High purity tin compounds containing unsaturated substituents and methods for preparing same

Abstract

Mono-organotin trialkoxide compounds are described having the formula R'Sn(OR)3 and containing less than about 5 mole percent di-organotin dialkoxide. R' is a linear or branched, optionally fluorinated, unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms. Methods for synthesizing and purifying these compounds are also presented. The mono-organotin compounds are attractive for use in producing high-resolution EUV lithography patterning precursors due to their high purity and minimal concentration of di-organotin impurities.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to co-pending U.S. Provisional Patent Application No. 63 / 397,541, filed August 12, 2022, the disclosure of which is incorporated herein by reference. [Background technology]

[0002] As semiconductor manufacturing continues to become more sophisticated, feature sizes continue to shrink, requiring new processing methods. Certain organotin compounds have been shown to be useful for the deposition of tin oxide and tin hydroxide coatings in applications such as extreme ultraviolet (EUV) lithography. For example, tin compounds containing unsaturated substituents result in radiation-sensitive Sn-C bonds that can be utilized to pattern structures lithographically.

[0003] Materials used in microelectronics manufacturing must be extremely pure, with strict limits on organic contamination (e.g., reaction by-products), metallic contamination, and particulate contamination. Purity requirements are generally stringent, particularly for lithography applications, where the chemicals are in contact with the semiconductor substrate and organometallic impurities in the compound, such as diisopropylbis(dimethylamino)tin (iPr)2Sn(NMe2)2, can affect the physical properties of the resulting film. The exact purity target is dictated by various factors, including performance metrics, but a minimum purity target of 3N+ is typically used. Residual metals present in the chemicals can deposit on the semiconductor substrate and degrade the electrical properties of the fabricated device. Typical specifications for metals are less than 10 ppb for each individual metal, with the total amount of metal not exceeding approximately 100 ppb.

[0004] The processing and performance of semiconductor materials can also be sensitive to dialkyltin contaminants. Dialkyltin impurities, such as RSn(NMe) (where R is an alkyl group), are a source of outgassing after vapor deposition or spin-coating processes, due to the low density of tin oxide cluster films when the films contain dialkyl groups. Proper control of dialkyltin contaminants is necessary for the fabrication of microelectronic products using EUV lithography. The high purity required from the monoalkyltin precursor manufacturing process is challenging. Conventional synthesis of monoalkyltin triamides typically involves the reaction of the tin tetraamide with an alkyltin trichloride using lithium dimethylamide reagent, or the subsequent reaction with a lithium / Grignard reagent (alkylating agent) to convert the tin tetraamide to the desired triamide.

[0005] However, similar synthetic methods cannot be applied to the synthesis of tin compounds containing unsaturated substituents, such as vinyl, allyl, or alkenyl. Rather, the strong base lithium dimethylamide can react not only with tin-chlorine bonds but also with double or triple bonds in organic substituents. Furthermore, primary and secondary monoorganotin compounds cannot be synthesized from alkylating agents and tetra-amides, even when the correct stoichiometry is used: primary alkylating agents convert tin tetra-amides to trialkyltin amides and unreacted tetra-amides, and secondary alkylating agents can convert tin tetra-amides to polyalkyltin compounds.

[0006] Furthermore, monoalkenyltin trialkoxides cannot be prepared via reaction of the corresponding tin triamides with alcohols; reaction of organotin trichlorides with dialkylamines followed by reaction with alcohols leads to a mixture of products.

[0007] Graf ("Tin, Tin Alloys, and Tin Compounds," Ullmann's Encyclopedia of Industrial Chemistry; Weinheim: Wiley-VCH (2005)) reports the preparation of monoorganotin trichlorides containing vinyl or allyl substituents using the Kocheshkov compromisation reaction without the use of catalysts or heat; the electron-donating groups enable the compromisation reaction. As a result, unsaturated groups / electron-donating groups from both alkenyl and alkoxy groups can promote Kocheshkov-like compromisation reactions during the reaction, resulting in a mixture of products, particularly when preparing monovinyl or monoallyltin trialkoxy compounds according to the disproportionation reactions in Scheme (I) and Scheme (II) shown below.

[0008] [ka] [Prior art documents] [Non-patent literature]

[0009] [Non-Patent Document 1] Graf ("Tin, Tin Alloys, and Tin Compounds", Ullmann's Encyclopedia of Industrial Chemistry; Weinheim: Wiley-VCH (2005)) [Non-patent document 2] Davies et al., eds.; Tin Chemistry: Fundamentals, Frontiers, and Applications; Wiley (2008) [Non-patent document 3] J. Med. Chem.(57, 22, 9220-9231(2014)) [Non-patent document 4] Rosenberg and Gibbons(JACS, 79, 2138-40(1957)) [Non-patent document 5] Jousseaume, Lehcini, and Rascle(Organometallics 14, 685-689(1995)) [Non-patent document 6] Organometallics 19, 1940-1949(2000) Summary of the Invention [Problem to be solved by the invention]

[0010] The ability to prepare and isolate trialkoxytin compounds containing unsaturated groups and having desirable high purity levels has not previously been reported. Such high purity tin compounds could be very attractive for use in the microelectronics industry. [Means for solving the problem]

[0011] In one embodiment, aspects of the present disclosure relate to monoorganotin trialkoxide compounds having formula (1) having a purity of at least about 95 mole % and containing less than about 5 mole % diorganotin dialkoxide compounds having formula (2). R'Sn(OR)3(1) R'2Sn(OR)2(2) (wherein R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms).

[0012] In a second embodiment, aspects of the present disclosure relate to monoorganotin trialkoxide compounds having the formula (1): R'Sn(OR)3(1) (wherein R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms).

[0013] In a further embodiment, aspects of the present disclosure relate to a method for synthesizing a mono-organotin trialkoxide compound having formula (1) that has a purity of at least about 95 mol% and contains less than about 5 mol% of a di-organotin dialkoxide compound having formula (2), the method comprising reacting an alkali metal alkoxide with an R'SnX3 compound (where X is a halogen atom or an alkoxy group). R'Sn(OR)3 (1) R'2Sn(OR)2 (2) (where R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R independently is a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms).

[0014] Aspects of the present disclosure further relate to a method for synthesizing a mono-organotin trialkoxide compound having formula (1), the method comprising reacting an alkali metal alkoxide with an R'SnX3 compound (where X is a halogen atom or an alkoxy group). R'Sn(OR)3 (1) R'2Sn(OR)2 (2) (where R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R independently is a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms).

[0015] A further aspect of the present disclosure relates to an organotin compound having formula (3). R'SnO (3 / 2-x / 2) (OH) x (3) (where 0 < x < 3, and R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms).

[0016] A further aspect of the present disclosure relates to a composition comprising an organotin compound having the formula (3) and an organotin compound having the formula (4). R'SnO (3 / 2-x / 2) (OH) x (3) R''SnO (3 / 2-x / 2) (OH) x (4) (where 0 < x < 3, R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and R'' is an optionally substituted hydrocarbon group having from about 2 to about 20 carbon atoms)

[0017] Advantageous improvements of the present invention can be implemented alone or in combination, and are embodied in the dependent claims.

[0018] In summary, the following embodiments are proposed as being particularly preferred within the scope of the present invention.

[0019] Embodiment 1: A monoorganotin trialkoxide compound having the formula (1) and having a purity of at least about 95 mol% and containing less than about 5 mol% of a diorganotin dialkoxide compound having the formula (2). R'Sn(OR)3(1) R'2Sn(OR)2(2) (where R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms)

[0020] Embodiment 2: The monoorganotin trialkoxide compound according to Embodiment 1, wherein R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from 2 to about 10 carbon atoms, and each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 5 carbon atoms.

[0021] Embodiment 3: The monoorganotin trialkoxide compound of embodiment 1 or 2, wherein the content of diorganotin dialkoxide having formula (2) is less than about 1 mole %.

[0022] Embodiment 4: The monoorganotin trialkoxide compound of any one of embodiments 1 to 3, wherein the total tetrakis(alkoxy)tin content is less than about 1 mole %.

[0023] Embodiment 5: The monoorganotin trialkoxide compound of any one of embodiments 1 to 4, wherein the total content of tris(alkenyl)tin compounds is less than about 1 mole %.

[0024] Embodiment 6: The monoorganotin trialkoxide compound of any one of embodiments 1 to 6, wherein R′ is vinyl, allyl, 1-propenyl, 3-buten-1-yl, 3-buten-2-yl, 2-methylallyl, or 3-methyl-2-buten-1-yl, and each R is independently optionally fluorinated methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or t-butyl.

[0025] Embodiment 7: The monoorganotin trialkoxide compound of any one of embodiments 1 to 6, wherein the compound having formula (1) is selected from:

[0026] [ka]

[0027] Embodiment 8: A monoorganotin trialkoxide compound having the formula (1). R'Sn(OR)3(1) (wherein R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms).

[0028] Embodiment 9: The monoorganotin trialkoxide compound of embodiment 8, wherein R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from 2 to about 10 carbon atoms, and each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 5 carbon atoms.

[0029] Embodiment 10: The monoorganotin trialkoxide compound of embodiment 8 or 9, wherein R′ is vinyl, allyl, 1-propenyl, 3-buten-1-yl, 3-buten-2-yl, 2-methylallyl, or 3-methyl-2-buten-1-yl; and each R is independently optionally fluorinated methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or t-butyl.

[0030] Embodiment 11: The monoorganotin trialkoxide compound of any one of embodiments 8 to 10, wherein the compound having the formula (1) is selected from:

[0031] [ka]

[0032] Embodiment 12: A method for synthesizing a monoorganotin trialkoxide compound having formula (1) having a purity of at least about 95 mole % and containing less than about 5 mole % of a diorganotin dialkoxide compound having formula (2), comprising reacting an alkali metal alkoxide with an R'SnX3 compound, where X is a halogen atom or an alkoxy group. R'Sn(OR)3(1) R'2Sn(OR)2(2) (wherein R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R independently has a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms).

[0033] Embodiment 13: (a) preparing a solution of an alkali metal alkoxide; (b) adding R'SnCl3 at about -10°C to about 10°C to produce a crude product, wherein the amount of alkali metal alkoxide is at least about 3.03 equivalents relative to the amount of R'SnCl3 added; (c) distilling the crude product to obtain a product containing up to about 5 mole percent of a monoorganotin trialkoxide having formula (1) and a diorganotin dialkoxide having formula (2); 13. The method of embodiment 12, comprising:

[0034] Embodiment 14: The method of embodiment 12 or 13, wherein the content of diorganotin dialkoxide having formula (2) is less than about 1 mole %.

[0035] Embodiment 15: The method of any one of embodiments 12 to 14, wherein the total tetrakis(alkoxy)tin content is less than about 1 mol %.

[0036] Embodiment 16: The method of any one of embodiments 12 to 15, wherein R' is vinyl, allyl, 1-propenyl, 3-buten-1-yl, 3-buten-2-yl, 2-methylallyl, or 3-methyl-2-buten-1-yl; and each R is independently optionally fluorinated methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or t-butyl.

[0037] Embodiment 17: The method of any one of embodiments 12 to 16, wherein the reaction is carried out in a solvent containing greater than about 50% by volume of a hydrocarbon solvent and / or an aromatic solvent.

[0038] Embodiment 18: The method of any one of embodiments 12 to 17, wherein the reacting is carried out substantially without exposure to light.

[0039] Embodiment 19: A method of synthesizing a monoorganotin trialkoxide compound having formula (1), comprising reacting an alkali metal alkoxide with an R'SnX3 compound, where X is a halogen atom or an alkoxy group. R'Sn(OR)3(1) R'2Sn(OR)2(2) (wherein R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R independently has a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms).

[0040] Embodiment 20: (a) preparing a solution of an alkali metal alkoxide; (b) adding R'SnCl3 at about -10°C to about 10°C to produce a crude product, wherein the amount of alkali metal alkoxide is at least about 3.03 equivalents relative to the amount of R'SnCl3 added; (c) distilling the crude product to obtain a monoorganotin trialkoxide having formula (1); 20. The method of embodiment 19, comprising:

[0041] Embodiment 21: The method of embodiment 19 or 20, wherein R' is vinyl, allyl, 1-propenyl, 3-buten-1-yl, 3-buten-2-yl, 2-methylallyl, or 3-methyl-2-buten-1-yl; and each R is independently optionally fluorinated methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or t-butyl.

[0042] Embodiment 22: The method of any one of embodiments 19 to 21, wherein the reaction is carried out in a solvent containing greater than about 50% by volume of a hydrocarbon solvent and / or an aromatic solvent.

[0043] Embodiment 23: The method of any one of embodiments 19 to 22, wherein the method is performed substantially without exposure to light.

[0044] Embodiment 24: A method of storing a sample of a mono-organotin trialkoxide compound having formula (1) as described in embodiment 1, comprising storing the sample of the mono-organotin trialkoxide compound having formula (1) at a temperature of less than about 30° C. without substantial exposure to light.

[0045] Embodiment 25: The method of embodiment 24, wherein the sample of the monoorganotin trialkoxide compound having Formula (1) is stored for about 3 days to about 1 year.

[0046] Embodiment 26: The method of embodiment 24 or 25, wherein the sample of monoorganotin trialkoxide is substantially not decomposed after a storage period of about 3 days to about 1 year.

[0047] Embodiment 27: The method of any one of embodiments 24 to 26, comprising storing the compound having Formula (1) in a container under an inert atmosphere.

[0048] Embodiment 28: The method of any one of embodiments 24 to 27, comprising storing the compound having Formula (1) in a container substantially without exposure to light.

[0049] Embodiment 29: A method of storing a sample of a monoorganotin trialkoxide compound having formula (1) as described in embodiment 8, comprising storing the sample of the monoorganotin trialkoxide compound having formula (1) at a temperature of less than about 30° C. without substantial exposure to light.

[0050] Embodiment 30: The method of embodiment 29, wherein the sample of the monoorganotin trialkoxide compound having Formula (1) is stored for about 3 days to about 1 year.

[0051] Embodiment 31: The method of embodiment 29 or 30, wherein the sample of monoorganotin trialkoxide is substantially not decomposed after a storage period of about 3 days to about 1 year.

[0052] Embodiment 32: The method according to any one of Embodiments 29 to 31, including the step of storing a compound having the formula (1) in a container in an inert atmosphere.

[0053] Embodiment 33: The method according to any one of Embodiments 29 to 32, including the step of storing a compound having the formula (1) in a container substantially without exposure to light.

[0054] Embodiment 34: An organotin compound having the formula (3). R'SnO (3 / 2-x / 2) (OH) x (3) (where 0 < x < 3, and R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms)

[0055] Embodiment 35: An organotin compound having the formula (3) according to Embodiment 34, obtained by hydrolysis of a compound having the formula (1). R'Sn(OR)3(1) (where each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms)

[0056] Embodiment 36: A solution comprising an organotin compound having the formula (3) according to Embodiment 34 or 35 and an organic solvent.

[0057] Embodiment 37: The solution according to Embodiment 36, wherein the compound having the formula (3) is obtained by hydrolysis of a compound having the formula (1). R'Sn(OR)3(1) (where each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms)

[0058] Embodiment 38: A film comprising an organotin compound having the formula (3) according to Embodiment 34.

[0059] Embodiment 39: The film according to Embodiment 38, wherein the compound having the formula (3) is obtained by hydrolysis of the compound having the formula (1). R'Sn(OR)3(1) (In the formula, each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms)

[0060] Embodiment 40: A composition comprising the mono-organic tin trialkoxide compound having the formula (1) according to Embodiment 1 and an R'SnX3 compound (wherein X is a halogen atom or an alkoxy group).

[0061] Embodiment 41: A composition comprising the mono-organic tin trialkoxide compound having the formula (1) according to Embodiment 8 and an R'SnX3 compound (wherein X is a halogen atom or an alkoxy group).

[0062] Embodiment 42: A composition comprising an organotin compound having the formula (3) and an organotin compound having the formula (4). R'SnO (3 / 2-x / 2) (OH) x (3) R''SnO (3 / 2-x / 2) (OH) x (4) (In the formula, 0 < x < 3, R' is linear or branched, an optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and R'' is a hydrocarbon group having from 2 to about 20 carbon atoms, which may be substituted)

[0063] Embodiment 43: The composition according to Embodiment 42, wherein at least one of the compound having the formula (3) and the compound having the formula (4) is obtained by hydrolysis of the mono-organic tin trialkoxide compound having the formula (1). R'Sn(OR)3(1) (In the formula, each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms)

[0064] Embodiment 44: A solution comprising the composition of embodiment 42 or 43 and an organic solvent.

[0065] Embodiment 45: The solution of embodiment 44, wherein at least one of the compound having formula (3) and the compound having formula (4) is obtained by hydrolysis of a monoorganotin trialkoxide compound having formula (1). R'Sn(OR)3(1) wherein each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms.

[0066] Embodiment 46: A film comprising the composition of embodiment 42 or 43.

[0067] Embodiment 47: The film of embodiment 46, wherein at least one of the compound having formula (3) and the compound having formula (4) is obtained by hydrolysis of a monoorganotin trialkoxide compound having formula (1). R'Sn(OR)3(1) wherein each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms.

[0068] The foregoing summary, as well as the following detailed description, will be better understood when read in conjunction with the accompanying drawings. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are preferred in the invention. It being understood, however, that the invention is not limited to the precise arrangements and equipment shown. [Brief explanation of the drawings]

[0069] [Figure 1] FIG. 1 shows an ESI-mass spectrum of a compound according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0070] According to one aspect of the present disclosure, there is provided a monoorganotin trialkoxide compound having formula (1). For purposes of this disclosure, the term "monoorganic" refers to a substituent containing a primary or secondary monounsaturated hydrocarbon group having at least two carbon atoms, i.e., an alkenyl or alkynyl group in the 1- or 2-position relative to the tin. The compound having formula (1) preferably has a purity of at least about 95 mol% and preferably contains no more than about 5 mol%, preferably no more than about 4 mol%, no more than about 3 mol%, no more than about 2 mol%, more preferably no more than about 1 mol%, even more preferably no more than about 0.5 mol%, and even more preferably no more than about 0.1 mol% of a diorganotin dialkoxide compound having formula (2) based on the total amount of tin. R'Sn(OR)3(1) R'2Sn(OR)2(2) In formula (1) and formula (2), R′ is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, preferably from about 2 to about 10 carbon atoms, more preferably from about 2 to about 7 carbon atoms, even more preferably from about 2 to about 5 carbon atoms, and most preferably from about 2 to about 3 carbon atoms, such as an alkenyl or alkynyl group; and each R is independently a linear or branched (primary, secondary, or tertiary) optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms, preferably from about 1 to about 5 carbon atoms, and more preferably from 1 to about 4 carbon atoms, such as, but not limited to, optionally fluorinated methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc. Preferred R' groups in the present invention include, but are not limited to, vinyl (ethenyl), allyl, 1-propenyl, 3-buten-1-yl, 3-buten-2-yl, 2-methylallyl, and 3-methyl-2-buten-1-yl.

[0071] Examples of compounds having formula (1) according to this aspect of the disclosure include, but are not limited to, ethenyltintri(methoxide), ethenyltintri(ethoxide), ethenyltintri(n-propoxide), ethenyltintri(i-propoxide), ethenyltintri(n-butoxide), ethenyltintri(i-butoxide), ethenyltintri(t-butoxide), allyltintri(methoxide), allyltintri(ethoxide), allyltintri(n-propoxide), allyltintri(i-propoxide), allyltintri(n-butoxide), sido), allyltintri(i-butoxide), allyltintri(t-butoxide), 1-propenyltintri(methoxide), 1-propenyltintri(ethoxide), 1-propenyltintri(n-propoxide), 1-propenyltintri(i-propoxide), 1-propenyltintri(n-butoxide), 1-propenyltintri(i-butoxide), 1-propenyltintri(t-butoxide), 3-buten-1-yltintri(methoxide), 3-buten-1-yltintri(ethoxide), 3-buten-1-yltintri(n- propoxide), 3-buten-1-yltintri(i-propoxide), 3-buten-1-yltintri(n-butoxide), 3-buten-1-yltintri(i-butoxide), 3-buten-1-yltintri(t-butoxide), 3-buten-2-yltintri(methoxide), 3-buten-2-yltintri(ethoxide), 3-buten-2-yltintri(n-propoxide), 3-buten-2-yltintri(i-propoxide), 3-buten-2-yltintri(n-butoxide), 3-buten-2-yltintri(i-butoxide) tintri(methoxide), 3-methyl-2-buten-1-yltintri(ethoxide), 3-methyl-2-buten-1-yltintri(n-propoxide), 3-methyl-2-buten-1-yltintri(i-propoxide), 3-methyl-2-buten-1-yltintri(n-butoxide), 3-methyl-2-buten-1-yltintri(i-butoxide), and 3-methyl-2-buten-1-yltintri(t-butoxide).

[0072] The term "optionally fluorinated" means that at least one hydrogen atom of the hydrocarbon group of R' or the alkyl group of R is replaced with a fluorine atom; it is also within the scope of the present invention that one, two, or even all hydrogen atoms of the hydrocarbon group or alkyl group are replaced with fluorine atoms (commonly referred to as perfluorinated). Most preferably, only the R group may be fluorinated, such that one, two, or even all hydrogen atoms of the alkyl group are replaced with fluorine atoms.

[0073] Examples of fluorinated compounds having formula (1) according to this aspect of the disclosure include, but are not limited to, tris(trifluoromethoxy)(vinyl)stannane, allyltris(trifluoromethoxy)stannane, ((1,1,1-trifluoro-2-methylpropan-2-yl)oxy)bis((1,1,1-trifluoropropan-2-yl)oxy)(vinyl)stannane, ((1,1,1,3,3,3-hexafluoro-2-methylpropan-2-yl)oxy)bis( ... Allylbis((1,1,1-trifluoro-2-methylpropan-2-yl)oxy)(vinyl)stannane, allylbis((1,1,1-trifluoro-2-methylpropan-2-yl)oxy)((1,1,1-trifluoropropan-2-yl)oxy)stannane, allyl((1,1,1,3,3,3-hexafluoro-2-methylpropan-2-yl)oxy)bis((1,1,1,3,3,3-hexafluoropropan-2-yl)oxy)stannane, tris((1,1,1-trifluoro-2-methylpropan-2-yl)oxy)(vinyl)stannane , tris((1,1,1,3,3,3-hexafluoro-2-methylpropan-2-yl)oxy)(vinyl)stannane, tris((1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl)oxy)(vinyl)stannane, allyltris((1,1,1-trifluoro-2-methylpropan-2-yl)oxy)stannane, allyltris((1,1,1,3,3,3-hexafluoro-2-methylpropan-2-yl)oxy)stannane, allyltris((1,1,1,3, 3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl)oxy)stannane, (2-methylallyl)tris((1,1,1-trifluoro-2-methylpropan-2-yl)oxy)stannane, tris((1,1,1,3,3,3-hexafluoro-2-methylpropan-2-yl)oxy)(2-methylallyl)stannane, and tris((1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl)oxy)(2-methylallyl)stannane.

[0074] All numerical ranges expressed in this disclosure include all values within the range, including fractions and decimals. Thus, the content of the compound having formula (2) is preferably less than about 5 mol%, less than about 4 mol%, less than about 3 mol%, less than about 2 mol%, less than about 1 mol%, less than about 0.9 mol%, less than about 0.8 mol%, less than about 0.7 mol%, less than about 0.6 mol%, less than about 0.5 mol%, less than about 0.4 mol%, less than about 0.3 mol%, less than about 0.2 mol%, less than about 0.1 mol%, less than about 0.05 mol%, less than about 0.04 mol%, less than about 0.03 mol%, less than about 0.02 mol%, less than about 0.01 mol%, or 119 It is undetectable by Sn NMR, ie, the compound having formula (2) is in some embodiments undetectable in a sample of the compound having formula (1).

[0075] In some embodiments, the content of tetrakis(alkoxy)tin in the monoorganotin trialkoxide compound having formula (1) is less than about 1 mol%, more preferably less than about 0.7 mol%, less than about 0.5 mol%, or less than about 0.1 mol%. In some embodiments, the content of total tris(alkenyl)tin compounds in the monoorganotin trialkoxide compound having formula (1) is less than about 1 mol%, more preferably less than about 0.7 mol%, less than about 0.5 mol%, or less than about 0.1 mol%.

[0076] According to another aspect of the present disclosure, there is provided a monoorganotin trialkoxide compound having the formula (1): For purposes of this disclosure, the term "monoorganic" refers to a substituent containing a primary or secondary single unsaturated hydrocarbon group having at least two carbon atoms, i.e., one alkenyl group or one alkynyl group, located in the 1- or 2-position relative to the tin. R'Sn(OR)3(1) In formula (1), R′ is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, preferably from about 2 to about 10 carbon atoms, more preferably from about 2 to about 7 carbon atoms, even more preferably from about 2 to about 5 carbon atoms, and most preferably from about 2 to about 3 carbon atoms, such as an alkenyl or alkynyl group, and each R is independently a linear or branched (primary, secondary, or tertiary) optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms, preferably from about 1 to about 5 carbon atoms, and more preferably from 1 to about 4 carbon atoms, such as, but not limited to, optionally fluorinated methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc. Preferred R' groups in the present invention include, but are not limited to, vinyl (ethenyl), allyl, 1-propenyl, 3-buten-1-yl, 2-methylallyl, 3-buten-2-yl, and 3-methyl-2-buten-1-yl.

[0077] Examples of compounds having formula (1) according to this aspect of the disclosure include, but are not limited to, ethenyltintri(methoxide), ethenyltintri(ethoxide), ethenyltintri(n-propoxide), ethenyltintri(i-propoxide), ethenyltintri(n-butoxide), ethenyltintri(i-butoxide), ethenyltintri(t-butoxide), allyltintri(methoxide), allyltintri(ethoxide), allyltintri(n-propoxide), allyltintri(i-propoxide), allyltintri(n-butoxide), sido), allyltintri(i-butoxide), allyltintri(t-butoxide), 1-propenyltintri(methoxide), 1-propenyltintri(ethoxide), 1-propenyltintri(n-propoxide), 1-propenyltintri(i-propoxide), 1-propenyltintri(n-butoxide), 1-propenyltintri(i-butoxide), 1-propenyltintri(t-butoxide), 3-buten-1-yltintri(methoxide), 3-buten-1-yltintri(ethoxide), 3-buten-1-yltintri(n- propoxide), 3-buten-1-yltintri(i-propoxide), 3-buten-1-yltintri(n-butoxide), 3-buten-1-yltintri(i-butoxide), 3-buten-1-yltintri(t-butoxide), 3-buten-2-yltintri(methoxide), 3-buten-2-yltintri(ethoxide), 3-buten-2-yltintri(n-propoxide), 3-buten-2-yltintri(i-propoxide), 3-buten-2-yltintri(n-butoxide), 3-buten-2-yltintri(i-butoxide) tintri(methoxide), 3-methyl-2-buten-1-yltintri(ethoxide), 3-methyl-2-buten-1-yltintri(n-propoxide), 3-methyl-2-buten-1-yltintri(i-propoxide), 3-methyl-2-buten-1-yltintri(n-butoxide), 3-methyl-2-buten-1-yltintri(i-butoxide), and 3-methyl-2-buten-1-yltintri(t-butoxide).

[0078] The term "optionally fluorinated" means that at least one hydrogen atom of the hydrocarbon group of R' or the alkyl group of R is replaced with a fluorine atom; it is also within the scope of the present invention that one, two, or even all hydrogen atoms of the hydrocarbon group or alkyl group are replaced with fluorine atoms (commonly referred to as perfluorinated). Most preferably, only the R group may be fluorinated, such that one, two, or even all hydrogen atoms of the alkyl group are replaced with fluorine atoms.

[0079] Examples of fluorinated compounds having formula (1) include, but are not limited to, tris(trifluoromethoxy)(vinyl)stannane, allyltris(trifluoromethoxy)stannane, ((1,1,1-trifluoro-2-methylpropan-2-yl)oxy)bis((1,1,1-trifluoropropan-2-yl)oxy)(vinyl)stannane, ((1,1,1,3,3,3-hexafluoro-2-methylpropan-2-yl)oxy)bis((1,1,1,3,3,3-hexafluoropropane- 2-yl)oxy)(vinyl)stannane, allylbis((1,1,1-trifluoro-2-methylpropan-2-yl)oxy)((1,1,1-trifluoropropan-2-yl)oxy)stannane, allyl((1,1,1,3,3,3-hexafluoro-2-methylpropan-2-yl)oxy)bis((1,1,1,3,3,3-hexafluoropropan-2-yl)oxy)stannane, tris((1,1,1-trifluoro-2-methylpropan-2-yl)oxy)(vinyl)stannane, tris( (1,1,1,3,3,3-hexafluoro-2-methylpropan-2-yl)oxy)(vinyl)stannane, tris((1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl)oxy)(vinyl)stannane, allyltris((1,1,1-trifluoro-2-methylpropan-2-yl)oxy)stannane, allyltris((1,1,1,3,3,3-hexafluoro-2-methylpropan-2-yl)oxy)stannane, allyltris((1,1,1,3,3,3-hexafluoro-2-methylpropan-2-yl)oxy)stannane 3-hexafluoro-2-(trifluoromethyl)propan-2-yl)oxy)stannane, (2-methylallyl)tris((1,1,1-trifluoro-2-methylpropan-2-yl)oxy)stannane, tris((1,1,1,3,3,3-hexafluoro-2-methylpropan-2-yl)oxy)(2-methylallyl)stannane, and tris((1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl)oxy)(2-methylallyl)stannane.

[0080] Organometallic tin compounds having formula (1) can be utilized to generate high-resolution EUV lithography patterning precursors and are attractive due to their electron density, Sn-C bond strength, and potential to reduce radical formation and EUV exposure time.

[0081] Particularly preferred compounds having formula (1) are shown below.

[0082] [ka]

[0083] Synthesis method Aspects of the present disclosure further relate to methods for synthesizing high-purity tin compounds having the above formula (1), suitable for use in the microelectronics industry, preferably containing low levels of diorganotin compounds having formula (2). One method involves the reaction of organotin trichloride with an alkali metal alkoxide (a weak base) at a controlled molar ratio and temperature, without affecting the unsaturated substituents, to introduce water-reactive alkoxide groups at the tin sites. If desired, after initial purification, the levels of diorganotin compounds and other minor impurities can be further reduced using fractional distillation.

[0084] 119 Sn NMR spectroscopy is ideally suited for the quantitative analysis of monoorganotin compounds (containing both alkenyl and alkynyl substituents) due to its high sensitivity to small structural changes and broad spectral range of 6500 ppm (see Davies et al., eds.; Tin Chemistry: Fundamentals, Frontiers, and Applications; Wiley (2008)). 119 The high resolution of the Sn resonance allows for easy identification and quantification of monoorganotin compounds and their impurities. 119 Sn NMR can be performed by GC, HPLC, or 1A drawback of this method is its low sensitivity compared to other analytical techniques, such as H NMR. To improve sensitivity, monoorganotin compounds are analyzed undiluted, and multiple spectral acquisitions (2000+) are taken to measure the low levels of impurities described herein. Utilizing this approach, detection limits as low as 0.1 mol % for diorganotin dialkoxides can be achieved.

[0085] J. Med. Chem. (57, 22, 9220-9231 (2014)) using a method similar to the related purification method described herein. 119 Sn NMR data were acquired using a 40° pulse, a 1 second relaxation delay, and an inverse gated scan count sufficient to achieve the required sensitivity. 1 Using H decoupling 119 Sn NMR spectra were acquired. Samples were prepared without dilution with hydrogenation solvents. Quantification was performed by integrating all peaks in the spectrum and setting the total peak area to 100. Each peak in the spectrum represents a distinct tin compound, and the area of each peak represents the concentration or purity of that compound in mole percent.

[0086] A method for synthesizing a monoorganotin trialkoxide compound having formula (1) according to an embodiment of the present disclosure includes reacting an alkali metal alkoxide with an R'SnX3 compound, where X is a halogen atom or an alkoxy group.

[0087] Preferably, the method includes preparing a solution of an alkali metal alkoxide at a desired concentration in a suitable solvent, such as anhydrous hexane, for reaction with the R'SnX3 compound, followed by cooling the solution to a low temperature, such as, but not limited to, about 0°C to about -10°C. For example, if the desired compound having Formula (1) is allyltris(t-butoxy)tin, the alkali alkoxide can be potassium t-butoxide, sodium t-butoxide, or lithium t-butoxide. The concentration of the alkali metal alkoxide is preferably up to about 10 to 15% by weight, more preferably about 8 to 10% by weight, based on the amount of solvent. The appropriate solvent and concentration can be determined by iterative experimentation and based on the commercial availability of the desired alkali metal alkoxide.

[0088] For the methods and processes described herein, preferred solvents include hydrocarbon solvents (such as, but not limited to, hexane, hexane, heptane, and cyclohexane) and aromatic solvents (such as, but not limited to, toluene and xylene).

[0089] Suitable R'SnX compounds are those in which X is a halogen atom (e.g., fluoro, bromo, or preferably chloro) or an alkoxy group (e.g., containing from about 1 to about 5 carbon atoms, such as the methyl, ethyl, propyl, or butyl groups preferred herein). Most preferably, the R'SnX compound is R'SnCl. After reaction of the alkali metal alkoxide with the R'SnX compound to produce a compound having formula (1), the reaction mixture is processed and purified using methods well known in the art.

[0090] In some embodiments, the method further comprises: (a) preparing a solution of an alkali metal alkoxide; (b) adding R'SnCl3 at about -10°C to about 10°C to produce a crude product, wherein the amount of alkali metal alkoxide is at least about 3.03 equivalents relative to the amount of R'SnCl3 added; (c) distilling the crude product to obtain a monoorganotin trialkoxide having formula (1); Includes: These steps are described in more detail below.

[0091] A further method for preparing a monoorganotin trialkoxide compound having formula (1) according to a further aspect of the present disclosure comprises the steps of: (a) preparing an alkali metal alkoxide solution; (b) adding R'SnCl3 at about -10°C to about 10°C, wherein the amount of alkali metal alkoxide is at least about 3.03 equivalents relative to the amount of R'SnCl3 added; (c) warming the solution to room temperature; (d) removing the alkali metal chloride salt by-product to produce a crude product; (e) distilling the crude product to obtain a product containing a monoorganotin trialkoxide having formula (1) and up to about 5 mole percent of a diorganotin dialkoxide having formula (2); each of which is described in further detail below.

[0092] The first step of the above method involves preparing a solution of an alkali metal alkoxide at a desired concentration in a suitable solvent, such as anhydrous hexane, followed by cooling the solution to a low temperature, for example, about 0°C to about -10°C. For example, if the desired compound having Formula (1) is allyltris(t-butoxy)tin, the alkali alkoxide can be potassium t-butoxide, sodium t-butoxide, or lithium t-butoxide. The concentration of the alkali metal alkoxide can be preferably up to about 10 to 15% by weight, more preferably about 8 to 10% by weight, based on the amount of solvent. The appropriate solvent and concentration can be determined by iterative experimentation and based on the commercial availability of the desired alkali metal alkoxide.

[0093] In the second step, monoalkenyl or monoalkynyltin trichloride R'SnCl3 or other R'SnX3 compound is added to the alkali metal alkoxide solution at about -10°C to about 10°C so that the amount of alkali metal alkoxide is at least about 3.03 equivalents relative to the amount of organotin trichloride or organotin trialkoxide added. A slight molar excess ensures complete reaction of the organotin trichloride or organotin trialkoxide. Preferably, the molar excess is maintained as close to a 3% excess as possible to prevent polymerization of unsaturated groups, but it is also within the scope of the present disclosure to use molar excesses ranging from about 2% to about 4%, or 5%, or about 15%, such that the metal alkoxide is present in an amount of about 3.02 to about 3.15 equivalents, preferably about 3.02 to about 3.05 equivalents, relative to the amount of tin trichloride (or tin trialkoxide) added. For example, allyltrichlorotin can be used in the second step to prepare allyltin trialkoxides. R'SnCl3 compounds can be purchased commercially or prepared, for example, by redistribution of R'4Sn and SnCl4 to produce R'SnCl3=.

[0094] The organotin trichloride or organotin trialkoxide is preferably added dropwise to control the thermal reaction. The second method step is preferably carried out in an inert atmosphere, such as nitrogen or argon. While the monoorganotin trichloride or monoorganotin trialkoxide is preferably added neat (without solvent), it is also within the scope of the present disclosure to add the monoorganotin trichloride or monoorganotin trialkoxide to a solvent, such as, but not limited to, hexane, toluene, THF, xylene, heptane, dichloromethane, or benzene.

[0095] After the step of adding the organotin trichloride or organotin trialkoxide to the alkali metal alkoxide solution is complete, the reaction mixture is allowed to warm slowly to room temperature, for example, over about 4 hours, and then stirred at room temperature for an additional period of time, for example, about 2 to 4 hours. The reaction mixture is then filtered, for example, through Celite, to remove the alkali metal chloride by-product. Other filtration means known to those skilled in the art can also be used. The resulting salt is then rinsed, for example, with anhydrous hexane, and the solvent is removed under reduced pressure by means known to those skilled in the art to produce the crude product.

[0096] Finally, the crude product is distilled, e.g., at less than about 10 torr, preferably less than about 0.5 torr, to obtain the desired product, preferably greater than about 95 mol% pure and containing monoorganotin trialkoxide (e.g., allyltris(t-butoxy)tin) with about 5 mol% or less of diorganotin dialkoxide. Suitable distillation conditions can be determined on a case-by-case basis, depending on the desired product, through repeated experimentation. In preferred embodiments, the diorganotin dialkoxide content is less than about 4 mol%, less than about 3 mol%, less than about 2 mol%, less than about 1 mol%, less than about 0.5 mol%, less than about 0.1 mol%, or even lower, as described above. Unlike methods for producing organotin trialkoxide compounds from the reaction of diethylamine followed by an alcohol, which produce a mixture of products due to a comproportionation reaction, the methods described herein produce the desired product in high purity (containing low amounts of diorganotin dialkoxide impurities) and high yield.

[0097] All method steps are preferably carried out substantially without exposure to light. Shielding can be achieved by any method known to those skilled in the art, such as using a light-shielding container such as an amber glass or metal (SUS) container, covering the container with a light-shielding cover such as a cloth, foil or film, using a light-shielding coating, or carrying out the reaction in a dark room.

[0098] Distillation can be carried out using a stainless steel column packed with stainless steel packing material. Alternatively, distillation can be carried out in a light-tight apparatus including glass, such as a glass apparatus, a glass-lined apparatus, a glass-coated apparatus, etc. Shielding can be carried out by any method known to those skilled in the art, such as using a light-tight container such as amber glass or a metal (SUS) container, covering the container with a light-tight cover such as cloth, foil, or film, using a light-tight coating, or carrying out the distillation in a dark room.

[0099] In preferred embodiments, the methods described herein are carried out in a solvent containing greater than about 50% by volume of a hydrocarbon and / or aromatic solvent, such as, but not limited to, those exemplified above. In preferred embodiments, the methods described herein are carried out substantially without exposure to light. In preferred embodiments, the alkali metal alkoxide is dehydrated prior to reaction with the R'SnX3 compound.

[0100] During the alkoxylation reaction to produce monoorganotin trialkoxides, the Kocheshkov-like compromisation reaction shown in Scheme (I) above also occurs, and even lower temperatures, such as from about -78°C to 10°C, do not prevent the compromisation reaction from occurring. Furthermore, electron donation contributes to the Kocheshkov-like compromisation reaction, 119 It is possible to produce up to 15 mole % of the diorganotin alkoxide as determined by Sn NMR.

[0101] However, the method described herein provides a synthetic strategy for producing tin compounds with unsaturated substituents without using significant amounts of diorganotin dialkoxide impurities. It has been found that lithium dimethylamide reacts not only with tin chloride but also with unsaturated bonds. Therefore, as described herein, lithium dimethylamide is not used, and the concentration of the reagents is diluted, for example, by using a hexane slurry of the metal alkoxide at a concentration of about 10% by weight or less, limiting the formation of polyorganotin compounds. Furthermore, the temperature of the alkali alkoxide solution is carefully controlled before and during the addition of the organotin trichloride or organotin trialkoxide.

[0102] It is further within the scope of the present disclosure to use alcohols R'OH (or partially fluorinated alcohols) rather than alkali metal alkoxide reagents to prepare compounds having formula (1) described herein, and further to use partially fluorinated alkoxide groups in the alkali metal alkoxide reagents.

[0103] The addition of CF3 groups to alkoxide ligands may improve the volatility / vapor pressure of the resulting tin compounds, in part because fluorine atoms are more electronegative than carbon, increasing the amount of intermolecular repulsion. Furthermore, fluorine has a lower polarizability (compared to hydrogen), which reduces the intermolecular attractive interactions of the fluorinated ligand. Extending this concept, separation of unwanted by-products may also be simplified, since the vapor pressure difference between [CF3(CH3)CHO]2SnR2, [CF3(CH3)CHO]3SnR, and [CF3(CH3)CHO]4Sn may be greater than that observed for the related tert-butoxide or amide derivatives. In general, fluorinated alkoxides are weaker donors / bases than standard alkoxides due to the electronegativity of the fluorine atom. This means that the resulting tin compounds are less sensitive to residual moisture than related alkoxytin complexes, but can still react with water to deposit tin oxide under CVD conditions. In addition to stability against residual moisture, the weak donor from the fluorinated alkoxide to tin may provide a more stable tin alkenyl or tin alkynyl complex by strengthening the tin-carbon bond. Fluorinated alkoxides are also less nucleophilic than amide ligands and are therefore much less likely to attack the double bond of the allylic group.

[0104] Reduction of other impurities It is reasonable to assume that metal impurities in organotin trialkoxy compounds exist as metal chlorides. If so, removal can be effected by adsorbents, such as chloride adsorbents known to those skilled in the art, such as BASF CL-750. Other chloride impurities may also be present, such as lithium chloride, which is introduced into the manufacturing process and can be an impurity of interest. Removal by a chloride scavenger adsorbent, such as CL-750 or activated carbon, can be effective for removal.

[0105] storage A further aspect of the present disclosure relates to a method for storing a mono-organotin trialkoxide compound having formula (1) described herein. The method for storing a sample of a mono-organotin trialkoxide compound having formula (1) described herein (e.g., but not limited to, a sample greater than about 0.5 kg) comprises storing a sample of the mono-alkyltin triamide compound having formula (1) substantially without exposure to light at any temperature, for example, a temperature below about 30° C. The method may comprise storing the compound having formula (1) in a container in an inert atmosphere and / or storing the compound having formula (1) in the container without exposure to light, for example, in a dark room, by using a light-blocking container such as amber glass, metal (SUS), or the like, covering the container with a light-blocking cover such as cloth, foil, or film, or using a light-blocking coating, etc.

[0106] Samples of mono-organotin trialkoxide compounds having formula (1) can be stored for periods ranging from up to about 3 days to about 1 year, e.g., from about 1 week to about 10 months, from about 2 weeks to 6 weeks, and any intermediate period desired. Preferably, samples are stored at temperatures below about 30°C, below about 25°C, below about 20°C, and preferably above about -10°C. "Essentially without exposure to light" can be understood to mean that the samples are maximally protected from exposure to light, for example, by storage in amber or stainless steel containers, or other light-protecting techniques known to those skilled in the art and / or as described above. In embodiments, samples of mono-organotin trialkoxide compounds are substantially undecomposed after storage periods of several hours, from up to about 3 days to about 1 year or more, as described above.

[0107] Further aspects of the present disclosure The organometallic tin compound having formula (1) has at least one unsaturated bond in the carbon chain linked to the tin atom. These tin compounds form a tin oxide cluster film having an unsaturated bond on a silicon wafer after a vapor deposition process or a spin coating process. It has been found that these unsaturated bonds provide more radiation-sensitive Sn-C bonds that can be utilized for patterning the structure by lithography. Since the orbital interaction of the unsaturated bond may affect the Sn-C bond or the electronic state of tin, resulting in enhanced photosensitivity, they are advantageous for EUV photoresists. Furthermore, the unsaturated bond can react or polymerize upon EUV exposure, and the solubility of the tin cluster can be improved.

[0108] The radicals and anions generated by EUV light react with the unsaturated bond and polymerize to form a stronger R'SnO (3 / 2-x / 2) (0H) x (0 < x < 3) film. The above reaction greatly changes the R'SnO (3 / 2-x / 2) (0H) x (0 < x < 3) cluster film and results in a higher contrast as a resist.

[0109] A further aspect of the present disclosure relates to a compound of formula (3): R'SnO (3 / 2-x / 2) (OH) x :(3) having an organotin compound. In formula (3), 0 < x < 3, and R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms. The above compound having formula (3) can be obtained by hydrolysis of the monoorganotin trialkoxide compound having formula (1) described herein.

[0110] A further aspect of the present disclosure relates to a solution containing an organotin compound having formula (3) and an organic solvent, such as, but not limited to, the hydrocarbon solvent or aromatic solvent described above. A further aspect of the present disclosure relates to a film containing the organotin compound having formula (3) described herein.

[0111] A further aspect of the present disclosure relates to a composition or mixture containing a mono-organic tin trialkoxide compound having formula (1) and R'SnX3, where X is a halogen atom or an alkoxy group as described above.

[0112] A further aspect of the present disclosure relates to a composition containing an organotin compound having formula (3) and an organotin compound having formula (4). R'SnO (3 / 2-x / 2) (OH) x (3) R''SnO (3 / 2-x / 2) (OH) x (4)

[0113] In formulas (3) and (4), 0 < x < 3, R' is linear or branched and is an optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and R'' is an optionally substituted hydrocarbon group having from 2 to about 20 carbon atoms, such as a hydrocarbon group substituted with a halogen atom, an alkoxy group, or a dialkylamino group (e.g., dimethylamino, diethylamino, etc.). The above compounds having formulas (3) and (4) can be obtained by hydrolysis of the mono-organic tin trialkoxide compound having formula (1) described herein.

[0114] A further aspect of the present disclosure relates to a solution containing an organic solvent described herein and a composition containing an organotin compound having formulas (3) and (4), which in some embodiments can be obtained by hydrolysis of the mono-organic tin trialkoxide compound having formula (1) described herein. A further aspect of the present disclosure relates to a film prepared from a composition containing an organotin compound having formulas (3) and (4) or containing them.

[0115] The R' and R'' groups described in this specification have a hydrocarbon group of about 2 to about 20 carbons as a skeleton, and in addition to the substituents specified above, they may have various organic substituents that do not react with unsaturated carbon-carbon bonds or hydrolyzable Sn-O bonds within the molecule. For example, a halogen atom, an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino, an alkylthio group, an arylthio group, an acyl group, an acyloxy group, and an alkoxycarbonyl group may be included in the above organic substituents.

[0116] The compounds described in this specification can be used as a resist material after hydrolysis or other reactions such as those known to those skilled in the art. The compounds described in this specification have the formula R'SnO (3 / 2-x / 2) (OH) x (0 < x ≦ 3) and may contain groups capable of forming an alkyltin oxo-hydroxy-patterning composition that can be hydrolyzed with water or other suitable reagents under suitable conditions to form an alkyltin oxo-hydroxy-patterning composition. The hydrolysis and condensation reactions that can change the compound having a hydrolyzable group (X) are shown by the following reactions. RSnX3 + 3H2O → RSn(OH)3 + 3HX RSn(OH)3 → RSnO( 1.5-(x / 2) )OH x + (x / 2)H2O

[0117] The alkyloxohydroxytin compounds obtained by hydrolysis using a composition containing the above R'SnX3 compound as a raw material and the oxohydroxytin compounds of the formula R'SnO (3 / 2-x / 2) (0H) x (0 < x < 3) can be used as an EUV resist material.

[0118] A method for obtaining an oxohydroxytin compound (R'SnO) by hydrolyzing a composition containing an R'SnX3 compound may include, for example, a step of vaporizing the composition containing an R'SnX3 compound under heating or reduced pressure, and a step (dry method) of reacting the vapor generated by vaporizing the composition with water vapor or the like on a substrate on which the tin composition is to be deposited. In this method, a thin film containing the tin compound R'SnO can be formed on the substrate.

[0119] Another method may involve reacting a composition containing an R'SnX3 compound with water or the like, either in solution or in the solid state, and hydrolyzing it to obtain an oxo-hydroxytin compound (R'SnO). The oxo-hydroxytin compound (R'SnO) can then be used as a coating solution, for example, by dissolving it in an organic solvent.

[0120] The solution can be applied to a substrate by any coating or printing technique, and a thin film or coating containing the oxohydroxytin compound (R'SnO) can be formed on the substrate.

[0121] Films obtained by any of the above methods can be stabilized or partially condensed prior to exposure to light through drying, heating, or other processes. Typically, the average thickness of the film or coating is less than about 10 microns, and very thin submicron films, e.g., less than about 100 nanometers (nm), or even less than about 50 nm or less than about 30 nm, may be desirable for patterning very small feature sizes. The resulting film or coating is sometimes referred to as a resist, since exposure processes portions of the composition to impart development / etch resistance.

[0122] The thin film or coating may be exposed to suitable radiation (e.g., extreme ultraviolet, electron beam, or ultraviolet) using a selected pattern or a negative portion of the pattern to form a latent image with development-resistant and developer-soluble areas. After exposure to suitable radiation and before development, the thin film or coating can be heated or otherwise reacted to further distinguish the latent image from non-irradiated areas. The latent image is then contacted with a developer to form a physical image, i.e., a patterned thin film or coating. The patterned thin film or coating can be further heated to stabilize the remaining patterned coating on the surface. The patterned coating can be used as a physical mask to perform additional processing according to the pattern, such as etching the substrate and / or depositing other materials. After the patterned resist has been used as desired, the remaining patterned coating can be removed at an appropriate point in processing, or the patterned coating can be incorporated into a final structure.

[0123] The invention will now be described in connection with the following non-limiting examples. [Example]

[0124] Example 1 Synthesis of vinyltris(t-butoxy)tin Vinyltin trichloride was prepared by the redistribution reaction of tetravinyltin and tetrachlorotin according to the method of Rosenberg and Gibbons (JACS, 79, 2138-40 (1957)). A 5.0 L flask was charged with 189.08 g (0.75 mol) of vinyltin trichloride and 400 mL of anhydrous hexane (3 mol). To this was added 2.25 L (2.25 mol) of t-BuOK (1 M in THF) over 1 hour at a pot temperature of -10°C with vigorous stirring. The solution was allowed to warm to room temperature and stirred for an additional 2 hours. The mixture was filtered through Celite under N2 and washed twice with 200 mL of hexane. The solvent was removed under reduced pressure, and the residue was distilled under reduced pressure (129°C, 0.5 torr) to yield 128 g (47%) of vinyltris(t-butoxy)tin. 119 Sn NMR (400 mHz; pure): δ -256.87. 1 H NMR (400 mHz; C6D6): δ 5.8-6.2 (m, 3H, vinyl), δ 1.42 (s, 27H, Ot-Bu). Purity: 79%.

[0125] Example 2 Synthesis of allyltris(t-butoxy)tin Allyltin trichloride was prepared by the redistribution reaction of tetraallyltin and tetrachlorotin in benzene or toluene according to the method of Rosenberg and Gibbons (JACS, 79, 2138-40 (1957)). 252.47 g (2.25 mol) of t-BuOK and 3.5 L of hexane (26 mol) were added to a 5.0 L flask and cooled to 0°C. 189.08 g (0.75 mol) of allyltin trichloride was added dropwise while maintaining the vessel temperature between 0 and 10°C. After the addition, the solution was warmed to room temperature and stirred for an additional 2 hours. The mixture was filtered through Celite under N2 and washed twice with 200 mL of hexane. The solvent was removed under reduced pressure, and residual diallyltin impurities were removed by fractional distillation under reduced pressure. Allyltris(t-butoxy)tin was recovered at 53.0 to 55.0°C at 0.18 torr. 119 Sn NMR (400 mHz; pure): δ -222.084.1 H NMR (400 mHz; C6D6): δ 5.7-5.9 (m, 1H), δ 4.8-5.0 (m, 2H), δ 2.1 (d, 2H), δ 1.42 (d, 2H), δ 1.40 (s, 27H). Purity: 81%.

[0126] Example 3 Synthesis of allyltris((1,1,1-trifluoro-2-methylpropan-2-yl)oxy)stannane Allyltin trichloride was prepared by the redistribution reaction of tetraallyltin and tetrachlorotin according to the method of Rosenberg and Gibbons (JACS, 79, 2138-40 (1957)). A 2.5 M solution of n-butyllithium in hexane (230 g, 0.83 mol) was placed in a 2 L flask and cooled to -30°C. 2-Trifluoromethyl-2-propanol (100 g, 0.78 mol) was added dropwise to this solution over 30 minutes, resulting in a vigorous exothermic reaction. The reaction temperature was maintained below 5°C during the addition, during which time an orange solution and a small amount of white solid formed. The reaction was allowed to warm to room temperature, the reactor walls were rinsed with hexane (300 g), and the reaction was stirred for an additional 2 hours. After stirring at room temperature, the reaction mixture was cooled to -10°C, and a solution of allyltrichlorotin (69 g, 0.26 mol) in toluene (150 g) was added portionwise to the reaction mixture over 10 minutes, during which time the orange solution turned pale yellow and a white precipitate formed. The reaction mixture was allowed to warm to room temperature and stirred for 16 hours. The resulting pale yellow solution was isolated by filtration, and the solvent was removed from the filtrate under vacuum with gentle heating (5 torr, 35°C) to give a viscous yellow liquid. The product was isolated after distillation as a colorless liquid. Yield = 40 g (30%); boiling point 65°C at 0.5 torr. 1 H NMR (benzene-d6): δ 1.30 (s, 18H, OC(CH3)2CF3), δ 2.15 (d, 2H, SnCH2CHCH2), δ 4.86 (m, 2H, SnCH2CHCH2), δ 5.57 (m, 1H, SnCH2CHCH2). 119 Sn{ 1H} NMR: δ -253. Purity: >97%.

[0127] Example 4 Synthesis of 3-butene-1-yltris(t-butoxy)tin 3-Buten-1-yltin trichloride was prepared by the redistribution reaction of 3-buten-1-yltricyclohexyltin with tetrachlorotin or by the reaction of 3-buten-1-yltriphenyl-1-tin with tetrachlorotin in toluene according to the method of Jousseaume, Lehcini, and Rascle (Organometallics 14, 685-689 (1995)). A 3.0 L flask was charged with 850.0 g (3.07 mol) of n-hexyllithium under N2 and cooled to 0°C. A premix containing 57.43 g (0.62 mol) of toluene and 229.71 g (3.10 mol) of tert-butanol was added dropwise while maintaining the kettle temperature between 0 and 10°C. The mixture was allowed to warm to room temperature and stirred for an additional 2 hours before the dropwise addition of 3-buten-1-yltin trichloride at 0 to 10°C. The reaction was allowed to warm to room temperature and stirred overnight. The mixture was filtered through Celite under N2 and washed twice with 200 mL of hexane. The solvent was removed under reduced pressure, and the target compound was recovered at 59.4 to 62.8°C at 0.4 torr to give 3-buten-1-yltris(t-butoxy)tin. 119 Sn NMR (400 mHz; pure): δ -194.423. 1 H NMR (400 mHz; C6D6): δ 5.7-5.9 (m, 1H), δ 4.8-5.0 (m, 2H), δ 2.1 (d, 2H), δ 1.42 (d, 2H), δ 1.40 (s, 27H). Purity >99%.

[0128] Example 5 (prediction) Preparation of the mixture Three mixtures were prepared as follows: (a) a mixture containing the compound prepared in Example 1 and the compound RSnX3 (where R is a vinyl group and X is a halogen atom or an alkoxy group); (b) a mixture containing the compound prepared in Example 2 and the compound RSnX3 (where R is an allyl group and X is a halogen atom or an alkoxy group); and (c) a mixture containing the compound prepared in Example 4 and RSnX3 (where R is 3-buten-1-yl and X is a halogen atom or an alkoxy group).

[0129] (Example 6) Preparation and analysis of R'SnO(3 / 2 - x / 2)(OH)x compounds (where 0 < x < 3) by hydrolysis (Example 6-a) R' = vinyl 10 mL of dehydrated n-hexane and 1.0 g of vinyltris(t-butoxy)tin synthesized as described in Example 1 were added to a 100 mL flask under an inert gas atmosphere and dissolved while stirring at 150 rpm. After cooling the resulting solution from 0 to 10 °C, deionized water (1.0 mL, resistivity 18.2 MΩ) was added dropwise with a syringe over 10 minutes while stirring at 150 rpm and maintaining the temperature from 0 to 10 °C to form a suspension. The resulting suspension was filtered through a funnel (Tongshan filter paper 5B) to obtain a white solid. The white solid was washed with 3 mL of deionized water and then dried in vacuo at 40 °C for 8 hours. The mass of the resulting white solid (SnO-1) was 0.48 g.

[0130] (Example 6-b) R' = allyl Using a method similar to that described in Example 6-a, an amount of 0.47 g of a white solid (SnO-2) was obtained from allyltris(t-butoxy)tin (prepared as described in Example 2).

[0131] (Example 6-c) R' = 3-buten-1-yl Using a method similar to that described in Example 6-a, 0.53 g of a white solid (SnO-3) was obtained from 3-buten-1-yltris(t-butoxy)tin (prepared as described in Example 4).

[0132] SnO-3 was identified by NMR. Only two peak groups were 119 observed by Sn NMR (600 MHz, MeOD / CDCl3 1 / 1): 5-coordinate (R'SnO4): -280 to -296 ppm and 6-coordinate (R'SnO5): -450 to -490 ppm. 1 H NMR (600 MHz, MeOD / CDCl3 1 / 1): 5.7 - 5.9 (m, 1H), 4.8 - 5.2 (m, 2H), 2.1 - 2.8 (m, 2H), 0.8 - 1.6 (m, 2H). This correlates with the NMR results of the tin dodecamer cluster [(R'Sn) 12 O 14 (OH)6] reported in Organometallics 19, 1940 - 1949 (2000). The ESI-mass spectrum is shown in Figure 1 (system: Waters Xevo G2-XS Qtof, solvent CH3CN, mode: ESI positive), showing two main peaks [(C4H7Sn) 12 O 14 (OH) 10 monovalent ion m / z = 2480, divalent ion m / z = 1240. Thus, a compound corresponding to R'SnO (3 / 2-x / 2) (OH) x (where 0 < x < 3) was obtained.

[0133] (Example 6-d) R' = 3-buten-1-yl Using the same method as described in Example 6-a, 0.37 g of a white solid (SnO-4) was obtained from 0.3 g of 3-buten-1-yltris(t-butoxy)tin (prepared as described in Example 4) and 0.7 g of isopropyltris(dimethylamino)tin.

[0134] (Example 7) Preparation of the film SnO-3 from Example 6-c was dissolved in 4-methyl-2-pentanol (5 mL) to a concentration of 2.0 wt% using ultrasound. The resulting solution was filtered through a 0.45 μm syringe filter to obtain a transparent resist solution containing the tin compound. A silicon wafer with an oxide surface (Si substrate, 100 mm diameter) was treated with ozone and used as a substrate for the deposition of a thin resist film. Prior to resist deposition, the surface of the Si substrate was treated with hexamethyldisilazane (HMDS) vapor. The resist solution was spin-coated onto the substrate at 2000 rpm and baked on a hotplate at 90°C for 2 minutes. The film thickness after coating and baking was measured to be 20 nm using an ellipsometer.

[0135] Example 8 (prediction) Formation of an image on a substrate The pattern was used to illuminate the coated substrate (film) from Example 7 with ultraviolet light (light source: xenon excimer lamp (172 nm, 7.2 eV) manufactured by USHIO INC., light source intensity: 0.7 mW / cm). 2 The pattern was projected onto the substrate by exposure to 2-heptanone for 15 seconds, and then rinsed with the same developer for another 15 seconds to form a negative image, i.e., the unexposed portions of the film were removed, leaving only the pattern-exposed portions.

[0136] Those skilled in the art will appreciate that changes may be made in the embodiments described above without departing from the broader concept of the present invention. It is understood, therefore, that the invention is not limited to the particular embodiments disclosed, but is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.

Claims

1. A monoorganotin trialkoxide compound having formula (1) having a purity of at least about 95 mole percent and containing less than about 5 mole percent diorganotin dialkoxide compounds having formula (2). R'Sn(OR) 3 (1) R' 2 Sn(OR) 2 (2) (wherein R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms).

2. 2. The monoorganotin trialkoxide compound according to claim 1, wherein R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from 2 to about 10 carbon atoms, and each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 5 carbon atoms.

3. 3. The monoorganotin trialkoxide compound of claim 1 or 2, wherein the content of diorganotin dialkoxide having formula (2) is less than about 1 mole %.

4. 4. The monoorganotin trialkoxide compound of claim 1, wherein the total tetrakis(alkoxy)tin content is less than about 1 mole percent.

5. 5. The monoorganotin trialkoxide compound of claim 1, wherein the total content of tris(alkenyl)tin compounds is less than about 1 mole percent.

6. 6. The monoorganotin trialkoxide compound according to claim 1, wherein R′ is vinyl, allyl, 1-propenyl, 3-buten-1-yl, 3-buten-2-yl, 2-methylallyl, or 3-methyl-2-buten-1-yl, and each R is independently optionally fluorinated methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or t-butyl.

7. 7. The monoorganotin trialkoxide compound of any one of claims 1 to 6, wherein the compound having formula (1) is selected from the following: 【Chemical 1】

8. A monoorganotin trialkoxide compound having the formula (1): R'Sn(OR) 3 (1) (wherein R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms).

9. 9. The monoorganotin trialkoxide compound according to claim 8, wherein R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having 2 to about 10 carbon atoms, and each R is independently a linear or branched, optionally fluorinated alkyl group having about 1 to about 5 carbon atoms.

10. 10. The organotin monoalkoxide compound according to claim 8 or 9, wherein R′ is vinyl, allyl, 1-propenyl, 3-buten-1-yl, 3-buten-2-yl, 2-methylallyl, or 3-methyl-2-buten-1-yl, and R each independently represents optionally fluorinated methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or t-butyl.

11. 11. The monoorganotin trialkoxide compound according to any one of claims 8 to 10, wherein the compound having formula (1) is selected from the following: 【Chemistry 2】

12. 1. A method for synthesizing monoorganotin trialkoxide compounds having formula (1) having a purity of at least about 95 mole percent and containing less than about 5 mole percent diorganotin dialkoxide compounds having formula (2), comprising: 3 with a compound of formula (I) wherein X is a halogen atom or an alkoxy group. R'Sn(OR) 3 (1) R' 2 Sn(OR) 2 (2) (wherein R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R independently has a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms).

13. (a) preparing a solution of an alkali metal alkoxide; (b) R'SnCl at about -10°C to about 10°C 3 to prepare a crude product, wherein the amount of alkali metal alkoxide added is R'SnCl 3 at least about 3.03 equivalents relative to the amount of (c) distilling the crude product to obtain a product containing up to about 5 mole percent of a monoorganotin trialkoxide having formula (1) and a diorganotin dialkoxide having formula (2); 13. The method of claim 12, comprising:

14. 14. The method of claim 12 or 13, wherein the content of diorganotin dialkoxide having formula (2) is less than about 1 mol %.

15. 15. The method of any one of claims 12 to 14, wherein the total tetrakis(alkoxy)tin content is less than about 1 mol%.

16. 16. The method of any one of claims 12 to 15, wherein R' is vinyl, allyl, 1-propenyl, 3-buten-1-yl, 3-buten-2-yl, 2-methylallyl, or 3-methyl-2-buten-1-yl, and each R is independently optionally fluorinated methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or t-butyl.

17. 17. The process of any one of claims 12 to 16, wherein the reaction is carried out in a solvent containing more than about 50% by volume of a hydrocarbon solvent and / or an aromatic solvent.

18. 18. The method of any one of claims 12 to 17, wherein the reaction is carried out substantially without exposure to light.

19. A method for synthesizing a monoorganotin trialkoxide compound having the formula (1), comprising: 3 with a compound of formula (I) wherein X is a halogen atom or an alkoxy group. R'Sn(OR) 3 (1) R' 2 Sn(OR) 2 (2) (wherein R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R independently has a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms).

20. (a) preparing a solution of an alkali metal alkoxide; (b) R'SnCl at about -10°C to about 10°C 3 to prepare a crude product, wherein the amount of alkali metal alkoxide added is R'SnCl 3 at least about 3.03 equivalents relative to the amount of (c) distilling the crude product to obtain a monoorganotin trialkoxide having formula (1); 20. The method of claim 19, comprising:

21. 21. The method of claim 19 or 20, wherein R' is vinyl, allyl, 1-propenyl, 3-buten-1-yl, 3-buten-2-yl, 2-methylallyl, or 3-methyl-2-buten-1-yl, and each R is independently optionally fluorinated methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or t-butyl.

22. 22. The process of any one of claims 19 to 21, wherein the reaction is carried out in a solvent containing more than about 50% by volume of a hydrocarbon solvent and / or an aromatic solvent.

23. 23. The method of any one of claims 19 to 22, carried out substantially without exposure to light.

24. 10. A method for storing a sample of a mono-organotin trialkoxide compound having formula (1) according to claim 1, comprising storing the sample of the mono-organotin trialkoxide compound having formula (1) at a temperature of less than about 30° C. without substantial exposure to light.

25. 25. The method of claim 24, wherein the sample of the monoorganotin trialkoxide compound having formula (1) is stored for about 3 days to about 1 year.

26. 26. The method of claim 24 or 25, wherein a sample of the monoorganotin trialkoxide is substantially undecomposed after a storage period of about 3 days to about 1 year.

27. 27. The method of any one of claims 24 to 26, comprising storing the compound having formula (1) in a container under an inert atmosphere.

28. 28. The method of any one of claims 24 to 27, comprising storing the compound having formula (1) in a container substantially without exposure to light.

29. A method for storing a sample of a monoorganotin trialkoxide compound having the formula (1) according to claim 8, the method comprising the step of storing the sample of the monoorganotin trialkoxide compound having the formula (1) at a temperature of less than about 30 °C without substantially exposing it to light.

30. The method according to claim 29, wherein the sample of the monoorganotin trialkoxide compound having the formula (1) is stored for about 3 days to about 1 year.

31. The method according to claim 29 or 30, wherein the sample of the monoorganotin trialkoxide is substantially not decomposed after a storage period of about 3 days to about 1 year.

32. The method according to any one of claims 29 to 31, comprising the step of storing the compound having the formula (1) in a container in an inert atmosphere.

33. The method according to any one of claims 29 to 32, comprising the step of storing the compound having the formula (1) in a container without substantially exposing it to light.

34. An organotin compound having the formula (3). R'SnO (3 / 2-x / 2) (OH) x (3) (Where 0 < x < 3, R' is linear or branched and is an optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms)

35. The organotin compound having the formula (3) according to claim 34, obtained by hydrolysis of the compound having the formula (1). R'Sn(OR) 3 (1) (Where each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms)

36. A solution comprising the organotin compound having the formula (3) according to claim 34 or 35 and an organic solvent.

37. The solution according to claim 36, wherein the compound having the formula (3) is obtained by hydrolysis of the compound having the formula (1). R'Sn(OR) 3 (1) (Where each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms)

38. A film comprising the organotin compound having the formula (3) according to claim 34.

39. The film according to claim 38, wherein the compound having the formula (3) is obtained by hydrolysis of the compound having the formula (1). R'Sn(OR) 3 (1) (Where each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms)

40. The monoorganotin trialkoxide compound having the formula (1) according to claim 1 and R'SnX 3 A composition comprising a compound (wherein X is a halogen atom or an alkoxy group).

41. The monoorganotin trialkoxide compound having the formula (1) according to claim 8 and R'SnX 3 A composition comprising a compound (wherein X is a halogen atom or an alkoxy group).

42. A composition comprising an organotin compound having the formula (3) and an organotin compound having the formula (4). R'SnO (3 / 2-x / 2) (OH) x (3) R''SnO (3 / 2-x / 2) (OH) x (4) (where 0 < x < 3, R' is linear or branched, an optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and R'' is an optionally substituted hydrocarbon group having from about 2 to about 20 carbon atoms)

43. The composition according to claim 42, wherein at least one of the compound having the formula (3) and the compound having the formula (4) is obtained by hydrolysis of a monoorganotin trialkoxide compound having the formula (1). R'Sn(OR) 3 (1) (where each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms)

44. A solution comprising the composition according to claim 42 or 43 and an organic solvent.

45. The solution according to claim 44, wherein at least one of the compound having the formula (3) and the compound having the formula (4) is obtained by hydrolysis of a monoorganotin trialkoxide compound having the formula (1). R'Sn(OR) 3 (1) (where each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms)

46. A film comprising the composition according to claim 42 or 43.

47. The film according to claim 46, wherein at least one of the compound having the formula (3) and the compound having the formula (4) is obtained by hydrolysis of a monoorganotin trialkoxide compound having the formula (1). R'Sn(OR) 3 (1) (where each R is independently a linear or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms)

Images