Method for developing organotin photoresists and photolithography patterns

Abstract

The present invention relates to an organotin photoresist and a method for developing a photolithography pattern. The organotin photoresist comprises a (stanocenyl)tin compound. The stanocenyl is bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin, where cyclopentadienyl comprises a cyclopentadienyl C5H5 group or a substituted cyclopentadienyl C5H3R, C5H2R2, C5HR3, C5R4, or C5R5 group. The method for developing the photolithography pattern comprises sublimation or vaporization.

Description

[Technical Field]

[0001] Cross-references to related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 525,450, “Organotin photoresists and method of developing photolithography pattern,” filed by Lu on 7 July 2023, the contents of which are incorporated herein by reference in their entirety.

[0002] The present invention relates to an organotin photoresist for chemical radiation and a method for developing photolithography patterns. Here, the organotin photoresist contains a (stanocenyl)tin compound. [Background technology]

[0003] With the advancement of the semiconductor industry, nanoscale patterns are required in pursuit of higher device density, higher performance, and lower costs. Miniaturizing semiconductor feature sizes is a major challenge. Photolithography has been applied to the creation of microelectronic patterns for decades. Extreme ultraviolet (EUV) lithography is being developed to mass-produce smaller semiconductor device feature sizes and increase device density on semiconductor wafers. EUV lithography is a patterning technique that uses a wavelength of 13.5 nm as the exposure light source to manufacture high-performance integrated circuits containing high-density structures patterned on the nanometer scale. By applying EUV lithography, it is possible to form extremely fine pattern widths of 7 nm or less. Therefore, EUV lithography has become an important tool and technology for manufacturing next-generation semiconductor devices.

[0004] To improve EUV lithography to a finer level, wafer exposure throughput can be improved by increasing exposure power or improving photoresist sensitivity. Photoresist is a radiation-sensitive material, and irradiation causes relevant chemical mutations in the exposed area, resulting in different properties between the exposed and unexposed areas. Properties of EUV photoresist, such as resolution, sensitivity, line edge roughness (LER), line width roughness (LWR), etching resistance, and the ability to form thinner layers, are important in photolithography.

[0005] Because metals possess a variety of carbon-metal (CM) bond dissociation energies (BDEs) and have high adsorption capacity for ultraviolet radiation, organometallic compounds exhibit high UV adsorption. Therefore, they can be used as photoresists and / or precursors for fine-scale (e.g., less than 7 nm) lithography, attracting considerable interest in radiation lithography. Among these promising advanced materials, organotin compounds, in particular, have been demonstrated to offer photoresist patterning with significant advantages such as improved resolution, sensitivity, etching resistance, and reduced line width / edge roughness, without pattern collapse, thanks to the strong EUV radiation adsorption of tin.

[0006] Common development methods for photolithography patterning include wet liquid solvent development and dry gas development. Wet liquid solvent development utilizes liquid organic solvents or aqueous solvents to remove exposed or unexposed areas of the photoresist corresponding to positive or negative patterning. Organometallic compounds, particularly metallocene compounds, can be sublimated or vaporized under high vacuum and high temperature conditions. Therefore, organometallic photoresists can be deposited on the surface of semiconductor substrates by chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), spin coating, or other methods. After exposure to ultraviolet light (e.g., EUV 13.5 nm), the exposed or irradiated areas of the organometallic photoresist transform into non-sublimable, non-volatile, or insoluble metal complexes or multinuclear metal network complexes, such as metal oxides or metal oxide / hydroxide network complexes. Unexposed areas, on the other hand, can be selectively removed for pattern development by sublimation or vaporization under vacuum and temperature conditions. This sublimation or vaporization development method avoids the use of liquid organic solvents and aqueous solutions in wet development, as well as dry development methods using gases such as hydrogen halides, resulting in environmentally friendly development and reduced manufacturing costs. Furthermore, sublimation or vaporization development may avoid pattern collapse and defects caused by the rinsing process. It may even be possible to omit the subsequent post-development rinsing step. [Overview of the project]

[0007] In a first aspect, the present invention relates to organotin photoresists and methods for developing photolithographic patternings. The present invention aims to provide (stanocenyl)tin compound photoresists for photolithographic patterning. Furthermore, the present invention aims to provide a sublimation or vaporization method for performing patterning development under high vacuum and ambient temperature conditions without pattern collapse or defects in microelectronic patterning, particularly EUV lithography of less than 7 nm.

[0008] In another embodiment, the present invention relates to a method for developing a photolithography pattern by sublimation or vaporization, comprising the steps of: forming an organotin photoresist solution composition; wherein the formation of the organotin photoresist solution composition comprises a (stanocenyl)tin compound, a solvent, and / or additives, where stanocenyl is bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin, and cyclopentadienyl comprises a cyclopentadienyl C5H5 group or a substituted cyclopentadienyl C5H4R, C5H3R2, C5H2R3, C5HR4, or C5R5 group; depositing the organotin photoresist solution composition onto the surface of a substrate; exposing the organotin photoresist layer to chemical radiation to form a latent image pattern; and developing the latent image pattern to form a photolithography pattern by removing unexposed organotin photoresist by applying a sublimation or vaporization method.

[0009] In a further embodiment, the present invention relates to organometallic photoresists that are radiosensitive and transform into non-sublimable or non-vaporable metal complexes or multinuclear metal network complexes, such as metal oxides, after exposure to ultraviolet light such as EUV or DUV. On the other hand, unexposed organometallic photoresists can be sublimated or vaporized under ambient vacuum and temperature conditions such as high vacuum and high temperature without decomposition to form metal complexes. The present invention relates to radiosensitive organometallic photoresists including, but not limited to, organometallic tin (Sn), indium (In), antimony (Sb), bismuth (Bi), manganese (Mn), vanadium (V), titanium (Ti), chromium (Cr), selenium (Se), tellurium (Te), zirconium (Zr), hafnium (Hf), gallium (Ga), germanium (Ge) compounds, or combinations thereof.

[0010] In other embodiments, the present invention relates to radiosensitive organotin compound photoresists suitable for photolithography patterning such as EUV and DUV, or as precursors for synthesizing organotin photoresists or reacting them with a reactive gas atmosphere. In the present invention, organotin compound photoresists include, but are not limited to, (stanocenyl)tin compounds. In some embodiments, organotin photoresists can be sublimated or vaporized at pressures ranging from 0.0001 torr to 100 torr and temperatures ranging from 20 to 300°C.

[0011] In another embodiment, the present invention relates to a radiosensitive (stanocenyl)tin compound photoresist, wherein stanocenyl includes bis(cyclopentadienyl)tin and substituted bis(cyclopentadienyl)tin as shown below; TIFF2026530291000002.tif31119 Here, cyclopentadienyl includes a cyclopentadienyl C5H5 group, or a substituted cyclopentadienyl C5H4R, C5H3R2, C5H2R3, C5HR4, or C5R5 group, and hapticity is η 1 η 2 η 3 η 4 , or η 5 It is an isomer of , where R is H, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, or a cycloalkyl group, or an aryl group having 6 to 20 carbon atoms, or an amino group, a cyano group, an ether group, an ester group, a halide group, a nitro group, a silyl group, a thiol group, or a carbonyl group.

[0012] In an additional embodiment, the present invention relates to the synthesis of radiosensitive (stanocenyl)tin compounds, bis(cyclopentadienyl)tin((η 5-C5H5)2Sn, stannocene, or SnCp2) is used as the parent molecule, lithiation such as monolithiation or dilithiation is performed on one or two Cp rings with a strong base such as methyllithium (MeLi), n-butyllithium (n-BuLi), s-butyllithium (s-BuLi), or t-butyllithium (t-BuLi), and the desired derivative or compound is synthesized via further procedures thereafter. On the other hand, the as-synthesized (stannocenyl) tin compound may be further used as a precursor for forming an organotin photoresist, such as an organotin cluster, with an appropriate molecule such as water or oxygen.

[0013] In the disclosure of the present invention, the (stannocenyl) tin compound or precursor is one or more selected from the following: TIFF2026530291000003.tif33151TIFF2026530291000004.tif33151TIFF2026530291000005.tif34164TIFF2026530291000006.tif34164TIFF2026530291000007.tif37164TIFF2026530291000008.tif39164TIFF2026530291000009.tif43164TIFF2026530291000010.tif40164TIFF2026530291000011.tif30164TIFF2026530291000012.tif33150here, R 1 , R 2 , R 3Each of these is independently H, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or cycloalkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. E = O, S, Se, or Te; X = F, Cl, Br, or I. L is a linear or branched alkyl group, alkenyl group, alkylene group, alkynyl group, or cycloalkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an amino group, cyano group, ether group, ester group, halide group, nitro group, silyl group, thiol group, or carbonyl group.

[0014] Furthermore, the present invention relates to a method for developing photolithography patterns, including sublimation or vaporization, which offers advantages over conventional wet liquid solvent development and dry gas development methods for miniaturizing photolithography patterns of less than 7 nm, particularly 1-3 nm. Due to the wettability and surface tension on the semiconductor substrate surface, conventional development methods suffer from pattern collapse and defects due to liquid or gas flow and rinsing processes, making it difficult to achieve small patterning of less than 7 nm, especially 1-3 nm. In addition, conventional wet or dry development methods may not be able to completely remove unexposed areas of organometallic photoresist due to narrow spaces between two adjacent pitches at very small scales and etching yields of less than 100%.

[0015] In further embodiments, the present invention relates to a method for depositing organometallic photoresist on the surface of a semiconductor substrate by wet deposition such as spin coating, or dry deposition such as chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), or other methods. In some embodiments, the (stanocenyl)tin compound may be sublimated or vaporized to deposit on the substrate and form a layer. Sublimation deposition may not require the bake step that is commonly performed in wet deposition methods.

[0016] The present invention relates to a radiosensitive organotin photoresist that can efficiently form patterns in the presence of ultraviolet light, extreme ultraviolet (EUV), deep ultraviolet (DUV), or electron beam (EB), can form high-resolution patterns with low linewidth roughness (LWR) at less than 7 nm, and achieves high resolution, low dose, and high contrast at less than 7 nm. [Brief explanation of the drawing]

[0017] [Figure 1] This is a flowchart of the photolithography patterning process, including the deposition of organotin photoresist, pre-exposure baking (PAB), exposure, and sublimation / vapor development. [Modes for carrying out the invention]

[0018] The present invention relates to an organotin photoresist and a method for developing a photolithography pattern. Here, the organotin photoresist contains a (stanocenyl)tin compound. Stanocenyl refers to bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin, and cyclopentadienyl includes a cyclopentadienyl C5H5 group or a substituted cyclopentadienyl C5H3R, C5H2R2, C5HR3, C5R4, or C5R5 group. The method for developing a photolithography pattern includes sublimation or vaporization.

[0019] As used herein, the singular forms "a," "an," "one," and "the" are intended to include the plural form unless the context clearly indicates otherwise. Furthermore, when the expressions "one of," "at least one of," "any," and "selected from" precede a list of elements, they modify the entire list of elements, not the individual elements of the list.

[0020] As used herein, the terms “includes,” “including,” “comprise,” or “comprising” identify the features, processes, operations, elements, and components described herein, but do not exclude the presence or addition of one or more other features, processes, operations, elements, components, and / or groups thereof.

[0021] As used herein, the terms “and / or” include any combination of one or more of the relevant descriptions and all combinations thereof. Furthermore, the use of “may” when describing embodiments of the disclosure refers to “one or more embodiments of the disclosure.”

[0022] As used herein, the terms “use,” “using,” and “used” can be considered synonymous with “utilize,” “utilized,” and “applied,” respectively. In addition, “about,” “only,” and similar terms are used as approximations and are intended to take into account the inherent deviations of measured or calculated values ​​that would be recognized by a person skilled in the art, rather than as terms of degree.

[0023] The term "alkyl" or "alkyl group" refers to saturated straight-chain or branched-chain hydrocarbons having 1 to 20 carbon atoms. The terms "alkenyl, alkynyl, and cycloalkyl" refer to hydrocarbons having 1 to 20 carbon atoms. The term "aryl" refers to unsubstituted or substituted aromatic groups having 6 to 20 carbon atoms. The term "alkylene" refers to saturated divalent hydrocarbons obtained by removing two hydrogen atoms from saturated hydrocarbons having 1 to 20 carbon atoms, such as methylene (-CH2-), ethylene (-CH2CH2-), and propylene (-CH2CH2CH2-).

[0024] The term "halide" refers to F, Cl, Br, or I. The term "nitro" refers to -NO2. The term "silyl" refers to the -SiR2- or -SiR3 group. The term "thiol" refers to the -SH group. The term "carbonyl" refers to the -C=O group. The term "oxo" refers to -O- or =O. The term "amino" refers to the -NH2, -NHR, or NR2 group.

[0025] In this disclosure, the term “substituted” means that a hydrogen atom is replaced by a C1-C20 alkyl group, a C1-C20 alkene group, a C1-C20 alkyne group, a C1-C20 cycloalkyl group, a C6-C20 aryl group, or other related group.

[0026] EUV lithography is being developed for mass production of next-generation sub-7 nm nodes. EUV photoresists are required to achieve higher performance, higher sensitivity and resolution, and lower costs.

[0027] EUV light is used in photolithography at approximately 13.5 nm. EUV light can be generated from tin (Sn) or xenon (Xe) plasma sources excited using high-energy lasers or discharge pulses.

[0028] In the case of conventional organic polymer photoresists, if the aspect ratio (the ratio of height to width) is too large, the pattern structure tends to collapse, and problems related to surface tension also arise, thus limiting their application to fine features such as those smaller than 7 nm.

[0029] At small feature sizes of less than 7 nm (e.g., 1-3 nm), conventional chemically amplified (CA) organic polymer photoresists face significant problems such as insufficient absorption of EUV light, low resolution, high line-edge roughness (LER), and increased pattern collapse and defects. To overcome these shortcomings of organic polymer photoresists, organometallic photoresists and related organometallic photosensitive compositions are needed, particularly for EUV.

[0030] Because metals have a high absorption capacity for EUV radiation, organometallic photoresists are used in EUV lithography. Radiation sensitivity, as well as stability against heat, oxygen, and moisture, are important for organometallic photoresists. In some embodiments, organometallic photoresists may absorb moisture and oxygen, which can result in reduced stability and decreased solubility in the developer. Furthermore, in some embodiments, the photoresist layer may release volatile components (outgassing) before radiation exposure and development operations, which can adversely affect photolithography performance and pattern collapse, potentially increasing defects.

[0031] Organometallic tin photoresist layers are patterned by exposure to chemical radiation. Typically, the chemical properties of the photoresist region exposed to incident radiation change depending on the type of photoresist used. Photoresists are classified into positive and negative types. In some embodiments, a positive resist refers to a photoresist material that becomes soluble in the developer when exposed to radiation (e.g., EUV), while unexposed (or lightly exposed) regions remain insoluble in the developer. In some embodiments, conversely, a negative resist refers to a photoresist material that becomes insoluble in the developer when exposed to radiation, while unexposed (or lightly exposed) regions remain soluble in the developer.

[0032] The physical and chemical properties of organometallic compounds suitable for photoresists determine their relevant properties in photolithography (particularly EUV and DUV), where the bond dissociation energy (BDE) of the metal-carbon bond (MC) plays a crucial role. M is a metal and includes, but is not limited to, tin (Sn), indium (In), antimony (Sb), bismuth (Bi), manganese (Mn), vanadium (V), titanium (Ti), chromium (Cr), selenium (Se), tellurium (Te), zirconium (Zr), hafnium (Hf), gallium (Ga), or germanium (Ge). In particular, organotin photoresists are suitable for patterning in EUV or DUV photolithography.

[0033] Generally, the central metal plays a major role in determining the radiation absorption of organometallic photoresists. However, in organometallic compounds, the organic ligands bonded to the metal (MR, where M = metal and R = organic ligand) can also influence the relevant absorption through MC bonding. Tin atoms provide strong absorption of extreme ultraviolet (EUV) light at 13.5 nm, and their tin cations can be selected based on the desired radiation and absorption cross-section. On the other hand, organic ligands bonded to tin also absorb EUV light. Therefore, by adjusting and modifying the organic ligands, it is possible to change the desired control of sensitivity, radiation absorption, or material properties.

[0034] The bond dissociation energy (BDE) of a Sn-C bond determines the light absorption wavelength and the corresponding smaller feature or pattern structure.

[0035] Organotin photoresists exhibit excellent (e.g., adequate) sensitivity to high-energy light (e.g., EUV, DUV, X-rays, or lasers) due to the strong absorption of extreme ultraviolet (EUV) light by tin at approximately 13.5 nm. Therefore, organotin photoresists offer improved sensitivity, resolution, and stability compared to conventional organic polymer or inorganic photoresists.

[0036] In some embodiments, organometallic (stanocenyl) tin compound photoresists include, but are not limited to, hydroxides (stanonic acids), anhydrides, hydroxides, alkoxides, amides, halides, carboxylic acids, chalcogenides, distanoxanes (oxos), oxides, or esters.

[0037] In some embodiments, the organometallic (stanocenyl) tin compound photoresists include, but are not limited to, stanocenyl-based derivatives represented by chemical formulas (1) to (46).

[0038] In some embodiments, organometallic (stanocenyl) tin compound photoresists are suitable for EUV or DUV photolithography patterning and sublimation or vaporization development processes under ambient vacuum and temperature conditions such as high vacuum and high temperature.

[0039] Stanocenyl refers to bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin, where cyclopentadienyl is a cyclopentadienyl C5H5 group, or where the hapticity (number of coordination sites) varies depending on the isomer (η). 1 η 2 η 3 η 4 η 5 It contains a substituted cyclopentadienyl C5H4R, C5H3R2, C5H2R3, C5HR4, or C5R5 group, where R is H, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, or a cycloalkyl group, or an aryl group having 6 to 20 carbon atoms, or an amino group, a cyano group, an ether group, an ester group, a halide group, a nitro group, a silyl group, a thiol group, or a carbonyl group. For example, R is H, methyl, ethyl, isopropyl, n-butyl, tert-butyl, tert-amyl, sec-butyl, pentyl, hexyl, neopentyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, phenyl, or a combination thereof.

[0040] Organometallic (stanocenyl) tin compound photoresists, containing π bonds, C-Sn bonds, and related interactions, can exhibit excellent (e.g., appropriate) sensitivity to EUV radiation due to the adsorption of high-energy EUV rays at 13.5 nm by tin. Therefore, the associated solution compositions may possess improved sensitivity and stability compared to organic polymer or inorganic photoresists.

[0041] Cyclopentadienyl groups (C5H5, or Cp) can impart photosensitivity to compounds, and the formed Cp-Sn bond can promote proper solubility in organic solvents for organometallic sandwich-type or half-sandwich-type tin compounds. Therefore, these Cp-Sn bond-containing organometallic sandwich-type or half-sandwich-type tin compounds according to one embodiment have improved sensitivity, resolution, and stability and may be suitable as precursors for EUV lithography for forming EUV photoresists and / or tin oxide or tin hydroxide films.

[0042] Organometallic (stanocenyl) tin compounds contain a cyclopentadienyl-tin bond (Cp-Sn bond). The Cp-Sn bond is sensitive to ultraviolet light, and it has been demonstrated that exposure to UV light causes radiation-induced breakdown and generates free radicals (e.g., PJ Baker, AG Davies, M.-W. Tse, “The photolysis of cyclopentadienyl compounds of tin and mercury...”, Journal of Chemical Society, Perkin II, 1980, 941-948; SG Baxter, AH Cowley, JG Lasch, M. Lattman, WP Sharum, CA Stewart, “Electronic structures of bent-sandwich compounds of the main-group elements: A molecular orbital and UV photoelectron spectroscopic study of bis(cyclopentadieny1)tin and related compounds”, Journal of the American Chemical Society, 1982, 104, 4064-4069. All of these are incorporated herein by reference). Baker et al. reported that strong EPR spectra of the C5H5 radical were observed during UV photodegradation in toluene of unsubstituted sandwich and half-sandwich cyclopentadienyl tin(IV) (C5H5-Sn) compounds, namely C5H5SnMe3, C5H5SnBu3, (C5H5)2SnBu2, C5H5SnCl3, (C5H5)2SnCl2, (C5H5)3SnCl, and (C5H5)4Sn. This study demonstrated that, under identical conditions, cyclopentadienyl (C5H5) groups or substituted cyclopentadienyl (e.g., C5R5) groups are far more sensitive to ultraviolet light than alkyl (e.g., methyl, butyl) groups. This property is beneficial for reducing EUV exposure and improving resolution. TIFF2026530291000013.tif15132

[0043] Organometallic (stanocenyl) tin compound photoresists exhibit tin adsorption with high-energy EUV rays at 13.5 nm (low exposure photoresists, e.g., <20 mJ / cm²). 2 Due to the formation of free radicals, tin oxide, and related products by the breakdown of Cp-Sn bonds, as well as toughness, these materials exhibit excellent sensitivity to EUV radiation and have few or no pattern defects at the nanoscale. Therefore, solution compositions of organometallic (stanocenyl) tin compound photoresists can achieve narrow pitches (e.g., <10 nm) and provide high resolution while maintaining yield.

[0044] In this disclosure, the (stanocenyl)tin compound photoresist is one or more selected from the following: TIFF2026530291000014.tif32149TIFF2026530291000015.tif32150TIFF20265302910 00016.tif34150TIFF2026530291000017.tif35150TIFF2026530291000018.tif37151TI FF2026530291000019.tif39151TIFF2026530291000020.tif43151TIFF2026530291000021.tif40151TIFF2026530291000022.tif29151TIFF2026530291000023.tif32151Here, R 1 , R 2 , R 3Each of these is independently H, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group, or a cycloalkenyl group, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. E=O, S, Se, or Te; X=F, Cl, Br, or I. L is a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkylene group, an alkynyl group, or a cycloalkyl group, or an aryl group having 6 to 20 carbon atoms, or an amino group, a cyano group, an ether group, an ester group, a halide group, a nitro group, a silyl group, a thiol group, or a carbonyl group.

[0045] For example, R 1 , R 2 , R 3 is independently a methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl (isobutyl), t-butyl (tert-butyl), pentyl, hexyl, cyclopentyl, cyclohexyl, or cyclopentadienyl group; E=O, S, Se, or Te; X=Cl; L is methylene, ethylene, or propylene.

[0046] In some embodiments, the (stanocenyl)tin compound photoresist may contain a variety of functional groups, including but not limited to ethers, thiols, silyls, ketos, cyanos, carbonyls, halogens, or combinations thereof.

[0047] In some embodiments, the (stanocenyl)tin compound photoresist is expressed as η depending on the isomer. 1 η 2 η 3 η 4 , or η 5 It has a hapticity (number of coordination loci).

[0048] In the following, the cycloalkenyl group includes substituted and unsubstituted C4 to C8 aliphatic unsaturated organic groups (e.g., cyclopentadienyl or cycloheptatrieyl) containing at least one double bond.

[0049] In some embodiments, the (stanocenyl)tin compound photoresists according to embodiments of the present disclosure may be represented by at least one example. Specific examples of (stanocenyl)tin compound photoresists or precursors that may be used in the practice of the present invention are represented by chemical formulas (1) to (46).

[0050] In this disclosure, organometallic sandwich-type bis(cyclopentadienyl)tin (stanocene, or Sc) is used as a parent molecule for synthesizing (stanocenyl)tin compounds. Stanocene is synthesized according to the reference (C. Janiak, Zeitschrift fur Anorganische und Allgemeine Chemie, 2010, 636 (13-14), 2387-2391). The product is purified as pale yellow crystals by sublimation under high vacuum. In some embodiments, lithiation of stanocene at one or two C5 rings is applied to synthesize (stanocenyl)tin compounds. For example, monolithiation or dilithiation is performed using a strong base such as methyllithium (MeLi), n-butyllithium (n-BuLi), or t-butyllithium (t-BuLi), followed by further steps to synthesize related derivatives represented, for example, by chemical formulas (1) to (46).

[0051] In some embodiments, organometallic sandwich stanocenes can undergo multiple lithiation at one or two C5 rings, which may depend on the amount of strong base and reaction conditions. Those skilled in the art will recognize that synthetic strategies, reagents, or reaction conditions, including reactant ratios, temperatures, reaction times, or addition methods, are intended and within the scope of this disclosure, within the express range described above.

[0052] In exemplary embodiments, monolithiation at one C5 ring of stanocene is KO t This was carried out by t-BuLi in THF at -78°C in the presence of Bu, as shown in Scheme 1 (η 5-C5H5)Sn(η 5 -C5H4Li)(ScLi) is obtained. Scheme 1 TIFF2026530291000024.tif26135

[0053] In another exemplary embodiment, monosubstituted C5 ring (stanocenyl) tin compounds are synthesized under conditions including, but not limited to, ambient conditions, as shown in Scheme 2. Scheme 2 TIFF2026530291000025.tif54142

[0054] In an exemplary embodiment, dilithiation (bilithiation) of the two C5 rings of stanocene was carried out by n-BuLi in THF at -78°C, as shown in Scheme 3 (η 5 -C5H4Li)Sn(η 5 -C5H4Li)(ScLi2) is obtained. This is based on references (AH Cowley, P. Jutzi, FX Kohl, JG Lasch, NC Norman, E. Schluter, "Sequential Lithiation and Silylation of Stannocene", Angew. Chemie International Edition 23 (1984), 8, 616-617, etc.). In some embodiments, the addition of a coordination agent (e.g., N,N,N',N'-tetramethyl-1,2-diaminoethane (TMEDA)) is required to improve the yield of dilithiation at the two C5 rings. Scheme 3 TIFF2026530291000026.tif26140

[0055] In another exemplary embodiment, the illustrated disubstituted (bisubstituted) (stanosenyl) tin compound is subjected to conditions including, but not limited to, ambient conditions, as shown in Scheme 4, (η 5 -C5H4Li)Sn(η 5It is prepared by reacting -C5H4Li)(ScLi2) with appropriate reagents. Scheme 4 TIFF2026530291000027.tif61145

[0056] In one example embodiment, stanocenol (η 5 -C5H5)Sn(η 5 -C5H4OH) or (η 5 -C5H5)Sn(η 5 -C5H4OH)2Sn is (η) in THF at -78°C 5 -C5H5)Sn(η 5 -C5H4Li) or (η 5 -C5H5)Sn(η 5 -C5H4Li)2Sn can be prepared by reacting each with (CH3)3SiOOSi(CH3)3, followed by acidification or hydrolysis as shown in Scheme 5. This is referenced in (C. Elschenbroich, F. Lu, H. Klaus, [5]Trovacenol, (η 7 -C7H7)V(η 5 It is based on a similar method as in "-C5H4OH): Synthesis and Structural Characterization", Organometallics, 2002, 21 5152-5154). In some embodiments, (η 5 -C5H5)Sn(η 5 -C5H4OH) or (η 5 -C5H5)Sn(η 5 -C5H4OH)2Sn reacts with bases such as NaOH or n-BuLi to form (η 5 -C5H5)Sn(η 5 -C5H4ONa) or (η 5 They form -C5H4OLi)2Sn, which can be used as precursors for further organotin compound synthesis. Scheme 5 TIFF2026530291000028.tif44140

[0057] In one embodiment, (stanocenyl) chalcogenides and related derivatives are prepared by the same method as described in the following literature (all of which are incorporated herein by reference): C. Elschenbroich, F. Lu, K. Harms, O. Burghaus, “Synthesis, electrochemical behavior and EPR study of organometallic [5]trovacenylthiol (η 7 -C7H7)V(η 5C. Elschenbroich F. Lu, O. Burghaus, K. Harms, J. Pebler, “Bis([5]trovacenyl)dichalcogenides: Synthesis, Structure, and Study of Intramolecular Communication,” Zeitschrift fur Anorganische und Allgemeine Chemie, 2011, 637, 1750-1755; C. Elschenbroich, F. Lu, K. Harms, O. Burghaus, C. Pietzonka, J. Pebler, “α,ω-Di([5]trovacenyl) Sulfides TVC-Sn-TVC (n = 1-4) and TVC-SCH2S-TVC: a Study in Intramolecular Communication, European Journal of Inorganic Chemistry, 2012, 3929-3936; F. Lu, Inorganic Chemistry Communication, 37 (2013) 148-150. Those skilled in the art will recognize that the synthesis strategies, reagents, or reaction conditions, including reactant ratios, temperature, reaction time, and addition methods, within the expressly defined scope described above are within the assumptions and scope of this disclosure.

[0058] In one example embodiment, stanocenylcarboxylic acid (η 5 -C5H5)Sn(η 5 -C5H4COOH) or (η 5 -C5H4COOH)2Sn (shown in Scheme 6) is (η 5 -C5H5)Sn(η 5 -C5H4Li) or ((η 5 -C5H5)Sn(η 5-C5H4Li)2Sn is reacted with gaseous CO2 to form the intermediate (η 5 -C5H5)Sn(η 5 -C5H4H4COOLi) or (η 5 -C5H5)Sn(η 5 -C5H4COOLi)2Sn is obtained separately and then synthesized by acidification with an HCl solution. This is described in the reference (C. Elschenbroich, O. Schiemann, O. Burghaus, and K. Harms, “Exchange Interaction Mediated by OH…O Hydrogen Bonds: Synthesis, Structure, and EPR Study of the Paramagnetic Organometallic Carboxylic Acid (η 7 -C7H7)V(η 5 This method is based on the same approach as described in (-C5H4COOH), Journal of the American Chemical Society, 1997, 119, 7452-7457. Scheme 6 TIFF2026530291000029.tif57140

[0059] In this disclosure, purification methods include, but are not limited to, distillation, extraction, filtration, recrystallization, column chromatography, coordination and sublimation, and combinations thereof. For example, recrystallization can be carried out by slowly cooling a thermal solution of the compound to ambient temperature (e.g., room temperature or below). Solvents for recrystallization include, but are not limited to, hexane, petroleum ether, diethyl ether, THF, benzene, toluene, ethanol, or combinations thereof. In some embodiments, recrystallization yields single crystals, which are suitable for X-ray diffraction analysis to determine the relevant molecular structure. Column chromatography is usually carried out using silica or aluminum oxide in air or an inert atmosphere. In some embodiments, fractional distillation under reduced pressure is used for the purification of liquid products. In some embodiments, sublimation can be carried out under high vacuum and high temperature without decomposition.

[0060] In addition, (stanocenyl)tin compounds represented by chemical formulas (1) to (46) can be used as precursors for forming photolithographic latent image patterns on a substrate.

[0061] For example, in some embodiments, (stanocenyl)tin compounds can be applied as precursors for forming photoresists (such as organotin clusters) or patterned films by reacting with an oxygen source atmosphere such as air, oxygen (O2), ozone (O3), hydrogen peroxide (H2O2), or water (H2O). This promotes the oxidation of the irradiated organotin photoresist, forming a metal oxide or multinuclear oxide network under certain conditions.

[0062] In some embodiments, the (stanocenyl)tin compound may function as a first precursor and react with a second precursor, which is a reactive gas atmosphere such as H2S, SO2, S8, CO2, CO, HCOOH, NH3, PH3, or SiH4, to form a photoresist layer on the substrate. This can enhance the contrast between the irradiated and unirradiated areas of the organotin photoresist.

[0063] In some embodiments, organotin clusters are used as EUV photoresists. These are photosensitive but may not be volatile enough to sublimate or vaporize. As a result, after EUV exposure, unexposed areas may not be efficiently removed with wet developers due to wettability and surface tension at fine sizes such as 1-3 nm pitch.

[0064] In some embodiments, sublimation or vaporization development methods can also be applied to patterning beyond 10 nm, such as with deep ultraviolet (DUV) or far ultraviolet (FUV) radiation. Residual exposed or unexposed photoresist between pattern features can be removed. This requires a level of radiation-sensitive (stanosenyl) tin compound photoresist suitable for DUV or FUV, based on E=hν=hc / λ and BDE(MC), where E represents energy, h is Planck's constant, ν is frequency, c is the speed of light, and λ is the wavelength of light. For example, after exposure to ultraviolet light, unexposed areas of organotin photoresist can be removed for patterning by sublimation or vaporization under high vacuum and high temperature.

[0065] In some embodiments, exposure to chemical radiation causes a mixture of (stanocenyl)tin compound photoresists to undergo an in situ ultraviolet-induced radiation reaction, forming non-sublimable, non-volatile, or insoluble complexes (e.g., oxo / hydroxyl, polyatomic complexes, metal oxo or hydroxyl networks, or organometallic polymers). These complexes possess features characteristic of fine pitches such as less than 7 nm. Unexposed areas of the (stanocenyl)tin compound photoresist can be removed by sublimation or vaporization at a vacuum of 0.0001 torr to 100 torr and a temperature range of 20°C to 300°C. In some embodiments, the in situ radiation reaction may be carried out in a solvent such as an organic solvent, which is sprayed onto the substrate surface after the deposition of the (stanocenyl)tin compound photoresist or applied as a solution composition by spin-on deposition.

[0066] In some embodiments, the mixture of organometallic compound photoresists may have the same or different central metals having MC bonds. The metals include, but are not limited to, Sn, In, Sb, Bi, Mn, V, Ti, Cr, Se, Te, Zr, Hf, Ga, or Ge, and examples include sandwich-type or half-sandwich-type organometallic compounds.

[0067] In some embodiments, a mixture of organometallic photoresist [M1] and organometallic photoresist [M2] (or more) undergoes an ultraviolet-induced reaction. In some embodiments, M-M' bonds or MO-M' bonds can be formed by ultraviolet irradiation. These bonds are poorly soluble in organic solvents or neutral, basic, or acidic aqueous solutions and are non-volatile under high vacuum and ambient temperature (where M or M' represents a metal atom of [M1] or [M2]).

[0068] For example, upon exposure, the organometallic photoresist [M1] reacts with [M2] through hydrolysis or condensation to form a film containing a metal oxide or oxo / hydroxyl network. These cannot sublimate or vaporize under ambient vacuum and temperature conditions. In contrast, the unexposed organometallic photoresists [M1] and [M2] can be removed by sublimation or vaporization under ambient vacuum and temperature conditions, forming a desired pattern without collapse or defects.

[0069] Generally, the EUV photolithography process involves (1) depositing a photoresist as a thin film; (2) performing a pre-exposure bake (PAB); (3) subsequently exposing the film to EUV radiation to form a latent image; (4) performing a post-exposure bake (PEB); (5) developing the film with a liquid such as a basic / acidic aqueous solution or an organic solvent; and (6) then rinsing with a solvent to produce a developed resist pattern. This method is applicable to pitches greater than 10 nm, such as 30-60 nm. However, for pattern structures with pitches less than 10 nm, sublimation and vapor development methods can be used to avoid the use of large amounts of solvents and associated waste disposal, thereby reducing costs and environmental concerns.

[0070] Wet and dry deposition or coating methods can be performed on the surface of semiconductor substrates. Common wet coating methods for radiation-sensitive organometallic photoresists include spin coating, spray coating, dip coating, vapor deposition coating, knife-edge coating, inkjet printing, and screen printing.

[0071] In some embodiments, conventional spin-coating methods are used to deposit organometallic photoresists onto the surface of semiconductor substrates to form thin films for photolithography. Under these circumstances, a post-exposure bake (PAB) procedure, performed on a hot plate at an ambient temperature such as 100°C under normal pressure and in an inert atmosphere (e.g., dinitrogen), is controlled to avoid the potential sublimation of the photoresist at that temperature. This suppresses a reduction in the thickness of the photoresist, followed by the occurrence of defects and pattern collapse.

[0072] In some embodiments, organometallic photoresists can be deposited onto semiconductor substrates without decomposition by dry deposition methods such as chemical vapor deposition (CVD), physical vapor deposition (PVD), or atomic layer deposition (ALD).

[0073] In some embodiments, the advantages of chemical vapor deposition or atomic layer deposition can improve uniformity of thickness and composition and reduce the defect density of the photoresist film.

[0074] In some embodiments, (stanocenyl)tin compounds may be suitable for chemical vapor deposition or atomic layer deposition to form metal oxide films through photolithography patterning.

[0075] In some embodiments, (stanocenyl)tin compounds can be sublimated or vaporized onto a substrate under high vacuum and high temperature without decomposition. This differs from conventional deposition through decomposition by chemical vapor deposition, physical vapor deposition, or atomic layer deposition methods.

[0076] The developing process involves removing exposed areas to form a positive pattern or removing unexposed areas to form a negative pattern, using different developer compositions. This is achieved by bringing the patterned film material or latent image into contact with the developing solvent.

[0077] In some embodiments, conventional wet development processes using organic solvents or aqueous solutions (for example, immersing in a conventional 2-heptanone bath for 40 seconds to remove unexposed photoresist film and develop a negative-type pattern) can be replaced with sublimation or vaporization under high vacuum and appropriate temperature, thereby reducing pattern collapse. For patterns with pitches smaller than 7 nm, wet development may not efficiently remove unexposed photoresist between two adjacent pitches at fine sizes due to the effects of wettability and the surface tension of the solvent.

[0078] In additional embodiments, the post-development rinsing process (e.g., treating the patterned film with an aqueous solution of tetramethylammonium hydroxide (TMAH) for 10-30 seconds) can be omitted. Furthermore, eliminating the wet solvent development and rinsing processes can reduce costs and pollution, improve pattern resolution efficiency, and protect the environment.

[0079] In some embodiments, a typical wet developer composition may be a low to high concentration neutral, basic, or acidic aqueous solution or organic solvent. The temperature of the development process may be high or low. The temperature can be adjusted to control the speed or dynamics of the development process as needed.

[0080] In some embodiments, a typical wet liquid solvent developer composition includes an organic solvent blend. Non-limiting examples of organic solvents used in a pattern-forming method according to one embodiment include, but are not limited to, ketones (e.g., acetone, 2-heptanone, methyl ethyl ketone, cyclohexanone, 2-pyrrolidone, 1-ethyl-2-pyrrolidone, etc.), alcohols (e.g., methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 4-methyl-2-propanol, 1,2-propanediol, 1,2-hexanediol, 1,3-propanediol, pentanol, 2-hexanol, etc.), esters (e.g., ethyl acetate, n-butyl acetate, butyrolactone, propylene glycol methyl ether, ethylene glycol, propylene glycol, glycerol, ethylene glycol methyl ether, etc.), aromatic solvents (e.g., benzene, toluene, xylene), acids (e.g., formic acid, acetic acid, oxalic acid, 2-ethylhexanoic acid), and combinations thereof.

[0081] In some embodiments, the wet liquid solvent developing process is applied by immersing the exposed / unexposed substrate in a developing tank. In some embodiments, the wet solvent developer may be sprayed onto the exposed / unexposed photoresist layer.

[0082] In some embodiments, after development, the formed patterned film can be heated in the range of 100 to 600°C without the pattern collapsing. Heating can be carried out in air, under an inert atmosphere, or in a vacuum.

[0083] In some embodiments, for patterns with a pitch of less than 7 nm, the high thickness / pitch aspect ratio makes it difficult to remove unexposed areas of the photoresist with a liquid solvent. Wettability, surface tension, or straining forces can lead to structural pattern collapse or defects due to the narrow space between two adjacent pitches, making conventional wet development difficult.

[0084] In some embodiments, a radiation-sensitive organometallic photoresist having sublimation or vaporization capability is R a M b L c This is represented as follows: Here, R is an organic group having high radiation sensitivity in the radiation range, and includes, but is not limited to, alkyl, alkenyl, alkynyl, cycloalkyl, or cycloalkenyl groups (e.g., cyclopentadienyl). M is a metal (Sn, In, Sb, Bi, Mn, V, Ti, Cr, Se, Te, Zr, Hf, Ga, Ge). L is a hydrolyzable ligand containing a functional group, including, but not limited to, hydroxides, amines, amides, esters, halides, nitrides, oxides, or thiolates. Also, a, b, c ≥ 1. For example, (cyclopentadienyl)tin, (cyclopentadienyl)indium, (cyclopentadienyl)antimony, or (cyclopentadienyl)vanadium compounds.

[0085] The required characteristics of organotin photoresists or precursors are: (1) sufficient volatility or sublimation capability for gas-phase transport, (2) thermal stability to avoid premature decomposition, and (3) appropriate reactivity with co-precursors to form the target product under UV or EUV light irradiation.

[0086] In this disclosure, the present invention relates to a method for developing a photolithography pattern by sublimation or vaporization, comprising the following steps: (1) forming an organotin photoresist solution composition, wherein the formation of the organotin photoresist solution composition comprises a (stanocenyl)tin compound, a solvent, and / or additives; (2) depositing the organotin photoresist solution composition on the surface of a semiconductor substrate to form a photoresist layer for photolithography patterning; (3) exposing the organotin photoresist layer to chemical radiation to form a latent image pattern; and (4) developing the latent image pattern to form a photolithography pattern by removing unexposed organotin photoresist by applying a sublimation or vaporization method.

[0087] Figure 1 is a flowchart of the photolithography patterning process. This process includes a step of depositing an organotin photoresist on a substrate (100), a subsequent pre-exposure bake step (101) in some embodiments, a step of exposing the photoresist to chemical radiation (e.g., EUV) to form a latent image pattern (102), and a step of developing the formed latent image pattern by sublimation or vapor development (103).

[0088] In this disclosure, the organotin photoresist composition for photolithography patterning comprises a (stanocenyl)tin compound, a solvent, and / or additives.

[0089] The organometallic (stanocenyl) tin compound photoresist compositions according to embodiments of this disclosure, in which carbon, oxygen, nitrogen, or various groups are bonded to the tin metal, may have improved etching resistance, sensitivity, and resolution compared to conventional organic polymer or inorganic resists.

[0090] In some embodiments, the (stanocenyl)tin compound photoresist is dissolved in a suitable organic solvent for further photolithography pattern processing. The solution composition can be formed by dissolving the (stanocenyl)tin compound photoresist in an organic solvent, such as chloroform, tetrahydrofuran, dimethoxyethane, dimethylformamide, dimethyl sulfoxide, alcohols (e.g., 4-methyl-2-pentanol, ethanol, methanol, propanol, isopropanol, butanol), benzene, toluene, xylene, carboxylic acids, ethers (e.g., tetrahydrofuran, anisole), esters (e.g., ethyl acetate, ethyl lactate, butyl acetate), ketones (e.g., 2-heptanone, methyl ethyl ketone), or mixtures of two or more thereof.

[0091] In some embodiments, the solubility of (stanocenyl)tin compound photoresists in organic solvents may be improved, leading to enhanced dissolution during extreme ultraviolet exposure. This allows for the provision of nanoscale patterns with improved sensitivity and limiting resolution. In addition, the resulting patterns may retain their high aspect ratio while remaining intact.

[0092] In some embodiments, the (stanocenyl)tin compound photoresist composition may contain additives including, but not limited to, organic stabilizers, densifiers, or resins.

[0093] In some embodiments, the organic stabilizer includes organic thiols, organic alcohols, organic amines, organic amides, organic carboxylic acids, organic phosphines, organic phosphine oxides, organic phosphonic acids, or combinations thereof.

[0094] In some embodiments, the resin may be an organic polymer or small organic aromatic molecules. In some embodiments, the resin may be volatile under ambient vacuum and temperature.

[0095] After exposure to chemical radiation, the exposed and unexposed areas possess different chemical and physical properties. For example, the exposed areas are converted to metal oxides, eliminating the possibility of sublimation or vaporization. However, the unexposed areas still retain their volatility and can be removed by sublimation or vaporization under high vacuum and high temperature without decomposition or pattern collapse. This sublimation or vaporization method avoids the application of wet and dry developers, as well as / or rinsing processes, improving resolution and reducing pattern collapse.

[0096] In some embodiments, after exposure, the (stanocenyl)tin compound photoresist absorbs ultraviolet radiation. Organic ligand groups are cleaved from the (stanocenyl)tin compound photoresist, potentially forming a metal oxide or polynuclear oxide / oxo pattern. Unexposed areas on the substrate surface can be removed by sublimation or vaporization without pattern collapse or defects.

[0097] Sublimation or vaporization development methods avoid the drawbacks of wet development methods. Wet development methods involve development by immersion in organic solvents or aqueous solutions, washing and removal with solvents, pattern breakdown and defects caused by the washing process, relatively high costs, waste solvent disposal, and environmental concerns such as pollution control. These methods can avoid these problems.

[0098] The properties of organotin photoresists determine the availability of sublimation or vaporization development methods, where (stanocenyl)tin compound photoresists can be sublimated or vaporized without decomposition at vacuum levels of 0.0001 torr to 100 torr and temperatures in the range of 20 to 300°C. (Stanocenyl)tin compound photoresists have radiation sensitivity for photolithography patterning. Their exposed areas are converted into metal oxides or polynuclear oxide networks, which cannot be removed by sublimation or vaporization under ambient vacuum and temperature conditions.

[0099] Sublimation or vaporization developing methods do not use liquid solvents or gases, which can potentially improve pattern fidelity and eliminate microbridge defects.

[0100] Sublimation or vaporization developing methods can significantly improve efficiency, resolution, and product ratio, while potentially reducing costs associated with water consumption, wastewater / organic solvent treatment, and waste disposal.

[0101] The ability of radiosensitive (stanocenyl) tin compound photoresists to sublimate or vaporize without decomposition under high vacuum and high temperatures, as well as their thermal stability, play a crucial role in determining development methods that possess specific stability against radiation absorption and processing effectiveness.

[0102] In some embodiments, (stanocenyl)tin compound photoresists are exposed to ultraviolet light, such as EUV or DUV, under an inert atmosphere (e.g., dinitrogen or argon) or under normal pressure to avoid potential sublimation or vaporization, or pattern collapse or defects.

[0103] In some embodiments, the exposed (stanocenyl)tin compound photoresist may undergo radiation-induced oxidation or hydrolysis during chemical radiation irradiation in the presence of an oxygen source such as oxygen (O2), ozone (O3), hydrogen peroxide (H2O2), or water (H2O), converting to oxides, oxos, or hydroxyl network products. Unexposed areas may be removed by sublimation or vaporization under high vacuum and high temperature.

[0104] In some embodiments, the exposed area of ​​the (stanocenyl)tin compound photoresist can be treated by dry etching using a dry BCl3 plasma, hydrogen halide (HX), hydrogen gas (H2), or halogen gas.

[0105] In addition, the (stanocenyl)tin compound photoresist for photolithography patterning according to one embodiment is not necessarily limited to negative images, but may be configured to form positive images.

[0106] The present invention will be described in more detail below through examples relating to the preparation of (stanocenyl)tin compounds of this embodiment. The synthesis strategy, reagents, reaction mode, or reaction conditions may vary depending on the isomer. 1 η 2 η 3 η 4 , or η 5 The molecular structure of a (stanocenyl)tin compound having hapticity is determined. However, the present invention is not limited to these examples. Examples Example 1 TIFF2026530291000030.tif31144 This example and the following examples provide solid evidence for the synthesis of organotin compounds. Standard Schlenklein techniques were used for the synthesis and purification of organotin compounds, including the use of dry organic solvents under a dry, inert dinitrogen or argon atmosphere. Bis(cyclopentadienyl)tin or stanocene (Sc) as the parent molecule was synthesized according to the reference (C. Janiak, Zeitschrift fur Anorganische und Allgemeine Chemie., 2010, 636 (13-14), 2387-2391). The product was purified as pale yellow crystals by sublimation under high vacuum. (η 5 -C5H5)Sn(η 5 Synthesis of -C5H4SLi) (Sc-SLi): Sc-SLi was prepared according to the same method described in the following reference: C. Elschenbroich F. Lu, O. Burghaus, K. Harms, and J. Pebler, Zeitschrift fur Anorganische und Allgemeine Chemie, 2011, 637, 1750-1755. In THF at -78°C, KO t By reacting stanocene with t-BuLi in the presence of Bu, (η 5 -C5H5)Sn(η 5 -C5H4Li)(ScLi) was prepared. At -20°C, (η) was added to diethyl ether (60 mL). 5-C5H5)Sn(η 5 To a solution of -C5H4Li)(ScLi)stanocene (obtained from t-BuLi (2.0 mL / 1.6 M)), S8 powder (98 mg, 3.06 mmol) was added immediately after sublimation with vigorous stirring. After stirring overnight at room temperature, all volatile components were removed under vacuum to obtain the product described above. Yield: 790 mg, yield: 90%. Example 2 TIFF2026530291000031.tif30134(η 5 -C5H5)Sn(η 5 Synthesis of -C5H4SH): At 0°C, hydrochloric acid (15% HCl, 2 mL) was added to a solution of Sc-SLi (292 mg, 1.02 mmol) in dimethoxyethane (DME, 30 mL). The mixture was stirred at room temperature for 1 hour, dried over magnesium sulfate (MgSO4), and then filtered through Celite. The filtrate was evaporated under vacuum to obtain the marked compound. Yield: 260 mg, yield: 90%. 1 1HNMR (400.13MHz, CDCl) 3 ):δ=6.16(s, 5H), 6.32(m, 2H), 6.61(m, 2H). MS(EI): m / z 281(M + ). C 10 H 10 Elemental analysis of SSn (394.89): Theoretical values ​​C: 42.77%, H: 3.56%; Measured values ​​C: 42.92%, H: 3.88%. Example 3 TIFF2026530291000032.tif30126(η 5 -C5H5)Sn[(η 5-C5H4)OH) (Sc-OH) Synthesis: Sc-OH was prepared by reacting ScLi with Me3SiOOSiMe3 (bis(trimethylsilyl) peroxide) at -78°C. This method follows the reference (C. Elschenbroich, F. Lu, and H. Klaus, Organometallics, 2002, 21 5152-5154). At -78°C, Me3SiOOSiMe3 (0.5 mL, 2.3 mmol) was added to a ScLi solution (prepared from 573 mg (2.3 mmol) of stannocene) in diethyl ether (Et2O, 50 mL) under vigorous stirring. The mixture was slowly warmed to room temperature and stirred overnight. Thereafter, water (1 mL) was added. After 1 hour, the organic phase was separated, dried over MgSO4, and filtered through Celite. The filtrate was evaporated in vacuo, and the residue was extracted with hexane. The extract was filtered through Celite, and the filtrate was evaporated in vacuo to obtain the title compound. Yield: 366 mg, yield: 60%. 1 H NMR (400.13 MHz, C6D6): δ=5.96 (s, 5H), 6.12 (m, 2H), 6.35 (m, 2H). MS (EI): m / z 265 (M + ). Example 4 TIFF2026530291000033.tif33126(η 5 -C5H5)Sn[(η 5Synthesis of (η⁵-C₅H₄)COOH) (Sc-COOH): Sc-COOH was prepared by reacting ScLi with CO₂ followed by acidification. This method conforms to the reference (C. Elschenbroich, O. Schiemann, O. Burghaus, and K. Harms, Journal of the American Chemical Society, 1997, 119, 7452-7457). At -20°C, gaseous CO₂ was introduced into a Sc-Li solution (prepared from 651 mg (2.6 mmol) of stannocene) in diethyl ether (Et₂O, 50 mL) under vigorous stirring. After stirring at room temperature for several hours, the solvent was removed in vacuo, and the residue was dissolved in water (H₂O). Then, the mixture was acidified with aqueous hydrochloric acid (15% HCl) to obtain a precipitate. The precipitate was collected and dried in vacuo to afford the title compound. Yield: 580 mg, yield: 76%. 1 ¹H NMR (400.13 MHz, CDCl₃): δ = 5.81 (s, 5H), 5.73 (m, 2H), 5.90 (m, 2H). MS (EI): m / z 293 (M + +). Example 5 TIFF2026530291000034.tif30135(η 5 ⁵-C₅H₅)Sn[(η 5 ⁵-C₅H₄)SnCl₃) (Sc-SnCl₃): At -78°C, a solution of ScLi (prepared from 2.48 g (10 mmol) of stannocene) in diethyl ether (Et₂O, 50 mL) was added dropwise to a solution of SnCl₄ (1.36 mL, 10 mmol) in hexane (100 mL) over 1 hour under vigorous stirring. (Note: SnCl₄ hydrolyzes very violently when exposed to air or water, releasing HCl gas!!!). After stirring for several hours, the mixture was filtered through Celite. The filtrate was evaporated in vacuo to give the title compound. Yield: 72%. MS (EI): m / z 473 (M + +). Example 6 TIFF2026530291000035.tif33139(η 5 -C5H5)Sn[(η 5 Synthesis of [-C5H4)SnO(OH)]: At room temperature, 30 mL of deoxygenated aqueous ammonia was added to Sc-SnCl3 (516 mg, 1.09 mmol) with vigorous stirring. After stirring for 2 hours, the resulting precipitate was filtered and washed with deionized water (3 × 10 mL). The solid was dried overnight in vacuum to obtain the marked compound. Yield: 218 mg, yield: 50%. MS (EI): m / z 400(M + ). Example 7 TIFF2026530291000036.tif36139(η 5 -C5H5)Sn[(η 5 -C5H4)Sn(O t Synthesis of Bu)3: At 0°C, tBuOK (potassium tertoxide, 380 mg, 3.39 mmol) was added to a solution of Sc-SnCl3 (455 mg, 1.13 mmol) in toluene (60 mL). The mixture was stirred overnight at room temperature and then filtered through Celite. The product was obtained by evaporating the filtrate under vacuum. Yield: 463 mg, yield: 70%. 1 H NMR (400.13MHz, CDCl3): δ=1.36(s, 27H), 6.12(s, 5H), 6.26(m, 2H), 6.68(m, 2H). MS (EI): m / z 586(M + ). C 22 H 36 Elemental analysis of O3Sn2 (585.64): Theoretical values: C: 45.12%, H: 6.15%. Measured values: C: 45.60%, H: 6.36%. Example 8 TIFF2026530291000037.tif34140((η 5 -C5H5)Sn[(η 5Synthesis of [-C5H4)Sn(N(CH3)2)3]: At 0°C, LiN(CH3)2 (lithium dimethylamide, 178 mg, 3.5 mmol) was added to a solution of Sc-SnCl3 (462 mg, 1.16 mmol) in toluene (50 mL). The mixture was stirred overnight at room temperature and then filtered through Celite. The filtrate was evaporated under vacuum to obtain the compound. Yield: 460 mg, yield: 80%. 1 H NMR (400.13 MHz, CDCl3): δ= 2.71(s, 18H), 6.10(s, 5H), 6.23(m, 2H), 6.61(m, 2H). MS (EI): m / z 499(M + ). Example 9 TIFF2026530291000038.tif41138(η 5 -C5H5)Sn[(η 5 Synthesis of [-C5H4)Sn(OCOCH3)3]: At 0°C, 3 equivalents of CH3COONa (sodium acetate, 288 mg, 3.51 mmol) were added to a solution of Sc-SnCl3 (467 mg, 1.17 mmol) in toluene (50 mL). The mixture was stirred overnight at room temperature and then filtered through Celite. The product was obtained by evaporating the filtrate under vacuum. Yield: 450 mg, yield: 70%. MS(EI): m / z 544(M + ). Example 10 TIFF2026530291000039.tif34130(η 5 -C5H5)Sn[(η 5 Synthesis of [-C5H4)SSnCl3] (Sc-SSnCl3): At -78°C, a solution of Sc-SLi (2.87 g, 10 mmol) in 50 mL of DME (1,2-dimethoxyethane) was added dropwise to a solution of SnCl4 (1.36 mL, 10 mmol) in hexane (10 mL) with vigorous stirring. After stirring for several hours, all volatile substances were evaporated under vacuum. The residue was characterized by EI-MS and used directly in subsequent synthesis without further purification. Yield: 80%. MS (EI): m / z 505(M + ). Example 11 TIFF2026530291000040.tif38139(η 5 -C5H5)Sn[(η 5 -C5H4)SSn(O t Synthesis of Bu)3: At -20°C, in a solution of Sc-SSnCl3 (513 mg, 1.02 mmol) in THF (50 mL), t BuOK (343 mg, 3.06 mmol) was added. The mixture was stirred overnight at room temperature, and the solvent was removed. The residue was extracted with toluene and filtered through Celite. The filtrate was evaporated under vacuum to obtain the marked compound. Yield: 486 mg, yield: 77%. MS (EI): m / z 618(M + ). Example 12 TIFF2026530291000041.tif37133(η 5 -C5H5)Sn[(η 5 Synthesis of [-C5H4)SSn(N(CH3)2)3]: At -20°C, LiN(CH3)2 (162 mg, 3.18 mmol) was added to a solution of Sc-SSnCl3 (533 mg, 1.06 mmol) in toluene (50 mL). The mixture was stirred overnight at room temperature and then filtered through Celite. The filtrate was evaporated under vacuum to obtain the marked compound. Yield: 396 mg, yield: 70%. MS (EI): m / z 531(M + ). Example 13 TIFF2026530291000042.tif31140[(η 5 Synthesis of -C5H4SLi)]2Sn (Sc-(SLi)2): First, by reacting stanocene with 2 equivalents of n-BuLi in THF at -78°C, [(η 5 -C5H4Li)]2Sn (ScLi2) was prepared. Then, at 0°C, [(η) was added to Et2O (50 mL). 5S8 (sulfur) powder (316 mg, 9.88 mmol) was added to a solution of -C5H4Li)2Sn (prepared from 1.22 g, 4.9 mmol of stanocene and 6.12 mL, 9.8 mmol of 1.6 M n-BuLi). After stirring overnight at room temperature, the solvent was removed under vacuum to obtain the labeled compound. This product was used directly in subsequent reactions without further purification. Yield: 1.26 g, yield: 80%. Example 14 TIFF2026530291000043.tif34132[(η 5 Synthesis of -C5H4SH)2Sn: At 0°C, a solution of Sc-(SLi)2 (prepared from 336 mg of stanocene, 1.03 mmol) in 30 mL of DME (1,2-dimethoxyethane) was acidified with hydrochloric acid (2 mL, 15% HCl). The solution was then dried over MgSO4 and filtered. The filtrate was evaporated under vacuum. The residue was extracted with hexane and filtered through Celite. The filtrate was evaporated under vacuum to obtain the compound. Yield: 290 mg, yield: 90%. 1 H NMR (400.13 MHz, CDCl3): δ=6.32(m, 4H), 6.69(m, 4H). MS (EI): m / z 313(M+). Example 15 TIFF2026530291000044.tif40134[(η 5 Synthesis of -C5H4COOH)]2Sn: At -20°C, gaseous CO2 was introduced into a solution of ScLi2 (prepared from 670 mg of stanocene, 2.69 mmol) in THF (100 mL) with vigorous stirring. After stirring at room temperature for several hours, the solvent was removed under vacuum, and the residue was dissolved in water (H2O). The mixture was then acidified with aqueous hydrochloric acid (15% HCl) to obtain a precipitate. This precipitate was collected and dried under high vacuum to obtain the marked compound. Yield: 653 mg, yield: 72%. 1 H NMR (400.13 MHz, CDCl3): δ=5.78(m, 4H), 5.93(m, 4H). MS(EI): m / z 337(M + ). Example 16 TIFF2026530291000045.tif32130[(η 5 Synthesis of -C5H4SnCl3)]2Sn (Sc-(SnCl3)2): Sc-(SnCl3)2 was prepared by the same method as for Sc-SnCl3. At -78°C, a solution of ScLi2 (prepared from 2.63 g of stanocene, 10.6 mmol) in THF (100 mL) was added dropwise to a solution of SnCl4 (2.89 mL, 21.2 mmol) in hexane (100 mL) with vigorous stirring. After stirring the mixture for 1 hour, the marked compound was obtained by evaporating all volatile substances. Yield: 78%. MS (EI): m / z 697 (M+). Example 17 TIFF2026530291000046.tif42135[(η 5 -C5H4)Sn(O t Synthesis of Bu)3]2Sn: At 0°C, [(η) in THF (100 mL) 5 -C5H4)SnCl3]2Sn (767 mg, 1.1 mmol) solution, KO t Bu (739 mg, 6.6 mmol) was added with vigorous stirring. The mixture was then stirred overnight at room temperature. The solvent was removed under vacuum, and the residue was extracted with toluene. After filtration through Celite, the filtrate was evaporated under vacuum to obtain the marked compound. Yield: 609 mg, yield: 60%). 1 HNMR (400.13 MHz, CDCl3): δ=1.37(s, 54H), 6.30(m, 4H), 6.61(m, 4H). MS (EI): m / z 922(M + ). Example 18 TIFF2026530291000047.tif41132[(η 5 Synthesis of -C5H4)Sn(N(CH3)2)3]2Sn: At -20°C, [(η 5To a solution of [-C5H4)SnCl3]2Sn (782 mg, 1.12 mmol), LiNMe2 (345 mg, 6.77 mmol) was added with vigorous stirring. The mixture was slowly heated to room temperature and stirred overnight. After removing the solvent, the residue was extracted with toluene and filtered through Celite. The filtrate was evaporated under vacuum to obtain the marked compound. Yield: 670 mg, yield: 79%. 1 H NMR (400.13 MHz, CDCl3): δ=2.69(s, 54H), 6.2(m, 4H), 6.5(m, 4H). MS (EI): m / z 748(M + ). Example 19 TIFF2026530291000048.tif37136[(η 5 Synthesis of -C5H4)SSnCl3)]2Sn (Sc-(SSnCl3)2): Over 1 hour at -78°C, a solution of Sc-(SLi)2 (872 mg, 2.69 mmol) in DME (30 mL) was added dropwise to a solution of SnCl4 (0.8 mL, 5.87 mmol) in hexane (100 mL) with vigorous stirring. After stirring for several hours, all volatile substances were removed. The residue was extracted with toluene and filtered through Celite. The filtrate was evaporated under vacuum to obtain the marked compound. MS (EI): m / z 761(M + ). Example 20 TIFF2026530291000049.tif45130[(η 5 -C5H4)S-Sn(O t Synthesis of Bu)3)2Sn: At 0°C, KOtBu (296 mg, 2.64 mmol) was added to a solution of Sc-(SSnCl3)2 (1.01 g, 1.32 mmol) in THF (100 mL). The mixture was then stirred overnight at room temperature. After removing the solvent, the residue was extracted with toluene and filtered through Celite. The filtrate was evaporated under vacuum to obtain the marked compound. Yield: 810 mg, yield: 62%. MS (EI): m / z 986(M + ). Example 21 TIFF2026530291000050.tif35139[(η 5 -C5H5)Sn(η 5 Synthesis of -C5H4S]2SnBu2: At 0°C, Bu2SnCl2 (356 mg, 1.18 mmol) was added to a solution of Sc-SLi (677 mg, 2.36 mmol) in 30 ml of DME (1,2-dimethoxyethane) with vigorous stirring. After stirring overnight at room temperature, the mixture was filtered through Celite. The filtrate was evaporated under vacuum to obtain the marked compound. Yield: 710 mg, yield: 76%. 1 H NMR (400.13 MHz, CDCl3): δ=1.23(s, 18), 6.10(s, 10H), 6.26(m, 4H), 6.60(m, 4H). MS (EI): m / z 793(M + ).

[0107] The above examples and embodiments are for illustrative purposes only. The present invention is not limited to any particular embodiment and is subject to various modifications and variations. Those skilled in the art will recognize that the form and details can be modified without departing from the spirit and scope of the invention. Accordingly, such modified or altered embodiments are also included in the technical idea of ​​the invention and are construed to be within the scope of the appended claims and their equivalents.

Claims

1. Organotin compounds having a chemical structure containing a stanocenyl group selected from the following: ; Here, R 1 , R 2 , R 3 Each of these is independently H, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or cycloalkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; E = O, S, Se, or Te; X = F, Cl, Br, or I; The organotin compound wherein L is an alkyl group, alkenyl group, alkylene group, alkynyl group, or cycloalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, or an amino group, cyano group, ether group, ester group, halide group, nitro group, silyl group, thiol group, or carbonyl group.

2. The stannocenyl group is bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin, wherein the cyclopentadienyl is cyclopentadienyl C 5 H 5 group, or substituted cyclopentadienyl having hapticity η 1 , η 2 , η 3 , η 4 , or η 5 isomers, and contains C 5 H 3 R, C 5 H 2 R 2 , C 5 HR 3 , C 5 R 4 , or C 5 R 5 groups, wherein R is H, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, or a cycloalkyl group, or an aryl group having 6 to 20 carbon atoms, or an amino group, a cyano group, an ether group, an ester group, a halide group, a nitro group, a silyl group, a thiol group, or a carbonyl group. The organotin compound according to claim 1.

3. The organotin compound according to claim 2, wherein R is H, a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group.

4. R 1 , R 2 , R 3 The organotin compound according to claim 1, wherein each is independently an alkyl group, a cycloalkenyl group, or an aryl group; E = O, S, Se, or Te; and X = Cl.

5. R 1 , R 2 , R 3 The organotin compound according to claim 1, wherein each of the groups is independently a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, or a cyclopentadienyl group.

6. A method for developing photolithography patterns: To form an organotin photoresist solution composition; Here, forming the organotin photoresist solution composition involves a (stanocenyl)tin compound, a solvent, and / or additives; Depositing the organotin photoresist solution composition onto a substrate to form a photoresist layer; The method comprising: exposing the organotin photoresist layer to radiation to form a latent image pattern; and developing the latent image pattern to form a photolithography pattern by removing unexposed organotin photoresist by sublimation or vaporization.

7. The stanocenyl group is bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin, and the cyclopentadienyl is cyclopentadienyl C 5 H 5 C group, or substituted cyclopentadienyl C 5 H 3 R, C 5 H 2 R 2 , C 5 HR 3 , C 5 R 4 , or C 5 R 5 The method according to claim 6, comprising a group, where R is H, a C1-C20 alkyl group, an alkenyl group, an alkynyl group, or a cycloalkyl group, or a C6-C20 aryl group, or an amino group, a cyano group, an ether group, an ester group, a halide group, a nitro group, a silyl group, a thiol group, or a carbonyl group.

8. The (stanocenyl)tin compound is one or more selected from the following: ; Here, R 1 , R 2 , R 3 Each of these is independently H, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or cycloalkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; E = O, S, Se, or Te; X = F, Cl, Br, or I; The method according to claim 6, wherein L is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkylene group, an alkynyl group, or a cycloalkyl group, or an aryl group having 6 to 20 carbon atoms, or an amino group, a cyano group, an ether group, an ester group, a halide group, a nitro group, a silyl group, a thiol group, or a carbonyl group.

9. The method according to claim 8, wherein the cycloalkenyl group comprises substituted and unsubstituted C4-C8 aliphatic unsaturated organic groups containing at least one double bond.

10. The (stanocenyl)tin compound is a substituted cyclopentadienyl C 5 H 4 C group, and / or cyclopentadienyl group C 5 H 5 Including; R 1 , R 2 , R 3 The method according to claim 8, wherein is independently a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, or a cyclopentadienyl group; E = O, S, Se, or Te; and X = Cl.

11. The method according to claim 6, wherein the exposure of the organotin photoresist layer to radiation may be carried out in an atmosphere of molecular oxygen, air, ozone, water, or hydrogen peroxide for the formation of a photolithographic latent image pattern.

12. The method according to claim 6, wherein the radiation is extreme ultraviolet (EUV), deep ultraviolet (DUV), electron beam, X-ray, or ion beam radiation.

13. The method according to claim 6, wherein the sublimation or vaporization is carried out under a vacuum in the range of 0.0001 torr to 100 torr and at a temperature in the range of 20°C to 300°C.

14. The method according to claim 6, wherein the additive comprises an organic thiol, an organic alcohol, an organic amine, an organic amide, an organic carboxylic acid, an organic phosphine, an organic phosphine oxide, an organic phosphonic acid, or a combination thereof.

15. An organotin photoresist composition comprising a (stanosenyl)tin compound, a solvent, and / or additives: The (stanocenyl)tin compound is one or more selected from the following: ; Here, R 1 , R 2 , R 3 Each of these is independently H, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or cycloalkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; E = O, S, Se, or Te; X = F, Cl, Br, or I; The composition wherein L is an alkyl group, alkenyl group, alkylene group, alkynyl group, or cycloalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, or an amino group, cyano group, ether group, ester group, halide group, nitro group, silyl group, thiol group, or carbonyl group.

16. The stanocenyl group is bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin, and the cyclopentadienyl is cyclopentadienyl C 5 H 5 The basis, or hapticity, is η 1 η 2 η 3 η 4 , or η 5 Substituted cyclopentadienyl C having isomers 5 H 3 R, C 5 H 2 R 2 , C 5 HR 3 , C 5 R 4 , or C 5 R 5 The organotin photoresist composition according to claim 15, comprising a group, where R is H, a C1-C20 alkyl group, an alkenyl group, an alkynyl group, or a cycloalkyl group, or a C6-C20 aryl group, or an amino group, a cyano group, an ether group, an ester group, a halide group, a nitro group, a silyl group, a thiol group, or a carbonyl group.

17. The organotin photoresist composition according to claim 16, wherein R is H, a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group.

18. R 1 , R 2 , R 3 The organotin photoresist composition according to claim 15, wherein is independently a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, or a cyclopentadienyl group; E = O, S, Se, or Te; X = Cl; and L is a methylene group, an ethylene group, or a propylene group.

19. The organotin photoresist composition according to claim 15, wherein the solvent comprises 4-methyl-2-pentanol, ethanol, methanol, propanol, butanol, benzene, toluene, xylene, or a combination thereof.

20. The organotin photoresist composition according to claim 15, wherein the (stanocenyl)tin compound can be used as a precursor for preparing an organotin photoresist.

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