High-purity tin compound containing unsaturated substituent and preparation method thereof

Abstract

Mono-organotin trialkoxylate compounds having the formula R 'Sn (OR) 3 and containing less than about 5 mol% of diorganotin dialkoxylate are described. 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 of synthesizing and purifying these compounds are also provided. The single organotin compounds can be used to form high resolution EUV lithography patterning precursors and have attractive force due to their high purity and minimal concentration of diorganotin impurities.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to co-pending U.S. Provisional Application No. 63 / 397,541, filed on August 12, 2022, the disclosure of which is incorporated herein by reference. Background Art

[0003] As semiconductor manufacturing continues to advance, feature sizes continue to shrink, driving the need for new processing methods. Certain organotin compounds have proven useful for the deposition of tin oxide hydroxide coatings in applications such as extreme ultraviolet (EUV) lithography. For example, tin compounds containing unsaturated substituents provide radiation-sensitive Sn-C bonds that can be used to pattern structures in lithography.

[0004] Materials used in microelectronics manufacturing need to be very pure, with strict limits on organic contamination (e.g., reaction byproducts), metal contamination, and particle contamination. Purity requirements are often stringent, especially for photolithography applications, because the chemicals come into contact with the semiconductor substrate, and organic metal impurities in compounds such as diisopropylbis(dimethylamino)tin (iPr)2Sn(NMe2)2 can affect the properties of the resulting film. The exact purity target is determined by a variety of factors, including performance specifications, but a typical minimum purity target is 3N+. Residual metals present in the chemicals can deposit onto the semiconductor substrate and degrade the electrical performance of the manufactured device. Typical specifications for metals are less than 10 ppb for individual metals and no more than ~100 ppb for total metals.

[0005] Processing and properties of semiconductor materials can also be sensitive to dialkyltin contaminants. Dialkyltin impurities such as R2Sn(NMe2)2 (where R is an alkyl group) are a source of outgassing after vapor deposition or spin coating processes due to less dense oxostanate cluster films when the film contains a dialkyl group. Proper control of dialkyltin contaminants is required to produce microelectronics using EUV lithography. The high purity required for the manufacturing process of monoalkyltin precursors becomes a challenge. Typically, the synthesis of monoalkyltin triamides previously uses a lithium dimethylamide reagent reacted with an alkyltin trichloride, or subsequently uses a lithium / Grignard reagent (alkylating agent) to convert the tetraamide tin to the desired triamide.

[0006] However, similar synthetic methods are not suitable for the synthesis of tin compounds containing unsaturated substituents such as vinyl, allyl or alkenyl groups. In contrast, the strong base of lithium dimethylamide will react not only with the tin-chlorine bond, but also with double or triple bonds on the organic substituent. Furthermore, even when the correct stoichiometry is used, primary and secondary monoorganotin compounds cannot be synthesized from alkylating agents and tetraamides: primary alkylating agents convert tetraamide tin to trialkyltin amide and unreacted tetraamide, and secondary alkylating agents convert tetraamide tin to polyalkyltin compounds.

[0007] Furthermore, monoalkenyltin trialkoxides cannot be prepared by reaction of the corresponding tin triamides with alcohols, and reaction of organotin trichlorides with dialkylamines followed by alcohols yields a mixture of products.

[0008] Graf(“Tin,Tin Alloys,and Tin Compounds,” Ullmann's Encyclopedia of Industrial Chemistry ; Weinheim: Wiley-VCH (2005)) reported the use of Kocheshkov reduction reaction to prepare monoorganotin trichlorides containing vinyl or allyl substituents in the absence of catalyst or heating; electron-donating groups make reduction possible. Thus, unsaturated / electron-donating groups from alkenyl or alkoxy groups can promote Kocheshkov-like reduction during the reaction, especially when monovinyl or monoallyltin trialkoxy compounds are prepared according to scheme (I) shown below, as well as disproportionation during purification scheme (II), resulting in a mixture of products.

[0009]

[0010] The ability to prepare and isolate trialkoxytin compounds containing unsaturated groups and having the desired high purity levels has not been reported before. Such high purity tin compounds are very attractive for use in the microelectronics industry. Summary of the invention

[0011] In one embodiment, aspects of the present disclosure relate to a monoorganotin trialkoxylate compound having formula (1) having a purity of at least about 95 mol % and containing less than about 5 mol % of a diorganotin dialkoxylate compound having formula (2):

[0012] R'Sn(OR)3(1)

[0013] R'2Sn(OR)2(2)

[0014] 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.

[0015] In a second embodiment, aspects of the present disclosure relate to monoorganotin trialkoxylate compounds having formula (1):

[0016] R'Sn(OR)3(1)

[0017] Wherein R’ is a straight-chain or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R is independently a straight-chain or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms.

[0018] In another embodiment, aspects of the present disclosure relate to a method for synthesizing a monoorganotin trialkoxide compound having the formula (1), the monoorganotin trialkoxide compound 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):

[0019] R’Sn(OR)3 (1)

[0020] R’2Sn(OR)2 (2)

[0021] Wherein R’ is a straight-chain or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R is independently a straight-chain or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms, the method comprising reacting an alkali metal alkoxide with an R’SnX3 compound, wherein X is a halogen atom or an alkoxy group.

[0022] Aspects of the present disclosure also relate to a method for synthesizing a monoorganotin trialkoxide compound having the formula (1):

[0023] R’Sn(OR)3 (1)

[0024] R’2Sn(OR)2 (2)

[0025] Wherein R’ is a straight-chain or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R is independently a straight-chain or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms, the method comprising reacting an alkali metal alkoxide with an R’SnX3 compound, wherein X is a halogen atom or an alkoxy group.

[0026] Additional aspects of the present disclosure relate to an organotin compound having the formula (3):

[0027] R’SnO (3 / 2-x / 2) (OH) x (3)

[0028] Where 0 < x < 3 and R’ is a straight-chain or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms.

[0029] Additional aspects of the present disclosure relate to a composition comprising an organotin compound having the formula (3) and an organotin compound having the formula (4):

[0030] R’SnO(3 / 2-x / 2) (OH) x (3)

[0031] R”SnO (3 / 2-x / 2) (OH) x (4)

[0032] where 0 < x < 3, R’ is a straight-chain 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.

[0033] Advantageous improvements of the invention that can be implemented individually or in combination are specified in the dependent claims.

[0034] In summary, the following embodiments are proposed as particularly preferred within the scope of the present invention:

[0035] Embodiment 1: A mono-organotin trialkoxide compound having the formula (1), having a purity of at least about 95 mol% and containing less than about 5 mol% of a di-organotin dialkoxide compound having the formula (2):

[0036] R’Sn(OR)3 (1)

[0037] R’2Sn(OR)2 (2)

[0038] where R’ is a straight-chain or branched, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and each R is independently a straight-chain or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms.

[0039] Embodiment 2: The mono-organotin trialkoxide compound according to Embodiment 1, wherein R’ is a straight-chain or branched, optionally fluorinated unsaturated hydrocarbon group having from 2 to about 10 carbon atoms, and each R is independently a straight-chain or branched, optionally fluorinated alkyl group having from about 1 to about 5 carbon atoms.

[0040] Embodiment 3: The mono-organotin trialkoxide compound according to Embodiment 1 or 2, wherein the content of the di-organotin dialkoxide having the formula (2) is less than about 1 mol%.

[0041] Embodiment 4: The mono-organotin trialkoxide compound according to any one of Embodiments 1 to 3, wherein the total content of tetra(alkoxy)tin is less than about 1 mol%.

[0042] Embodiment 5: The mono-organotin trialkoxide compound according to any one of Embodiments 1 to 4, wherein the total content of tri(alkenyl)tin compounds is less than about 1 mol%.

[0043] Embodiment 6: A monoorganotin trialkoxide compound according to any one of embodiments 1 to 5, 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 methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, which is optionally fluorinated.

[0044] Embodiment 7: A monoorganotin trialkoxylate compound according to any one of Embodiments 1 to 6, wherein the compound of formula (1) is selected from:

[0045]

[0046] Embodiment 8: Monoorganotin trialkoxylate compound having formula (1):

[0047] R'Sn(OR)3(1)

[0048] 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.

[0049] Embodiment 9: A monoorganotin trialkoxylate compound according to embodiment 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 an optionally fluorinated linear or branched alkyl group having about 1 to about 5 carbon atoms.

[0050] Embodiment 10: A monoorganotin trialkoxide compound according to 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 methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, which is optionally fluorinated.

[0051] Embodiment 11: A monoorganotin trialkoxide compound according to any one of Embodiments 8 to 10, wherein the compound of formula (1) is selected from:

[0052]

[0053] Embodiment 12: A method for synthesizing a monoorganotin trialkoxylate compound having formula (1) having a purity of at least about 95 mol % and containing less than about 5 mol % of a diorganotin dialkoxylate compound having formula (2):

[0054] R'Sn(OR)3(1)

[0055] R'2Sn(OR)2(2)

[0056] 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, the method comprising reacting an alkali metal alkoxide with a R'SnX3 compound, wherein X is a halogen atom or an alkoxy group.

[0057] Embodiment 13: The method according to embodiment 12, comprising:

[0058] (d) preparing a solution of an alkali metal alkoxide;

[0059] (e) adding R'SnCl3 at a temperature of 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 to produce a crude product; and

[0060] (f) distilling the crude product to produce a product containing a monoorganotin trialkoxylate having formula (1) and no more than about 5 mole percent of a diorganotin dialkoxylate having formula (2).

[0061] Embodiment 14: The method of embodiment 12 or 13, wherein the content of diorganotin dialkoxylate having formula (2) is less than about 1 mol%.

[0062] Embodiment 15: The method of any one of Embodiments 12 to 14, wherein the total tetra(alkoxy)tin content is less than about 1 mol %.

[0063] Embodiment 16: A method according to 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 methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, optionally fluorinated.

[0064] 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.

[0065] Embodiment 18: The method of any one of Embodiments 12 to 17, wherein the reaction is performed in the substantial absence of light exposure.

[0066] Embodiment 19: A method for synthesizing a monoorganotin trialkoxylate compound having formula (1):

[0067] R'Sn(OR)3(1)

[0068] R'2Sn(OR)2(2)

[0069] 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, the method comprising reacting an alkali metal alkoxide with a R'SnX3 compound, wherein X is a halogen atom or an alkoxy group.

[0070] Embodiment 20: The method according to embodiment 19, comprising:

[0071] (d) preparing a solution of an alkali metal alkoxide;

[0072] (e) adding R'SnCl3 at a temperature of 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 to produce a crude product; and

[0073] (f) distilling the crude product to produce a monoorganotin trialkoxylate having formula (1).

[0074] Embodiment 21: A method according to 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 methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, which is optionally fluorinated.

[0075] 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.

[0076] Embodiment 23: The method of any one of Embodiments 19 to 22, wherein the method is performed in the substantial absence of light exposure.

[0077] Embodiment 24: A method for storing a sample of the monoorganotintrialkoxylate compound having formula (1) described in Embodiment 1, the method comprising storing the sample of the monoorganotintrialkoxylate compound having formula (1) in the absence of substantial light exposure and at a temperature of less than about 30°C.

[0078] Embodiment 25: The method according to Embodiment 24, wherein a sample of the mono-organotin trialkoxide compound having the formula (1) is stored for about three days to about one year.

[0079] Embodiment 26: The method according to Embodiment 24 or 25, wherein the sample of the mono-organotin trialkoxide substantially does not undergo decomposition after a storage time of about three days to about one year.

[0080] Embodiment 27: The method according to any one of Embodiments 24 to 26, which includes storing the compound having the formula (1) in a container in an inert atmosphere.

[0081] Embodiment 28: The method according to any one of Embodiments 24 to 27, which includes storing the compound having the formula (1) in a container substantially free of light exposure.

[0082] Embodiment 29: A method of storing a sample of a mono-organotin trialkoxide compound having the formula (1) according to Embodiment 8, the method including storing the sample of the mono-organotin trialkoxide compound having the formula (1) in the absence of substantially light exposure and at a temperature of less than about 30 °C.

[0083] Embodiment 30: The method according to Embodiment 29, wherein the sample of the mono-organotin trialkoxide compound having the formula (1) is stored for about three days to about one year.

[0084] Embodiment 31: The method according to Embodiment 29 or 30, wherein the sample of the mono-organotin trialkoxide substantially does not undergo decomposition after a storage time of about three days to about one year.

[0085] Embodiment 32: The method according to any one of Embodiments 29 to 31, which includes storing the compound having the formula (1) in a container in an inert atmosphere.

[0086] Embodiment 33: The method according to any one of Embodiments 29 to 32, which includes storing the compound having the formula (1) in a container substantially free of light exposure.

[0087] Embodiment 34: An organotin compound having the formula (3):

[0088] R’SnO (3 / 2-x / 2) (OH) x (3)

[0089] where 0 < x < 3 and R’ is a straight-chain or branched-chain, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms.

[0090] Embodiment 35: An organotin compound of formula (3) according to embodiment 34, wherein the compound of formula (3) is obtained by hydrolyzing a compound of formula (1):

[0091] R'Sn(OR)3(1)

[0092] wherein each R is independently a straight or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms.

[0093] Embodiment 36: A solution comprising the organotin compound of formula (3) according to embodiment 34 or 35 and an organic solvent.

[0094] Embodiment 37: A solution according to embodiment 36, wherein the compound of formula (3) is obtained by hydrolyzing a compound of formula (1):

[0095] R'Sn(OR)3(1)

[0096] wherein each R is independently a straight or branched chain optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms.

[0097] Embodiment 38: A film comprising the organotin compound of formula (3) described in Embodiment 34.

[0098] Embodiment 39: A membrane according to embodiment 38, wherein the compound having formula (3) is obtained by hydrolyzing a compound having formula (1):

[0099] R'Sn(OR)3(1)

[0100] wherein each R is independently a straight or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms.

[0101] Embodiment 40: A composition comprising the monoorganotin trialkoxylate compound having the formula (1) according to Embodiment 1 and a R'SnX3 compound, wherein X is a halogen atom or an alkoxy group.

[0102] Embodiment 41: A composition comprising a monoorganotin trialkoxylate compound having formula (1) according to Embodiment 8 and a R'SnX3 compound, wherein X is a halogen atom or an alkoxy group.

[0103] Embodiment 42: A composition comprising an organotin compound having formula (3) and an organotin compound having formula (4):

[0104] R'SnO (3 / 2-x / 2) (OH) x (3)

[0105] R”SnO (3 / 2-x / 2) (OH) x (4)

[0106] where 0 < x < 3, R’ is a straight-chain or branched, optionally fluorinated unsaturated hydrocarbyl group having from about 2 to about 20 carbon atoms, and R” is an optionally substituted hydrocarbyl group having from about 2 to about 20 carbon atoms.

[0107] 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-organotin trialkoxide compound having the formula (1):

[0108] R’Sn(OR)3 (1)

[0109] where each R is independently a straight-chain or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms.

[0110] Embodiment 44: A solution comprising the composition according to Embodiment 42 or 43 and an organic solvent.

[0111] Embodiment 45: The solution according to Embodiment 44, 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-organotin trialkoxide compound having the formula (1):

[0112] R’Sn(OR)3 (1)

[0113] where each R is independently a straight-chain or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms.

[0114] Embodiment 46: A film comprising the composition according to Embodiment 42 or 43.

[0115] Embodiment 47: The film according to Embodiment 46, 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-organotin trialkoxide compound having the formula (1):

[0116] R’Sn(OR)3 (1)

[0117] where each R is independently a straight-chain or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms. Description of the Drawings

[0118] The foregoing summary of the invention as well as the following detailed description of the invention will be better understood when read in conjunction with the accompanying drawings. For the purpose of illustrating the invention, presently preferred embodiments are shown in the accompanying drawings. However, it should be understood that the invention is not limited to the precise arrangements and instrumentalities shown. In the accompanying drawings:

[0119] Figure 1 is an ESI-mass spectrum of a compound according to one embodiment of the present disclosure. DETAILED DESCRIPTION

[0120] According to one aspect of the present disclosure, a monoorganotin trialkoxylate compound of formula (1) is provided. For the purposes of the present disclosure, the term "monoorganic group" refers to a substituent containing a single unsaturated primary or secondary hydrocarbon group having at least two carbon atoms (i.e., an alkene group or an alkynyl group in a primary or secondary position relative to tin). The compound of formula (1) preferably has a purity of at least about 95 mol%, and preferably contains no more than about 5 mol% of a diorganotin dialkoxylate compound of formula (2) relative to the total amount of tin, 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%, even more preferably no more than about 0.1 mol%.

[0121] R'Sn(OR)3(1)

[0122] R'2Sn(OR)2(2)

[0123] In formula (1) and (2), R' is a linear or branched, optionally fluorinated unsaturated hydrocarbon group, such as alkenyl or alkynyl, 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, 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, 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, tert-butyl, etc., vinyl, ethenyl, allyl, 1-propenyl, 3-buten-1-yl, 3-buten-2-yl, 2-methylallyl and 3-methyl-2-buten-1-yl.

[0124] Exemplary compounds of formula (1) according to this aspect of the present disclosure include, but are not limited to, tri(methoxy)vinyltin, tri(ethoxy)vinyltin, tri(n-propoxy)vinyltin, tri(isopropoxy)vinyltin, tri(n-butoxy)vinyltin, tri(isobutoxy)vinyltin, tri(tert-butoxy)vinyltin, tri(methoxy)allyltin, tri(ethoxy)allyltin, tri(n-propoxy)allyltin, tri(isopropoxy)allyltin, tri(n-butoxy)allyltin , tri(isobutoxy)allyltin, tri(tert-butoxy)allyltin, 1-propenyltri(methoxy)tin, 1-propenyltri(ethoxy)tin, 1-propenyltri(n-propoxy)tin, 1-propenyltri(isopropoxy)tin, 1-propenyltri(n-butoxy)tin, 1-propenyltri(isobutoxy)tin, 1-propenyltri(tert-butoxy)tin, 3-buten-1-yltri(methoxy)tin, 3-buten-1-yltri(ethoxy)tin, 3-buten-1-yltri(n-propoxy)tin , 3-butene-1-yltri(isopropoxy)tin, 3-butene-1-yltri(n-butoxy)tin, 3-butene-1-yltri(isobutoxy)tin, 3-butene-1-yltri(tert-butoxy)tin, 3-butene-2-yltri(methoxy)tin, 3-butene-2-yltri(ethoxy)tin, 3-butene-2-yltri(n-propoxy)tin, 3-butene-2-yltri(isopropoxy)tin, 3-butene-2-yltri(n-butoxy)tin, 3-butene-2-yltri(isobutoxy)tin, 3-Buten-2-yltri(tert-butoxy)tin, 3-methyl-2-buten-1-yltri(methoxy)tin, 3-methyl-2-buten-1-yltri(ethoxy)tin, 3-methyl-2-buten-1-yltri(n-propoxy)tin, 3-methyl-2-buten-1-yltri(isopropoxy)tin, 3-methyl-2-buten-1-yltri(n-butoxy)tin, 3-methyl-2-buten-1-yltri(isobutoxy)tin and 3-methyl-2-buten-1-yltri(tert-butoxy)tin.

[0125] The term "optionally fluorinated" means that at least one hydrogen atom in the hydrocarbon group in R' or the alkyl group in R is replaced by a fluorine atom; one, two or even all hydrogen atoms in the hydrocarbon group or the alkyl group are replaced by fluorine atoms (commonly referred to as perfluorination) are also within the scope of the present invention. Most preferably, only the R group is optionally fluorinated, so that one, two or even all hydrogen atoms in the alkyl group are replaced by fluorine atoms.

[0126] Exemplary fluorinated compounds of 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-methylpropane-2-yl)oxy)bis((1,1,1-trifluoropropane-2-yl)oxy)(vinyl)stannane, ((1,1,1,3,3,3-hexafluoro-2-methylpropane-2-yl)oxy)bis((1,1,1,3,3,3-hexafluoro ... bis((1,1,1-trifluoro-2-methylpropane-2-yl)oxy)(vinyl)stannane, allylbis((1,1,1-trifluoro-2-methylpropane-2-yl)oxy)((1,1,1-trifluoropropane-2-yl)oxy)stannane, allyl((1,1,1,3,3,3-hexafluoro-2-methylpropane-2-yl)oxy)bis((1,1,1,3,3,3-hexafluoropropane-2-yl)oxy)stannane, tris((1,1,1-trifluoro-2-methylpropane-2-yl)oxy)(vinyl) Stannane, tris((1,1,1,3,3,3-hexafluoro-2-methylpropane-2-yl)oxy)(vinyl)stannane, tris((1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propane-2-yl)oxy)(vinyl)stannane, allyl tris((1,1,1-trifluoro-2-methylpropane-2-yl)oxy)stannane, allyl tris((1,1,1,3,3,3-hexafluoro-2-methylpropane-2-yl)oxy)stannane, allyl tris((1,1,1,3,3,3-hexafluoro-2-methylpropane-2-yl)oxy)stannane, ,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.

[0127] All numerical ranges expressed in the present disclosure encompass all values ​​within the range, including fractions and small numbers. Therefore, 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 by 119Sn NMR is not detectable, ie, in some embodiments, the compound of formula (2) is not detectable in a sample of the compound of formula (1).

[0128] In some embodiments, the content of tetra(alkoxy)tin in the monoorganotin trialkoxylate compound of 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 total content of tri(alkenyl)tin compounds in the monoorganotin trialkoxylate compound of 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%.

[0129] According to another aspect of the present disclosure, a monoorganotin trialkoxylate compound having formula (1) is provided. For the purposes of the present disclosure, the term "monoorganic group" refers to a substituent containing a single unsaturated primary or secondary hydrocarbon group having at least two carbon atoms (i.e., an alkenyl group or an alkynyl group in a primary or secondary position relative to tin).

[0130] R'Sn(OR)3(1)

[0131] 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, most preferably from about 2 to about 3 carbons, such as alkenyl or alkynyl, 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, 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, tert-butyl, etc. Presently preferred R' groups include, but are not limited to, vinyl, allyl, 1-propenyl, 3-buten-1-yl, 2-methylallyl, 3-buten-2-yl, and 3-methyl-2-buten-1-yl.

[0132] Exemplary compounds of formula (1) according to this aspect of the present disclosure include, but are not limited to, tri(methoxy)vinyltin, tri(ethoxy)vinyltin, tri(n-propoxy)vinyltin, tri(isopropoxy)vinyltin, tri(n-butoxy)vinyltin, tri(isobutoxy)vinyltin, tri(tert-butoxy)vinyltin, tri(methoxy)allyltin, tri(ethoxy)allyltin, tri(n-propoxy)allyltin, tri(isopropoxy)allyltin, tri(n-butoxy)allyltin , tri(isobutoxy)allyltin, tri(tert-butoxy)allyltin, 1-propenyltri(methoxy)tin, 1-propenyltri(ethoxy)tin, 1-propenyltri(n-propoxy)tin, 1-propenyltri(isopropoxy)tin, 1-propenyltri(n-butoxy)tin, 1-propenyltri(isobutoxy)tin, 1-propenyltri(tert-butoxy)tin, 3-buten-1-yltri(methoxy)tin, 3-buten-1-yltri(ethoxy)tin, 3-buten-1-yltri(n-propoxy)tin , 3-butene-1-yltri(isopropoxy)tin, 3-butene-1-yltri(n-butoxy)tin, 3-butene-1-yltri(isobutoxy)tin, 3-butene-1-yltri(tert-butoxy)tin, 3-butene-2-yltri(methoxy)tin, 3-butene-2-yltri(ethoxy)tin, 3-butene-2-yltri(n-propoxy)tin, 3-butene-2-yltri(isopropoxy)tin, 3-butene-2-yltri(n-butoxy)tin, 3-butene-2-yltri(isobutoxy)tin, 3-Buten-2-yltri(tert-butoxy)tin, 3-methyl-2-buten-1-yltri(methoxy)tin, 3-methyl-2-buten-1-yltri(ethoxy)tin, 3-methyl-2-buten-1-yltri(n-propoxy)tin, 3-methyl-2-buten-1-yltri(isopropoxy)tin, 3-methyl-2-buten-1-yltri(n-butoxy)tin, 3-methyl-2-buten-1-yltri(isobutoxy)tin and 3-methyl-2-buten-1-yltri(tert-butoxy)tin.

[0133] The term "optionally fluorinated" means that at least one hydrogen atom in the hydrocarbon group in R' or the alkyl group in R is replaced by a fluorine atom; one, two or even all hydrogen atoms in the hydrocarbon group or the alkyl group are replaced by fluorine atoms (commonly referred to as perfluorination) are also within the scope of the present invention. Most preferably, only the R group is optionally fluorinated, so that one, two or even all hydrogen atoms in the alkyl group are replaced by fluorine atoms.

[0134] Exemplary fluorinated compounds having formula (1) include, but are not limited to, tris(trifluoromethoxy)(vinyl)stannane, allyltris(trifluoromethoxy)stannane, ((1,1,1-trifluoro-2-methylpropane-2-yl)oxy)bis((1,1,1-trifluoropropane-2-yl)oxy)(vinyl)stannane, ((1,1,1,3,3,3-hexafluoro-2-methylpropane-2-yl)oxy)bis((1,1,1,3,3,3-hexafluoropropane-2-yl)oxy 1,1,1-trifluoro-2-methylpropane-2-yl)oxy)(vinyl)stannane, allylbis((1,1,1-trifluoro-2-methylpropane-2-yl)oxy)((1,1,1-trifluoropropane-2-yl)oxy)stannane, allyl((1,1,1,3,3,3-hexafluoro-2-methylpropane-2-yl)oxy)bis((1,1,1,3,3,3-hexafluoropropane-2-yl)oxy)stannane, tris((1,1,1-trifluoro-2-methylpropane-2-yl)oxy)(vinyl)stannane, tris( (1,1,1,3,3,3-hexafluoro-2-methylpropane-2-yl)oxy)(vinyl)stannane, tris((1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propane-2-yl)oxy)(vinyl)stannane, allyl tris((1,1,1-trifluoro-2-methylpropane-2-yl)oxy)stannane, allyl tris((1,1,1,3,3,3-hexafluoro-2-methylpropane-2-yl)oxy)stannane, allyl tris((1,1,1,3,3,3-hexafluoro-2-methylpropane-2-yl)oxy)stannane, 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.

[0135] Organometallic tin compounds having formula (1) can be used to form high-resolution EUV lithography patterning precursors and are attractive due to their electron density, Sn-C bond strength and free radical formation as well as the potential for reducing EUV dose time.

[0136] Particularly preferred compounds of formula (1) are shown below:

[0137]

[0138] Synthesis method

[0139] Aspects of the present disclosure further relate to methods for synthesizing high purity tin compounds of formula (1) as described above, which are suitable for use in the microelectronics industry and preferably contain low levels of diorganotin compounds of formula (2). One method comprises reacting an organotin trichloride with an alkali metal alkoxide (weak base) at a controlled molar ratio and temperature to introduce water-reactive alkoxide groups into the tin moiety without affecting the unsaturated substituents. If desired, after initial purification, fractionation can be used to further reduce the levels of diorganotin compounds and other minor impurities.

[0140] 119 Sn NMR spectroscopy is ideally suited for the quantitative analysis of monoorganotin compounds (containing alkenyl and alkynyl substituents) due to its high sensitivity to small structural changes and large spectral range of 6500 ppm (see Davies et al., Eds.; Tin Chemistry:Fundamentals,Frontiers,andApplications ; Wiley (2008)). This allows easy identification and quantification of single organotin compounds and their impurities because 119 Sn resonances are highly resolved. Compared with other analytical methods such as GC, HPLC or 1 Compared with H NMR, 119 Sn NMR has reduced sensitivity. To improve sensitivity, the mono-organotin compounds were analyzed without dilution and a large number of spectral acquisitions (2000+) were obtained to measure the low-level impurities described in this work. Using this approach, detection limits as low as 0.1 mol% di-organotin dialkoxylates can be achieved.

[0141] Described in this article 119 Sn NMR data were obtained using a relative purity method similar to that described in J. Med. Chem. (57, 22, 9220–9231 (2014)). 1 H decoupling was performed using a 40° pulse, a 1 second relaxation delay, and sufficient scans to obtain 119 Sn NMR spectrum to achieve the required sensitivity. The samples were prepared without dilution in deuterated 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 different tin compound, and the area of ​​each peak represents the concentration or purity (in mol%) of the compound.

[0142] According to aspects of the present disclosure, a method of synthesizing a monoorganotin trialkoxylate compound having formula (1) comprises reacting an alkali metal alkoxylate with a R'SnX3 compound, wherein X is a halogen atom or an alkoxy group.

[0143] Preferably, the method comprises preparing a solution of the desired concentration of an alkali metal alkoxide in an appropriate solvent such as anhydrous hexane, and then cooling the solution to a low temperature, such as but not limited to about 0°C to about -10°C, to react with the R'SnX3 compound. For example, if the desired compound of formula (1) is allyl tri(tert-butoxy)tin, the alkali metal alkoxide can be tert-butoxy potassium, tert-butoxy sodium or tert-butoxy lithium. The concentration of the alkali metal alkoxide is preferably up to about 10 to 15 weight percent relative to the amount of solvent, more preferably about 8 to 10 weight percent. Suitable solvents and concentrations can be determined by routine experimentation and based on the commercial availability of the desired alkali metal alkoxide.

[0144] For the methods and steps described herein, preferred solvents include hydrocarbon solvents (such as, but not limited to, hexane, hexanes, heptane, and cyclohexane) and aromatic solvents (such as, but not limited to, toluene and xylene).

[0145] Suitable R'SnX3 compounds are compounds wherein X is a halogen atom (e.g., fluorine, bromine, or preferably chlorine) or an alkoxy group (e.g., an alkoxy group containing from about 1 to about 5 carbon atoms, such as the currently preferred methyl, ethyl, propyl, or butyl group). Most preferably, the R'SnX3 compound is R'SnCl3. After the alkali metal alkoxide is reacted with the R'SnX3 compound, the reaction mixture is post-treated and purified using methods well known in the art to produce a compound having formula (1).

[0146] In some embodiments, the method comprises:

[0147] (a) preparing a solution of an alkali metal alkoxide;

[0148] (b) adding R'SnCl3 at a temperature of 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 to produce a crude product; and

[0149] (c) distilling the crude product to produce a monoorganotin trialkoxylate having the formula (1).

[0150] These steps are described in further detail below.

[0151] According to other aspects of the present disclosure, another method for preparing a monoorganotin trialkoxylate compound having formula (1) involves the following steps, each of which is described in further detail below:

[0152] (a) preparing a solution of an alkali metal alkoxide;

[0153] (b) adding R'SnCl3 at a temperature of 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;

[0154] (c) heating the solution to room temperature;

[0155] (d) removing the alkali metal chloride salt by-product to produce a crude product; and

[0156] (e) distilling the crude product to produce a product containing a monoorganotin trialkoxylate having formula (1) and not more than about 5 mole percent of a diorganotin dialkoxylate having formula (2).

[0157] The first step in the process comprises preparing a solution of an alkali metal alkoxide at a desired concentration in a suitable solvent (e.g., anhydrous hexane) and then cooling the solution to a low temperature, e.g., from about 0°C to about -10°C. For example, if the desired compound of formula (1) is allyl tri(tert-butoxy)tin, the alkali metal alkoxide may be potassium tert-butoxide, sodium tert-butoxide, or lithium tert-butoxide. The concentration of the alkali metal alkoxide is preferably at most about 10 to 15 weight percent, more preferably about 8 to 10 weight percent, relative to the amount of solvent. Suitable solvents and concentrations can be determined by routine experimentation and based on the commercial availability of the desired alkali metal alkoxide.

[0158] In the second step, a monoalkenyl or monoalkynyltin trichloride R'SnCl3 or other R'SnX3 compound is added to an alkali metal alkoxide solution at about -10°C to about 10°C, such that the amount of alkali metal alkoxide is at least about 3.03 equivalents relative to the amount of organic tin trichloride or organic tin trialkoxide added. A slight molar excess ensures complete reaction of the organic tin trichloride or organic tin trialkoxide. Preferably, the molar excess is kept as close to about 3% excess as possible to avoid polymerization of unsaturated groups, but it is also within the scope of the present disclosure to use a molar excess of about 2% to about 4% or 5% or up to about 15%, so 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, allyl tin trichloride can be used in the second step of preparing allyl tin trialkoxide. R'SnCl3 compounds can be purchased commercially or prepared, for example, by a redistribution reaction of R'4Sn and SnCl4 to produce R'SnCl3=.

[0159] The organotin trichloride or organotin trialkoxylate is preferably added in a dropwise manner to control the exothermic reaction. The second method step is preferably carried out in an inert atmosphere, such as nitrogen or argon. The monoorganotin trichloride or monoorganotin trialkoxylate is preferably added as a pure substance (solvent-free), but it is also within the scope of the present disclosure to add the monoorganotin trichloride or monoorganotin trialkoxylate in a solvent, such as but not limited to hexane, toluene, THF, xylene, heptane, dichloromethane or benzene.

[0160] After the addition of the organotin trichloride or organotin trialkoxylate to the alkali metal alkoxylate solution is completed, the reaction mixture is slowly warmed to room temperature, for example, over a period of 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 diatomaceous earth, to remove the alkali metal chloride by-product. Other filtering methods known in the art may also be used. The resulting salt is then rinsed, for example, with anhydrous hexane, and the solvent is removed under reduced pressure by methods known in the art to produce a crude product.

[0161] Finally, the crude product is distilled, for example, at less than about 10 torr, preferably less than about 0.5 torr, to obtain the desired product, which contains a monoorganotin trialkoxylate (e.g., allyl tri(tert-butoxy)tin) preferably in a purity greater than about 95 mol% and no more than about 5 mol% diorganotin dialkoxylate. Appropriate distillation conditions can be determined on a case-by-case basis using routine experimentation based on the desired product. In a preferred embodiment, the content of diorganotin dialkoxylate 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 of forming organotin trialkoxylate compounds by reaction of diethylamine followed by alcohol (which forms a mixture of products due to neutralization), the methods described herein produce the desired product with high purity (containing a small amount of diorganotin dialkoxylate impurities) and yield.

[0162] All method steps are preferably carried out in the absence of substantial light exposure. Shielding can be accomplished by any method known in the art, such as using a light-shielding container such as amber glass, metal (SUS) container, wrapping the container with a light-shielding cover such as cloth, foil or film, using a light-shielding coating, or conducting the reaction in a dark room.

[0163] The distillation can be carried out using a stainless steel column filled with a stainless steel packing material. Alternatively, the distillation can be carried out in a light-shielding device including glass, such as a glass device, a glass-lined device, a glass-coated device, etc. Shielding can be accomplished by any method known in the art, such as using a light-shielding container such as amber glass, a metal (SUS) container, wrapping the container with a light-shielding cover such as a cloth, foil or film, using a light-shielding coating, or carrying out the distillation in a dark room.

[0164] In a preferred embodiment, the method described herein is carried out in a solvent containing greater than about 50% by volume of a hydrocarbon solvent and / or an aromatic solvent (such as, but not limited to, those exemplified above). In a preferred embodiment, the method described herein is carried out in the absence of substantial light exposure. In a preferred embodiment, the alkali metal alkoxide is dehydrated prior to reacting with the R'SnX3 compound.

[0165] While the alkoxylation reaction to form the monoorganotin trialkoxylate is proceeding, the Kocheshkov-like centralization reaction shown in the above scheme (I) also occurs, and even low temperatures, such as about -78°C to 10°C, do not prevent the centralization reaction from occurring. In addition, electron donation can assist the Kocheshkov-like centralization and form up to 15 mol% of the diorganotin alkoxylate, such as by 119 Sn determined by NMR.

[0166] However, the methods described herein provide a synthetic strategy for forming tin compounds having unsaturated substituents without the presence of large amounts of diorganotin dialkoxylate impurities. It has been found that lithium dimethylamide reacts not only with tin chlorides, but also with unsaturated bonds. Therefore, as described herein, lithium dimethylamide is not used, and the concentration of the reactants is diluted, such as by using a metal alkoxide in a hexane slurry at a concentration of no more than about 10% by weight, to limit the formation of polyorganotin compounds. In addition, the temperature of the alkali metal alkoxide solution is carefully controlled before and during the addition of the organotin trichloride or organotin trialkoxylate.

[0167] It is also within the scope of the present disclosure to use an alcohol R'OH (or a partially fluorinated alcohol) rather than an alkali metal alkoxylate reactant to prepare compounds of formula (1) as described herein, and further to use a partially fluorinated alkoxylate group in the alkali metal alkoxylate reactant.

[0168] Adding CF3 groups to alkoxylate ligands can partially improve the volatility / vapor pressure of the resulting tin compounds because the fluorine atom provides an increased amount of intermolecular repulsion due to its high electronegativity relative to carbon. In addition, fluorine has a reduced polarizability (compared to hydrogen), which results in the fluorinated ligand having fewer intermolecular attractive interactions. Extending this concept, the separation of unwanted byproducts can also be simplified because the vapor pressure difference between [CF3(CH3)CHO]2SnR2, [CF3(CH3)CHO]3SnR and [CF3(CH3)CHO]4Sn will be greater than the vapor pressure difference observed for related tert-butane alkoxides 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 the related alkoxytin complexes, but should still react with water to deposit tin oxide under CVD conditions. In addition to stability against residual moisture, the weaker contribution of the fluorinated alkoxylate to tin can also serve to strengthen the tin-carbon bond, thereby providing a more stable tin alkenyl or alkynyl complex. The fluorinated alkoxylate is also less likely to attack the allylic double bond since it is less nucleophilic than the amide ligand.

[0169] Reduce additional impurities

[0170] It is reasonable to speculate that the metal impurities in the organotin trialkoxyl compound exist as metal chlorides. If so, removal can be achieved on an adsorbent, such as BASF CL-750, which is a chloride adsorbent known in the industry. There may be additional chloride impurities, such as lithium chloride, which may continue to migrate during the production process and become an impurity of concern. Removal on an adsorbent that removes chlorides (such as CL-750 or activated carbon) can effectively remove.

[0171] store

[0172] Other aspects of the present disclosure relate to methods for storing monoorganotin trialkoxylate compounds of formula (1) as described herein. Methods for storing samples of monoorganotin trialkoxylate compounds of formula (1) as described herein (e.g., but not limited to, samples greater than about 0.5 kg) include storing samples of monoalkyltin triamide compounds of formula (1) in the absence of substantial light exposure and at any temperature (e.g., a temperature below about 30° C.). The method may include storing the compound of formula (1) in a container in an inert atmosphere and / or storing the compound of formula (1) in a container without light exposure, such as in a dark room, by using a light-shielding container such as amber glass, metal (SUS), wrapping the container with a light-shielding cover such as cloth, foil or film, using a light-shielding coating, etc.

[0173] Samples of the mono-organotin trialkoxide compound having the formula (1) can be stored for up to about three days to about one year, such as about one week or longer, not exceeding about ten months, about two to six weeks, and all intermediate times as needed. Preferably, the sample is stored at a temperature less than about 30 °C, less than about 25 °C, less than about 20 °C, and preferably greater than about -10 °C. "Substantially free of light exposure" can be understood to mean protecting the sample from light exposure to the greatest possible extent, for example by storing in an amber or stainless steel container or other light-shielding means known in the art and / or as described above. In an embodiment, as described above, a sample of the mono-organotin trialkoxide compound does not substantially undergo decomposition after a storage time of several hours, up to about three days to about one year or longer.

[0174] Additional Aspects of the Disclosure

[0175] The organometallic tin compound having the formula (1) has at least one unsaturated bond in the carbon chain attached to the tin atom. After a chemical vapor deposition or spin-coating process, these tin compounds form an oxysilicate cluster film having unsaturated bonds on a silicon wafer. It has been found that these unsaturated bonds provide Sn-C bonds that are more sensitive to radiation, which can be used for lithographic patterning structures. These are advantageous for EUV photoresists because the orbital interactions of the unsaturated bonds affect the Sn-C bonds or the electronic state of tin, and thus the photosensitivity can be higher. In addition, the unsaturated bonds can react or polymerize with EUV exposure, and the solubility of the tin clusters will be improved.

[0176] Free radicals and anions generated by EUV light react with the unsaturated bonds and polymerize to form stronger R'SnO (3 / 2-x / 2 )(OH) x (0 < x < 3) film. The above reaction causes a significant change in the R'SnO (3 / 2-x / 2) (OH) x (0 < x < 3) cluster film in the irradiated area, resulting in a higher contrast as a resist.

[0177] Other aspects of the present disclosure relate to organotin compounds having the formula (3):

[0178] R'SnO (3 / 2-x / 2) (OH) x (3)

[0179] In formula (3), 0 < x < 3 and R' is a straight-chain or branched-chain, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms. Such compounds having the formula (3) can be obtained by hydrolyzing a mono-organotin trialkoxide compound having the formula (1) as described herein.

[0180] Another aspect of the present disclosure relates to a solution containing an organotin compound having the formula (3) and an organic solvent, such as but not limited to, a hydrocarbon solvent or an aromatic solvent as described above. Another aspect of the present disclosure relates to a film containing an organotin compound having the formula (3) as described herein.

[0181] Other aspects of the present disclosure relate to a composition or mixture containing a mono-organotin trialkoxide compound having the formula (1) and R'SnX3, where X is a halogen atom or an alkoxy group, as described above.

[0182] Another aspect of the present disclosure relates to a composition containing an organotin compound having the formula (3) and an organotin compound having the formula (4):

[0183] R'SnO (3 / 2-x / 2) (OH) x (3)

[0184] R''SnO (3 / 2-x / 2) (OH) x (4)

[0185] In formulas (3) and (4), 0 < x < 3, R' is a straight-chain or branched-chain, optionally fluorinated unsaturated hydrocarbon group having from about 2 to about 20 carbon atoms, and R'' is an optionally substituted hydrocarbon group having 2 to about 20 carbon atoms, such as a hydrocarbon group substituted by a halogen atom, an alkoxy group, or a dialkylamino group (such as dimethylamino, diethylamino, etc.). Such compounds having the formulas (3) and (4) can be obtained by hydrolyzing a mono-organotin trialkoxide compound having the formula (1) as described herein.

[0186] Another aspect of the present disclosure relates to a solution containing an organic solvent as described herein and a composition containing an organotin compound having the formulas (3) and (4). In some embodiments, the organotin compound can be obtained by hydrolysis of a mono-organotin trialkoxide compound having the formula (1) as described herein. Another aspect of the present disclosure relates to a film prepared from or containing a composition containing an organotin compound having the formulas (3) and (4).

[0187] The R' and R'' groups described herein have a hydrocarbon group having from about 2 to about 20 carbons as the main chain, and in addition to the substituents specified above, can also have various organic substituents, provided that they do not react with the unsaturated carbon-carbon bonds or the hydrolyzable Sn-O bonds in the molecule. For example, halogen atoms, alkoxy groups, aryloxy groups, dialkylamino groups, diarylamino groups, alkylthio groups, arylthio groups, acyl groups, acyloxy groups, and alkoxycarbonyl groups can be included as such organic substituents.

[0188] The compounds described herein can be used as resist materials after hydrolysis or other reactions (such as those known in the art). The compounds described herein can contain groups capable of forming an alkyltin oxo-hydroxy patterning composition, which can be hydrolyzed with water or other suitable reagents under suitable conditions to form an alkyltin oxo-hydroxy patterning composition, which can be represented by the formula R'SnO (3 / 2-x / 2) (OH) x (0 < x < 3). The hydrolysis and condensation reactions of compounds having a hydrolyzable group (X) can be shown in the following reactions:

[0189] RSnX3 + 3H2O → RSn(OH)3 + 3HX

[0190] RSn(OH)3 → RSnO( 1.5-(x / 2) )OH x +(x / 2)H2O

[0191] The alkyl oxo-hydroxy tin compounds obtained by hydrolyzing a composition containing the R'SnX3 compound described above as a raw material and the oxo-hydroxy tin compounds represented by the formula R'SnO (3 / 2-x / 2) (OH) x (0 < x < 3) can be used as EUV resist materials.

[0192] As a method for hydrolyzing a composition containing the R'SnX3 compound to obtain an oxo-hydroxy tin compound (R'SnO), for example, it can include: volatilizing the composition containing the R'SnX3 compound under heating or reduced pressure, and reacting the vapor generated by volatilization on a substrate on which a tin composition is deposited with water vapor, etc. (dry method). In this method, a thin film containing the tin compound R'SnO can be formed on the substrate.

[0193] Another method can include reacting a composition containing the R'SnX3 compound in solution or in solid state with water, etc., and hydrolyzing it to obtain an oxo-hydroxy tin compound (R'SnO). Then, the oxo-hydroxy tin compound (R'SnO) can be used as a coating solution by dissolving it in, for example, an organic solvent.

[0194] The solution can be applied to a substrate by any coating or printing technique, and a thin film or coating containing the oxo-hydroxy tin compound (R'SnO) can be formed on the substrate.

[0195] The film obtained by any of the above methods can be stabilized or partially condensed by drying, heating or other processes before light exposure. Typically, the film or coating has an average thickness of less than about 10 microns, and very thin submicron films (e.g., less than about 100 nanometers (nm), even less than about 50 nm or less than about 30 nm) may be desirable for patterning very small features. The resulting film or coating may be referred to as a resist because a portion of the exposure treatment composition is resistant to development / etching.

[0196] The film or coating can be exposed to appropriate radiation (e.g., extreme ultraviolet light, electron beam, or ultraviolet light) using a selected pattern or negative portion of the pattern to form a latent image having developer-resistant areas and developer-soluble areas. After exposure to appropriate radiation and before development, the film or coating can be heated or otherwise reacted to further distinguish between the latent image and non-radiated areas. The latent image is contacted with a developer to form a physical image, i.e., a patterned film or coating. The patterned 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 further processing according to the pattern, such as etching a substrate and / or attaching additional materials. After using a patterned resist as needed, the remaining patterned coating can be removed at an appropriate point in the process, but the patterned coating can also be incorporated into the final structure.

[0197] The invention will now be described with reference to the following non-limiting examples.

[0198] Example 1: Synthesis of vinyl tri(tert-butoxy)tin

[0199] Vinyl tin trichloride is prepared by the redistribution reaction of trivinyl tin and tin tetrachloride according to the method of Rosenberg and Gibbons (JACS, 79, 2138-40 (1957)). 189.08 g (0.75 mole) of vinyl tin trichloride and 400 mL of anhydrous hexane (3 moles) are placed in a 5.0 L flask. At a pot temperature of -10°C, 2.25 L (2.25 moles) of t-BuOK (1M in THF) are added thereto over 1 hour with good stirring. The solution is warmed to room temperature and stirred for another 2 hours. The mixture is filtered through diatomaceous earth under N2 and washed twice with an additional 200 ml of hexane. The solvent is removed under reduced pressure and the residue is distilled under reduced pressure (129°C, 0.5 torr) to obtain 128 g (47%) of vinyl tri(tert-butoxy)tin. 119 Sn NMR (400 mHz; pure): δ-256.87.1H NMR (400 mHz; C6D6): δ5.8-6.2 (m.3H, vinyl), δ1.42 (s, 27H, Ot-Bu). Purity: 79%.

[0200] Example 2: Synthesis of allyl tri(tert-butoxy)tin

[0201] According to the method of Rosenberg and Gibbons (JACS, 79, 2138-40 (1957)), allyltin trichloride is prepared by the redistribution reaction of tetraallyltin and tin tetrachloride in benzene or toluene. 252.47g (2.25 mol) of t-BuOK and 3.5L hexane (26 mol) were placed in a 5.0L flask and cooled to 0°C. 189.08 grams (0.75 mol) of allyltin trichloride were added dropwise while the pot temperature was maintained at 0 to 10°C. After addition, the solution was warmed to room temperature and stirred for another 2 hours. The mixture was filtered through diatomaceous earth under N2 and washed twice with an additional 200ml of hexane. The solvent was removed under reduced pressure and the diallyltin impurity residue was removed by reduced pressure fractionation. Allyl tri(tert-butoxy)tin was collected at 53.0-55.0°C and 0.18 torr. 119 Sn NMR (400 mHz; neat): δ-222.084. 1 H NMR (400mHz; C6D6): δ5.7-5.9 (m.1H), δ4.8-5.0 (m, 2H), δ2.1 (d, 2H), δ1.42 (d, 2H), δ1.40 (S27H). Purity: 81%.

[0202] Example 3: Synthesis of allyl tris((1,1,1-trifluoro-2-methylpropane-2-yl)oxy)stannane

[0203] According to the method of Rosenberg and Gibbons (JACS, 79, 2138-40 (1957)), allyltin trichloride is prepared by the redistribution reaction of tetraallyltin and tin tetrachloride. A 2.5M hexane solution of n-butyl lithium (230 g, 0.83 mol) is charged into a 2L flask and cooled to -30°C. 2-Trifluoromethyl-2-propanol (100 g, 0.78 mol) is added dropwise to the solution over 30 minutes, resulting in a violent exothermic reaction. The reaction temperature is maintained below 5°C during the addition, during which an orange solution and some white solids are formed. The reaction is warmed to room temperature, the reactor wall is rinsed with hexane (300 g), and the reaction is stirred for another 2 h. After stirring at room temperature, the reaction mixture is cooled to -10°C, and a toluene (150 g) solution of allyltin trichloride (69 g, 0.26 mol) is added in batches to the reaction mixture over 10 minutes, during which the orange solution becomes light yellow and a white precipitate is formed. The reaction mixture was warmed to room temperature and stirred for 16 h. The resulting light yellow solution was isolated by filtration and the solvent was removed from the filtrate under vacuum with mild 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%): bp 65° C. at 0.5 torr. 1H NMR (benzene-d6): δ1.30(s,18H,OC(CH3)2CF3), δ2.15(d,2H,SnCH2CHCH2), δ4.86(m,2H,SnCH2CHCH2), δ5.57(m,1H,SnCH2CHCH2). 119 Sn{ 1 H}NMR:δ-253. Purity:>97%.

[0204] Example 4: Synthesis of 3-butene-1-yltri(tert-butoxy)tin

[0205] 3-Butene-1-yltin trichloride is prepared by the redistribution reaction of 3-butene-1-yltricyclohexyltin and tin tetrachloride or the reaction of 3-butene-1-yltriphenyl-1-tin and tin tetrachloride in toluene according to the method of Jousseaume, Lehcini and Rascle (Organometallics 14, 685-689 (1995)). 850.0 g (3.07 moles) of n-hexyllithium are placed in a 3.0 L flask under N2 and cooled to 0°C. A premix containing 57.43 g (0.62 moles) of toluene and 229.71 g (3.10 moles) of tert-butyl alcohol is added dropwise while the pot temperature is maintained at 0 to 10°C. The mixture is warmed to room temperature and stirred for an additional 2 hours, and then 3-butene-1-yltin trichloride is added dropwise at 0 to 10°C. The reaction is warmed to room temperature and stirred overnight. The mixture was filtered through celite under N2 and washed twice with an additional 200 ml of hexane. The solvent was removed under reduced pressure and the title compound was collected at 59.4-62.8°C and 0.4 torr to give 3-buten-1-yltri(tert-butoxy)tin. 119 Sn NMR (400 mHz; pure): δ-194.423. 1 HNMR (400mHz; C6D6): δ5.7-5.9 (m.1H), δ4.8-5.0 (m, 2H), δ2.1 (d, 2H), δ1.42 (d, 2H), δ1.40 (S27H). Purity>99%.

[0206] Example 5 (prophetic): Preparation of mixture

[0207] Three mixtures were prepared as follows: (a) a mixture containing the compound prepared in Example 1 and a compound RSnX3 (wherein 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 a compound RSnX3, wherein 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, wherein R is a 3-buten-1-yl group and X is a halogen atom or an alkoxy group.

[0208] Example 6: Preparation and analysis of R'SnO(3 / 2-x / 2)(OH)x compounds (where 0 <x<3)

[0209] Example 6-a: R' = vinyl

[0210] 10 mL of n-hexane (dehydrated) and 1.0 g of vinyl tri(tert-butoxy)tin (synthesized as described in Example 1) were added to a 100 mL flask under an inert gas atmosphere and dissolved under stirring at 150 rpm. After the resulting solution was cooled to 0-10 ° C, demineralized water (1.0 mL, resistance 18.2 MΩ) was added by a syringe within 10 minutes, while stirring at 150 rpm and maintaining a temperature of 0-10 ° C to form a suspension. The resulting suspension was filtered through a funnel (Kiriyama filter paper 5B) to obtain a white solid. The resulting white solid was washed with 3 mL of demineralized water and then vacuum dried at 40 ° C for 8 h. The resulting white solid (SnO-1) weighed 0.48 g.

[0211] Example 6-b; R' = allyl

[0212] Using a procedure similar to that described in Example 6-a, a white solid (SnO-2) in an amount of 0.47 g was obtained from allyltri(tert-butoxy)tin (prepared as described in Example 2).

[0213] Example 6-c; R' = 3-butene-1-yl

[0214] Using a procedure similar to that described in Example 6-a, a white solid (SnO-3) in an amount of 0.53 g was obtained from 3-buten-1-yltri(tert-butoxy)tin (prepared as described in Example 4).

[0215] SnO-3 was identified by NMR. 119 Sn NMR (600 MHz, MeOD / CDCl3 1 / 1) observed only two peak groups: 5-coordinated (R'SnO4): -280 to -296 ppm and 6-coordinated (R'SnO5): -450 to -490 ppm. 1 H NMR (600MHzMeOD / 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 is consistent with the tin dodecamer cluster [(R'Sn) reported in Organometallics 19, 1940-1949 (2000) 12 O 14 (OH)6] NMR results are related. ESI-mass spectrometry is as follows Figure 1 As shown (system: Waters Xevo G2-XS Qtof, solvent CH3CN, mode: ESI positive), there are two main peaks [(C4H7Sn) 12 O14 (OH) 10 The monovalent ion has m / z = 2480 and the divalent ion has m / z = 1240. Thus, a compound corresponding to R’SnO (3 / 2-x / 2) (OH)x (where 0 < x < 3) is obtained.

[0216] Example 6-d: R'=3-butene-1-yl

[0217] Using the same method 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(tert-butoxy)tin (prepared as described in Example 4) and 0.7 g of isopropyltris(dimethylamino)tin.

[0218] Example 7 - Preparation of membranes

[0219] While using ultrasonic waves, SnO-3 of Example 6-c was dissolved in 4-methyl-2-pentanol (5 mL) to a concentration of 2.0 wt%, and the resulting solution was filtered through a 0.45 μm syringe filter to obtain a resist solution containing a transparent tin compound. A silicon wafer (Si substrate, 100 mm in diameter) having an oxide surface was ozonated and used as a substrate for resist film deposition. Before 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 hot plate at 90 °C for 2 minutes. The film thickness after coating and baking was measured by ellipsometry to be 20 nm.

[0220] Example 8 (Prophetic) - Forming an Image on a Substrate

[0221] The coated substrate (film) in Example 7 was exposed to ultraviolet light (light source: a xenon excimer lamp (172 nm, 7.2 eV) manufactured by USHIO INC., light source intensity: 0.7 mW / cm 2 ), and a pattern was projected onto the substrate using a mask. Then the substrate was immersed in 2-heptanone for 15 seconds and rinsed with the same developer for another 15 seconds to form a negative image, that is, an image in which the unexposed part of the film was removed and only the pattern-exposed part was retained.

[0222] Those skilled in the art will understand that the above-described embodiments can be changed without departing from their broad inventive concept. Therefore, it should be understood that the present invention is not limited to the specific embodiments disclosed, but is intended to cover modifications within the spirit and scope of the invention defined by the appended claims.

Claims

1. A monoorganotin trialkoxylate compound having formula (1) having a purity of at least about 95 mol % and containing less than about 5 mol % of a diorganotin dialkoxylate compound 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.

2. The monoorganotin trialkoxylate compound of claim 1, 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.

3. The monoorganotin trialkoxylate compound according to claim 1 or 2, wherein the content of the diorganotin dialkoxylate having formula (2) is less than about 1 mol%.

4. The monoorganotin trialkoxide compound according to any one of claims 1 to 3, wherein the total content of tetra(alkoxy)tin is less than about 1 mol%.

5. The monoorganotin trialkoxylate compound according to any one of claims 1 to 4, wherein the total content of tri(alkenyl)tin compounds is less than about 1 mol%.

6. A monoorganotin trialkoxylate compound according to any one of claims 1 to 5, 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 methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, optionally fluorinated.

7. The monoorganotin trialkoxylate compound according to any one of claims 1 to 6, wherein the compound having formula (1) is selected from:

8. Monoorganotin trialkoxylate 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.

9. The monoorganotin trialkoxylate compound of 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. The monoorganotin trialkoxylate 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 each R is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, which is optionally fluorinated.

11. The monoorganotin trialkoxylate compound according to any one of claims 8 to 10, wherein The compound having formula (1) is selected from:

12. A method for synthesizing a monoorganotin trialkoxylate compound having formula (1) having a purity of at least about 95 mol % and containing less than about 5 mol % of a diorganotin dialkoxylate compound 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, the method comprising reacting an alkali metal alkoxide with a R'SnX3 compound, wherein X is a halogen atom or an alkoxy group.

13. The method according to claim 12, comprising: (a) preparing a solution of an alkali metal alkoxide; (b) adding R'SnCl3 at a temperature of 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 to produce a crude product; and (c) distilling the crude product to produce a product containing a monoorganotin trialkoxylate having formula (1) and no more than about 5 mole percent of a diorganotin dialkoxylate having formula (2).

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

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

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 methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, optionally fluorinated.

17. The process of any one of claims 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.

18. The method of any one of claims 12 to 17, wherein the reaction is carried out in the substantial absence of light exposure.

19. A method for synthesizing a monoorganotin trialkoxylate compound having the formula (1): 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, the method comprising reacting an alkali metal alkoxide with a R'SnX3 compound, wherein X is a halogen atom or an alkoxy group.

20. The method according to claim 19, comprising: (a) preparing a solution of an alkali metal alkoxide; (b) adding R'SnCl3 at a temperature of 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 to produce a crude product; and (c) distilling the crude product to produce a monoorganotin trialkoxylate having formula (1).

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 methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, optionally fluorinated.

22. The process of any one of claims 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.

23. The method of any one of claims 19 to 22, wherein the method is performed in the substantial absence of light exposure.

24. A method of storing a sample of the monoorganotin trialkoxylate compound of claim 1 having the formula (1), the method comprising storing the sample of the monoorganotin trialkoxylate compound of formula (1) in the absence of substantial light exposure and at a temperature of less than about 30°C.

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

26. The method of claim 24 or 25, wherein the sample of the monoorganotin trialkoxylate undergoes substantially no decomposition after a storage period of about three days to about one year.

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

28. A method according to any one of claims 24 to 27 comprising storing the compound of formula (1) in a container substantially free of light exposure.

29. A method of storing a sample of the monoorganotintrialkoxylate compound of claim 8 having the formula (1), the method comprising storing the sample of the monoorganotintrialkoxylate compound of claim 8 in the absence of substantial light exposure and at a temperature of less than about 30°C.

30. The method of claim 29, wherein the sample of the monoorganotin trialkoxylate compound of formula (1) is stored for about three days to about one year.

31. The method of claim 29 or 30, wherein the sample of the monoorganotin trialkoxylate undergoes substantially no decomposition after a storage time of about three days to about one year.

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

33. A method according to any one of claims 29 to 32 comprising storing the compound of formula (1) in a container substantially free from light exposure.

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 straight-chain or branched, 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, 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 straight-chain 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 straight-chain 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 straight-chain or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms.

40. A composition comprising the monoorganotin trialkoxide compound having the formula (1) according to claim 1 and an R’SnX3 compound, wherein X is a halogen atom or an alkoxy group.

41. A composition comprising the monoorganotin trialkoxide compound having the formula (1) according to claim 8 and an R’SnX3 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 a straight-chain 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.

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 the monoorganotin trialkoxide compound having the formula (1): R’Sn(OR)3 (1) where each R is independently a straight-chain 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 the monoorganotin trialkoxide compound having the formula (1): R’Sn(OR)3 (1) where each R is independently a straight-chain 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 of claim 46, wherein at least one of the compound of formula (3) and the compound of formula (4) is obtained by hydrolyzing a monoorganotin trialkoxylate compound of formula (1): R'Sn(OR)3 (1) wherein each R is independently a straight or branched, optionally fluorinated alkyl group having from about 1 to about 10 carbon atoms.

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