Monosubstituted tin compounds and related methods

Abstract

A method of synthesizing a monosubstituted tin compound includes: contacting a stannous halide with a metallization reactant to form a stanene compound; contacting the stanene compound with a halide compound to form a tin-containing compound; and contacting the tin-containing compound with a reactant to form a monosubstituted tin compound via ligand exchange. Also provided are compositions including the monosubstituted tin compounds, as well as other compositions and methods.

Description

Technical Field

[0001] This disclosure relates to monosubstituted tin compounds and related methods.

[0002] Cross-citation of related applications

[0003] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 453,611, filed March 21, 2023, pursuant to 35 USC 119, the disclosure of which is incorporated herein by reference in its entirety. Background Technology

[0004] Some precursors can be used to fabricate microelectronic devices. The fabrication of such devices may involve forming thin films using extreme ultraviolet (EUV) lithography. Summary of the Invention

[0005] Some embodiments relate to a synthetic method. In some embodiments, the synthetic method includes any one or more of the following steps: contacting a stannous halide with a metallization reactant to form a stannylene compound; contacting the stannylene compound with a halide compound to form a stannic compound; and contacting the stannic compound with a reactant to form a monosubstituted tin compound via ligand exchange.

[0006] Some embodiments relate to a composition comprising a tinene compound. In some embodiments, the tinene compound is a reaction product of a stannous halide and a metallization reactant. In some embodiments, the tinene compound comprises a compound of the following formula:

[0007] SnL n ,

[0008] in:

[0009] L is a monoanion ligand or a dianion ligand; and

[0010] n can be 1 or 2, provided that n is 1 when L is a dianion ligand and n is 2 when L is a monoanion ligand.

[0011] Some embodiments relate to a composition comprising a tin-containing compound. In some embodiments, the tin-containing compound is a reaction product of a halide compound and a tinene compound. In some embodiments, the tin-containing compound comprises a compound of the following formula:

[0012] RSn(L) n X,

[0013] in:

[0014] R is at least one of the following or includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogen, imide, cyanate, nitrile, alkoxide, or any combination thereof.

[0015] L is a monoanion ligand or a dianion ligand;

[0016] n can be 1 or 2, provided that n is 1 when L is a dianion ligand and 2 when L is a monoanion ligand; and

[0017] X is a halogen group.

[0018] Some embodiments relate to a composition comprising a monosubstituted tin compound. In some embodiments, the monosubstituted tin compound comprises a compound of the following formula:

[0019] ,

[0020] in:

[0021] R is at least one of the following or includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogen, imide, cyanate, nitrile, alkoxide, or any combination thereof; and

[0022] L 1 It can be a monoanion ligand, a dianion ligand, or a halogen group independently. Attached Figure Description

[0023] Some embodiments of this disclosure are described herein with reference to the accompanying drawings, using only examples. Reference is now made in particular detail to the drawings, and it should be emphasized that the embodiments are shown by way of example and for the purpose of illustrative discussion of embodiments of this disclosure. In this regard, the description taken in conjunction with the drawings makes it apparent to those skilled in the art how embodiments of this disclosure can be practiced.

[0024] Figure 1 This is a flowchart of a synthesis method according to some embodiments.

[0025] Figure 2 This is a flowchart of a method for preparing a tin-containing film according to some embodiments.

[0026] Figure 3 A reaction scheme is described according to some embodiments for forming monosubstituted tin compounds.

[0027] Figure 4The reaction flow of a method for forming a monosubstituted tin compound according to some embodiments is described.

[0028] Figure 5 A schematic cross-sectional view depicting a non-limiting embodiment of an ampoule according to some embodiments is provided.

[0029] Figure 6 Describing Sn(pip) according to some embodiments Me4 )2 is a three-dimensional solid structure.

[0030] Figure 7 A three-dimensional solid structure of CF3CH2Sn(N(SiMe3)2)2I according to some embodiments is depicted.

[0031] Figure 8 A three-dimensional solid-state structure of iPrSn(N(SiMe3)2)2I is depicted according to some embodiments. Detailed Implementation

[0032] Among the benefits and improvements already disclosed, other objectives and advantages of this disclosure will become apparent from the following description taken in conjunction with the accompanying drawings. Detailed embodiments of this disclosure are disclosed herein; however, it should be understood that the disclosed embodiments are merely illustrative of how this disclosure may be implemented in various forms. Furthermore, the examples given with respect to the various embodiments of this disclosure are intended to be illustrative and not restrictive.

[0033] Any prior patents and publications mentioned herein are incorporated herein by reference in their entirety.

[0034] Throughout this specification and claims, unless the context clearly requires otherwise, the following terms shall have the meanings explicitly associated herein. The phrases “in one embodiment,” “in an embodiment,” and “in some embodiments” as used herein do not necessarily refer to the same embodiment, but may refer to the same embodiment. Similarly, the phrases “in another embodiment” and “in some other embodiments” as used herein do not necessarily refer to different embodiments, but may refer to different embodiments. All embodiments of this disclosure are intended to be combined without departing from the scope or spirit of this disclosure.

[0035] As used herein, unless the context clearly indicates otherwise, the term "based on" is not exclusive and may be based on additional factors not described. Furthermore, throughout this specification, the meanings of "a / an" and "the" include multiple references. The meaning of "in" includes both "in" and "on".

[0036] As used herein, the term “contact” refers to bringing two or more components into close proximity or direct contact.

[0037] As used herein, the term "alkyl" refers to a hydrocarbon group having 1 to 30 carbon atoms. Alkyl groups can be linked by single bonds. An alkyl group having n carbon atoms can be represented as "C". n Alkyl group. For example, "C3 alkyl" can include n-propyl and isopropyl. Alkyl groups having a series of carbon atoms, such as 1 to 30 carbon atoms, can be represented as C1-C. 30 Alkyl group. In some embodiments, the alkyl group is straight-chain. In some embodiments, the alkyl group is branched. In some embodiments, the alkyl group is substituted. In some embodiments, the alkyl group is unsubstituted. In some embodiments, the alkyl group comprises at least one of the following or the group selected from at least one of the following: C1-C 30 Alkyl, C1-C 29 Alkyl, C1-C 28 Alkyl, C1-C 27 Alkyl, C1-C 27 Alkyl, C1-C 26 Alkyl, C1-C 25 Alkyl, C1-C 24 Alkyl, C1-C 23 Alkyl, C1-C 22 Alkyl, C1-C 21 Alkyl, C1-C 20 Alkyl, C1-C 19 Alkyl, C1-C 18 Alkyl, C1-C 17 Alkyl, C1-C 16 Alkyl, C1-C 15 Alkyl, C1-C 14 Alkyl, C1-C 13 Alkyl, C1-C 12 Alkyl, C1-C 11 Alkyl, C1-C 10 Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, C2-C 30 Alkyl, C3-C 30 Alkyl, C4-C 30 Alkyl, C5-C 30 Alkyl, C6-C 30 Alkyl, C7-C 30 Alkyl, C8-C 30 Alkyl, C9-C 30 Alkyl, C 10 -C 30 Alkyl, C11 -C 30 Alkyl, C 12 -C 30 Alkyl, C 13 -C 30 Alkyl, C 14 -C 30 Alkyl, C 15 -C 30 Alkyl, C 16 -C 30 Alkyl, C 17 -C 30 Alkyl, C 18 -C 30 Alkyl, C 19 -C 30 Alkyl, C 20 -C 30 Alkyl, C 21 -C 30 Alkyl, C 22 -C 30 Alkyl, C 23 -C 30 Alkyl, C 24 -C 30 Alkyl, C 25 -C 30 Alkyl, C 26 -C 30 Alkyl, C 27 -C 30 Alkyl, C 28 -C 30 Alkyl, C 29 -C 30 Alkyl, C2-C 10 Alkyl, C3-C 10 Alkyl, C4-C 10 Alkyl, C5-C 10 Alkyl, C6-C 10 Alkyl, C7-C 10 Alkyl, C8-C 10 Alkyl, C2-C9 alkyl, C2-C8 alkyl, C2-C7 alkyl, C2-C6 alkyl, C2-C5 alkyl, C3-C5 alkyl, or any combination thereof. In some embodiments, alkyl includes at least one of or the group selected from at least one of: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, isobutyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (tert-butyl), n-pentyl, isopentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof. In some embodiments, the term "alkyl" generally refers to alkyl, alkenyl, ynyl, and / or cycloalkyl.

[0038] As used herein, the term "alkenyl" refers to a hydrocarbon group having 1 to 30 carbon atoms and at least one carbon-carbon double bond. In some embodiments, an alkenyl group comprises at least one of the following or a group selected from at least one of the following: C1-C 30 alkenyl, C1-C 29 alkenyl, C1-C 28 alkenyl, C1-C 27 alkenyl, C1-C 27 alkenyl, C1-C 26 alkenyl, C1-C 25 alkenyl, C1-C 24 alkenyl, C1-C 23 alkenyl, C1-C 22 alkenyl, C1-C 21 alkenyl, C1-C 20 alkenyl, C1-C 19 alkenyl, C1-C 18 alkenyl, C1-C 17 alkenyl, C1-C 16 alkenyl, C1-C 15 alkenyl, C1-C 14 alkenyl, C1-C 13 alkenyl, C1-C 12 alkenyl, C1-C 11 alkenyl, C1-C 10 alkenyl, C1-C9 alkenyl, C1-C8 alkenyl, C1-C7 alkenyl, C1-C6 alkenyl, C1-C5 alkenyl, C1-C4 alkenyl, C1-C3 alkenyl, C1-C2 alkenyl, C2-C 30 alkenyl, C3-C 30 alkenyl, C4-C 30 alkenyl, C5-C 30 alkenyl, C6-C 30 alkenyl, C7-C 30 alkenyl, C8-C 30 alkenyl, C9-C 30 alkenyl, C 10 -C 30 alkenyl, C 11 -C 30 alkenyl, C 12 -C 30 alkenyl, C 13 -C 30 alkenyl, C 14 -C 30 alkenyl, C 15 -C 30 alkenyl, C 16 -C 30 alkenyl, C 17 -C30 alkenyl, C 18 -C 30 alkenyl, C 19 -C 30 alkenyl, C 20 -C 30 alkenyl, C 21 -C 30 alkenyl, C 22 -C 30 alkenyl, C 23 -C 30 alkenyl, C 24 -C 30 alkenyl, C 25 -C 30 alkenyl, C 26 -C 30 alkenyl, C 27 -C 30 alkenyl, C 28 -C 30 alkenyl, C 29 -C 30 alkenyl, C2-C 10 alkenyl, C3-C 10 alkenyl, C4-C 10 alkenyl, C5-C 10 alkenyl, C6-C 10 alkenyl, C7-C 10 alkenyl, C8-C 10 Alkenyl, C2-C9 alkenyl, C2-C8 alkenyl, C2-C7 alkenyl, C2-C6 alkenyl, C2-C5 alkenyl, C3-C5 alkenyl, or any combination thereof. Examples of alkenyl include (but are not limited to) at least one of the following: vinyl, allyl, 1-methylvinyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1,3-pentadienyl, 2,4-pentadienyl, 1,4-pentadienyl, 3-methyl-2 -Butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1,3-hexadienyl, 1,4-hexadienyl, 2-methylpentenyl, 1-heptenyl, 3-heptenyl, 1-octenyl, 1,3-octadienyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3-decenyl, 1-undecenyl, oleyl, linoleyl, linolenyl, or any combination thereof.

[0039] As used herein, the term "alkynyl" refers to a hydrocarbon group having 1 to 30 carbon atoms and at least one carbon-carbon triple bond. In some embodiments, an alkynyl group includes at least one of the following or a group selected from at least one of the following: C1-C 30 Alkyne group, C1-C 29 Alkyne group, C1-C 28 Alkyne group, C1-C 27 Alkyne group, C1-C 27 Alkyne group, C1-C 26 Alkyne group, C1-C 25 Alkyne group, C1-C 24 Alkyne group, C1-C 23 Alkyne group, C1-C 22 Alkyne group, C1-C 21 Alkyne group, C1-C 20 Alkyne group, C1-C 19 Alkyne group, C1-C 18 Alkyne group, C1-C 17 Alkyne group, C1-C 16 Alkyne group, C1-C 15 Alkyne group, C1-C 14 Alkyne group, C1-C 13 Alkyne group, C1-C 12 Alkyne group, C1-C 11 Alkyne group, C1-C 10 Alkynyl, C1-C9 alkynyl, C1-C8 alkynyl, C1-C7 alkynyl, C1-C6 alkynyl, C1-C5 alkynyl, C1-C4 alkynyl, C1-C3 alkynyl, C1-C2 alkynyl, C2-C 30 alkynyl group, C3-C 30 alkynyl group, C4-C 30 alkynyl group, C5-C 30 alkynyl group, C6-C 30 alkynyl group, C7-C 30 alkynyl group, C8-C 30 alkynyl group, C9-C 30 alkynyl group, C 10 -C 30 alkynyl group, C 11 -C 30 alkynyl group, C 12 -C 30 alkynyl group, C 13 -C 30 alkynyl group, C 14 -C 30 alkynyl group, C 15 -C 30 alkynyl group, C 16 -C 30 alkynyl group, C 17 -C 30 alkynyl group, C18 -C 30 alkynyl group, C 19 -C 30 alkynyl group, C 20 -C 30 alkynyl group, C 21 -C 30 alkynyl group, C 22 -C 30 alkynyl group, C 23 -C 30 alkynyl group, C 24 -C 30 alkynyl group, C 25 -C 30 alkynyl group, C 26 -C 30 alkynyl group, C 27 -C 30 alkynyl group, C 28 -C 30 alkynyl group, C 29 -C 30 alkynyl group, C2-C 10 alkynyl group, C3-C 10 alkynyl group, C4-C 10 alkynyl group, C5-C 10 alkynyl group, C6-C 10 alkynyl group, C7-C 10 alkynyl group, C8-C 10 Alkynyl, C2-C9 alkynyl, C2-C8 alkynyl, C2-C7 alkynyl, C2-C6 alkynyl, C2-C5 alkynyl, C3-C5 alkynyl, or any combination thereof. Examples of alkynyl include (but are not limited to) at least one of the following: ethynyl, propynyl, n-butynyl, n-pentynyl, 3-methyl-1-butynyl, n-hexynyl, methyl-pentynyl, or any combination thereof.

[0040] As used herein, the term "cycloalkyl" refers to a non-aromatic carbon ring having 3 to 8 carbon atoms in a ring. The term includes both monocyclic and polycyclic non-aromatic carbon rings. When used as a modifier, the term "monocyclic" refers to a cycloalkyl group having a single cyclic ring structure. When used as a modifier, the term "polycyclic" refers to a cycloalkyl group having more than one cyclic ring structure, which may be a fused, bridged, helicaled, or otherwise bonded ring structure. For example, two or more cycloalkyl groups may be fused, bridged, or fused and bridged to obtain a polycyclic non-aromatic carbon ring. In some embodiments, a cycloalkyl group may include at least one of, consist of at least one of, or substantially consist of at least one of, or optionally consist of the group consisting of at least one of: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or any combination thereof.

[0041] As used herein, the term "aryl" refers to a monocyclic or polycyclic aromatic hydrocarbon. The number of carbon atoms in an aryl group can range from 5 to 100 carbon atoms. In some embodiments, the aryl group has 5 to 20 carbon atoms. For example, in some embodiments, the aryl group has 6 to 8 carbon atoms, 6 to 10 carbon atoms, 6 to 12 carbon atoms, 6 to 15 carbon atoms, or 6 to 20 carbon atoms. When used as a modifier, the term "monocyclic" refers to an aryl group having a single aromatic ring structure. When used as a modifier, the term "polycyclic" refers to an aryl group having more than one aromatic ring structure, which can be a fused, bridged, helicaled, or otherwise bonded ring structure. In some embodiments, the aryl group is -C6H5.

[0042] As used herein, the term "amino" refers to the formula -N(R) a R b The functional groups of ) where R a and R b Independently hydrogen, alkyl (as defined herein), or silyl (as defined herein), or R a and R b They bond together to form C3-C 20N-heterocyclic. In some embodiments, the amino group may include alkylamino or dialkylamino. In some embodiments, the amino group may include at least one of the following: methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, di-isopropylamino, butylamino, sec-butylamino, tert-butylamino, di-sec-butylamino, isobutylamino, di-isobutylamino, di-tert-pentylamino, ethylmethylamino, isopropyl-n-propylamino, or any combination thereof. Examples of alkylamino groups may include (but are not limited to) one or more of the following: primary alkylamino groups, such as, but not limited to, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, sec-butylamino, isobutylamino, tert-butylamino, pentylamino, 2-aminopentane, 3-aminopentane, 1-amino-2-methylbutane, 2-amino-2-methylbutane, 3-amino-2-methylbutane, 4-amino-2-methylbutane, hexylamino, 5-amino-2-methylpentane, heptylamino, octylamino, nonylamino, decylamino, undecylamino, dodecylamino, tridecylamino, tetradecylamino, pentadecylamino, hexadecylamino, heptadecanylamino, and octadecylamino. The amino group; and secondary alkylamino groups, such as, but not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di-sec-butylamino, di-tert-butylamino, dipentylamino, dihexylamino, diheptylamino, dioctylamino, dinonylamino, didecylamino, methylethylamino, methylpropylamino, methyl isopropylamino, methyl butylamino, methyl isobutylamino, methyl-sec-butylamino, methyl-tert-butylamino, methylpentylamino, methyl isopentylamino, ethylpropylamino, ethyl isopropylamino, ethyl butylamino, ethyl isobutylamino, ethyl-sec-butylamino, ethylamino, ethyl isopentylamino, propyl butylamino, and propyl isobutylamino. Unless the context otherwise indicates, the terms amino and amine are used interchangeably herein.

[0043] As used in this article, the term "alkoxy" refers to the formula -OR c Functional groups, of which R c It is an alkyl (as defined herein), silylalkyl, cycloalkyl, or aryl. In some embodiments, the alkoxy group may include at least one of, consist of at least one of, or substantially consist of at least one of, or be selected from the group consisting of at least one of: methoxy, ethoxy, methoxy, ethoxy, n-propoxy, 1-methylethoxy (isopropoxy), n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, or any combination thereof.

[0044] As used in this article, the term "silicon-based" refers to the formula -Si(R) e R f R gThe functional groups of ) where R e R f and R g Each of these components is independently hydrogen or an alkyl group as defined herein. In some embodiments, the silicon group is a functional group of the formula -SiH3. In some embodiments, the silicon group is a functional group of the formula -SiR. e The functional groups of H2, of which R e Not hydrogen. In some embodiments, silicon-based is of the formula -SiR e R f H's functional groups, of which R e and R f Not hydrogen. In some embodiments, silicon-based is of the formula -Si(R e R f R g The functional groups of ) where R e R f and R g Not hydrogen. In some embodiments, the silicon group is a functional group of the formula -Si(CH3)3.

[0045] As used herein, the term "alkoxyalkyl" refers to an alkyl group as defined herein, wherein at least one of the hydrogen atoms of the alkyl group is substituted with an alkoxy group as defined herein. In some embodiments, the term "alkoxyalkyl" refers to the formula -(alkyl)OR a The functional group, wherein the alkyl group is defined above and wherein R is a functional group. a As defined above. In some embodiments, the alkoxyalkyl group is of the formula -(CH2). n OR a The functional groups, where n is 1 to 10 and R a As defined above. In some embodiments, the alkoxyalkyl group is a functional group of the formula -CH2CH2OCH3.

[0046] As used herein, the term "aralkyl" refers to an alkyl group as defined herein, wherein at least one of the hydrogen atoms of the alkyl group is substituted with an aryl group as defined herein. In some embodiments, the term "aralkyl" refers to a functional group of the formula -(alkyl)(aryl), wherein an alkyl group is defined herein and an aryl group is defined herein. In some embodiments, the aralkyl group is -CH2(C6H5).

[0047] As used herein, the term "aminoalkyl" refers to an alkyl group as defined herein, wherein at least one of the hydrogen atoms of the alkyl group is replaced by an amino group as defined herein. In some embodiments, the term "aminoalkyl" refers to the formula -(alkyl)N(R b R c R d The functional group of ), wherein the alkyl group is defined above and wherein R is a functional group of ). b R c and Rd As defined above. In some embodiments, the aminoalkyl group is -CH2N(CH3)2. In some embodiments, the aminoalkyl group is -(CH2)3N(CH3)2. In some embodiments, the aminoalkyl group is aminomethyl (-CH2NH2). In some embodiments, the aminoalkyl group is N,N-dimethylaminoethyl (-CH2CH2N(CH3)2). In some embodiments, the aminoalkyl group is 3-(N-cyclopropylamino)propyl (-CH2CH2CH2NH-Pr).

[0048] As used herein, the term "silyl alkyl" refers to an alkyl group as defined herein, wherein at least one of the hydrogen atoms of the alkyl group is substituted with a silyl group as defined herein. In some embodiments, the term "silyl alkyl" refers to the formula -(alkyl)Si(R e R f R g The functional group of ), wherein the alkyl group is defined above and wherein R is a functional group of ). e R f and R g As defined above. In some embodiments, the silane-alkyl group is of the formula -(CH2). m Si(R e R f R g The functional groups of ), where m is 1 to 10 and R e R f and R g As defined above. In some embodiments, the silane group is a functional group of the formula -CH2Si(CH3)3.

[0049] As used herein, the term "haloalkyl" refers to an alkyl group as defined herein, wherein at least one of the hydrogen atoms of the alkyl group is substituted with a halogen group as defined herein. In some embodiments, the haloalkyl group includes a fluoroalkyl group. In some embodiments, the fluoroalkyl group includes at least one of the following: -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, or any combination thereof.

[0050] As used in this article, the term "halogen" refers to -Cl, -Br, -I, or -F.

[0051] As used herein, the term "metal cation" refers to at least one of the following: alkali metal cation, alkaline earth metal cation, transition metal cation, post-transition metal cation, or any combination thereof. In some embodiments, the metal cation includes: lithium cation, sodium cation, potassium cation, rubidium cation, cesium cation, francium cation, beryllium cation, magnesium cation, calcium cation, strontium cation, barium cation, radium cation, scandium cation, titanium cation, vanadium cation, chromium cation, manganese cation, iron cation, cobalt cation, nickel cation, copper cation, zinc cation, yttrium cation, zirconium cation, niobium cation, molybdenum cation, technetium cation, ruthenium cation, rhodium cation, palladium cation, silver cation, cadmium cation, hafnium cation, tantalum cation, tungsten cation, rhenium cation, osmium cation, iridium cation, platinum cation, gold cation, mercury cation, aluminum cation, gallium cation, indium cation, tin cation, thallium cation, lead cation, bismuth cation, or polonium cation. The charges of metal cations are known and, for simplicity, will not be repeated here; however, it should be understood that metal cations can have any known charge. For example, in some embodiments, the metal cation includes Li. + Na + K + 、Rb + Cs + Mg 2+ Ca 2 + 、Sr 2+ Ba 2+ or Zn 2+ In some embodiments, the metal cation is Sn(II) or Sn(IV).

[0052] Some embodiments relate to compositions and related methods that can be used in extreme ultraviolet (EUV) lithography and other applications. The compositions disclosed herein comprise monosubstituted tin compounds. Monosubstituted tin compounds can be used to form tin-containing films that can be used to manufacture microelectronic devices, including semiconductor devices. For example, precursor compositions can be used to form functionalized tin oxide films (RSnO). x Functionalized tin oxide films can be used, in particular, in dry resist applications or as reflective coatings for extreme ultraviolet (EUV) lithography. Precursor compositions can be formed in high yield and high purity (i.e., with low content of disubstituted tin compounds, such as, but not limited to, dialkyltin compounds and others) according to the methods disclosed herein, while minimizing the number of steps required to produce the precursor composition.

[0053] As disclosed herein, it has been unexpectedly found that the ligands disclosed herein, such as, but not limited to, 2,2,6,6-tetramethylpiperidine, can promote the formation of the monomer Sn(II)stanene upon reaction with stannous halides. Further unexpectedly, it has been found that the stanene compounds disclosed herein readily undergo easy oxidative addition with halide compounds, such as, but not limited to, alkyl halides. Further unexpectedly, it has been found that the ligands disclosed herein readily exchange with other ligands to provide broad versatility in the synthesis of monosubstituted tin compounds. It should be understood that other benefits exist with the compositions and methods disclosed herein, and therefore these benefits should not be limiting.

[0054] Tin-containing films can also be formed according to the methods disclosed herein. That is, the tin-containing films disclosed herein can be formed by one or more deposition processes using a precursor composition. Examples of deposition processes include (but are not limited to) at least one of the following: chemical vapor deposition (CVD) processes, digital or pulsed chemical vapor deposition processes, plasma-enhanced cyclic chemical vapor deposition (PECCVD) processes, flowable chemical vapor deposition (FCVD) processes, atomic layer deposition (ALD) processes, thermal atomic layer deposition, plasma-enhanced atomic layer deposition (PEALD) processes, metal-organic chemical vapor deposition (MOCVD) processes, plasma-enhanced chemical vapor deposition (PECVD) processes, or any combination thereof.

[0055] Figure 1 This is a flowchart of a synthesis method according to some embodiments. For example... Figure 1 As shown, the synthesis method 100 includes one or more of the following steps: contacting stannous halide with metallization reactants 102 to form a tinene compound; contacting the tinene compound with a halide compound 104 to form a tin-containing compound; and contacting the tin-containing compound with reactants 106 to form a monosubstituted tin compound via ligand exchange.

[0056] At step 102, the synthesis method 100 includes contacting a stannous halide with a metallization reactant to form a tinene compound. In some embodiments, the tinene compound is formed via a substitution reaction, wherein a ligand from the metallization reactant replaces a halogen group on the stannous halide. In some embodiments, the contact includes reacting the stannous halide with the metallization reactant. In some embodiments, the contact includes mixing the stannous halide with the metallization reactant. In some embodiments, the contact includes stirring the stannous halide and the metallization reactant. In some embodiments, the contact includes adding the stannous halide and the metallization reactant to a reactor vessel. In some embodiments, the contact includes dissolving the stannous halide and the metallization reactant. In some embodiments, the contact includes combining the stannous halide with the metallization reactant. In some embodiments, the contact is carried out in solution.

[0057] In some embodiments, tin halides include at least one of the following: SnCl2, SnBr2, SnI2, SnF2, or any combination thereof.

[0058] In some embodiments, the metallization reactants include compounds of the following formula:

[0059] ML,

[0060] in:

[0061] M is an alkali metal cation, an alkaline earth metal cation, a transition metal cation, or a post-transition metal cation; and

[0062] L can be a monoanion ligand or a dianion ligand.

[0063] In some embodiments, the metal cation includes an alkali metal cation and the ligand is a monoanion ligand. In some embodiments, the metal cation includes an alkali metal cation and the ligand is a dianion ligand. In some embodiments, the metal cation includes an alkaline earth metal cation and the ligand is a monoanion ligand. In some embodiments, the metal cation includes an alkaline earth metal cation and the ligand is a dianion ligand. In some embodiments, the metal cation includes a transition metal cation and the ligand is a monoanion ligand. In some embodiments, the metal cation includes a transition metal cation and the ligand is a dianion ligand. In some embodiments, the metal cation includes a post-transition metal cation and the ligand is a monoanion ligand. In some embodiments, the metal cation includes a post-transition metal cation and the ligand is a dianion ligand.

[0064] In some embodiments, the monoanion ligand is large enough that, upon contact with tin halide, the ligand promotes the formation of a monomeric tin center. In some embodiments, the dianion ligand is large enough that, upon contact with tin halide, the ligand promotes the formation of a monomeric tin center.

[0065] In some embodiments, L is an amino group. That is, for example, in some embodiments, L is:

[0066] -NR a R b ,

[0067] in:

[0068] R a and R b Independently hydrogen, alkyl, or silicon-based, or R a and R b They bond together to form C3-C 20 N-heterocyclic ring.

[0069] In some embodiments, L is an alkoxy group. That is, for example, in some embodiments, L is:

[0070] -OR c ,

[0071] in:

[0072] R c It can be alkyl, silylalkyl, cycloalkyl, or aryl.

[0073] In some embodiments, L is 2,2,6,6-tetramethylpiperidine. In some embodiments, L is N,N'-di-tert-butylethylenediamide. In some embodiments, L is bis(trimethylsilyl)amino. In some embodiments, L is -N(Si(CH3)3)2.

[0074] In some embodiments, the metallization reactant includes lithium tetramethylpiperidine.

[0075] In some embodiments, the tinene compound is a reaction product of tin halides and a metallization reactant. In some embodiments, the tinene compound includes compounds of the following formula:

[0076] SnL n ,

[0077] in:

[0078] L is a monoanion ligand or a dianion ligand; and

[0079] n is 1 or 2, provided that n is 1 when L is a dianion ligand. In some embodiments, n is 2 when L is a monoanion ligand.

[0080] In some embodiments, L is a ligand from the metallization reactant. For example, in some embodiments, L is an amino group. That is, for example, in some embodiments, L is:

[0081] -NR a R b ,

[0082] in:

[0083] R a and R b Independently hydrogen, alkyl, or silicon-based, or R a and R b They bond together to form C3-C 20 N-heterocyclic ring.

[0084] In some embodiments, L is an alkoxy group. That is, for example, in some embodiments, L is:

[0085] -OR c ,

[0086] in:

[0087] R c It can be alkyl, silylalkyl, cycloalkyl, or aryl.

[0088] In some embodiments, L is 2,2,6,6-tetramethylpiperidine. In some embodiments, L is N,N'-di-tert-butylethylenediamide. In some embodiments, L is bis(trimethylsilyl)amino. In some embodiments, L is -N(Si(CH3)3)2.

[0089] In some embodiments, the tinene compound comprises (2,2,6,6-tetramethylpiperidine)2tin(II). In some embodiments, the tinene compound is a compound of the following formula:

[0090] .

[0091] In some embodiments, the tinene compound comprises (N,N'-di-tert-butylethylenediamide)2tin(II). In some embodiments, the tinene compound comprises ((trimethylsilyl)amino)2tin(II).

[0092] At step 104, the synthesis method 100 includes contacting a tinene compound with a halide compound to form a tin-containing compound. In some embodiments, the tin-containing compound is formed via oxidative addition, wherein the halide compound is oxidatively added to form a tinene compound (e.g., a low-coordinated tinene compound). In some embodiments, the contact includes reacting the tinene compound with the halide compound. In some embodiments, the contact includes mixing the tinene compound with the halide compound. In some embodiments, the contact includes stirring the tinene compound and the halide compound. In some embodiments, the contact includes adding the tinene compound and the halide compound to a reactor vessel. In some embodiments, the contact includes dissolving the tinene compound and the halide compound. In some embodiments, the contact includes combining the tinene compound with the halide compound. In some embodiments, the contact is carried out in solution.

[0093] In some embodiments, the halide compound includes compounds of the following formula:

[0094] RX,

[0095] in:

[0096] R is at least one of the following or includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogen, imide, cyanate, nitrile, alkoxide, or any combination thereof; and

[0097] X is a halogen group.

[0098] In some embodiments, R is at least one of the following or includes at least one of the following: -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH(CH3)CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -(CH2)3CH3, - C6H5, -CH2(C6H5), -CH=CH2, -C≡CCH3, -CH2C≡CH, -CH2C≡CCH3, -C(CH3)=CH2, -HC=CHCH3, -CH2CH=CH2, -CH2N(CH3)2, -(CH2)3N(CH3)2, -CH2CH2OCH3, -CH(CH2)2O, -CH2Si(CH3)3, -Si(CH3)3 or any combination thereof.

[0099] In some embodiments, the tin-containing compound is a reaction product of a stannous halide and a tinene compound. In some embodiments, the tin-containing compound is an alkylated mixed ligand tin (IV) compound. In some embodiments, the tin-containing compound comprises compounds of the following formula:

[0100] RSn(L) n X,

[0101] in:

[0102] R is at least one of the following or includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogen, imide, cyanate, nitrile, alkoxide, or any combination thereof.

[0103] L is a monoanion ligand or a dianion ligand (as defined above);

[0104] n is either 1 or 2, provided that n is 1 when L is a dianionic ligand. In some embodiments, n is 2 when L is a monoanionic ligand; and

[0105] X is a halogen group.

[0106] In some embodiments, R is a functional group derived from a halide compound. In some embodiments, R is at least one of or includes at least one of the following: -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH(CH3)CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -(CH2)3CH3, - C6H5, -CH2(C6H5), -CH=CH2, -C≡CCH3, -CH2C≡CH, -CH2C≡CCH3, -C(CH3)=CH2, -HC=CHCH3, -CH2CH=CH2, -CH2N(CH3)2, -(CH2)3N(CH3)2, -CH2CH2OCH3, -CH(CH2)2O, -CH2Si(CH3)3, -Si(CH3)3 or any combination thereof.

[0107] In some embodiments, L is a ligand from a tinene compound. In some embodiments, L is an amino group. That is, for example, in some embodiments, L is:

[0108] -NR a R b ,

[0109] in:

[0110] R a and R b Independently hydrogen, alkyl, or silicon-based, or R a and R b They bond together to form C3-C 20 N-heterocyclic ring.

[0111] In some embodiments, L is an alkoxy group. That is, for example, in some embodiments, L is:

[0112] -OR c ,

[0113] in:

[0114] R c It can be alkyl, silylalkyl, cycloalkyl, or aryl.

[0115] In some embodiments, L is 2,2,6,6-tetramethylpiperidine. In some embodiments, L is N,N'-di-tert-butylethylenediamide. In some embodiments, L is bis(trimethylsilyl)amino.

[0116] In some embodiments, X is a halogen group derived from a halide compound.

[0117] In some embodiments, the tin-containing compound is a compound of the following formula:

[0118]

[0119]

[0120] .

[0121] At step 106, the synthesis method 100 includes contacting a tin-containing compound with reactants to form a monosubstituted tin compound. In some embodiments, the monosubstituted tin compound is formed via ligand exchange, wherein ligands and / or halogens from the reactants replace ligands and / or halogens on the tin-containing compound. In some embodiments, contacting includes reacting the tin-containing compound with the reactants. In some embodiments, contacting includes mixing the tin-containing compound with the reactants. In some embodiments, contacting includes stirring the tin-containing compound and the reactants. In some embodiments, contacting includes adding the tin-containing compound and the reactants to a reactor vessel. In some embodiments, contacting includes dissolving the tin-containing compound and the reactants. In some embodiments, contacting includes combining the tin-containing compound with the reactants. In some embodiments, contacting is carried out in solution.

[0122] In some embodiments, the reactants include at least one compound having the following formula:

[0123] HL 1 Or M q 1 L z 1 ,

[0124] in:

[0125] L 1 It can be a monoanion ligand, a dianion ligand, or a halide group;

[0126] M is an alkali metal cation, an alkaline earth metal cation, a transition metal cation, or a post-transition metal cation.

[0127] q is 1 or 2; and

[0128] z can be 1, 2, 3 or 4.

[0129] In some embodiments, L 1 For -OR d -NR d R e -NCO, -OC(=O)NR d R e -NR d C(=O)OR e -OC(=O)CH3, -NRd (CH2) n NR d R e -NR d (CH2) n R e N-, -O(CH2) n O-, -O(CH2) n OR d -O(CH2) n NR d R e -O(CH2) n R d N- or -C≡CR d , where R d and R e Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; and n is 1 to 30. In some embodiments, R d Or R e At least one of them is -Si(CH3)3. In some embodiments, each L 1 Independently:

[0130]

[0131]

[0132] in:

[0133] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 It is independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl or aralkyl.

[0134] In some embodiments, L 1 It is -N(CH3)2. In some embodiments, L 1 It is -OC(CH3)3. In some embodiments, L 1 L1 is -C≡CC(CH3)3. In some embodiments, L1 is -C≡CCH3. In some embodiments, L 1 For -OSi(CH3)3. In some embodiments, L 1 Independently:

[0135] .

[0136] In some embodiments, the reactants include at least one of the following: HC≡CCH3, HOC(CH3)3, HC≡CC(CH3)3, HOSi(CH3)3, HNEt2, NEt3, 2,2,6,6-tetramethylpiperidine, Sn(N(CH3)2)2, Sn(N(CH3)2)4, Sn(OC(CH3)3)2, Sn(OC(CH3)3)4, SnCl2, SnCl4, SnI2, SnI4, SnBr2, SnBr4, LiN(CH3)2, Na(OC(CH3)3), K(OC(CH3)3), HOC(CH3)3, NaOSi(CH3)3, LiOSi(CH3)3, CH3C≡CMgBr, NaCl, KCl, or any combination thereof. In some embodiments, the reactants include at least one of the following: HC≡CCH3, HOC(CH3)3, HC≡CC(CH3)3, HOSi(CH3)3, or any combination thereof. In some embodiments, the reactants further include at least one of the following: HNEt2, NEt3, 2,2,6,6-tetramethylpiperidine, or any combination thereof. In some embodiments, the reactants include at least one of the following: Sn(N(CH3)2)2, Sn(N(CH3)2)4, Sn(OC(CH3)3)2, Sn(OC(CH3)3)4, SnCl2, SnCl4, SnI2, SnI4, SnBr2, SnBr4, or any combination thereof. In some embodiments, the reactants include at least one of the following: LiN(CH3)2, Na(OC(CH3)3), K(OC(CH3)3), HOC(CH3)3, NaOSi(CH3)3, LiOSi(CH3)3, CH3C≡CMgBr, NaCl, KCl, or any combination thereof.

[0137] In some embodiments, monosubstituted tin compounds include compounds of the following formula:

[0138] ,

[0139] in:

[0140] R is at least one of the following or includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogen, imide, cyanate, nitrile, alkoxide, or any combination thereof; and

[0141] L 1 It can be a monoanion ligand, a dianion ligand, or a halogen group independently.

[0142] In some embodiments, R is a functional group derived from a tin-containing compound. In some embodiments, R is at least one of or includes at least one of the following: -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH(CH3)CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -(CH2)3CH3, - C6H5, -CH2(C6H5), -CH=CH2, -C≡CCH3, -CH2C≡CH, -CH2C≡CCH3, -C(CH3)=CH2, -HC=CHCH3, -CH2CH=CH2, -CH2N(CH3)2, -(CH2)3N(CH3)2, -CH2CH2OCH3, -CH(CH2)2O, -CH2Si(CH3)3, -Si(CH3)3 or any combination thereof.

[0143] In some embodiments, L 1 From the reactants. In some embodiments, each L 1 Different. In some embodiments, each L 1 Same. In some embodiments, at least two L 1 Same. In some embodiments, at least two L 1 Different. In some embodiments, L 1 For -OR d -NR d R e -NCO, -OC(=O)NR d R e -NR d C(=O)OR e -OC(=O)CH3, -NR d (CH2) n NR d R e -NR d (CH2) n R e N-, -O(CH2) n O-, -O(CH2) n OR d -O(CH2) n NR d R e -O(CH2) n R d N- or -C≡CR d , where R d and Re Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; and n is 1 to 30. In some embodiments, R d Or R e At least one of them is -Si(CH3)3. In some embodiments, each L 1 Independently:

[0144]

[0145]

[0146]

[0147] in:

[0148] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 It is independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl or aralkyl.

[0149] In some embodiments, L 1 It is -N(CH3)2. In some embodiments, L 1 It is -OC(CH3)3. In some embodiments, L 1 L1 is -C≡CC(CH3)3. In some embodiments, L1 is -C≡CCH3. In some embodiments, L 1 For -OSi(CH3)3. In some embodiments, L 1 Independently:

[0150] .

[0151] In some embodiments, the monosubstituted tin compound is a compound of the following formula:

[0152]

[0153]

[0154]

[0155] .

[0156] Some embodiments relate to a composition comprising a tinene compound. In some embodiments, the tinene compound is a reaction product of a stannous halide and a metallization reactant. In some embodiments, the tinene compound comprises a compound of the following formula:

[0157] SnL n ,

[0158] in:

[0159] L is a monoanion ligand or a dianion ligand; and

[0160] n is 1 or 2, provided that n is 1 when L is a dianion ligand. In some embodiments, n is 2 when L is a monoanion ligand.

[0161] In some embodiments, L is a ligand from the metallization reactant. For example, in some embodiments, L is an amino group. That is, for example, in some embodiments, L is:

[0162] -NR a R b ,

[0163] in:

[0164] R a and R b Independently hydrogen, alkyl, or silicon-based, or R a and R b They bond together to form C3-C 20 N-heterocyclic ring.

[0165] In some embodiments, L is an alkoxy group. That is, for example, in some embodiments, L is:

[0166] -OR c ,

[0167] in:

[0168] R c It can be alkyl, silylalkyl, cycloalkyl, or aryl.

[0169] In some embodiments, L is 2,2,6,6-tetramethylpiperidine. In some embodiments, L is N,N'-di-tert-butylethylenediamide. In some embodiments, L is bis(trimethylsilyl)amino. In some embodiments, L is -N(Si(CH3)3)2.

[0170] In some embodiments, the tinene compound comprises (2,2,6,6-tetramethylpiperidine)2tin(II). In some embodiments, the tinene compound is a compound of the following formula:

[0171] .

[0172] In some embodiments, the tinene compound comprises (N,N'-di-tert-butylethylenediamide)2tin(II). In some embodiments, the tinene compound comprises ((trimethylsilyl)amino)2tin(II).

[0173] Some embodiments relate to a composition comprising a tin-containing compound. In some embodiments, the tin-containing compound is a reaction product of a stannous halide and a tinene compound. In some embodiments, the tin-containing compound is an alkylated mixed ligand tin (IV) compound. In some embodiments, the tin-containing compound comprises a compound of the following formula:

[0174] RSn(L) n X,

[0175] in:

[0176] R is at least one of the following or includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogen, imide, cyanate, nitrile, alkoxide, or any combination thereof.

[0177] L is a monoanion ligand or a dianion ligand (as defined above);

[0178] n is either 1 or 2, provided that n is 1 when L is a dianionic ligand. In some embodiments, n is 2 when L is a monoanionic ligand; and

[0179] X is a halogen group.

[0180] In some embodiments, R is a functional group derived from a halide compound. In some embodiments, R is at least one of or includes at least one of the following: -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH(CH3)CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -(CH2)3CH3, - C6H5, -CH2(C6H5), -CH=CH2, -C≡CCH3, -CH2C≡CH, -CH2C≡CCH3, -C(CH3)=CH2, -HC=CHCH3, -CH2CH=CH2, -CH2N(CH3)2, -(CH2)3N(CH3)2, -CH2CH2OCH3, -CH(CH2)2O, -CH2Si(CH3)3, -Si(CH3)3 or any combination thereof.

[0181] In some embodiments, L is a ligand from a tinene compound. In some embodiments, L is an amino group. That is, for example, in some embodiments, L is:

[0182] -NR a R b ,

[0183] in:

[0184] R a and R b Independently hydrogen, alkyl, or silicon-based, or R a and R b They bond together to form C3-C 20 N-heterocyclic ring.

[0185] In some embodiments, L is an alkoxy group. That is, for example, in some embodiments, L is:

[0186] -OR c ,

[0187] in:

[0188] R c It can be alkyl, silylalkyl, cycloalkyl, or aryl.

[0189] In some embodiments, L is 2,2,6,6-tetramethylpiperidine. In some embodiments, L is N,N'-di-tert-butylethylenediamide. In some embodiments, L is bis(trimethylsilyl)amino.

[0190] In some embodiments, X is a halogen group derived from a halide compound.

[0191] In some embodiments, the tin-containing compound is a compound of the following formula:

[0192]

[0193]

[0194] .

[0195] Some embodiments relate to a composition comprising a monosubstituted tin compound. In some embodiments, the monosubstituted tin compound comprises a compound of the following formula:

[0196] ,

[0197] in:

[0198] R is at least one of the following or includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogen, imide, cyanate, nitrile, alkoxide, or any combination thereof; and

[0199] L 1 It can be a monoanion ligand, a dianion ligand, or a halogen group independently.

[0200] In some embodiments, R is at least one of the functional groups derived from or including at least one of the functional groups in a tin-containing compound. In some embodiments, R is -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH(CH3)CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -(CH2)3CH3, -C6H5, -CH2(C6H5), -CH=CH2, -C≡CCH3, -CH2C≡CH, -CH2C≡CCH3, -C(CH3)=CH2, -HC=CHCH3, -CH2CH=CH2, -CH2N(CH3)2, -(CH2)3N(CH3)2, -CH2CH2OCH3, -CH(CH2)2O, -CH2Si(CH3)3, -Si(CH3)3, or any combination thereof.

[0201] In some embodiments, L 1 From the reactants. In some embodiments, each L 1 Different. In some embodiments, each L 1 Same. In some embodiments, at least two L 1 Same. In some embodiments, at least two L 1 Different. In some embodiments, L 1 For -OR d -NR d R e -NCO, -OC(=O)NR d R e -NR d C(=O)OR e -OC(=O)CH3, -NR d (CH2) n NR d R e -NR d (CH2) n R e N-, -O(CH2)n O-, -O(CH2) n OR d -O(CH2) n NR d R e -O(CH2) n R d N- or -C≡CR d , where R d and R e Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; and n is 1 to 30. In some embodiments, R d Or R e At least one of them is -Si(CH3)3. In some embodiments, each L 1 Independently:

[0202]

[0203]

[0204] in:

[0205] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 It is independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl or aralkyl.

[0206] In some embodiments, L 1 It is -N(CH3)2. In some embodiments, L 1 It is -OC(CH3)3. In some embodiments, L 1 L1 is -C≡CC(CH3)3. In some embodiments, L1 is -C≡CCH3. In some embodiments, L 1 For -OSi(CH3)3. In some embodiments, L 1 Independently:

[0207] .

[0208] In some embodiments, the monosubstituted tin compound is a compound of the following formula:

[0209]

[0210]

[0211]

[0212] .

[0213] In some embodiments, the presence of disubstituted tin (IV) compounds, such as, but not limited to, dialkyltin (IV) compounds, negatively impacts crosslinking during EUV exposure. Therefore, in some embodiments, high-purity compositions with low levels of disubstituted tin (IV) compounds are desired. At least one advantage of the synthetic method is the formation of monosubstituted tin compounds with high purity, and in some cases, with undetectable levels of disubstituted tin (IV) compounds.

[0214] In some embodiments, the composition comprises less than 5% by weight of a disubstituted tin (IV) compound, based on the total weight of the composition. For example, in some embodiments, the composition comprises less than 4.5% by weight, less than 4% by weight, less than 3.5% by weight, less than 3% by weight, less than 2.5% by weight, less than 2% by weight, less than 1.5% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.1% by weight, less than 0.01% by weight, less than 0.001% by weight, or less than 0.0001% by weight of a disubstituted tin (IV) compound, based on the total weight of the composition. In some embodiments, the composition comprises at least 95% by weight, at least 95.5% by weight, at least 96% by weight, at least 96.5% by weight, at least 97% by weight, at least 97.5% by weight, at least 98% by weight, at least 98.5% by weight, at least 99% by weight, at least 99.5% by weight, at least 99.9% by weight, at least 99.99% by weight, at least 99.999% by weight, and at least 99.9999% by weight of a monosubstituted tin compound, based on the total weight of the composition. In some embodiments, the composition comprises 95% to 99.9999%, 95.5% to 99.9999%, 96% to 99.9999%, 96.5% to 99.9999%, 97% to 99.9999%, 97.5% to 99.9999%, 98% to 99.9999%, 98.5% to 99.9999%, 99% to 99.9999%, 99.5% to 99.9999%, 99. 9% to 99.9999%, 99.99% to 99.9999%, 99.999% to 99.9999%, 95% to 99.999%, 95% to 999%, 95% to 99%, 95% to 99.5%, 95% to 99%, 95% to 98.5%, 95% to 98%, 95% to 97.5%, 95% to 97%, 95% to 96.5%, 95% to 96% or 95% to 95.5%.

[0215] In some embodiments, the disubstituted tin (IV) compound is a compound of the following formula:

[0216] ,

[0217] in:

[0218] R is at least one of the following or includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogen, imide, cyanate, nitrile, alkoxide, or any combination thereof; and

[0219] L 1 It can be a monoanion ligand, a dianion ligand, or a halogen group independently.

[0220] Figure 2 This is a flowchart of a method 200 for preparing a tin-containing film according to some embodiments. Figure 2 As shown, the method 200 for preparing a tin-containing film may include one or more of the following steps, consist of one or more of the following steps, or consist substantially of one or more of the following steps: obtaining a precursor 202; obtaining at least one co-reactant precursor 204; vaporizing the precursor 206 to obtain a vaporized precursor; vaporizing at least one co-reactant precursor 208 to obtain at least one vaporized co-reactant precursor; contacting at least one of the vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof with a substrate 210 under vapor deposition conditions to form a tin-containing film on the substrate.

[0221] Step 202 may include, consist of, or substantially consist of obtaining a precursor. The precursor may include, consist of, or substantially consist of any one or more compositions comprising the monosubstituted tin compounds disclosed herein. Obtaining may include obtaining a container or other vessel comprising the precursor. In some embodiments, the precursor may be obtained in a container or other vessel in which it is to be vaporized.

[0222] Step 204 may include, consist of, or substantially consist of: obtaining at least one co-reactant precursor. In some embodiments, the at least one co-reactant precursor includes at least one of, consists of, or substantially consists of at least one of, or is selected from the group consisting of at least one of: oxidizing gas, reducing gas, hydrocarbon, or any combination thereof. At least one co-reactant precursor may be selected to obtain the desired tin-containing film. In some embodiments, the at least one co-reactant precursor may include at least one of, consists of, or substantially consists of at least one of: N2, H2, NH3, N2H4, CH3HNNH2, CH3HNNHCH3, NCH3H2, NCH3CH2H2, N(CH3)2H, N(CH3CH2)2H, N(CH3)3, N(CH3CH2)3, Si(CH3)2NH, pyrazoline, pyridine, ethylenediamine, or any combination thereof. In some embodiments, at least one co-reactant precursor may include, consist of, or substantially consist of at least one of the following: H2, O2, O3, H2O, H2O2, NO, N2O, NO2, CO, CO2, carboxylic acid, alcohol, diol, or any combination thereof. In some embodiments, at least one co-reactant precursor may include, consist of, or substantially consist of at least one of the following: methane, ethane, ethylene, acetylene, or any combination thereof. Obtaining may include obtaining a container or other vessel comprising at least one co-reactant precursor. In some embodiments, at least one co-reactant precursor may be obtained in a container or other vessel in which at least one co-reactant precursor is to be vaporized. In some embodiments, the method further includes an inert gas, such as argon, helium, nitrogen, or any combination thereof.

[0223] Step 206 may include, consist of, or substantially consist of: vaporizing the precursor to obtain a vaporized precursor. Vaporization may include, consist of, or substantially consist of: heating the precursor sufficiently to obtain a vaporized precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating a container comprising the precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating the precursor in a deposition chamber where a vapor deposition process is performed. In some embodiments, vaporization may include, consist of, or substantially consist of: heating a conduit for delivering the precursor, the vaporized precursor, or any combination thereof to, for example, a deposition chamber. In some embodiments, vaporization may include, consist of, or substantially consist of: operating a vapor delivery system comprising the precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating to a temperature sufficient to vaporize the precursor to obtain a vaporized precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating to a temperature below the decomposition temperature of at least one of the precursor, the vaporized precursor, or any combination thereof. In some embodiments, the precursor may be present in a gaseous form, in which case step 206 is optional and not required. For example, the precursor may include, consist of, or substantially consist of a vaporized precursor.

[0224] Step 208 may include, consist of, or substantially consist of: vaporizing at least one co-reactant precursor to obtain at least one vaporized co-reactant precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating at least one co-reactant precursor sufficient to obtain at least one vaporized co-reactant precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating a container comprising at least one co-reactant precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating at least one co-reactant precursor in a deposition chamber where a vapor deposition process is performed. In some embodiments, vaporization may include, consist of, or substantially consist of: heating a conduit for delivering at least one co-reactant precursor, at least one vaporized co-reactant precursor, or any combination thereof to, for example, a deposition chamber. In some embodiments, vaporization may include, consist of, or substantially consist of: operating a vapor delivery system comprising at least one co-reactant precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating to a temperature sufficient to vaporize at least one co-reactant precursor to obtain at least one vaporized co-reactant precursor. In some embodiments, vaporization may include, consist of, or substantially consist of heating to a temperature below the decomposition temperature of at least one co-reactant precursor, at least one vaporized co-reactant precursor, or any combination thereof. In some embodiments, at least one co-reactant precursor may be present in a gaseous form, in which case step 108 is optional and not required. For example, at least one co-reactant precursor may include, consist of, or substantially consist of at least one vaporized co-reactant precursor.

[0225] Step 210 may include, consist of, or substantially consist of contacting at least one of a vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof with a substrate under vapor deposition conditions sufficient to form a tin-containing film on the surface of the substrate. Contact may be performed in any system, apparatus, device, assembly, chamber, or component thereof suitable for a vapor deposition process (including, for example, but not limited to, deposition chambers and others). The vaporized precursor and at least one co-reactant precursor may be contacted with the substrate simultaneously or at different times. For example, each of the vaporized precursor, at least one vaporized co-reactant precursor, and the substrate may be present simultaneously in the deposition chamber. That is, in some embodiments, contact may include simultaneously or synchronously contacting the vaporized precursor and at least one vaporized co-reactant precursor with the substrate. Alternatively, each of the vaporized precursor and at least one vaporized co-reactant precursor may be present in the deposition chamber at different times. That is, in some embodiments, the contact may include alternating and / or sequentially contacting the vaporized precursor with the substrate in one or more cycles, and subsequently contacting at least one vaporized co-reactant precursor with the substrate.

[0226] Vapor deposition conditions may include conditions for a vapor deposition process. Examples of vapor deposition conditions include (but are not limited to) vapor deposition conditions for a vapor deposition process comprising at least one of the following: chemical vapor deposition (CVD) process, digital or pulsed chemical vapor deposition process, plasma-enhanced cyclic chemical vapor deposition (PECCVD) process, flowable chemical vapor deposition (FCVD) process, atomic layer deposition (ALD) process, thermal atomic layer deposition, plasma-enhanced atomic layer deposition (PEALD) process, metal-organic chemical vapor deposition (MOCVD) process, plasma-enhanced chemical vapor deposition (PECVD) process, or any combination thereof.

[0227] Vapor deposition conditions may include, consist of, or substantially consist of a deposition temperature. The deposition temperature may be a temperature below the thermal decomposition temperature of at least one of the vaporized precursor, at least one of the vaporized co-reactant precursors, or any combination thereof. The deposition temperature may be high enough to reduce or avoid condensation of at least one of the vaporized precursor, at least one of the vaporized co-reactant precursors, or any combination thereof. In some embodiments, the substrate may be heated to the deposition temperature. In some embodiments, a chamber or other vessel that contacts the substrate with the vaporized precursor and at least one of the vaporized co-reactant precursors may be heated to the deposition temperature. In some embodiments, at least one of the vaporized precursor, at least one of the vaporized co-reactant precursors, or any combination thereof may be heated to the deposition temperature.

[0228] The deposition temperature can be from 200°C to 2500°C. In some embodiments, the deposition temperature can be from 500°C to 700°C. For example, in some embodiments, the deposition temperature can be the following temperatures: 500°C to 680°C, 500°C to 660°C, 500°C to 640°C, 500°C to 620°C, 500°C to 600°C, 500°C to 580°C, 500°C to 560°C, 500°C to 540°C, 500°C to 520°C, 520°C to 700°C, 540°C to 700°C, 560°C to 700°C, 580°C to 700°C, 600°C to 700°C, 620°C to 700°C, 640°C to 700°C, 660°C to 700°C, or 680°C to 700°C. In other embodiments, the deposition temperature may be a temperature greater than 200°C to 2500°C, such as, but not limited to, the following temperatures: 400°C to 2000°C, 500°C to 2000°C, 550°C to 2400°C, 600°C to 2400°C, 625°C to 2400°C, 650°C to 2400°C, 675°C to 2400°C, 700°C to 2400°C, 725°C to 2400°C, 750°C to 2400°C. 775℃ to 2400℃, 800℃ to 2400℃, 825℃ to 2400℃, 850℃ to 2400℃, 875℃ to 2400℃, 900℃ to 2400℃, 925℃ to 2400℃, 950℃ to 2400℃, 975℃ to 2400℃, 1000℃ to 2400℃, 1025℃ to 2400℃, 1050℃ to 2400℃, 1075℃ to 2400℃, 1100℃ ℃ to 2400℃, 1200℃ to 2400℃, 1300℃ to 2400℃, 1400℃ to 2400℃, 1500℃ to 2400℃, 1600℃ to 2400℃, 1700℃ to 2400℃, 1800℃ to 2400℃, 1900℃ to 2400℃, 2000℃ to 2400℃, 2100℃ to 2400℃, 2200℃ to 2400℃, 2300℃ to 2400℃ 500℃ to 2000℃, 500℃ to 1900℃, 500℃ to 1800℃, 500℃ to 1700℃, 500℃ to 1600℃, 500℃ to 1500℃, 500℃ to 1400℃, 500℃ to 1300℃, 500℃ to 1200℃, 500℃ to 1100℃, 500℃ to 1000℃, 500℃ to 1000℃, 500℃ to 900℃, or 500℃ to 800℃.

[0229] Vapor deposition conditions may include, consist of, or substantially consist of deposition pressure. In some embodiments, deposition pressure may include, consist of, or substantially consist of the vapor pressure of at least one of a vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof. In some embodiments, deposition pressure may include, consist of, or substantially consist of chamber pressure.

[0230] The deposition pressure can be from 0.001 Torr to 100 Torr. For example, in some embodiments, the deposition pressure can be the following: 1 Torr to 30 Torr, 1 Torr to 25 Torr, 1 Torr to 20 Torr, 1 Torr to 15 Torr, 1 Torr to 10 Torr, 5 Torr to 50 Torr, 5 Torr to 40 Torr, 5 Torr to 30 Torr, 5 Torr to 20 Torr, or 5 Torr to 15 Torr. In other embodiments, the deposition pressure may be one of the following: 1 to 100 tor, 5 to 100 tor, 10 to 100 tor, 15 to 100 tor, 20 to 100 tor, 25 to 100 tor, 30 to 100 tor, 35 to 100 tor, 40 to 100 tor, 45 to 100 tor, 50 to 100 tor, 55 to 100 tor, 60 to 100 tor, 65 to 100 tor, 70 to 100 tor, 75 to 100 tor, 80 to 100 tor, 85 to 100 tor, 90 to 100 tor, 95 to 100 tor, 1 to 95 tor, 1 to 85 tor, 1 to 80 tor, 1 to 75 tor, or 1 to 70 tor. In other embodiments, the deposition pressure may be one of the following: 1 mTorr to 100 mTorr, 1 mTorr to 90 mTorr, 1 mTorr to 80 mTorr, 1 mTorr to 70 mTorr, 1 mTorr to 60 mTorr, 1 mTorr to 50 mTorr, 1 mTorr to 40 mTorr, 1 mTorr to 30 mTorr, 1 mTorr to 20 mTorr, 1 mTorr to 10 mTorr, 100 mTorr to 300 mTorr, 150 mTorr to 300 mTorr, 200 mTorr to 300 mTorr, or 150 mTorr to 250 mTorr, or 150 mTorr to 225 mTorr.

[0231] The substrate may include at least one of the following, consist of at least one of the following, or consist substantially of at least one of the following: Si, Co, Cu, Al, W, WN, WC, TiN, Mo, MoC, SiO2, W, SiN, WCN, Al2O3, AlN, ZrO2, La2O3, TaN, RuO2, IrO2, Nb2O3, Y2O3, hafnium oxide, or any combination thereof.

[0232] The tin-containing film may include tin oxide or a tin oxide film. In some embodiments, the tin-containing film includes functionalized tin oxide. In some embodiments, the tin-containing film includes functionalized tin oxide having the following formula: RSnO z, where z is 1 to 6. In some embodiments, R is at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, ether, amine, halogen, imide, cyanate, nitrile, or alkoxide.

[0233] Some embodiments relate to a tin-containing film on a substrate surface. In some embodiments, the tin-containing film comprises any film formed according to the methods disclosed herein. In some embodiments, the tin-containing film comprises any film prepared from the precursors disclosed herein.

[0234] Figure 3 The reaction flow of a method 300 for forming a monosubstituted tin compound according to some embodiments is described. For example... Figure 3 As shown, method 300 for forming a monosubstituted tin compound includes reacting a tin halide with a metallizing reactant to form a tinene compound via substitution. The tinene compound includes a monoanionic ligand on tin(II). The halide compound is reacted with the tinene compound to form a tin-containing compound via oxidative addition. The tin-containing compound is reacted with a reactant to form a monosubstituted tin compound via ligand exchange.

[0235] Figure 4 The reaction flow of a method 400 for forming a monosubstituted tin compound according to some embodiments is described. For example... Figure 4 As shown, method 400 for forming a monosubstituted tin compound includes reacting a tin halide with a metallizing reactant to form a tinene compound via substitution. The tinene compound includes a dianionic ligand on tin(II). The halide compound is reacted with the tinene compound to form a tin-containing compound via oxidative addition. The tin-containing compound is reacted with a reactant to form a monosubstituted tin compound via ligand exchange.

[0236] Figure 5A schematic cross-sectional view depicting a non-limiting embodiment of an ampoule 500 according to some embodiments is shown. The ampoule 500 includes a tray assembly 502 within an internal chamber 504 of the ampoule 500. The internal chamber 504 has an inner wall surface 506. The tray assembly 502 includes trays 508, each configured to contain a vaporizable precursor. In some embodiments, the vaporizable precursor includes any one or more of the compositions disclosed herein, the compositions comprising a composition including a monosubstituted tin compound. Each of the trays 508 of the tray assembly 502 includes a portion 510 configured to contact (e.g., thermal contact, physical contact, etc.) the inner wall surface 506 of the ampoule 500. The surface-to-surface contact between the portion 510 and the inner wall surface 506 enhances heat transfer from the ampoule 500 to each tray 508, and thus enhances heat transfer from each tray 508 to the vaporizable precursor on each tray 508. Various fluid flow paths are defined within the internal chamber 504 of the ampoule 500 to allow fluid to flow upward, downward, or both through the ampoule 500. The ampoule 500 is shown to have a generally cylindrical internal chamber. However, it should be understood that the internal chamber 504 of the ampoule may have other shapes without departing from the scope of this disclosure.

[0237] Example 1

[0238] Sn(pip Me4 Synthesis of 2

[0239] 2,2,6,6-Tetramethylpiperidine (Hpip) Me4 SnCl2 (29.3 g, 208 mmol) was transferred to a 500 mL Schlenk flask equipped with a magnetic stir bar and diluted with 200 mL of hexane. After a 30-minute time series, nBuLi (1.6 M in hexane, 130.0 mL, 209 mmol) was added to the amine solution, resulting in a slightly exothermic reaction and the formation of a white mixture. After stirring the reaction mixture for 2 hours, 100 mL of THF was added to form a slightly turbid amber solution. Separately, a THF (100 mL) solution of SnCl2 (20.0 g, 104 mmol) was prepared in a 1 L Schlenk flask equipped with a magnetic stir bar. After a 1-hour time series, Lipip... Me4The solution was added to the SnCl2 solution via a feeding funnel, and the reactants immediately turned into a blood-red solution upon addition. After the addition was complete, the resulting deep red mixture was stirred overnight at room temperature. The next morning, the volatiles were removed from the reaction mixture under reduced pressure, the product was extracted with 200 mL of hexane, filtered through a disposable polyethylene frit filter, and the resulting deep red solution was dried under reduced pressure to give a red solid product. Mass: 24.1 g, 57.7% yield. Melting point: 73.3 °C (DSC). X-ray quality crystals were grown by cooling a saturated PhMe solution at -35 °C. 1 H-NMR (400 MHz, C6D6, 298K): 1.39 (t, 8H); 1.50 (s, 24H); 1.71 (m, 4H) ppm; 13 C{ 1 H}-NMR (100 MHz, C6D6, 298K): 19.07; 34.50; 43.15; 57.90 ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6, 298K): 752.5 ppm. Figure 6 Describing Sn(pip) according to some embodiments Me4 )2 is a three-dimensional solid structure.

[0240] Example 2

[0241] CF3CH2Sn(pip Me4 Synthesis of 2I

[0242] Sn(pip) Me4 2 (5.0 g, 12.4 mmol) was placed in a 40 mL amber vial equipped with a magnetic stir bar and dissolved in 30 mL of hexane to form a deep red solution. ICH2CF3 (2.72 g, 13.0 mmol) was diluted with 5 mL of hexane and added to the Sn-amide solution via pipette over a two-minute time interval. The resulting deep red solution was stirred overnight. The next morning, the volatiles were removed from the deep red solution under reduced pressure to give a thick, red / brown viscous liquid product. Mass: 7.22 g, yield 95.6%. 1 H-NMR (400 MHz, C6D6, 298K): 1.37 (m, 8H); 1.48 (s, 12H); 1.50 (s, 12H); 1.53 (m, 4H); 2.55 (q, 2H) ppm; 13 C{ 1H}-NMR (100 MHz, C6D6, 298K): 17.28; 33.92; 34.42; 41.33; 42.84(q); 59.20; 128.52(q) ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6, 298K): -342.42(q) ppm. 19 F-NMR (376 MHz, C6D6, 298K): -49.54 (t) ppm.

[0243] Example 3

[0244] FCH2Sn(pip Me4 Synthesis of 2I

[0245] Sn(pip) Me4 2.5 g (6.23 mmol) was placed in a 40 mL amber vial equipped with a magnetic stir bar and dissolved in 20 mL of tetrahydrofuran to form a deep red solution, which was cooled to -35°C. ICH2F (1.04 g, 6.54 mmol) was diluted with 5 mL of THF and added to the Sn-amide solution via pipette over a two-minute time interval. The resulting deep red solution was stirred overnight. The next morning, the volatiles were removed from the deep red solution under reduced pressure to give a thick, red / brown viscous liquid product. Mass: 2.99 g, yield 85.9%. 1 H-NMR (400 MHz, C6D6,298K): 1.25-1.55 (bm, 36H); 4.75 (d, 2H) ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6,298K): -258.32(d) ppm. 19 F-NMR (376 MHz, C6D6, 298K): -226.24 (t) ppm.

[0246] Example 4

[0247] O(CH2)2HCSn(pip Me4 Synthesis of 2I

[0248] In a nitrogen-filled glove box, Sn(pip) Me42.0 g (4.98 mmol) was placed in an amber 40 mL vial equipped with a magnetic stir bar, dissolved in 10 mL of THF, and cooled to -35 °C. After a two-minute time course, 5 mL of a THF solution of 1-iodooxycyclobutane (0.96 g, 5.22 mmol) was added dropwise to the cooled Sn-amide solution with stirring. The reaction mixture was stirred at room temperature for 12 hours. The resulting dark red / brown solution was dried under reduced pressure to obtain a viscous, dark red / brown oil. 1 H-NMR (400 MHz, C6D6, 298K): 1.1-1.5 (bm, 36H); 3.16 (pent, 1H); 4.63 (t, 2H); 5.02 (t, 2H) ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6,298K): -190.88 ppm.

[0249] Example 5

[0250] Synthesis of CF3CH2Sn(C≡CCH3)3

[0251] CF3CH2Sn(pip) Me4 CF3CH2Sn (0.500 g, 0.769 mmol) was placed in a 40 mL amber vial equipped with a magnetic stir bar and dissolved in 5 mL of THF. Propylene (1 M in THF, 4.61 mL, 4.61 mmol) was added directly to CF3CH2Sn (pip). Me4 The mixture was added to a 2I solution and stirred overnight at room temperature. The next morning, the reactants were an orange-red mixture. Volatile substances were removed under reduced pressure, and the product was extracted with 2 mL of C6D6 and filtered through a 0.2 µm syringe filter to obtain an orange product solution. 1 H-NMR (400 MHz, C6D6, 298K): 1.40 (s, 9H); 1.60 (q, 2H)ppm; 13 C{ 1 H}-NMR (100 MHz, C6D6, 298K): 4.47; 21.11(q); 75.07; 108.96; 128.39(q)ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6, 298K): -275.37(q) ppm. 19F-NMR (376 MHz, C6D6,298K): -52.74 (t) ppm.

[0252] Example 6

[0253] Synthesis of CF3CH2Sn(N(SiMe3)2)2I

[0254] Sn(N(SiMe3)2)2 (25.0 g, 56.5 mmol) was dissolved in hexane (100 mL) in a 250 mL round-bottom flask equipped with a magnetic stir bar to form a deep orange / red solution. ICH2CF3 (11.8 g, 56.6 mmol) was concentrated in a separate vial and then added to the hexane solution over a ten-minute time interval, during which slight exothermic reaction and a lightening of the solution color were observed. The resulting light orange solution was stirred at room temperature for 20 minutes, at which point the solvent was removed under reduced pressure to obtain a free-flowing, pale yellow solid. Mass: 34.34 g, 93.4% yield. X-ray quality crystals were grown by cooling the saturated hexane solution at -35 °C. 1 H-NMR (400 MHz, C6D6, 298K): 0.32 (s, 36H); 2.42 (q, 2H)ppm; 13 C{ 1 H}-NMR (100 MHz, C6D6, 298K): 5.98; 34.86(q); 127.72(q) ppm; 19 F-NMR (376 MHz, C6D6, 298K): -50.2(t) ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6, 298K): -249.82(q) ppm. Figure 7 A three-dimensional solid structure of CF3CH2Sn(N(SiMe3)2)2I according to some embodiments is depicted.

[0255] Example 7

[0256] Synthesis of iPrSn(N(SiMe3)2)2I

[0257] Sn(N(SiMe3)2)2 (2.0 g, 4.53 mmol) was placed in a 40 mL vial equipped with a magnetic stir bar and diluted with 20 mL of hexane. Separately, 2-iodopropane (0.807 g, 4.75 mmol) was diluted with 5 mL of hexane and added directly to the Sn-amide solution with stirring over a 1-minute time interval. The resulting deep red solution was stirred for 12 hours, at which point the reactants became a slightly turbid pale yellow solution. The reactants were filtered through a 0.2 µm syringe filter, and the resulting pale yellow solution was dried under reduced pressure to obtain a pale yellow solid product (iPrSn(N(SiMe3)2)2I). The isolate was 2.40 g, yield: 86.9%. X-ray quality crystals were grown by cooling the hexane solution in a freezer at -35 °C. 1 H-NMR (400MHz, C6D6, 298K): 0.36 (s, 36H); 1.27 (d, 6H); 2.06 (sept, 1H) ppm; 13 C{ 1 H}-NMR (100 MHz, C6D6, 298K): 6.35; 21.76; 31.40 ppm; 29 Si-NMR (79 MHz, C6D6, 298K): 5.70 ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6, 298K): -102.91 ppm. Figure 8 A three-dimensional solid-state structure of iPrSn(N(SiMe3)2)2I is depicted according to some embodiments.

[0258] Example 8

[0259] CF3CH2Sn(O t Synthesis of Bu)3

[0260] CF3CH2Sn(pip) Me4 )2I (1.0 g, 1.64 mmol) was placed in an amber vial equipped with a magnetic stir bar and dissolved in 5 mL of tetrahydrofuran. Separately, tert-butanol (0.382 g, 5.16 mmol) and triethylamine (0.497 g, 4.92 mmol) were diluted with 5 mL of tetrahydrofuran and added to CF3CH2Sn(pip) with stirring over a two-minute time interval. Me4 The reactants were stirred in a 2I solution at room temperature for 12 hours. The resulting yellow mixture was filtered through a 0.2 µm syringe filter to obtain a yellow solution, and the volatiles were removed under reduced pressure to obtain a pale yellow liquid, Hpip. Me4and CF3CH2Sn(O t The product mixture of Bu)3, which is obtained through 119 The purity determined by Sn-NMR was 96.8%. Total mass: 0.89 g, calibrated mass: 0.61 g, yield: 88.4%. 1 H-NMR (400 MHz, C6D6, 298K): 1.31 (s, 27H); 1.80 (q, 2H) ppm; 13 C{ 1 H}-NMR (100 MHz, C6D6, 298K): 28.54(q); 33.57; 74.40; 127.30(q) ppm; 19 F-NMR (376 MHz, C6D6, 298K): -51.93(t) ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6, 298K): -228.35(q) ppm.

[0261] Example 9

[0262] FCH2Sn(O t Synthesis of Bu)3

[0263] In a nitrogen-filled glove box, Sn(pip) Me4 ICH2 (15.0 g, 37.3 mmol) was placed in a 250 mL round-bottom Schrank flask equipped with a magnetic stir bar and dissolved in 250 mL THF to form a deep red solution. ICH2F (CAS No. 373-53-5, 5.96 g, 37.3 mmol) was added dropwise to the tinamide solution over a 5-minute time interval. The resulting deep red solution was stirred at room temperature for 2 hours, during which time KO was added over a 15-minute time interval. t Bu (CAS No. 865-47-4, 4.16 g, 37.1 mmol) was added to the reactants with stirring, resulting in the formation of a pale yellow precipitate. The addition was carried out over a 10-minute timeframe. t Before adding 20 mL of THF solution of BuOH (CAS No. 75-65-0, 5.55 g, 74.9 g), the reaction mixture was stirred for 20 minutes, resulting in slight exotherm. The resulting deep orange reaction mixture was stirred for 12 hours, and volatiles were removed under reduced pressure. The pink product matrix was extracted with 250 mL of hexane and filtered through a diatomaceous earth stopper suspended above a disposable polyethylene filter stock. The filter stock was washed with 25 mL of hexane, and the combined organic solutions were dried under reduced pressure to give a deep red liquid, FCH2Sn(O t Bu)3 and HpipMe4 The mixture. Mass: 17.27 g. 7.82 g of the crude mixture was aliquoted into a 50 mL round-bottom Schrank flask equipped with a short-path distillation head containing a receiving flask and thermometer. The product was distilled under reduced pressure at a head temperature of 22–25 °C (50–60 mTorr) to obtain a colorless liquid, FCH₂Sn(O₂). t Bu )3, which is through 119 Sn-NMR and 19 The purity determined by F-NMR was 98.5%. Mass: 2.43 g. 1 H-NMR (400 MHz, C6D6,298K): 1.34 (s, 27H); 4.69 (d, 2H) ppm; 13 C{ 1 H}-NMR (100 MHz, C6D6, 298K): 33.78;73.51; 84.51(d) ppm; 19 F-NMR (376 MHz, C6D6, 298K): -261.01(t) ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6, 298K): -256.19(d) ppm.

[0264] Example 10

[0265] O(CH2)2HCSn(O t Synthesis of Bu)3

[0266] Sn(pip) Me4 2 (5.0 g, 12.4 mmol) was placed in an amber vial and dissolved in THF (20 mL). 1-Iodoxetane (2.39 g, 13.0 mmol) was diluted with 5 mL of THF and added to the Sn-amide solution over a 2-minute time interval. The resulting deep red solution was stirred for 1.5 hours, during which time the solid K+ was added over a 5-minute time interval. t Bu (1.38 g, 12.3 mmol) was added directly to the reaction mixture, resulting in an orange precipitate. The reaction mixture was stirred for 1 hour. t 10 mL of a BuOH (1.83 g, 24.8 mmol) THF solution was added to the mixture. The resulting deep orange / red mixture was stirred at room temperature for 60 hours, during which time the mixture was filtered through a 0.2 µm syringe filter and dried under reduced pressure to obtain the product from Hpip. Me4 and O(CH2)2HCSn(Ot A dark red, viscous, oily substance composed of a mixture of Bu and 3. Mass: 2.73 g. 1 H-NMR(400 MHz, C6D6, 298K): 1.28 (s, 27H); 2.89 (pent, 1H); 4.67 (dd, 2H); 4.95 (dd,2H) ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6, 298K): -218.38 ppm.

[0267] Example 11

[0268] CH3C≡CCH2Sn(pip Me4 Synthesis of 2Br

[0269] Sn(pip) Me4 1.0 g (2.49 mmol) was placed in a 40 mL vial equipped with a magnetic stir bar and diluted with 2 mL of C6D6. For the solution, 0.331 g (2.49 mmol) of 1-bromo-2-butyne was added directly to the Sn-amide solution with stirring over a 1-minute time course. The resulting deep red solution was stirred for 4 hours, at which point the reactants became a slightly turbid deep yellow solution. The reactants were filtered through a 0.2 µm syringe filter to obtain a deep yellow product solution. 1 H-NMR (400MHz, C6D6, 298K): 1.04 (s, 3H); 1.38 (t, 8H); 1.49 (s, 12H), 1.57 (s, 12H), 1.62 (m, 4H), 2.42 (s, 2H) ppm; 13 C{ 1 H}-NMR (100 MHz, C6D6, 298K): 3.81, 17.81, 33.89, 34.47, 42.33, 58.12, 78.21, 77.25 ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6,298K): -139.6 ppm.

[0270] Example 12

[0271] Synthesis of CH3C≡CCH2Sn(OtBu)3

[0272] In a 100 mL Schrank flask in the glove box, Sn(pip) Me41-Bromobut-2-yne (5 g, 12.4 mmol) was dissolved in 10 mL of THF. 1-Bromobut-2-yne (1.64 g, 12.4 mmol) was added to this deep red solution. After a few minutes, the color of the solution changed from deep red to deep orange / brown. The solution was stirred overnight at room temperature. 119 Sn NMR showed CH3CCCH2Sn(pipMe) 4 2Br showed a clear peak at -140.4 ppm. Triethylamine (3.76 g, 37.2 mmol) was added to the solution, followed by tert-butanol (2.76 g, 37.2 mmol). Solid formation was observed. The solution was stirred overnight at room temperature. The solution was then filtered and the solid was washed with hexane. Volatiles were removed under reduced pressure to give Hpip as a deep orange liquid. Me4 With CH3CCCH2Sn(O t The product mixture of Bu)3, which is obtained through 119 The purity determined by Sn-NMR was 78%. 1 H-NMR (400 MHz, C6D6, 298K): 1.31 (s, 3H); 1.35 (s, 27H); 1.98 (s, 2H) ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6,298K): -233.8 ppm.

[0273] Table 1. Crystal data and structure refinement of CF3CH2Sn(N(SiMe3)2)2I.

[0274] Empirical formula C14 H38 F3 I N2 Si4 Sn

[0275] Molecular formula C14 H38 F3 I N2 Si4 Sn

[0276] Molecular weight 649.41

[0277] Temperature 100.0 K

[0278] Wavelength 0.71073 Å

[0279] Crystal system: Monoclinic

[0280] Space group C 1 2 / c 1

[0281] Cell size a = 17.4520(7) Åa=90°.

[0282] b = 8.8141(4) Åb=113.8730(10)°.

[0283] c = 18.8726(11) Åg=90°.

[0284] Volume 2654.7(2) Å 3

[0285] Z4

[0286] Density (calculated): 1.625 Mg / m³ 3

[0287] Absorption coefficient 2.329 mm -1

[0288] F(000)1288

[0289] Crystal size: 0.08 × 0.06 × 0.05 mm 3

[0290] Crystal color, habit, colorless bulk

[0291] The range of θ for data collection is 2.360 to 26.733°.

[0292] The index ranges are -22 <= h <= 22, -11 <= k <= 11, and -23 <= l <= 23.

[0293] The collected reflections 45843

[0294] Independent reflection 2831 [R(int) = 0.0532]

[0295] Achieving 100.0% integrity at θ=25.242°.

[0296] Absorption correction is derived from the semi-empirical correction of the equivalent.

[0297] Maximum and minimum transmittances are 0.4912 and 0.4110, respectively.

[0298] Refinement methods for F 2 Least square of the entire matrix

[0299] Data / Limitations / Parameters 2831 / 0 / 147

[0300] For F 2 The goodness of fit is 1.062.

[0301] The final R-index [I>2δ(I)]R1=0.0184, wR2=0.0388

[0302] R-index (all data): R1=0.0207, wR2=0.0394

[0303] The largest difference peak and hole values ​​are 0.332 and -0.303 e.Å. -3

[0304] Table 2. Crystal data and structure refinement of iPrSn(N(SiMe3)2)2I.

[0305] Empirical formula C15 H43 I N2 Si4 Sn

[0306] Molecular formula C15 H43 I N2 Si4 Sn

[0307] Molecular weight 609.46

[0308] Temperature 100.15 K

[0309] Wavelength 0.71073 Å

[0310] Crystal system: Orthorhombic

[0311] Space group Iba2

[0312] Cell size a = 36.219(2) Åa=90°.

[0313] b = 17.6925(11) Åb=90°.

[0314] c = 8.9108(5) Åg=90°.

[0315] Volume 5710.1(6) Å 3

[0316] Z8

[0317] Density (calculated): 1.418 Mg / m³ 3

[0318] Absorption coefficient 2.146 mm -1

[0319] F(000)2448

[0320] Crystal size: 0.2 × 0.085 × 0.025 mm 3

[0321] Crystal color, habit, colorless plate

[0322] The range of θ for data collection is 1.281 to 26.370°.

[0323] The index ranges are -45 <= h <= 32, -21 <= k <= 22, and -11 <= l <= 11.

[0324] 29285 collected reflections

[0325] Independent reflection 5827 [R(int) = 0.0243]

[0326] Achieving 100.0% integrity at θ=25.242°.

[0327] Absorption correction is derived from the semi-empirical correction of the equivalent.

[0328] Maximum and minimum transmittance: 0.0937 and 0.0627, respectively.

[0329] Refinement methods for F 2 Least square of the entire matrix

[0330] Data / Limitations / Parameters 5827 / 19 / 222

[0331] For F 2 The goodness of fit is 1.330.

[0332] The final R-index [I>2δ(I)]R1=0.0440, wR2=0.1105

[0333] R-index (all data): R1=0.0444, wR2=0.1107

[0334] Absolute structural parameter 0.062(7)

[0335] The maximum difference peaks and pore sizes are 1.266 and -2.043 e.Å. -3

[0336] Table 3. Sn(pip) Me4 Crystal data and structure refinement of )2.

[0337] Empirical formula C18 H36 N2 Sn

[0338] Molecular formula C18 H36 N2 Sn

[0339] Molecular weight 399.18

[0340] Temperature 100.00 K

[0341] Wavelength 0.71073 Å

[0342] Crystal system: Monoclinic

[0343] Space group P 1 21 / n 1

[0344] Cell size a = 12.4274(5) Åa=90°.

[0345] b = 12.5458(5) Åb=107.3590(10)°.

[0346] c = 12.9252(5) Åg=90°.

[0347] Volume 1923.41(13) Å 3

[0348] Z4

[0349] Density (calculated): 1.378 Mg / m³ 3

[0350] Absorption coefficient 1.327 mm -1

[0351] F(000)832

[0352] Crystal size: 0.22 × 0.2 × 0.16 mm 3

[0353] Crystal color and habit: red block

[0354] The range of θ for data collection is 2.573 to 27.535°.

[0355] The index range is -16 <= h <= 16, -16 <= k <= 16, -16 <= l <= 16

[0356] 57,925 reflections were collected.

[0357] Independent reflection 4433 [R(int) = 0.0308]

[0358] Achieving 99.9% integrity at θ=25.242°.

[0359] Absorption correction is derived from the semi-empirical correction of the equivalent.

[0360] Maximum and minimum transmittance: 0.5629 and 0.5238, respectively.

[0361] Refinement methods for F 2 Least square of the entire matrix

[0362] Data / Limitations / Parameters: 4433 / 0 / 198

[0363] For F 2 The goodness of fit is 1.049.

[0364] The final R-index [I>2δ(I)]R1=0.0147, wR2=0.0351

[0365] R-index (all data): R1=0.0163, wR2=0.0358

[0366] The maximum difference peaks and pore sizes are 0.412 and -0.490 e.Å. -3

[0367] aspect

[0368] The following describes various aspects. It should be understood that any one or more of the features described in the following aspects may be combined with any one or more other aspects.

[0369] Aspect 1. A method comprising:

[0370] By contacting the tin-containing compound with the reactants, a monosubstituted tin compound can be formed via ligand exchange.

[0371] The tin-containing compound mentioned above is a compound of the following formula:

[0372] RSn(L) n X,

[0373] in:

[0374] R includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, ether, amine, haloyl, imide, cyanate, nitrile, alkoxide, or any combination thereof;

[0375] L is a large-volume monoanion ligand or a large-volume dianion ligand;

[0376] n can be 1 or 2, provided that n is 1 when L is a large-volume dianion ligand and 2 when L is a large-volume monoanion ligand; and

[0377] X is a halogen group.

[0378] Aspect 2. The method according to aspect 1, wherein R includes at least one of the following: -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3 or any combination thereof.

[0379] Aspect 3. The method according to any one of Aspects 1 to 2, wherein R comprises at least one of the following: -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH(CH3)CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -(CH2)3CH3, -C6H5, -CH2(C6H5), -CH=CH2, -C≡CCH3, -CH2C≡CH, -CH2C≡CCH3, -C(CH3)=CH2, -HC=CHCH3, -CH2CH=CH2, -CH2N(CH3)2, -(CH2)3N(CH3)2, -CH2CH2OCH3, -CH(CH2)2O, -CH2Si(CH3)3, -Si(CH3)3, or any combination thereof.

[0380] Aspect 4. The method according to any one of Aspects 1 to 3, wherein L is:

[0381] -NR a R b ,

[0382] in:

[0383] R a and R b Independently hydrogen, alkyl, or silicon-based, or R a and R b They bond together to form C3-C 20 N-heterocyclic ring.

[0384] Aspect 5. The method according to any one of Aspects 1 to 4, wherein L is:

[0385] -OR c ,

[0386] in:

[0387] R c It can be alkyl, silylalkyl, cycloalkyl, or aryl.

[0388] Aspect 6. The method according to any one of Aspects 1 to 5, wherein at least one L is 2,2,6,6-tetramethylpiperidine.

[0389] Aspect 7. The method according to any one of Aspects 1 to 6, wherein at least one L is N,N'-di-tert-butylethylenediamide.

[0390] Aspect 8. The method according to any one of Aspects 1 to 7, wherein at least one L is -N(Si(CH3)3)2.

[0391] Aspect 9. The method according to any one of Aspects 1 to 8, wherein the tin-containing compound is an alkylated mixed ligand tin (IV) compound.

[0392] Aspect 10. The method according to any one of Aspects 1 to 9, wherein the reactants comprise at least one compound having the following formula:

[0393] HL 1 Or M q 1 L z 1 ,

[0394] in:

[0395] L 1 It can be a monoanion ligand or a dianion ligand;

[0396] M 1 It is a metal cation;

[0397] X 1 It is a halogenated group;

[0398] q is 1 or 2; and

[0399] z can be 1, 2, 3 or 4.

[0400] Aspect 11. The method according to aspect 10, wherein L 1 For -OR d -NR d R e -NCO, -OC(=O)NR d R e -NR d C(=O)OR e -OC(=O)CH3, -NR d (CH2) n NR d R e -NR d (CH2) n R e N-, -O(CH2) n O-, -O(CH2) n OR d -O(CH2) n NR d R e -O(CH2) n R d N- or -C≡CR d ,

[0401] in:

[0402] Rd and R e Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; and

[0403] n is between 1 and 30.

[0404] Aspect 12. The method according to any one of Aspects 10 to 11, wherein R d Or R e At least one of them is trimethylsilyl.

[0405] Aspect 13. The method according to any one of aspects 10 to 12, wherein L 1 It is -N(CH3)2, -OC(CH3)3, -C≡CC(CH3)3, -C≡CCH3 or -OSi(CH3)3.

[0406] Aspect 14. The method according to any one of aspects 10 to 13, wherein M 1 It can be an alkali metal cation, an alkaline earth metal cation, a transition metal cation, or a post-transition metal cation.

[0407] Aspect 15. The method according to any one of aspects 10 to 14, wherein M 1 Let Sn(II) be the denoted Sn(II).

[0408] Aspect 16. The method according to any one of Aspects 10 to 15, wherein M 1 Let Sn(IV) be the value.

[0409] Aspect 17. The method according to any one of Aspects 10 to 16, wherein M 1 For Li + Na + K + 、Rb + Cs + Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ or Zn 2+ .

[0410] Aspect 18. The method according to any one of Aspects 1 to 17, wherein the reactants comprise at least one of the following: HC≡CCH3, HOC(CH3)3, HC≡CC(CH3)3, HOSi(CH3)3, or any combination thereof.

[0411] Aspect 19. The method according to aspect 18, wherein the reactant further comprises at least one of the following: HNEt2, NEt3, 2,2,6,6-tetramethylpiperidine or any combination thereof.

[0412] Aspect 20. The method according to any one of Aspects 18 to 19, wherein the reactants comprise at least one of the following: Sn(N(CH3)2)2, Sn(N(CH3)2)4, Sn(OC(CH3)3)2, Sn(OC(CH3)3)4, SnCl2, SnCl4, SnI2, SnI4, SnBr2, SnBr4, or any combination thereof.

[0413] Aspect 21. The method according to any one of Aspects 18 to 20, wherein the reactants further comprise at least one of the following: LiN(CH3)2, Na(OC(CH3)3), K(OC(CH3)3), HOC(CH3)3, NaOSi(CH3)3, LiOSi(CH3)3, CH3C≡CMgBr, NaCl, KCl, or any combination thereof.

[0414] Aspect 22. The method according to any one of Aspects 1 to 21, wherein the monosubstituted tin compound is a compound of the following formula:

[0415] ,

[0416] in:

[0417] R includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogroup, imide, cyanate, nitrile, alkoxide, or any combination thereof; and

[0418] L 1 It can be a monoanion ligand, a dianion ligand, or a halogen group independently.

[0419] Aspect 23. The method according to any one of aspects 1 to 22, further comprising:

[0420] Contacting tin halides with metallization reactants to form tinene compounds; and

[0421] The tinene compound is contacted with a halide compound to form the tin-containing compound.

[0422] Aspect 24. The method according to aspect 23, wherein the tin halide comprises at least one of SnCl2, SnBr2 or SnI2.

[0423] Aspect 25. The method according to any one of Aspects 23 to 24, wherein the metallizing reactant comprises a compound of the following formula:

[0424] ML,

[0425] in:

[0426] M is an alkali metal cation, an alkaline earth metal cation, a transition metal cation, or a post-transition metal cation; and

[0427] L is a large-volume monoanion ligand or a large-volume dianion ligand.

[0428] Aspect 26. The method according to aspect 25, wherein M is Li + Na + K + 、Rb + Cs + Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ or Zn 2+ .

[0429] Aspect 27. The method according to any one of Aspects 25 to 26, wherein the metallizing reactant comprises lithium tetramethylpiperidine.

[0430] Aspect 28. The method according to any one of Aspects 23 to 27, wherein the tinene compound comprises a compound of the following formula:

[0431] SnL n ,

[0432] in:

[0433] L is a monoanion ligand or a dianion ligand; and

[0434] n can be 1 or 2, provided that n is 1 when L is a dianion ligand and n is 2 when L is a monoanion ligand.

[0435] Aspect 29. The method according to any one of Aspects 23 to 28, wherein the tinene compound comprises (2,2,6,6-tetramethylpiperidine)2tin(II).

[0436] Aspect 30. The method according to any one of Aspects 23 to 29, wherein the halide compound comprises a compound of the following formula:

[0437] RX,

[0438] in:

[0439] R includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogroup, imide, cyanate, nitrile, alkoxide, or any combination thereof; and

[0440] X is a halogen group.

[0441] Aspect 31. A composition comprising:

[0442] Tinene compounds having the following formula:

[0443] SnL n ,

[0444] in:

[0445] L is a large-volume monoanion ligand or a large-volume dianion ligand; and

[0446] n can be 1 or 2, provided that n is 1 when L is a large-volume dianion ligand and 2 when L is a large-volume monoanion ligand.

[0447] Aspect 32. The composition according to aspect 31, wherein the tinene compound is a compound of the following formula:

[0448] .

[0449] Aspect 33. A composition comprising:

[0450] Tin-containing compounds having the following formula:

[0451] RSn(L) n X,

[0452] in:

[0453] R includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogroup, imide, cyanate, nitrile, alkoxide, or any combination thereof;

[0454] L is a large-volume monoanion ligand or a large-volume dianion ligand;

[0455] n can be 1 or 2, provided that n is 1 when L is a large-volume dianion ligand and 2 when L is a large-volume monoanion ligand; and

[0456] X is a halogen group.

[0457] Aspect 34. The composition according to aspect 33, wherein R comprises at least one of the following: -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3 or any combination thereof.

[0458] Aspect 35. The composition according to any one of Aspects 33 to 34, wherein R comprises at least one of the following: -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH(CH3)CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -(CH2)3CH3, -C6H5, -CH2(C6H5), -CH=CH2, -C≡CCH3, -CH2C≡CH, -CH2C≡CCH3, -C(CH3)=CH2, -HC=CHCH3, -CH2CH=CH2, -CH2N(CH3)2, -(CH2)3N(CH3)2, -CH2CH2OCH3, -CH(CH2)2O, -CH2Si(CH3)3, -Si(CH3)3, or any combination thereof.

[0459] Aspect 36. The composition according to any one of Aspects 33 to 35, wherein L is:

[0460] -NR a R b ,

[0461] in:

[0462] R a and R b Independently hydrogen, alkyl, or silicon-based, or R a and R b They bond together to form C3-C 20 N-heterocyclic ring.

[0463] Aspect 37. The composition according to any one of Aspects 33 to 36, wherein L is:

[0464] -OR c ,

[0465] in:

[0466] R c It can be alkyl, cycloalkyl, or aryl.

[0467] Aspect 38. The composition according to any one of Aspects 33 to 37, wherein at least one L is 2,2,6,6-tetramethylpiperidine.

[0468] Aspect 39. The composition according to any one of Aspects 33 to 38, wherein at least one L is N,N'-di-tert-butylethylenediamide.

[0469] Aspect 40. The composition according to any one of aspects 33 to 39, wherein at least one L is -N(Si(CH3)3)2.

[0470] Aspect 41. The composition according to any one of Aspects 33 to 40, wherein the tin-containing compound is:

[0471]

[0472]

[0473]

[0474] .

[0475] Aspect 42. A composition comprising:

[0476] Monosubstituted tin compounds having the following formula:

[0477] ,

[0478] in:

[0479] R includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogroup, imide, cyanate, nitrile, alkoxide, or any combination thereof; and

[0480] L 1 It can be a monoanion ligand, a dianion ligand, or a halogen group independently.

[0481] Aspect 43. The composition according to aspect 42, wherein the monosubstituted tin compound comprises at least two different ligands (L 1 ).

[0482] Aspect 44. The composition according to any one of aspects 42 to 43, wherein each L 1 different.

[0483] Aspect 45. The composition according to any one of aspects 42 to 44, wherein each L 1 same.

[0484] Aspect 46. The composition according to any one of aspects 42 to 45, wherein L 1 For -OR d -NR d R e -NCO, -OC(=O)NR d Re -NR d C(=O)OR e -OC(=O)CH3, -NR d (CH2) n NR d R e -NR d (CH2) n R e N-, -O(CH2) n O-, -O(CH2) n OR d -O(CH2) n NR d R e -O(CH2) n R d N- or -C≡CR d ,

[0485] in:

[0486] R d and R e Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; and

[0487] n is between 1 and 30.

[0488] Aspect 47. The composition according to any one of aspects 42 to 46, wherein L 1 It is -N(CH3)2.

[0489] Aspect 48. The composition according to any one of Aspects 42 to 47, wherein L 1 It is -OC(CH3)3.

[0490] Aspect 49. The composition according to any one of aspects 42 to 48, wherein L 1 Independently:

[0491]

[0492]

[0493] in:

[0494] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R10 It is independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl or aralkyl.

[0495] Aspect 50. The composition according to any one of Aspects 42 to 49, wherein L 1 Independently:

[0496] .

[0497] Aspect 51. The composition according to any one of aspects 42 to 50, wherein said compound is at least one of the following:

[0498]

[0499]

[0500]

[0501] .

[0502] Aspect 52. The composition according to any one of Aspects 42 to 51, wherein the composition comprises less than 5% by weight of a disubstituted tin (IV) compound based on the total weight of the composition.

[0503] Aspect 53. The composition according to aspect 52, wherein the disubstituted tin (IV) compound is a compound of the following formula:

[0504] ,

[0505] in:

[0506] R includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, ether, amine, imide, cyanate, nitrile, alkoxide, or any combination thereof; and

[0507] L 1 It can be a monoanion ligand or a dianion ligand independently.

[0508] Aspect 54. The composition according to any one of Aspects 42 to 53, wherein the composition comprises at least 99.5% by weight of the monosubstituted tin compound based on the total weight of the composition.

[0509] Aspect 55. The composition according to any one of Aspects 42 to 54, wherein the composition comprises at least 99.9% by weight of the monosubstituted tin compound based on the total weight of the composition.

[0510] It should be understood that detailed changes may be made without departing from the scope of this disclosure, particularly in terms of the construction materials used and the shape, size, and arrangement of components. This specification and the described embodiments are examples, wherein the true scope and spirit of this disclosure are indicated by the appended claims.

Claims

1. A method comprising: By contacting the tin-containing compound with the reactants, a monosubstituted tin compound can be formed via ligand exchange. The tin-containing compound mentioned above is a compound of the following formula: RSn(L) n X, in: R includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, ether, amine, haloyl, imide, cyanate, nitrile, alkoxide, or any combination thereof; L is a large-volume monoanion ligand or a large-volume dianion ligand; n can be 1 or 2, provided that n is 1 when L is a large-volume dianion ligand and 2 when L is a large-volume monoanion ligand; and X is a halogen group.

2. The method of claim 1, wherein R comprises at least one of the following: -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3 or any combination thereof.

3. The method according to claim 1, wherein R comprises at least one of the following: -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH(CH3)CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -(CH2)3CH3, -C6H5, -CH2(C6H5), -CH=CH2, -C≡CCH3, -CH2C≡CH, -CH2C≡CCH3, -C(CH3)=CH2, -HC=CHCH3, -CH2CH=CH2, -CH2N(CH3)2, -(CH2)3N(CH3)2, -CH2CH2OCH3, -CH(CH2)2O, -CH2Si(CH3)3, -Si(CH3)3, or any combination thereof.

4. The method according to claim 1, wherein L is: -NR a R b , in: R a and R b Independently hydrogen, alkyl, or silicon-based, or R a and R b They bond together to form C3-C 20 N-heterocyclic ring.

5. The method according to claim 1, wherein L is: -OR c , in: R c It can be alkyl, silylalkyl, cycloalkyl, or aryl.

6. The method according to claim 1, wherein at least one L is 2,2,6,6-tetramethylpiperidine.

7. The method according to claim 1, wherein at least one L is N,N'-di-tert-butylethylenediamide.

8. The method according to claim 1, wherein at least one L is -N(Si(CH3)3)2.

9. The method according to claim 1, wherein the tin-containing compound is an alkylated mixed ligand tin (IV) compound.

10. The method according to claim 1, wherein the reactants comprise at least one compound of the following formula: HL 1 or M q 1 L z 1 , in: L 1 It can be a monoanion ligand or a dianion ligand; M 1 It is a metal cation; X 1 It is a halogenated group; q is 1 or 2; and z can be 1, 2, 3 or 4.

11. The method of claim 10, wherein L 1 For -OR d -NR d R e -NCO, -OC(=O)NR d R e -NR d C(=O)OR e -OC(=O)CH3, -NR d (CH2) n NR d R e -NR d (CH2) n R e N-, -O(CH2) n O-, -O(CH2) n OR d -O(CH2) n NR d R e -O(CH2) n R d N- or -C≡CR d , in: R d and R e Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; and n is between 1 and 30.

12. The method of claim 11, wherein R d Or R e At least one of them is trimethylsilyl.

13. The method of claim 10, wherein L 1 It is -N(CH3)2, -OC(CH3)3, -C≡CC(CH3)3, -C≡CCH3 or -OSi(CH3)3.

14. The method of claim 10, wherein M 1 It can be an alkali metal cation, an alkaline earth metal cation, a transition metal cation, or a post-transition metal cation.

15. The method of claim 10, wherein M 1 Let Sn(II) be the denoted Sn(II).

16. The method of claim 10, wherein M 1 Let Sn(IV) be the value.

17. The method of claim 10, wherein M 1 For Li + Na + K + 、Rb + Cs + Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ or Zn 2+ .

18. The method according to claim 1, wherein the reactant comprises at least one of the following: HC≡CCH3, HOC(CH3)3, HC≡CC(CH3)3, HOSi(CH3)3, or any combination thereof.

19. The method of claim 18, wherein the reactant further comprises at least one of the following: HNEt2, NEt3, 2,2,6,6-tetramethylpiperidine, or any combination thereof.

20. The method according to claim 1, wherein the reactants comprise at least one of the following: Sn(N(CH3)2)2, Sn(N(CH3)2)4, Sn(OC(CH3)3)2, Sn(OC(CH3)3)4, SnCl2, SnCl4, SnI2, SnI4, SnBr2, SnBr4, or any combination thereof.

21. The method according to claim 18, wherein the reactants further comprise at least one of the following: LiN(CH3)2, Na(OC(CH3)3), K(OC(CH3)3), HOC(CH3)3, NaOSi(CH3)3, LiOSi(CH3)3, CH3C≡CMgBr, NaCl, KCl, or any combination thereof.

22. The method according to claim 1, wherein the monosubstituted tin compound is a compound of the following formula: ， in: R includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogroup, imide, cyanate, nitrile, alkoxide, or any combination thereof; and L 1 It can be a monoanion ligand, a dianion ligand, or a halogen group independently.

23. The method of claim 1, further comprising: To bring tin halides into contact with metallization reactants to form tinene compounds; and The tinene compound is contacted with a halide compound to form the tin-containing compound.

24. The method of claim 23, wherein the tin halide comprises at least one of SnCl2, SnBr2, or SnI2.

25. The method of claim 23, wherein the metallizing reactant comprises a compound of the following formula: ML, in: M is an alkali metal cation, an alkaline earth metal cation, a transition metal cation, or a post-transition metal cation; and L is a large-volume monoanion ligand or a large-volume dianion ligand.

26. The method of claim 25, wherein M is Li + Na + K + 、Rb + Cs + Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ or Zn 2 + .

27. The method of claim 23, wherein the metallizing reactant comprises lithium tetramethylpiperidine.

28. The method of claim 23, wherein the tinene compound comprises a compound of the following formula: SnL n , in: L is a monoanion ligand or a dianion ligand; and n can be 1 or 2, provided that n is 1 when L is a dianion ligand and n is 2 when L is a monoanion ligand.

29. The method of claim 23, wherein the tinene compound comprises (2,2,6,6-tetramethylpiperidine)2tin(II).

30. The method of claim 23, wherein the halide compound comprises a compound of the following formula: RX, in: R includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogroup, imide, cyanate, nitrile, alkoxide, or any combination thereof; and X is a halogen group.

31. A composition comprising: Tinene compounds having the following formula: SnL n , in: L is a large-volume monoanion ligand or a large-volume dianion ligand; and n can be 1 or 2, provided that n is 1 when L is a large-volume dianion ligand and 2 when L is a large-volume monoanion ligand.

32. The composition according to claim 31, wherein the tinene compound is a compound of the following formula: 。 33. A composition comprising: Tin compounds having the following formula: RSn(L) n X, in: R includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogroup, imide, cyanate, nitrile, alkoxide, or any combination thereof; L is a large-volume monoanion ligand or a large-volume dianion ligand; n can be 1 or 2, provided that n is 1 when L is a large-volume dianion ligand and 2 when L is a large-volume monoanion ligand; and X is a halogen group.

34. The composition according to claim 33, wherein R comprises at least one of the following: -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3 or any combination thereof.

35. The composition according to claim 33, wherein R comprises at least one of the following: -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH(CH3)CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -(CH2)3CH3, -C6H5, -CH2(C6H5), -CH=CH2, -C≡CCH3, -CH2C≡CH, -CH2C≡CCH3, -C(CH3)=CH2, -HC=CHCH3, -CH2CH=CH2, -CH2N(CH3)2, -(CH2)3N(CH3)2, -CH2CH2OCH3, -CH(CH2)2O, -CH2Si(CH3)3, -Si(CH3)3, or any combination thereof.

36. The composition according to claim 33, wherein L is: -NR a R b , in: R a and R b Independently hydrogen, alkyl, or silicon-based, or R a and R b They bond together to form C3-C 20 N-heterocyclic ring.

37. The composition according to claim 33, wherein L is: -OR c , in: R c It can be alkyl, cycloalkyl, or aryl.

38. The composition according to claim 33, wherein at least one L is 2,2,6,6-tetramethylpiperidine.

39. The composition according to claim 33, wherein at least one L is N,N'-di-tert-butylethylenediamide.

40. The composition according to claim 33, wherein at least one L is -N(Si(CH3)3)2.

41. The composition according to claim 33, wherein the tin-containing compound is: 。 42. A composition comprising: Monosubstituted tin compounds having the following formula: ， in: R includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silanized alkoxide, ether, amine, halogroup, imide, cyanate, nitrile, alkoxide, or any combination thereof; and L 1 It can be a monoanion ligand, a dianion ligand, or a halogen group independently.

43. The composition of claim 42, wherein the monosubstituted tin compound comprises at least two different ligands (L... 1 ).

44. The composition according to claim 42, wherein each L 1 different.

45. The composition according to claim 42, wherein each L 1 same.

46. ​​The composition according to claim 42, wherein L 1 For -OR d -NR d R e -NCO, -OC(=O)NR d R e -NR d C(=O)OR e -OC(=O)CH3, -NR d (CH2) n NR d R e -NR d (CH2) n R e N-, -O(CH2) n O-, -O(CH2) n OR d -O(CH2) n NR d R e -O(CH2) n R d N- or -C≡CR d , in: R d and R e Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; and n is between 1 and 30.

47. The composition according to claim 42, wherein L 1 It is -N(CH3)2.

48. The composition according to claim 42, wherein L 1 It is -OC(CH3)3.

49. The composition according to claim 42, wherein L 1 Independently: in: R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 It is independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl or aralkyl.

50. The composition according to claim 42, wherein L 1 Independently: 。 51. The composition according to claim 42, wherein the compound is at least one of the following: 。 52. The composition of claim 42, wherein the composition comprises less than 5% by weight of a disubstituted tin (IV) compound based on the total weight of the composition.

53. The composition according to claim 52, wherein the disubstituted tin (IV) compound is a compound of the following formula: ， in: R includes at least one of the following: alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, ether, amine, imide, cyanate, nitrile, alkoxide, or any combination thereof; and L 1 It can be a monoanion ligand or a dianion ligand independently.

54. The composition of claim 42, wherein the composition comprises at least 99.5% by weight of the monosubstituted tin compound based on the total weight of the composition.

55. The composition of claim 42, wherein the composition comprises at least 99.9% by weight of the monosubstituted tin compound based on the total weight of the composition.

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