated area is removed by hydrogen or methane plasma to expose the underlying substrate material, and the underlying substrate material contains amorphous carbon. x A method. Application Example 40: The method of Application Example 39, wherein the processing step further includes the step of etching the underlying substrate using oxygen plasma.

Claims

1. 1. A method of producing an imaging layer on a substrate, the method comprising: Providing a substrate having a surface including exposed hydroxyl groups; a hydrocarbyl-terminated SnO x and forming a film of said hydrocarbyl-terminated SnO x The method wherein the film has a tin-carbon bond that is cleavable by irradiating said imaging layer.

2. 2. The method of claim 1, wherein the hydrocarbyl-terminated SnO x The method of claim 1, wherein the step of forming the imaging layer of the film comprises contacting the surface of the substrate with a hydrocarbyl-substituted tin capping agent, the hydrocarbyl-substituted tin capping agent undergoing tin-carbon bond cleavage upon irradiation of the imaging layer.

3. 10. The method of claim 1, wherein the hydrocarbyl-substituted tin capping agent functions as a blocking agent to prevent the deposition or growth of soluble metal oxide precursors from solution in contact with the surface.

4. The method of any one of claims 1 to 3, wherein the hydrocarbyl-substituted tin capping agent has the formula: R n SnX 4-n and R is a C 2 -C 10 alkyl or substituted alkyl, X is a leaving group upon reaction of said exposed hydroxyl group with a hydroxyl group, and n=1-3.

5. 5. The method of claim 4, wherein R is selected from the group consisting of t-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n-pentyl, or n-hexyl, and derivatives thereof having a heteroatom substituent at the beta position.

6. 6. The method of claim 4 or 5, wherein X is selected from the group consisting of dialkylamide (e.g., dimethylamide, methylethylamide, or diethylamide), alcohol (e.g., t-butoxy, isopropoxy), and halogen (e.g., F, Cl, Br, or I).

7. 3. The method of claim 2, wherein the hydrocarbyl substituted tin capping agent is selected from the group consisting of t-butyltris(dimethylamino)tin, n-butyltris(dimethylamino)tin, t-butyltris(diethylamino)tin, isopropyltris(dimethylamino)tin, t-butyltris(t-butoxy)tin, n-butyl(tris(t-butoxy)tin, di(t-butyl)di(dimethylamino)tin, secbutyltris(dimethylamino)tin, n-pentyltris(dimethylamino)tin, isobutyltris(dimethylamino)tin, isopropyltris(dimethylamino)tin, t-butyltris(t-butoxy)tin, n-butyl(tris(t-butoxy)tin, and isopropyltris(t-butoxy)tin.

8. The method according to any one of claims 1 to 7, wherein the substrate is made of amorphous carbon (aC), SnO x , SiO 2 , SiO x N y , SiO x C, Si 3 N 4 , TiO 2 , TiN, W, W-doped carbon, WO x , HfO 2 , ZrO 2 , Al 2 O 3 , or Bi 2 O 3 A method comprising:

9. 9. The method according to claim 1, wherein the providing step comprises providing a hydroxyl-terminated SnO x The method includes forming a layer.

10. 10. The method of claim 9, wherein the forming step comprises vapor-depositing hydroxyl-terminated SnO on the surface. x The method comprises depositing a layer.

11. 11. The method of claim 10, wherein the depositing step comprises depositing Sn-X n with an oxygen-containing counter reactant, where X is a dialkylamide (e.g., dimethylamide, methylethylamide, diethylamide), an alcohol (t-butoxy, isopropoxy), or a halogen (e.g., F, Cl, Br, and I).

12. The method according to claim 11, comprising the steps of: n is SnCl 4 , SnI 4 , or Sn(NR 2 ) 4 where R is methyl or ethyl, or Sn(t-BuO) 4 That is, the method.

13. 13. The method of claim 11 or 12, wherein the oxygen-containing counter reactant is selected from the group consisting of water, hydrogen peroxide, formic acid, alcohol, oxygen, ozone, oxygen plasma, water plasma, and combinations thereof.

14. 14. The method according to any one of claims 10 to 13, wherein the vapor deposition is chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma enhanced chemical vapor deposition (PECVD), or plasma enhanced atomic layer deposition (PEALD).

15. The method according to any one of claims 10 to 14, wherein the depositing step comprises depositing the Sn-X n and depositing said oxygen-containing counter reactant.

16. The method according to any one of claims 10 to 14, wherein the depositing step comprises depositing the Sn-X n and said oxygen-containing counter reactant.

17. The method of any one of claims 1 to 16, wherein the imaging layer has a thickness of from 0.5 nm to 5 nm.

18. The method of any one of claims 1 to 17, wherein the substrate comprises underlying topographical features.

19. 19. The method of any one of claims 1 to 18, further comprising the step of irradiating the imaging layer to form at least one exposed area, wherein the hydrocarbyl-terminated SnO x is hydrogen-terminated SnO in the exposed areas. x The method is to convert it into

20. 20. The method of claim 19, wherein the irradiating step comprises the use of DUV, EUV, X-ray, or electron beam radiation.

21. 20. The method of claim 19, wherein irradiation of the imaging layer forms a hydroxy-terminated SnO 2 film on the surface of the substrate material. x The method, wherein the layer enhances absorption of radiation.

22. The method according to any one of the preceding claims, wherein the step of irradiating comprises the use of EUV radiation.

23. 1. A method for producing a lithographic hard mask on a surface of a substrate, comprising: Providing a substrate comprising a substrate material having a surface including exposed hydroxyl groups; Hydrocarbyl-terminated SnO x depositing an imaging layer on said surface comprising: selectively irradiating the imaging layer, the SnO of the imaging layer being hydrocarbyl terminated; x The hydrocarbyl substitution has been removed in the moiety, and / or the hydrogen-terminated SnO x and the imaging layer is formed of the hydrocarbyl-terminated SnO x and a non-irradiated area comprising the imaging layer; and treating the imaging layer by reacting the irradiated areas, the non-irradiated areas, or both, with one or more reagents to selectively add material to or remove material from the imaging layer.

24. 24. The method of claim 23, wherein the providing step comprises vapor deposition of hydroxyl-terminated SnO on the surface of the substrate material. x The method comprises depositing a layer.

25. 24. The method of claim 23, wherein the hydrocarbyl-terminated SnO x The method of claim 1, wherein the step of depositing the imaging layer of the film comprises contacting the surface of the substrate with a hydrocarbyl-substituted tin capping agent, the hydrocarbyl-substituted tin capping agent undergoing tin-carbon bond cleavage upon irradiation of the imaging layer.

26. 26. The method of claim 25, wherein the hydrocarbyl-substituted tin capping agent has the formula: R n SnX 4-n and R is a C with a beta hydrogen 2 -C 10 alkyl or substituted alkyl, X is a suitable leaving group upon reaction of said exposed hydroxyl group with a hydroxyl group, and n=1-3.

27. 27. The method of claim 26, wherein the hydrocarbyl-substituted tin capping agent is t-butyltris(dimethylamino)tin, n-butyltris(dimethylamino)tin, t-butyltris(diethylamino)tin, isopropyltris(dimethylamino)tin, and t-butyltris(t-butoxy)tin, or n-butyl(tris(t-butoxy)tin.

28. The method of any one of claims 23 to 27, wherein the irradiation comprises the use of DUV, EUV, X-ray, or electron beam radiation.

29. 30. The method of claim 28, wherein the irradiating comprises the use of EUV radiation.

30. 24. The method of claim 23, wherein the SnO of the imaging layer is hydrocarbyl-terminated. x The hydrocarbyl substitution at the moiety is catalyzed by beta hydrogen elimination to form hydrogen-terminated SnO x The method is to convert it into

31. 31. The method according to claim 23, wherein the treating step comprises removing the hydrogen-terminated SnO x is oxidized to give hydroxy-terminated SnO x The method includes forming a

32. 32. The method of claim 31 , wherein the oxidizing step comprises exposing the irradiated area to oxygen or water.

33. 32. The method of claim 31, wherein the treating step comprises: x to expose the underlying substrate material, wherein the underlying substrate material comprises amorphous carbon.

34. 34. The method of claim 33, wherein the removing step comprises treating the irradiated area with dilute hydrofluoric acid or dilute aqueous tetramethylammonium hydroxide (TMAH).

35. 34. The method of claim 33, wherein the treating step further comprises etching the underlying substrate material of amorphous carbon using an oxygen plasma.

36. 32. The method of claim 31, wherein the treating step comprises: x The method further comprises depositing a metal oxide hardmask thereon.

37. 37. The method of claim 36, wherein the metal oxide hard mask is SnO x , SiO 2 , SiO x N y , SiO x C, TiO 2 , W.O. x , HfO 2 , ZrO 2 , Al 2 O 3 and Bi 2 O 3 The method of claim 1, further comprising the step of:

38. 24. The method of claim 23, wherein the hydrogen-terminated SnO 2 is produced by selectively irradiating the imaging layer. x selectively depositing a metal layer only on said first conductive layer by atomic layer deposition.

39. 24. The method of claim 23, wherein the hydrocarbyl-terminated SnO in the non-irradiated areas is x is removed by a hydrogen or methane plasma to expose the underlying substrate material, the underlying substrate material comprising amorphous carbon.

40. 40. The method of claim 39, wherein the treating step further comprises etching the underlying substrate using an oxygen plasma.

Images