Organosin photoresist composition and stabilization method

Abstract

This document describes an organosin photoresist composition and a stabilization method. The organosin photoresist composition contains a (stanocenyl)tin compound, a solvent, and an additive. The stanocenyl includes bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin, where cyclopentadienyl includes a cyclopentadienyl C5H5 group, or a substituted cyclopentadienyl C5H4R, C5H3R2, C5H2R3, C5HR4, or C5R5 group. The stabilization method involves stabilizing the (stanocenyl)tin compound photoresist using an organic molecule as an additive.

Description

[Technical Field]

[0001] Cross-references to related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 532,373, filed by Lu on 12 August 2023, entitled “Organotin photoresist composition and method of stabilization,” which is incorporated herein by reference in its entirety.

[0002] The present invention relates to an organosin photoresist composition for chemical beams and a stabilization method, wherein the organosin photoresist composition contains a (stanocenyl)tin compound, a solvent, and an additive. The stabilization method comprises stabilizing the (stanocenyl)tin compound photoresist by applying an organic molecule as an additive. The stanocenyl includes organometallic bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin. [Background technology]

[0003] With the development of the semiconductor industry, nanoscale patterns are required to pursue higher density, higher performance, and lower costs for devices. Miniaturization of semiconductors is a major challenge. Photolithography has been applied to the formation of microelectronic patterns for decades. Extreme ultraviolet (EUV) lithography is being developed as a mass production technology that enables further miniaturization of semiconductor devices and improvement of device density on semiconductor wafers. EUV lithography is a pattern formation technique for manufacturing high-performance integrated circuits, including high-density structures patterned on a nanometer scale, using an exposure light source with a wavelength of 13.5 nm. By applying EUV lithography, it is possible to form extremely fine patterns of 7 nm or less. Therefore, EUV lithography has become an important tool and technology for manufacturing next-generation semiconductor devices.

[0004] To further 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 changes 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] Organometallic compounds exhibit high UV absorption rates because the metals have high UV absorption capabilities with various carbon-metal (CM) bond dissociation energies (BDEs). Therefore, they can be used as photoresists and / or precursors for photolithography at finer levels (e.g., less than 7 nm), attracting considerable interest in radiation lithography. Among these promising advanced materials, organometallic tin (organosin) compounds, in particular, have demonstrated the ability to provide photoresist patterning with significant advantages such as improved resolution, sensitivity, etching resistance, and low line width / edge roughness without pattern collapse, due to the strong EUV radiation absorption of tin.

[0006] Organosin compounds have been demonstrated as EUV photoresists, offering a promising approach to developing even finer patterns, such as those less than 7 nm. However, poor stability and solubility after storage, as well as short shelf life due to aggregation and precipitation formation, pose serious challenges to distribution and application in photolithography patterning. To overcome the aging and low stability of as-formed organosin photoresist compositions, organic molecules containing functional groups such as -SH, -OH, -COOH, -NH2, or phosphine can be used as additives to stabilize organosin photoresists containing clusters or nanoclusters and improve stability and / or solubility. The organic molecules include organic thiols, organic alcohols, organic amines, organic amides, organic carboxylic acids, organic phosphines, phosphine oxides, or phosphonic acids, which can be adsorbed, grafted, immobilized, anchored, or coordinated onto organosin photoresists to avoid potential aggregation and precipitation. After exposure, the exposed areas of the organosin photoresist, stabilized by organic molecules, can be converted into a multinuclear oxohydroxylate network or metal oxide with low solubility in the solvent. On the other hand, the unexposed areas of the photoresist can be removed by the developer. [Overview of the project]

[0007] In a first embodiment, the present invention relates to an organosin photoresist composition and stabilization method for chemical beams, wherein the organosin photoresist composition comprises a (stanocenyl)tin compound, a solvent, and an additive. The stanocenyl includes bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin, wherein the cyclopentadienyl group includes a cyclopentadienyl C5H5 group and / or a substituted cyclopentadienyl C5H4R, C5H3R2, C5H2R3, C5HR4 or C5R5 group, where R is a hydrogen atom (H), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group, or a cycloalkenyl group, a substituted or unsubstituted 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. Furthermore, (stanosenyl)tin compounds can also be used as precursors for photolithography or organosin photoresist preparation.

[0008] In another embodiment, the present invention relates to a radiosensitive (stanocenyl)tin compound photoresist, where the (stanocenyl)tin compound is one or more selected from the following: TIFF2026529081000001.tif41148TIFF2026529081000002.tif25148TIFF2026529081000003.tif25148TIFF2026529081000004.tif44148TIFF2026 529081000005.tif26155TIFF2026529081000006.tif40155TIFF2026529081000007.tif21155TIFF2026529081000008.tif23155TIFF2026529081000 009.tif22155TIFF2026529081000010.tif40155TIFF2026529081000011.tif22155TIFF2026529081000012.tif22155TIFF2026529081000013.tif23155TIFF2026529081000014.tif46151TIFF2026529081000015.tif23151TIFF2026529081000016.tif27151TIFF2026529081000017.tif38151 Here, R 1 , R 2 , R 3 Each of these is independently a hydrogen atom (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 is an oxygen atom (O), a sulfur atom (S), a selenium atom (Se), or a tellurium atom (Te); X is a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I); and L is a substituted or unsubstituted alkyl group, alkenyl group, alkylene 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.

[0009] In a further embodiment, the present invention relates to a stabilization method in which an organic molecule as an additive stabilizes a (stanocenyl)tin photoresist for photolithography patterning. Stabilization with organic molecular additives can overcome the drawbacks of conventional unstabilized organosin photoresists, such as low stability and solubility, and / or short shelf life. This stabilization method involves adding an organic additive to a solution of as-formed organosin compounds, particularly organosin clusters, thereby preventing the formation of aggregation and precipitation. Aggregation and precipitation can cause scum and defects on the substrate surface during photolithography patterning. Organic molecular additives contain various functional groups such as -SH, -OH, -NH2, -COOH, and -CONH2, including, but not limited to, organic thiols, organic alcohols, organic amines, organic amides, organic carboxylic acids, organic phosphines, phosphine oxides, or phosphonic acids.

[0010] In another embodiment, the present invention relates to a radiosensitive organometallic sandwich type stanocene (Sc)(η) as a matrix molecule for synthesizing (stanocenyl)tin compounds represented by chemical formulas (1) to (50) as photoresists or precursors using a standard Schlenk method. 5 This relates to -C5H5)2Sn or bis(cyclopentadienyl)tin. Monolithiation or dilithiation of the cyclopentadienyl ring of stanocene is carried out under ambient conditions by the reaction of stanocene with an appropriate amount of strong base such as n-BuLi or t-BuLi. The resulting monolith is (η 5 -C5H4Li)Sn(η 5 -C5H5) or dilithio form (η 5 -C5H4Li)Sn(η 5 -C5H4Li) is then reacted under ambient conditions with a suitable reagent such as SnCl4, RSnCl3, R2SnCl2, R3SnCl, amine, Me3SiOOSiMe3, S8, Se, Te powder, or CO2 to give the target product as a photoresist or precursor.

[0011] In another aspect, the present invention aims to provide a method for preparing and purifying a high purity (stannocenyl)tin compound for photolithography (e.g., EUV, less than 7 nm). The purification method includes, but is not limited to, distillation, extraction, filtration, recrystallization, column chromatography, coordination, sublimation, or combinations thereof.

[0012] The present invention further aims to provide an alternative organotin (stannocenyl)tin compound photoresist with higher resolution, sensitivity, and lower line width roughness without pattern collapse during microelectronics patterning. The photosensitivity, thermal stability, and uniformity of the organotin photoresist composition determine the high resolution and efficiency of the photoresist for photolithography. The present invention aims to provide improved stability, solubility, uniformity, and shelf life of a (stannocenyl)tin compound photoresist composition stabilized by organic molecules for coating on a substrate surface without aggregation, precipitation, or change over time.

[0013] In a further aspect, the present invention relates to a radiation-sensitive (stannocenyl)tin photoresist composition, which can efficiently form a high-resolution pattern with low line width roughness, high resolution, low dose amount, and high contrast, such as less than � nm, after exposure to extreme ultraviolet (EUV), deep ultraviolet (DUV), electron beam, X-ray, or ion beam radiation, or the like.

Brief Description of the Drawings

[0014] [Figure 1] It is a diagram showing a flowchart of a radiation photolithography patterning process of an organotin photoresist on the surface of a semiconductor substrate.

Modes for Carrying Out the Invention

[0015] The present invention relates to organosin photoresist compositions and stabilization methods, wherein the organosin photoresist composition comprises a (stanocenyl)tin compound, a solvent, and an additive. The stanocenyl includes organometallic bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin. The present invention aims to provide a stabilization method for organosin photoresists suitable for EUV lithography (e.g., less than 7 nm). This stabilization method involves applying an organic molecule as an additive to stabilize the (stanocenyl)tin compound, particularly the cluster. The present invention further aims to provide an organic molecule-stabilized organosin photoresist with higher resolution, sensitivity, solubility, stability, and shelf life, as well as lower line width roughness, without causing pattern collapse during microelectronic patterning. The photosensitivity and thermal stability of organosin photoresists determine the high resolution and efficiency of photolithography patterning.

[0016] In this specification, the singular forms "a, an, one" and "the" are intended to include the plural form unless the context clearly indicates otherwise. Furthermore, the expressions "one of," "at least one of," "any," and "selected from," when placed before a list of elements, modify the entire list of elements, not the individual elements of the list.

[0017] Where the terms “includes,” “including,” “comprise,” and “comprising” are used herein, they identify the presence of 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.

[0018] In this specification, the term "and / or" includes any combination of one or more of the relevant enumerated items. Furthermore, the use of "may" when describing embodiments of this disclosure refers to "one or more embodiments of this disclosure."

[0019] In this specification, the terms “use,” “using,” and “used” may be considered synonymous with “utilize,” “utilized,” and “applied,” respectively. In addition, “about,” “only,” and similar terms are used as approximations rather than terms of degree, and are intended to take into account the inherent deviations in measured or calculated values ​​that would be recognized by those skilled in the art.

[0020] The term "alkyl" or "alkyl group" refers to saturated linear or branched 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. Substituents include, but are not limited to, amide, amine, cyano, ether, cyclic ether, ester, cyclic ester, halide, imine, nitro, silyl, thiol, or carbonyl groups. 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-).

[0021] The term "amine" refers to primary (-NH2), secondary (-NHR), and tertiary (-NR2) amine groups. The term "cyclic amine" refers to [R-NH-R'], where [R-R'] is a substituted and unsubstituted C3-C8 cyclic organic group, including but not limited to the following: TIFF2026529081000018.tif19141 The term "ether" refers to the R-O-R' group. The term "cyclic ether" refers to [R-O-R'], where [R-R'] refers to a C3-C8 substituted and unsubstituted cyclic organic group, such as the following: TIFF2026529081000019.tif18141 The term "ester" refers to the R-(C=O)-O-R' group. The term "cyclic ester" refers to [R-(C=O)-O-R'], where [R-R'] refers to a C4-C8 substituted and unsubstituted cyclic organic group, such as the following: TIFF2026529081000020.tif18139 The term "halide" refers to F, Cl, Br, or I. The term "nitro" refers to -NO2. The term "silyl" refers to a -SiR-, -SiR2-, or -SiR3 group. The term "thiol" refers to a -SH group. The term "carbonyl" refers to a -C=O group. The term "oxo" refers to -O- or =O. In the above description, R and R' are independently 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.

[0022] In the present disclosure, the term "substituted" refers to replacing a hydrogen atom with a C1-C20 alkyl group, C1-C20 alkene group, C1-C20 alkyne group, C1-C20 cycloalkyl group, C6-C20 aryl group, or other related groups such as an amino group, cyano group, ether group, ester group, halide group, nitro group, silyl group, thiol group, or carbonyl group.

[0023] [[ID=U]] The term "η 1 " refers to one carbon atom bonded to one metal atom. The term "η 2 " refers to two carbon atoms bonded to one metal atom. The term "η 3 " refers to three carbon atoms bonded to one metal atom. The term "η 4The term "η" refers to four carbon atoms bonded to one metal atom. 5 The term "metal atom" refers to five carbon atoms bonded to a single metal atom.

[0024] EUV lithography is being developed for mass production of next-generation nodes below 7 nm. EUV photoresists are required to achieve higher performance, higher sensitivity and resolution, and lower costs. EUV light is applied to photolithography at approximately 13.5 nm. EUV light can be generated from a Sn or Xe plasma source excited using a high-energy laser or discharge pulse.

[0025] In conventional organic polymer photoresists, if the aspect ratio (the ratio of height to width) is too large, the pattern structure tends to collapse, and surface tension also plays a role, limiting their application to finer patterns such as those smaller than 7 nm.

[0026] At fine pattern sizes of less than 7 nm, such as 1-3 nm, conventional chemically amplified (CA) organic polymer photoresists face serious challenges including low absorption of EUV light, low resolution, high line edge roughness (LER), and increased pattern collapse and defects. To overcome the shortcomings of conventional organic polymer and inorganic photoresists, there is a need for novel organometallic photoresists or organometallic photosensitive compositions, especially for EUV applications.

[0027] Because metals have a high absorption capacity for EUV radiation, organometallic photoresists are used in EUV lithography. For organometallic photoresists, radiation sensitivity, as well as stability against heat, oxygen, and moisture, are important. In some embodiments, organometallic photoresists may absorb moisture and oxygen, resulting in reduced stability and decreased solubility in the developer. Furthermore, in some embodiments, the photoresist layer may outgasse volatile components before radiation exposure and development operations, which can adversely affect lithography performance, pattern collapse, and increase defects.

[0028] Generally, the metal center plays a major role in determining the absorption of light radiation. The physical and chemical properties of organometallic compounds suitable for photoresists determine the properties relevant to photolithography (especially EUV and DUV), where the bond dissociation energy (BDE) of the MC (metal-carbon bond) plays a major 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, organosin photoresists are suitable for EUV or DUV photolithography patterning.

[0029] On the other hand, in organometallic compounds, the organic ligand (MR, where M = metal and R = cleavable / hydrolyzable organic ligand) bound to the metal may also influence the relevant UV absorption through MC bonding.

[0030] Tin atoms provide strong absorption of extreme ultraviolet (EUV) light at 13.5 nm, where tin cations can be selected based on desired radiation and absorption cross-section. Organic ligands bound to tin also absorb EUV light. By tuning and modifying the organic ligand, resolution, sensitivity, radiation absorption, and material properties can be altered.

[0031] In some embodiments, the organosin photoresist comprises a small organometallic tin compound or an organosin cluster having a large molecular weight. In some embodiments, the small organometallic tin compound contains one, two, or three tin atoms. In some embodiments, the organosin cluster contains more than three tin atoms, for example, twelve.

[0032] Organosin photoresists contain organometallic stanocenyl units, organic ligands, and Sn-C, Sn-O, Sn-S, Sn-Se, Sn-Te, Sn-N, or Sn-O-Sn bonds, which provide desirable radiation sensitivity and stability to precursor metal cations. Organosin photoresists possess excellent properties for photolithography and patterning.

[0033] The (stanocenyl)tin compound photoresist compositions containing a cyclopentadienyl group or a substituted cyclopentadienyl group according to embodiments of the present disclosure, in which oxygen, nitrogen, or various other groups are bonded to the tin metal as described above, may offer improved etching resistance, sensitivity, and resolution compared to the conventional organic polymer or inorganic photoresists associated with this invention.

[0034] The organosin photoresist layer is patterned by exposure to chemical radiation. Typically, the chemical properties of the photoresist region irradiated with incident radiation change in a manner that depends on the type of photoresist used. The photoresist can be a positive-type or negative-type resist. In some embodiments, a positive-type resist refers to a photoresist material that becomes soluble in the developer when exposed to radiation, while unexposed (or less exposed) regions remain insoluble in the developer. In some embodiments, conversely, a negative-type resist refers to a photoresist material that becomes insoluble in the developer when exposed to radiation, while unexposed (or less exposed) regions remain soluble in the developer.

[0035] Examples of specific organosin compounds that may be used as photoresists in embodiments of the present invention are represented by the following chemical formulas (1) - (50): TIFF2026529081000021.tif42145TIFF2026529081000022.tif25145TIFF202 6529081000023.tif25154TIFF2026529081000024.tif41154TIFF20265290810 00025.tif25154TIFF2026529081000026.tif24154TIFF2026529081000027.ti f40154TIFF2026529081000028.tif21154TIFF2026529081000029.tif22154TI FF2026529081000030.tif22154TIFF2026529081000031.tif43157TIFF2026529081000032.tif22157TIFF2026529081000033.tif22157TIFF2026529081000034.tif22157TIFF2026529081000035.tif43157TIFF2026529081000036.tif23157TIFF2026529081000037.tif27157TIFF2026529081000038.tif38157Here, R 1 , R2 , 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, and E=O, S, Se, or Te, and X=F, Cl, Br, or I.

[0036] L is a substituted or unsubstituted alkyl group, alkylene group, alkenyl group, alkynyl group, cycloalkyl group, or cycloalkenyl group having 1 to 20 carbon atoms, or a substituted or unsaturated aryl group having 6 to 20 carbon atoms, such as methylene or ethylene.

[0037] The term "cycloalkenyl group" includes substituted and unsubstituted cyclic aliphatic unsaturated organic groups of C4-C8 containing at least one double bond, such as the following: TIFF2026529081000039.tif44127

[0038] In some embodiments, the organosin photoresists according to embodiments of the present disclosure may be represented by at least one example.

[0039] As those skilled in the art will recognize, the compounds listed herein are merely illustrative examples of organosin compound photoresists and are not intended to limit the embodiments to the organosin compound photoresists specifically described. Rather, any suitable organosin compound photoresist can be used, and all such organosin compound photoresists are entirely intended to fall within the scope of these embodiments.

[0040] The organosin compounds represented by chemical formulas (1) to (50) contain a stanocenyl group, where stanocenyl includes bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin, where cyclopentadienyl includes a cyclopentadienyl C5H5(Cp) group or a substituted cyclopentadienyl C5H4R, C5H3R2, C5H2R3, C5HR4, or C5R5 group, and the hapticity (coordination site number) of the isomers is η 1 η 2 η 3 η 4 , or η 5 Here, R is H, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group, or a cycloalkenyl group, a substituted or unsubstituted 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.

[0041] This invention relates to methods for preparing and purifying organometallic (stanocenyl) tin compounds represented by chemical formulas (1) to (50), or organically stabilized organosin photoresists. All chemical operations, including preparation and purification, are carried out using standard Schlenk techniques in a dried and degassed solvent under an inert atmosphere of purified nitrogen or argon. Methods for purifying organometallic (stanocenyl) tin compounds, organosin photoresists, or organically stabilized organosin photoresists include distillation, extraction, filtration, recrystallization, column chromatography, coordination, sublimation, or a combination thereof. In some embodiments, recrystallization may yield single crystals, which are suitable for X-ray diffraction analysis to determine the molecular structure.

[0042] Organometallic sandwich stanocene (η) as the parent molecule 5-C5H5)2Sn (Cp2Sn, or bis(cyclopentadienyl)tin) can be lithium-ionized with a strong base at one or two cyclopentadienyl rings using appropriate reagents to prepare organometallic (stanocenyl)tin compounds represented by chemical formulas (1) - (50).

[0043] Here, the strong base includes, but is not limited to, methyllithium (MeLi), n-butyllithium (n-BuLi), or t-butyllithium (t-BuLi). The lithiation of one or two cyclopentadienyl rings depends on the reaction conditions, such as the amount of base, solvent, temperature, or addition rate.

[0044] In exemplary embodiments, (stanocenyl)tin compounds represented by chemical formulas (1) - (50) are converted to monolithion products (η) using standard Schlenk techniques. 5 -C5H4Li)Sn(η 5 -C5H5) or dilithiation product (η 5 -C5H4Li)Sn(η 5 -C5H4Li) can be synthesized by reaction with a suitable reagent, such as SnCl4, RSnCl3, R2SnCl2, R3SnCl, amines, Me3SiOOSiMe3, S8, Se powder, Te powder, or CO2, where R includes, but is not limited to, substituted or unsubstituted alkyl groups, alkenyl groups, alkylene groups, alkynyl groups, cycloalkyl groups, or cycloalkenyl groups having 1 to 20 carbon atoms, or substituted or unsubstituted aryl groups having 6 to 20 carbon atoms.

[0045] In an exemplary embodiment, the organosin compound [(C5H5)Sn(C5H4)]2Sn( t Bu)2 can be prepared according to the following method: Those skilled in the art will recognize that synthetic strategies, reagents, solvents, or reaction conditions, including reactant ratios, temperatures, reaction times, or addition methods, have been considered and are within the express scope described above.

[0046] In another exemplary embodiment, the organosin compound [(C5H5)Sn(C5H4S)]3Sn( t Bu) can be prepared according to the following method: Those skilled in the art will recognize that synthetic strategies, reagents, solvents, or reaction conditions, including reactant ratios, temperatures, reaction times, or addition methods, have been considered and are within the scope of this disclosure, within the express range described above.

[0047] In the present invention, the (stanocenyl)tin compounds represented by chemical formulas (1) - (50) may contain four, three, two, or one stanocenyl groups having various functional groups, for example, tetrakis(stanocenyl)tin [(C5H5)Sn(C5H4)]4Sn represented by chemical formula (1), or [(C5H5)Sn(C5H4E)]4Sn (E = O, S, Se, or Te) represented by chemical formula (11).

[0048] The cyclopentadienyl group (C5R5, or Cp) can impart photosensitivity to the compound, and the formed C p -Sn bonds can promote proper solubility of organometallic (stanocenyl) tin compounds in organic solvents. Therefore, according to one embodiment, these C p -Sn-bond-containing organometallic (stanocenyl) tin compounds may have improved sensitivity, resolution, and stability, and may be suitable as precursors for EUV photoresists and / or EUV lithography patterning.

[0049] The organosin compounds represented by chemical formulas (1) - (50) contain Sn-C, Sn-N, Sn-O, Sn-S, Sn-Se, or Sn-Te bonds with different bond dissociation energies (BDE), are sensitive to extreme ultraviolet light, and can absorb extreme ultraviolet light at 13.5 nm.

[0050] The organosin compounds represented by chemical formulas (1) - (50) are cyclopentadienyl-tin bonds (C p Contains a -Sn bond. p-Sn bonds are highly sensitive to ultraviolet (UV) light, and it has been demonstrated that exposure to UV light causes radiation damage and generates free radicals (see, for example, the following references: PJ Baker, AG Davies, M.-W. Tse, “The photolysis of cyclopentadienyl compounds of tin and mercury. Electron spin resonance spectra and electronic configuration of the cyclopentadienyl, deuteriocyclopentadienyl, and alkylcyclopentadienyl radicals”, 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(cyclopentadienyl1)tin and related compounds”, Journal of the American Chemical Society, 1982, 104). 4064-4069. These are all incorporated herein by reference. Baker et al. reported that the UV photolysis of unsubstituted sandwich and half-sandwich cyclopentadienyl tin(IV) (C5H5-Sn) compounds in toluene, namely C5H5SnMe3, C5H5SnBu3, (C5H5)2SnBu2, C5H5SnCl3, (C5H5)2SnCl2, (C5H5)3SnCl, and (C5H5)4Sn, revealed potent EPR spectra of the C5H5· radical.This study demonstrated that cyclopentadienyl (C5H5) groups or substituted cyclopentadienyl (C5R5) groups exhibit higher UV photosensitivity compared to alkyl groups (e.g., methyl and butyl groups) under identical conditions. This property is beneficial for reducing EUV light irradiation and improving resolution. TIFF2026529081000042.tif13124

[0051] (Stanocenyl)tin photoresists contain cyclopentadienyl groups or substituted cyclopentadienyl groups, π bonds, C-Sn bonds, and related interactions, and tin absorbs high-energy EUV rays at 13.5 nm, thus potentially exhibiting excellent sensitivity to high-energy light (e.g., EUV or DUV). Therefore, the associated solution compositions may have improved resolution, sensitivity, and stability compared to inorganic photoresists such as organic polymers or metal oxides.

[0052] (Stanocenyl)tin compound photoresists absorb high-energy EUV rays at 13.5 nm (low exposure photoresist, e.g., 20 mJ / cm²). 2 Due to the formation of free radicals, tin oxide, and related products by the disruption of Cp-Sn bonds (less than 10 nm), and their toughness, they exhibit excellent sensitivity to EUV synchrotron radiation and may have few or no pattern defects at the nanoscale. Therefore, (stanocenyl)tin compound photoresist compositions can have a tight pitch (e.g., less than 10 nm) and can provide high resolution while maintaining yield.

[0053] (Stanocenyl)tin compound photoresists are soluble in suitable organic solvents and possess improved homogeneity for subsequent photolithography pattern processing. Solutions of organosin photoresists can be formed by dissolving (stanocenyl)tin photoresists in organic solvents, which include, but are not limited to, pentane, hexane, cyclohexane, dichloromethane, chloroform, tetrahydrofuran, dimethoxyethane, dimethylformamide, dimethyl sulfoxide, alcohols (e.g., 4-methyl-2-pentanol, methanol, ethanol, 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. Those skilled in the art will recognize that the selection of solvents and solution composition components within the express range described above are considered and are within the scope of this disclosure.

[0054] The organosin photoresist composition may contain 0.1% to 60% by weight of an organometallic (stanocenyl) tin compound represented by chemical formulas (1) to (50), based on the total weight of the organosin photoresist composition.

[0055] In some embodiments, (stanocenyl)tin compounds represented by chemical formulas (1)-(50) may also be used as precursors for forming organosin photoresists, for example, by hydrolysis with water or moisture, or by condensation reaction with organic acids (e.g., formic acid, acetic acid, citric acid, propionic acid, isovaleric acid, butyric acid, valeric acid, caproic acid, glycolic acid, lactic acid, oxalic acid, or succinic acid). In some embodiments, (stanocenyl)tin compounds represented by chemical formulas (1)-(50) may be used as precursors for transparent conductive oxides, thermoelectric materials, or catalysts.

[0056] In some embodiments, the organometallic (stanocenyl) tin compounds used as precursors for organosin cluster photoresist preparation according to embodiments of the present disclosure may contain hydrolyzable functional groups such as -OR, -SR, -SeR, -TeR, -X, -NR2, or -OCO.

[0057] In some embodiments, conventional organosin photoresists have insufficient stability in solution after aging, resulting in a short shelf life (storage period) in photolithography, causing aggregation or precipitation, which can lead to scum or defects in photolithography patterning.

[0058] In some embodiments, hydrolysates or condensates such as organosin nanoclusters have insufficient solubility in organic solvents such as toluene, hexane, acetone, heptanone, and 2-butanone. Therefore, filtration through a membrane such as 0.25 mm PTFE (polytetrafluoroethylene) is required before spin-coating the substrate surface. This demonstrates that the size and uniformity of organosin clusters or nanoclusters are important for thin-film formation and subsequent photolithography.

[0059] In some embodiments, blends of organosin photoresists having different organic ligands result in further improvements in photolithography patterning compared to single-component organosin compound photoresists.

[0060] In some embodiments, an organosin photoresist precursor solution is deposited on the surface of a substrate or layer by in situ hydrolysis with water, or via an alternative base such as tetramethylammonium hydroxide, to form a photoresist layer. The formed photoresist layer is then baked at a high temperature, causing hydrolysis and subsequent condensation of the organosin compound, forming organosin oxide hydroxide clusters. After exposure, patterning radiation induces cleavage of the Sn-C bond and crosslinking of the organosin oxide hydroxide clusters in the exposed areas of the photoresist, resulting in the formation of stable metal oxides (MO). x ) occurs.

[0061] In some embodiments, the stability of (stanocenyl)tin photoresist in solution can be improved by organic molecules as stabilizers. (Stanocenyl)tin photoresist stabilized with organic molecules has improved stability, solubility, homogeneity, or shelf life for photolithography.

[0062] In some embodiments, the organic molecular stabilizer includes, but is not limited to, organic thiols, organic alcohols, organic amines, organic amides, organic carboxylic acids, organic phosphines, phosphine oxides, phosphonic acids, or combinations thereof.

[0063] In some embodiments, the organic thiols include, but are not limited to, 1-dodecanethiol, 2-dodecanethiol, 1,12-dodecanedithiol, 1-docosanethiol, 1-decanethiol, 1-heptanethiol, 2-heptanethiol, 1-heptadecanethiol, 1-hexanethiol, 1-hexadecanethiol, 1-nonanthiol, 1-octadecanethiol, 1-octanethiol, 1-pentadecanethiol, 1-tetradecanethiol, 1-tridecanethiol, 1-undecanethiol, 1,8-octanethiol, 1,2-ethanedithiol, or combinations thereof.

[0064] In some embodiments, the organic alcohols include, but are not limited to, 1-dodecanol, 1-octanol, 1-hexadecanol, 1-heptanol, 1-heptadecanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-nonanol, 1,10-decanediol, 1,2-hexadecanediol, 1,12-dodecanediol, 1,8-octanediol, 1,11-undecanediol, 2-mercaptoethanol, or combinations thereof.

[0065] In some embodiments, the organic amines include, but are not limited to, 1-heptadecyloctadecylamine, decylamine, dodecylamine, heptylamine, heptadecylamine, hexadecylamine, isotridecaneamine, nonylamine, octadecylamine, octanamin, octylamine, pentadecylamine, tetradecylamine, tridecylamine, triethylamine, undecylamine, undecanemin, 1,8-diaminooctane, 1,9-diaminononane, 1,12-dodecanediamine, 1,11-undecanediamine, or combinations thereof.

[0066] In some embodiments, organic amides include, but are not limited to, decanamide, docosanamide, dodecanamide, hexanoamide, heptanamide, heptadecanamide, hexadecanamide, eicosanamide, nonanamide, nonadecanamide, nonanediamide, octanamide, oleamide, octadecanamide, octanediamide, pentadecanamide, tetradecanamide, tridecanamide, undecanamide, or combinations thereof.

[0067] In some embodiments, the organic carboxylic acids include, but are not limited to, oleic acid, citric acid, decanoic acid, hexadecanedioic acid, lauric acid, nonanoic acid, octanoic acid, palmitic acid, suberic acid, undecanoic acid, 1,11-undecanedicarboxylic acid, thioglycolic acid, mercaptoacetic acid, mercaptopropionic acid, or combinations thereof.

[0068] In some embodiments, the organophosphine, phosphine oxide, or phosphonic acid includes, but is not limited to, trioctylphosphine, tributylphosphine, tris(dimethylamino)phosphine, tris(diethylamino)phosphine, trioctylphosphine oxide, hexylphosphonic acid, octadecylphosphonic acid, 11-undecenylphosphonic acid, or combinations thereof.

[0069] In some embodiments, the (stanocenyl)tin photoresist contains, but is not limited to, functional groups including ether groups, thiol groups, silyl groups, keto groups, cyano groups, carbonyl groups, or halogenated groups, or combinations thereof.

[0070] In some embodiments, the organic molecular stabilizer may be adsorbed, grafted, immobilized, anchored, or coordinated onto a (stanocenyl)tin photoresist as a support. For example, an organic thiol or thiolate may coordinate with the tin of (stanocenyl)tin to form a Sn-S bond.

[0071] An organic molecular stabilized (stanocenyl)tin photoresist composition according to one embodiment can be prepared by adding an organic molecular stabilizer to a (stanocenyl)tin compound solution in an organic solvent or water of various concentrations under ambient conditions (e.g., a temperature range of -196 to 300°C, an inert N2 or Ar atmosphere, or an air atmosphere). The addition of the organic molecular stabilizer can be performed between 0 and 24 hours after the preparation of the (stanocenyl)tin compound photoresist solution.

[0072] In some embodiments, organic molecular stabilized organosin photoresists can be dissolved in a suitable organic solvent to form a homogeneous solution composition for deposition on a substrate surface for photolithography patterning. Organic solvents include, but are not limited to, aromatic solvents, pentane, hexane, cyclohexane, tetrahydrofuran, dimethoxyethane, alcohols, ethers, esters, methylene chloride, chloroform, or combinations thereof.

[0073] In an exemplary embodiment, the preparation of an organic thiol-stabilized (stanocenyl) tin photoresist involves dodecanethiolate stabilization [(C5H5)Sn(C5H4S)]3Sn( t It can be expressed by the preparation of Bu), and here, in THF, [(C5H5)Sn(C5H4S)]3Sn( t 1-dodecanethiol was added to the Bu) solution.

[0074] (Stanocenyl)tin photoresist solution compositions can be used for further processing and patterning in photolithography, including deep ultraviolet (DUV), extreme ultraviolet (EUV), electron beam (e-beam), X-ray, or ion beam radiation.

[0075] A method for forming a photolithography pattern using an organosin photoresist composition is illustrated in Figure 1. The (stanocenyl)tin photoresist composition is deposited on a substrate 102 such as silicon or silicon oxide to form a thin photoresist layer 104. After baking at an appropriate temperature, the organosin photoresist layer is exposed to chemical radiation to form a latent image pattern 106. After post-exposure baking (PEB), the latent image is developed with an appropriate developer such as an aqueous base / acid solution or an organic solvent to produce a developed resist photolithography pattern 108. The formed latent image pattern is developed to form a photolithography pattern by applying a developer to remove unexposed or exposed areas of the photoresist.

[0076] Methods for depositing organosin photoresist on the surface of a semiconductor substrate include wet deposition methods such as spin coating, spray coating, dip coating, vapor deposition, and knife-edge coating, as well as dry deposition methods such as chemical vapor deposition (CVD), physical vapor deposition (PVD), and atomic layer deposition (ALD), or other techniques.

[0077] In some embodiments, after exposure, the exposed and unexposed areas of the organosin photoresist have different chemical and physical properties. The cleavage of the organic ligands in the organosin photoresist can form metal oxides or multinuclear oxo / hydroxo network patterns. The unexposed areas of the photoresist can be removed by a developer depending on their different characteristics, solubility, and properties. In one embodiment, the developer is a wet developer, such as an organic solvent or aqueous solution. In another embodiment, the developer is a dry developer. In some embodiments, the development method is sublimation or evaporation under high pressure ranging from 0.00001 Torr to 100 Torr and / or high temperature ranging from 20 to 200 °C.

[0078] Furthermore, the patterning of the (stanocenyl)tin compound photoresist composition according to one embodiment is not necessarily limited to negative images, but may be configured to form positive images.

[0079] The advantages of (stanocenyl)tin compound photoresists, or organic molecule-stabilized (stanocenyl)tin compound photoresist compositions, are evident compared to organic molecule or organic polymer photoresists, or inorganic photoresists, as described above. However, it will be understood that not all advantages are necessarily discussed here in order to include all embodiments or examples. Other embodiments or examples may offer different advantages.

[0080] The present invention will be described in more detail below through examples relating to the preparation of (stanocenyl)tin compounds as photoresists or precursors for organosin photoresist compositions for photolithography and patterning, in addition to the stabilization methods in embodiments of the present invention. However, the present invention is not limited by these examples. Those skilled in the art will recognize that the sample and solution composition components within the express range described above are considered and are within the scope of this disclosure. Examples Example 1 TIFF2026529081000043.tif33132Sn(η 5 -C5H4)2Sn t Synthesis of Bu2: At -78 °C, in ether (20 mL) t Bu2SnCl2 (486 mg, 1.6 mmol) solution in THF (100 mL) (η 5 -C5H4Li)(η 5 The solution (prepared from stanocene 788 mg / 3.3 mmol and t-BuLi 2.1 mL / 1.6 M, 3.36 mmol) was added dropwise with vigorous stirring. After stirring overnight at room temperature, all volatile components were removed by distillation under reduced pressure. The residue was extracted with toluene and filtered through a silica short pad. The filtrate was evaporated under reduced pressure to obtain the product described above. Yield: 460 mg, yield: 61%. 1 H NMR (400.13 MHz, CDCl3): δ = 1.33 (s, 18H), 6.16 (s, 10H), 6.29 (m, 4H), 6.68 (m, 4H). EI-MS (70 eV): m / z 470 (M + ). Example 2 TIFF2026529081000044.tif48134[(C5H5)Sn(C5H4S)]3Sn t Synthesis of Bu: At -78 °C, (η) in THF (100 mL) 5 -C5H5)Sn(η 5 -C5H4SLi) (916 mg, 3.3 mmol) solution in diethyl ether (20 mL) tA solution of BuSnCl3 (310 mg, 1.1 mmol) was added dropwise with vigorous stirring. After addition, the mixture was gradually heated to room temperature and stirred overnight. The reaction solution was then removed by distillation under reduced pressure. The resulting residue was extracted with toluene and filtered through a silica short pad. The product was obtained by removing the solvent. Yield: 0.5 g, yield: 46%. 1 H NMR (400.13 MHz, CDCl3): δ = 1.26 (s, 9H), 6.11 (s, 15H), 6.22 (m, 6H), 6.63 (m, 6H). EI-MS (70 eV): m / z 985 (M + ).

[0081] It is understood that the above-described examples and embodiments are for illustrative purposes only. The present invention has been described with reference to specific embodiments and is not limited to the described exemplary embodiments, and is clearly subject to various modifications and variations. 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 invention. Accordingly, such modified or altered exemplary embodiments are understood in accordance with the technical idea and aspects of the invention and, therefore, fall within the scope of the appended claims and equivalents of the present invention.

Claims

1. Organosin compounds containing a stanocenyl group and used as photoresists for chemical beams are represented by the following chemical formulas (1) to (50): Here, R 1 , R 2 , R 3 Each of these is independently a hydrogen atom (H), a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or cycloalkynyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; E is an oxygen atom (O), a sulfur atom (S), a selenium atom (Se), or a tellurium atom (Te); X is a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I); and L is a substituted or unsubstituted alkyl group, alkylene group, alkenyl group, alkynyl group, cycloalkyl group, or cycloalkenyl group having 1 to 20 carbon atoms, or a substituted or unsaturated aryl group having 6 to 20 carbon atoms.

2. In the organotin compound photoresist according to claim 1, the stannocenyl contains a bis(cyclopentadienyl)tin group or a substituted bis(cyclopentadienyl)tin group, where the cyclopentadienyl is cyclopentadienyl C 5 H 5 , or the hapticity of the isomer is η 1 , η 2 , η 3 , η 4 or η 5 , and the substituted cyclopentadienyl C 5 H 4 R, C 5 H 3 R 2 , C 5 H 2 R 3 , C 5 HR 4 or C 5 R 5 group, where R is a hydrogen atom (H), a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or cycloalkenyl group having 1 to 20 carbon atoms, 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. An organotin compound characterized by the above.

3. In the organosin compound photoresist according to claim 1, R 1 , R 2 , and R 3 An organosin compound characterized in that each of the following is independently an alkyl group, an alkenyl group, or an aryl group, E is an oxygen atom (O), a sulfur atom (S), a selenium atom (Se), or a tellurium atom (Te), X is a chlorine atom (Cl), and L is an alkylene group.

4. The organosin compound photoresist according to claim 1, characterized in that the chemical beam is extreme ultraviolet radiation, deep ultraviolet radiation, electron beam radiation, X-ray radiation, or ion beam radiation.

5. An organosin photoresist composition for photolithography and patterning, comprising a (stanocenyl)tin compound, a solvent, and an additive, wherein the (stanocenyl)tin compound is one or more selected from the following: Here, R 1 , R 2 , R 3 Each of these is independently a hydrogen atom (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 is an oxygen atom (O), a sulfur atom (S), a selenium atom (Se), or a tellurium atom (Te); X is a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I); and L is a substituted or unsubstituted alkyl group, alkylene group, alkenyl group, alkynyl group, cycloalkyl group, or cycloalkenyl group having 1 to 20 carbon atoms, or a substituted or unsaturated aryl group having 6 to 20 carbon atoms.

6. In the organosin photoresist composition according to claim 5, the stanocenyl comprises bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin, wherein the cyclopentadienyl group is cyclopentadienyl C 5 H 5 The hapticity of the base or isomer is η 1 η 2 η 3 η 4 or η 5 This is a substituted cyclopentadienyl C 5 H 4 R, C 5 H 3 R 2 , C 5 H 2 R 3 , C 5 HR 4 Or C 5 R 5 An organosin photoresist composition characterized by containing a group, where R is a hydrogen atom (H), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group, or a cycloalkenyl group, a substituted or unsubstituted 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.

7. The organosin photoresist composition according to claim 5, characterized in that the cycloalkenyl group comprises a substituted or unsubstituted cyclic aliphatic unsaturated organic group having 4 to 8 carbon atoms and containing at least one double bond.

8. The organosin photoresist composition according to claim 5, characterized in that the additive for stabilizing the (stanocenyl)tin compound photoresist comprises an organic thiol, an organic alcohol, an organic amine, an organic amide, an organic carboxylic acid, an organic phosphine, an organic phosphine oxide, or an organic phosphonic acid.

9. The organosin photoresist composition according to claim 5, characterized in that the additive comprises 1-dodecanethiol, 2-dodecanethiol, 1,12-dodecanedithiol, 1-dodecanol, 1-octanol, 1-hexadecanol, 1-heptadecyloctadecylamine, decylamine, dodecylamine, decanamide, docosanamide, dodecaneamide, oleic acid, citric acid, decanoic acid, hexadecanedioic acid, trioctylphosphine, tributylphosphine, trioctylphosphine oxide, hexylphosphonic acid, octadecylphosphonic acid, 11-undecenylphosphonic acid, or a combination thereof.

10. An organosin photoresist composition according to claim 5, characterized in that the (stanocenyl)tin compound is used as a precursor for photolithography patterning.

11. The organosin photoresist composition according to claim 5, characterized in that the photolithography patterning includes extreme ultraviolet radiation, deep ultraviolet radiation, electron beam radiation, X-ray radiation, or ion beam radiation.

12. The organosin photoresist composition according to claim 6, characterized in that R is a hydrogen atom (H), an alkyl group, or an aryl group.

13. In the organosin photoresist composition according to claim 5, R 1 , R 2 , and R 3 An organosin photoresist composition characterized in that each of these groups is independently an alkyl group, an alkenyl group, or a cycloalkenyl group.

14. The organosin photoresist composition according to claim 5, characterized in that L is an alkylene group.

15. The organosin photoresist composition according to claim 6, characterized in that R is a hydrogen atom (H), a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, or a phenyl group.

16. In the organosin photoresist composition according to claim 5, R 1 , R 2 , and R 3 An organosin photoresist composition characterized in that each of these groups is independently a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, or a cyclopentadienyl group.

17. The organosin photoresist composition according to claim 5, characterized in that E is an oxygen atom (O) or a sulfur atom (S).

18. The organosin photoresist composition according to claim 5, characterized in that X is a chlorine atom (Cl).

19. Organosin compounds containing a stanocenyl group are represented by the following chemical formula: Here, R 1 , R 2 Each of these is independently 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, and E is an oxygen atom (O), a sulfur atom (S), a selenium atom (Se), or a tellurium atom (Te).

20. In the organosin compound according to claim 19, stanocenyl is bis(cyclopentadienyl)tin or substituted bis(cyclopentadienyl)tin, where cyclopentadienyl is cyclopentadienyl C 5 H 5 The hapticity of the base or isomer is η 1 η 2 η 3 η 4 or η 5 This is a substituted cyclopentadienyl C 5 H 3 R, C 5 H 2 R 2 , C 5 HR 3 Or C 5 R 4 An organosin compound characterized by containing a group, where R is a hydrogen atom (H), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, or a cycloalkyl group, a substituted or unsubstituted 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.

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