Method for producing an organotin composition having a ligand that is convenient for supplying reactants

Abstract

This invention provides a method for forming an organotin composition that provides radiatively sensitive Sn-C bonds that can be used for patterning thin films using lithography. [Solution] A synthetic reaction is described for efficiently and specifically forming compounds of the structure RSnL3 (where R is an organic ligand for tin, and L is a hydrolyzable ligand or its hydrolysis product). This synthesis is effective for a variety of R ligands. This synthesis is based on the use of alkali metal ions and optionally alkaline earth (pseudo-alkaline earth) metal ions. The compounds are formed in structures represented by the formula RSn(C≡CSiR'3)3, R'R''ACSnL3 (wherein A is a halogen atom (F, Cl, Br, or I), or an aromatic ring containing at least one halogen substitution), R'R''(R'''O)CSnL3, or R'R''(N≡C)CSnZ3.

Description

Cross-reference of related applications

[0001] This application claims priority to Edson et al.'s concurrently pending U.S. Provisional Patent Application No. 63 / 070,098, filed on 25 August 2020, entitled "Methods to Produce Monoalkyl Tin Compositions Wit Low Concentration of Contaminants," and Cardineau et al.'s concurrently pending U.S. Provisional Patent Application No. 63 / 191,646, filed on 21 May 2021, entitled "High EUV Absorption Organotin Patterning Compositions and Coatings," both of which are incorporated herein by reference. [Technical Field]

[0002] The present invention relates to an improved method for producing monoorganosudrin triamides and monoorganosudrin triacetides, wherein the organic groups therein are defined as hydrocarbyls having or not having one or more heteroatoms. [Background technology]

[0003] Organometallic compounds supply metal ions in solution-processable and gas-phase forms for thin film deposition. Organotin compounds provide radiatively sensitive Sn-C bonds that can be used for lithographic patterning of thin films. The fabrication of semiconductor devices at increasingly smaller dimensions requires new, versatile materials to achieve the necessary patterning resolution. Organotin compounds promise to provide the required patterning advantages. [Overview of the project] [Means for solving the problem]

[0004] In one embodiment, the present invention relates to a solution containing an organic solvent, and an organometallic composition (or organometallic composition) that is soluble in (or dissolved in) the solvent. The organometallic composition comprises an alkali metal ion, a tin ion, and an organic ligand (or organic ligand) that binds to tin as -SnL3, wherein the organic ligand (L) is -NR'2, -C≡CR s , or a mixture thereof, R s is SiR''3 or R', where the three R'' are independently H or R', and R' is independently a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom. In some embodiments, the organometallic composition further comprises alkaline earth ions (Be(+2), Mg(+2), Ca(+2), Sr(+2), Ba(+2)) or pseudo-alkaline earth ions (or pseudo-alkaline earth ions) (Zn(+2), Cd(+2), or Hg(+2 / +1 (or +2 or +1))).

[0005] In another aspect, the present invention relates to a method for forming an alkali metal tin composition, the method comprising, in an organic solvent, ML, tin(II) halide (or tin(II) halide) (SnX2, X=F, Cl, B, I, or a mixture thereof), and optionally M'OR 0 (In the formula, M is Li, Na, K, Cs, or a combination thereof, M' is Na, K, Cs, or a combination thereof, and L is dialkylamide (-NR'2) or acetylide (-C≡CR) s) by reacting with) to form the corresponding organometallic composition having the moiety SnL3, where the moiety SnL3 is present with (or present with the associated metal cation M'') the metal cation M'', and is tin triamide (M''Sn(NR'2)3) or tin triacetylide (M''Sn(C≡CL s )3) (or M''Sn(C≡CR s )3) (alternatively, tin triamide (M''Sn(NR'2)3) or tin triacetylide (M''Sn(C≡CL s )3) (or M''Sn(C≡CR s )3) present with the metal cation M'', where M'' is M' if M' is present and M if M' is not present, and R 0 is a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, and R s is SiR''3 or R', where the three R'' are independently H or R', and R' is independently a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom. In some embodiments, the method further comprises reacting an (alkaline earth / pseudo-alkaline earth) metal halide (or metal halide) (M'''X2, X = F, Cl, B, I, or a mixture thereof) with an alkali metal tin composition to form an alkali metal (alkaline earth / pseudo-alkaline earth) metal tin composition, where the alkaline earth / pseudo-alkaline earth metal is beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, or a combination thereof.

[0006] In a further aspect, the present invention relates to a method for synthesizing a monohydrocarbyl tin compound, the method comprising reacting a primary halide hydrocarbyl compound (or primary halide hydrocarbyl compound) (RX, where X is a halide atom (or halide atom, halide atom, or halide atom)) with an organometallic composition containing a SnL3 moiety (L is either an amide ligand that produces an alkali metal tin triamide compound or an acetylide ligand that produces an alkali metal tin triacetide) corresponding to a metal cation M (where M is an alkali metal, alkaline earth metal, and / or pseudo-alkali metal (Zn, Cd, or Hg)) to form an alkali metal tin composition, thereby producing the corresponding monohydrocarbyl tin triamide (RSn(NR'2)3) or monohydrocarbyl tin triacetide (RSn(C≡CL s )3)(or RSn(C≡CR s )3) comprising the formation of a monohydrocarbyl ligand (R), the monohydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, L s is SiR''3 or R', where the three R''s are independently H or R', and R' is independently a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom.

[0007] In an additional aspect, the present invention relates to a compound represented by the formula RSn(C≡CSiR'3)3, where R' and R are, independently, a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom.

[0008] Furthermore, the present invention relates to a halogenated hydrocarbyl tin compound (or hydrocarbyl tin halide compound) represented by the formula R'R''ACSnL3, wherein A is an aromatic ring having a halogen atom (F, Cl, Br, or I) or at least one halogen substitution (or halogen substitution or halogen substituent), R' and R'' are independently H, a halogen, or a hydrocarbyl group having 1 to 15 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, and L is L H And L H is a hydrolyzable ligand (or a ligand that can be hydrolyzed), or O x (OH) 3-x (0 <x<3)である。

[0009] Furthermore, the present invention relates to a hydrocarbyl tin compound represented by the formula R'R''(R'''O)CSnL3, wherein R', R'', and R''' are independently H, or a hydrocarbyl group having 1 to 15 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, and L is L H And L H is a hydrolyzable ligand, or O x (OH) 3-x (0 <x<3)である。

[0010] In some embodiments, the present invention relates to a hydrocarbyl tin compound represented by the formula R'R''(N≡C)CSnL3, where R' and R'' are independently H, or a hydrocarbyl group having 1 to 15 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, and L is L H And L H is a hydrolyzable ligand, or O x (OH) 3-x (0 <x<3)である。 [Brief explanation of the drawing]

[0011] [Figure 1] This is the 119Sn NMR spectrum of LiSn(NEt2)3 in benzene-d6. [Figure 2] This is the 119Sn NMR spectrum of n-PrSn(NEt2)3 in benzene-d6. [Figure 3] This is the 1H NMR spectrum of n-PrSn(NEt2)3 in benzene-d6. [Figure 4] This is the 119Sn NMR spectrum of n-PrSn(O-tAm)3 in benzene-d6. [Figure 5] This is the 1H NMR spectrum of n-PrSn(O-tAm)3 in benzene-d6. [Figure 6] This is the 119Sn NMR spectrum of EtSn(NEt2)3 in benzene-d6. [Figure 7] This is the 119Sn NMR spectrum of EtSn(O-tAm)3 in benzene-d6. [Figure 8] This is the 119Sn NMR spectrum of t-BuSn(NEt2)3 in benzene-d6. [Figure 9] This is the 119Sn NMR spectrum of t-BuSn(O-tAm)3 in benzene-d6. [Figure 10] This is the 119Sn NMR spectrum of (NC(CH3)2C)Sn(NEt2)3 in benzene-d6. [Figure 11] This is the 119Sn NMR spectrum of LiSn(CCSiMe3)3 in benzene-d6. [Figure 12] This is the 119Sn NMR spectrum of (CH3OCH2)Sn(CCSiMe3)3 in benzene-d6. [Figure 13] This is the 119Sn NMR spectrum of (NC(CH3)2C)Sn(CCSiMe3)3 in benzene-d6. [Figure 14] This is the 119Sn NMR spectrum of 2-iodopropyl tin tris(tert-butoxide)(2IP). [Figure 15] This is the 1H NMR spectrum of 2IP. [Figure 16] This is the 119Sn NMR spectrum of 3-iodobenzylsutris (tert-butoxide) (IBT). [Figure 17] This is the 1H NMR spectrum of IBT. [Modes for carrying out the invention]

[0012] A more versatile and efficient technique for synthesizing monohydrocarbyltin compounds involves organoalkali metal compounds and tin halides (stannosalides) (SnX2, where X is the halide (or halogenated part, halogenated site, halide)) and (sp 3The process is described based on reactions involving an organohalide (or organohalide) contributing to the R group for the ligand to tin with a carbon-tin bond, an optional additional metal compound, and an amine or acetylide (NR'2 or -C≡CR') contributing to the three hydrolyzable ligands to tin. The improved synthesis is based on the presumed formation of an alkali metal (and / or alkaline earth metal or pseudo-alkaline earth metal, as defined below) tin composition as an intermediate in the synthesis of monohydrocarbyl tin compounds, although various metallic tin compositions may also be useful intermediates in other contexts. The intermediate metallic tin composition then reacts with an organohalide to form an R-SnL3 structure (where R forms a C-Sn bond and L represents a hydrolyzable ligand). Although metallic tin compounds are known to be stable in solution and can be characterized, their isolation has been difficult until now. These metallic tin compositions provide convenient precursors for forming carbon-tin bonds through metal substitution (alkali metals and / or alkaline earth elements and / or pseudo-alkaline earth elements) with good yield and good specificity for a variety of ligands. This is thought to be due to the energy of the reaction. These synthetic approaches can be extended to the synthesis of organotin trialalkides (triorganoxides) from either triamides or triacetides by substitution with hydrolyzable ligands, or oxo / hydroxo compounds by hydrolysis of ligands. Monoorganotin compounds, i.e., compounds with hydrolysis-stable C-Sn bonds, can be synthesized directly with very low polyorgano contamination, and monoorganotin compounds have been found to be more desirable as radiosensitive compositions for patterning applications. While monoorganotin triamides can be used directly as precursors for radiation-patternable compositions, trialalkides have been found to be particularly useful precursors for either solution deposition or vapor deposition of radiation-patternable coatings.This synthetic technique allows for the incorporation of heteroatom-substituted organic ligands, such as halogenated ligands, and functionalized organic ligands (or halogenated functionalized organic ligands), including, for example, cyano groups and ether groups, which may be impractical using other known synthetic techniques. This synthetic technique has been found to be effective for the efficient formation of a wide range of organic ligands, and halogenated ligands that absorb a large amount of radiation, particularly iodide ligands, are described and exemplified. Compounds of this classification are excellent for providing radiation-patternable coatings.

[0013] As used herein, “monoalkyl” is generally consistent with its use in the art and can be used interchangeably with “monoorgano” or “monohydrocarbyl” having an “alkyl” ligand, which is bonded to tin at carbon and is not typically hydrolyzed by contact with water. 3 or sp 2While suggesting the formation of bonds that may include hybridized carbons, the "alkyl" group may have internal unsaturated bonds that do not participate in the bonding with tin, and heteroatoms, i.e., atoms other than carbon and hydrogen. The novel synthetic methods described herein produce monohydrocarbyl tin triamides (trihydrocarbilamides) and monohydrocarbyl tin triacetylides (trihydrocarbyl acetylides) in high yield and with low (non-tin) metal and polyalkyl (i.e., polyhydrocarbil) contamination. This synthetic approach is suitable for efficient scale-up for commercial production of the corresponding cost-effective products. The improved synthetic approaches described herein allow for more effective adoption of a wider variety of organic functional groups for bonding to tin and / or within the amide or acetylide hydrolyzable ligands. The use of reactant species to form the target compounds involves endothermic reactions. While we do not wish to be bound by theory, the reactants selected herein are considered to allow for the dissipation of generated heat and / or a reduction in the amount of heat generated by altering, and in some cases slowing down, the formation of less stable R-Sn bonds and / or higher product yields. The alternative terms described in the first sentence of this paragraph are carried over throughout this specification, but may be further clarified by the adoption of terms that more directly reflect the range of ligand species commonly used. Thus, sp bonded to tin 3 or sp 2 Although the term hydrocarbyl is used to describe ligands containing carbon atoms, these groups do not necessarily need to have hydrogen atoms. Acetylide ligands, in which sp carbon atoms are bonded to tin, form hydrolyzable bonds and can therefore be easily distinguished.

[0014] The use of alkyl metal coordination compounds in high-performance radiation-based patterning compositions is described, for example, in U.S. Patent No. 9,310,684, entitled "Organometallic Solution Based High Resolution Patterning Compositions" by Meyers et al., which is incorporated herein by reference. Improvements to these organometallic compositions for patterning are described in U.S. Patent No. 10,642,153, entitled "Organometallic Solution Based High Resolution Patterning Compositions and Corresponding Methods" by Meyers et al., and in U.S. Patent No. 10,228,618, entitled "Organotin Oxide Hydroxide Patterning Compositions, Precursors, and Patterning" by Meyers et al. (hereinafter referred to as the '618 patents), which are both incorporated herein by reference.

[0015] The compositions synthesized herein may serve as effective precursors for forming alkyltin oxo-hydroxo compositions advantageous for high-resolution patterning in, for example, extreme ultraviolet (EUV), ultraviolet (UV), and electron beam lithography. The alkyltin precursor compositions contain groups that, under appropriate conditions, can be hydrolyzed with water or other suitable reagents to form monohydrocarbyltin oxo-hydroxo patterning compositions, which, upon complete hydrolysis, are of the formula RSnO (1.5-(x / 2)) (OH) xIt can be represented by (0 < x ≤ 3). It may be convenient to perform hydrolysis in the system, such as during deposition and / or after the first coating formation, to form an oxo-hydroxy composition. The triamides and triacetylides described herein can be used under hydrolysis conditions to form a radiation-sensitive coating for patterning, but it may be desirable to further form an intermediate hydrocarbyltin trialkoxide (trihydrocarbyloxide) to form the coating. The processes for forming hydrocarbyltin trialkoxides are described herein. Various precursor compounds having hydrolyzable ligands generally carry the R ligand to tin through the process and are synthesized from this perspective.

[0016] Regarding precursors having hydrolyzable ligands, representative hydrolysis and condensation reactions capable of converting a composition having a hydrolyzable Sn-X group are shown by the following reactions: RSnL3 + 3H2O → RSn(OH)3 + 3HL, RSn(OH)3 → RSnO x / 2 OH 3-x + (x / 2)H2O

[0017] When the hydrolysis product HL is sufficiently volatile, hydrolysis can be carried out in the system using water vapor during the substrate coating process, but the hydrolysis reaction can also be carried out in solution to form an alkyltin oxo-hydroxy composition. These treatment options are further explained in the '618 patent. The overall synthesis process for forming a radiation-patternable coating includes the formation of the desired R-Sn(C-Sn) bond with three hydrolyzable ligands, and there is a possibility of exchanging the hydrolyzable ligands under appropriate circumstances while maintaining the R ligand.

[0018] R forms a carbon-tin bond, and the carbon bonded to tin is sp 3 or sp 2It is a hybrid, and R may include a heteroatom other than carbon or hydrogen. As stated above, for convenience and consistency in the art, R may be interchangeably referred to as an alkyl ligand, an organic ligand, or a hydrocarbyl ligand (or hydrocarbyl ligand). In some embodiments, the compound is generally R 1 R 2 R 3 CSnO (2-(z / 2)-(x / 2)) (OH) x (In the formula, R 1 , R 2 , and R 3 For some patterning compositions, alkyl ligands may be preferable, as R can be expressed independently as hydrogen or an alkyl group having 1 to 10 carbon atoms. Similarly, this expression of alkyl ligand R is generally R 1 R 2 R 3 The same applies to other embodiments having CSn(L)3, where L corresponds to a hydrolyzable ligand such as an alkoxide (hydrocarbyl oxide), acetylide, or amide moiety. In some embodiments, R 1 and R 2 It can form a cyclic alkyl moiety, R 3 It can also bond with other groups in the cyclic region. Suitable branched alkyl ligands include, for example, isopropyl(R 1 and R 2 is methyl, and R 3 (is hydrogen), tert-butyl (R 1 , R 2 , and R 3 ( is methyl), tert-amyl (R 1 and R 2 is methyl, and R 3 (is -CH2CH3), sec-butyl (or secondary butyl) (R 1 is methyl, and R 2 is -CH2CH3, and R 3 (is hydrogen), neopentyl (R 1 and R 2 is hydrogen, R 3The group may be -C(CH3)3, cyclohexyl, cyclopentyl, cyclobutyl, and cyclopropyl. Suitable examples of cyclic groups include, for example, 1-adamantyl (metal-bonded at a tertiary carbon (-C(CH2)3(CH)3(CH2)3 or tricyclo(3.3.1.13,7)decane)) and 2-adamantyl (metal-bonded at a secondary carbon (-CH(CH)2(CH2)4(CH)2(CH2) or tricyclo(3.3.1.13,7)decane)). In another embodiment, the hydrocarbyl group may include an aryl or alkenyl group, such as benzyl or allyl, or an alkynyl group. In another embodiment, the hydrocarbyl ligand R may include any group consisting only of C and H and containing 1 to 31 carbon atoms. In summary, suitable aryl groups bonded to tin Some examples of R groups include, for example, linear or branched alkyl groups (i-Pr((CH3)2CH-), t-Bu((CH3)3C-), Me(CH3-), n-Bu(CH3CH2CH2CH2-)), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl), olefin groups (alkenyl, aryl, allyl), or alkynyl groups, or combinations thereof. In further embodiments, suitable R groups may be cyano, thio, silyl (and germanium analogs), ether, keto, ester, or halogenated groups. Hydrocarbyl groups may include those substituted with heteroatomic functional groups, including those of the group, or combinations thereof. As is common in the art, hydrocarbyl groups can be called alkyl groups, although they may have unsaturated bonds, aryl groups, heteroatoms, etc. R groups having halogen atoms are exemplified below and described in more detail with respect to specific structures. R groups having cyano or ether groups are also exemplified below. R groups having silyl moieties are described in the concurrently pending Provisional Patent Application No. 63 / 210,769, entitled "Organotin Patterning Materials: Compositions and Methods" by Jilek et al., which is incorporated herein by reference.The R group having a deuterated site is described in the concurrently pending U.S. Provisional Patent Application No. 63 / 215,720, entitled "Deuterated Organotin Compounds" by Jilek et al., which is incorporated herein by reference.

[0019] The precursor composition can be used to form an organotin oxo / hydroxo coating composition incorporated into a common oxo / hydroxo network. The precursor composition may include one or more soluble organotin oxo / hydroxo compounds, or corresponding compounds having hydrolyzable ligands that form oxo and / or hydroxo ligands by hydrolysis and / or condensation. For precursor compositions comprising multiple compounds, the compounds may have separate organic ligands having metal-carbon bonds, and the same or separate hydrolyzable ligands. Therefore, precursor compositions for forming radiosensitive coatings may typically include solutions of one or more compounds represented by RSnL3, where R is a hydrocarbyl group having 1 to 31 carbon atoms as described above, and L is a ligand having a hydrolyzable ML bond, and mixtures thereof. For the compositions described herein, the hydrolyzable ligands may include dialkylamides and alkylacetylides (-C≡CR 0 Examples include: Dialkylamides and alkylacetylides may be useful as readily substituted and / or reactable ligands for preparing other organotin compositions such as organotin carboxylates, organotin alkoxides, and organotin hydroxides, which may be advantageous for subsequent processing. Organotin carboxylates can be readily formed by reaction with carboxylic acids. The preparation of organotin alkoxides is described in the following examples, and the formation of organotin hydroxides is summarized below. Organotin alkoxides are formed by alkoxy ligands (-OR 0 ) including R 0 The group can be one of the same sites as described above for R, so that it can have a heteroatom and an unsaturated carbon-carbon bond. In particular, organotin trialkoxide compositions are of the formula RSn(OR 0)3 can be represented by the formula RSn(NR). Similarly, an organotin tridialkylamide composition can be represented by the formula RSn(NR). a R b ) can be expressed as 3, and in the formula, R a and R b The group can independently be one of the same sites as described above for R, and hydrocarbyl tin trialkyl acetylide is given by the formula RSn(C≡CR 0 ) can be represented as 3. Similar to the R ligand, the hydrolyzable ligand refers to an alkylamide or alkylacetylide, and it is recognized in the art that these are not limited to alkyl groups in the strict sense of organic chemistry, but can be equivalently represented as an organic group or a hydrocarbyl group. However, for these ligands, the terminology can quickly become very complicated, so under the understanding that this expression should be interpreted broadly as is common in the art, the alkyl is retained for hydrolyzable ligands, and silyl derivatives in hydrolyzable ligands are exemplified. In some embodiments, R a , R b , R 0 These are independently linear or branched alkyl (-C) n H 2n+1 (where n is between 1 and 5)

[0020] A monohydrocarbyltin composition having a hydrolyzable ligand can generally be represented by the formula RSn(L)3, where R is sp 3 or sp 2 As defined above in relation to forming a carbon-tin bond via carbon, the broad considerations regarding R above can be considered to be repeated in detail here. With respect to hydrolyzable ligands, L can be -OR', NR'2, or -C≡CR'. Typically, R', like R, has sp bonds to its neighboring atoms. 3 or sp 2R can be any of the species described above for R, which is bonded to a carbon atom, and may optionally include unsaturated carbon-carbon bonds, aromatic moieties, and heteroatoms. Silicon heteroatoms are specifically exemplified below. Similar to R, the terms “alkyl” or “alk” are not intended to imply limitation to saturated hydrocarbons that do not contain heteroatoms, as in the case of alkoxys, and are instead sometimes called hydrocarbyl or organic groups. In some embodiments, R' may contain ≤10 carbon atoms and may be, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, or t-amyl. The R group may be linear, branched (i.e., secondary or tertiary at the carbon atoms bonded to the metal), or cyclic. Several embodiments in which R' contains a silicon atom are further described and exemplified below.

[0021] Various synthetic embodiments are described herein based on the common concept of first synthesizing a mixture of intermediates represented by the formula MSnL3 (wherein M is one or more (+1) or (+2) metal ions, and L is a hydrolyzable ligand, particularly a dialkylamide or alkylacetylide). Typically, the intermediate is formed at concentrations based on a tin content of about 0.005 M to about 2 M, in further embodiments about 0.01 M to about 1.75 M, and in other embodiments about 1.5 M to about 0.025 M. Those skilled in the art will recognize that further concentration ranges are conceivable within these distinct ranges and are included in this disclosure. This intermediate reacts with RX (where X is a halide atom (or halide atom, halide atom, or halogenated atom)) to form RSnL3, which can be used further as needed. In some embodiments, M may be Li. In other embodiments, M may be another alkali metal, such as Na, K, Rb, or Cs. In some embodiments, M may further comprise an alkaline earth metal, such as Mg, Ca, Sr, or Ba, along with the alkali metal. In further embodiments, M may further comprise a pseudo-alkaline earth ion, such as Zn, Cd, or Hg, along with the alkali metal. In some embodiments, M may be a mixture of any of the aforementioned alkali metals, alkaline earth metals, or pseudo-alkaline earth metals. The appropriate selection of M can be determined by thermodynamic and / or kinetic factors, such as the difference in electronegativity between M and Sn, which allows the alkylation (i.e., formation of a Sn-C bond) reaction to proceed in appropriate yield and purity. Other factors that may influence the appropriate selection of M may be physical considerations, such as the hazards posed by the reactants / products (e.g., spontaneous combustion, toxicity) and the physical properties of the reactants / products. In any case, it has been found that in some situations, better yields and purer products can be achieved by using another alkali metal ion instead of or in addition to lithium, or by introducing alkaline earth or pseudo-alkaline earth ions in addition to lithium or other alkali metal ions.Although the intermediates are stable (e.g., do not form precipitates), they are reactive, making their isolation difficult. Therefore, the structure of the intermediates is inferred from available measurements and consideration of reasonable alternative methods. More precisely, the idealized formula MSnL3 can be understood as a complex mixture of intermediates in which M can contain one or more of the aforementioned metals.

[0022] While we do not wish to be bound by theory, the appropriate selection of M may be influenced by the reactivity of the alkylation reaction between the nucleophilic MSnL3 intermediate and the electrophilic RX. For more reactive R groups, such as those with low C-Sn bond dissociation energy and / or high electrophilicity, the energy release resulting from the alkylation reaction is thought to contribute to the decomposition of the Sn-C bond, resulting in insufficient product yield. Therefore, it may be desirable for M to contain a metal with higher electronegativity (i.e., lower electropositivity) to reduce the energy released when the electrophilic alkyl halide (or electrophilic alkyl halide, electrophilic alkyl halide, or electrophilic alkyl halide) reacts with the nucleophilic MSnL3 intermediate. Conversely, for less reactive R groups, it may be desirable to select a metal with lower electronegativity (i.e., higher electropositivity) to increase the yield of the desired RSn bond.

[0023] The synthetic approach utilizes tin(II) halides (SnX2 such as SnCl2), secondary amines or acetylides, alkyl metals (MR''), and alkyl halides (or alkyl halides or alkyl halides) (RX), where R'' and R are organic groups, M is an alkali metal (Li, Na, K, Rb, and / or Cs), and X is a halide (or halogenated part, halogenated site, or halide). Secondary amines can be represented by the formula HNR'2, and acetylides can be represented by R'C≡CH, where R' is an organic group, i.e., a hydrocarbyl group. In embodiments where M is a non-lithium alkali metal, the alkali metal is MOR 0It may be more convenient and efficient to introduce M as such so that it is incorporated into the alkali metal-tin intermediate. Since M can be introduced in a lower stoichiometric amount corresponding to the molar amount of tin rather than the stoichiometric amount of the hydrolyzable ligand, it is not determined whether LiR'' is converted to MR''. Nevertheless, the introduction of non-lithium alkali metals can lead to a more efficient overall reaction and improved yield, even if such substitutions increase the complexity of the reaction and additional reactants are added. The synthetic intermediate is considered to be an MSnL3 composition in which L is -NR'2 or -C≡CR'. This alkali metal-tin compound may also be a useful intermediate in the synthesis of other compounds.

[0024] In addition to the use of alkali metals, usually lithium and optionally non-lithium alkali metals, the incorporation of alkaline earth metal ions (Be, Mg, Ca, Sr, Ba), or pseudo-alkaline earth metal ions (Zn, Cd, Hg), or mixtures thereof, can be useful in some reactions, promoting the formation of products in higher yield and / or higher purity. These +2 metal ions can be introduced as halide salts (or halide salts or halide salts) MX2, where X is the halide (or halogenated part, halogenated site, halide). Alkaline earth metals such as magnesium are known to form equilibrium mixtures of compositions having nucleophilic ligands containing alkyl ligands, as in Grignard reagents. When mixed with lithium compounds bonded to nucleophilic ligands, the alkaline earth metals are expected to form equilibrium compositions with the lithium composition. Pseudo-alkaline earth metals refer to group 12 metals of the periodic table (zinc, cadmium, mercury) that exhibit similar chemical properties to group 2 alkaline earth metals. Zinc is used as an example in the following synthetic reactions. Compositions such as Q(Sn(L3)2 and Li(Q(Sn(L3)3)) (where Q is an alkaline earth metal or pseudo-alkaline earth metal) are thought to form in solution, but the exact composition has not been directly evaluated, and relatively complex equilibria may exist. Although we do not wish to be limited by theory, the introduction of alkaline earth metals and / or pseudo-alkaline earth metals promotes the subsequent formation of tin-carbon bonds by altering the reaction pathway and / or intermediates so that the energy released during the reaction promotes the formation of Sn-C bonds. Alkaline earth or pseudo-alkaline earth metals may be added stoichiometrically or not, and can be selected to provide the desired nucleophilicity of the resulting MSnL3 intermediate.

[0025] Monoalkyltin compositions can generally be prepared from monoalkyltin trichlorides produced by the following types of redistribution reactions. R4Sn+3SnX4→4RSnX3 R2SnX2+SnX4→2RSnX3 (In the formula, R is an alkyl group, and X is a halide (or halogenated part, halogenated site, or halide), generally a chloride). Langer et al. reported the formation of CH3SnCl3 from a redistribution reaction involving (CH3)2SnCl2 and SnCl4 in high-temperature dimethyl sulfoxide (DMSO). (Tetrahedron Letters, 1967, 1, 43-47; U.S. Patent No. 3,454,610, 1969, both incorporated herein by reference). DMSO forms adducts with monoalkyltin products, which aid in the separation and purification of the products.

[0026] Catalysts can be used to produce monoalkyl derivatives that may be difficult or impossible to prepare without them. The use of phosphorus-halogen compounds as catalysts in mixtures of phosphorus pentoxide and hydrochloric acid is described, for example, in Neumann's U.S. Patent No. 3,459,779, entitled "Process for the production of alkyltin trihalides," which is incorporated herein by reference. The redistribution of dialkyltin dihalides or tetraalkyltin compositions using tin tetrahalides can also be catalyzed with quaternary ammonium salts at temperatures above 150°C (TGKugele and DHParker's U.S. Patent No. 3,867,198, "Catalyzed redistribution of alkyltin halides," which is incorporated herein by reference). SnF2 has been found to catalyze the redistribution reaction (Buschhoff and Neumann's U.S. Patent No. 4,604,475, "Method for making organotin halides," which is incorporated herein by reference). In U.S. Patent No. 6,768,017, titled "Process for the production of monoalkyl tin trihalides" (which is incorporated herein by reference), Thoonen et al. describe the use of transition metals to catalyze redistribution reactions.

[0027] In U.S. Patent No. 7,592,472, titled "Process for the Preparation of Monoalkyl Tin Trihalides and Dialkyl Dihalides" (which is incorporated herein by reference), Boele et al. describe the reaction of an alkene, tin dihalide, and hydrogen halide in the presence of a transition metal catalyst to produce monoalkyltin trihalides. In U.S. Patent No. 8,198,352, titled "High Purity Monoalkyltin Compounds and Uses Thereof" (which is incorporated herein by reference), Deelman et al. describe the purification of monoalkyltin trichlorides and their conversion to derivative compositions by substituting the chloride with a mercaptoacetate.

[0028] While several methods are available for preparing monoalkyltin compositions, their applicability is often limited by practical considerations regarding specific alkyl groups. Furthermore, reported reactions may result in low product yields and multiple mono and polyalkyl products, requiring subsequent purification steps to isolate the target compound. Catalyst residue in the product can impair applications requiring very low concentrations of trace metals.

[0029] Edson et al., in U.S. Patent Application Publication No. 2019 / 0315781A1, entitled "Monoalkyl Tin Compounds with Low Polyalkyl Contamination, Their Compositions and Methods" (which is incorporated herein by reference), describe an improved method for synthesizing monohydrocarbyl tin triamides and monohydrocarbyl tin trialkoxides. Triamides are prepared by substitution reactions between alkylzinc or alkylmagnesium reagents and tin tetraamides. Polalkyl impurities are removed from the resulting triamide by fractional distillation. The triamide can then be converted to a trialkoxide by reaction of the amide with a stoichiometric amount of alcohol. In this study, very little polyalkyl impurity was generated from the initial reaction, but fractional distillation was used to further reduce the impurity level.

[0030] Conventional methods for preparing monoalkyltin triamides have involved using lithium reagents to convert tintetraamides to the desired triamides. For example, t-butyltris(diethylamide)tin (t-BuSn(NEt2)3) can be synthesized using lithium reagents according to the method described by Haenssgen, D.; Puff, H.; and Beckerman, NJ Organomet. Chem. 1985, 293, 191 (which is incorporated herein by reference). However, these methods using lithium reagents may produce a mixture of monoalkyl and dialkyl tin products. Reported methods for preparing monoalkyltin triamides containing secondary alkyl groups produce a mixture containing a large proportion of mono, di, and trialkyltin products.

[0031] The methods described herein focus on the synthesis of monoalkyltin triamides and monoalkyltin triacetides with low polyalkyl concentrations before distillation. This method can also be applied to synthesize monoalkyltin products containing hydrocarbyl groups that cannot be readily prepared in pure form by other methods known in the art. In this synthetic reaction, the hydrocarbyl ligand is generated from an organohalide reactant (or organohalide reactant). A wide range of compounds are readily available to supply ligands. While other synthetic techniques may be broadly applicable to the synthesis of various hydrocarbyl ligands, practical limitations may exist in terms of the composition of the reactants for ligand introduction, as well as yield, reaction time, choice of appropriate solvent, and other potential practical constraints. The synthesis of alkali metal tin compounds provides useful intermediates that may also be useful in other situations.

[0032] With regard to the design of improved EUV patterning compositions, it may be advantageous to adjust the hydrocarbyl ligand to include atoms with high EUV absorption, such as iodine, in order to improve the efficiency of the patterning process. In the methods described herein, the reactant (or organohalide reactant, I X may be an iodinated organohalide (or iodinated organic halide, iodinated organohalide, or iodinated organohalide), where R IX is a hydrocarbyl group (alkyl, cycloalkyl, alkenyl, alkynyl, aryl) having 1 to 30 carbon atoms, in which at least one hydrogen atom is substituted with an iodine atom. X is a halide (or halogenated group, halogenated moiety, halide) such as iodide (or iodide), chloride (or chloride), and bromide (or bromide). In some embodiments, other halide groups (or halogenated group, halogenated moiety group, or halide group) can be introduced instead of the iodized group, and therefore R I It can also be considered that it has other halides (or halogenated sites, halogenated groups, or halides) to replace iodine. Typically, reactants (or reactants) have multiple halogenated atoms (or halide atoms, halogenated groups, or halogenated group atoms). This is because one is substituted by nucleophilic substitution to form a tin-carbon bond, while the other halides then remain in the halogenated ligand. If the halides are not equivalent, the carbon atom directly bonded to the halide will have different electrophilic properties depending on what the halide is. In such cases, it is possible to lead the reaction to the correct product by ensuring that the appropriate halide is on the carbon of interest. Generally, the smaller the halide, the more electrophilic the carbon will be, but other considerations are always present. Typically, the reaction can be highly selective to add to the more electrophilic carbon.

[0033] R 1can optionally have other heteroatom substitutions such as N, O, P, S, or other halogenated atoms (or halide atoms, haloid atoms or halogenated moiety atoms). Non-limiting examples of iodinated organohalide reactants include 2,2-diiodopropane and 3-iodobenzyl bromide. Other possible iodinated organohalide reactants (or iodinated organohalide reactant, iodinated organohalide reactant or iodinated organohalide reactant) have two or three or more iodine atoms on a hydrocarbyl group. A fully iodinated aryl halide is also contemplated. The iodinated organohalide reactant can be utilized to synthesize monoalkyltin triamides and acetylide products containing an iodinated hydrocarbyl ligand. Iodinated hydrocarbyltin trialkoxides can be further formed as described for the non-iodinated hydrocarbyltin trialkoxides herein. For the purposes of this disclosure, reactions involving RX or RSnL3 compounds are construed to be exchangeable with R I X or R I SnL3 compounds. In some desirable embodiments, the halogenated ligand has a structure represented by the formula R 1 R 2 XC−, where R 1 and R 2 are independently H or any other organic moiety that conforms to the broad definition of R above, provided that both R and R' are not H, and X is a halide (or halogenated moiety, halogenated site, halide), F, Cl, Br, or I. Thus, in these compounds, the halogen atom is directly bonded to the carbon forming the tin bond. After completion of the synthesis, the compounds, which are products with optional hydrolysis and / or condensation, can be represented by the formula R 1 R 2 XCSnZ3, where Z is L and L is a hydrolyzable ligand or O x(OH) 3-x where 0 < x < 3. In another desirable embodiment, the halogenated ligand has the formula AR 1 R 2 C−, where A is an aromatic ring having at least one halogen substitution (or halogen substitution moiety or halogen substituent), and R 1 and R 2 are each independently H or any other organic moiety consistent with the broader definition of R above. A can be C6H4X, C6H3X2, C6X5, or any other suitable aromatic ring, and X is a halide (or halogenated moiety, halogenated site, halide), F, Cl, Br, or I. After completion of the synthesis, the compound, which is a product with optional hydrolysis and / or condensation, can be represented by the formula AR 1 R 2 CSnZ3, where Z is L and L is a hydrolyzable ligand or O x (OH) 3-x where 0 < x < 3. In particular, iodine has a large EUV absorption. Although the EUV absorption of other halogens is not so significant, they can still be advantageous for replacing hydrogen because the EUV absorption of hydrogen is slight.

[0034] The exemplified precursor compounds also include R groups having a cyano (also called nitrile) group or an ether group. The cyano compound can have the formula R'R''(N≡C)CSnZ3, where R' and R'' are each independently a hydrocarbyl group having 1 to 15 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, and Z is L and L is a hydrolyzable ligand or O x (OH) 3-x (0 < x < 3). In some embodiments, R' and R'' are such that R' is a linear or branched alkyl (-C n H 2n+1 , n is 1 to 5). The compound having an ether group can have the formula.

[0035] Although the overall synthesis can be considered as two steps, more generally, this synthesis can be considered a multi-step process. However, the number of steps can be subjective, as intermediates are usually not isolated and purified. While we do not wish to be limited by theory, conceptually, it can be useful to consider the overall synthetic process as involving two steps. The first step involves the formation of a four-coordinate tin with three amide / acetylide ligands and a metal-tin bond (the metal being an alkali metal and / or alkaline earth / pseudo-alkaline earth metal), which can have both ionic and covalent characteristics, but the concept is not limited by structural theory. In the second step, the metal-tin interaction is sp 3 or sp 2 The carbon-tin bond is replaced with a hydrocarbyl ligand to tin. The overall reaction involves oxidation from tin(II) to tin(IV) and exchange of the carbon-tin bond with three amide / acetylide ligands and two corresponding halide ligands (or halide ligands). The first step in forming the metallic tin triamide / acetylide can usually be conceptually divided into several steps depending on the specific starting materials.

[0036] As illustrated, monohydrocarbyl tin triamide and monohydrocarbyl tin triacetide can be prepared by the following overall reaction: 3HNR'2+3MR''(+M'Z)+SnX2+RX→RSn(NR'2)3+by-product, or 3R'CCH+3MR''(+M'Z)+SnX2+RX→RSn(CCR')3+byproduct. (1)

[0037] In these reactions, M is usually lithium, but lithium can be replaced with other alkali metals, namely sodium, potassium, rubidium, and cesium. M'Z in parentheses represents an optional reactant M''OR'' or M'''X2, where M'' is an alkali metal ion, OR'' is an alkoxide that remains inert (or passive), M''' is an alkaline earth / pseudo-alkaline earth metal provided as a halide (or halogenated moiety), and X is a halide ion (or halogenated ion, halogenated moiety ion). From a practical standpoint for some target products, an alkali metal alkoxide (MOR) can be added as the first step of the reaction. 0 The addition of ) results in a more favorable reaction yield and reaction rate. In addition, the desired reactants are more readily obtained in such treatment. Nevertheless, for some organic ligands, better yields can be obtained by introducing non-lithium alkali metal compounds. Therefore, a further exemplary embodiment containing potassium has the following overall reaction: 3HNR'2+3LiR''+KOR 0 +SnX2+RX→RSn(NR'2)3+byproduct, or 3R'CCH+3LiR''+KOR 0 +SnX2+RX→RSn(CCR')3+byproduct(2)

[0038] In the reactions represented by these formulas, potassium (K) can be replaced with other non-Li alkali metal ions. Example 7 describes the synthesis of alkyltin iodide triamide represented by formula (CH3)2ICSn(N(CH2)2)3 by a reaction following reaction (2). This synthesis involves both n-butyllithium and potassium tert-butoxide, and alkyl iodide halide (or alkyl iodide halide or alkyl iodide halide). Example 8 describes the synthesis of aryltin iodide triacetide represented by (C6H5I)CH2Sn(CCSi(CH3)3) by a reaction following reaction (2). This synthesis involves both n-butyllithium and potassium tert-butoxide, and aryl iodide halide (or aryl iodide halide or aryl iodide halide). In reactions (1) and (2), X is a halide (or halogenated part, halogenated site, halide), and R'' is a hydrocarbyl group having ≤10 carbon atoms. Since R'' is incorporated into a byproduct, usually HR'', what it is is generally not particularly limited or important and can be selected for general availability, low cost, ease of byproduct removal, and good reactivity. The R' group provides substituents on the corresponding ligands of the product composition. In formula (2), potassium can be introduced in a stoichiometric amount relative to tin for the formation of a potassium-tin composition, rather than in a stoichiometric amount for the introduction of an amide ligand, which is the situation for lithium in this reaction. In additional or alternative embodiments, KOR 0 This can be substituted or supplemented with M''X2 such as ZnCl2, where M'' is an alkaline earth metal ion or pseudo-alkaline earth metal ion.

[0039] In some embodiments, it may be beneficial to carry out the above reaction in the presence of a suitable additive, such as tris(2-aminoethyl)amine (TREN), as described in Edson et al.'s U.S. Patent Application Publication No. 2019 / 0315781, entitled "Monoalykyl Tin Compounds with Low Polyalkyl Contamination, Their Compositions and Methods" (hereinafter referred to as the '781 application, which is incorporated herein by reference). Such additives can improve the purity of the product, reduce the activation energy of the reaction process, or catalyze the reaction process. The above reaction can be carried out in a suitable solvent selected for various properties of the reactants and products, such as solvation, toxicity, and flammability. After the preparation of the improved photosensitive composition, the composition can be further purified as needed. In some embodiments, fractional distillation methods, such as those described in the '781 application, can be effectively used.

[0040] RX organohalide compounds (or RX organohalide compounds, RX halogenated organic compounds, RX organohalide compounds) are selected to provide desirable organic ligands to monoorganotin products. Due to the wide availability of RX compounds as reactants and the broad reactivity of the compounds in the corresponding reactions, the ability to introduce diverse organic ligands into the resulting monoorganotin products in practical yields and reasonable reaction times is provided. This versatility is demonstrated to some extent by the exemplified products.

[0041] As will be further explained below, the overall reaction can be considered the result of two or more consecutive reactions, although the isolation or purification of intermediates is usually not performed. The first reaction involves the synthesis of alkali metal amides or alkali metal acetylides, such as lithium amides or lithium acetylides. Lithium amides and lithium acetylides are known compounds, some of which may be commercially available in some form, but because these compounds are highly reactive and spontaneously combustible, it is convenient and advantageous to synthesize them in situ as part of the overall reaction. Non-lithium alkali metal amides or non-lithium alkali metal acetylides can be synthesized in a similar manner. However, in some embodiments, the non-lithium alkali metal can be introduced in a stoichiometric amount similar to tin, rather than three times the amount corresponding to the amide / acetylide ligand. Non-lithium metal ions can be more readily available than other alkali metal precursor compounds and / or can be more conveniently supplied as alkali metal alkoxide compounds and / or alkaline earth / pseudo-alkaline earth dihalides (or alkaline earth / pseudo-alkaline earth dihalide(s)). Tin dihalides (such as tin dichloride) react with alkali metal amides to form alkali metal tin triamides or alkali metal tin triacetides.

[0042] Currently, the isolation of alkali metal tin triamides or alkali metal tin triacetides has not been achieved. Improved synthetic techniques do not depend on exactly what the intermediate is, and the general discussion herein focuses on the entire starting material and the final product that can be isolated and characterized. That said, the estimation of what the intermediate is is based on strong assumptions derived from the species present. In the specific solvents used, the metal ions are not expected to be sufficiently solvated. However, since the composition remains in solution, the formation of large clusters or gelation is not observed. While we do not wish to be limited by theory, organometallic reagents, such as alkyllithium, alkylmagnesium (Grignard reagents), and potassium tert-butoxide, are known to form clusters such as tetramers, hexamers, and cubanes with metal-metal bonds, and therefore it is reasonable to assume that similar species are formed in solution as perhaps complex equilibrium mixtures, which have been difficult to characterize until now. In that case, the relative stability of known species suggests which intermediate species can be expected to exist, but rigorous structural characterization is not necessary to understand the fundamental chemical involvement in the reaction. The reactivity of the species would not be inconsistent with the fact that species cannot be isolated by removing the solvent.

[0043] Although the overall reaction is shown above, these reactions are carried out in multiple steps. Since one of the reactants is a tin dihalide, such as tin dichloride, considerations for solvent selection include the appropriate solubility of the tin dihalide. Other initial reactants, such as dihydrocarbylamines and monoalkyllithium (or generally monoalkyl alkali metals), can be dissolved in different solvents. The reaction is usually carried out in a dry organic solvent in an oxygen-free or depleted atmosphere, such as a nitrogen-purged atmosphere. The solvent can be selected to provide solubility for various components. Due to the interaction between the solvent and metal ions, the choice of solvent can be based at least partially on the reaction rate in the selected solvent, which can be assessed empirically. If different solvents are selected, they are usually miscible. Aprotic polar solvents (or aprotic polar solvents or polar organic solvents) such as ethers (e.g., dimethyl ether, diethyl ether), tetrahydrofuran (THF), acetone, and mixtures thereof are generally useful. The solvent should generally be selected to be inert to the reactants, intermediates, and products. For example, if multiple solvents are used to introduce distinct reactants, the solvents should generally be miscible with each other. The initial reaction can be considered the synthesis of an MSnL3 intermediate, where L is a dialkylamide (dihydrocarbylamide) or alkylacetylide (hydrocarbylacetylide), although the specific structure has not been confirmed. From the reactants and reaction conditions, the evidence suggests the formation of a tin-ligand bond, making the presence of an SnL3 moiety highly probable, and the metal cation likely accompanied by a tin moiety for stabilization, although the specific structure may exist in a complex equilibrium mixture. This initial reaction can, if necessary, be considered as two distinct reactions: an initial partial reaction aimed at forming a metal ligand composition (ML) and a subsequent partial reaction with SnCl2 or other tin dihalides. As described in detail, M may be an alkali metal, as well as an alkaline earth metal and / or pseudo-alkaline earth metal.Typically, in the first reaction, the solution is cooled to below 10°C, and in some embodiments to 0°C, which may be a convenient temperature for the use of an ice bath. However, there is nothing special about this temperature for non-aqueous solutions. Cooling allows the reaction to be controlled as desired while maintaining a moderate reaction rate. The first partial reaction can be carried out as long as it is practical and is not particularly limited. The first partial reaction can be continued for at least about 30 seconds, at least about 2 minutes in other embodiments, from 1 minute to 5 hours in some embodiments, and from about 2 minutes to about 3 hours in some embodiments. In some embodiments, two partial reactions can be combined and carried out as essentially a single reaction, which is virtually zero time for the first partial reaction or a short time for the first partial reaction. When non-lithium alkali metal alkoxides and / or alkaline earth (or pseudo-alkaline earth) dihalides are introduced as reactants, these compounds can be added conceptually as part of the first or second partial reaction, or possibly as a third partial reaction between the first and second partial reactions. Those skilled in the art will assume that additional ranges of time and temperature within the express ranges described above are assumed and will be recognized as being within the scope of this disclosure.

[0044] Typically, alkyllithium reactants and amine / acetylene reactants are used in approximately stoichiometric amounts, but usually, the amine / acetylene reactant is used in small to moderate excess amounts, for example, from about 1 mole percent (mol%) to about 50 mol%. When non-lithium alkyl alkali metal compounds are used, similar stoichiometric amounts or ligand precursors (dialkylamine or alkylacetylene) can be used. Typically, it is desirable to have a ML composition in a 3:1 ratio to the molar amount of Sn in order to attach three ligands to each tin. When non-lithium metal alkoxy alkali metal compounds are used with alkyllithium, the amount of alkyllithium can be based on the molar equivalent of the amine / acetylene reactant, while the non-alkali metal compound can be in an equal molar amount to the tin compound added, but more amounts of metal (alkali metal or alkaline earth metal or pseudo-alkaline earth metal) can be used as needed, as long as no additional ML is formed. In corresponding embodiments, tin reactants can be added in an approximate molar equivalent (1:3) of the reactants contributing to the ML ligands in order to form three ligand-tin bonds for each tin atom. The reduced amount of contaminants from tin products with 1, 2, or 4 ligands underscores the effectiveness of controlling the molar ratio of tin to the ML reactants. The metal concentration in the reactant solution is typically about 0.025 M to about 2 M, and in further embodiments, about 0.5 to about 1.5 M. Those skilled in the art will recognize that the above-mentioned express range of concentrations and acceptable stoichiometric ratios are assumed to be within the scope of this disclosure.

[0045] The second reaction involves the introduction of a carbon-tin bond, along with the formation of an organic ligand bonded to tin. The carbon-tin bond conceptually replaces the metal-tin bond, and the metal is an alkali metal, alkaline earth metal, and / or pseudo-alkaline earth metal. The organic ligand bonded to tin arises from the reaction with an organic halide (or organohalide) RX. Typically, at least a nearly stoichiometric amount of organic halide is introduced to form the carbon-tin bond, although an excess of organic halide may also be introduced. In some embodiments, up to a 3-fold molar excess of organic halide can be used in the reaction, and in further embodiments, about 1 to about 2 molar equivalents of RX per mole of Sn can be used. The solvent can be the same as that used in the first reaction, or selected from the same available solvents and mixtures thereof. The product of the first reaction is usually not purified before the second reaction, but by-products can be removed if convenient. The metal concentration is generally similar to that of the first reaction step, but usually slightly lower due to dilution. To account for the exothermic nature of the reaction, the second reaction can be initiated at a low temperature, typically around 0°C, more commonly around -78.5°C to 10°C, although it is not strictly necessary. In some embodiments, the reactants can be mixed at room temperature. After mixing the reactants for the second reaction, the reaction can be continued at the same temperature or gradually warmed to a temperature of about 20°C to 50°C or room temperature (20-24°C). The reaction can be carried out for at least about 15 minutes, from about 15 minutes to about 24 hours in some embodiments, and from about 30 minutes to about 15 hours in some embodiments, although longer reaction times can be used as needed. Those skilled in the art will recognize that additional ranges of concentration, molar ratio, temperature, and time shown above for the second reaction are assumed and are within the scope of this disclosure.

[0046] Since the reactions described herein are exothermic, it may be beneficial to modify various synthesis parameters such as the amount of reactants, reaction temperature, reagent addition time, and reaction time. Such considerations are known to those skilled in the art. A useful analytical technique for analyzing a reaction and informing the implementer of appropriate process conditions is reaction calorimetry. Calorimetry data can provide thermodynamic variables useful for a given reaction. In particular, scale-dependent variables (e.g., heat of enthalpy) for the reaction of interest can be measured, which can be used to properly carry out the reaction on a larger scale. In this way, process variables can be appropriately controlled for reactions at different scales. Reaction calorimetry data are included in some of the following examples. Within the guidelines shown above, along with the guidance of the following examples, those skilled in the art will recognize that specific parameters of a particular reaction can be adjusted to obtain the desired results. Those skilled in the art can optimize using routine experiments based on these teachings for a wide range of product compositions. The illustrated reactions yield good yields and high specificity for the product compositions.

[0047] After the product has formed, the organotin tri(dihydrocarbylamide / hydrocarbyl acetylide) can be purified. Purification generally involves separating the target product from by-products and any possible unreacted reagents, although this varies depending on the nature of the product. Purification can usually be carried out by methods known in the art. Typical means of purification can include filtration, recrystallization, extraction, distillation, or a combination thereof. Filtration is typically performed on the crude product mixture to remove insoluble contaminants and / or by-products, such as metal halide salts (or metal halide salts) such as LiCl, from the solution containing the target product. Recrystallization can be useful for purifying solid compounds by forming a saturated solution by heating and then allowing it to cool. Extraction techniques can include, for example, liquid-liquid extraction, which separates the target compound based on its relative solubility using two immiscible solvents with different densities. Purification may also include the removal of any volatile compounds, including solvents, from the product mixture by drying or exposure to vacuum. For products with high vapor pressure, it may be desirable to purify the product by vacuum distillation or fractional distillation designed to achieve high purity as needed. See U.S. Patent Application Publication 2020 / 0241413 by Clark et al., entitled "Monoalkyl Tin Trialkoxides and / or Monoalkyl Tin Triamides With Low Metal Contamination and / or Particulate Contamination and Corresponding Methods" (which is incorporated herein by reference). The product may also be reacted to form derivatives such as organotin trialkoxides, which can be further purified by the above techniques and other means known in the art.

[0048] The organotin precursor compositions described herein can be effectively used for radiation patterning, particularly EUV patterning. Due to their greater flexibility in ligand selection, ligands can be designed to be particularly effective for specific applications, and patterning results can be further improved. Generally, any suitable coating process can be used to supply the precursor solution to the substrate. Suitable coating techniques include, for example, solution deposition techniques such as spin coating, spray coating, dip coating, and knife-edge coating, as well as printing such as inkjet printing and screen printing. Many precursors are also suitable for deposition onto substrates, as described in the '618 patent mentioned above. In some R ligand compositions and / or specific process studies, deposition may be useful for preparing radiation-sensitive coatings.

[0049] For use in solution deposition patterning compositions, it is sometimes desirable to convert the product to an organotin trialkoxide. This reaction is usually carried out by purifying the product by distillation and then reacting it with the corresponding alcohol. Additional solvents may or may not be used. To better control the reaction, the reaction may be first cooled to an ice bath temperature and then heated to room temperature (or left to warm to room temperature or left to warm to room temperature). The resulting organotin trialkoxide is usually an oil that can be purified by distillation. These steps are outlined in the following examples. Although it is not necessary to convert the precursor composition to a trialkoxide to form a coating precursor, organotin trialkoxides can be convenient precursors for deposition because they produce harmless volatile products, such as alcohols, after hydrolysis and coating formation.

[0050] After preparing the desired organotin precursor, the precursor solution can be prepared by dissolving the precursor in a suitable solvent, such as an organic solvent, e.g., alcohol, aromatic and aliphatic hydrocarbons, esters, or combinations thereof. Suitable solvents include, for example, aromatic compounds (e.g., xylene, toluene), ethers (anisole, tetrahydrofuran), esters (propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), alcohols (e.g., 4-methyl-2-pentanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol), ketones (e.g., methyl ethyl ketone), and mixtures thereof. Typically, the selection of an organic solvent may be influenced by its solubility parameters, volatility, flammability, toxicity, viscosity, and potential chemical interactions with other processing materials. After dissolving and mixing the components of the solution, the characteristics of the species may change as a result of partial hydrolysis in situ, hydration, and / or condensation.

[0051] Organotin precursors can be dissolved in a solvent at a concentration that provides a suitable concentration of Sn for forming a coating of appropriate thickness for the treatment. The concentration of the species in the precursor solution can be selected to achieve the desired physical properties of the solution. In particular, lower overall concentrations can yield desirable properties of the solution for certain coating techniques, such as spin coating, which allow for thinner coatings using reasonable coating parameters. It may be desirable to use thinner coatings to achieve ultrafine patterning and reduce material costs. Typically, the concentration can be selected to be appropriate for the chosen coating technique. Coating properties will be further described below. Typically, tin concentrations range from about 0.005 M to about 1.4 M, in further embodiments from about 0.02 M to about 1.2 M, and in additional embodiments from about 0.1 M to about 1.0 M. Those skilled in the art will assume that additional tin concentration ranges within the express ranges described above are assumed and will be recognized as being within the scope of this disclosure.

[0052] In some embodiments, an improved photosensitive precursor composition, R n Sn4-n R can be present in a blended solution together with one or more organotin compositions, such as and their hydrolysates, and R is selected from a variety of parts described in detail herein and explicitly detailed above. Such a blended solution can be adjusted to optimize various performance considerations, such as solution stability, coating uniformity, and patterning performance. In some embodiments, the improved photosensitive composition may contain at least 1 mol% of the target component in the blended solution, in a further embodiment at least 10 mol% of the blended solution, in a further embodiment at least 20 mol% of the blended solution, and in a further embodiment at least 50 mol% of the specific target component in the blended solution. Further ranges of mol% of the improved photosensitive composition within a clear range of the blended solution are assumed and are within the scope of this disclosure.

[0053] Due to their generally high vapor pressure, the organotin compositions described herein may be useful as precursors for forming coatings by vapor deposition. Vapor deposition methods typically include chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), and modified forms thereof. In a typical vapor deposition process, organotin compositions can be reacted with small molecule gas-phase reagents such as H2O, O2, H2O2, O3, CH3OH, HCOOH, CH3COOH, etc. (or similar), which serve as sources of O and H for the production of radiation-sensitive organotin oxide and oxide hydroxide coatings. The vapor deposition of radiation-patternable organotin coatings is described in Wu et al., International Patent Application No. PCT / US2019 / 031618, entitled "Methods for Making EUV Patternable Hard Masks," which is incorporated herein by reference. The production of radiation-sensitive organotin coatings can typically be achieved by reacting the volatile organotin precursor RSnL3 with small gas-phase molecules. The reaction may involve hydrolysis / condensation of an organotin precursor to hydrolyze the hydrolyzable ligand while leaving the Sn-C bond substantially intact.

[0054] Regarding a typical process for radiation-based patterning, such as extreme ultraviolet (EUV) lithography, a photoresist material is deposited or coated as a thin film on a substrate, baked before exposure, exposed to radiation patterns to form a latent image, baked after exposure, and then developed with a liquid (typically an organic solvent) to produce a developed pattern of the resist. Fewer steps may be used as needed, and additional steps may be used to remove residues and improve pattern fidelity.

[0055] The thickness of a radiation-patternable coating may depend on the desired process. When used in single-pattern EUV lithography, the coating thickness is typically selected to obtain a pattern with few defects and reproducibility. In some embodiments, suitable coating thicknesses can be 0.1 nm to 100 nm, in further embodiments about 1 nm to 50 nm, and in even further embodiments about 2 nm to 25 nm. Those skilled in the art will understand that an additional range of coating thicknesses is conceivable and falls within the scope of this disclosure.

[0056] The coating thickness of radiation-patternable coatings fabricated by vapor deposition can generally be controlled by appropriately selecting the reaction time or process cycle. The thickness of radiation-patternable coatings may depend on the desired process. In use in single-pattern EUV lithography, the coating thickness is typically selected to obtain a pattern with a low defect rate and high patterning reproducibility. In some embodiments, a suitable coating thickness can be 0.1 nm to 100 nm, in further embodiments about 1 nm to 50 nm, and in even further embodiments about 2 nm to 25 nm. Those skilled in the art will understand that further ranges of coating thicknesses are conceivable and within the scope of this disclosure.

[0057] The substrate generally represents a surface on which a coating material can be deposited, and that surface may comprise multiple layers, with the uppermost layer being the uppermost layer. The substrate is not particularly limited and may include any suitable material such as silicon, silica, other inorganic materials such as ceramics, and polymer-based materials.

[0058] After depositing and forming a radiation-patternable coating, further processing may be performed before exposure to radiation. In some embodiments, the coating can be heated to 30°C to 300°C, in further embodiments to 50°C to 200°C, and in even further embodiments to 80°C to 150°C. Heating can be performed for about 10 seconds to about 10 minutes in some embodiments, about 30 seconds to about 5 minutes in even further embodiments, and in even further embodiments to about 45 seconds to about 2 minutes. Additional ranges for temperature and heating time within the above express ranges are expected and assumed.

[0059] Composition patterning: Typically, radiation can be directed through a mask onto a coated substrate, or the radiation beam can be controlled and scanned across the entire substrate. The radiation can typically include electromagnetic radiation, electron beams (beta rays), or other suitable radiation. Generally, electromagnetic radiation can have a desired wavelength or wavelength range, such as visible radiation, ultraviolet radiation, or X-ray radiation. The achievable resolution for a radiation pattern generally depends on the radiation wavelength, and higher resolution patterns can generally be achieved with shorter wavelength radiation. Therefore, it may be desirable to use ultraviolet light, X-ray radiation, or electron beams, especially to obtain high-resolution patterns.

[0060] According to the international standard ISO 21348 (2007), incorporated herein by reference, ultraviolet light extends to wavelengths from 100 nm to less than 40030 nm. A krypton fluoride laser can be used as a light source for 248 nm ultraviolet light. The ultraviolet range can be subdivided in several ways based on accepted standards, such as extreme ultraviolet (EUV) from 10 nm to less than 121 nm and far ultraviolet (FUV) from 122 nm to less than 200 nm. For FUV radiation sources, the 193 nm line from an argon fluoride laser can be used. For lithography, 13.5 nm EUV light is used, which is generated from a plasma source of Xe or Sn excited using a high-energy laser or discharge pulse. Soft X-rays can be defined from 0.1 nm to less than 5 or 10 nm.

[0061] Based on the design of the coating material, a significant contrast in material properties can exist between the irradiated area with condensed coating material and the unirradiated coating material with substantially intact Sn-C bonds. In embodiments where post-irradiation heat treatment is used, the post-irradiation heat treatment can be performed at temperatures of approximately 45°C to approximately 250°C, in additional embodiments approximately 50°C to approximately 190°C, and in further embodiments approximately 60°C to approximately 175°C. Post-exposure heating can typically be performed for at least approximately 0.1 minutes, in further embodiments approximately 0.5 minutes to approximately 30 minutes, and in additional embodiments approximately 0.75 minutes to approximately 10 minutes. Those skilled in the art will recognize that additional ranges of post-irradiation heating temperatures and times within the above express ranges are assumed and within the scope of this disclosure. This high contrast in material properties further facilitates the formation of high-resolution lines with smooth edges in the developed pattern, as described in the following sections.

[0062] For negative image formation, the developer can be an organic solvent, such as the solvent used to form the precursor solution. Generally, the choice of developer may be influenced by the solubility parameters of both irradiated and unirradiated coating materials, as well as the volatility, flammability, toxicity, viscosity, and potential chemical interactions with other process materials of the developer. Suitable developers include, for example, alcohols (e.g., 4-methyl-2-pentanol, 1-butanol, isopropanol, 1-propanol, methanol), ethyl lactate, ethers (e.g., tetrahydrofuran, dioxane, anisole), and ketones (pentanone, hexanone, 2-heptanone, octanone). Development can be carried out for about 5 seconds to about 30 minutes, in further embodiments about 8 seconds to about 15 minutes, and in additional embodiments about 10 seconds to about 10 minutes. Those skilled in the art will assume that additional ranges beyond the express range described above are within the scope of this disclosure. In addition to the main developer composition, the developer may include additional compositions that facilitate the development process. Suitable additives include, for example, viscosity modifiers, solubilizers, or other processing aids. Where optional additives are present, the developer may contain additives in a range of about 10% by weight or less, and in further embodiments, about 5% by weight or less. Those skilled in the art will recognize that additional additive concentrations beyond the express range described above are conceivable and fall within the scope of this disclosure.

[0063] With weaker developers, such as diluted organic developers or coatings with a lower development rate, a higher temperature development process can be used to increase the process speed. With stronger developers, the temperature of the development process can be lowered to reduce the development speed and / or to control the dynamics of development. Generally, the development temperature can be adjusted between appropriate values ​​that match the volatility of the solvent. Furthermore, developers in which the coating material is dissolved near the developer-coating interface can be dispersed by sonication during development. The developer can be applied to the patterned coating material using any reasonable approach. For example, the developer can be sprayed onto the patterned coating material. Spin coating can also be used. In automated processes, a paddle method can be used, which involves pouring the developer onto the coating material in a stationary form. If necessary, spin rinsing and / or drying can be used to complete the development process. Suitable rinsing solutions include, for example, ultrapure water, aqueous tetraalkylammonium hydroxide solution, methyl alcohol, ethyl alcohol, propyl alcohol, and combinations thereof. After the image is developed, the coating material is placed on the substrate as a pattern.

[0064] In some embodiments, solvent-free (dry) development processes can be carried out by using suitable thermal or plasma development processes, such as those described in Tan et al.'s International Patent Application No. PCT / US2020 / 039615, entitled "Photoresist Development With Halide Chemistries" (which is incorporated herein by reference). For organotin photoresist coatings, dry development can be carried out by using a halogen-containing plasma and a gas such as HBr or BCl3. In some cases, dry development can offer advantages over wet development, such as reduced pattern collapse, reduced scum, and finer control of the developer composition, i.e., the plasma and / or etching gas.

[0065] After the developing step is complete, the coating material may be heat-treated to further condense the material and to further dehydrate, densify, or remove any residual developer from the material. While heat treatment may be desirable in some embodiments where the coating material is used as a resist and ultimately removed, if stabilization of the coating material is desirable to facilitate further patterning, this heat treatment may be particularly desirable in embodiments where the oxide coating material is incorporated into the final device. In particular, the baking of the patterned coating material can be carried out under conditions that allow the patterned coating material to exhibit the desired level of etching selectivity. In some embodiments, the patterned coating material can be heated to a temperature of about 100°C to about 600°C, in further embodiments about 175°C to about 500°C, and in additional embodiments about 200°C to about 400°C. Heating can be carried out for at least about 1 minute, in another embodiment about 2 minutes to about 1 hour, and in further embodiments about 2.5 minutes to about 25 minutes. Heating can be carried out in air, vacuum, or an inert gas atmosphere (such as Ar or N2). Those skilled in the art will recognize that additional ranges of temperature and time for heat treatment within the express range described above are assumed and are within the scope of this disclosure. Similarly, non-heat treatments, including blanket UV exposure or exposure to an oxidizing plasma such as O2, can also be used for similar purposes. [Examples]

[0066] The following examples demonstrate the synthesis and NMR characterization of monoalkyltin triamides, triacetides, and trialkoxide products with low polyalkyl contamination. The following reaction calorific data are shown for some examples: Maximum temperature reached: MAT (°C) Heat of reaction: ΔH r (kJ / mol) Heat conversion rate %: TC(%)

[0067] Example 1. Preparation of CH3CH2CH2Sn(N(CH2CH3)2)3 and CH3CH2CH2Sn(OC(CH3)2CH2CH3)3 This example demonstrates the synthesis of n-propyl tin triamide, CH3CH2CH2Sn(N(CH2CH3)2)3 (abbreviated as n-PrSn(NEt2)3), via an oxidative stanylation reaction involving SnCl2, diethylamine, n-butyllithium, and n-propyl iodide, and its subsequent conversion to n-propyl tin trialkoxide, CH3CH2CH2Sn(OC(CH3)2CH2CH3)3 (abbreviated as n-PrSn(O-tAm)3).

[0068] (a) Synthesis of CH3CH2CH2Sn(N(CH2CH3)2)3 In a 400 mL reactor equipped with a bubbler outlet, diethylamine (175 mmol, Aldrich) and anhydrous diethyl ether (53 ml, Aldrich) were mixed under positive N2 (g) pressure while flowing N2. The reactor was cooled to 0°C, and then 150 mmol of n-butyllithium (Aldrich, 1.6 M in hexane) was added dropwise. After stirring for 30 minutes, the intermediate product LiNEt2 was formed, and a double sample was taken and used for characterization. Next, SnCl2 (50 ml, 1 M, Fisher) in tetrahydrofuran was added dropwise to the solution. The reactor was heated to 18°C ​​and stirred for 30 minutes. The intermediate product LiSn(NEt2)3 was formed, and a double sample was taken and used for characterization. The solution was cooled again to 0°C, and then n-propyl iodide (75 mmol, Oakwood) was added dropwise. The solution was heated to 18°C ​​and stirred overnight. Subsequently, volatile components of the solution were removed under vacuum. Anhydrous pentane (200 ml, Aldrich) was added to the flask, and the mixture was filtered through Celite® S (Aldrich). The flask was washed with an additional 200 ml of anhydrous pentane, and the mixture was also filtered. After concentrating the filtrate to remove volatile components, it was purified by vacuum distillation (250 mTorr, 70-76°C) to obtain n-propylsutris(diethylamide), n-PrSn(NEt2)3 as a colorless liquid in 65.4% yield.

[0069] The heat of reaction was measured to determine the maximum temperature (MAT) and heat of reaction (ΔH) for each reaction type. r The heat transfer rate (TC) was evaluated. TC corresponds to the relative amount of total heat generated during the addition of the reagent alone.

[0070] [Table 1]

[0071] Figure 1 shows the LiSn(NEt2)3 in benzene-d6. 119 The Sn NMR spectrum is shown. The spectrum shows a single peak at 31.53 ppm. Figure 2 shows the n-PrSn(NEt2)3 in benzene-d6. 119 The Sn NMR spectrum is shown. The spectrum exhibits the following chemical shifts: 119 Sn NMR (149 MHz, benzene-d6) δ 17.35, -43.75, -68.88. The peak at -43.75 ppm accounts for 99% of the peak integral and is associated with the high purity of the monoalkyltin triamide product. Figure 3 shows n-PrSn(NEt2)3 in benzene-d6. 1 This is the 1H NMR spectrum. The spectrum shows the following chemical shifts: 1 ¹H NMR (400MHz, benzene-d6) δ 3.08-2.88 (m,6H,-N-CH2-), 1.67-1.53 ​​(m,1H,-Sn-CH2-CH2-), 1.11-0.89 (m,11H,-CH3).

[0072] (b) Conversion to CH3CH2CH2Sn(OC(CH3)2CH2CH3)3 N-propylsutris(diethylamide) (31.4 mmol) from step (a) of Example 1 was placed in a 50 mL round-bottom flask equipped with a stirring bar. The flask was cooled to 0°C in an ice bath, and then t-amyl alcohol (97.3 mmol, Aldrich) was slowly added dropwise. The reaction mixture was then brought to room temperature and stirred for 30 minutes. Volatile components of the solution were removed under vacuum, and the crude product was purified by vacuum distillation (400 mTorr, 65-70°C) to produce n-PrSn(O-tAm)3 as a colorless oil in 81% yield.

[0073] Figure 4 shows n-PrSn(O-tAm)3 in benzene-d6. 119 The Sn spectrum is shown. The spectrum shows the following chemical shifts: 119 Sn NMR (149 MHz, benzene-d6) δ-195.65. The single peak corresponds to a single tin environment and is therefore a monoalkyltin product. Figure 5 shows n-PrSn(O-tAm)3 in benzene-d6. 1 This is the H spectrum, and it has the following chemical shifts: 1 ¹H NMR (400 MHz, benzene-d6) δ 1.65 (hept, J=7.5 Hz, 1H), 1.45 (qd, J=7.5, 1.8 Hz, 3H), 1.30-1.17 (m, 9H), 0.96 (d, J=7.2 Hz, 1H), 0.94-0.78 (m, 5H). Quantitative proton-tin NMR and proton NMR were performed using selected standards to evaluate the purity of the product. 119 Sn qNMR, standard CH3Sn(C6H6)3, monoalkyltin with a purity of 94.2(7) mol%; 1 ¹H qNMR, standard 1,3,5-trimethoxybenzene, monoalkyltin with a purity of 95.60(2) mol%.

[0074] Example 2. Preparation of CH3CH2Sn(N(CH2CH3)2)3 and CH3CH2Sn(OC(CH3)2CH2CH3)3 This example demonstrates the synthesis of ethyl tin triamide, CH3CH2Sn(N(CH2CH3)2)3 (abbreviated as EtSn(NEt2)3), by an oxidative stanylation reaction involving SnCl2, diethylamine, n-butyllithium, and iodoethane, and its subsequent conversion to ethyl tin trialkoxide, CH3CH2Sn(OC(CH3)2CH2CH3)3 (abbreviated as EtSn(O-tAm)3).

[0075] (a) Synthesis of CH3CH2Sn(N(CH2CH3)2)3 In a 3 L round-bottom flask equipped with a bubbler and pressure relief port to support a continuous flow of N2(g), diethylamine (1442 mmol, Aldrich) and anhydrous diethyl ether (437 ml, Aldrich) were mixed under positive N2(g) pressure while N2 was flowing. The reactor was cooled to 0°C in an ice bath, and then 1236 mmol of n-butyllithium (Aldrich, 1.55 M in hexane) was added dropwise. After stirring for 1 hour, the intermediate product LiNEt2 was formed, and two samples were taken and prepared for characterization. Next, SnCl2 (412 ml, 1 M, Fisher) in tetrahydrofuran was added dropwise to the solution, and then the mixture was stirred for 1 hour. The intermediate product LiSn(NEt2)3 was formed, and two samples were taken and prepared for characterization. Subsequently, iodoethane (618 mmol, Aldrich) was added dropwise, and the reaction was then warmed to room temperature and stirred overnight. Volatile components of the solution were removed under vacuum. 500 mL of anhydrous pentane was added to the flask twice, and the solution was filtered through Celite® S (Aldrich). The filtrate was concentrated to remove volatile components, and then purified by vacuum distillation (60 mTorr, 80-85°C) to obtain ethyl-tin [tris(diethylamide)], EtSn(NEt2)3, as a colorless liquid in 78.6% yield.

[0076] Figure 6 shows EtSn(NEt2)3 119 The Sn NMR spectrum is shown. The spectrum exhibits the following chemical shifts: 119Sn NMR (149 MHz, benzene-d6) δ -40.69. A single peak at -40.69 ppm is associated with the high purity of the monoalkyltin triamide product.

[0077] (b) Conversion to CH3CH2Sn(OC(CH3)2CH2CH3)3 Ethyltin [tris(diethylamide)] (324 mmol) from step (a) of Example 2 was placed in a 400 mL reactor containing 50 mL of pentane. The flask was cooled to 0°C using a condenser, and then t-amyl alcohol (1004 mmol, Aldrich) was slowly added dropwise. The reaction was allowed to reach room temperature and stirred for 30 minutes. Volatile components of the solution were removed under vacuum, and the crude product was purified by vacuum distillation (40 mTorr, 82-88°C) to produce EtSn(O-tAm)3 as a colorless oil in 97% yield.

[0078] Figure 7 shows the EtSn(O-tAm)3 in benzene-d6. 119 The Sn NMR spectrum is shown. The spectrum exhibits the following chemical shifts: 119 Sn NMR (149 MHz, benzene-d6) δ-194.24. The single peak corresponds to a single tin environment and is therefore a monoalkyltin product. Quantitative proton tin NMR and proton NMR were performed using selected standards to assess the purity of the product. 119 Sn qNMR, standard CH3Sn(C6H6)3, monoalkyltin with a purity of 95.5(8) mol%; 1 ¹H qNMR, standard 1,3,5-trimethoxybenzene, monoalkyltin with a purity of 96.8(1) mol%.

[0079] The thermal behavior of the reactions for forming ethyl tin triamide and ethyl tin trialkoxide is summarized below.

[0080] [Table 2]

[0081] Example 3. Preparation of (CH3)3CSn(N(CH2CH3)2)3 and (CH3)3CSn(OC(CH3)2CH2CH3)3 This example demonstrates the synthesis of t-butyltin triamide, (CH3)3CSn(N(CH2CH3)2)3 (abbreviated as t-BuSn(NEt2)3) via an oxidative stanylation reaction involving SnCl2, diethylamine, n-butyllithium, and t-butyl iodide, and its subsequent conversion to t-butyltin trialkoxide ((CH3)3CSn(OC(CH3)2CH2CH3)3 (abbreviated as t-BuSn(O-tAm)3)).

[0082] (a) Synthesis of (CH3)3CSn(N(CH2CH3)2)3 In a 400 mL reactor equipped with a bubbler outlet, diethylamine (88 mmol, Aldrich) and anhydrous diethyl ether (27 ml, Aldrich) were mixed under positive N2 (g) pressure while flowing N2. The reactor was cooled to 0°C, and then 50 mmol of n-butyllithium (Aldrich, 1.6 M in hexane) was added dropwise. After stirring for 30 minutes, the intermediate product LiNEt2 was formed, and a portion was separated for characterization. Next, SnCl2 (28 ml, 1 M, Fisher) in tetrahydrofuran was added dropwise to the solution. The reactor was heated to 20°C and stirred for 30 minutes. The intermediate product LiSn(NEt2)3 was formed, and a portion was separated for characterization. The solution was cooled again to 0°C, and then t-butyl iodide (38 mmol, Aldrich) was added dropwise. The solution was heated to 40°C and stirred overnight. Subsequently, volatile components of the solution were removed under vacuum. Anhydrous pentane (2 × 60 ml, Aldrich) was added to the flask, and the mixture was filtered through Celite® S (Aldrich). The flask was washed with an additional 60 ml of anhydrous pentane, and the mixture was also filtered. After concentrating the filtrate to remove volatile components, it was purified by vacuum distillation (250 mTorr, 72-76°C) to obtain t-butylsutris(diethylamide), t-BuSn(NEt2)3 as a colorless liquid in 53% yield.

[0083] Figure 8 shows the t-BuSn(NEt2)3 in benzene-d6. 119 The Sn NMR spectrum is shown. The spectrum exhibits the following chemical shifts: 119 Sn NMR (149 MHz, benzene-d6) δ-81.69. A sharp single peak at -81.69 ppm is associated with the high purity of the monoalkyltin triamide product. No additional peaks were observed after distillation of the triamide.

[0084] (b) Conversion to (CH3)3CSn(OC(CH3)2CH2CH3)3 t-butylsutris(diethylamide) (13.2 mmol) from step (a) of Example 3 was placed in a 50 mL round-bottom flask equipped with a stirring bar. The flask was cooled to 0°C in an ice bath, and then t-amyl alcohol (41 mmol, Aldrich) was slowly added dropwise. The reaction mixture was then brought to room temperature and stirred for 30 minutes. Volatile components of the solution were removed under vacuum, and the crude product was purified by vacuum distillation (60 mTorr, 90°C) to produce t-BuSn(O-tAm)3 as a colorless oil in 94% yield.

[0085] Figure 9 shows the t-BuSn(O-tAm)3 in benzene-d6. 119 The Sn NMR spectrum is shown. The spectrum exhibits the following chemical shifts: 119 Sn NMR (149 MHz, benzene-d6) δ -219.45, -241.08, -369.97. The peak at -219.45 ppm has an integral value of 0.0018 and is not related to the bialkyl product. The peak at -241.08 ppm has an integral value of 0.9897 and is consistent with the monoalkyl t-BuSn(O-tAm)3 product. The peak at -369.97 ppm has an integral value of 0.0086 and is attributed to Sn(O-tAm)4.

[0086] The NMR results clearly demonstrate the ability to selectively synthesize monoalkyltin triamide and trialkoxide products.

[0087] Example 4. Preparation of (NC(CH3)2C)Sn(N(CH2CH3)2)3 This example demonstrates the synthesis of isobutyronitrile tin triamide (NC(CH3)2C)Sn(N(CH2CH3)2)3 (abbreviated as (NC(CH3)2C)Sn(NEt2)3) by an oxidative stanylation reaction involving SnCl2, diethylamine, n-butyllithium, and 2-bromo-2-methylpropanenitrile.

[0088] In a 250 mL round-bottom flask equipped with a bubbler pressure relief port, diethylamine (87.5 mmol, Aldrich) and anhydrous diethyl ether (26.5 ml, Aldrich) were mixed while flowing N2 (g). The reactor was cooled to 0°C in an ice bath, and then 75 mmol of n-butyllithium (Aldrich, 2.53 M in hexane) was added dropwise. After stirring for 30 minutes, SnCl2 (25 ml, 1 M, Fisher) in tetrahydrofuran was added dropwise to the solution, and the mixture was stirred for 1 hour. Subsequently, 2-bromo-2-methylpropanenitrile (37.5 mmol, synthesized in-house) was added. The reaction was warmed to room temperature and stirred for 1 hour. Volatile solution components were removed under vacuum. After adding 100 mL of anhydrous pentane twice to the flask, the mixture was filtered through Celite® S (Aldrich). After concentrating the filtrate to remove volatile components, the mixture was purified by vacuum distillation (250 mTorr, 70-76°C) to obtain isobutyronitrile tin tris(diethylamide) as a yellow oil in a yield of 21%.

[0089] Figure 10 shows (NC(CH3)2C)Sn(NEt2)3 in benzene-d6. 119 The Sn NMR spectrum is shown. After concentrating the filtrate to remove all volatile components, the result is shown in Figure 10. 119 Sn NMR spectra were obtained. The spectra show the primary singlet and the second-largest singlet with the following chemical shifts: 119 Sn NMR (149 MHz, benzene-d6) δ -94.73, -120.28.

[0090] Example 5. Preparation of (CH3OCH2)Sn(CCSi(CH3)3)3 This example demonstrates the synthesis of methoxymethyltin triacetide, (CH3OCH2)Sn(CCSi(CH3)3)3 (abbreviated as (CH3OCH2)Sn(CCSiMe3)3 or MOMSn(CCTMS)3) by an oxidative stanylation reaction involving trimethylsilylacetylene, SnCl2, n-butyllithium, and chloromethyl methyl ether.

[0091] In a 400 mL reactor equipped with a pressure-relieving bubbler, trimethylsilylacetylene (248 mmol, Oakwood, abbreviated as "HCCTMS") and anhydrous diethyl ether (123 ml, Aldrich) were mixed while flowing N2(g) to create a positive N2 pressure. The reactor was cooled to 0°C in a condenser, and then 240 mmol of n-butyllithium (Aldrich, 1.64 M in hexane) was slowly added dropwise. After stirring for 30 minutes, the intermediate product LiCCSiMe3 (also abbreviated as LiCCTMS) was formed, and a double sample was prepared for characterization. Next, SnCl2 in tetrahydrofuran (80 ml, 1 M, Fisher) was added dropwise to the solution. The solution was stirred at room temperature for 2 hours. The intermediate product LiSn(CCSiMe3)3 (also abbreviated as LiSn(CCTMS)3) was formed, and a double sample was prepared for characterization. The reactor was then cooled to 0°C using a condenser, followed by the dropwise addition of chloromethyl methyl ether (88 mmol, Aldrich, abbreviated as "MOM-Cl"), and the mixture was stirred overnight at room temperature. Volatile components of the solution were removed under vacuum. Two aliquots of 200 mL each of anhydrous pentane were added to the flask and then filtered through Celite® S (Aldrich). The filtrate was concentrated and volatile components were removed (250 mTorr, 70-76°C) to obtain methoxymethyl tin tris (trimethylsilyl acetylide), MOMSn (CCTMS)3 as a white powder in 31% yield.

[0092] Figure 11 shows the relationship between LiSn(CCSiMe3)3 in benzene-d6. 119The Sn NMR spectrum is shown. The spectrum shows a single peak at -478.5 ppm. Figure 12 shows the (CH3OCH2)Sn(CCSiMe3)3 in benzene-d6 with the following chemical shifts. 119 The Sn NMR spectrum is shown: 119 Sn NMR (149 MHz, benzene-d6) δ-324.23. A single sharp peak at -324.23 ppm is associated with the high purity of the monoalkyltin triacetylide product.

[0093] The thermal behavior of the reactions for forming each product is summarized below.

[0094] [Table 3]

[0095] Example 6. Preparation of (NC(CH3)2C)Sn(CCSi(CH3)3)3 This example demonstrates the synthesis of isobutyronitrile tin triacetide, (NC(CH3)2C)Sn(CCSi(CH3)3)3 (abbreviated as (NC(CH3)2C)Sn(CCSiMe3)3) via an oxidative stanylation reaction involving trimethylsilylacetylene, SnCl2, n-butyllithium, and 2-bromo-2-methylpropanenitrile.

[0096] In a 400 mL reactor equipped with a bubbler pressure release port, trimethylsilylacetylene (232.5 mmol, Oakwood) and anhydrous diethyl ether (116 ml, Aldrich) were mixed while flowing N2 (g). The reactor was cooled to 0°C using a condenser, and then 225 mmol of n-butyllithium (Aldrich, 2.53 M in hexane) was slowly added dropwise. After stirring for 30 minutes, the intermediate product LiSnCCSiMe3 (also abbreviated as LiCCTMS) was formed, and a double sample was prepared for characterization. Next, SnCl2 in tetrahydrofuran (75 ml, 1 M, Fisher) was added dropwise to the solution. The solution was heated to 20°C and stirred for 1 hour. The intermediate product LiSn(CCSiMe3)3 (also abbreviated as LiSn(CCTMS)3) was formed, and a double sample was prepared for characterization. The solution was cooled again to 0°C using a condenser, and then ZnBr2 (75 ml, 1 M, Aldrich) in THF (Aldrich) was added dropwise. The reaction was stirred for 10 minutes. The intermediate product Li[Zn(Sn(CCTMS)3)3] was formed, and an additional sample was prepared for characterization. Subsequently, 82.5 mmol of 2-bromo-2-methylpropanenitrile (IBN, synthesized in-house) was added to the reaction. The reactor temperature was maintained at 0°C and stirred overnight. After adding 100 mL of anhydrous pentane to the flask, the mixture was filtered through silica (Aldrich). The flask was then washed with another 200 mL of anhydrous pentane and filtered. By concentrating the filtrate and removing volatile components, isobutyronitrile tin tris(trimethylsilylacetylide), (NC(CH3)2C)Sn(CCSiMe3)3 was produced in 76% yield as a viscous off-white semi-solid.

[0097] Figure 13 shows the (NC(CH3)2C)Sn(CCSiMe3)3 in benzene-d6. 119 The Sn NMR spectrum is shown. The spectrum exhibits the following chemical shifts: 119Sn NMR (149 MHz, benzene-d6) δ -73.55, -151.23, -166.08, -175.87, -264.02, -274.33, -384.39. The main and secondary singlelines are at -264.02 and -166.08, with peak integrals of 0.75 and 0.17, respectively.

[0098] The thermal behavior of reactions involving ZnBr2 and IBN is summarized below.

[0099] [Table 4]

[0100] The above examples show the NMR spectra of synthesized organotin compounds that do not exhibit peaks associated with polyalkyltin compounds.

[0101] Example 7. Preparation of (CH3)2ICSn(N(CH2CH3)2)3 and (CH3)2ICSn(OC(CH3)3)3 This example demonstrates the synthesis of iodopropyl tin triamide, (CH3)2ICSn(N(CH2CH3)2)3 (abbreviated as 2-iodo-PrSn(NEt2)3) via an oxidative stanylation reaction involving SnCl2, diethylamine, n-butyllithium, potassium tert-butoxide, and 2,2-diiodopropane, and its subsequent conversion to 2-iodopropyl tin tris(tert-butoxide), (CH3)2ICSn(OC(CH3)3)3 (abbreviated as iodo-PrSn(O-tBu)3).

[0102] n-butyllithium (1.03 mL, 2.53 mmol, 2.45 M in hexane) was added to a cold solution (-50°C) of diethylamine (0.262 g, 2.53 mmol) in diethyl ether (4 mL). After a few minutes, a slurry of tin(II) chloride (0.160 g, 0.845 mmol) and potassium tert-butoxide (0.095 g, 0.845 mmol) in THF (4 mL) was added. The contents were warmed to 0°C and stirred for 2 hours. The flask was cooled again to -50°C and 2,2-diiodopropane (0.25 g, 0.845 mmol) was added. The resulting reaction mixture was left to stand and warmed to room temperature over 16 hours, at which point the solvent was removed under vacuum. The product, 2,2-diiodopropyl tin tris(diethylamide), was recrystallized from pentane, and tert-butanol (3.1 equivalents) was added. The trialkoxide product was distilled at 60°C under dynamic vacuum and further purified by fractional distillation. The isolated product 119 Sn NMR and 1 The 1H NMR spectra are shown in Figures 14 and 15, respectively.

[0103] Example 8. Preparation of (C6H4I)CH2Sn(CCSi(CH3)3)3 and (C6H4I)CH2Sn(OC(CH3)3)3 This example demonstrates the synthesis of iodobenzyl tin triacetide, (C6H4I)CH2Sn(CCSi(CH3)3)3 (abbreviated as 3-iodobenzyl Sn(CCSiMe3)3) via an oxidative stanylation reaction involving trimethylsilylacetylene (TMSA), SnCl2, n-butyllithium, potassium tert-butoxide, and iodobenzyl bromide, and its subsequent conversion to 3-iodobenzyl tin tris(tert-butoxide), (C6H4I)CH2Sn(OC(CH3)3)3 (abbreviated as iodobenzyl Sn(O-tBu)3).

[0104] n-butyllithium was added to a cold solution (-50°C) of trimethylsilylacetylene (TMSA) in diethyl ether. After a few minutes, a slurry of tin(II) chloride and potassium tert-butoxide in THF was added. The contents were stirred for at least 2 hours while being warmed to room temperature. The newly formed presumed intermediate, potassium tris(trimethylsilylacetylide)stannane, was slowly added to a cold solution (-50°C) of 3-iodobenzyl bromide in THF. After stirring overnight, the solvent was removed under vacuum, and the product was extracted with pentane. A white semi-solid was obtained by removing the salt by filtration and removing the pentane under vacuum. Triethylamine (5.0 equivalents) and tert-butanol (5.0 equivalents) were added, and the solution was heated to 80°C for 40 hours. Excess TEA / tBuOH was removed under vacuum, and the trialkoxide product was isolated by distillation. Further purification was performed by fractional distillation. 119 Sn NMR and 1 The 1H NMR spectra are shown in Figures 16 and 17, respectively.

[0105] The embodiments described above are illustrative and not limiting. Additional embodiments are available in the claims. Furthermore, although the present invention has been described with reference to specific embodiments, those skilled in the art will recognize that modifications to form and details can be made without departing from the spirit and scope of the invention. Any incorporation by reference to the above literature is limited so as not to incorporate subject matter contrary to the express disclosure herein. To the extent that a particular structure, composition, and / or process is described herein with its components, elements, ingredients, or other divisions, the disclosure herein should be understood, unless otherwise specifically indicated, to encompass specific embodiments, as well as embodiments comprising specific components, elements, ingredients, other divisions, or combinations thereof, and embodiments that are essentially comprised of such specific components, ingredients, or other divisions, or combinations thereof, which may include additional features that do not alter the fundamental nature of the subject matter as suggested in the discussion. The use of the term “about” herein represents the expected uncertainty in the relevant value that a person skilled in the art will understand in a particular context.

Claims

1. Organic solvents, and The alkali metal ions, tin ions, and -SnL are dissolved in the aforementioned organic solvent. ３ An organometallic composition comprising an organic ligand bonded to tin, wherein the organic ligand (L) is -NR' ２ -C≡CR ｓ , or a mixture thereof, R ｓ is SiR'' ３ or R', where three R'' are independently H or R', and R' is independently a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, organometallic composition A solution containing [the specified ingredient].

2. The solution according to claim 1, wherein the organometallic composition further comprises alkaline earth ions (Be(+2), Mg(+2), Ca(+2), Sr(+2), Ba(+2)), pseudo-alkaline earth ions (Zn(+2), Cd(+2), Hg(+2 / +1)), or a combination thereof.

3. The solution according to claim 1 or claim 2, wherein the organic solvent is an aprotic polar organic solvent.

4. The solution according to any one of claims 1 to 3, wherein the alkali metal ion is a lithium metal ion.

5. L is -NR' ２ R' is a linear or branched alkyl (-C ｎ H ２ｎ＋１ The solution according to any one of claims 1 to 4, wherein n is 1 to 5.

6. L is -C≡CR'', and R'' is a linear or branched alkyl (-C ｎ H ２ｎ＋１ , n is from 1 to 5), the solution according to any one of claims 1 to 4.

7. A solution according to any one of claims 1 to 6, having a tin concentration of approximately 0.005 M to approximately 2 M.

8. The solution according to any one of claims 1 to 7, wherein the organometallic composition further comprises zinc ions.

9. A method for forming an alkali metal tin composition, To form the alkali metal tin composition, tin(II) halide (SnX) is dissolved in an organic solvent. ２ X = F, Cl, B, I, or a mixture thereof), and ML (where M is Li, Na, K, Cs, or a combination thereof, M' is Na, K, Cs, or a combination thereof, and L is a dialkylamide (-NR' ２ ) or acetylide (-C≡CL ｓ ) is reacted with the metal cation M'' present in the tin triamide (Sn(NR' ２ ) ３ ) or tin triacetide (M''Sn(C≡CR ｓ ) ３ ) the part SnL ３ The process involves forming a corresponding organometallic composition having M'', where M'' is M' if M' is present, or M if M' is not present, and R ｓ is SiR'' ３ A method in which R'' is either H or R'', and R'' is independently a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom.

10. (Alkaline earth / pseudo-alkaline earth) metal halide (M'''X ２ The method according to claim 9, further comprising reacting X = F, Cl, B, I, or a mixture thereof with the alkali metal tin composition to form an alkali metal (alkaline earth / pseudo-alkaline earth) metal tin composition, wherein the alkaline earth / pseudo-alkaline earth metal is beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, or a combination thereof.

11. M'''X ２ ZnCl ２ The method according to claim 10.

12. ML and SnX ２ The above reaction is M'OR ０ This reaction further includes, R ０ The method according to any one of claims 9 to 11, wherein is a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom.

13. M is Li, and M'OR ０ The method according to any one of claims 9 to 12, wherein the above does not exist.

14. The method according to any one of claims 9 to 13, wherein M is Li and M' is K.

15. The method according to any one of claims 9 to 14, wherein the reaction is started at a temperature of about 0°C or lower and the reaction is continued for at least about 2 minutes.

16. R is methyl (CH ３ -), ethyl (CH ３ CH ２ -), isopropyl (CH ３ CH ３ HC-), t-butyl((CH ３ ) ３ C-), t-amyl (CH ３ CH ２ (CH ３ ) ２ C-), sec-butyl (CH ３ (CH ３ CH ２ )CH-), Neopentyl ((CH ３ ) ３ CCH ２ The method according to any one of claims 9 to 15, wherein the material is cyclohexyl, cyclopentyl, cyclobutyl, or cyclopropyl.

17. A method for synthesizing monohydrocarbyltin compounds, To form an alkali metal tin composition, a primary halide hydrocarbyl compound (R-X, where X is a halide atom) is combined with a metal cation M (where M is an alkali metal, alkaline earth metal, pseudo-alkaline earth metal (Zn, Cd, or Hg), or a mixture thereof) and SnL ３ The compound is reacted with an organometallic composition containing a moiety (L is either an amide ligand that produces an alkali metal tin triamide compound, or an acetylide ligand that produces an alkali metal tin triacetide) to produce the corresponding monohydrocarbyl tin triamide (RSn(NR'). ２ ) ３ ) or monohydrocarbyl tin triacetide (RSn(C≡CR ｓ ) ３ The process includes forming a monohydrocarbyl ligand (R), wherein the monohydrocarbyl ligand (R) is a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, ｓ is SiR'' ３ A method in which R'' is either H or R'', and R'' is independently a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom.

18. L is -C≡CSiR' ３ The formula is such that R' is a linear or branched alkyl (-C ｎ H ２ｎ＋１ The method according to claim 17, wherein n is 1 to 5.

19. The method according to claim 17 or claim 18, wherein M is Li.

20. The method according to claim 17 or claim 18, wherein M includes K.

21. The method according to claim 17, claim 18, or claim 20, wherein M contains Zn.

22. R is methyl (CH ３ -), ethyl (CH ３ CH ２ -), isopropyl (CH ３ CH ３ HC-), t-butyl((CH ３ ) ３ C-), t-amyl (CH ３ CH ２ (CH ３ ) ２ C-), sec-butyl (CH ３ (CH ３ CH ２ )CH-), Neopentyl ((CH ３ ) ３ CCH ２ The method according to any one of claims 17 to 21, comprising cyclohexyl, cyclopentyl, cyclobutyl, or cyclopropyl.

23. The method according to any one of claims 17 to 22, wherein the reaction is initiated at room temperature or heated to room temperature and continued for at least about 15 minutes.

24. Formula RSn(C≡CSiR' ３ ) ３ A compound represented by the formula (wherein R' and R are independently a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom).

25. R is methyl (CH ３ -), ethyl (CH ３ CH ２ -), isopropyl (CH ３ CH ３ HC-), t-butyl ((CH ３ )) ３ C-), t-amyl (CH ３ CH ２ (CH ３ )) ２ C-), sec-butyl (CH ３ (CH ３ CH ２ ))CH-), neopentyl ((CH ３ )) ３ CCH ２ -), cyclohexyl, cyclopentyl, cyclobutyl, or cyclopropyl, the compound according to claim 24.

26. R' is a linear or branched alkyl (-C ｎ H ２ｎ＋１ The compound according to claim 24 or claim 25, wherein n is 1 to 5.

27. A solution comprising an aprotic organic solvent and the compound according to any one of claims 24 to 26, having a tin concentration of about 0.0001 M to about 1 M.

28. Formula R'R''ACS n L ３ (In the formula, A is a halogen atom (F, Cl, Br or I) or an aromatic ring having at least one halogen substitution, and R' and R'' are independently H, a halogen, or a hydrocarbyl group having 1 to 15 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, and L is L Ｈ and L Ｈ is a hydrolyzable ligand, or O ｘ (OH) ３－ｘ (0 < x < 3)), a hydrocarbyl tin halide compound represented by

29. The halogenated hydrocarbyltin compound according to claim 28, wherein A is I.

30. R' and R'' are both CH ３ The halogenated hydrocarbyltin compound according to claim 29.

31. A is C ６ H ４ The halogenated hydrocarbyltin compound according to claim 28, wherein I.

32. L is NR' ２ The halogenated hydrocarbyltin compound according to any one of claims 28 to 31, wherein R' is a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom.

33. L is C≡CR ｓ And R ｓ is SiR １ ３ or R ２ And the three R's １ H or R ２ And the R ２ The halogenated hydrocarbyltin compound according to any one of claims 28 to 31, wherein the hydrocarbyl group independently comprises 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom.

34. A solution comprising an aprotic organic solvent and the compound according to any one of claims 28 to 33, having a tin concentration of about 0.0001 M to about 1 M.

35. Formula R'R''(R'''O)CSnL ３ (wherein R', R'', and R'''' are independently H, or a hydrocarbyl group having 1 to 15 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, and L is L Ｈ And L Ｈ is a hydrolyzable ligand, or O ｘ (OH) ３－ｘ A hydrocarbyltin compound represented as (0 < x < 3).

36. R' and R'' are H, and R''' is CH ３ The hydrocarbyltin compound according to claim 35.

37. L is NR' ２ The hydrocarbyltin compound according to claim 35 or claim 36, wherein R' is a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom.

38. L is C≡CR ｓ And R ｓ is SiR １ ３ or R ２ And the three R's １ H or R ２ And the R ２ The hydrocarbyltin compound according to claim 35 or claim 36, wherein the hydrocarbyl group independently comprises 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom.

39. A solution comprising an aprotic organic solvent and the compound according to any one of claims 35 to 38, having a tin concentration of about 0.005 M to about 1.4 M.

40. Formula R'R''(N≡C)CSnZ ３ (In the formula, R' and R'' are independently hydrocarbyl groups having 1 to 15 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, Z is L, and L is a hydrolyzable ligand or O ｘ (OH) ３－ｘ A hydrocarbyltin compound represented as (0 < x < 3).

41. R' and R'' independently form linear or branched alkyl (-C) ｎ H ２ｎ＋１ The hydrocarbyltin compound according to claim 40, wherein n is 1 to 5.

42. Z is NR' ２ The hydrocarbyltin compound according to claim 40 or claim 41, wherein R' is a hydrocarbyl group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom.

43. L is C≡CR ｓ And R ｓ is SiR １ ３ or R ２ And the three R's １ H or R ２ And the R ２ The hydrocarbyltin compound according to claim 40 or claim 41, wherein the hydrocarbyl group independently comprises 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom.

44. A solution comprising an aprotic organic solvent and the compound according to any one of claims 40 to 43, having a tin concentration of about 0.005 M to about 1.4 M.

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