Apparatus for high resolution latent image processing, contrast enhancement and thermal development and processing

Abstract

A gaseous form of a contrast enhancing agent can be used to facilitate patterning of an organometallic radiation sensitive composition, which may include carboxylic acids, amides, sulfonic acids, alcohols, diols, silyl halides, germanium halides, tin halides, amines, thiols, or mixtures thereof (where the mixtures may be of the same or different classes of compounds). Irradiation of the organometallic composition is followed by contact with a contrast enhancing reactive compound to form a latent image. The contrast enhancing agent can be delivered before or after development of the physical pattern, and processing with the contrast enhancing agent may require removal in a thermal process of some or substantially all of the non-irradiated organometallic composition. The contrast enhancing agent can be used in a dry thermal development step. If the contrast enhancing agent is used after a separate development step, the use of the contrast enhancing agent can be accompanied by improved pattern quality. An apparatus for carrying out processing with the contrast enhancing agent is described.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to pending U.S. Provisional Patent Application No. 63 / 247,885 to Cardineau et al., filed September 24, 2021, entitled “High Resolution Latent Image Processing and Thermal Development,” which is incorporated herein by reference.

[0002] The present invention relates to post-deposition and irradiation processing of organometallic radiation patterning compositions, which may require contact with a contrast enhancing agent and development of the physical image after irradiation. In particular, the present invention relates to reactive vapor treatments that improve image contrast and may facilitate thermal removal of material, facilitating improved pattern development and / or pattern formation. The present invention also relates to apparatus for carrying out the processing. [Background technology]

[0003] Semiconductor patterning requires high performance and high resolution photoresists that enable smaller and smaller features. The fabrication of semiconductor devices typically requires many repeated processing steps of deposition, patterning, and etching to achieve the desired device. Patterning is typically achieved through the use of lithographic techniques. In lithography, an aerial pattern of radiation is transformed into a physical pattern through the use of photoresists and development processes.

[0004] The effort to bring about further changes in the pattern resolution obtained by photolithography has driven the development of new photoresist chemistries. In this context, organometallic radiation patternable compositions have been developed. Due to the new chemistry introduced by these compositions, many new process capabilities may be available to further improve the patterning process. Summary of the Invention [Means for solving the problem]

[0005] One aspect of the invention relates to a method for developing an organotin resist with a composition comprising a contrast enhancing agent, where the contrast enhancing agent can be selected from, for example, amines, silyl halides, alcohols, amides, sulfonic acids, carboxylic acids, thiols, tin halides, germanium halides, and mixtures thereof. In some embodiments, the contrast enhancing agent can be used in combination with gaseous acid halides, HF, HCl, HBr, and / or HI to facilitate the reaction. Some water vapor may be desired in combination with other desired reactants.

[0006] Another aspect of the invention relates to a method for developing an organotin resist with a contrast enhancing agent composition comprising trimethylsilyl halide.

[0007] Another aspect of the invention relates to a method for developing an organotin resist with a composition that contains alkyl groups.

[0008] In another aspect, the invention relates to a method for removing material from a patterned substrate after an initial development process, where the method comprises contacting the patterned substrate with a contrast enhancing agent in vapor form.

[0009] In a first aspect, the present invention relates to a method for enhancing the contrast of development between irradiated and non-irradiated portions of a radiation-sensitive organometallic composition on a surface of a substrate bearing a latent image, the method comprising: The step of contacting the organometallic composition with a reactive gas in a separate chamber to alter the composition of the irradiated portion, the non-irradiated portion, or both, wherein the reactive gas comprises an amide, a sulfonic acid, an alcohol, a diol, a silyl halide, a germanium halide, a tin halide, an amine, or a mixture thereof.

[0010] In a second aspect, the present invention relates to a method for modifying a radiation-sensitive organometallic composition on a substrate surface having a latent image formed by respective irradiated and non-irradiated portions, comprising: The method includes contacting the organometallic composition with carboxylic acid vapor in an independent chamber at a partial pressure of about 0.1 Torr to about 50 Torr, a temperature of about 100° C. to about 250° C., a flow rate of about 0.1 sccm to about 5000 sccm, and a temperature of about −45° C. to about 250° C. to remove a relative amount of the non-irradiated portion ((initial non-irradiated thickness−final non-irradiated thickness) / initial non-irradiated thickness), wherein the relative amount of the thickness of the irradiated portion removed ((initial irradiated thickness−final irradiated thickness) / initial irradiated thickness) is ⅓ or less of the relative amount of the non-irradiated portion removed, while the relative amount of the non-irradiated portion removed is at least about 10%.

[0011] In a third aspect, the present invention relates to a method for improving the quality of a patterned structure having a negative pattern corresponding to the irradiated organometallic composition on a substrate surface having the non-irradiated organometallic composition substantially removed or a positive pattern corresponding to the non-irradiated organometallic composition on a substrate surface having the irradiated organometallic composition substantially removed, the method comprising: developing a pattern from a latent image formed by irradiating a radiation sensitive organometallic composition on a surface of a substrate to form a patterned structure; and after completion of the developing step, contacting the patterned structure in a separate chamber with a reactive gas to remove scum from the pattern, wherein the reactive gas is selected from water, a carboxylic acid, an amide, a sulfonic acid, an alcohol, a diol, a silyl halide, a germanium halide, a tin halide, an amine, a thiol, a hydrogen halide, or mixtures thereof.

[0012] In a fourth aspect, the present invention relates to a method for dry developing a radiation-sensitive organometallic composition having a radiation-patterned latent image on a substrate, the method comprising: The method includes contacting the composition bearing the latent image with a reactive gas to remove a substantial portion of the non-irradiated areas of the coating, wherein the non-irradiated areas of the coating contain Sn-C bonds, and the reactive gas contains an amide, a sulfonic acid, an alcohol, a diol, a silyl halide, a germanium halide, a tin halide, an amine, a thiol, or a mixture thereof.

[0013] In a fifth aspect, the present invention relates to a method for developing a radiation-sensitive organometallic composition having a radiation-patterned latent image on a substrate, the method comprising: contacting the radiation patterning material with a first reactive gas composition to modify non-irradiated areas of the coating to form an initial pattern, wherein the non-irradiated areas of the coating comprise Sn-C bonds, and the first reactive gas composition comprises a carboxylic acid, an amide, a sulfonic acid, an alcohol, a diol, a silyl halide, a germanium halide, a tin halide, an amine, a thiol, or a mixture thereof; and contacting the initial pattern with a second reactive gas composition different from the first reactive gas composition to remove portions of the initial pattern, wherein the second reactive gas composition comprises a carboxylic acid, an amide, a sulfonic acid, an alcohol, a diol, a silyl halide, a germanium halide, a tin halide, an amine, a thiol, or a mixture thereof.

[0014] In a sixth aspect, the present invention provides a method for producing a composition comprising the steps of: with a sealed chamber; a substrate support configured to rotate the substrate on the substrate support within the enclosed chamber; a gas supply subsystem including a gas source reservoir, a gas mist dispenser having a plurality of openings directed toward a substrate mounted on a substrate support and distributed to provide gas distribution over an area of ​​the substrate surface, a gas flow controller, and a gas conduit connecting the gas source reservoir and the gas mist dispenser with flow through the conduit regulated by the gas flow controller; a liquid supply subsystem including a liquid reservoir, a nozzle, a nozzle support having a translatable arm for positioning the nozzle, a flow control device, and tubing providing a flow path between the liquid reservoir and the nozzle, the nozzle support having a structure that configures the nozzle to deposit liquid on a substrate mounted on a substrate support; one or more exhaust pipes exiting the chamber; and a pump. [Brief description of the drawings]

[0015] [Figure 1] 1 is a flow chart of latent image processing of a patterned organotin coating by processing with a contrast enhancing agent and a dry developer. [Diagram 2] 1 is a flow chart for latent image processing of patterned organotin coatings by post-development treatment with a contrast enhancing agent. [Diagram 3] 1 is a flow chart for latent image processing of patterned organotin coatings using a contrast enhancing agent as a vapor reactive developer. [Figure 4] 1 is a schematic diagram of a process system shown with a vapor delivery system connected to a process chamber. [Diagram 5] 1 is a schematic diagram of a process system having a showerhead vapor distribution apparatus. [Figure 6] 1 is a schematic diagram of a process system shown with a vapor delivery system and a liquid delivery system connected to a process chamber. [Figure 7] 1 is a series of plots of coating thickness versus time for irradiated and non-irradiated areas of a patterned coated substrate subjected to a contrast enhancing agent under various processing conditions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The compound is delivered by a dry process, i.e., a vapor delivery process, to a substrate having an organometallic patterning composition with a latent image that facilitates the development of a physical pattern. Organometallic photoresists have been developed that provide a high degree of contrast between exposed and unexposed regions. In some embodiments, the patterning material can include organotin compositions that form oxo-hydrooxo networks with tin-carbon bonds that form radiation-sensitive metal-ligand interactions. Although this process and auxiliary equipment and compositions may be more broadly effective, the discussion focuses primarily on organotin compositions that are of more immediate commercial importance. This high contrast can be used directly to form a physical pattern, which can be used to transfer the pattern to a substrate by addition or etching using the patterned resist as a mask. Nevertheless, improvements in the process as described herein can result in improved patterning efficiency and pattern quality and reduced pattern defects. In some embodiments, contrast enhancer compounds are used to amplify the chemical differences between the unirradiated portions of the organometallic patterning composition and adjacent irradiated regions. A vapor processing step may be desirable to introduce the contrast enhancing agent and to control the process conditions for the reaction induced by the contrast enhancing agent. In some embodiments, treatment with the contrast enhancing agent results in thermal development of the treated non-irradiated portions by conversion to a compound with sufficient vapor pressure for proper thermal development of the patterned substrate. In a continuum of process possibilities, the contrast enhancing agent can react differentially with the organometallic composition of the latent image to further increase the contrast between the irradiated and non-irradiated portions of the composition, possibly with removal of the non-irradiated material (which, if sufficiently removed, results in development of the pattern). Thus, at one end of the continuum, the contrast enhancing treatment actually results in a dry development process. At the opposite end of the continuum, the contrast enhancing treatment improves the contrast during a subsequent wet or dry development step without removing much material during treatment with the contrast enhancing agent. Between these ranges of the continuum of process possibilities is intermediate processing.

[0017] In a one-step process, the contrast enhancing reaction and thermal development are performed simultaneously for particularly effective development, and for these embodiments, the contract enhancing agent can be referred to as a vapor-reactive developer. Thermal development provides an alternative dry development process that avoids the plasma generation used for plasma-based development. In alternative or further embodiments, wet development or separate dry development can be used after treatment with the contrast enhancing agent. Separate dry development can include the use of a different reactive gas or the use of a plasma-driven process. In further or additional embodiments, the contrast enhancing agent and / or thermal development can be applied after the traditional development process to remove residues and reduce defects. Furthermore, a cleaning step can be used after development according to any of these embodiments or between the development step and the dry scum removal step to reduce the occurrence of patterning defects. Organometallic patterning compositions hold great promise for high resolution patterning, especially in the context of EUV patterning, and reducing patterning defects is a key step in the development process that allows the full exploitation of the organometallic potential.

[0018] In summary, contrast enhancing gases can be used for development, whether they directly result in the removal of the non-irradiated organometallic composition or not, and can be used for pattern refinement in a separate processing step after the development is completed, or can be performed separately for both separate steps, generally using different contrast enhancing gas compositions. For development, contrast enhancing agents can be required in any degree of sequence from changing the composition of the non-irradiated organometallic composition to effectively removing substantially all of the non-irradiated organometallic composition in dry thermal development, or between no removal and substantially complete removal. If substantially complete removal of the non-irradiated organometallic composition is not achieved, the subsequent step to finish the development can be any wet development or any dry development step, which can be thermally or plasma driven. After finishing the development to remove substantially all of the non-irradiated organometallic composition, a pattern refinement step can be performed. The wet treatment for pattern refinement can be performed as described below. In some embodiments, a contrast enhancing gas can be used in a separate step for pattern refinement in a thermal process, regardless of the way the development is performed. Pattern refinement using contrast enhancing gases is a separate form for using these agents. The integration of these processes with other process aspects is described below.

[0019] The demand for ever-shrinking patterned semiconductor devices has prompted the development of more sophisticated photoresist materials capable of producing small and high-fidelity features. Photoresists are materials that undergo chemical changes when irradiated with radiation. It is desirable for such materials to faithfully reproduce the blank image of the radiation as a physical and chemical image between irradiated and non-irradiated areas. This chemical image can be developed by removing selected areas of the photoresist by wet or dry methods. The radiation source is generally any source of photons (such as visible, ultraviolet, extreme ultraviolet, or X-ray) or ion beam (such as electron beam) that can be directed to form the desired pattern by the use of a photomask or by controllably rastering the radiation source across the photoresist. For state-of-the-art applications, it is generally desirable for device and feature sizes to be as small as possible, and generally a direct relationship between feature size and the wavelength of the radiation source is exhibited. For example, in current state-of-the-art commercial lithography processes, an extreme ultraviolet (EUV) source with a wavelength of 13.5 nm is used.

[0020] Wafer processing generally includes a series of individual processes that a substrate or wafer undergoes, ranging from coating / deposition to removal of the pattern mask from the substrate. In some embodiments, the substrate is a semiconductor wafer, such as a silicon wafer, with any surface coatings or other modifications. Additionally, a tone reversal process can be performed to reverse the tone of the photoresist pattern. In general, wafer processing can include, among others, coating, baking, transfer steps, backside and edge bead cleaning, radiation exposure, developing, annealing, and etch, often with multiple steps of each type. To perform these steps, liquid, plasma, and gas / vapor processes are often used during semiconductor device manufacturing. For organometallic photoresists, such as organotin compositions, the use of gas / vapor processes can provide useful steps, and are described herein in the context of the overall process progression.

[0021] Recently, organotin compounds have been shown to be effective EUV photoresists capable of achieving very high resolution. To enable high resolution patterning, these organotin materials can be deposited as thin films / coatings and have high etch contrast relative to traditional polymeric photoresist materials, thus enabling more efficient pattern transfer to the underlying substrate. As described further below, precursors containing hydrolyzable ligands can be used to form radiation-sensitive patterning compositions. Organotin deposition can be performed by wet or dry processing, but spin-on organotin resists are now commercially available from Inpria Corporation (Oregon, USA). The post-irradiation processing described herein aims to increase the contrast of development by selective reaction with the non-irradiated portions of the photoresist.

[0022] Metal oxide hydroxide photoresists, such as organotin photoresists, have been shown to have excellent photoresist properties for use in photolithographic patterning. Examples of metal oxide hydroxide photoresists include hafnium and zirconium oxide hydroxides, as described in U.S. Patent No. 9,176,377 B2, entitled "Patterned Inorganic Layers, Radiation Based Patterning Compositions And Corresponding Methods" by Stowers et al., and U.S. Patent No. 9,281,207 B2, entitled "Solution Processible Hardmasks for High Resolution Lithography" by Stowers et al., both of which are incorporated herein by reference. Organotin oxide hydroxide photoresists, in particular, have been shown to achieve high resolution and high sensitivity. Suitable organotin oxide hydroxide photoresists include organotin materials such as those described in U.S. Pat. No. 9,310,684 B2 to Meyers et al. (the '684 patent), entitled "Organometallic Solution Based High Resolution Patterning Compositions," U.S. Patent Application Publication No. 2016 / 0116839 A1 to Meyers et al., entitled "Organometallic Solution Based High Resolution Patterning Compositions and Corresponding Methods," and U.S. Pat. No. 10,228,618 B2 to Meyers et al., entitled "Organotin Oxide Hydroxide Patterning Compositions, Precursors, and Patterning" (the '618 patent), all of which are incorporated herein by reference. More details regarding specific organotin compositions are provided below.

[0023] Without wishing to be limited by theory, during exposure to ionizing radiation, such as EUV photons, UV photons, and ion beams, Sn-C bonds are broken, possibly with the formation of species bearing R. The scission of the bonds results in the volatilization of the hydrocarbyl R groups and the generation of highly reactive Sn sites with unsatisfied coordination numbers. Densification can then occur by crosslinking and / or condensation between Sn sites by reaction with other moieties in the coating, or by reaction with species in the processing environment, e.g., water. In this way, irradiating the coating with a pattern of radiation produces a latent image with a corresponding pattern of density in the coating, where the irradiated areas are generally denser than the non-irradiated areas. In a typical EUV lithography process, the coating is exposed to ambient air after exposure to EUV radiation, where additional reactions with water and / or CO2 can occur in the irradiated areas of the coating to promote the formation of a condensed network, thereby producing significant chemical contrast between the irradiated and non-irradiated areas.

[0024] To achieve a physical image of chemical contrast, photoresists are typically developed in either a negative-tone process, in which non-irradiated material is selectively removed, or a positive-tone process, in which irradiated material is selectively removed. Organotin photoresists can function in either form. The irradiated areas of the organotin oxide hydroxide coating are generally hydrophilic and therefore soluble in aqueous acids or bases and insoluble in organic solvents. Conversely, the non-irradiated areas are generally hydrophobic and therefore soluble in organic solvents and insoluble in aqueous acids or bases. Some useful developer compositions for these organotin oxide photoresists are described in U.S. Patent Application Publication No. 2020 / 0326627 to Jiang et al., entitled "Organometallic Photoresist Developer Compositions and Processing Methods" (hereinafter Application No. '627), which is incorporated herein by reference. The processing described herein deals with contrast enhancing agents that are designed to increase chemical contrast by preferentially reacting with the non-irradiated portions of the coating, making the non-irradiated coating portions more hydrophobic and / or more volatile. In some embodiments, the contrast enhancing agent can form a product coating composition that has significant volatility to allow thermal development to be accomplished as a dry development process without requiring plasma assistance in dry development (which may reduce contrast due to plasma glow). One-step dry development with concurrent reaction of the contrast enhancing agent as a vapor-reactive developer can be particularly efficient by taking advantage of penetration when the prior reacted coating is removed. In general, the contrast enhancing agent can modify the non-irradiated and optionally irradiated organometallic patterning composition, removing a portion of the non-irradiated patterning composition or substantially completely removing the non-irradiated patterning composition.

[0025] Contrast enhancers can also be used after the development step, where they can be used to improve pattern quality, such as by removing scum, i.e., incompletely removed residual patterning material, which can form microbridges and other pattern defects that can result in rejected device level components due to quality control issues. As described in the '627 application, instead or in addition to solution cleaning, vapor contrast enhancers can be used to remove scum and other defects to improve the quality of negative tone patterns.

[0026] Processing with reactive gases to alter irradiated organotin patterning compositions is described in U.S. Patent Application Publication No. 2021 / 0271170 to Telecky et al., entitled "Process Environment for Inorganic Resist Patterning" (hereinafter Application No. '170), which is incorporated herein by reference. As described in Application No. '170, reactive gases can be used as contrast enhancing agents to reactively process the irradiated organometallic coating. In some embodiments, compounds taught in Application No. '170 can be delivered after irradiation to react with the irradiated portions of the coating to increase hydrophilic properties. Reactive gases in Application No. '170 include CO2, SO2, H2S, CH3SH, CO, COS, HOOH, NH3, H2, O3, nitric oxide, PH3, SiH4, CH4, ethylene oxide, or combinations thereof. This processing of the irradiated portions of the coating can generally be combined with a contrast enhancing agent as described herein to react with the non-irradiated portions of the coating.

[0027] It has also been described that solvent-free development, also referred to as dry development, can be used with organotin materials. Dry development can include, for example, selective removal of irradiated or non-irradiated areas of the photoresist by exposing the material to a suitable plasma or a suitable flowing gas. Dry development of organotin resists is described in PCT Publication No. 2020 / 132281A1 by Volosskiy et al., entitled "Dry Development of Resists," which is incorporated herein by reference. See also PCT Application No. WO2020 / 264158 by Tan et al., entitled "Photoresist Development With Halide Chemistries," which is incorporated herein by reference. In such dry development processes, development is performed using small molecule R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 y Z x This can be accomplished by exposing the irradiated substrate to a plasma or thermal process while flowing a gas containing a halide (F, Cl, Br), such as BCl3, a methyl group, or hydrogen. The Tan publication refers to plasma or thermal development using hydrogen halides or other halide-containing chemistries.

[0028] Further dry etching methods are described in PCT Application WO2022 / 125388 to Dictus et al., entitled "Photoresist Development with Organic Vapor" (hereinafter Application '388), which is incorporated herein by reference. In Application '388, carboxylic acid vapors are described that can be combined with acid halides HX, X=F, Cl, Br, I for use in dry development. No examples are given in Application '388, and suitable conditions are not described. The process in Application '388 is further taught to be useful for cleaning the chamber of residues that are deposited therethrough as a by-product of the deposition of resist material. The preferred organic acids in Application '388 are halogenated to increase acidity. As described herein, suitable operating conditions for differential removal of non-irradiated material using carboxylic acids are described. Application '388 emphasizes all vapor processing.

[0029] This disclosure describes the development of organotin coatings through the use of contrast enhancing agents that can selectively react with non-irradiated areas of the coating to make the selected areas more volatile and improve material removal. Appropriate selection of the contrast enhancing agent can improve removal of non-irradiated areas, for example, by converting low density organotin moieties to more volatile low molecular weight species.

[0030] In some embodiments, exposure to the contrast enhancing agent can be performed during the thermal process, where the contrast enhancing agent can function as a vapor-reactive developer. In some embodiments, the thermal process can include controlling the temperature of the contrast enhancing agent before contacting it with the substrate. In other embodiments, the thermal process can include controlling the temperature of the substrate during contacting it with the contrast enhancing agent. Such thermal processes can generally include cooling or heating, where cooling can be performed, for example, if the reaction with the contrast enhancing agent is exothermic and generates significant heat. In particular, for highly reactive contrast enhancing agents (i.e., agents that react rapidly with the coating), it may be beneficial to cool the substrate during its exposure to the contrast enhancing agent to better control the removal rate and subsequent pattern fidelity. In other embodiments, the thermal process can include heating the substrate and / or the contrast enhancing agent to improve the removal rate. The contract enhancing agent can be delivered with an inert gas.

[0031] To improve the development of irradiated organotin coatings, it may be beneficial to expose the substrate to a contrast enhancing agent that can selectively react with non-irradiated regions of the coating to facilitate removal of that material during development. In some embodiments, exposure of the coating to a contrast enhancing agent can occur prior to a subsequent developer step. For example, exposure to a contrast enhancing agent can convert the non-irradiated regions to lower molecular weight and / or more volatile species with little immediate removal (volatilization) of that material, which can then be removed in a subsequent development step, where said regions are substantially removed from the substrate. In other embodiments, exposure of the coating to a contrast enhancing agent can occur during the development step. For example, exposure of the substrate to a volatilizing agent can result in significant volatilization (i.e., removal and / or development) of the non-irradiated material to result in a physical pattern.

[0032] Patterning Compositions and Coating Formation In particularly important embodiments, the organometallic pattern-forming composition is an organotin composition that forms an oxo-hydroxo network structure on the substrate surface. These compositions can be formed using solution coating or vapor deposition methods, and an oxo-hydroxo solution can be used for vapor deposition, although alternative embodiments require the use of precursors with hydrolyzable ligands that hydrolyze during and / or after vapor deposition to form an oxo-hydroxo network structure. Substrates having an organotin oxo-hydroxo composition can optionally be subjected to a post-deposition bake to stabilize the material. Radiation is used to pattern the coating to form a latent image. In the following columns, post-irradiation processing and pattern development are considered.

[0033] In some embodiments, the organometallic radiation-sensitive resist is represented by 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 or organic group that forms a bond between a carbon and a tin atom, and generally the carbon atoms are in the sp 3 hybrid state or the sp 2 hybrid state) and is developed based on an alkyltin composition such as alkyltin hydroxide oxide. The formula is RSnO( 3 / 2-x / 2 )(OH) xz=1 compositions may be of particular interest when: z=1=1, where ... Each R group individually and generally has 1 to 31 carbon atoms, with 3 to 31 carbon atoms for groups having a secondary bonded carbon atom and 4 to 31 carbon atoms for groups having a tertiary bonded carbon atom. In particular, branched alkyl ligands may be desirable for some pattern-forming compositions, where the compound is R 1 R 2 R 3 CSn(NR')3(R 1 and R 2 are independently an alkyl group having 1 to 10 carbon atoms, and R 3 is hydrogen or an alkyl group having 1 to 10 carbon atoms. As mentioned below, this representation of the alkyl ligand R is generally 1 R 2 R 3 The same is applicable to other embodiments of CS(X)3, where X corresponds to a trialkoxide or triamide moiety. In some embodiments, R 1 and R 2 can form a cyclic alkyl moiety, R 3 can also be joined to other groups in the cyclic moiety. Suitable branched alkyl ligands are, for example, isopropyl (R1 and R 2 is methyl, R 3 is hydrogen), tert-butyl (R 1 , R 2 and R 3 is methyl), t-amyl (R 1 and R 2 is methyl, R 3 is -CH2CH3), sec-butyl (R 1 is methyl, R 2 is -CH2CH3, and R 3 is hydrogen), neopentyl (R 1 and R 2 is hydrogen, and R 3 is -C(CH3)3), cyclohexyl, cyclopentyl, cyclobutyl, and cyclopropyl. Examples of suitable cyclic groups include, for example, 1-adamantyl (the tertiary carbon is bonded to the metal, -C(CH2)3(CH)3(CH2)3 or tricyclo(3.3.1.13,7)decane) and 2-adamantyl (the secondary carbon is bonded to the metal, -CH(CH)2(CH2)4(CH)2(CH2) or tricyclo(3.3.1.13,7)decane). In other embodiments, the hydrocarbyl group can include an aryl or alkenyl group, such as benzyl or allyl, or an alkynyl group. In other embodiments, the hydrocarbyl ligand R can include any group consisting of only C and H and containing 1 to 31 carbon atoms. In summary, some examples of suitable alkyl groups bonded to tin include, for example, linear or branched alkyl (i-Pr((CH3)2CH-), t-Bu((CH3)3C-), Me(CH3-), n-Bu(CH3CH2CH2CH2-)), cyclo-alkyl (cyclo-propyl, cyclo-butyl, cyclo-pentyl), olefinic (alkenyl, aryl, allyl derivatives), or alkynyl groups (which generally do not have sp carbons directly bonded to the tin), or combinations thereof. In further embodiments, suitable R groups can include hydrocarbyl groups substituted with heteroatom functional groups such as cyano, thio, silyl, ether, keto, ester, or halogenated groups, or combinations thereof.

[0034] In some embodiments, RSnX3 (or generally R n SnX 4-n Where n=1, 2, or 3), precursors containing the alkyl tin oxide hydroxide compositions can be used to form coatings, but the alkyl tin oxide hydroxide compositions can be deposited directly. Suitable hydrolyzable ligands include, for example, alkynides (R 0 C≡C-), alkoxides (R 0 O-), carboxylate (R 0 COO-), halides, dialkylamides, or combinations thereof, where R 0 The group can be one of the same moieties described above for R. In particular, the organotin trialkoxide composition has the formula RS(OR 0 )3. Also, organotin tridialkylamide compositions can be represented by the formula RSn(NR a R b )3, where R a and R b The group can be one of the same moieties described above for R. In some embodiments, the organotin composition can be present in a blended composition such that the blended composition contains two or more distinct R groups.

[0035] Properly selected organotin compounds with hydrolyzable ligands have suitable vapor pressures at moderate temperatures for deposition. Alternatively, the organotin compounds can be dissolved in organic solvents and deposited, for example, by spin-coating. Water vapor or other oxygen sources can be used to hydrolyze the hydrolyzable ligands in situ to form oxo-hydroxo networks. Hydrolysis can be carried out during the coating process, after the coating process, or some combination thereof.

[0036] For solution-based deposition, the thickness of the coating can generally be a function of the concentration, viscosity, and process parameters of the precursor solution, such as spin speed. For other coating processes, such as vapor deposition, the thickness can also generally be controlled by selection of deposition and coating parameters, such as flow rate, cycle time, number of cycles, and the like. In some embodiments, it may be desirable to use thin coatings to facilitate the formation of small and high-resolution features. In some embodiments, the average dry thickness of the coating material before development can be about 1 micron or less, in further embodiments about 250 nanometers (nm) or less, in further embodiments about 1 nanometer (nm) to about 100 nm, in further embodiments about 1 nm to about 50 nm, in other embodiments about 1 nm to about 40 nm, and in some embodiments about 1 nm to about 25 nm. A person of ordinary skill in the art will recognize that additional ranges of thickness within the above explicit ranges are contemplated and are within the scope of the present disclosure.

[0037] An experimental evaluation of the properties of the resulting coating material can typically be performed to select processing conditions that are effective for the patterning process. Although heating may not be required for better application of the process, it may be desirable to heat the coated substrate to densify the coating to improve processing, increase process reproducibility, and / or promote evaporation of volatile by-products. In embodiments where heat is applied to the coating material after deposition in a post-apply bake (PAB), the coating material can be heated to a temperature of about 45° C. to about 250° C., and in further embodiments, about 55° C. to about 225° C. Heating for solvent removal can typically be performed for at least about 0.1 minutes, in further embodiments, about 0.5 minutes to about 30 minutes, and in further embodiments, about 0.75 minutes to about 10 minutes. The thickness of the final film is determined by the baking temperature and time and the initial concentration of the precursor. One of ordinary skill in the art will recognize that additional ranges of heating temperatures and times within the above explicit ranges are contemplated and are within the scope of the present disclosure. As a result of heat treatment, latent hydrolysis, and densification of the coating material, the coating material can exhibit an increase in refractive index and radiation absorption with little loss in dissolution rate contrast.

[0038] Suitable radiation sources include extreme ultraviolet (EUV), ultraviolet (UV), or electron beam (EB) radiation. For semiconductor device manufacturing, EUV radiation may be desirable due to its higher resolution compared to ultraviolet radiation and its higher throughput compared to electron beam (EB) processing. Typically, radiation can be directed to the support material through a mask, or a radiation beam can be controllably scanned across the substrate to form a latent image in a resist coating. According to the international standard ISO 21348 (2007), which is incorporated herein by reference, ultraviolet radiation spans wavelengths between 100 nm and less than 400 nm, and extreme ultraviolet (EUV) radiation spans wavelengths between 10 nm and less than 121 nm. EUV radiation at 13.5 nm has been used for lithography, and the light is generated from Xe or Sn plasma sources excited using high energy lasers or discharge pulses. Commercial sources of EUV photons include scanners manufactured by ASML Holding NV (Netherlands).

[0039] Post-exposure processing and development of images with contrast enhancing agents Once the latent image is formed by exposure to patterning radiation, the structure can be further processed, for example, by optional post-exposure bake with or without aging, by vapor delivery of contrast enhancing agents, by image development, and / or by pattern refinement, for example, by scum removal. The steps can be arranged in any suitable order, and some of the steps can be mixed together. If a separate development step is used, such development can be liquid-based or dry using thermal or plasma methods. Contrast enhancing agents can generally be small molecule reactants that can selectively diffuse and / or migrate into the less dense (e.g., non-irradiated) areas of the coating to facilitate immediate or subsequent removal of the material. Such contrast enhancing agents can interact with the non-irradiated areas of the coating, for example, by complexation, coordination, acid / base chemistry, redox chemistry, or combinations thereof. In either case, it is desirable for the contrast enhancing agent to have the necessary reactivity with the organotin matrix in the non-irradiated areas so that oxo and hydroxo bonds (e.g., Sn-O-Sn and Sn-OH bonds, or more generally MOM and M-OH) can be cleaved or interrupted to form more volatile or more soluble species.

[0040] After exposure to radiation and formation of the latent image, a subsequent post-exposure bake (PEB) is typically performed. In some embodiments, the PEB can be performed in an ambient environment, and in further embodiments, the PEB can be performed in the presence of a reactive gas such as H2O, CO2, CO, SO2, H2S, phosphine s, H2, or other reactive gases described in the above-cited application '170. In some embodiments, the PEB can be performed at a temperature of about 40°C to about 350°C, in further embodiments about 45°C to about 300°C, in further embodiments about 60°C to about 275°C, and in some embodiments about 100°C to about 250°C. The post-exposure bake can typically be performed for at least about 0.1 minutes, in further embodiments about 0.2 minutes to about 5 minutes, in further embodiments about 0.25 minutes to about 3 minutes, and in other embodiments about 0.3 minutes to about 2 minutes. One of ordinary skill in the art will recognize that additional ranges of PEB temperatures and times within the stated ranges, as well as ranges with the upper and lower limits above interchanged (e.g., 0.1 minutes to about 3 minutes), are contemplated and are within the scope of the present disclosure. The PEB can be designed to further densify and / or consolidate the exposed areas without decomposing the unexposed areas into metal oxides.

[0041] It may also be desirable to have a post-exposure delay during which the exposed wafer is aged. A post-exposure delay can be used as an alternative to a post-exposure bake (although in some embodiments neither can be used), or a post-exposure delay can be performed before a post-exposure bake, or a post-exposure delay can be performed after a post-exposure bake, or a post-exposure bake can be performed both after the first post-exposure delay and before the second post-exposure bake. The aging step can be blurred relative to the post-exposure bake, since the temperature can only be allowed to cool to the aging temperature in successive time frames and / or the temperature can be increased to transition from the aging step to the PEB step. If heating is performed during the post-exposure delay, the heating temperature is generally lower than that of the post-exposure bake, and an appropriate temperature ramp is used to transition between the different heating zones.

[0042] The post-exposure delay can be at least about 10 minutes, in further embodiments at least about 20 minutes, in further embodiments from about 25 minutes to about 7 days, in some embodiments from about 30 minutes to about 3 days, and in other embodiments from about 40 minutes to about 2 days, with further ranges expressly including any and all combinations of delay endpoints in these ranges. The post-exposure delay (PED) can be performed using a specified atmosphere on the wafer as described herein, for example, air, air with modified gas content, N2, argon or other inert gas, or vacuum. The post-exposure delay can generally be performed at a pressure of about 200 Torr to about 1200 Torr, and can be performed at about atmospheric pressure. Process pressures are further described below. The post-exposure delay can be performed at ambient or elevated temperatures, which can accelerate process times to allow for shorter delays. The temperature during or selected portions of the post-exposure delay can be from about 30°C to about 150°C, in further embodiments from about 40°C to about 130°C, in further embodiments from about 50°C to about 120°C, in some embodiments from about 55°C to about 95°C, as well as explicitly including additional ranges based on these temperature endpoints, such as 30°C to 95°C. One of ordinary skill in the art will recognize that additional ranges of time and temperature within the above explicit ranges are contemplated and are within the scope of the present disclosure. Higher temperatures are generally not maintained for extended periods of time. However, various process parameters can be optimized based on the teachings herein to obtain desired improvements in pattern formation.

[0043] Exposure of organometallic resist compositions to radiation generally involves bond scission. In resist compositions of particular interest, bond scission generally requires scission of carbon-metal bonds. Scission of carbon-metal bonds can leave reactive species such as radicals and / or metal atoms that can form another ligand-metal bond. Organic species generally form gas by-products that exit the material, and metal oxide hydroxides condense into more metal oxide-like structures and / or form a network of strongly bonded species that densify, allowing the patterned structures to have high etch contrast between irradiated and non-irradiated areas. For example, densified irradiated coatings become more insoluble in the organic solvents used to solubilize the original organometallic composition.

[0044] Post-exposure processing is generally aimed at promoting and enhancing the reticulation and densification of the exposed coating. Heating can generally accelerate the solid-state reorganization of the lattice structure, which is generally part of the densification process, and heating can also promote certain reactions. However, excessive heating can affect the non-irradiated parts of the coating, which can reduce the contrast of the development, so heating should be properly controlled. Further aging due to post-exposure delay before the development of the latent image can provide additional time for the densification process to take place. During the post-coating processing, the atmosphere surrounding the coated wafer can significantly affect the effectiveness of the processing. The atmosphere can be characterized by composition and pressure.

[0045] The densification process involves small volume changes, where an increase in pressure tends to thermodynamically promote densification. The reverse is also generally true, so that a decrease in pressure tends to thermodynamically hinder densification. Results shown in application '170, where a vacuum is applied during the post-exposure delay, were shown to result in a decrease in etch contrast. Similarly, the chemistry of the atmosphere can alter the effect of the post-exposure process. Suitable gaseous atmospheres can include, for example, air, air plus additional gases, nitrogen, argon and other inert gases, and reactive gases. During or together with the post-exposure delay separate from the separate post-exposure bake, a specific heat can be applied, which can be at a higher temperature than the heating during the post-exposure delay, allowing the two process regimes to be differentiated.

[0046] Regardless of the chemical composition of the atmosphere above the wafer at various process points, the pressure can be adjusted accordingly. The atmospheric pressure at the process facility can serve as a baseline. Since most facilities are above sea level, the actual mean atmospheric pressure is less than standard atmospheric pressure, with additional temporary variations due to weather. Additionally, the ventilation system can be set to maintain a slight negative pressure relative to the outside pressure to control the relative flow of gas into and out of the facility. Within the process chamber, a slight overpressure can be maintained to exchange gas within the chamber. Those skilled in the art will recognize these pressure issues and from a practical standpoint, pressures from about 600 Torr to about 800 Torr can be considered atmospheric pressure, and in some embodiments pressures from 800 Torr to 1200 Torr can be important with respect to maintaining a positive pressure flow of the atmosphere in contact with the wafer. Other pressure ranges can be useful for processing. Other ranges of potential importance include pressures of at least about 200 Torr, and vacuum or low pressure can be considered any pressure of about 1 Torr or less for processing of the wafer. Those skilled in the art will recognize that additional pressure ranges within the above stated ranges are contemplated and are within the scope of the present disclosure.

[0047] The reaction of the contrast enhancing agent with the organotin matrix can result in the formation of more easily removable, possibly more volatile species that can then be immediately or subsequently removed from the substrate. Reactions induced by the contrast enhancing agent can generally include addition reactions, substitution reactions, and / or acid / base neutralization reactions. In some embodiments, reactions with oxo and hydrooxo bonds can generally be achieved by replacing network-forming -O- and / or -OH ligands with ligands that have a much less tendency to form networks. In some embodiments, reactions involving replacement of ligands of the organotin matrix can include acid / base neutralization reactions, for example: RSnOH+HX → RSnX+H2O RSnO+XOH → RSnX+H2O The tendency of a contrast enhancing agent to react with and displace -O- or -OH ligands may generally depend on its pKa. In some embodiments, the contrast enhancing agent may be protic and may cause protonation of -O- and / or -OH ligands to disrupt the organotin oxo-hydroxo network, resulting in lower molecular weight species that are easily removed upon development. In other embodiments, the contrast enhancing agent may be aprotic.

[0048] In some embodiments, the contrast enhancing agent may include compounds capable of undergoing a substitution reaction in which replacement of the ligand is achieved in the organotin matrix, for example: RSnOH+AX → RSnX+AOH In some embodiments, the contrast enhancing agent may include nucleophilic compounds that allow the contrast enhancing agent to undergo addition reactions to complex, coordinate, or similarly interact with the organotin matrix to produce new compositions, such as: RSnOH+X → RSnXOH For the general reactions above, it may be advantageous to introduce the contrast enhancing agent as a continuous or pulsed flow into the thermal development process to advance the reaction equilibrium by continuously removing the product, e.g., H2O, while continuously supplying the reactants. Similarly, if the tin product is similarly evaporated in a one-step process, this will further advance the equilibrium while achieving the development goal, whether or not the development is thus terminated, or if further development is performed. It should also be understood that the reactions above are intended to be illustrative and not limiting.

[0049] The use of a contrast enhancing agent can be used in one or more roles in the process flow. For example, it can be used after irradiation and after any post-exposure bake to differentially improve the pattern. At this stage of processing, the contrast enhancing agent can result in partial or essentially complete removal of the non-irradiated organometallic composition. The processing can span a continuum of these boundaries, from little tin removal from the non-irradiated areas to essentially complete tin removal. Further processing can be selected accordingly, as described below. In yet another or alternative embodiment, the contrast enhancing agent can be provided after a separate development step, which can be a liquid development step or a dry development step, such as a vapor development (dry thermal development) using a separate contrast enhancing agent or a plasma etch as a dry development, as well as a dry development step using a contrast enhancing agent as described herein. The use of a post-development step of a contrast enhancing agent can result in pattern improvement, such as scum removal, microbridge removal, etc. In either case, the tin reaction products can be removed in situ, i.e., while the reaction is in progress, to facilitate development of the pattern.

[0050] Also, the appropriate choice of contrast enhancer may depend on the difference in relative density between irradiated and non-irradiated materials. For negative tone development, it may be desirable for the contrast enhancer to selectively diffuse into non-irradiated regions to facilitate removal of material in those regions. Thus, it may be desirable for the contrast enhancer to have a balance between steric bulkiness and acidity. In other words, it may be desirable for the contrast enhancer to selectively bind and diffuse in non-irradiated regions so that it only reacts substantially in those regions. Depending on the composition and processing of the organotin coating, a wide range of material densities may be present in the coating. For example, for organotin compositions with bulkier R groups as defined above, decomposition by radiation may result in a larger volume loss compared to compositions with smaller R groups.

[0051] The density of organotin photoresist coatings may generally depend on both the chemical composition and processing of the coating involved. In general, prior to irradiation, organotin compositions with larger or bulkier R groups, such as tert-butyl(CH3)3C-, have a lower tin number density than compositions with smaller R groups, such as methylCH3. Density may be roughly correlated with the number of Sn-O-Sn and / or Sn-OH bonds in a given volume, with bulkier R groups generally increasing the distance between such bonds. After irradiation by a suitable radiation source, such as EUV photons, the irradiated material may condense to a greater extent than the non-irradiated material due to the reduction in R groups that inhibit condensation in the irradiated regions.

[0052] Processing of the coating can also affect its density, particularly processes or steps that increase the concentration of Sn-O-Sn and / or Sn-OH bonds. For example, baking the substrate at a higher temperature generally densifies and concentrates the coating, thus increasing the concentration of Sn-O-Sn and / or Sn-OH bonds. The Sn-O-Sn and Sn-OH bonds can be terminal or bridged, e.g., bridged to two or more Sn atoms via O and / or OH bonds. The density of the material generally increases with the bridge concentration of O and OH bonds, thereby making it more difficult for contrast enhancing agents and other reactants to diffuse into the matrix. As described above, the density of irradiated materials is generally higher than that of non-irradiated materials.

[0053] Also, the hydrophobicity and / or polarity of the organotin coating may affect the appropriate choice of contrast enhancing agent. Coatings with more carbon, e.g. compositions with more C atoms in the R group, are generally less polar than coatings with less carbon. Similarly, after exposure to radiation, non-irradiated areas generally contain substantially complete Sn-C bonds, i.e. complete R groups, while irradiated areas generally contain significantly fewer Sn-C bonds, i.e. significantly less C content. In this way, the polarity of the coating can be specifically controlled by the processing and chemical composition of the organotin coating. Less polar reactants are generally more penetrative into the less polar non-irradiated parts of the coating.

[0054] Suitable contrast enhancing agents include, for example, amines (e.g., RNH, RNH, RN), silicon and silyl halides (e.g., SiX, R n Six 4-n), alcohols (e.g., ROH) and thiols (e.g., RSH), diols (e.g., ROHR'OH), carboxylic acids (e.g., RCOOH) and amide derivatives (e.g., RCONH2), sulfonic acids (e.g., RSO2OH), and combinations and mixtures thereof, where R and R' are independently linear, branched, or cyclic hydrocarbon groups having 1-10 carbons. For vapor delivery, the contrast enhancing agent should have sufficient vapor pressure at the processing temperature. In some embodiments, the substrate can be exposed to one or more of these agents simultaneously or separately.

[0055] In some embodiments, contrast enhancing agents that undergo an addition reaction can be used, for example, amines can be used. Specifically, suitable amines can include ammonia NH3 and / or alkylamines and their isomers with alkyl chains having 1-4 carbons, such as trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine dibutylamine, diisobutylamine, methylamine, ethylamine, propylamine, butylamine, pyridine, pyrrolidine, etc., and mixtures thereof. Further examples of suitable amines can include silyl derivatives, such as trimethylsilylamines, such as trimethylsilyltris(dimethylamine)(CH3)3Si(NMe2)3 and trimethylsilyltris(diethylamine)(CH3)3Si(NEt2)3. In some embodiments, mixtures of silylamides and alkylamines can be used. As further described below, the contrast enhancing agent can be delivered with an inert gas.

[0056] In some embodiments, contrast enhancing agents that undergo a substitution reaction can be used, such as silicon and / or group 14 halides, such as silyl halides, germanium halides, and / or tin halides. Suitable group 14 halides include, for example, those of the formula R n MX 4-n(M=Si, Ge, or Sn, R=CH3 or CH3CH2, n=0-3, and X=Cl or Br). Suitable compositions where M=Si can be, for example, trimethylsilyl chloride (CH3)3SiCl, trimethylsilyl bromide (CH3)3SiBr, dimethylsilyl chloride (CH3)2SiCl2, dimethylsilyl bromide (CH3)2SiBr2, monomethylsilyl chloride (CH3)SiCl3, monomethylsilyl bromide (CH3)SiBr3, tetrachlorosilane SiCl4, tetrabromosilane SiBr4, and combinations thereof. Similar Ge and Sn halide compositions can also be used. The steric bulkiness of the Group 14 halides can generally be correlated with the degree of alkylation of the M atom, for example, (CH3)3SiCl is generally bulkier than (CH3)SiCl3. Furthermore, the acidity of the Group 14 halide generally correlates indirectly with the degree of alkylation of the M atom, e.g., (CH3)3SiCl is generally less acidic than (CH3)SiCl3. The appropriate selection of the Group 14 halide can be determined by the difference in density and / or hydrophobicity between the irradiated and non-irradiated areas of the photoresist coating, as well as by the pKa of the Group 14 halide.

[0057] In some embodiments, alcohols can be used to effect addition reactions, substitution reactions, or combinations thereof. Suitable alcohols can include R-OH (R is a linear, branched, or cyclic alkyl group having 1-10 carbons), such as, but not limited to, methanol, ethanol, n-propanol, iso-propanol, 1-butanol, iso-butanol, tert-butanol, 1-pentanol, 4-methyl-2-pentanol, cyclopentanol, 1-hexanol, cyclohexanol, phenol, and the like, and combinations thereof. In some embodiments, the alkyl group can include a hydrogen atom substituted with a halogen (e.g., F, Cl, I, Br), such as nonafluoro-tert-butyl alcohol ((CF3)3COH), pentafluorophenol (CF5OH), and the like. The appropriate selection of the alcohol contrast enhancing agent can be determined by the hydrophobicity and / or steric hindrance of the -OH group, to optimize diffusion of the agent to the non-irradiated areas of the coating. For example, primary alcohols are generally less sterically hindered than secondary alcohols, which in turn are generally less sterically hindered than tertiary alcohols. In some embodiments, thiol derivatives of alcohols can be used, such as methanethiol, ethanethiol, propanethiol, isopropanethiol, butyrothiol, isobutyrothiol, tert-butylthiol, and the like, and combinations thereof. The alcohols can be halogenated, e.g., fluorinated. In some embodiments, mixtures of alcohols and thiols can be used. In some embodiments, the selection of the alcohol can be based, in part, on the volatility of the tin-containing reaction product.

[0058] In some embodiments, diols can be used. Suitable diols can include compositions having 1-10 carbon atoms and their isomers, as well as their cyclic and ether analogs, such as, but not limited to, methylene glycol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, cyclohexanediol, mixtures thereof, and the like.

[0059] In some embodiments, carboxylic acids can be used. Suitable carboxylic acids can include compounds with alkyl chains having 1-10 carbon atoms and their isomers, such as formic acid HCOOH, acetic acid CH3COOH, propionic acid CH3CH2COOH, butyric acid CH3(CH2)2COOH, isobutyric acid (CH3)2CHOOH, benzoic acid (C6H5)COOH, and the like, and combinations thereof. In some embodiments, the alkyl chain can include hydrogen atoms replaced with halogens (e.g., F, Cl, I, Br), such as trifluoroacetic acid (CF3COOH), trichloroacetic acid (CCl3COOH), and the like. In some embodiments, amide derivatives of carboxylic acids can be used, such amides can include, for example, formamide, N-methylformamide, acetamide, urea, propanamide, butyramide, isobutyramide, and the like, and combinations thereof. In some embodiments, mixtures of carboxylic acids and amides can be used.

[0060] In some embodiments, sulfonic acids can be used. Suitable sulfonic acids can include compositions represented by the general formula RSO2OH, where R is a linear, branched, or cyclic alkyl chain having 1-10 carbon atoms, such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid (C7H7SO2OH), and the like, and combinations thereof. In some embodiments, R can include an alkyl chain in which the hydrogen atoms are replaced with halogens (e.g., F, Cl, I, Br), such as triflic acid (CF3SO2OH). In other embodiments, R can include functional groups such as amines (-NH2), thiols (-SH), and alcohols (-OH).

[0061] In some embodiments, the contrast enhancing agent composition can further include water. For some contrast enhancing agents, such as carboxylic acids, water can be difficult to completely remove from the source, which can further facilitate the delivery of the contrast enhancing agent to the surface of the substrate. It may also be desirable to contain hydrogen halide (HF, HCl, HBr, HI, or mixtures thereof) gas in addition to water or as an alternative option as a reactant aid for delivery with the contrast enhancing agent described herein. Water and hydrogen halide can be provided as a reaction promoter in the same partial pressure range as the contrast enhancing agent. Similarly, it may be desirable to use a mixture of contrast enhancing agents that can be delivered simultaneously or in sequence, or some combination thereof.

[0062] Those skilled in the art will appreciate that the desired selection of contrast enhancing agents may depend on the particular organotin composition and process variables, and routine experimentation can provide an appropriate selection based on the teachings herein. As noted above, the pKa of a given contrast enhancing agent may affect reaction rates during development. Without wishing to be limited by theory, it is generally expected that contrast enhancing agents with low pKa, such as carboxylic acids and sulfonic acids, or high pKa relative to the organotin matrix, may cause acid / base neutralization reactions to facilitate removal of the neutralized species. Thus, the appropriate selection of contrast enhancing agents may be provided by the desired pKa along with other factors discussed herein.

[0063] Steric bulk is also a factor in the diffusion of contrast enhancing agents to the reactive surface and into the organotin matrix. For example, without wishing to be limited by theory, it is believed that compositions containing trimethylsilyl (TMS) groups may be useful in tailoring a particular contrast enhancing agent composition due to the size of the TMS group and its generally similar behavior to H-substituents, thus providing a unique opportunity to tailor the composition of the contrast enhancing agent appropriately for development of a given organotin composition. In other examples, by substituting the R groups of the contrast enhancing agent with bulkier groups, the reaction rate of the irradiated regions can be reduced due to their reduced ability to diffuse into the dense organotin oxo-hydroxo matrix. In some embodiments, multiple contrast enhancing agents can be used simultaneously or sequentially. In some embodiments, the contrast enhancing agents can be delivered in the presence of or using an inert gas such as N2, He, Ne, Ar, Kr, and / or Xe, which generally requires a pulsed or continuous flow through the system.

[0064] Introducing a contrast enhancing agent, which may function as a volatile gas, to react with the irradiated coating can generally be performed after exposure to radiation. In some embodiments, it may be beneficial to perform a post-exposure bake (PEB) on the irradiated substrate to heat the coating and further condense the irradiated regions, thereby increasing the chemical (e.g., hydrophobicity) and / or physical (e.g., density) contrast between the irradiated and non-irradiated regions. The application of the post-exposure bake is further described above. The specific conditions of the post-exposure bake can be adjusted to be compatible with the choice of contrast enhancing agent to achieve the desired performance from the contrast enhancing agent. After exposure to radiation, the irradiated regions generally have less carbon content than the non-irradiated regions, and therefore can generally be promoted to a higher density relative to the non-irradiated regions.

[0065] Regardless of whether a post-exposure bake is performed, it may be desirable to apply heat simultaneously with development and / or exposure to the contrast enhancing agent. Heat may be useful to volatilize reaction products to allow for their removal from the process chamber and for facilitating reaction with the contrast enhancing agent. The wafer / substrate, gases and / or the chamber itself may be heated or cooled to provide the desired temperature for processing. Temperatures may be from about -45°C to about 350°C, in further embodiments from about -10°C to about 300°C, and in further embodiments from about 0°C to about 250°C. Reaction times may be at least about 0.1 minutes, in further embodiments from about 10 seconds to about 5 minutes, and in further embodiments from about 20 seconds to about 3 minutes. In some embodiments, the chamber pressure may be from about 100 Torr to about 1200 Torr, and in further embodiments from about 200 Torr to about atmospheric pressure (about 760 Torr), although as noted below, gases in the chamber are generally flowing and flow rates are also important. To maintain these pressures given the lower partial pressures of the reactant gases, an inert diluent gas may be delivered along with the contrast enhancing agent. In alternative embodiments, an inert gas may not be used and the chamber pressure is approximately equal to the partial pressure of the contrast enhancing agent, as indicated below. A person of ordinary skill in the art will recognize that additional ranges of reaction / heating times, pressures, and temperatures within the explicit ranges above are contemplated and are within the present disclosure.

[0066] The contrast enhancing agent can be introduced into the process chamber holding the substrate by flowing the vaporized contrast enhancing agent into the chamber at a desired flow rate and / or constant pressure. If more than one contrast enhancing agent and / or inert gas is used in the process, the partial pressure and / or flow rate of each individual contrast enhancing agent or inert gas can be controlled. In some embodiments, the partial pressure of each contrast enhancing agent and / or inert gas in the chamber can be between about 1 mTorr and about 10 Torr in some embodiments, about 10 mTorr and about 8 Torr in other embodiments, about 50 mTorr and about 7 Torr in other embodiments, and about 100 mTorr and about 5 Torr in further embodiments. The pressure can be controlled at a particular pumping speed by varying the flow rate of each individual reactive gas into the process chamber, for example, from about 0.5 sccm to about 1000 sccm in some embodiments, from about 1 sccm to about 500 sccm in other embodiments, and about 2 sccm to about 200 sccm in further embodiments. Whether a higher or lower chamber pressure is used, the chamber pressure can be varied during the course of processing as desired. When used, the inert gas can be delivered at a higher rate and can be used to maintain a higher chamber pressure without changing the selected flow rate of the reactive gas. The inert gas flow rate can be from about 0.5 standard liters per minute (SLM) to about 30 SLM, in further embodiments from about 1 SLM to about 20 SLM, and in further embodiments from about 3 SLM to about 15 SLM. It should be generally understood by those skilled in the art that the desired gas flow rate can depend on the size of the chamber used to perform the process. Generally, lower gas flow rates can be used for smaller chambers and higher flow rates can be used for larger chambers. For example, for a process involving a chamber having a size of about 1 L and a gas flow rate of 1 to 100 sccm, a larger 50 L chamber can be expected to correspondingly require about a 50 times higher flow rate of 50 to 5000 sccm.A person of ordinary skill in the art will recognize that additional ranges of pressures and flow rates within the explicit ranges are contemplated and are within the present disclosure.

[0067] It is convenient to provide a process flow for the use of a contrast enhancing agent in three figures to illustrate more specific embodiments related to some currently preferred implementations. Figure 1 shows a flow chart of latent image processing of patterned organotin coatings where the contrast enhancing agent is used prior to treatment with a dry developer, although alternative embodiments may require a liquid developer. Figure 2 shows a flow chart of latent image processing of patterned organotin coatings where the contrast enhancing agent is used after the development step for pattern refinement. Figure 3 shows a flow chart of latent image processing of patterned organotin coatings where the contrast enhancing agent is used as a vapor reactive developer.

[0068] In the flow chart of FIG. 1, an organotin composition is deposited 100 on a substrate. Deposition can use a solution-based method such as spin-coating, or a vapor-based method such as physical vapor deposition (PVD), chemical vapor deposition (CVD), atomic layer deposition (ALD), or modifications thereof. After an optional pre-exposure bake 102, the coated substrate is exposed 104 to radiation, such as EUV radiation, to form a coating bearing a latent image. After an optional post-exposure bake (PEB) and / or delay 106, the patterned coated substrate is subjected to treatment 108 with a vapor-based contrast enhancing agent / dry developer in a suitable chamber. Optional heating protocols for use with the contrast enhancing agent can include controlling the temperature of the contrast enhancing agent, controlling the temperature of the substrate, and / or performing a post-treatment bake. After contact with the contrast enhancing agent for a selected time and at a selected flow rate / chamber pressure, the coated substrate is then contacted with a vapor-based dry developer separate from the contrast enhancing agent. The optional heating protocol may include controlling the temperature of the dry developer, controlling the temperature of the substrate, or performing a post-development bake. The treatment 108 with the vapor-based contrast enhancing agent may be repeated.

[0069] Partial development of the image, in other words removal of non-irradiated material, may occur simultaneously with treatment with the contrast enhancing agent. Reaction products such as volatile species may be removed from the chamber during the treatment steps. In some embodiments, the volatile species are removed from the surface of the coating and / or from the chamber using a reactive gas flow. In some embodiments, pulses of purge gas may be used. Removal of volatile species may be continuous during treatment with the contrast enhancing agent and / or dry developer or at discrete times during treatment. In other embodiments, reaction products are removed using a wash liquid, for example after treatment with the contrast enhancing agent and before treatment with the dry developer, although alternative embodiments may include the use of a liquid developer. The wash liquid may be delivered at a selected temperature, such as room temperature. If a separate development step is used, dry development may be performed using the reactive gases already identified for thermal development or using a plasma. The contrast enhancing agents described herein may be effective to accelerate the development process and act as effective agents for pattern refinement and / or as dry development reactants after separate development as an alternative to liquid washes.

[0070] After development, the substrate is then subjected to an optional cleaning / de-scumming 110 to provide an improved patterned substrate, for example, by de-scumming, micro-bridging, or enhancing other features. Cleaning / de-scumming 110 can remove portions of the developed coating to control pattern dimensions. In some embodiments, cleaning / de-scumming 110 can remove products of reaction with contrast enhancing agents. Cleaning / de-scumming 100 can require cleaning with a liquid that is a solvent for the developed coating and / or de-scumming with a vapor-based contrast enhancing agent, optionally with the introduction of a drying or baking step. Conditions for use of the vapor-based contrast enhancing agent for pattern improvement / de-scumming can be within the same ranges described above for contrast enhancement prior to development, and adjustments can be made to obtain desired results based on the teachings herein. The use of cleaning solutions to improve patterns is further described in U.S. Patent Application Publication No. 2020 / 0124970 to Kocsis et al., entitled "Patterned Organometallic Photoresists and Methods of Patterning" (hereinafter Application No. '970), which is incorporated herein by reference.

[0071] Referring to the flow chart of FIG. 2, an organotin composition is deposited 120 on a substrate. Deposition can be by solution-based methods such as spin-coating, or vapor-based methods such as physical vapor deposition (PVD), chemical vapor deposition (CVD), atomic layer deposition (ALD), or modifications thereof. After an optional pre-exposure bake 122, the coated substrate is exposed to radiation 124, such as EUV radiation, to form a coating having a latent image. After an optional post-exposure bake (PEB) and / or delay 126 and optional treatment 128 with a vapor-based contrast enhancing agent, the patterned coated substrate is subjected to development 130. Development 130 can be a liquid-based or vapor-based process. Vapor-based development is exemplified below. In general, processing with a contrast enhancing agent may involve some volatilization of the non-irradiated organotin patterning composition along with chemical modification. Any degree of material removal can be beneficial. As long as the contrast enhancing agent results in all or essentially the removal of the non-irradiated organotin composition, the contrast enhancing agent can be considered a dry developer. The optional wet development or alternative dry development process is described further below.

[0072] After development 130, the patterned coated substrate can be subjected to treatment 132 with a vapor-based contrast enhancing agent in a suitable chamber to provide an improved patterned substrate. Treatment time, flow rate of contrast enhancing agent vapor, and / or chamber pressure can be adjusted, with suitable parameter ranges being discussed in detail above. Optional heating protocols can include controlling the temperature of the contrast enhancing agent, controlling the temperature of the substrate, performing a post-development drying and / or baking step, and / or performing a post-treatment bake. As a further option, a cleaning / descumming step can be performed after treatment 132 with the vapor-based contrast enhancing agent. Reaction products such as volatile species can be removed from the chamber during treatment 132 with the vapor-based contrast enhancing agent. In some embodiments, the volatile species are removed from the surface of the coating and / or from the chamber during the vapor treatment process or optionally using a purge gas. In some embodiments, a pulse of purge gas may be used. In other embodiments, reaction products are removed using a cleaning liquid after treatment 132 with the vapor-based contrast enhancing agent, which can instead be considered a liquid developer. The cleaning liquid can be delivered at a selected temperature, such as room temperature. The process according to Figure 2 can be carried out sequentially using suitable chambers for organotin deposition on substrate 120, optional treatment with vapor-based contrast enhancing agent 128, development 130, and treatment with vapor-based contrast enhancing agent 132. Alternatively, the process according to Figure 2 can be carried out in a multi-chamber processing system designed to accommodate both liquid-based and vapor-based processes, such as described below for the embodiment of Figure 6.

[0073] In the procedure outlined with reference to the flow chart of FIG. 3, an organotin composition is deposited on a substrate 140. Deposition can be by solution-based methods such as spin-coating, or vapor-based methods such as physical vapor deposition (PVD), chemical vapor deposition (CVD), atomic layer deposition (ALD), or modifications thereof. After an optional pre-exposure bake 142, the coated substrate is exposed to radiation 144, such as EUV radiation, to form a coating having a latent image. After an optional post-exposure bake (PEB) and / or delay 146, the patterned coated substrate is subjected to treatment 148 with a vapor-reactive developer in a suitable chamber to provide a physically patterned coating on the substrate. The temperature of the vapor-reactive developer, the temperature of the substrate, and the outflow of volatile species from the chamber can be controlled during treatment 148 with the vapor-reactive developer. Reaction products such as volatile species can be removed from the chamber between treatment steps. In some embodiments, the volatile species are removed from the surface of the coating and / or from the chamber using a reactive gas flow or separately using a purge gas. In some embodiments, pulses of purge gas may be used. The removal of the volatile species may be continuous during the process 148 or at discrete times during the process 148. In other embodiments, the reaction products and / or residual materials may be removed after the process 148 using a cleaning liquid. The cleaning liquid may be delivered 150 at a selected temperature, such as room temperature. During any contact with the cleaning liquid, the substrate is subjected to cleaning / descumming 150 to provide an improved patterned substrate, for example, by scum removal, microbridging removal, or enhancement of other features. The cleaning / descumming 150 may remove portions of the developed coating to control pattern dimensions. In some embodiments, the cleaning / descumming 150 may remove products of reaction with a vapor-reactive developer resulting from the process 148. The cleaning / descumming 150 may require cleaning with a liquid that is a solvent for the developed coating and / or descumming with a vapor-based contrast enhancing agent, optionally with the introduction of a drying or baking step.In an alternative or further embodiment, a different contrast enhancing composition can be used to deliver contrast enhancing agents after development 148 to effect the process of pattern refinement.

[0074] It may be desirable to control the temperature of the development process to help selectively tailor the etch, for example, between irradiated and non-irradiated areas, or between any areas of the resist and other layers that may be at least partially exposed to the contrast enhancing agent and / or plasma ions and / or radicals. In some embodiments, various heating and / or cooling elements and associated controls may be present in or about the chamber. In some embodiments, the substrate mount may include a heating element capable of heating the wafer in the chamber. In other embodiments, the substrate mount may include a cooling element capable of cooling the wafer in the chamber. In other embodiments, the substrate mount may include an element capable of heating or cooling the wafer.

[0075] In some embodiments of the process, multiple inlets and outlets can be attached to the chamber to provide for delivery of desired gases into the chamber, and species can be removed from the chamber by vacuum or gas flow. A mount for a substrate containing photoresist that is desired to be developed can be present within the chamber or in sufficient proximity to the chamber so that the contrast enhancing agent and / or associated plasma generated ions and / or radicals can reach the photoresist on the substrate surface.

[0076] A schematic diagram of a suitable process system 300 for vapor-based processing is shown in FIG. 4. The process system 300 includes a vapor delivery system 301 and a process chamber 314. In some embodiments, the vapor delivery system 301 includes a process gas 302. In some embodiments, the vapor delivery system 301 includes a reservoir 303 of process liquid for vapor delivery. The process gas supply 302 and / or the process liquid reservoir 303 include a contrast enhancing agent as described above. In some embodiments, the vapor delivery system 301 includes a source 304 of inert gas. The process liquid 303 can be delivered to a vaporizer 306 by a liquid flow controller 305. A mixer 307 receives controlled flows of the process gas 302, vaporized process liquid, and / or inert gas 304, each controlled by one or more inlet valves 308. In some embodiments, the vapor delivery system 301 includes a plasma device 309. A temperature regulator 310 is provided to control the temperature of the process vapor 312 entering the process chamber 314.

[0077] The process chamber 314 has a vapor distributor 316. The vapor distributor 316 can have a selection from a variety of suitable shapes and designs. In some embodiments, the vapor distributor 316 has a showerhead shape with multiple hole designs, one embodiment of which is shown in FIG. 5. The process chamber 314 has a support 318. The substrate 320 is disposed below the vapor distributor 316 and rests on the support 318. In some embodiments, the support 318 can be temperature controlled by a heating / cooling device 322. The support 318 can be connected to a motor to rotate the support 318 for substrate processing. The support 318 can be raised or lowered manually or remotely to adjust the distance between the substrate and the vapor distributor. A pressure valve 324 provides control of the pressure and concentration of volatile reaction products in the process chamber 314. The pressure valve 324 can be connected to a pump, such as a vacuum pump. In some embodiments, a controller 326 is provided to remotely control the elements of the process system 300.

[0078] 5 illustrates one embodiment of the vapor distributor 306 as part of a simplified diagram of a process system 300. The process system 400 is shown having a vapor delivery system 402 and a process chamber 404 having a pressure valve 412. Within the process chamber 404 is a showerhead vapor distributor 406, a substrate 408, and a support 410. The showerhead vapor distributor 406 is shown with an optional gated nanochannel grid to provide more uniform vapor contact on the substrate surface.

[0079] FIG. 6 shows a schematic diagram of a suitable multi-functional chamber process system 600. The process system 600 includes a vapor delivery system 601 and a process chamber 614. In some embodiments, the vapor delivery system 601 includes a reservoir of process gas 602. In some embodiments, the vapor delivery system 601 includes a reservoir of process liquid 603. The reservoir of process gas 602 and / or the reservoir of process liquid 603 include a contrast enhancing agent as described above. In some embodiments, the vapor delivery system 601 includes a reservoir of inert gas 604. The process liquid 603 can be delivered to a vaporizer 606 by a liquid flow controller 605. A mixer 607 receives controlled flows of the process gas 602, the vaporized process liquid, and / or the inert gas 604, each controlled by one or more inlet valves 608. In some embodiments, the vapor delivery system 601 includes a plasma device 609. A temperature regulator 610 is provided to control the temperature of the process vapor 612 entering the process chamber 614 .

[0080] The process chamber 614 has a vapor distributor 616. The vapor distributor can have a selection from a variety of suitable shapes and designs. In some embodiments, the vapor distributor 616 has a showerhead shape with multiple hole designs, one embodiment of which is shown in FIG. 6. The process chamber 614 has a support 618. A substrate 620 is disposed below the vapor distributor 616 and rests on the support 618. In some embodiments, the support 618 can be temperature controlled by a heating / cooling device 622. The fluid delivery nozzle 628 receives a controlled flow from a process liquid reservoir 630, a process liquid reservoir 632, or a process liquid reservoir 634, which are controlled by inlet valves 636, 638, and 640, and an inlet valve 642, respectively. In some embodiments, the process liquid reservoir 630 stores an organotin precursor solution. In some embodiments, the process liquid reservoir 632 stores a developer liquid. In some embodiments, the process liquid reservoir 634 stores a cleaning liquid. A retractable arm 644 is provided to support the fluid delivery nozzle 628 and allow adjustment of the position of the fluid delivery nozzle 628, which may also provide movement of the delivery nozzle 628 after vapor delivery. The support 618 is connected to a motor 646 to rotate the support 618 for substrate processing, such as deposition of a film on a substrate by spin coating, liquid-based development, and / or cleaning / descumming. A drain 648 is provided for removal of processing liquids. The support 618 may be raised or lowered manually or remotely to adjust the distance between the substrate and the vapor distributor. A pressure valve 624 provides control of the pressure and concentration of volatile reaction products in the process chamber 614. The pressure valve 624 may be connected to a vacuum pump. In some embodiments, a controller 626 is provided to remotely control elements of the process system 600.

[0081] More specifically, the development process may generally include introducing and contacting the treated coating onto a substrate in a thermal and / or plasma process. In some embodiments, the thermal process may include controlling the temperature of the contrast enhancing agent prior to contacting the coated substrate. In yet another or alternative embodiment, the thermal process may include controlling the temperature of the substrate during contacting with the contrast enhancing agent. Such a thermal process may generally include cooling or heating. In some embodiments using highly reactive contrast enhancing agents (i.e., contrast enhancing agents having a significantly higher or lower pKa), it may be beneficial to cool the substrate during its exposure to the contrast enhancing agent to better control the removal rate and improve subsequent pattern fidelity. In embodiments using cooling, the thermal process may be from about -80°C to about 0°C, in other embodiments from about -60°C to about -20°C, and in further embodiments from about -50°C to about -30°C. For some cooling embodiments, liquid nitrogen may be a particularly useful cooling liquid. In other embodiments, the thermal process may include heating the substrate. In some embodiments, a suitable temperature range for carrying out the thermal process may be from about 20° C. to about 400° C., in other embodiments from about 40° C. to about 300° C., and in further embodiments from about 50° C. to about 200° C. The duration of the thermal process may be from about 0.1 minutes to about 10 minutes in some embodiments, from about 0.2 minutes to about 5 minutes in further embodiments, and from about 0.3 minutes to about 2 minutes in still further embodiments. A person of ordinary skill in the art will recognize that additional ranges of temperatures and times within the above ranges are contemplated and are within the scope of the present disclosure.

[0082] When considered in the context of the process flow of Figures 1-3, in some embodiments, a contrast enhancing agent can be used in support of a separate development step. For the separate development step, a liquid development step or a dry development step can be used. The dry development step can be gas-based that develops the non-irradiated material in a thermal process and / or by the use of plasma. As described above, a development step can be used at the process location selected for the use of the contrast enhancing agent.

[0083] In some embodiments, it may be desirable to contact the irradiated substrate with a plasma to develop as a separate step from the treatment with the gas / vapor contrast enhancing agent. In a plasma dry development process, the photoresist is exposed to suitable chemical species, such as ions and / or radicals of one or more gases. The dry development process can be carried out in or near a plasma generation chamber, allowing the ions and / or radicals to reach the photoresist material. The plasma generation chamber can include any suitable plasma reactor, such as an inductively coupled plasma (ICP) reactor, a transformer coupled plasma (TCP) reactor, or a capacitively coupled plasma (CCP) reactor. Such reactors can be constructed using suitable techniques and equipment known in the art. Dry development using plasma is further described above, along with a summary of suitable compounds for plasma generation.

[0084] The organotin compositions described herein can generally be patterned with solutions for negative or positive patterning, although the focus here is on negative patterning. Useful developer compositions for these organotin oxide photoresists are described in U.S. Patent Application Publication No. 2020 / 0326627 to Jiang et al., entitled "Organometallic Photoresist Developer Compositions and Processing Methods," which is incorporated herein by reference. Generally, negative tone patterning is achieved when an organic solvent is used as the developer, where unexposed material is dissolved away and exposed material remains.

[0085] In particular, for negative-tone imaging, the developer may include an organic solvent, such as the solvent used to form the precursor solution. In general, the selection of a suitable developer solvent composition may be influenced by the solubility parameters for both irradiated and non-irradiated coating materials, as well as the volatility, flammability, toxicity, viscosity, and potential chemical interactions with other process materials of the developer. In particular, suitable developer solvents include, for example, aromatic compounds (e.g., benzene, xylene, toluene), esters (e.g., propylene glycol monomethyl ester 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), ethers (e.g., tetrahydrofuran, dioxane, anisole), and the like. Development can be carried out for from about 5 seconds to about 30 minutes, in further embodiments from about 8 seconds to about minutes, and in further embodiments from about 10 seconds to about 10 minutes. A person of ordinary skill in the art will recognize that additional ranges within the explicit ranges above are contemplated and are within the present disclosure.

[0086] As in negative or positive tone development processes, a significant amount of material is removed from the substrate during initial development based on the above considerations. However, in some cases, the initial development process may result in a pattern with detrimentally high line width roughness (LWR) and / or defects, such as scum, residue, micro-bridges, etc., remaining on the substrate due to incomplete development, material inhomogeneity, and stochastic effects. In some embodiments, it may therefore be desirable to carry out additional processes, such as liquid, thermal, or plasma methods, to remove unwanted material that may become more susceptible to development chemistries including the contrast enhancer compositions described herein. In the case of Figures 1-3 above, the use of contrast enhancers for pattern refinement is considered in various process flows. Thus, delivery of contrast enhancers and thermal development or other subsequent development of contrast enhancer modified coatings can be applied to the initially developed pattern to refine the pattern. All of the above process options for the use of contrast enhancers can be applied to the initially developed substrate as well.

[0087] Alternatively or additionally, in some embodiments, a subsequent development step or washing step involving liquid chemistry may be desirable to remove unwanted material. For example, after carrying out a development step using a contrast enhancing agent, such as a dry development step (thermal or plasma), a negative tone liquid developer, such as a suitable organic solvent, may be provided. Furthermore, it has been discovered that a washing step may be effective for significantly reducing the defect rate. The washing step may include, for example, treatment with an alkaline aqueous solution to remove partially irradiated material as well as the edges of the pattern.

[0088] In the above discussion, those skilled in the art will understand that the terms substrate and wafer should be interpreted as commonly used in the art. As understood in the art, the "substrate" itself may be structured by multiple layers, where at least some of the layers may be patterned, and the formation of the device may include multiple successive lithography steps that create a layered patterned structure. For a particular lithography step, the preceding processed structure becomes the substrate for that process step. The above embodiments are intended to be illustrative and not limiting. Further embodiments are within the scope of the claims. Furthermore, although the present invention has been described with reference to specific embodiments, those skilled in the art will recognize that changes can be made in form and detail without departing from the spirit and scope of the present invention. Any incorporation by reference of the above documents is limited so as not to incorporate subject matter contrary to the express disclosure herein. To the extent that particular structures, compositions and / or processes are described herein using components, elements, ingredients, or other proportions, the disclosure herein should be understood to extend to specific embodiments that may include additional features that do not alter the basic nature of the subject matter, as suggested in the discussion, embodiments that include particular components, elements, ingredients, other proportions, or combinations thereof, and embodiments that consist essentially of such particular components, ingredients, ingredients, other proportions, or combinations thereof, unless otherwise indicated. As will be understood by one of ordinary skill in the art, the use of the term "about" herein refers to the degree of error in the measurement of the particular parameter, unless expressly stated otherwise.

[0089] Post-development processing After the photoresist is developed to form the patterned coating material, along with any optional pattern refinement steps, a subsequent anneal can be performed to further solidify and stabilize the patterned features. As with other processing steps, this anneal can be performed in an environment with a specific concentration of a specific reactive gas. It may be desirable for a reactive gas not present in the previous step to be present in this anneal. Since radiation patterning has already occurred, the photosensitivity of the material does not need to be preserved, but instead the material can be converted to a new composition to facilitate additional processing, such as an etch. For example, a reducing reactive gas, such as carbon monoxide, hydrogen gas, methane, etc., and mixtures thereof, can be present during this anneal to convert at least a portion of the material to a new composition. The reactive gas present during this anneal step can enable a subsequent etch step or other processing by converting at least a portion of the patterned material to a new composition. In this way, tailoring a subsequent etch or other process step that interacts with the composition formed by reacting the patterned material with a reactive gas can enable post-processing techniques that can reduce or mitigate scum formation, microbridging, or other defects. Post-development thermal processing with reactive gases is further described in the above-referenced application Ser. No. '170.

[0090] The temperature for this anneal is not particularly limited, so long as the auxiliary layers or materials can retain their respective properties, such as sufficient etch contrast, and so long as the reactivity of the selected reactive gas is sufficient. In some embodiments, the anneal can be between 100° C. and 500° C., in other embodiments 200° C. and 500° C., and in further embodiments 300° C. and 400° C. A person of ordinary skill in the art will recognize that additional ranges of temperatures within the explicit ranges above are contemplated and are within the scope of the present disclosure.

[0091] To aid in evaluating the development, the wafers can be patterned to evaluate the patterning as a function of EUV dose. First, the imaging is considered as a step function of irradiated and non-irradiated areas. The patterned structures can be evaluated using automated imaging equipment, and scanning electron microscope imagers are commonly used. For example, certain commercial CD-SEM metrology instruments can measure critical line dimensions (line widths) and can also evaluate defects such as micro-bridging. In some embodiments, the improved processing described herein can result in an increase in the critical dimension using equivalent development, coating, and irradiation. In some embodiments, the increase in the critical dimension can be at least about 0.25 nm, in further embodiments at least about 0.50 nm, and in further embodiments at least about 0.75 nm. One of ordinary skill in the art will recognize that additional ranges of increase in the critical dimension within the above stated ranges are contemplated and are within the scope of the present disclosure. In other words, the concept of critical dimension can be expressed as a dose-size value, which is the radiation dose used to obtain a particular feature size. An increase in the critical dimension then corresponds to a decrease in the dose-size value.

[0092] After forming the patterned coating material, the coating material can be further processed to facilitate the formation of selected devices. Further deposition, etching and / or patterning of additional materials can generally be performed to complete the structure. The coating material may or may not be finally removed. In any case, the quality of the patterned coating material can be developed to form improved devices, such as devices with smaller footprints. If the layer is not removed, a patterned coating (resist) material is introduced into the structure. For embodiments in which a patterned coating (resist) material is introduced into the structure, the properties of the coating (resist) material can be selected to provide the desired patterning properties as well as the properties of the material in the structure. EXAMPLES

[0093] Example: Dry Development of Organotin Photoresists with Reactive Vapors This example illustrates the effectiveness of developing an organotin photoresist with carboxylic acid vapor. This example also demonstrates the effect of various processing conditions on contrast enhancement.

[0094] Common coating and processing processes Silicon wafers with a 10 nm layer of spin-on-glass (SOG) were used as substrates. An organotin resist composition was deposited on each wafer by spin coating at 1394 rpm to yield a layer having a thickness of about 15 nm as measured by ellipsometry. The organotin resist composition used in this example was YATU1011, manufactured by Inpria Corporation, having the composition described in the above-cited '618 patent. The coated wafers were baked at 100°C for 60 seconds. The wafers were then exposed to 50 mJ / cm2 exposure using open frame exposure conditions. 2 A set of wafer samples were exposed to KrF radiation in a chamber at a dose of 1000 nm to form a radiation-patterned layer on the surface of the wafer having irradiated and non-irradiated areas. Selected wafer samples were further subjected to an additional bake at 200° C. for 90 seconds as a post-exposure bake.

[0095] Processing with acetic acid vapor Each wafer sample was exposed to acetic acid vapor using an apparatus similar to that described above and illustrated in FIG. 4. Each wafer sample 320 was mounted on a wafer stage 318 in a chamber 314 configured to deliver a flow of developer gas 312 to the wafer surface. The wafer samples subjected to an extra bake (set A in FIG. 7) and those not subjected to an extra bake (set B in FIG. 7) were processed under acetic acid vapor atmosphere with different chamber pressure and wafer temperature conditions. The acetic acid vapor flow rate was adjusted from a value of 5-10 sccm (standard cubic centimeters per minute) to give a measured chamber pressure of either about 0.5 Torr or about 5 Torr. The wafer samples were heated to a temperature of either 120° C. or 180° C. The heated wafer samples were exposed to the flowing acetic acid vapor for various times ranging from 0 seconds to 600 seconds. According to the selected processing conditions using acetic acid vapor, ellipsometry was performed to estimate the film thickness of the irradiated and non-irradiated areas of each wafer sample.

[0096] FIG. 7 shows the film thickness as a function of time for the non-irradiated areas (labeled "a") of each wafer sample and the irradiated areas (labeled "b") of each wafer sample. Processing at a wafer temperature of 120° C. resulted in the irradiated areas ("b") generally being thinner than the non-irradiated areas ("a") prior to contact with acetic acid vapor (e.g., at t=0). This difference in initial thickness between the non-irradiated and irradiated areas is attributed to a reduction in organic content caused by radiation scission of Sn-C bonds, and is further described in U.S. Patent Application No. 10 / 732,505 to Meyers et al., entitled "Organotin Oxide Hydroxide Patterning Compositions, Precursors, And Patterning," which is incorporated herein by reference. FIG. 7 also shows that the initial thickness of the non-irradiated areas ("a") of the wafer sample heated at 180° C. is less than the initial thickness of the non-irradiated areas ("a") of the wafer sample heated at 120° C. This difference is attributed to the temperature pre-shrinkage of the non-irradiated layer.

[0097] As shown in FIG. 7, higher chamber pressures (i.e., higher flow rates of acetic acid vapor) resulted in improved removal of non-irradiated material. For example, in Set A at 180° C., the thickness of non-irradiated material was reduced to about 1 nm in 125 seconds at a chamber pressure of 5 Torr versus about 4 nm at a chamber pressure of 0.5 Torr. Separately, higher wafer temperatures resulted in improved removal of non-irradiated material. For example, in Set A at 5 Torr, the thickness of non-irradiated material was reduced to about 1 nm in 125 seconds at a wafer temperature of 180° C. versus about 9 nm at a wafer temperature of 120° C. When comparing Set A to Set B, it is believed that the additional high temperature post-exposure bake given to the Set A wafer samples improved the stability of the irradiated region based on the thickness of the irradiated region being relatively constant over the test time. In contrast, the thickness of the Set B wafer samples generally decreased slightly over the test time. The combination of higher chamber pressure and higher wafer temperature resulted in the most rapid selective removal of non-irradiated material. For example, at 5 Torr and 180° C., the thickness of the unirradiated material was reduced from about 9 nm to about 1 nm in about 125 seconds (in Set A) and from about 10.5 nm to about 0.5 nm in about 125 seconds (in Set B).

[0098] This example shows that exposure of wafer samples to acetic acid vapor can result in selective removal of non-irradiated material as a function of time for better thermal pattern development. The results are consistent with the negative tone development behavior seen in liquid development processes using carboxylic acid compositions. The results suggest that vapor-based development, cleaning, and / or contrast enhancement of patterned organometallic resists can result in improved processing over standard processing, such as the ability to fine-tune the process by adjusting temperature, pressure, and vapor composition.

[0099] The above embodiments are intended to be illustrative and not limiting. Further embodiments are within the scope of the claims. Moreover, although the present invention has been described with reference to specific embodiments, those skilled in the art will recognize that changes can be made in form and detail without departing from the spirit and scope of the present invention. Any incorporation by reference of the above documents is limited so as not to incorporate subject matter contrary to the express disclosure herein. To the extent that specific structures, compositions and / or processes are described herein using components, elements, ingredients or other proportions, the disclosure herein should be understood to extend to specific embodiments that may include additional features that do not alter the basic nature of the subject matter, as suggested in the discussion, as well as embodiments that include specific components, elements, ingredients, other proportions or combinations thereof, and embodiments that consist essentially of such specific components, ingredients or other proportions or combinations thereof, unless otherwise indicated. The use of the term "about" herein refers to the expected uncertainty of the associated value as understood in a particular context by a person of ordinary skill in the art.

Claims

1. A method for enhancing the contrast of development between the irradiated and non-irradiated portions of a radiation-sensitive organometallic composition on the surface of a substrate having a latent image, the method comprising contacting the organometallic composition with a reactive gas in a separate chamber to change the composition of the irradiated portion, the non-irradiated portion, or both, wherein the reactive gas comprises an amide, a sulfonic acid, an alcohol, a diol, a silyl halide, a germanium halide, a tin halide, an amine, or a mixture thereof.

2. The method according to claim 1, wherein the non-irradiated portion contains a Sn—C bond.

3. wherein the organometallic composition has the formula R ｚ SnO( ２－ｚ／２－ｘ／２ )(OH) ｘ (wherein 0 < x < 3, 0 < z ≤ 2, and x + z ≤ 4, The method according to claim 1, comprising a composition represented by R which is a hydrocarbyl or organic group having 1 to 31 carbon atoms, having a carbon atom bonded to Sn, and wherein one or more carbon atoms may be optionally substituted with one or more heteroatom functional groups).

4. The method according to claim 1, wherein the organometallic composition contains an oxo-hydroxo network structure.

5. The method according to claim 1, wherein the reactive gas comprises a compound having 1 to 10 carbon atoms.

6. The method according to claim 1, wherein the reactive gas comprises formamide, N-methylformamide, acetamide, urea, propanamide, butyramide, isobutyramide, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanol, ethanol, n-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, 4-methyl-2-pentanol, cyclopentanol, 1-hexanol, cyclohexanol, phenol, methanethiol, ethanethiol, propanethiol, isopropanethiol, butanethiol, isobutanethiol, tert-butylthiol, methylene glycol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, cyclohexanediol, trimethylsilyl chloride, trimethylsilyl bromide, dimethylsilyl chloride, dimethylsilyl bromide, monomethylsilyl chloride, monomethylsilyl bromide, tetrachlorosilane, tetrabromosilane, and combinations thereof.

7. The method according to claim 1, wherein the reactive gas further comprises water.

8. The method according to claim 1, wherein the contact results in cleavage of M—O—M and / or M—OH bonds in the organometallic composition.

9. The method according to claim 1, wherein the contact results in release of volatile tin-containing species from the organometallic composition.

10. The method according to claim 1, wherein the non-irradiated portion has an initial thickness and the contact results in a non-irradiated portion having an adjusted thickness, the adjusted thickness being less than the initial thickness.

11. The method according to claim 10, wherein the adjusted thickness is 90% or less of the initial thickness.

12. The method according to claim 10, wherein the adjusted thickness is 50% or less of the initial thickness.

13. The method according to claim 1, wherein the non-irradiated portion is essentially completely removed after contact for 10 minutes or less to form a developed structure.

14. The method according to claim 13, further comprising processing the developed structure using a liquid wash and / or a pattern-improving reactive gas to improve the pattern.

15. The method according to claim 14, wherein the pattern-improving reactive gas comprises water, carboxylic acid, amide, sulfonic acid, alcohol, diol, halosilane, hydrogen halide, germanium halide, tin halide, amine, or a mixture thereof.

16. The method according to claim 1, wherein the substrate comprises a semiconductor wafer.

17. The method according to claim 1, wherein the contact is performed using a reactive gas having a selected flow rate.

18. The method according to claim 17, wherein the selected flow rate is from about 1 standard cubic centimeter per minute (sccm) to about 1000 sccm.

19. The method according to claim 18, wherein the inert gas flow rate is from about 0.5 standard liter per minute (SLM) to about 30 SLM.

20. The method according to claim 19, wherein the contact is performed at a chamber pressure of from about 100 torr to about 1200 torr.

21. The method according to claim 1, wherein the contact is performed for from about 3 seconds to about 15 minutes.

22. The method according to claim 1, wherein the contact is performed at a chamber pressure of from about 0.001 torr to about 10 torr.

23. The method according to claim 1, wherein the chamber pressure is adjusted by varying the flow rate of the gas into the independent chamber, and the chamber pressure can vary during the time of the contact.

24. The method according to claim 1, wherein the substrate, the reaction gas, and / or the independent chamber are at a temperature of from about -45°C to about 350°C during contact.

25. The method according to claim 1, wherein the contact is carried out at a temperature of from about 100°C to about 250°C for at least about 10 seconds and a chamber pressure of at least about 0.1 torr.

26. The method according to claim 1, wherein the contact is carried out before the development process.

27. The method according to claim 1, wherein the contact is carried out after the development process.

28. The method according to claim 27, wherein the development process is a liquid-based development process.

29. The method according to claim 27, wherein the development process is a dry development process carried out using a development reactive gas or using plasma.

30. The method according to claim 27, wherein the development process forms a negative pattern that substantially maintains the irradiated portion of the organometallic composition.

31. The method according to claim 27, wherein the development process forms a positive pattern that substantially maintains the irradiated portion of the organometallic composition.

32. The method according to claim 1, wherein the contact is carried out with a plurality of reaction gases used simultaneously or continuously.

33. The method according to any one of claims 1 to 32, further comprising heating the organometallic composition to a temperature of from about 45°C to about 300°C for at least about 0.1 minutes and / or aging the organometallic composition for at least about 10 minutes before contact.

34. A method for modifying a radiation-sensitive organometallic composition on a substrate surface having a latent image formed by each irradiated portion and non-irradiated portion, contacting the organometallic composition with a vapor of a carboxylic acid in an independent chamber at a partial pressure of from about 0.1 torr to about 50 torr and / or a flow rate of from about 1 sccm to about 5000 sccm, at a temperature of from about -45°C to about 250°C, to remove the relative amount ((initial non-irradiated thickness - final non-irradiated thickness) / initial non-irradiated thickness) of the non-irradiated portion, wherein the relative amount ((initial irradiated thickness - final irradiated thickness) / initial irradiated thickness) of the thickness of the irradiated portion to be removed is 1 / 3 or less of the relative amount of the non-irradiated portion to be removed while the relative amount of the non-irradiated portion to be removed is at least about 10%.

35. The method according to claim 34, wherein the non-irradiated portion contains Sn-C bonds.

36. wherein the organometallic composition has the formula R ｚ SnO( ２－ｚ／２－ｘ／２ )(OH) ｘ where 0 < x < 3, 0 < z ≤ 2, and x + z ≤ 4, The method according to claim 34, comprising a composition represented by R being a hydrocarbyl or organic group having 1 to 31 carbon atoms, having a carbon atom bonded to Sn, and optionally one or more carbon atoms being substituted with one or more heteroatom functional groups).

37. The method according to claim 34, wherein the carboxylic acid comprises a compound having an alkyl chain having 1 to 10 carbon atoms, isomers thereof, halogenated derivatives thereof, and / or amide derivatives thereof.

38. The method according to claim 34, wherein the carboxylic acid comprises formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, benzoic acid, formamide, N-methylformamide, acetamide, urea, propanamide, butylamide, isobutylamide, and combinations thereof.

39. The method according to claim 34, wherein the carboxylic acid comprises acetic acid.

40. The method according to claim 34, wherein the organometallic composition comprises an oxo-hydroxy network structure.

41. The method according to claim 34, wherein the contact results in the release of volatile species from the organometallic composition.

42. The method according to claim 34, which results in the removal of 10% to about 90% of the non-irradiated portion.

43. The method according to claim 34, wherein the non-irradiated portion is essentially completely removed after contact with the organometallic composition.

44. The method according to claim 34, wherein the contact is carried out for about 10 seconds to about 15 minutes and the flow rate is about 1 sccm to about 5000 sccm.

45. The method according to claim 34, wherein the contact is carried out at a chamber pressure of about 0.001 torr to about 10 torr and a flow rate of about 1 to about 5000 sccm of at least one gas for at least about 10 seconds.

46. The method according to any one of claims 34 to 45, further comprising heating the organometallic composition to a temperature of about 45 °C to about 300 °C for at least about 0.1 minute and / or aging the radiation-sensitive organometallic composition for at least about 10 minutes before contact.

47. A method for improving the quality of a pattern-forming structure having a negative pattern corresponding to an irradiated organometallic composition on a substrate surface having a non-irradiated organometallic composition that is substantially removed or a positive pattern corresponding to a non-irradiated organometallic composition on a substrate surface having an irradiated organometallic composition that is substantially removed, A step of developing a pattern from a latent image formed by irradiating a radiation-sensitive organometallic composition on a substrate surface to form a pattern-forming structure, In the step of removing scum from the pattern by bringing the pattern-forming structure into contact with a reaction gas in an independent chamber after the development step, the method comprising the step of selecting the reaction gas from water, carboxylic acid, amide, sulfonic acid, alcohol, diol, silicon halide, germanium halide, tin halide, amine, thiol, hydrogen halide or a mixture thereof. Claim 48 The method according to claim 47, wherein the pattern-forming material contains Sn—C and / or Sn—O bonds. Claim 49 The method according to claim 47, wherein the scum contains an incompletely removed non-irradiated organometallic composition mixed in a negative pattern, an incompletely removed irradiated organometallic composition mixed in a positive pattern, a partially irradiated organometallic composition, or a mixture thereof. Claim 50 The method according to claim 47, wherein the scum contains microbridges. Claim 51 The method according to claim 47, wherein the contact changes the composition of the scum to result in the release of volatile species from the scum. Claim 52 The method according to any one of claims 47 to 51, wherein the reaction gas contains a compound having 1 to 10 carbon atoms. Claim 53 The method according to any one of claims 47 to 51, wherein the reaction gas includes formamide, N-methylformamide, acetamide, urea, propanamide, butyramide, isobutyramide, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanol, ethanol, n-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, 4-methyl-2-pentanol, cyclopentanol, 1-hexanol, cyclohexanol, phenol, methanethiol, ethanethiol, propanethiol, isopropanethiol, butanethiol, isobutanethiol, tert-butylthiol, methylene glycol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, cyclohexanediol, trimethylsilyl chloride, trimethylsilyl bromide, dimethylsilyl chloride, dimethylsilyl bromide, monomethylsilyl chloride, monomethylsilyl bromide, tetrachlorosilane, tetrabromosilane, and combinations thereof.

54. The method according to any one of claims 47 to 51, wherein the contacting is carried out at a temperature of about -45°C to about 350°C and at a chamber pressure of at least about 0.001 torr for at least about 3 seconds.

55. The method according to any one of claims 47 to 51, wherein the contacting is carried out with a plurality of reaction gases used simultaneously or sequentially.

56. A method for dry-developing a radiation-sensitive organometallic composition having a latent image pattern-formed by radiation on a substrate, In the step of contacting the composition having the latent image with a reaction gas to remove a substantial portion of the non-irradiated region of the coating, the non-irradiated region of the coating contains Sn-C bonds, and the reaction gas includes amide, sulfonic acid, alcohol, diol, halogenated silyl, germanium halide, tin halide, amine, thiol, or a mixture thereof.

57. The method according to claim 56, wherein the non-irradiated region of the coating contains Sn—C bonds, and the reaction gas contains a mixture of at least two gases selected from carboxylic acids, amides, sulfonic acids, alcohols, diols, silyl halides, germanium halides, tin halides, amines, or thiols.

58. The method according to claim 56, wherein the non-irradiated region of the coating contains Sn—C bonds, and the reaction gas contains a mixture of at least two carboxylic acids, at least two amides, at least two sulfonic acids, at least two alcohols, at least two diols, at least two silyl halides, at least two germanium halides, at least two tin halides, at least two amines, or at least two thiols.

59. wherein the composition is of formula R ｚ SnO( ２－ｚ／２－ｘ／２ )(OH) ｘ where 0 < x < 3, 0 < z ≤ 2, x + z ≤ 4, R is a hydrocarbyl or organic group having from 1 to 31 carbon atoms, having a carbon atom bonded to Sn, and one or more of the carbon atoms may be optionally substituted with one or more heteroatom functional groups), the method according to any one of claims 56 to 58.

60. The method according to any one of claims 56 to 58, wherein the reaction gas contains a compound having 1 to 10 carbon atoms, which may be optionally substituted with one or more heteroatom functional groups.

61. The method according to any one of claims 56 to 58, wherein the reaction gas contains formamide, N-methylformamide, acetamide, urea, propanamide, butyramide, isobutyramide, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanol, ethanol, n-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, 4-methyl-2-pentanol, cyclopentanol, 1-hexanol, cyclohexanol, phenol, methanethiol, ethanethiol, propanethiol, isopropanethiol, butanethiol, isobutanethiol, tert-butylthiol, methylene glycol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, cyclohexanediol, trimethylsilyl chloride, trimethylsilyl bromide, dimethylsilyl chloride, dimethylsilyl bromide, monomethylsilyl chloride, monomethylsilyl bromide, tetrachlorosilane, tetrabromosilane, and combinations thereof.

62. The method according to any one of claims 56 to 58, wherein the reaction gas further contains water.

63. The method according to any one of claims 56 to 58, wherein the contact results in cleavage of Sn—O—Sn and / or Sn—OH bonds in the non-irradiated region of the coating.

64. The method according to any one of claims 56 to 58, wherein the contact results in release of volatile species from the composition.

65. The method according to any one of claims 56 to 58, wherein the contact is carried out at a flow rate of reaction gas of from about 1 sccm to about 5000 sccm.

66. The method according to any one of claims 56 to 58, wherein the contact is carried out for from about 3 seconds to about 15 minutes.

67. The method according to any one of claims 56 to 58, wherein the contact is carried out in an independent chamber at a pressure of from about 0.001 torr to about 50 torr.

68. The method according to claim 67, wherein the pressure is adjusted by varying the flow rate of the reaction gas into the independent chamber.

69. The method according to claim 67, wherein the contact is carried out at a temperature of from about -45 °C to about 350 °C.

70. The method according to claim 67, further comprising heating the organometallic composition to a temperature of from about 45 °C to about 300 °C for at least about 0.1 minute and / or aging the organometallic composition for at least about 10 minutes prior to the contact.

71. A method for developing a radiation-sensitive organometallic composition having a latent image pattern-formed by radiation on a substrate, In the step of contacting a radiation pattern-forming material with a first reaction gas composition to modify a non-irradiated region of a coating and form an initial pattern, the non-irradiated region of the coating contains Sn—C bonds, and the first reaction gas composition contains a carboxylic acid, an amide, a sulfonic acid, an alcohol, a diol, a silyl halide, a germanium halide, a tin halide, an amine, a thiol, or a mixture thereof; In the step of contacting the initial pattern with a second reaction gas composition different from the first reaction gas composition to remove a portion of the initial pattern, the second reaction gas composition contains a carboxylic acid, an amide, a sulfonic acid, an alcohol, a diol, a silyl halide, a germanium halide, a tin halide, an amine, a thiol, or a mixture thereof.

72. The method according to claim 71, wherein contacting the initial pattern with the second reaction gas substantially removes the non-irradiated region of the coating to form a developed pattern.

73. The method according to claim 71, further comprising heating the initial pattern at a temperature of about 45°C to about 300°C for at least about 0.1 minute and / or aging the initial pattern for at least about 10 minutes prior to contacting the initial pattern with the second reaction gas composition.

74. The method according to any one of claims 71 to 73, wherein the first and / or second reaction gas further comprises water.

75. wherein the composition is of formula R ｚ SnO( ２－ｚ／２－ｘ／２ )(OH) ｘ wherein 0 < x < 3, 0 < z ≤ 2, x + z ≤ 4, R is a hydrocarbyl or organic group having from 1 to 31 carbon atoms, having a carbon atom bonded to Sn, and one or more carbon atoms may be optionally substituted with one or more heteroatom functional groups), the method according to any one of claims 71 to 73.

76. The method according to claim 75, wherein the contact with the first and / or second reaction gas results in cleavage of Sn—O—Sn and / or Sn—OH bonds in the non-irradiated region of the coating.

77. The method according to any one of claims 71 to 73, wherein the first and / or second reaction gas comprises a fluorinated carboxylic acid and / or a fluorinated alcohol.

78. A sealed chamber; A substrate support configured to rotate a substrate on the substrate support within the sealed chamber; A gas supply subsystem including a gas source reservoir, a gas spray dispenser having a plurality of apertures dispersed to provide gas distribution directed in the direction of the substrate mounted on the substrate support and over the surface of the substrate, a gas flow control device, and a gas conduit connecting the gas source reservoir and the gas spray dispenser to a flow through a conduit regulated by the gas flow control device; A liquid supply subsystem including a liquid reservoir, a nozzle, a nozzle support having a translatable arm for positioning the nozzle, a flow control device, and a pipe providing a flow path between the liquid reservoir and the nozzle, wherein the nozzle support has a structure configured to cause the nozzle to accumulate liquid on the substrate mounted on the substrate support; One or more exhaust pipes exiting the chamber; An apparatus including a pump.

79. The apparatus according to claim 78, further comprising a control device coupled to a motor of the substrate support to control rotation of the substrate, the gas supply subsystem to control gas flow, and the liquid supply subsystem to control delivery of liquid from the liquid supply subsystem.

80. The apparatus according to claim 78, wherein the gas source reservoir includes a first reservoir of a first contrast enhancer including a carboxylic acid, an amide, a sulfonic acid, an alcohol, a diol, a silicon halide, a germanium halide, a tin halide, an amine, a thiol, or a mixture thereof.

81. The apparatus according to claim 80, wherein the gas source reservoir further includes an inert gas supply source.

82. The apparatus according to claim 80, wherein the contrast enhancer is liquid within the reservoir, and the gas supply subsystem is configured to deliver the contrast enhancer as a vapor through a mass flow controller.

83. The apparatus according to any one of claims 80, wherein the gas source reservoir further includes a second reservoir of a second contrast enhancer.

84. The apparatus according to any one of claims 78 to 83, wherein the liquid reservoir includes a developer.

85. The apparatus according to claim 84, wherein the developer includes an organic liquid.

86. The apparatus according to claim 84, wherein the developer includes an aqueous liquid.

87. The apparatus according to any one of claims 78 to 83, further including one or more heating elements configured to heat a substrate, a chamber, a reservoir, a flow line, a gas / vapor, or a combination thereof.

88. The apparatus according to any one of claims 78 to 83, wherein an actuator arm is capable of moving the nozzle out of a flow path from the gas spray dispenser.

89. The apparatus according to any one of claims 78 to 83, wherein the gas distribution subsystem and the liquid metering distribution subsystem are configured using a pump having sufficient pumping capacity to operate at a pressure of 0.001 torr to atmospheric pressure.

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