Tin compound, method for producing same, and method for forming thin film using same

Abstract

The present invention relates to a tin compound, a method for producing same, and a method for forming a thin film using same. The tin compound according to the present invention is thermally stable and has a high volatility and vapor pressure, and thus can be employed as a precursor for a tin-containing thin film to form a high-quality tin-containing thin film. In addition, since the tin compound has excellent extreme ultraviolet (EUV) photosensitivity, a photoresist composition comprising the tin compound can be used to form a fine circuit pattern having high resolution, and thus the tin compound can be highly effectively used in the semiconductor industry.

Description

Tin compound, method for producing the same, and method for forming a thin film using the same

[0001] The present invention relates to a novel tin compound, a method for producing the same, and a method for forming a thin film using the same.

[0002] Photolithography, a key semiconductor manufacturing process, is a key step in various semiconductor manufacturing processes, creating precise circuit patterns on semiconductors. Photoresist, a type of photosensitive liquid that reacts to light and undergoes chemical changes, is applied to a silicon substrate. This, along with the exposure light source, determines the degree of detail achieved by photolithography.

[0003] Research is underway to develop a new method using extreme ultraviolet (EUV) light as a light source for exposure machines. The short wavelength and high energy of EUV light make EUV lithography more advantageous than other photolithography processes for producing finer patterns.

[0004] In the development of high-sensitivity EUV photoresists, the development of materials with excellent photosensitivity to extreme ultraviolet rays is important. Among metallic elements, elements with d orbitals have high EUV absorption rates, and precursors containing these elements can have high absorption rates, making them suitable as materials for manufacturing high-performance EUV photoresist materials.

[0005] Furthermore, as the semiconductor industry continues to miniaturize devices, the development of thin films with high permittivity and low electrical resistance is essential. Various metal atoms can be used as materials for thin-film semiconductors, but some metals, such as indium (In) and gallium (Ga), are expensive due to limited reserves, while cadmium (Cd) is toxic.

[0006] Tin sulfide has a light absorption coefficient of 10 -4 cm -1Due to its high valence, low price, and appropriate band gap energy of approximately 1.3 eV, it can be an excellent material for thin-film solar cell materials. In addition, tin sulfide has a layered structure with P-type and N-type semiconductor properties depending on the oxidation state of tin. Compared to other layered materials, it has a lower melting point, allowing for stable thin film formation even through low-temperature processes. Therefore, the development of thermally stable and highly volatile tin sulfide-based precursors is attracting attention in the semiconductor industry.

[0007] Chemical vapor deposition (CVD) or atomic layer deposition (ALD) are commonly used processes for forming thin films. When forming thin films using these processes, differences in deposition degree, deposition control characteristics, purity, etc. can occur depending on the properties of the metal precursor, making the development of metal precursors with superior properties essential.

[0008] The present invention aims to provide a novel tin compound.

[0009] Specifically, one object of the present invention is to provide a thermally stable, high volatility and high vapor pressure tin compound precursor useful as a precursor for forming a tin thin film.

[0010] In addition, the present invention aims to provide a method for forming a thin film with excellent properties using the above tin compound.

[0011] In addition, the present invention aims to provide a method for producing the above tin compound.

[0012] In addition, one object of the present invention is to provide a tin compound precursor having excellent extreme ultraviolet light sensitivity, which is useful as a photoresist composition material in a photolithography process.

[0013] To achieve the above purpose, the present invention provides a tin compound represented by the following chemical formula 1.

[0014] [Chemical Formula 1]

[0015]

[0016] (In the above chemical formula 1,

[0017] R1 and R2 are each independently C1-C7 alkyl;

[0018] R3 and R4 are each independently hydrogen or C1-C7 alkyl;

[0019] R5 is C1-C7 alkyl, C6-C12 aryl, C1-C7 alkylC6-C12 aryl or and;

[0020] R6 and R7 are each independently C1-C7 alkyl, halogen, C6-C12 aryl or C1-C7 alkylC6-C12 aryl;

[0021] R8 and R9 are each independently C1-C7 alkyl;

[0022] R 10 and R 11 are each independently hydrogen or C1-C7 alkyl.)

[0023] In one embodiment, the tin compound may be represented by the following chemical formula 2 or 3.

[0024] [Chemical Formula 2]

[0025]

[0026] [Chemical Formula 3]

[0027]

[0028] (In the above chemical formulas 2 and 3,

[0029] R3, R4, R 10 and R 11 are each independently C1-C4 alkyl;

[0030] R5 to R7 are each independently C1-C4 alkyl, halogen or C6-C12 aryl.)

[0031] In addition, the present invention provides a method for producing a tin compound of chemical formula 1-1 by reacting a compound of chemical formula 4-1 and a compound of chemical formula 5-1.

[0032] [Chemical Formula 1-1]

[0033]

[0034] [Chemical Formula 4-1]

[0035]

[0036] [Chemical Formula 5-1]

[0037]

[0038] (In the above chemical formulas 1-1, 4-1 and 5-1,

[0039] R1 and R2 are each independently C1-C7 alkyl;

[0040] R3 and R4 are each independently hydrogen or C1-C7 alkyl;

[0041] R 5a Inland R 7a are each independently C1-C7 alkyl, C6-C12 aryl or C1-C7 alkylC6-C12 aryl;

[0042] X1 is a halogen;

[0043] M1 is an alkali metal.)

[0044] In addition, the present invention provides a method for producing a tin compound of chemical formula 1-2 by reacting a compound of chemical formula 4-2 and a compound of chemical formula 5-1.

[0045] [Chemical Formula 1-2]

[0046]

[0047] [Chemical Formula 4-2]

[0048]

[0049] [Chemical Formula 5-1]

[0050]

[0051] (In the above chemical formulas 1-2, 4-2 and 5-1,

[0052] R1 and R2 are each independently C1-C7 alkyl;

[0053] R3 and R4 are each independently hydrogen or C1-C7 alkyl;

[0054] R 5a and R 7a are each independently C1-C7 alkyl, C6-C12 aryl or C1-C7 alkylC6-C12 aryl;

[0055] R 6b and X1 is a halogen;

[0056] M1 is an alkali metal.)

[0057] In addition, the present invention provides a method for producing a tin compound of chemical formula 1-3 by reacting a compound of chemical formula 4-3, a compound of chemical formula 5-1, and a compound of chemical formula 5-2.

[0058] [Chemical Formula 1-3]

[0059]

[0060] [Chemical Formula 4-3]

[0061]

[0062] [Chemical Formula 5-1]

[0063]

[0064] [Chemical Formula 5-2]

[0065]

[0066] (In the above chemical formulas 1-3, 4-3, 5-1 and 5-2,

[0067] R1 and R2 are each independently C1-C7 alkyl;

[0068] R3 and R4 are each independently hydrogen or C1-C7 alkyl;

[0069] R 6a and R 7aare each independently C1-C7 alkyl, halogen, C6-C12 aryl or C1-C7 alkylC6-C12 aryl;

[0070] R8 and R9 are each independently C1-C7 alkyl;

[0071] R 10 and R 11 are each independently hydrogen or C1-C7 alkyl;

[0072] X1 and X2 are halogens;

[0073] M1 is an alkali metal.)

[0074] In addition, the present invention provides a composition for thin film deposition comprising the above-described tin compound.

[0075] In addition, the present invention provides a method for manufacturing a tin-containing thin film using the above-described thin film deposition composition.

[0076] In addition, the present invention provides a photoresist composition comprising the above-described tin compound, wherein the photoresist may be a photoresist for extreme ultraviolet (EUV).

[0077] The tin compound of the present invention is a novel compound containing an aminothiolate ligand, and the tin compound according to the present invention can be provided as a precursor of a thermally stable and highly volatile tin-containing thin film, thereby forming a high-quality tin-containing thin film.

[0078] In addition, the method for producing a tin compound according to the present invention can produce a tin compound in a high yield through a relatively simple process under mild conditions.

[0079] In addition, the tin compound according to the present invention has excellent extreme ultraviolet light sensitivity, and a photoresist composition including the tin compound can form a fine circuit pattern with excellent resolution.

[0080] Figure 1 shows the TGA results of Examples 1 to 3.

[0081] Figure 2 is the crystal structure of Example 1.

[0082] Figure 3 shows the vapor pressure measurement results of Example 1.

[0083] Figure 4 shows the vapor pressure measurement results of Example 2.

[0084] Figure 5 shows the vapor pressure measurement results of Example 3.

[0085] Hereinafter, the present invention will be described in more detail. Unless otherwise defined, the technical and scientific terms used herein have the meanings commonly understood by those of ordinary skill in the art to which this invention pertains. In the following description, descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention will be omitted.

[0086] The term "alkyl" as used herein refers to a monovalent straight-chain or branched saturated hydrocarbon radical composed solely of carbon and hydrogen atoms. The alkyl may have 1 to 7 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. The alkyl includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, ethylhexyl, and the like.

[0087] The term “aryl” as used herein refers to a monovalent organic radical of an aromatic ring derived from an aromatic hydrocarbon by the removal of one hydrogen, including single or fused ring systems, each ring suitably containing 4 to 7, preferably 5 or 6, ring atoms, and even including a form in which multiple aryls are linked by single bonds. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, and fluorenyl.

[0088] The term “alkylaryl” as used herein means an aryl radical substituted with at least one alkyl, wherein “alkyl” and “aryl” are as defined above. Examples of such alkylaryl radicals include, but are not limited to, tolyl.

[0089] The terms “halogen” and “halo” as used herein mean fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0090] Additionally, the term “includes” in this specification is an open-ended description equivalent to expressions such as “comprises,” “contains,” “has,” or “characterizes,” and does not exclude additional elements, materials, or processes not listed.

[0091] Additionally, the singular forms used herein may be intended to include the plural forms as well, unless the context specifically indicates otherwise.

[0092] In addition, units used in this specification without special mention are based on weight, and for example, units of % or ratio mean weight% or weight ratio.

[0093] In addition, the term “tin compound” in this specification can be represented by Chemical Formula 1 and has an equivalent meaning to expressions such as “tin compound precursor” or “precursor of tin-containing thin film.”

[0094] Additionally, the term “thermal stability” in this specification may mean that the physical properties do not change even during a continuous heating process or a high temperature process, and specifically means that the structural changes do not occur even when exposed for a long period of time under the harsh conditions described above.

[0095] The present inventors developed a tin precursor combined with an aminothiolate ligand and confirmed that a high-quality thin film can be formed using the same, thereby completing the present invention.

[0096] The present invention provides a novel tin compound precursor, a tin compound represented by the following chemical formula 1.

[0097] [Chemical Formula 1]

[0098]

[0099] (In the above chemical formula 1,

[0100] R1 and R2 are each independently C1-C7 alkyl;

[0101] R3 and R4 are each independently hydrogen or C1-C7 alkyl;

[0102] R5 is C1-C7 alkyl, C6-C12 aryl, C1-C7 alkylC6-C12 aryl or and;

[0103] R6 and R7 are each independently C1-C7 alkyl, halogen, C6-C12 aryl or C1-C7 alkylC6-C12 aryl;

[0104] R8 and R9 are each independently C1-C7 alkyl;

[0105] R 10 and R 11 are each independently hydrogen or C1-C7 alkyl.)

[0106] The tin compound of the present invention is a novel compound containing an aminothiolate ligand, and can be usefully used as a precursor for a photolithography process and forming a tin-containing thin film. The tin compound according to one embodiment can include all structural isomeric forms of the ligand, including the cis-trans form and the EZ form. Furthermore, the tin compound of the present invention has good thermal stability and high volatility and vapor pressure, and thus can be employed as a precursor for a tin-containing thin film to form a tin-containing thin film with excellent properties. In addition, since the tin compound has excellent extreme ultraviolet light sensitivity, a photoresist composition containing the tin compound can form a fine circuit pattern with excellent resolution.

[0107] In the above chemical formula 1 according to one embodiment, R1 to R4 are each independently C1-C4 alkyl; R5 is C1-C4 alkyl, phenyl or and R6 and R7 are each independently C1-C4 alkyl, halogen or phenyl; R8 to R 11are each independently C1-C4 alkyl; and the phenyl may be further substituted with C1-C4 alkyl.

[0108] In a preferred embodiment, the tin compound according to the present invention may be represented by the following chemical formula 2 or 3.

[0109] [Chemical Formula 2]

[0110]

[0111] [Chemical Formula 3]

[0112]

[0113] (In the above chemical formulas 2 and 3,

[0114] R3, R4, R 10 and R 11 are each independently C1-C4 alkyl;

[0115] R5 to R7 are each independently C1-C4 alkyl, halogen or phenyl.)

[0116] In one embodiment, in the above formula 2, R5 is halogen or C1-C4 alkyl; and R6 and R7 can each independently be C1-C4 alkyl.

[0117] As a specific example, in the above chemical formula 2, R5 to R7 may be methyl.

[0118] As a specific example, in the above chemical formula 2, R5 may be Cl and R6 and R7 may be methyl.

[0119] In one embodiment, R5 to R7 in the above chemical formula 2 may be phenyl.

[0120] In one embodiment, R6 and R7 in the above formula 3 may be phenyl or C1-C4 alkyl, respectively. In one specific example, R6 and R7 may be methyl.

[0121] The annotated compound according to one specific example may be selected from the following structures, but is not limited thereto.

[0122]

[0123]

[0124] In the above structure, Ph is phenyl, and X is any one halogen selected from F, Cl, Br and I, and preferably Cl.

[0125] The tin compound of the present invention has excellent thermal stability, improved volatility and vapor pressure due to the introduction of an aminothiolate ligand that strongly binds to tin, which is a central metal ion, and thus, when employed as a thin film precursor to manufacture a thin film, a high-quality thin film with excellent reliability and uniformity can be formed at a relatively low temperature. Furthermore, compared to a conventional tin thin film precursor having a structure in which only the same ligand is bonded to a central metal, the tin compound of the present invention has at least two different ligands bonded, so that the reactivity of each ligand acts differently, making it easy to control the characteristics, and thus can be applied to a wider range of thin film precursors.

[0126] In addition, the present invention provides a method for producing a tin compound of chemical formula 1-1 by reacting a compound of chemical formula 4-1 and a compound of chemical formula 5-1.

[0127] [Chemical Formula 1-1]

[0128]

[0129] [Chemical Formula 4-1]

[0130]

[0131] [Chemical Formula 5-1]

[0132]

[0133] (In the above chemical formulas 1-1, 4-1 and 5-1,

[0134] R1 and R2 are each independently C1-C7 alkyl;

[0135] R3 and R4 are each independently hydrogen or C1-C7 alkyl;

[0136] R 5a Inland R 7a are each independently C1-C7 alkyl, C6-C12 aryl or C1-C7 alkylC6-C12 aryl;

[0137] X1 is a halogen;

[0138] M1 is an alkali metal.)

[0139] In addition, the present invention provides a method for producing a tin compound of chemical formula 1-2 by reacting a compound of chemical formula 4-2 and a compound of chemical formula 5-1.

[0140] [Chemical Formula 1-2]

[0141]

[0142] [Chemical Formula 4-2]

[0143]

[0144] [Chemical Formula 5-1]

[0145]

[0146] (In the above chemical formulas 1-2, 4-2 and 5-1,

[0147] R1 and R2 are each independently C1-C7 alkyl;

[0148] R3 and R4 are each independently hydrogen or C1-C7 alkyl;

[0149] R 5a and R 7a are each independently C1-C7 alkyl, C6-C12 aryl or C1-C7 alkylC6-C12 aryl;

[0150] R 6b and X1 is a halogen;

[0151] M1 is an alkali metal.)

[0152] In addition, the present invention provides a method for producing a tin compound of chemical formula 1-3 by reacting a compound of chemical formula 4-3, a compound of chemical formula 5-1, and a compound of chemical formula 5-2.

[0153] [Chemical Formula 1-3]

[0154]

[0155] [Chemical Formula 4-3]

[0156]

[0157] [Chemical Formula 5-1]

[0158]

[0159] [Chemical Formula 5-2]

[0160]

[0161] (In the above chemical formulas 1-3, 4-3, 5-1 and 5-2,

[0162] R1 and R2 are each independently C1-C7 alkyl;

[0163] R3 and R4 are each independently hydrogen or C1-C7 alkyl;

[0164] R 6a and R 7a are each independently C1-C7 alkyl, halogen, C6-C12 aryl or C1-C7 alkylC6-C12 aryl;

[0165] R8 and R9 are each independently C1-C7 alkyl;

[0166] R 10 and R 11 are each independently hydrogen or C1-C7 alkyl;

[0167] X1 and X2 are halogens;

[0168] M1 is an alkali metal.)

[0169] In a method for producing a tin compound according to one embodiment, the alkali metal of M1 may be Li, Na or K, and preferably may be Li.

[0170] In a method for producing a tin compound according to one embodiment, the halogen of X1 and X2 may be any one halogen selected from F, Cl, Br and I, and preferably may be Cl.

[0171] In a method for producing a tin compound according to one embodiment, the reaction may be performed at 20 to 30°C for 8 to 16 hours.

[0172] In a method for producing a tin compound according to one embodiment, for 1 mol of the compounds of Chemical Formulas 4-1 to 4-3, the compounds of Chemical Formulas 5-1 and 5-2 may be used in an amount of 1.0 to 1.5 mol, preferably 1.0 to 1.2 mol.

[0173] In a method for producing a tin compound according to one embodiment, all of the above reactions can be performed in an organic solvent, and any organic solvent having high solubility in the reactants can be used without limitation. Specifically, one or more mixed organic solvents selected from hexane, diethyl ether, toluene, tetrahydrofuran, etc. can be used.

[0174] After the above reaction, if necessary, the purity can be maximized by purification using filtration, extraction, recrystallization, distillation, sublimation, chromatography, etc.

[0175] The tin compound produced by the above-described production method is thermally stable and has high volatility and vapor pressure, and thus can be used as a thin film precursor for forming a tin-containing thin film with excellent properties. In addition, since the tin metal ion is thermodynamically stable when present in a +4 valence state within the thin film, the tin compound precursor according to the present invention has superior stability compared to the known +2 valence tin compound precursor, and the composition of the thin film to be deposited can be varied due to the different oxidation states.

[0176] In addition, the present invention provides a composition for thin film deposition comprising the above-described tin compound.

[0177] The composition for thin film deposition according to the present invention includes a tin compound represented by the above chemical formula 1, and the content of the organic tin compound in the composition of the present invention may be included within a range that can be recognized by a person skilled in the art in consideration of the film deposition conditions of the thin film or the thickness and characteristics of the thin film.

[0178] The thin film deposition composition of the present invention can form a high-quality thin film with excellent reliability and uniformity by including the tin compound of the above chemical formula 1.

[0179] In addition, the present invention provides a method for manufacturing a tin-containing thin film using the above-described thin film deposition composition.

[0180] In a method for manufacturing a tin-containing thin film according to one embodiment, the tin-containing thin film may be a tin metal thin film, a tin oxide thin film, a tin nitride thin film, or a tin nitride thin film.

[0181] A method for manufacturing a tin-containing thin film according to one embodiment can be performed on a substrate using a deposition method known in the art. Specifically, the deposition method may be chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD), low-pressure vapor deposition, plasma-enhanced atomic layer deposition, etc. Preferably, it may be chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0182] In one embodiment, the method for manufacturing the thin film may include the steps of: a) heating a substrate mounted in a chamber; b) injecting a tin compound according to one embodiment or a thin film deposition composition containing the same into the chamber and adsorbing the tin compound or a thin film deposition composition containing the tin compound onto the substrate; and c) injecting a reaction gas to manufacture a thin film on the substrate. Steps b) and c) may be repeated several times depending on the thickness of the tin-containing thin film.

[0183] In one embodiment, the method for manufacturing the thin film can be controlled by the deposition conditions according to the structure or thermal characteristics of the desired thin film, and the deposition conditions may include, but are not limited to, the input flow rate of the organotin compound or the organotin-containing thin film deposition composition including the organotin compound, the input flow rate of the reaction gas, the input flow rate of the carrier gas, the pressure, the RF power, the substrate temperature, etc. of the organotin compound or the organotin-containing thin film deposition composition including the organotin compound, and the deposition conditions may be exemplified by, but not limited to, the input flow rate of the organotin-containing thin film deposition composition may be 10 to 1000 cc / min, the carrier gas may be 10 to 1000 cc / min, the reaction gas may be 1 to 1000 cc / min, the pressure may be 0.5 to 10 torr, the RF power may be 200 to 1000 W, and the substrate temperature may be controlled in the range of 80 to 400°C, preferably 200 to 400°C.

[0184] The above reaction gas is not limited, but one or more mixed gases selected from oxygen (O2), ozone (O3), water vapor (H2O), hydrogen peroxide (H2O2), nitrogen monoxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), nitrogen (N2), hydrazine (N2H4), amine, diamine, hydrogen (H2), argon (Ar), and helium (He) can be used, and the carrier gas is not limited as long as it is a common gas that does not react with the organotin compound of the present invention, and a non-limiting example thereof may be one or more mixed gases selected from nitrogen, helium, neon, argon, krypton, xenon, radon, etc.

[0185] The above substrate is not limited to a conventional substrate, and non-limiting examples thereof include a substrate including one or more semiconductor materials selected from Ru, TiN, Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP, a rigid substrate such as a silicon on insulator (SOI) substrate, a quartz substrate, or a glass substrate for a display, or a flexible plastic substrate such as polyimide, polyethylene terephthalate (PET, PolyEthylene Terephthalate), polyethylene naphthalate (PEN, PolyEthylene Naphthalate), polymethyl methacrylate (PMMA, Poly Methyl MethAcrylate), polycarbonate (PC, PolyCarbonate), polyethersulfone (PES), and polyester.

[0186] In addition, the present invention provides a photoresist composition comprising the above-described tin compound.

[0187] In a photoresist composition according to one embodiment, the photoresist may be a photoresist for extreme ultraviolet (EUV) light. Since tin element has high light absorbance for extreme ultraviolet (EUV) light, a photoresist composition including tin element can realize excellent EUV sensitivity.

[0188] The above extreme ultraviolet (EUV) refers to a wavelength band encompassing approximately 10 nm to 100 nm between the X-ray and deep UV spectral regions, and specifically, a wavelength of 13.5 nm is used as an exposure light source in the photolithography process, but is not limited thereto.

[0189] A photoresist composition according to one embodiment of the present invention includes a tin compound represented by the chemical formula 1, and the content of the tin compound in the photoresist composition of the present invention may be included within a range that can be recognized by a person skilled in the art.

[0190] In one embodiment, the photoresist composition may include only a tin compound when the tin compound represented by the chemical formula 1 is in a liquid state.

[0191] In one embodiment, the photoresist composition may further include one or more mixed organic solvents selected from hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, dodecane, ethylcyclohexane, propylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene, diethylbenzene, and ethyl toluene; alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, and isobutanol; ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, butyl ethyl ether, and tetrahydrofuran; and ester solvents such as methyl butyrate, ethyl butyrate, and propylpropionate. In this case, the tin compound represented by the chemical formula 1 may be included in an amount of 1 to 40% of the total weight of the photoresist composition, and specifically, 5 to 25%.

[0192] The photoresist composition according to the present invention has excellent light sensitivity and mechanical properties, and can be used to form a strong photoresist pattern with high resolution, so that it can be very usefully used in the semiconductor industry.

[0193] Hereinafter, embodiments of the present invention will be described in detail. However, these are provided to enable those skilled in the art to easily implement the present invention. The present invention may be implemented in various different forms, and the spirit of the present invention is not necessarily limited to the embodiments.

[0194] The tin compound according to the present invention is as follows: 1 H NMR and 13 The structure of the tin compound obtained was analyzed through C NMR spectrum.

[0195] Additionally, the thermal stability, volatility, and decomposition temperature of the obtained tin compounds were measured through thermogravimetric analysis (TGA).

[0196] The above TGA method was measured under a nitrogen gas flow of 5 ml / min while heating the product to 500 ℃ at a rate of 10 ℃ min.

[0197] In addition, the theoretical and measured values ​​of the composition ratios of tin compounds obtained through elemental analysis (EA) were compared.

[0198] Additionally, the vapor pressure of the obtained tin compound was measured while heating using a pressure gauge.

[0199] [Example 1] Preparation of tin compound SnMe2(dmampS)Cl

[0200]

[0201] SnMe2Cl2 (0.22 g, 1.0 mmol) was dissolved in THF (50 ml) in a Schlenk flask, and Li(dmampS) (0.14 g, 1.0 mmol) was added. The mixture was stirred at room temperature for 12 h. The reaction mixture was filtered, and the solvent was removed under reduced pressure from the resulting solution. The resulting solution was sublimed at 100 °C (500 mTorr) to obtain a white solid SnMe2(dmampS)Cl compound (yield: 94%).

[0202] As shown in Fig. 1, the TG analysis results of SnMe2(dmampS)Cl manufactured in Example 1 show a single weight loss above 150°C, and the final residue amount is 15%.

[0203] 1 H NMR (400 MHz, C6D6) δ(ppm): 1.67 (s, 1H), 1.49 (s, 3H), 1.16 (s, 3H), 0.72 (s, 3H)

[0204] 13C NMR (101 MHz, C6D6) δ(ppm): 71.94, 46.48, 44.62, 35.31, 5.22

[0205] 119 Sn NMR (186.5MHz,, C6D6) δ (ppm): -30.79

[0206] Elemental Analysis Calc.(Found): C, 30.36(30.65); H, 6.37(6.50); N, 4.43(4.43); S, 10.13(10.12)

[0207] In order to confirm the specific structure of SnMe2(dmampS)Cl manufactured in Example 1, the crystal structure was confirmed using XRD (X-ray Diffractometer) and is shown in Fig. 2.

[0208] Additionally, the results of measuring the vapor pressure to confirm the vapor pressure characteristics are shown in Fig. 3.

[0209] Based on the vapor pressure measurement results, the equation Log(Torr)=-3.79x+8.97 was obtained, and through this, it was confirmed that the vapor pressure at 149.5 ℃ was 1.0 Torr.

[0210]

[0211] [Example 2] Preparation of tin compound SnMe2(dmampS)2

[0212]

[0213] SnMe2Cl2 (0.22 g, 1.0 mmol) was dissolved in THF (50 ml) in a Schlenk flask, and Li(dmampS) (0.308 g, 2.2 mmol) was added. The mixture was stirred at room temperature for 12 hours. The reaction product was filtered, and the solvent was removed under reduced pressure from the resulting solution. Sublimation at 110 °C (300 mTorr) yielded a colorless, viscous liquid SnMe2(dmampS)2 compound (yield: 73%).

[0214] As shown in Fig. 1, the TG analysis results of SnMe2(dmampS)2 manufactured in Example 2 show that a single weight loss occurs above 120°C and the final residue amount is 8%.

[0215] 1 H NMR (400 MHz, C6D6) δ(ppm): 2.40 (s, 2H), 2.20 (s, 6H), 1.46 (s, 6H), 0.33 (s, 9H)

[0216] 13 C NMR (101 MHz, C6D6) δ(ppm): 73.72, 48.52, 48.23, 33.41, 3.27

[0217] 119 Sn NMR (186.5MHz, , C6D6) δ (ppm): 14.47

[0218] Elemental Analysis Calc.(Found): C, 40.69(41.08); H, 8.29(8.32); N, 6.78(6.78); S, 15.52(16.42)

[0219] Additionally, the results of measuring the vapor pressure to confirm the vapor pressure characteristics are shown in Fig. 4.

[0220] Based on the vapor pressure measurement results, the equation Log(Torr)=-2.45x+6.74 was obtained, and through this, it was confirmed that the vapor pressure at 90.5 ℃ was 1.0 Torr.

[0221]

[0222] [Example 3] Preparation of tin compound SnMe3(dmampS)

[0223]

[0224] SnMe3Cl (0.22 g, 1.0 mmol) was dissolved in THF (50 ml) in a Schlenk flask, and Li(dmampS) (0.14 g, 1.0 mmol) was added. The mixture was stirred at room temperature for 12 h. The reaction mixture was filtered, and the solvent was removed under reduced pressure from the resulting solution. The mixture was sublimed at 100 °C (500 mTorr) to obtain a colorless liquid SnMe3(dmampS) compound (yield: 86%).

[0225] As shown in Fig. 1, the TG analysis results of SnMe3(dmampS) manufactured in Example 3 show a single weight loss above 50°C, and the final residue amount is 2%.

[0226] 1 H NMR (400 MHz, C6D6) δ (ppm): 2.35 (s, 2H), 2.10 (s, 6H), 1.51 (s, 6H), 0.70 (s, 3H)

[0227] 13 C NMR (101 MHz, C6D6) δ (ppm): 74.30, 48.53, 32.68, -3.62

[0228] 119 Sn NMR (186.5MHz, , C6D6) δ (ppm): 54.05

[0229] Elemental Analysis Calc.(Found): C, 36.51(37.29); H, 7.83(7.72); N, 4.73(4.62); S, 10.83(11.45)

[0230] Additionally, the results of measuring the vapor pressure to confirm the vapor pressure characteristics are shown in Fig. 5.

[0231] Based on the vapor pressure measurement results, the equation Log(Torr)=-4.96x+16.16 was obtained, and through this, it was confirmed that the vapor pressure at 34 ℃ was 1.0 Torr.

[0232]

[0233] [Example 4] Preparation of tin compound SnPh3(dmampS)

[0234]

[0235] SnPh3Cl (0.38 g, 1.0 mmol) was dissolved in toluene (50 ml) in a Schlenk flask, and Li(dmampS) (0.14 g, 1.0 mmol) was added. The mixture was stirred at room temperature for 12 h. The reaction product was filtered, and the solvent was removed from the solution under reduced pressure to obtain a white solid SnPh3(dmampS) compound (yield: 73%).

[0236] 1 H NMR (400 MHz, C6D6) δ(ppm): 7.79 (m, 6H), 7.16 (m, 9H), 2.36 (s, 2H), 1.97 (s, 6H), 1.48 (s, 6H)

[0237] 13 C NMR (101 MHz, C6D6) δ(ppm): 140.35, 137.17, 129.57, 129.05, 73.85, 49.41, 48.32, 32.73

[0238]

[0239] [Example 5] Preparation of tin compound SnPh2(dmampS)2

[0240]

[0241] SnPh2Cl2 (0.34 g, 1.0 mmol) was dissolved in Tol (50 ml) in a Schlenk flask, and Li(dmampS) (0.28 g, 2.0 mmol) was added. The mixture was stirred at room temperature for 12 hours. The reaction product was filtered, and the solvent was removed from the solution under reduced pressure to obtain a white solid SnPh2(dmampS)2 compound (yield: 71%).

[0242] 1H NMR (400 MHz, C6D6) δ (ppm): 7.91 (m, 2H), 7.16 (m, 3H), 2.27 (s, 2H), 1.91 (s, 6H), 1.47 (s, 6H)

[0243] 13 C NMR (101 MHz, C6D6) δ(ppm): 144.07, 136.53, 129.47, 128.93, 73.39, 49.36, 48.24, 33.10

[0244] Elemental Analysis Calc.(Found): C, 53.64 (53.56); H, 7.13 (7.19); N, 5.21 (5.22); S, 11.93 (12.04).

[0245]

[0246] That is, the tin compound according to the present invention has a high vapor pressure and does not undergo decomposition even during a continuous heating process, so it has excellent thermal stability and volatility, making it very useful as a thin film precursor. In addition, since it has excellent extreme ultraviolet (EUV) photosensitivity, a photoresist composition containing it can form a photoresist pattern with high sensitivity and resolution. In addition, the method for producing the tin compound according to the present invention can produce the desired tin compound in a high yield through a relatively simple process under mild conditions.

[0247] As described above, the present invention has been described through specific matters and limited examples and comparative examples, but these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and those skilled in the art to which the present invention pertains can make various modifications and variations based on this description.

[0248] Therefore, the idea of ​​the present invention should not be limited to the described embodiments, and all things that are equivalent or equivalent to the claims described below as well as the claims are considered to fall within the scope of the idea of ​​the present invention.

Claims

1. A tin compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R1 and R2 are each independently C1-C7 alkyl; R3 and R4 are each independently hydrogen or C1-C7 alkyl; R5 is C1-C7 alkyl, C6-C12 aryl, C1-C7 alkylC6-C12 aryl or and; R6 and R7 are each independently C1-C7 alkyl, halogen, C6-C12 aryl or C1-C7 alkylC6-C12 aryl; R8 and R9 are each independently C1-C7 alkyl; R 10 and R 11 are each independently hydrogen or C1-C7 alkyl.

2. In paragraph 1, In the above chemical formula 1, R1 to R4 are each independently C1-C4 alkyl; R5 is C1-C4 alkyl, phenyl or and; R6 and R7 are each independently C1-C4 alkyl, halogen or phenyl; R8 to R 11 are each independently C1-C4 alkyl; A tin compound wherein the above phenyl may be further substituted with C1-C4 alkyl.

3. In paragraph 1, The above tin compound is a tin compound represented by the following chemical formula 2 or 3. [Chemical Formula 2] [Chemical Formula 3] In the above chemical formulas 2 and 3, R3, R4, R 10 and R 11 are each independently C1-C4 alkyl; R5 to R7 are each independently C1-C4 alkyl, halogen or C6-C12 aryl.

4. In paragraph 3, In the above chemical formula 2, R5 is halogen or C1-C4 alkyl; A tin compound, wherein R6 and R7 are each independently C1-C4 alkyl.

5. In paragraph 3, A tin compound in which R5 to R7 in the above chemical formula 2 are phenyl.

6. In paragraph 3, A tin compound in which R6 and R7 in the above chemical formula 3 are each phenyl or C1-C4 alkyl.

7. In paragraph 1, A tin compound, wherein the above tin compound is selected from the following structures. In the above, Ph is phenyl and X is halogen.

8. A method for producing a tin compound of chemical formula 1-1 by reacting a compound of chemical formula 4-1 and a compound of chemical formula 5-1. [Chemical Formula 1-1] [Chemical Formula 4-1] [Chemical Formula 5-1] In the above chemical formulas 1-1, 4-1 and 5-1, R1 and R2 are each independently C1-C7 alkyl; R3 and R4 are each independently hydrogen or C1-C7 alkyl; R 5a Inland R 7a are each independently C1-C7 alkyl, C6-C12 aryl or C1-C7 alkylC6-C12 aryl; X1 is a halogen; M1 is an alkali metal.

9. A method for producing a tin compound of chemical formula 1-2 by reacting a compound of chemical formula 4-2 and a compound of chemical formula 5-1. [Chemical Formula 1-2] [Chemical Formula 4-2] [Chemical Formula 5-1] In the above chemical formulas 1-2, 4-2 and 5-1, R1 and R2 are each independently C1-C7 alkyl; R3 and R4 are each independently hydrogen or C1-C7 alkyl; R 5a and R 7a are each independently C1-C7 alkyl, C6-C12 aryl or C1-C7 alkylC6-C12 aryl; R 6b and X1 is a halogen; M1 is an alkali metal.

10. A method for producing a tin compound of chemical formula 1-3 by reacting a compound of chemical formula 4-3, a compound of chemical formula 5-1, and a compound of chemical formula 5-2. [Chemical Formula 1-3] [Chemical Formula 4-3] [Chemical Formula 5-1] [Chemical Formula 5-2] In the above chemical formulas 1-3, 4-3, 5-1 and 5-2, R1 and R2 are each independently C1-C7 alkyl; R3 and R4 are each independently hydrogen or C1-C7 alkyl; R 6a and R 7a are each independently C1-C7 alkyl, halogen, C6-C12 aryl or C1-C7 alkylC6-C12 aryl; R8 and R9 are each independently C1-C7 alkyl; R 10 and R 11 are each independently hydrogen or C1-C7 alkyl; X1 and X2 are halogens; M1 is an alkali metal.

11. A composition for thin film deposition, comprising a tin compound according to any one of claims 1 to 7.

12. A method for manufacturing a tin-containing thin film using a thin film deposition composition according to Article 11.

13. In paragraph 12, A method for manufacturing a tin-containing thin film, wherein the tin-containing thin film is a tin metal thin film, a tin oxide thin film, a tin nitride thin film or a tin oxynitride thin film.

14. In paragraph 12, A method for manufacturing a tin-containing thin film by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

15. A photoresist composition comprising a tin compound according to any one of claims 1 to 7.

16. In paragraph 15, The above photoresist is a photoresist for extreme ultraviolet (EUV) lithography, a photoresist composition.

Images