Monosubstituted tin compounds and related methods

Abstract

Methods for synthesizing monosubstituted tin compounds include contacting stannous halide with a metallation reactant to form a stannylene compound; contacting a stannylene compound with a halogen compound to form a stannic compound; and contacting a stannic compound with a reactant to form a monosubstituted tin compound by ligand exchange. Compositions containing monosubstituted tin compounds are also provided, along with other compositions and methods.

Description

[Technical Field]

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

[0002] Cross-reference of related applications This application claims the benefits pursuant to U.S. Provisional Patent Application No. 63 / 453,611, filed on 21 March 2023, which is incorporated herein by reference in its entirety. [Background technology]

[0003] Some precursors are useful in the fabrication of microelectronic devices. The fabrication of such devices may involve the use of extreme ultraviolet (EUV) lithography to form thin films. [Overview of the project]

[0004] Some embodiments relate to synthesis methods. In some embodiments, the synthesis method includes one or more of the following steps: contacting stannous halide with a metallization reactant to form a stannylene compound; contacting the stannylene compound with a halogen compound to form a stannice compound; and contacting the stannice compound with a reactant to form a monosubstituted stannice compound by ligand exchange.

[0005] Some embodiments relate to compositions comprising a stannylene compound. In some embodiments, the stannylene compound is a reaction product of a stannous halide and a metallized reaction product. In some embodiments, the stannylene compound is of formula: SnL n [In the formula, L is a monoanionic ligand or a dianionic ligand; The compounds include n, where n is 1 or 2, except when L is a dianionic ligand, n is 1, and when L is a monoanionic ligand, n is 2.

[0006] Some embodiments relate to compositions comprising a tin compound. In some embodiments, the tin compound is a reaction product of a halogen compound and a stannylene compound. In some embodiments, the tin compound is of formula: RSn(L) n X [In the formula, R is at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, arylalkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof, or comprises them; L is a monoanionic ligand or a dianionic ligand; n is either 1 or 2, where n is 1 if L is a dianionic ligand, and n is 2 if L is a monoanionic ligand; It contains compounds where X is a halide.

[0007] Some embodiments relate to compositions comprising a monosubstituted tin compound. In some embodiments, the monosubstituted tin compound is of formula: TIFF2026509563000002.tif36170[In the formula, R is at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof, or comprises them; L 1 This includes compounds that are independently monoanionic ligands, dianionic ligands, or halides.

[0008] Some embodiments of the present disclosure are described herein, merely as examples, with reference to the accompanying drawings. A detailed and specific reference to the drawings hereafter emphasizes that the embodiments shown are illustrative and for illustrative purposes only, for illustrative purposes of the embodiments of the present disclosure. In this regard, a description in conjunction with the drawings will make it clear to those skilled in the art how embodiments of the present disclosure may be put into practice. [Brief explanation of the drawing]

[0009] [Figure 1] This is a flowchart of the synthesis method according to several embodiments. [Figure 2] This is a flowchart of a method for producing a tin-containing film according to several embodiments. [Figure 3] The reaction schemes for forming monosubstituted tin compounds according to several embodiments are shown. [Figure 4] The reaction schemes for forming monosubstituted tin compounds according to several embodiments are shown. [Figure 5] This is a schematic cross-sectional view of one non-limiting embodiment of an ampoule according to several embodiments. [Figure 6] The three-dimensional solid structure of Sn(pipMe4)2 according to several embodiments is shown. [Figure 7] The three-dimensional solid structure of CF3CH2Sn(N(SiMe3)2)2I according to several embodiments is shown. [Figure 8] The three-dimensional solid structure of iPrSn(N(SiMe3)2)2I according to several embodiments is shown. [Modes for carrying out the invention]

[0010] Among these disclosed benefits and improvements, other objectives and advantages of this disclosure will become apparent from the following description 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 examples of the various forms in which this disclosure may be embodied. Furthermore, each of the examples given with respect to the various embodiments of this disclosure is illustrative and not limiting.

[0011] Prior patent publications and other publications referenced herein are invoked in their entirety.

[0012] Throughout this specification and the claims, the following terms have the meanings expressly associated herein unless otherwise explicitly indicated by the context. The phrases “in one embodiment,” “in an embodiment,” and “in some embodiments” as used herein may refer to the same embodiment, though not necessarily. Furthermore, the phrases “in another embodiment” and “in some other embodiments” as used herein may refer to different embodiments, though not necessarily. All embodiments of this disclosure are intended to be combinatorial without departing from the scope or spirit of this disclosure.

[0013] As used herein, the term “based on” is not exclusive and, unless otherwise explicitly indicated by the context, may be based on additional factors not listed. Furthermore, throughout this specification, the meanings of “a,” “an,” and “the” include multiple references. The meaning of “in” includes “in” and “on.”

[0014] As used in the present invention, the term "bring into contact" means bringing two or more components into very close or extremely close proximity, or into direct contact.

[0015] As used herein, the term "alkyl" refers to a hydrocarbyl having 1 to 30 carbon atoms. The alkyl may be bonded through a single bond. An alkyl having n carbon atoms may be designated as "C n alkyl". For example, "C3 alkyl" may include n-propyl and isopropyl. An alkyl having a range of carbon atoms such as 1 to 30 carbon atoms may be designated as C1-C 30 alkyl. In some embodiments, the alkyl is linear. In some embodiments, the alkyl is branched. In some embodiments, the alkyl is substituted. In some embodiments, the alkyl is unsubstituted. In some embodiments, the alkyl is C1-C 30 alkyl, C1-C 29 alkyl, C1-C 28 alkyl, C1-C 27 ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​Alkyl, C7~C 30 Alkyl, C8~C 30 Alkyl, C9~C 30 Alkyl, C 10 ~C 30 Alkyl, C 11 ~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 10It is selected from the group consisting of or including at least one of 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, the alkyl is at least one of methyl, ethyl, n-propyl, 1-methylethyl (iso-propyl), n-butyl, iso-butyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, isopentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof, or is selected from the group consisting of them. In some embodiments, the term "alkyl" generally refers to alkyl, alkenyl, alkynyl, and / or cycloalkyl.

[0016] As used herein, the term "alkenyl" refers to a hydrocarbyl having 1 to 30 carbon atoms and at least one carbon-carbon double bond. In some embodiments, the alkenyl is 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-C11 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 Alkenil, C3~C 30 Alkenyl, C4~C 30 Alkenil, C5~C 30 Alkenil, C6~C 30 Alkenil, C7~C 30 Alkenil, C8~C 30 Alkenil, C9~C 30 Alkenil, C 10 ~C 30 Alkenil, C 11 ~C 30 Alkenil, C 12 ~C 30 Alkenil, C 13 ~C 30 Alkenil, C 14 ~C 30 Alkenil, C 15 ~C 30 Alkenil, C 16 ~C 30 Alkenil, C 17 ~C 30 Alkenil, C 18 ~C 30 Alkenil, C 19 ~C 30 Alkenil, C 20 ~C 30 Alkenil, C 21 ~C 30 Alkenil, C 22 ~C 30 Alkenil, C 23 ~C 30 Alkenil, C 24 ~C 30 Alkenil, C 25 ~C 30 Alkenil, C 26 ~C 30 Alkenil, C 27 ~C 30 Alkenil, C 28 ~C 30 Alkenil, C 29 ~C30 Alkenyl, C2~C 10 Alkenil, C3~C 10 Alkenyl, C4~C 10 Alkenil, C5~C 10 Alkenil, C6~C 10 Alkenil, C7~C 10 Alkenil, C8~C 10 The alkenyl group comprises at least one of the following: alkenyl, C2-C9 alkenyl, C2-C8 alkenyl, C2-C7 alkenyl, C2-C6 alkenyl, C2-C5 alkenyl, C3-C5 alkenyl, or any combination thereof, or is selected from the group consisting of these. Examples of alkenyl groups, but not limited to, include vinyl, allyl, 1-methylvinyl, 1-propenyl, 1-butenyl, 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, Examples include 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.

[0017] As used herein, the term "alkynyl" refers to a hydrocarbyl having 1 to 30 carbon atoms and at least one carbon-carbon triple bond. In some embodiments, the alkynyl is C1-C 30 Alkinyl, C1~C 29 Alkinyl, C1~C 28 Alkinyl, C1~C 27 Alkinyl, C1~C 27 Alkinyl, C1~C 26 Alkinyl, C1~C 25 Alkinyl, C1~C 24 Alkinyl, C1~C 23Alkinyl, C1~C 22 Alkinyl, C1~C 21 Alkinyl, C1~C 20 Alkinyl, C1~C 19 Alkinyl, C1~C 18 Alkinyl, C1~C 17 Alkinyl, C1~C 16 Alkinyl, C1~C 15 Alkinyl, C1~C 14 Alkinyl, C1~C 13 Alkinyl, C1~C 12 Alkinyl, C1~C 11 Alkinyl, C1~C 10 Alkinyl, C1-C9 alkinyl, C1-C8 alkinyl, C1-C7 alkinyl, C1-C6 alkinyl, C1-C5 alkinyl, C1-C4 alkinyl, C1-C3 alkinyl, C1-C2 alkinyl, C2-C 30 Alkinyl, C3~C 30 Alkinyl, C4~C 30 Alkinyl, C5~C 30 Alkinyl, C6~C 30 Alkinyl, C7~C 30 Alkinyl, C8~C 30 Alkinyl, C9~C 30 Alkinyl, C 10 ~C 30 Alkinyl, C 11 ~C 30 Alkinyl, C 12 ~C 30 Alkinyl, C 13 ~C 30 Alkinyl, C 14 ~C 30 Alkinyl, C 15 ~C 30 Alkinyl, C 16 ~C 30 Alkinyl, C 17 ~C 30 Alkinyl, C 18 ~C 30 Alkinyl, C 19 ~C 30 Alkinyl, C 20 ~C 30 Alkinyl, C 21 ~C 30 Alkinyl, C22 ~C 30 Alkinyl, C 23 ~C 30 Alkinyl, C 24 ~C 30 Alkinyl, C 25 ~C 30 Alkinyl, C 26 ~C 30 Alkinyl, C 27 ~C 30 Alkinyl, C 28 ~C 30 Alkinyl, C 29 ~C 30 Alkinyl, C2~C 10 Alkinyl, C3~C 10 Alkinyl, C4~C 10 Alkinyl, C5~C 10 Alkinyl, C6~C 10 Alkinyl, C7~C 10 Alkinyl, C8~C 10 The alkynyl group comprises at least one of the following: alkynyl, C2-C9 alkynyl, C2-C8 alkynyl, C2-C7 alkynyl, C2-C6 alkynyl, C2-C5 alkynyl, C3-C5 alkynyl, or any combination thereof, or is selected from the group consisting of these. Examples of alkynyl groups, but not limited to, include at least one of ethynyl, propynyl, n-butynyl, n-pentynyl, 3-methyl-1-butynyl, n-hexynyl, methyl-pentynyl, or any combination thereof.

[0018] As used herein, the term “cycloalkyl” refers to a non-aromatic carbocyclic ring having 3 to 8 carbon atoms in the ring. This term includes monocyclic non-aromatic carbocyclic rings and polycyclic non-aromatic carbocyclic rings. When used as a modifier, the term “monocyclic” refers to a cycloalkyl having a monocyclic ring structure. When used as a modifier, the term “polycyclic” refers to a cycloalkyl having two or more cyclic ring structures that may be condensed, crosslinked, spiro, or otherwise linked ring structures. For example, two or more cycloalkyls may be condensed, crosslinked, or condensed and crosslinked to obtain a polycyclic non-aromatic carbocyclic ring. In some embodiments, the cycloalkyl may include, consist of, essentially consist of, or be selected from the group consisting of, at least one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or any combination thereof.

[0019] As used herein, the term “aryl” refers to monocyclic or polycyclic aromatic hydrocarbons. The number of carbon atoms in an aryl can range from 5 to 100. In some embodiments, an aryl has 5 to 20 carbon atoms. For example, in some embodiments, an aryl 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 having a single aromatic ring structure. When used as a modifier, the term “polycyclic” refers to an aryl having two or more aromatic ring structures that may be condensed, cross-linked, spiro-linked, or otherwise bonded ring structures. In some embodiments, the aryl is -C6H5.

[0020] As used herein, the term "amino" refers to the formula -N(R a R b ) refers to the functional group, and in the formula, R a and R bThese are independently hydrogen, alkyl (as defined herein), or silyl (as defined herein), or R a and R b These combine with each other to form C3~C 20It forms an N-heterocycle. In some embodiments, the amino may include an alkylamino or dialkylamino. In some embodiments, the amino may include at least one of methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, diisopropylamino, butylamino, sec-butylamino, tert-butylamino, di-sec-butylamino, isobutylamino, diisobutylamino, di-tert-pentylamino, ethylmethylamino, isopropyl-n-propylamino, or any combination thereof. Examples of alkylaminos include, but are not limited to, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, sec-butylamino, isobutylamino, t-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, heptadecylamino, and octadecylamino; and secondary alkylaminos, but are not limited to, However, one or more of the following may be listed: dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di-sec-butylamino, di-t-butylamino, dipentylamino, dihexylamino, diheptylamino, dioctylamino, dinonylamino, didecylamino, methylethylamino, methylpropylamino, methylisopropylamino, methylbutylamino, methylisobutylamino, methyl-sec-butylamino, methyl-t-butylamino, methylamylamino, methylisoamylamino, ethylpropylamino, ethylisopropylamino, ethylbutylamino, ethylisobutylamino, ethyl-sec-butylamino, ethylamino, ethylisoamylamino, propylbutylamino, and propylisobutylamino.Unless otherwise indicated, the terms amino and amine may be used interchangeably in this specification.

[0021] As used herein, the term "alkoxy" refers to the formula -OR c This refers to the functional group represented by R. c The alkoxy is an alkyl (as defined herein), silylalkyl, cycloalkyl, or aryl. In some embodiments, the alkoxy may include, consist of, essentially consist of, or be selected from the group consisting of, methoxy, ethoxy, methoxy, ethoxy, n-propoxy, 1-methylethoxy (isopropoxy), n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, or any combination thereof.

[0022] As used herein, the term "silyl" refers to the formula -Si(R e R f R g ) refers to the functional group, R e , R f , and R g Each of these is independently a hydrogen or alkyl as defined herein. In some embodiments, silyl is a functional group of formula -SiH3. In some embodiments, silyl is a functional group of formula -SiR e H2 is a functional group, and in the formula, R e It is not hydrogen. In some embodiments, silyl is of the formula -SiR e R f H is a functional group, and in the formula, R e and R f It is not hydrogen. In some embodiments, silyl is of the formula -Si(R e R f R g ) is a functional group, in the formula R e , R f , and R g It is not hydrogen. In some embodiments, silyl is a functional group of the formula -Si(CH3)3.

[0023] As used herein, the term “alkoxyalkyl” means an alkyl as defined herein, wherein at least one of the hydrogen atoms of the alkyl is substituted with an alkoxy as defined herein. In some embodiments, the term “alkoxyalkyl” means the formula -(alkyl)OR a It refers to the functional group, where alkyl is defined above, R a is defined above. In some embodiments, the alkoxyalkyl is of formula -(CH2) n Ure a It is a functional group, where n is 1 to 10, and R a The above definition is used. In some embodiments, the alkoxyalkyl group is a functional group of the formula -CH2CH2OCH3.

[0024] As used herein, the term “aralkyl” means an alkyl as defined herein, wherein at least one of the hydrogen atoms of the alkyl is substituted with an aryl as defined herein. In some embodiments, the term “aralkyl” means a functional group of the formula -(alkyl)(aryl), where alkyl is as defined herein and aryl is as defined herein. In some embodiments, the aralkyl is -CH2(C6H5).

[0025] As used herein, the term “aminoalkyl” means an alkyl as defined herein, wherein at least one of the hydrogen atoms of the alkyl is substituted with an amino as defined herein. In some embodiments, the term “aminoalkyl” means the formula -(alkyl)N(R b R c R d ) refers to the functional group, where alkyl is defined above, R b , R c , and R dThe above definition is used. In some embodiments, the aminoalkyl is -CH2N(CH3)2. In some embodiments, the aminoalkyl is -(CH2)3N(CH3)2. In some embodiments, the aminoalkyl is aminomethyl (-CH2NH2). In some embodiments, the aminoalkyl is N,N-dimethylaminoethyl (-CH2CH2N(CH3)2). In some embodiments, the aminoalkyl is 3-(N-cyclopropylamino)propyl (-CH2CH2CH2NH-Pr).

[0026] As used herein, the term “silylalkyl” means an alkyl as defined herein, wherein at least one of the hydrogen atoms of the alkyl is substituted with a silyl as defined herein. In some embodiments, the term “silylalkyl” means the formula -(alkyl)Si(R e R f R g ) refers to the functional group, where alkyl is defined above, R e , R f , and R g is defined above. In some embodiments, sillylalkyl is of formula -(CH2) m Si(R e R f R g ) is a functional group, where m is 1 to 10, and R e , R f , and R g The above definition is used. In some embodiments, the silylalkyl group is a functional group of the formula -CH2Si(CH3)3.

[0027] As used herein, the term “haloalkyl” means an alkyl as defined herein, wherein at least one of the hydrogen atoms of the alkyl is substituted with a halide as defined herein. In some embodiments, haloalkyls include fluoroalkyls. In some embodiments, fluoroalkyls include at least one of -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, or any combination thereof.

[0028] As used herein, the term "halogenate" refers to -Cl, -Br, -I, or -F.

[0029] As used herein, the term “metal cation” refers to at least one of alkali metal cations, alkaline earth metal cations, transition metal cations, post-transition metal cations, or any combination thereof. In some embodiments, the metal cations include lithium cations, sodium cations, potassium cations, rubidium cations, cesium cations, francium cations, beryllium cations, magnesium cations, calcium cations, strontium cations, barium cations, radium cations, scandium cations, titanium cations, vanadium cations, chromium cations, manganese cations, iron cations, cobalt cations, nickel cations, copper cations, zinc cations, yttrium cations, zirconium cations, niobium cations, molybdenum cations, technetium cations, ruthenium cations, rhodium cations, palladium cations, silver cations, cadmium cations, hafnium cations, tantalum cations, tungsten cations, rhenium cations, osmium cations, iridium cations, platinum cations, gold cations, mercury cations, aluminum cations, gallium cations, indium cations, tin cations, thallium cations, lead cations, bismuth cations, or polonium cations. The charges of the metal cations are known and therefore will not be repeated here for brevity; however, it will be understood that the metal cations can have any known charge. For example, in some embodiments, the metal cation is Lithium + kaNa + , K + , Rb + , Cs + Mg 2+ Ca 2+ Sr 2+ Ba 2+ , or Zn 2+ This includes. In some embodiments, the metal cation is Sn(II) or Sn(IV).

[0030] Some embodiments relate, in particular, to compositions and related methods useful for extreme ultraviolet (EUV) lithography. The compositions disclosed herein include monosubstituted tin compounds. Monosubstituted tin compounds can be used to form tin-containing films useful for the manufacture of microelectronic devices, including semiconductor devices. For example, a precursor composition may be a functionalized tin oxide film (RSnO x It can be used to form a functionalized tin oxide film. Functionalized tin oxide films can be used in particular for 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., low content of disubstituted tin compounds such as, for example, dialkyltin compounds) by the methods disclosed herein, while minimizing the number of steps required for the production of the precursor compositions.

[0031] As disclosed herein, it was unexpectedly discovered that ligands disclosed herein, such as, but not limited to, 2,2,6,6-tetramethylpiperidide, can promote the formation of monomeric Sn(II) stannylenes when reacted with stannous halides. Further unexpectedly, it was discovered that the stannylene compounds disclosed herein readily undergo oxidative addition by halogen compounds, such as, but not limited to, alkyl halides. It was further unexpectedly discovered that the ligands disclosed herein are readily interchangeable with other ligands, offering broad versatility in the synthesis of monosubstituted tin compounds. It will be understood that other advantages exist and are therefore not limited to the compositions and methods disclosed herein.

[0032] 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 utilizing the precursor composition. Examples of deposition processes include, but are not limited to, chemical vapor deposition (CVD) processes, digital or pulsed chemical vapor deposition processes, plasma-enhanced periodic chemical vapor deposition (PECCVD), fluid chemical vapor deposition (FCVD), 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.

[0033] Figure 1 is a flowchart of a synthesis method according to several embodiments. As shown in Figure 1, the synthesis method 100 includes one or more of the following steps: step 102, in which stannous halide is contacted with a metallation reactant to form a stannylene compound; step 104, in which the stannylene compound is contacted with a halogen compound to form a stannous compound; and step 106, in which the stannous compound is contacted with a reactant to form a monosubstituted tin compound by ligand exchange.

[0034] In process 102, synthesis method 100 includes contacting stannous halide with a metallating reactant to form a stannylene compound. In some embodiments, the stannylene compound is formed by a substitution reaction in which a ligand from the metallating reactant replaces the halide on the stannous halide. In some embodiments, contacting includes reacting the stannous halide with the metallating reactant. In some embodiments, contacting includes mixing the stannous halide and the metallating reactant. In some embodiments, contacting includes stirring the stannous halide and the metallating reactant. In some embodiments, contacting includes adding the stannous halide and the metallating reactant to a reaction vessel. In some embodiments, contacting includes dissolving the stannous halide and the metallating reactant. In some embodiments, contacting includes combining the stannous halide and the metallating reactant. In some embodiments, contacting is carried out in solution.

[0035] In some embodiments, the stannous halide includes at least one of SnCl2, SnBr2, SnI2, SnF2, or any combination thereof.

[0036] In some embodiments, the metallating reactant is a compound of the formula: ML [where: M is an alkali metal cation, an alkaline earth metal cation, a transition metal cation, or a post-transition metal cation; L is a monoanionic ligand or a dianionic ligand].

[0037] In some embodiments, the metal cation includes an alkali metal cation and the ligand is a monoanionic ligand. In some embodiments, the metal cation includes an alkali metal cation and the ligand is a dianionic ligand. In some embodiments, the metal cation includes an alkaline earth metal cation and the ligand is a monoanionic ligand. In some embodiments, the metal cation includes an alkaline earth metal cation and the ligand is a dianionic ligand. In some embodiments, the metal cation includes a transition metal cation and the ligand is a monoanionic ligand. In some embodiments, the metal cation includes a transition metal cation and the ligand is a dianionic ligand. In some embodiments, the metal cation includes a post-transition metal cation and the ligand is a monoanionic ligand. In some embodiments, the metal cation includes a post-transition metal cation and the ligand is a dianionic ligand.

[0038] In some embodiments, the monoanionic ligand is sterically bulky enough to promote the formation of monomeric tin centers when contacted with stannous halide. In some embodiments, the dianionic ligand is sterically bulky enough to promote the formation of monomeric tin centers when contacted with stannous halide.

[0039] In some embodiments, L is amino. That is, for example, in some embodiments, L is: -NR a R b [where ]R a and R b are independently hydrogen, alkyl, or silyl, or R a and R b are bonded to each other to form a C3-C 20 N-heterocycle].

[0040] ]END]] In some embodiments, L is alkoxy. That is, for example, in some embodiments, L is: -OR c [where R c [The elements are alkyl, silylalkyl, cycloalkyl, or aryl.]

[0041] In some embodiments, L is 2,2,6,6-tetramethylpiperidide. 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.

[0042] In some embodiments, the metallation reaction product includes lithium tetramethylpiperidide.

[0043] In some embodiments, the stannylene compound is a reaction product of stannous halide and a metallized product. In some embodiments, the stannylene compound is of formula: SnL n [In the formula, L is a monoanionic ligand or a dianionic ligand; The compound includes [where n is 1 or 2, except when L is a dianionic ligand, n is 1]. In some embodiments, when L is a monoanionic ligand, n is 2.

[0044] In some embodiments, L is a ligand derived from the metallation reaction product. For example, in some embodiments, L is an amino acid. That is, for example, in some embodiments, L is: -NR a R b [In the formula, R a and R b These are independently hydrogen, alkyl, or silyl, or R a and R b They bond with each other to form C3~C 20 It forms an N-heterogenetic ring.

[0045] In some embodiments, L is an alkoxy. That is, for example, in some embodiments, L is: -OR c [In the formula, R c [The elements are alkyl, silylalkyl, cycloalkyl, or aryl.]

[0046] In some embodiments, L is 2,2,6,6-tetramethylpiperidide. 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.

[0047] In some embodiments, the stannylene compound comprises tin(II)(2,2,6,6-tetramethylpiperidide)2. In some embodiments, the stannylene compound comprises formula: This is the compound TIFF2026509563000003.tif77170.

[0048] In some embodiments, the stannylene compound comprises tin(II)(N,N'-di-tert-butylethylenediamide)2. In some embodiments, the stannylene compound comprises tin(II)((trimethylsilyl)amino)2.

[0049] In step 104, the synthesis method 100 includes contacting a stannylene compound with a halogen compound to form a stannice compound. In some embodiments, the stannice compound is formed by oxidative addition, in which the halogen compound is oxidatively added to the stannylene compound (e.g., a low-coordination stannylene compound). In some embodiments, contacting includes reacting the stannylene compound with the halogen compound. In some embodiments, contacting includes mixing the stannylene compound and the halogen compound. In some embodiments, contacting includes stirring the stannylene compound and the halogen compound. In some embodiments, contacting includes adding the stannylene compound and the halogen compound to a reaction vessel. In some embodiments, contacting includes dissolving the stannylene compound and the halogen compound. In some embodiments, contacting includes combining the stannylene compound and the halogen compound. In some embodiments, contacting is performed in solution.

[0050] In some embodiments, the halogen compound is given by formula: RX [In the formula, R is at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, arylalkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof, or comprises them; X contains compounds of a halogen.

[0051] In some embodiments, R is at least one of or includes -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.

[0052] In some embodiments, the ditin compound is a reaction product of stannous halide and a stannylene compound. In some embodiments, the ditin compound is an alkylated mixed ligand tin(IV) compound. In some embodiments, the ditin compound has the formula: RSn(L) n X [where: R is at least one of or includes alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, arylalkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof; L is a monoanionic ligand or a dianionic ligand (as defined above); n is 1 or 2, provided that when L is a dianionic ligand, n is 1]. In some embodiments, when L is a monoanionic ligand, n is 2; X is a halide.

[0053] In some embodiments, R is a functional group derived from a halogen 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, at least one of these or containing them.

[0054] In some embodiments, L is a ligand derived from a stannylene compound. In some embodiments, L is an amino acid. That is, for example, in some embodiments, L is: -NR a R b [In the formula, R a and R b These are independently hydrogen, alkyl, or silyl, or R a and R b They bond with each other to form C3~C 20 It forms an N-heterogenetic ring.

[0055] In some embodiments, L is an alkoxy. That is, for example, in some embodiments, L is: -OR c [In the formula, R c [The elements are alkyl, silylalkyl, cycloalkyl, or aryl.]

[0056] In some embodiments, L is 2,2,6,6-tetramethylpiperidide. In some embodiments, L is N,N'-di-tert-butylethylenediamide. In some embodiments, L is bis(trimethylsilyl)amino.

[0057] In some embodiments, X is a halide derived from a halogen compound.

[0058] In some embodiments, the tin compound is of the formula: These are compounds of TIFF2026509563000004.tif177170, TIFF2026509563000005.tif255170, and TIFF2026509563000006.tif147170.

[0059] In step 106, synthesis method 100 includes contacting a stannous compound with a reactant to form a monosubstituted stannous compound. In some embodiments, the monosubstituted stannous compound is formed by ligand exchange, in which ligands and / or halides from the reactant replace ligands and / or halides on the stannous compound. In some embodiments, contacting includes reacting the stannous compound with the reactant. In some embodiments, contacting includes mixing the stannous compound and the reactant. In some embodiments, contacting includes stirring the stannous compound and the reactant. In some embodiments, contacting includes adding the stannous compound and the reactant to a reaction vessel. In some embodiments, contacting includes dissolving the stannous compound and the reactant. In some embodiments, contacting includes combining the stannous compound and the reactant. In some embodiments, contacting is performed in solution.

[0060] In some embodiments, the reactants are given by formula: HL 1 or M q1 L z1 [In the formula, L 1These are monoanionic ligands, dianionic ligands, or halides; M is an alkali metal cation, alkaline earth metal cation, transition metal cation, or post-transition metal cation; q is either 1 or 2; The compound comprises at least one of the compounds [where z is 1, 2, 3, or 4].

[0061] In some embodiments, L 1 is -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 Ure d -O(CH2) n NR d R e -O(CH2) n R d N-, or -C≡CR d [In the formula, R d and R e Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; 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: TIFF2026509563000007.tif232170TIFF2026509563000008.tif157170[In the formula, R 1 , R2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 [These are independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl.]

[0062] In some embodiments, L 1 is -N(CH3)2. In some embodiments, L 1 is -OC(CH3)3. In some embodiments, L 1 In some embodiments, L 1 In some embodiments, L 1 is -OSi(CH3)3. In some embodiments, L 1 Independently: The filename is TIFF2026509563000009.tif94170.

[0063] In some embodiments, the reactants include at least one of 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 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 HNEt2, NEt3, 2,2,6,6-tetramethylpiperidine, or any combination thereof. In some embodiments, the reactants include at least one of 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 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.

[0064] In some embodiments, the monosubstituted tin compound is of the formula: TIFF2026509563000010.tif36170[In the formula, R is at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof, or comprises them; L 1 The compounds include, independently, monoanionic ligands, dianionic ligands, or halides.

[0065] In some embodiments, R is a functional group derived from a tin-second 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, at least one of these or containing them.

[0066] In some embodiments, L 1 It originates from the reactants. In some embodiments, each L 1 They are different. In some embodiments, each L 1 They are the same. In some embodiments, at least two L 1 They are the same. In some embodiments, at least two L 1 They are different. In some embodiments, L 1 is -OR d , -NR d R e -NCO, -OC(=O)NR d R e , -NRd 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 Ure d -O(CH2) n NR d R e -O(CH2) n R d N-, or -C≡CR d [In the formula, R d and R e Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; 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: TIFF2026509563000011.tif232170TIFF2026509563000012.tif157170[In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 [These are independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl.]

[0067] In some embodiments, L 1 is -N(CH3)2. In some embodiments, L 1is -OC(CH3)3. In some embodiments, L 1 In some embodiments, L 1 In some embodiments, L 1 is -OSi(CH3)3. In some embodiments, L 1 Independently: The filename is TIFF2026509563000013.tif94170.

[0068] In some embodiments, the monosubstituted tin compound is of the formula: These are compounds of TIFF2026509563000014.tif226170, TIFF2026509563000015.tif241170, and TIFF2026509563000016.tif49170.

[0069] Some embodiments relate to compositions comprising a stannylene compound. In some embodiments, the stannylene compound is a reaction product of a stannous halide and a metallized reaction product. In some embodiments, the stannylene compound is of formula: SnL n [In the formula, L is a monoanionic ligand or a dianionic ligand; The compound includes [where n is 1 or 2, except when L is a dianionic ligand, n is 1]. In some embodiments, when L is a monoanionic ligand, n is 2.

[0070] In some embodiments, L is a ligand derived from the metallation reaction product. For example, in some embodiments, L is an amino acid. That is, for example, in some embodiments, L is: -NR a R b [In the formula, R a and R b These are independently hydrogen, alkyl, or silyl, or R a and Rb They bond with each other to form C3~C 20 It forms an N-heterogenetic ring.

[0071] In some embodiments, L is an alkoxy. That is, for example, in some embodiments, L is: -OR c , [In the formula, R c [The elements are alkyl, silylalkyl, cycloalkyl, or aryl.]

[0072] In some embodiments, L is 2,2,6,6-tetramethylpiperidide. 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.

[0073] In some embodiments, the stannylene compound comprises tin(II)(2,2,6,6-tetramethylpiperidide)2. In some embodiments, the stannylene compound comprises formula: This is the compound TIFF2026509563000017.tif77170.

[0074] In some embodiments, the stannylene compound comprises tin(II)(N,N'-di-tert-butylethylenediamide)2. In some embodiments, the stannylene compound comprises tin(II)((trimethylsilyl)amino)2.

[0075] Some embodiments relate to compositions comprising stannous compounds. In some embodiments, the stannous compound is a reaction product of stannous halide and stannylene compounds. In some embodiments, the stannous compound is an alkylated mixed ligand tin(IV) compound. In some embodiments, the stannous compound is of formula: RSn(L) n X [In the formula, R is at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, arylalkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof, or comprises them; L is a monoanionic ligand or a dianionic ligand (as defined above); The compound includes [where n is 1 or 2, except when L is a dianionic ligand, n is 1]. In some embodiments, when L is a monoanionic ligand, n is 2; X is a halide.

[0076] In some embodiments, R is a functional group derived from a halogen 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, at least one of these or containing them.

[0077] In some embodiments, L is a ligand derived from a stannylene compound. In some embodiments, L is an amino acid. That is, for example, in some embodiments, L is: -NR a R b [In the formula, R a and R bThese are independently hydrogen, alkyl, or silyl, or R a and R b They bond with each other to form C3~C 20 It forms an N-heterogenetic ring.

[0078] In some embodiments, L is an alkoxy. That is, for example, in some embodiments, L is: -OR c [In the formula, R c [The elements are alkyl, silylalkyl, cycloalkyl, or aryl.]

[0079] In some embodiments, L is 2,2,6,6-tetramethylpiperidide. In some embodiments, L is N,N'-di-tert-butylethylenediamide. In some embodiments, L is bis(trimethylsilyl)amino.

[0080] In some embodiments, X is a halide derived from a halogen compound.

[0081] In some embodiments, the tin-second compound is given by formula: These are compounds of TIFF2026509563000018.tif177170, TIFF2026509563000019.tif255170, and TIFF2026509563000020.tif147170.

[0082] Some embodiments relate to compositions comprising a monosubstituted tin compound. In some embodiments, the monosubstituted tin compound is of formula: TIFF2026509563000021.tif36170[In the formula, R is at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof, or comprises them; L 1 The compounds include, independently, monoanionic ligands, dianionic ligands, or halides.

[0083] In some embodiments, R includes at least one of the functional groups derived from a tin-second 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.

[0084] In some embodiments, L 1 It originates from the reactants. In some embodiments, each L 1 They are different. In some embodiments, each L 1 They are the same. In some embodiments, at least two L 1 They are the same. In some embodiments, at least two L 1 They are different. In some embodiments, L 1 is -OR d , -NR d R e -NCO, -OC(=O)NR d R e , -NR dC(=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 Ure d -O(CH2) n NR d R e -O(CH2) n R d N-, or -C≡CR d [In the formula, R d and R e Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; 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: TIFF2026509563000022.tif232170TIFF2026509563000023.tif157170[In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 [These are independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl.]

[0085] In some embodiments, L 1 is -N(CH3)2. In some embodiments, L 1is -OC(CH3)3. In some embodiments, L 1 In some embodiments, L 1 In some embodiments, L 1 is -OSi(CH3)3. In some embodiments, L 1 Independently: The filename is TIFF2026509563000024.tif94170.

[0086] In some embodiments, the monosubstituted tin compound is of the formula: These are compounds of TIFF2026509563000025.tif226170, TIFF2026509563000026.tif241170, and TIFF2026509563000027.tif49170.

[0087] In some embodiments, disubstituted tin(IV) compounds, such as dialkyltin(IV) compounds, if present, adversely affect crosslinking during EUV exposure. Therefore, in some embodiments, a high-purity composition with low levels of disubstituted tin(IV) compounds is desirable. At least one advantage of this synthesis method is that the monosubstituted tin compound is formed with high purity, and in some cases, the disubstituted tin(IV) compound is formed at an undetectable level.

[0088] In some embodiments, the composition contains less than 5% by weight of a disubstituted tin(IV) compound based on the total weight of the composition. In some embodiments, the composition contains 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, based on the total weight of the composition, 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. In some embodiments, the composition is 95%~99.9999%, 95.5%~99.9999%, 96%~99.9999%, 96.5%~99.9999%, 97%~99.9999%, 97.5%~99.9999%, 98%~99.9999%, 98.5%~99.9999%, 99%~99.9999%, 99.5%~99.9999%, 99.9 Includes %~99.9999%, 99.99%~99.9999%, 99.999%~99.9999%, 95%~99.999%, 95%~999%, 95%~99%, 95%~99.5%, 95%~99%, 95%~98.5%, 95%~98%, 95%~97.5%, 95%~97%, 95%~96.5%, 95%~96%, or 95%~95.5%.

[0089] In some embodiments, the disubstituted tin(IV) compound is of formula: TIFF2026509563000028.tif35170[In the formula, R is at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof, or comprises them; L 1 [These compounds are independently monoanionic ligands, dianionic ligands, or halides.]

[0090] Figure 2 is a flowchart of a method for producing a tin-containing film 200 according to several embodiments. As shown in Figure 2, a method for producing a tin-containing film 200 may include, consist of, or essentially consist of, one or more of the following steps: a step 202 for obtaining a precursor; a step 204 for obtaining at least one co-reactant precursor; a step 206 for vaporizing the precursor to obtain a vaporized precursor; a step 208 for vaporizing at least one co-reactant precursor to obtain at least one vaporized co-reactant precursor; and a step 210 for contacting at least one of the vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof with a substrate under vapor-phase deposition conditions to form a tin-containing film on the substrate.

[0091] Step 202 may include, may consist of, or may be essentially composed of, any one or more compositions comprising the monosubstituted tin compounds disclosed herein. Obtaining may include obtaining a container or other vessel containing the precursor. In some embodiments, the precursor may be obtained in a container or other vessel in which the precursor is vaporized.

[0092] Step 204 may include, consist of, or essentially consist of, at least one co-reactant precursor. In some embodiments, the at least one co-reactant precursor includes, consists of, or essentially consists of, at least one of oxidizing gases, reducing gases, hydrocarbons, or any combination thereof. The at least one co-reactant precursor may be selected to obtain a desired tin-containing film. In some embodiments, the at least one co-reactant precursor may include, consist of, or essentially consist 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, the at least one co-reactant precursor may comprise, consist of, or be essentially comprised of, at least one of H2, O2, O3, H2O, H2O2, NO, N2O, NO2, CO, CO2, carboxylic acids, alcohols, diols, or any combination thereof. In some embodiments, the at least one co-reactant precursor may comprise, consist of, or be essentially comprised of, at least one of methane, ethane, ethylene, acetylene, or any combination thereof. Obtaining may involve obtaining a container or other vessel containing the at least one co-reactant precursor. In some embodiments, the at least one co-reactant precursor may be obtained in a container or other vessel in which the at least one co-reactant precursor is vaporized. In some embodiments, the method further comprises an inert gas, such as at least one of argon, helium, nitrogen, or any combination thereof.

[0093] Step 206 may, may, or may be essentially, include vaporizing the precursor to obtain a vaporized precursor. Vaporizing may, may, or may be essentially, include heating the precursor sufficiently to obtain a vaporized precursor. In some embodiments, vaporizing may, may, or may be essentially, include heating a container containing the precursor. In some embodiments, vaporizing may, may, or may be essentially, include heating the precursor in a deposition chamber in which a vapor-phase deposition process is performed. In some embodiments, vaporizing may, may, or may be essentially, include heating conduits for delivering the precursor, vaporized precursor, or any combination thereof to, for example, the deposition chamber. In some embodiments, vaporizing may, may, or may be essentially, include activating a vapor delivery system containing the precursor. In some embodiments, vaporizing may, may, or may be essentially, include heating the precursor to a temperature sufficient to vaporize it to obtain a vaporized precursor. In some embodiments, vaporization may include, may be, or essentially involve 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 the gas phase, in which case step 206 is optional and not required. For example, the precursor may include, may be, or essentially involve the vaporized precursor.

[0094] Step 208 may, may, or essentially include vaporizing at least one co-reactant precursor to obtain at least one vaporized co-reactant precursor. In some embodiments, vaporization may, may, or essentially include heating at least one co-reactant precursor to a sufficient extent to obtain at least one vaporized co-reactant precursor. In some embodiments, vaporization may, may, or essentially include heating a container containing at least one co-reactant precursor. In some embodiments, vaporization may, may, or essentially include heating at least one co-reactant precursor in a deposition chamber in which a gas-phase deposition process is performed. In some embodiments, vaporization may, may, or essentially include 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, the deposition chamber. In some embodiments, vaporization may include, may be, or essentially include, operating a vapor delivery system containing at least one co-reactant precursor. In some embodiments, vaporization may include, may be, or essentially include, heating at least one co-reactant precursor to a temperature sufficient to vaporize it to obtain at least one vaporized co-reactant precursor. In some embodiments, vaporization may include, may be, or essentially include, heating at least one of the co-reactant precursors, at least one vaporized co-reactant precursor, or any combination thereof to a temperature below its decomposition temperature. In some embodiments, at least one co-reactant precursor may be present in the gas phase, in which case step 108 is optional and not required. For example, at least one co-reactant precursor may include, may be, or essentially include at least one vaporized co-reactant precursor.

[0095] Step 210 may, may be, or essentially be, contact a vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof, with a substrate under vapor-phase deposition conditions sufficient to form a tin-containing film on the substrate surface. Contacting can be performed in any system, apparatus, device, assembly, their chamber, or components suitable for a vapor-phase deposition process, such as, in particular, but not limited to, a deposition chamber. 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 in the deposition chamber at the same time. That is, in some embodiments, contacting may include contacting the vaporized precursor and at least one vaporized co-reactant precursor with the substrate simultaneously, or simultaneously. Alternatively, each of the vaporized precursor and at least one vaporized co-reactant precursor may be present in the deposition chamber at different times. In other words, in some embodiments, contact may involve alternately and / or sequentially contacting vaporized precursors with the substrate in one or more cycles, followed by contacting at least one vaporized co-reactant precursor with the substrate.

[0096] Gas phase deposition conditions can include conditions for gas phase deposition processes. Examples of gas phase deposition conditions include, but are not limited to, chemical vapor deposition (CVD) processes, digital or pulsed chemical vapor deposition processes, plasma-enhanced periodic chemical vapor deposition (PECCVD), fluid chemical vapor deposition (FCVD), 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 at least one of any combination thereof.

[0097] The gas phase deposition conditions may include, may consist of, or may essentially consist of a deposition temperature. The deposition temperature may be below the thermal decomposition temperature of at least one of the vaporized precursors, at least one vaporized co-reactant precursor, or any combination thereof. The deposition temperature may be high enough to reduce or avoid condensation of at least one of the vaporized precursors, at least one vaporized co-reactant precursor, or any combination thereof. In some embodiments, the substrate may be heated to the deposition temperature. In some embodiments, the chamber or other container in which the substrate comes into contact with the vaporized precursors and at least one vaporized co-reactant precursor is heated to the deposition temperature. In some embodiments, at least one of the vaporized precursors, at least one vaporized co-reactant precursor, or any combination thereof may be heated to the deposition temperature.

[0098] The deposition temperature can be between 200°C and 2500°C. In some embodiments, the deposition temperature can be between 500°C and 700°C. For example, in some embodiments, the deposition temperature can be between 500°C and 680°C, 500°C and 660°C, 500°C and 640°C, 500°C and 620°C, 500°C and 600°C, 500°C and 580°C, 500°C and 560°C, 500°C and 540°C, 500°C and 520°C, 520°C and 700°C, 540°C and 700°C, 560°C and 700°C, 580°C and 700°C, 600°C and 700°C, 620°C and 700°C, 640°C and 700°C, 660°C and 700°C, or 680°C and 700°C. In other embodiments, the deposition temperature is between 200°C and 2500°C, for example, but not limited to, 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, and 775°C. ~2400℃, 800℃~2400℃, 825℃~2400℃, 850℃~2400℃, 875℃~2400℃, 900℃~2400℃, 925℃~2400℃, 950℃~2400℃, 975℃~2400℃, 1000℃~2400℃, 1025℃~2400℃, 1050℃~2400℃, 1075℃~2400℃, 1100℃~2400℃, 1200℃~2400℃, 1300℃~2400℃, 1400℃~2400℃, 1500℃~2400℃, 1600℃~2400℃, 1700℃~2400℃, 1800℃~2400℃, 1900℃~2400℃, 2000℃~2400℃, 2100℃~2400℃, 2200℃~2400℃, 2300℃~2400℃, 500℃~2000℃ The temperature could be between 500°C and 1900°C, 500°C and 1800°C, 500°C and 1700°C, 500°C and 1600°C, 500°C and 1500°C, 500°C and 1400°C, 500°C and 1300°C, 500°C and 1200°C, 500°C and 1100°C, 500°C and 1000°C, 500°C and 1000°C, 500°C and 900°C, or 500°C and 800°C.

[0099] The gas phase deposition conditions may include, may consist of, or may essentially consist of, the deposition pressure. In some embodiments, the deposition pressure may include, may consist of, or may essentially consist of, the vapor pressure of at least one of the vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof. In some embodiments, the deposition pressure may include, may consist of, or may essentially consist of, the chamber pressure.

[0100] The deposition pressure can range from 0.001 Torr to 100 Torr. For example, in some embodiments, the deposition pressure can be 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 is 1 Torr~100 Torr, 5 Torr~100 Torr, 10 Torr~100 Torr, 15 Torr~100 Torr, 20 Torr~100 Torr, 25 Torr~100 Torr, 30 Torr~100 Torr, 35 Torr~100 Torr, 40 Torr~100 Torr, 45 Torr~100 Torr, 50 Torr~100 Torr, 55 Torr~100 Torr, 60 Torr~1 The pressure can be 00 Torr, 65 Torr to 100 Torr, 70 Torr to 100 Torr, 75 Torr to 100 Torr, 80 Torr to 100 Torr, 85 Torr to 100 Torr, 90 Torr to 100 Torr, 95 Torr to 100 Torr, 1 Torr to 95 Torr, 1 Torr to 90 Torr, 1 Torr to 85 Torr, 1 Torr to 80 Torr, 1 Torr to 75 Torr, or 1 Torr to 70 Torr. In other further embodiments, the deposition pressure may be a pressure of 1mTorr~100mTorr, 1mTorr~90mTorr, 1mTorr~80mTorr, 1mTorr~70mTorr, 1mTorr~60mTorr, 1mTorr~50mTorr, 1mTorr~40mTorr, 1mTorr~30mTorr, 1mTorr~20mTorr, 1mTorr~10mTorr, 100mTorr~300mTorr, 150mTorr~300mTorr, 200mTorr~300mTorr, or 150mTorr~250mTorr, or 150mTorr~225mTorr.

[0101] The substrate may contain, consist of, or essentially consist 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.

[0102] 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 is of the formula:RSnO z The formula includes functionalized tin oxides [wherein z is 1 to 6]. In some embodiments, R is at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, ether, amine, halide, imide, cyanate, nitrile, or alkoxide.

[0103] Some embodiments relate to tin-containing films on the surface of a substrate. In some embodiments, the tin-containing film includes any film formed according to the methods disclosed herein. In some embodiments, the tin-containing film includes any film prepared from the precursors disclosed herein.

[0104] Figure 3 shows reaction schemes of Method 300 for forming monosubstituted tin compounds according to several embodiments. As shown in Figure 3, Method 300 for forming monosubstituted tin compounds comprises reacting a stannous halide with a metallization reactant to form a stannylene compound by substitution. The stannylene compound contains a monoanionic ligand on tin(II). The halogen compound is reacted with the stannylene compound to form a stannice compound by oxidative addition. The stannice compound is reacted with a reactant to form a monosubstituted tin compound by ligand exchange.

[0105] Figure 4 shows reaction schemes of Method 400 for forming monosubstituted tin compounds according to several embodiments. As shown in Figure 4, Method 400 for forming monosubstituted tin compounds comprises reacting a stannous halide with a metallization reactant to form a stannylene compound by substitution. The stannylene compound contains a dianionic ligand on tin(II). The halogen compound is reacted with the stannylene compound to form a stannice compound by oxidative addition. The stannice compound is reacted with a reactant to form a monosubstituted tin compound by ligand exchange.

[0106] Figure 5 is a schematic cross-sectional view of one non-limiting embodiment of the ampoule 500, according to several embodiments. The ampoule 500 houses 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 comprises trays 508, each configured to contain a vaporizable precursor. In some embodiments, the vaporizable precursor comprises one or more of the compositions disclosed herein, including compositions comprising a monosubstituted tin compound. Each of the trays 508 of the tray assembly 502 comprises a portion 510 configured to be in contact (e.g., thermal contact, physical contact, etc.) with the inner wall surface 506 of the ampoule 500. 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 from each tray 508 to the vaporizable precursor on each tray 508. Various fluid pathways are defined within the chamber 504 of the ampoule 500, allowing the fluid to flow through the ampoule 500 upward, downward, or in both directions. The ampoule 500, as shown in the figures, has a generally cylindrical inner chamber. However, it will be understood that the interior of the ampoule's chamber 504 may have other shapes without departing from the scope of this disclosure. [Examples]

[0107] Example 1 Sn(pip Me4 ) Synthesis of 2 2,2,6,6-tetramethylpiperidine (HpipMe4 )(29.3g, 208 mmol) was transferred to a 500 mL Schlenk flask equipped with a magnetic stirring rod and diluted with 200 mL of hexane. When nBuLi (1.6 M in hexane, 130.0 mL, 209 mmol) was added to the amine solution over 30 minutes, a slight exothermic reaction occurred, and a white mixture was obtained. After stirring the reaction mixture for 2 hours, 100 mL of THF was added to form a slightly cloudy amber solution. Separately, a solution of SnCl2 (20.0 g, 104 mmol) in THF (100 mL) was prepared in a 1 L Schlenk flask equipped with a magnetic stirring rod. Me4 The solution was added to the SnCl2 solution over 1 hour using an addition funnel. Immediately after addition, the reactants began to appear as a blood-red solution. After the addition was complete, the resulting dark red mixture was stirred overnight at room temperature. The following morning, volatile substances were removed from the reaction mixture under reduced pressure, the product was extracted with 200 mL of hexane, filtered through a disposable polyethylene filter frit, and the resulting dark red solution was dried under reduced pressure to obtain a red solid product. Mass: 24.1 g, yield 57.7%. MP: 73.3°C (DSC). X-ray quality crystals were grown by cooling the saturated PhMe solution to -35°C. 1 H-NMR(400MHz,C6D6,298K):1.39(t,8H);1.50(s,24H);1.71(m,4H)ppm; 13 C{ 1 H}-NMR(100MHz,C6D6,298K):19.07;34.50;43.15;57.90ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6, 298 K): 752.5 ppm. Figure 6 shows Sn(pip) in several embodiments. Me4 This shows the three-dimensional solid structure of )2.

[0108] Example 2 CF3CH2Sn(pip Me4 ) Synthesis of 2I Sn(pip Me4)2 (5.0 g, 12.4 mmol) was placed in a 40 mL amber vial equipped with a magnetic stirring rod and dissolved in 30 mL of hexane to form a dark red solution. ICH2CF3 (2.72 g, 13.0 mmol) was diluted in 5 mL of hexane and added to the Sn-amide solution over 2 minutes using a pipette. The resulting dark red solution was stirred overnight. The following morning, volatile substances were removed from the dark red solution under reduced pressure, and the product was obtained as a thick red / brown viscous liquid. Mass: 7.22 g, Yield: 95.6%. 1 H-NMR(400MHz,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{ 1 H}-NMR(100MHz,C6D6,298K):17.28;33.92;34.42;41.33;42.84(q);59.20;128.52(q)ppm; 119 Sn{ 1 H}-NMR (149MHz, C6D6, 298K): -342.42(q)ppm. 19 F-NMR (376MHz, C6D6, 298K): -49.54(t)ppm.

[0109] Example 3 FCH2Sn(pip Me4 ) Synthesis of 2I Sn(pip Me4 )2 (2.5 g, 6.23 mmol) was placed in a 40 mL amber vial equipped with a magnetic stirring rod and dissolved in 20 mL of tetrahydrofuran to form a dark red solution, which was cooled to -35°C. ICH2F (1.04 g, 6.54 mmol) was diluted in 5 mL of THF and added to the Sn-amide solution over 2 minutes using a pipette. The resulting dark red solution was stirred overnight. The following morning, volatile substances were removed from the dark red solution under reduced pressure, and the product was obtained as a thick red / brown viscous liquid. Mass: 2.99 g, yield 85.9%. 1 H-NMR(400MHz,C6D6,298K):1.25-1.55(bm,36H);4.75(d,2H)ppm; 119 Sn{ 1H}-NMR (149MHz, C6D6, 298K): -258.32(d)ppm. 19 F-NMR (376MHz, C6D6, 298K): -226.24(t)ppm.

[0110] Example 4 O(CH2)2HCSn(pip Me4 ) Synthesis of 2I Inside the nitrogen-filled glove box, Sn(pip Me4 )2 (2.0 g, 4.98 mmol) was packed into a 40 mL amber vial equipped with a magnetic stirring rod, dissolved in 10 mL of THF, and cooled to -35°C. A 5 mL solution of 1-iodooxetane (0.96 g, 5.22 mmol) in THF was added dropwise to the cooled Sn-amide solution over 2 minutes with stirring, and the reaction mixture was stirred at room temperature for 12 hours from that point. The resulting dark reddish-brown solution was dried under reduced pressure to obtain a sticky, highly viscous dark red / brown oily substance. 1 H-NMR(400MHz,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(149MHz,C6D6,298K):-190.88ppm.

[0111] Example 5 Synthesis of CF3CH2Sn(C≡CCH3)3 CF3CH2Sn(pip Me4 Synthesis of CF3CH2Sn(pip) 2I (0.500g, 0.769mmol) Me4 )2I) was placed in a 40 mL amber vial equipped with a magnetic stirring rod and dissolved in 5 mL of THF. Propyne (1 M in THF, 4.61 mL, 4.61 mmol) was added to CF3CH2Sn (pip Me4 The 2I solution was added directly, and the resulting bright orange solution was stirred overnight at room temperature. The next morning, the reaction product appeared as a tangerine-colored mixture. The volatile substances were removed under reduced pressure, the product was extracted with 2 mL of C6D6, and filtered through a 0.2 μm syringe filter to obtain a solution of the orange product. 1H-NMR(400MHz,C6D6,298K):1.40(s,9H);1.60(q,2H)ppm; 13 C{ 1 H}-NMR(100MHz,C6D6,298K):4.47;21.11(q);75.07;108.96;128.39(q)ppm; 119 Sn{ 1 H}-NMR (149MHz, C6D6, 298K): -275.37(q)ppm. 19 F-NMR (376MHz, C6D6, 298K): -52.74(t)ppm.

[0112] Example 6 Synthesis of CF3CH2Sn(N(SiMe3)2)2I A 250 mL round-bottom flask equipped with a magnetic stirring rod was filled with Sn(N(SiMe3)2)2 (25.0 g, 56.5 mmol) and dissolved in hexane (100 mL) to form a dark orange / red solution. ICH2CF3 was weighed into another vial (11.8 g, 56.6 mmol) and added to the hexane solution over 10 minutes, during which slight exothermic reaction and a brightening of the solution's color were observed. The resulting bright orange solution was stirred at room temperature for 20 minutes, and from there, the solvent was removed under reduced pressure to obtain a free-flowing bright yellow solid. Mass: 34.34 g, yield 93.4%. X-ray quality crystals were grown by cooling the saturated hexane solution to -35°C. 1 H-NMR(400MHz,C6D6,298K):0.32(s,36H);2.42(q,2H)ppm; 13 C{ 1 H}-NMR(100MHz,C6D6,298K):5.98;34.86(q);127.72(q)ppm; 19 F-NMR(376MHz,C6D6,298K):-50.2(t)ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6, 298 K): -249.82 (q) ppm. Figure 7 shows the three-dimensional solid structure of CF3CH2Sn(N(SiMe3)2)2I according to several embodiments.

[0113] Example 7 Synthesis of iPrSn(N(SiMe3)2)2I Sn(N(SiMe3)2)2 (2.0 g, 4.53 mmol) was placed in a 40 mL vial equipped with a magnetic stirring rod and diluted with 20 mL of hexane. Separately, 2-iodopropane (0.807 g, 4.75 mmol) was diluted with 5 mL of hexane and this solution was directly added to the Sn-amide solution with stirring over 1 minute. The resulting dark red solution was stirred for 12 hours, at which point the reaction product appeared as a slightly cloudy pale yellow solution. The reaction product was filtered through a 0.2 μm syringe filter, and the resulting bright yellow solution was dried under reduced pressure to obtain the product (iPrSn(N(SiMe3)2)2I) as a pale yellow solid. 2.40 g was isolated, yield: 86.9%. X-ray quality crystals were grown by cooling the hexane solution to -35°C in a freezer. 1 H-NMR(400MHz,C6D6,298K):0.36(s,36H);1.27(d,6H);2.06(sept,1H)ppm; 13 C{ 1 H}-NMR(100MHz,C6D6,298K):6.35;21.76;31.40ppm; 29 Si-NMR(79MHz,C6D6,298K):5.70ppm; 119 Sn{ 1 H}-NMR (149 MHz, C6D6, 298 K): -102.91 ppm. Figure 8 shows the three-dimensional solid structure of iPrSn(N(SiMe3)2)2I according to several embodiments.

[0114] Example 8 CF3CH2Sn(O t Synthesis of Bu)3 CF3CH2Sn(pip Me4 )2I (1.0g, 1.64 mmol) was placed in an amber vial equipped with a magnetic stirring rod and dissolved in 5 mL of tetrahydrofuran. Separately, tert-butanol (0.382g, 5.16 mmol) and triethylamine (0.497g, 4.92 mmol) were diluted in 5 mL of tetrahydrofuran and CF3CH2Sn(pip Me4The 2I solution was added over 2 minutes with stirring. The reaction mixture was stirred at room temperature for 12 hours, and the resulting yellow mixture was filtered through a 0.2 μm syringe filter to obtain a yellow solution. The volatile substances were removed under reduced pressure, and the solution was collected in an HCl Me4 and CF3CH2Sn(O t The mixed product of Bu)3 is obtained as a bright yellow liquid. 119 Sn-NMR revealed a purity of 96.8%. Total mass: 0.89 g, corrected mass: 0.61 g, yield: 88.4%. 1 H-NMR(400MHz,C6D6,298K):1.31(s,27H);1.80(q,2H)ppm; 13 C{ 1 H}-NMR(100MHz,C6D6,298K):28.54(q);33.57;74.40;127.30(q)ppm; 19 F-NMR(376MHz,C6D6,298K):-51.93(t)ppm; 119 Sn{ 1 H}-NMR (149MHz, C6D6, 298K): -228.35(q)ppm.

[0115] Example 9 FCH2Sn(O t Synthesis of Bu)3 In a nitrogen-filled glove box, Sn(pip) is added to a 250 mL round-bottom Schlenk flask equipped with a magnetic stirring rod. Me4 )2 (15.0 g, 37.3 mmol) was packed into a container and dissolved in 250 mL of THF to form a dark red solution. ICH2F (CAS number 373-53-5, 5.96 g, 37.3 mmol) was added dropwise to the tinamide solution over 5 minutes. The resulting dark red solution was stirred at room temperature for 2 hours, and knockout was performed from that point. t When Bu (CAS number: 865-47-4, 4.16 g, 37.1 mmol) was added to the reaction mixture while stirring for 15 minutes, a pale yellow precipitate was formed. After stirring the reaction mixture for 20 minutes, tWhen 20 mL of a THF solution of BuOH (CAS number: 75-65-0, 5.55 g, 74.9 g) was added over 10 minutes, a slight exothermic reaction occurred. The resulting dark orange reaction mixture was stirred for 12 hours, volatile substances were removed under reduced pressure, the pink product matrix was extracted with 250 mL of hexane, filtered through a Celite plug suspended on a disposable polyethylene filter frit, the frit was washed with 25 mL of hexane, and the combined organic solution was dried under reduced pressure to obtain a dark red liquid FCH2Sn(O2O2). t Bu)3 and Hpip Me4 A mixture was obtained. Mass: 17.27 g. 7.82 g aliquots of the crude mixture were packed into a 50 mL round-bottom Schlenk flask, and a short-pass distillation head equipped with a receiver flask and thermometer was attached. The product was distilled under reduced pressure at a head temperature of 22-25°C (50-60 mTorr) to obtain FCH2Sn(O) as a colorless liquid. t Obtaining Bu)3, 119 Sn NMR and 19 The purity was determined to be 98.5% by F-NMR. Mass: 2.43g 1 H-NMR(400MHz,C6D6,298K):1.34(s,27H);4.69(d,2H)ppm; 13 C{ 1 H}-NMR(100MHz,C6D6,298K):33.78;73.51;84.51(d)ppm; 19 F-NMR(376MHz,C6D6,298K):-261.01(t)ppm; 119 Sn{ 1 H}-NMR (149MHz, C6D6, 298K): -256.19(d)ppm.

[0116] Example 10 O(CH2)2HCSn(O t Synthesis of Bu)3 Sn(pip Me4)2 (5.0g, 12.4 mmol) was placed in an amber vial and dissolved in THF (20 mL). I-iodooxetane (2.39g, 13.0 mmol) was diluted in 5 mL of THF and added to the Sn-amide solution over 2 minutes. The resulting dark red solution was stirred for 1.5 hours, and solid knockout was observed from that point. t When Bu (1.38 g, 12.3 mmol) was added directly to the reaction mixture over 5 minutes, an orange precipitate appeared. The reaction mixture was stirred for 1 hour, and from that point onward... t 10 mL of THF solution of BuOH (1.83 g, 24.8 mmol) was added to the mixture. The resulting dark orange / red mixture was stirred at room temperature for 60 hours, then filtered through a 0.2 μm syringe filter, dried under reduced pressure, and hydrated using Hpip. Me4 and O(CH2)2HCSn(O t A dark red, viscous oily substance composed of a mixture of Bu)3 was obtained. Mass: 2.73 g. 1 H-NMR(400MHz,C6D6,298K):1.28(s,27H);2.89(pent,1H);4.67(dd,2H);4.95(dd,2H)ppm; 119 Sn{ 1 H}-NMR(149MHz,C6D6,298K):-218.38ppm.

[0117] Example 11 CH3C≡CCH2Sn(pip Me4 ) Synthesis of 2Br Sn(pip Me4 )2 (1.0 g, 2.49 mmol) was placed in a 40 mL vial equipped with a magnetic stirring rod and diluted with 2 mL of C6D6. 1-Bromo-2-butine (0.331 g, 2.49 mmol) was added directly to the Sn-amide solution and stirred for 1 minute. The resulting dark red solution was stirred for 4 hours, at which point the reaction product appeared as a slightly cloudy dark yellow solution. The reaction product was filtered through a 0.2 μm syringe filter to obtain a dark yellow solution of the product. 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; 13C{ 1 H}-NMR(100MHz,C6D6,298K):3.81,17.81,33.89,34.47,42.33,58.12,78.21,77.25ppm; 119 Sn{ 1 H}-NMR (149MHz, C6D6, 298K): -139.6ppm.

[0118] Example 12 Synthesis of CH3C≡CCH2Sn(OtBu)3 In a 100 mL Schlenk flask inside a glove box, Sn(pip Me4 )2 (5g, 12.4 mmol) was dissolved in 10 mL of THF. To this dark red solution, 1-bromobuto-2-in (1.64 g, 12.4 mmol) was added. Over several minutes, the color of the solution changed from deep red to deep dark orange / brown. The solution was stirred overnight at room temperature. 119 In SnNMR, CH3CCCH2Sn(pipMe 4 A distinct peak for 2Br was detected at -140.4 ppm. Triethylamine (3.76 g, 37.2 mmol) was added to the solution, followed by t-butanol (2.76 g, 37.2 mmol). The formation of a solid was observed. The mixture was stirred overnight at room temperature. The solution was then filtered, and the solid was washed with hexane. Volatile substances were removed under reduced pressure, and the mixture was hydrated using HCl. Me4 and CH3CCCH2Sn(O t The mixed product of Bu)3 was obtained as a dark orange liquid. 119 Sn-NMR determined the purity to be 78%. 1 H-NMR(400MHz,C6D6,298K):1.31(s,3H);1.35(s,27H);1.98(s,2H)ppm; 119 Sn{ 1 H}-NMR (149MHz, C6D6, 298K): -233.8ppm. Table 1. Crystal data and structural refinement of CF3CH2Sn(N(SiMe3)2)2I. Experimental formula C14 H38 F3 I N2 Si4 Sn Molecular formula C14 H38 F3 I N2 Si4 Sn Formula weight 649.41 Temperature 100.0K Wavelength 0.71073Å Crystal system: Monoclinic space group C 1 2 / c 1 Unit cell dimensions a = 17.4520 (7) Å, a = 90°. b=8.8141(4)Å b= 113.8730(10)°. c = 18.8726 (11) Å g = 90°. Volume 2654.7(2)Å 3 Z 4 Density (calculated value): 1.625 Mg / m³ 3 Absorption coefficient: 2.329 mm -1 F(000) 1288 Crystal size: 0.08 × 0.06 × 0.05 mm 3 Crystal color, irregularities, colorless blocky The theta range for data acquisition is 2.360 to 26.733°. Exponential range: -22<=h<=22, -11<=k<=11, -23<=l<=23 Number of reflections collected: 45843 Number of independent reflections 2831[R(int)=0.0532] Completeness for theta = 25.242°: 100.0% Absorption correction: Semi-empirical method based on equivalent values. Maximum and minimum transmittance: 0.4912 and 0.4110 Refinement method F 2 Complete matrix least squares method for Data / Constraints / Parameters 2831 / 0 / 147 F 2 Goodness of fit in: 1.062 Final R-factors [I>2 sigma(I)]: R1=0.0184, wR2=0.0388 R-factor (all data): R1 = 0.0207, wR2 = 0.0394 Maximum difference, peak and hole values: 0.332 and -0.303 e. Å -3 Table 2. Crystal data and structural refinement of iPrSn(N(SiMe3)2)2I Experimental formula: C15 H43 I N2 Si4 Sn Molecular formula C15 H43 I N2 Si4 Sn Formula weight 609.46 Temperature 100.15K Wavelength 0.71073Å Crystal system Rectangular system space group Iba2 Unit cell dimensions a = 36.219 (2) Å, a = 90°. b = 17.6925 (11) Å b = 90°. c = 8.9108 (5) Å g = 90°. Volume 5710.1(6) Å 3 Z 8 Density (calculated value): 1.418 Mg / m³ 3 Absorption coefficient: 2.146 mm -1 F(000) 2448 Crystal size: 0.2 × 0.085 × 0.025 mm 3 Crystal color, characteristics: Colorless, plate-like Theta range for data acquisition is 1.281 to 26.370°. Exponential range: -45 <= h <= 32, -21 <= k <= 22, -11 <= l <= 11 Number of reflections collected: 29,285 Number of independent reflections 5827[R(int)=0.0243] Completeness with respect to theta = 25.242° 100.0% Absorption correction: Semi-empirical method based on equivalent values. Maximum and minimum transmittance: 0.0937 and 0.0627 Refinement method F 2 Complete matrix least squares method for Data / Constraints / Parameters 5827 / 19 / 222 F 2 Goodness of fit in: 1.330 Final R-factors [I>2 sigma(I)]: R1=0.0440, wR2=0.1105 R-factor (all data): R1 = 0.0444, wR2 = 0.1107 Absolute structure parameter 0.062(7) Maximum difference, peak and hole: 1.266 and -2.043 e. Å -3 Table 3. Sn(pip Me4 )2. Crystal data and structural refinement. Experimental formula C18 H36 N2 Sn Molecular formula C18 H36 N2 Sn Formula weight 399.18 Temperature 100.00K Wavelength 0.71073Å Crystal system: Monoclinic Space group P 1 21 / n 1 Unit cell dimensions a = 12.4274 (5) Å, a = 90°. b=12.5458(5)Å b=107.3590(10)°. c = 12.9252 (5) Å g = 90°. Volume 1923.41(13)Å 3 Z 4 Density (calculated value): 1.378 Mg / m³ 3 Absorption coefficient 1.327 mm -1 F(000) 832 Crystal size: 0.22 × 0.2 × 0.16 mm 3 Crystal color, irregular shape, red blocky Theta range for data acquisition is 2.573 to 27.535°. Exponential range -16<=h<=16, -16<=k<=16, -16<=l<=16 Number of reflections collected: 57,925 Number of independent reflections 4433[R(int)=0.0308] Completeness with respect to theta = 25.242° 99.9% Absorption correction: Semi-empirical method based on equivalent values. Maximum and minimum transmittance: 0.5629 and 0.5238 Refinement method F 2 Complete matrix least squares method for Data / Constraints / Parameters 4433 / 0 / 198 F 2 Goodness of fit in: 1.049 Final R-factor [I>2 sigma(I)]: R1=0.0147, wR2=0.0351 R-factor (all data): R1 = 0.0163, wR2 = 0.0358 Maximum difference, peak and hole values: 0.412 and -0.490 e. Å -3

[0119] manner Various embodiments are described below. It should be understood that one or more of the features listed in the following embodiments can be combined with one or more other embodiments. Embodiment 1. The method involves contacting a stannous compound with a reactant to form a monosubstituted stannous compound by ligand exchange, The stannous compound is, formula: RSn(L) n X [In the formula, R comprises at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof; L is a bulky monoanionic ligand or a bulky dianionic ligand; n is either 1 or 2, where n is 1 if L is a bulky dianionic ligand, and n is 2 if L is a bulky monoanionic ligand; X is a compound of a halide, by method. Embodiment 2. The method according to Embodiment 1, wherein R includes at least one of -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, or any combination thereof. Embodiment 3. The method according to any one of Embodiments 1 to 2, wherein R includes at least one of 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. Applicable form 4. The method according to any one of Applicable forms 1 to 3, wherein L is -NR a R b [In the formula, R a and R b These are independently hydrogen, alkyl, or silyl, or R a and R b They bond with each other to form C3~C 20 A method for forming an N-heterogenetic ring. Applicable form 5. The method according to any one of Applicable forms 1 to 4, wherein L is -OR c [In the formula, R c A method in which [is alkyl, silylalkyl, cycloalkyl, or aryl]. Embodiment 6. The method according to any one of Embodiments 1 to 5, wherein at least one L is 2,2,6,6-tetramethylpiperidide. Embodiment 7. The method according to any one of Embodiments 1 to 6, wherein at least one L is N,N'-di-tert-butylethylenediamide. Embodiment 8. The method according to any one of Embodiments 1 to 7, wherein at least one L is -N(Si(CH3)3)2. Embodiment 9. The method according to any one of Embodiments 1 to 8, wherein the stannous compound is an alkylated mixed ligand tin(IV) compound. Apparatus 10. The reactants are of formula: HL 1 or M q1 L z1 [In the formula, L 1 is a monoanionic ligand or a dianionic ligand; M 1 It is a metal cation; X 1 It is a halide; q is 1 or 2; and The method according to any one of embodiments 1 to 9, comprising at least one compound of [z is 1, 2, 3, or 4]. Appearance 11. L 1 However, -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 Ure d -O(CH2) n NR d R e -O(CH2) n R d N-, or -C≡CR d [In the formula, R d and R eEach of these is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; The method according to embodiment 10, wherein n is between 1 and 30. Appearance 12. R d or R e The method according to any one of embodiments 10 to 11, wherein at least one of the is trimethylsilyl. Appearance 13. L 1 The method according to any one of embodiments 10 to 12, wherein is -N(CH3)2, -OC(CH3)3, -C≡CC(CH3)3, -C≡CCH3, or -OSi(CH3)3. Appearance 14. M 1 The method according to any one of embodiments 10 to 13, wherein the cation is an alkali metal cation, an alkaline earth metal cation, a transition metal cation, or a post-transition metal cation. Appearance 15. M 1 The method according to any one of embodiments 10 to 14, wherein is Sn(II). Appearance 16. M 1 The method according to any one of embodiments 10 to 15, wherein is Sn(IV). Appearance 17. M 1 However, Li + kaNa + , K + , Rb + , Cs + Mg 2+ Ca 2+ Sr 2+ Ba 2+ , or Zn 2+ The method according to any one of embodiments 10 to 16. Embodiment 18. The method according to any one of Embodiments 1 to 17, wherein the reactant comprises at least one of HC≡CCH3, HOC(CH3)3, HC≡CC(CH3)3, HOSi(CH3)3, or any combination thereof. Embodiment 19. The method according to Embodiment 18, wherein the reactant further comprises at least one of HNEt2, NEt3, 2,2,6,6-tetramethylpiperidine, or any combination thereof. Embodiment 20. The method according to any one of Embodiments 18 to 19, wherein the reactant comprises at least one of 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. Embodiment 21. The method according to any one of Embodiments 18 to 20, wherein the reactant further comprises at least one of 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. Embodiment 22. A monosubstituted tin compound, formula: TIFF2026509563000029.tif36170[In the formula, R comprises at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof; L 1 The method according to any one of embodiments 1 to 21, wherein is a compound of [a monoanionic ligand, a dianionic ligand, or a halide] independently. Embodiment 23. Contacting stannous halide with a metallization reaction product to form a stannylene compound; and The method according to any one of embodiments 1 to 22, further comprising contacting a stannylene compound with a halogen compound to form a stannice compound. Embodiment 24. The method according to Embodiment 23, wherein the stannous halide comprises at least one of SnCl2, SnBr2, or SnI2. Apparatus 25. The metallation reaction product is of formula: ML [In the formula, M is an alkali metal cation, alkaline earth metal cation, transition metal cation, or post-transition metal cation; The method according to any one of embodiments 23 to 24, comprising a compound in which L is a bulky monoanionic ligand or a bulky dianionic ligand. Embodiment 26. M is Li + kaNa + , K + , Rb + , Cs + Mg 2+ Ca 2+ Sr 2+ Ba 2+ , or Zn 2+ The method according to embodiment 25. Embodiment 27. The method according to any one of Embodiments 25 to 26, wherein the metallation reaction product comprises lithium tetramethylpiperidide. Embodiment 28. A stannylene compound, of formula: SnL n [In the formula, L is a monoanionic ligand or a dianionic ligand; The method according to any one of embodiments 23 to 27, comprising a compound of the form n is 1 or 2, provided that n is 1 when L is a dianionic ligand and n is 2 when L is a monoanionic ligand. Embodiment 29. The method according to any one of Embodiments 23 to 28, wherein the stannylene compound comprises tin(II)(2,2,6,6-tetramethylpiperidide)2. Embodiment 30. A halogen compound, of formula: RX [In the formula, R comprises at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof; The method according to any one of embodiments 23 to 29, wherein X is a compound of [a halide]. Appearance 31. Formula: SnL n [In the formula, L is a bulky monoanionic ligand or a bulky dianionic ligand; A composition comprising a stannylene compound, wherein n is 1 or 2, provided that n is 1 when L is a bulky dianionic ligand, and n is 2 when L is a bulky monoanionic ligand. Embodiment 32. A stannylene compound, of formula: The composition according to embodiment 31, wherein the compound is TIFF2026509563000030.tif77170. Appearance 33. Formula: RSn(L) n X [In the formula, R comprises at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof; L is a bulky monoanionic ligand or a bulky dianionic ligand; n is either 1 or 2, where n is 1 if L is a bulky dianionic ligand, and n is 2 if L is a bulky monoanionic ligand; A composition comprising a tin-dic compound [where X is a halide]. Embodiment 34. The composition according to Embodiment 33, wherein R comprises at least one of -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, or any combination thereof. Embodiment 35. The composition according to any one of Embodiments 33 to 34, wherein R comprises at least one of 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. Embodiment 36. L is -NR a R b [In the formula, R a and R b These are independently hydrogen, alkyl, or silyl, or R a and R b They bond with each other to form C3~C 20 The composition according to any one of embodiments 33 to 35, which forms an N-heterocycle. Embodiment 37. L is -OR c [In the formula, R c The composition according to any one of embodiments 33 to 36, wherein [ is alkyl, cycloalkyl, or aryl]. Embodiment 38. The composition according to any one of Embodiments 33 to 37, wherein at least one L is 2,2,6,6-tetramethylpiperidide. Embodiment 39. The composition according to any one of Embodiments 33 to 38, wherein at least one L is N,N'-di-tert-butylethylenediamide. Embodiment 40. The composition according to any one of Embodiments 33 to 39, wherein at least one L is -N(Si(CH3)3)2. Appearance 41. The tinnic compound is A composition according to any one of embodiments 33 to 40, wherein the names are TIFF2026509563000031.tif177170, TIFF2026509563000032.tif255170, and TIFF2026509563000033.tif147170. Appearance 42. Formula: TIFF2026509563000034.tif36170[In the formula, R comprises at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof; L 1 A composition comprising a monosubstituted tin compound, which is independently a monoanionic ligand, a dianionic ligand, or a halide. Embodiment 43. A monosubstituted tin compound having at least two different ligands (L 1 The composition according to embodiment 42, comprising ) Appearance 44. Each L 1 A composition according to any one of embodiments 42 to 43, wherein the composition differs from the one described above. Appearance 45. Each L 1 A composition according to any one of embodiments 42 to 44, wherein the same property is found. Appearance 46. L 1 However, -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 Ure d -O(CH2)n NR d R e -O(CH2) n R d N-, or -C≡CR d [In the formula, R d and R e Each of these is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; The composition according to any one of embodiments 42 to 45, wherein n is 1 to 30. Appearance 47. L 1 The composition according to any one of embodiments 42 to 46, wherein the composition is -N(CH3)2. Appearance 48. L 1 The composition is -OC(CH3)3, as described in any one of embodiments 42 to 47. Appearance 49. L 1 However, independently: TIFF2026509563000035.tif232170TIFF2026509563000036.tif157170[In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 The composition according to any one of embodiments 42 to 48, wherein [ is independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl]. Appearance 50. L 1 However, independently: A composition according to any one of embodiments 42 to 49, which is TIFF2026509563000037.tif94170. Embodiment 51. The composition according to any one of Embodiments 42 to 50, wherein the compound is at least one of the following. TIFF2026509563000038.tif226170TIFF2026509563000039.tif226170TIFF2026509563000040.tif140170. Embodiment 52. The composition according to any one of Embodiments 42 to 51, comprising less than 5% by weight of a disubstituted tin(IV) compound based on the total weight of the composition. Appearance 53. A disubstituted tin(IV) compound, formula: TIFF2026509563000041.tif35170[In the formula, R comprises at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, ether, amine, imide, cyanate, nitrile, alkoxide, or any combination thereof; L 1 The composition according to embodiment 52, wherein is a compound of [a monoanionic ligand or a dianionic ligand, independently]. Embodiment 54. The composition according to any one of Embodiments 42 to 53, comprising at least 99.5% by weight of a monosubstituted tin compound based on the total weight of the composition. Embodiment 55. The composition according to any one of Embodiments 42 to 54, comprising at least 99.9% by weight of a monosubstituted tin compound based on the total weight of the composition. In particular, it should be understood that detailed changes to the construction materials used, as well as the shape, size, and arrangement of components, may be made without departing from the scope of this disclosure. This specification and the embodiments described herein are examples, and the true scope and spirit of this disclosure are shown by the subsequent claims.

Claims

1. This includes contacting a stannous compound with a reactant to form a monosubstituted stannous compound by ligand exchange, The stannous compound is, formula: RSn(L) ｎ X [In the formula, R comprises at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof; L is a bulky monoanionic ligand or a bulky dianionic ligand; n is either 1 or 2, where n is 1 if L is a bulky dianionic ligand, and n is 2 if L is a bulky monoanionic ligand; X is a compound of a halide, by method.

2. R is -CH ２ CF ３ , -CH(CF ３ ), ２ , -CH ２ F, -CH ２ CH ２ F, -CF ３ , -CF ２ CF ３ The method according to claim 1, comprising at least one of them or any combination thereof.

3. R is -CH ３ ien-CH ２ CH ３ ien-CH ２ CH ２ CH ３ , -CH(CH ３ ) ２ , -CH(CH ３ )CH ２ CH ３ ien-CH ２ CH (CH ３ ) ２ , -C(CH ３ ) ３ ,-(CH ２ ) ３ CH ３ , -C ６ H ５ ien-CH ２ (C ６ H ５ ), -CH=CH ２ -C≡CCH ３ ien-CH ２ C≡CH, -CH ２ C≡CCH ３ , -C(CH ３ ) = CH ２ -HC=CHCH ３ ien-CH ２ CH=CH ２ ien-CH ２ N(CH ３ ) ２ ,-(CH ２ ) ３ N(CH ３ ) ２ ien-CH ２ CH ２ OCH ３ , -CH(CH ２ ) ２ O, -CH ２ Si(CH) ３ ) ３ ,-Si(CH ３ ) ３ The method according to claim 1, comprising at least one of the following, or any combination thereof.

4. L, -NR ａ R ｂ [In the formula, R ａ and R ｂ These are independently hydrogen, alkyl, or silyl, or R ａ and R ｂ They combine with each other to form C ３ ~C ２０ The method according to claim 1, wherein an N-heterogeneous ring is formed.

5. L, -OR ｃ [In the formula, R ｃ The method according to claim 1, wherein [ is alkyl, silylalkyl, cycloalkyl, or aryl].

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

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

8. At least one L is -N(Si(CH) ３ ) ３ ) ２ The method according to claim 1.

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

10. The reactants are, formula: HL １ or M ｑ１ L ｚ １ [In the formula, L １ is a monoanionic ligand or a dianionic ligand; M １ It is a metal cation; X １ It is a halide; q is either 1 or 2; The method according to claim 1, comprising at least one compound of [z is 1, 2, 3, or 4].

11. L １ が、-OR ｄ 、-82 ｄ 2 ｅ 、-_83O、-OC(=O)82 ｄ 2 ｅ 、-82 ｄ 3(49) 92 ｅ 、-OC(=O)32 ３ 、-82 ｄ (32) ２ ) ) ｎ 82 ｄ 2 ｅ 、-82 ｄ (32) ２ ) ) ｎ 2 ｅ 8-、-9(3) ２ ) ) ｎ 9-、-9(32) ２ ) ) ｎ 92 ｄ 、-O(3H ２ ) ) ｎ 82 ｄ 2 ｅ 、-O(3H ２ ) ) ｎ 2 ｄ N-、またはCC≡CR ｄ [In the formula, R ｄ and R ｅ Each of these is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; The method according to claim 10, wherein n is 1 to 30.

12. R ｄ or R ｅ The method according to claim 11, wherein at least one of the is trimethylsilyl.

13. L １ However, -N(CH ３ ) ２ , -OC(CH ３ ) ３ -C≡CC(CH ３ ) ３ -C≡CCH ３ , or -OSi(CH ３ ) ３ The method according to claim 10.

14. M １ The method according to claim 10, wherein the cation is an alkali metal cation, an alkaline earth metal cation, a transition metal cation, or a post-transition metal cation.

15. M １ The method according to claim 10, wherein is Sn(II).

16. M １ The method according to claim 10, wherein is Sn(IV).

17. M １ However, Li ＋ Na ＋ _K ＋ , Rb ＋ , Cs ＋ Mg ２＋ Ca ２＋ , Sr ２＋ Ba ２＋ , or Zn ２＋ The method according to claim 10.

18. The reactants are HC≡CCH ３ , HOC (CH ３ ) ３ , HC≡CC(CH ３ ) ３ , HOSi (CH ３ ) ３ The method according to claim 1, comprising at least one of the following, or any combination thereof.

19. The reactant is HNET ２ ,NET ３ The method according to claim 18, further comprising at least one of , 2,2,6,6-tetramethylpiperidine, or any combination thereof.

20. The reactants are Sn(N(CH) ３ ) ２ ) ２ , Sn(N(CH ３ ) ２ ) ４ , Sn(OC(CH ３ ) ３ ) ２ , Sn(OC(CH ３ ) ３ ) ４ SnCl ２ SnCl ４ SnI ２ SnI ４ SnBr ２ SnBr ４ The method according to claim 1, comprising at least one of the following, or any combination thereof.

21. The reactants are LiN(CH ３ ) ２ Na(OC(CH) ３ ) ３ ), K(OC(CH ３ ) ３ ), HOC (CH ３ ) ３ NaOSi(CH ３ ) ３ , LiOSi (CH ３ ) ３ ,CH ３ The method according to claim 18, further comprising at least one of C≡CMgBr, NaCl, KCl, or any combination thereof.

22. A monosubstituted tin compound, formula: [In the formula, R comprises at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof; L １ The method according to claim 1, wherein is a compound of [a monoanionic ligand, a dianionic ligand, or a halide].

23. Contacting stannous halide with a metallization reactant to form a stannylene compound; and The method according to claim 1, further comprising contacting a stannylene compound with a halogen compound to form a tin compound.

24. Stannous halogens, SnCl ２ SnBr ２ or SnI ２ The method according to claim 23, comprising at least one of the following.

25. The metallation reaction product is given by formula: ML [In the formula, M is an alkali metal cation, alkaline earth metal cation, transition metal cation, or post-transition metal cation; The method according to claim 23, comprising a compound in which L is a bulky monoanionic ligand or a bulky dianionic ligand.

26. M is Li ＋ Na ＋ _K ＋ , Rb ＋ , Cs ＋ Mg ２＋ Ca ２＋ , Sr ２＋ Ba ２＋ , or Zn ２＋ The method according to claim 25.

27. The method according to claim 23, wherein the metallation reaction product comprises lithium tetramethylpiperidide.

28. The stannylene compound has the formula: SnL ｎ [In the formula, L is a monoanionic ligand or a dianionic ligand; The method according to claim 23, comprising a compound in which n is 1 or 2, provided that n is 1 when L is a dianionic ligand, and n is 2 when L is a monoanionic ligand.

29. The stannylene compound is tin(II)(2,2,6,6-tetramethylpiperidide). ２ The method according to claim 23, including the method described in claim 23.

30. The halogen compound is, formula: RX [In the formula, R comprises at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof; The method according to claim 23, comprising a compound of [X is a halide].

31. formula: SnL ｎ [In the formula, L is a bulky monoanionic ligand or a bulky dianionic ligand; The stannylene compound in which n is 1 or 2, provided that n is 1 when L is a bulky dianionic ligand, and n is 2 when L is a bulky monoanionic ligand. A composition containing the following:

32. The stannylene compound has the formula: The composition according to claim 31, which is a compound of the above.

33. formula: RSn(L) ｎ X [In the formula, R comprises at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof; L is a bulky monoanionic ligand or a bulky dianionic ligand; n is either 1 or 2, where n is 1 if L is a bulky dianionic ligand, and n is 2 if L is a bulky monoanionic ligand; A composition comprising a tin-dic compound [where X is a halide].

34. R is -CH ２ CF ３ , -CH(CF ３ ) ２ ien-CH ２ F, -CH ２ CH ２ F, -CF ３ , -CF ２ CF ３ The composition according to claim 33, comprising at least one of the following, or any combination thereof.

35. R is -CH ３ ien-CH ２ CH ３ ien-CH ２ CH ２ CH ３ , -CH(CH ３ ) ２ , -CH(CH ３ )CH ２ CH ３ ien-CH ２ CH (CH ３ ) ２ , -C(CH ３ ) ３ ,-(CH ２ ) ３ CH ３ , -C ６ H ５ ien-CH ２ (C ６ H ５ ), -CH=CH ２ -C≡CCH ３ ien-CH ２ C≡CH, -CH ２ C≡CCH ３ , -C(CH ３ ) = CH ２ -HC=CHCH ３ ien-CH ２ CH=CH ２ ien-CH ２ N(CH ３ ) ２ ,-(CH ２ ) ３ N(CH ３ ) ２ ien-CH ２ CH ２ OCH ３ , -CH(CH ２ ) ２ O, -CH ２ Si(CH) ３ ) ３ ,-Si(CH ３ ) ３ The composition according to claim 33, comprising at least one of the following, or any combination thereof.

36. L, -NR ａ R ｂ [In the formula, R ａ and R ｂ These are independently hydrogen, alkyl, or silyl, or R ａ and R ｂ They combine with each other to form C ３ ~C ２０ The composition according to claim 33, which forms an N-heterocyclic ring.

37. L, -OR ｃ [In the formula, R ｃ The composition according to claim 33, wherein [ is alkyl, cycloalkyl, or aryl].

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

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

40. At least one L is -N(Si(CH) ３ ) ３ ) ２ The composition according to claim 33.

41. Stannic compounds, The composition according to claim 33.

42. formula: [In the formula, R comprises at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, or any combination thereof; L １ A composition comprising a monosubstituted tin compound, which is independently a monoanionic ligand, a dianionic ligand, or a halide.

43. A monosubstituted tin compound has at least two different ligands (L １ The composition according to claim 42, comprising ).

44. Each L １ The composition according to claim 42, wherein the above is different.

45. Each L １ The composition according to claim 42, wherein the same as the above.

46. L １ が、-OR ｄ 、-82 ｄ 2 ｅ 、-_83O、-OC(=O)82 ｄ 2 ｅ 、-82 ｄ 3(49) 92 ｅ 、-OC(=O)32 ３ 、-82 ｄ (32) ２ ) ) ｎ 82 ｄ 2 ｅ 、-82 ｄ (32) ２ ) ) ｎ 2 ｅ 8-、-9(3) ２ ) ) ｎ 9-、-9(32) ２ ) ) ｎ 92 ｄ 、-O(3H ２ ) ) ｎ 82 ｄ 2 ｅ 、-O(3H ２ ) ) ｎ 2 ｄ N-、またはCC≡CR ｄ [In the formula, R ｄ and R ｅ Each of these is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl; The composition according to claim 42, wherein n is 1 to 30.

47. L １ However, -N(CH ３ ) ２ The composition according to claim 42.

48. L １ However, -OC(CH ３ ) ３ The composition according to claim 42.

49. L １ However, they became independent, [In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , and R １０ The composition according to claim 42, wherein is independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, or aralkyl.

50. L １ However, independently: The composition according to claim 42.

51. The compounds are as follows: The composition according to claim 42, wherein at least one of the following.

52. The composition according to claim 42, comprising less than 5% by weight of a disubstituted tin(IV) compound based on the total weight of the composition.

53. Disubstituted tin(IV) compounds, formula: [In the formula, R comprises at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, ether, amine, imide, cyanate, nitrile, alkoxide, or any combination thereof; L １ The composition according to claim 52, wherein is a compound of [which is independently a monoanionic ligand or a dianionic ligand].

54. The composition according to claim 42, comprising at least 99.5% by weight of a monosubstituted tin compound based on the total weight of the composition.

55. The composition according to claim 42, comprising at least 99.9% by weight of a monosubstituted tin compound based on the total weight of the composition.

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