Compositions for extreme ultraviolet lithography and related methods

Abstract

Mono-substituted tin silanolate compounds and related methods are provided. A method includes contacting a mono-substituted tin (IV) compound with a silanolate reactant to form a mono-substituted silanolate tin compound. A composition includes a mono-substituted tin silanolate compound.

Description

Technical Field

[0001] The present disclosure relates to compositions and related methods useful in extreme ultraviolet (EUV) lithography and related applications. Background Art

[0002] Some precursors can be used to fabricate microelectronic devices. Fabrication of such devices can involve the use of extreme ultraviolet (EUV) lithography to form thin films. Summary of the invention

[0003] Some embodiments relate to Formula I: A n M(X) 4-n (I) a compound wherein: M is Sn; n is 0, 1, 2, 3 or 4; and A is alkyl, alkenyl, alkynyl, formate, enolate, ester, imide, alkoxide, cyclopentadienyl, ether, nitrile, cyano, isocyanate or a combination thereof.

[0004] Some embodiments relate to a method comprising contacting a monosubstituted tin(IV) compound with a silicon alkoxide reactant to form a monosubstituted tin(IV) compound; wherein the monosubstituted tin(IV) compound comprises a compound of formula: RSnQ3, wherein: R is alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silyl alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, carboxylate, alkene Q is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, silanolate, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, carboxylate, enolate, ester, cyclopentadienyl or any combination thereof; wherein the silanolate reactant comprises the formula: M(OSiR 2 3) n A compound wherein: M is an alkali metal cation, an alkaline earth metal cation, a transition metal cation or a post-transition metal cation; R 2 is independently at least one of hydrogen, halide, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkaryl or haloalkyl; and n is 1 to 4.

[0005] Some embodiments relate to a composition comprising: a monosubstituted tin silanol compound of the formula: RSn(OSiR 23) 3, wherein: R is at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silyl alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, carboxylate, enolate, ester, cyclopentadienyl or any combination thereof; and R 2 and independently at least one of hydrogen, halide, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkaryl or haloalkyl. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] Some embodiments of the present disclosure are described herein only by way of example and with reference to the accompanying drawings. With particular reference now to the drawings in detail, it should be emphasized that the embodiments shown are given by way of example and for the purpose of illustrative discussion of the embodiments of the present disclosure. In this regard, the description in conjunction with the drawings makes it clear to those skilled in the art how the embodiments of the present disclosure can be practiced.

[0007] Figure 1 is a flow chart of a method for producing a mono-substituted tin silanol compound according to some embodiments.

[0008] Figure 2 Depicted is a schematic cross-sectional view of a non-limiting embodiment of an ampoule according to some embodiments.

[0009] Figure 3 3 is a thermogravimetric analysis (TGA) of iPrSn(OSi(CH3)3)3 according to some embodiments.

[0010] Figure 4 3 is a thermogravimetric analysis (TGA) of vinyl Sn(OSi(CH3)3)3 according to some embodiments. DETAILED DESCRIPTION

[0011] In addition to the benefits and improvements disclosed, other objects and advantages of the present disclosure may be apparent from the following description and the accompanying drawings. Detailed embodiments of the present disclosure are disclosed herein; however, it should be understood that the disclosed embodiments are merely illustrative of the disclosure that can be embodied in various forms. In addition, each example given for each embodiment of the present disclosure is intended to be illustrative and not limiting.

[0012] Any prior patents and publications mentioned herein are incorporated by reference in their entirety.

[0013] Throughout the specification and claims, unless the context clearly dictates otherwise, the following terms adopt the meanings clearly associated with this document. The phrases "in one embodiment," "in an embodiment," and "in some embodiments" as used herein do not necessarily refer to the same embodiment, but they may. In addition, the phrases "in another embodiment" and "in some other embodiments" as used herein do not necessarily refer to different embodiments, but they may. All embodiments of the present disclosure are intended to be combined without departing from the scope or spirit of the present disclosure.

[0014] As used herein, unless the context clearly dictates otherwise, the term "based on" is not exclusive and allows for being based on other undescribed factors. In addition, throughout the specification, the meanings of "a, an" and "the" include plural references. The meaning of "in..." includes "in..." and "on...".

[0015] As used herein, the term "aliphatic hydrocarbon" refers to a monovalent or multivalent aliphatic hydrocarbon group. The term includes, for example and without limitation, at least one of a monovalent alkyl, a multivalent alkyl, a monovalent alkenyl, a multivalent alkenyl, a monovalent alkynyl, a multivalent alkynyl, or any combination thereof. The term multivalent includes, for example and without limitation, at least one of a divalent group, a trivalent group, a tetravalent group, or any combination thereof and other multivalent groups. Non-limiting examples of aliphatic hydrocarbons include at least one of a monovalent alkyl, a divalent alkyl, a trivalent alkyl, or a tetravalent alkyl. In some embodiments, aliphatic hydrocarbons do not include heteroatoms. In some embodiments, aliphatic hydrocarbons do not include any cyclic compounds, for example and without limitation, cycloalkanes.

[0016] As used herein, the term "alkyl" refers to a hydrocarbon group having 1 to 30 carbon atoms. The alkyl group may be connected by a single bond. An alkyl group having n carbon atoms may be referred to as a "C n "C3 alkyl" may include n-propyl and isopropyl. Alkyl groups having multiple carbon atoms (e.g., 1 to 30 carbon atoms) may be referred to as C1-C 30 In some embodiments, the alkyl group is linear. In some embodiments, the alkyl group is branched. In some embodiments, the alkyl group is substituted. In some embodiments, the alkyl group is unsubstituted. In some embodiments, the alkyl group includes at least one of the following or is selected from the group consisting of: C1-C 30 Alkyl, C1-C 29 Alkyl, C1-C 28 Alkyl, C1-C 27 Alkyl, C1-C 27 Alkyl, C1-C 26 Alkyl, C1-C 25 Alkyl, C1-C 24 Alkyl, C1-C 23 Alkyl, C1-C22 Alkyl, C1-C 21 Alkyl, C1-C 20 Alkyl, C1-C 19 Alkyl, C1-C 18 Alkyl, C1-C 17 Alkyl, C1-C 16 Alkyl, C1-C 15 Alkyl, C1-C 14 Alkyl, C1-C 13 Alkyl, C1-C 12 Alkyl, C1-C 11 Alkyl, C1-C 10 Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, C2-C 30 Alkyl, C3-C 30 Alkyl, C4-C 30 Alkyl, C5-C 30 Alkyl, C6-C 30 Alkyl, C7-C 30 Alkyl, C8-C 30 Alkyl, C9-C 30 Alkyl, C 10 -C 30 Alkyl, 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, C26 -C 30 Alkyl, C 27 -C 30 Alkyl, C 28 -C 30 Alkyl, C 29 -C 30 Alkyl, C2-C 10 Alkyl, C3-C 10 Alkyl, C4-C 10 Alkyl, C5-C 10 Alkyl, C6-C 10 Alkyl, C7-C 10 Alkyl, C8-C 10 In some embodiments, the term "alkyl" refers to 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 includes at least one of the following or is selected from the group consisting of: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, isobutyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (tert-butyl), n-pentyl, isopentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof. In some embodiments, the term "alkyl" generally refers to alkyl, alkenyl, alkynyl, and / or cycloalkyl.

[0017] As used herein, the term "alkenyl" refers to a hydrocarbon group having 1 to 30 carbon atoms and at least one carbon-carbon double bond. In some embodiments, the alkenyl group includes at least one of the following or is selected from the group consisting of: 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 12Alkenyl, C1-C 11 Alkenyl, C1-C 10 alkenyl, C1-C9 alkenyl, C1-C8 alkenyl, C1-C7 alkenyl, C1-C6 alkenyl, C1-C5 alkenyl, C1-C4 alkenyl, C1-C3 alkenyl, C1-C2 alkenyl, C2-C 30 Alkenyl, C3-C 30 Alkenyl, C4-C 30 Alkenyl, C5-C 30 Alkenyl, C6-C 30 Alkenyl, C7-C 30 Alkenyl, C8-C 30 Alkenyl, C9-C 30 Alkenyl, C 10 -C 30 Alkenyl, C 11 -C 30 Alkenyl, C 12 -C 30 Alkenyl, C 13 -C 30 Alkenyl, C 14 -C 30 Alkenyl, C 15 -C 30 Alkenyl, C 16 -C 30 Alkenyl, C 17 -C 30 Alkenyl, C 18 -C 30 Alkenyl, C 19 -C 30 Alkenyl, C 20 -C 30 Alkenyl, C 21 -C 30 Alkenyl, C 22 -C 30 Alkenyl, C 23 -C 30 Alkenyl, C 24 -C 30 Alkenyl, C 25 -C 30 Alkenyl, C 26 -C 30 Alkenyl, C 27 -C 30 Alkenyl, C 28 -C 30 Alkenyl, C 29 -C 30 Alkenyl, C2-C 10 Alkenyl, C3-C 10 Alkenyl, C4-C 10 Alkenyl, C5-C 10 Alkenyl, C6-C10 Alkenyl, C7-C 10 Alkenyl, C8-C 10 The invention relates to a vinyl group, a C2-C9 alkenyl group, a C2-C8 alkenyl group, a C2-C7 alkenyl group, a C2-C6 alkenyl group, a C2-C5 alkenyl group, a C3-C5 alkenyl group, or any combination thereof. Examples of alkenyl groups include, but are not limited to, at least one of the following: vinyl, allyl, 1-methylvinyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1,3-pentadienyl, 2,4-pentadienyl, 1,4-pentenyl, 1-decenyl, 3-decenyl, 1-undecenyl, oleyl, linoleyl, linolenic acid, or any combination thereof.

[0018] As used herein, the term "alkynyl" refers to a hydrocarbon group having 1 to 30 carbon atoms and at least one carbon-carbon triple bond. In some embodiments, the alkynyl group includes at least one of the following or is selected from the group consisting of: C1-C 30 Alkynyl, C1-C 29 Alkynyl, C1-C 28 Alkynyl, C1-C 27 Alkynyl, C1-C 27 Alkynyl, C1-C 26 Alkynyl, C1-C 25 Alkynyl, C1-C 24 Alkynyl, C1-C 23 Alkynyl, C1-C 22 Alkynyl, C1-C 21 Alkynyl, C1-C 20 Alkynyl, C1-C 19 Alkynyl, C1-C 18 Alkynyl, C1-C 17 Alkynyl, C1-C 16 Alkynyl, C1-C 15 Alkynyl, C1-C 14 Alkynyl, C1-C 13 Alkynyl, C1-C 12 Alkynyl, C1-C 11 Alkynyl, C1-C 10Alkynyl, C1-C9 alkynyl, C1-C8 alkynyl, C1-C7 alkynyl, C1-C6 alkynyl, C1-C5 alkynyl, C1-C4 alkynyl, C1-C3 alkynyl, C1-C2 alkynyl, C2-C 30 Alkynyl, C3-C 30 Alkynyl, C4-C 30 Alkynyl, C5-C 30 Alkynyl, C6-C 30 Alkynyl, C7-C 30 Alkynyl, C8-C 30 Alkynyl, C9-C 30 Alkynyl, C 10 -C 30 Alkynyl, C 11 -C 30 Alkynyl, C 12 -C 30 Alkynyl, C 13 -C 30 Alkynyl, C 14 -C 30 Alkynyl, C 15 -C 30 Alkynyl, C 16 -C 30 Alkynyl, C 17 -C 30 Alkynyl, C 18 -C 30 Alkynyl, C 19 -C 30 Alkynyl, C 20 -C 30 Alkynyl, C 21 -C 30 Alkynyl, C 22 -C 30 Alkynyl, C 23 -C 30 Alkynyl, C 24 -C 30 Alkynyl, C 25 -C 30 Alkynyl, C 26 -C 30 Alkynyl, C 27 -C 30 Alkynyl, C 28 -C 30 Alkynyl, C 29 -C 30 Alkynyl, C2-C 10 Alkynyl, C3-C 10 Alkynyl, C4-C 10 Alkynyl, C5-C 10 Alkynyl, C6-C 10 Alkynyl, C7-C 10 Alkynyl, C8-C10 The alkynyl group may be any of a C-C alkynyl, a C-C alkynyl, a C-C alkynyl, a C-C alkynyl, a C-C alkynyl, a C-C alkynyl, a C-C alkynyl, a C-C alkynyl, or any combination thereof. Examples of alkynyl groups include, but are not limited to, at least one of an ethynyl, a propynyl, an n-butynyl, an n-pentynyl, a 3-methyl-1-butynyl, an n-hexynyl, a methyl-pentynyl, or any combination thereof.

[0019] As used herein, the term "cycloalkyl" refers to a non-aromatic carbocyclic ring having 3 to 8 carbon atoms in the ring. The term includes monocyclic non-aromatic carbocyclic rings and polycyclic non-aromatic carbocyclic rings. The term "monocyclic" when used as a modifier refers to a cycloalkyl having a single cyclic ring structure. The term "polycyclic" when used as a modifier refers to a cycloalkyl having more than one cyclic ring structure, which may be a fused, bridged, spiral or otherwise bonded ring structure. For example, two or more cycloalkyls may be fused, bridged or fused and bridged to obtain a polycyclic non-aromatic carbocyclic ring. In some embodiments, the cycloalkyl may include, consist of, or consist essentially of, at least one of a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or any combination thereof, or may be selected from a group consisting of.

[0020] As used herein, the term "aryl" refers to a monocyclic or polycyclic aromatic hydrocarbon. The number of carbon atoms of the aryl group may be in the range of 5 carbon atoms to 100 carbon atoms. In some embodiments, the aryl group has 5 to 20 carbon atoms. For example, in some embodiments, the aryl group has 6 to 8 carbon atoms, 6 to 10 carbon atoms, 6 to 12 carbon atoms, 6 to 15 carbon atoms, or 6 to 20 carbon atoms. The term "monocyclic" when used as a modifier refers to an aryl group having a single aromatic ring structure. The term "polycyclic" when used as a modifier refers to an aryl group having more than one aromatic ring structure, and the cyclic ring structure may be a fused, bridged, spiral or otherwise bonded ring structure. In some embodiments, the aryl group is -C6H5.

[0021] As used herein, the term "amino" and / or "amine" refers to an amino group of the formula -N(R a R b ) functional group, where R a and R b is independently hydrogen, alkyl (as defined herein) or silyl (as defined herein), or R a and R b bond to each other to form C3-C 20N-heterocycle. In some embodiments, the amino group may include an alkylamino group or a dialkylamino group. In some embodiments, the amino group may include at least one of a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an isopropylamino group, a di-isopropylamino group, a butylamino group, a sec-butylamino group, a tert-butylamino group, a di-sec-butylamino group, an isobutylamino group, a di-isobutylamino group, a di-tert-amylamino group, an ethylmethylamino group, an isopropyl-n-propylamino group, or any combination thereof. Examples of alkylamino groups may include, but are not limited to, one or more of the following: primary alkylamino groups such as, for example and without limitation, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, sec-butylamino, isobutylamino, tert-butylamino, pentylamino, 2-aminopentane, 3-aminopentane, 1-amino-2-methylbutane, 2-amino-2-methylbutane, 3-amino-2-methylbutane, 4-amino-2-methylbutane, hexylamino, 5-amino-2-methylpentane, heptylamino, octylamino, nonylamino, decylamino, undecylamino, dodecylamino, tridecylamino, tetradecylamino, pentadecylamino, hexadecylamino, heptadecylamino, and octadecylamino. amino; and secondary alkylamino groups such as, for example and without limitation, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di-sec-butylamino, di-tert-butylamino, dipentylamino, dihexylamino, diheptylamino, dioctylamino, dinonylamino, didecylamino, methylethylamino, methylpropylamino, methylisopropylamino, methylbutylamino, methylisobutylamino, methyl-sec-butylamino, methyl-tert-butylamino, methylpentylamino, methylisopentylamino, ethylpropylamino, ethylisopropylamino, ethylbutylamino, ethylisobutylamino, ethyl-sec-butylamino, ethylamino, ethylisopentylamino, propylbutylamino, and propylisobutylamino.

[0022] As used herein, the term "alkoxy" refers to a radical of the formula -OR c The functional group, R c is alkyl (as defined herein), silylalkyl, cycloalkyl or aryl. In some embodiments, the alkoxy group may include, consist of, consist essentially of, or be selected from the group consisting of, at least one of methoxy, ethoxy, methoxy, ethoxy, n-propoxy, 1-methylethoxy (isopropoxy), n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or any combination thereof.

[0023] As used herein, the term "silicon-based" refers to a compound of the formula -Si(R e R f R g ) functional group, where R e , R f and Rg Each of is independently hydrogen or alkyl as defined herein. In some embodiments, the silicon group is a functional group of the formula -SiH3. In some embodiments, the silicon group is a functional group of the formula -SiR e The functional group of H2, where R e In some embodiments, the silicon group is of the formula -SiR e R f H functional group, where R e and R f In some embodiments, the silicon group is of the formula -Si(R e R f R g ) functional group, where R e , R f and R g In some embodiments, the silicon group is a functional group of the formula -Si(CH3)3.

[0024] As used herein, the term "alkoxyalkyl" refers to an alkyl group as defined herein, wherein at least one hydrogen atom of the alkyl group is replaced by an alkoxy group as defined herein. In some embodiments, the term "alkoxyalkyl" refers to a group of the formula -(alkyl)OR a wherein alkyl is as defined above and wherein R a As defined above. In some embodiments, alkoxyalkyl is of the formula -(CH2) n OR a A functional group, wherein n is 1 to 10 and R a As defined above. In some embodiments, alkoxyalkyl is a functional group of formula -CH2CH2OCH3.

[0025] As used herein, the term "aralkyl" refers to an alkyl group as defined herein, wherein at least one hydrogen atom of the alkyl group is replaced by an aryl group as defined herein. In some embodiments, the term "aralkyl" refers to a functional group of the formula -(alkyl)(aryl), wherein alkyl is defined herein and aryl is defined herein. In some embodiments, the aralkyl group is -CH2(C6H5).

[0026] As used herein, the term "aminoalkyl" refers to an alkyl group as defined herein, wherein at least one of the hydrogen atoms of the alkyl group is replaced by an amino group as defined herein. In some embodiments, the term "aminoalkyl" refers to a group of the formula -(alkyl)N(R b R c R d ) wherein alkyl is as defined above and wherein R b , R c and R dAs defined above. In some embodiments, aminoalkyl is -CH2N(CH3)2. In some embodiments, aminoalkyl is -(CH2)3N(CH3)2. In some embodiments, aminoalkyl is aminomethyl (-CH2NH2). In some embodiments, aminoalkyl is N,N-dimethylaminoethyl (-CH2CH2N(CH3)2). In some embodiments, aminoalkyl is 3-(N-cyclopropylamino)propyl (-CH2CH2CH2NH-Pr).

[0027] As used herein, the term "silylalkyl" refers to an alkyl group as defined herein, wherein at least one hydrogen atom of the alkyl group is replaced by a silicon group as defined herein. In some embodiments, the term "silylalkyl" refers to an alkyl group of the formula -(alkyl)Si(R e R f R g ) wherein alkyl is as defined above and wherein R e , R f and R g As defined above. In some embodiments, the silylalkyl group is of the formula -(CH2) m Si(R e R f R g ) wherein m is 1 to 10 and wherein R e , R f and R g As defined above. In some embodiments, the silylalkyl group is a functional group of the formula -CH2Si(CH3)3.

[0028] As used herein, the term "haloalkyl" refers to an alkyl group as defined herein, wherein at least one hydrogen atom of the alkyl group is replaced by a halide as defined herein. In some embodiments, the haloalkyl group includes a fluoroalkyl group. In some embodiments, the fluoroalkyl group includes at least one of -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, or any combination thereof.

[0029] As used herein, the term "halide" refers to -Cl, -Br, -I, or -F.

[0030] As used herein, the term "metal cation" refers to at least one of an alkali metal cation, an alkaline earth metal cation, a transition metal cation, a post-transition metal cation, or any combination thereof. In some embodiments, the metal cation includes a lithium cation, a sodium cation, a potassium cation, a rubidium cation, a cesium cation, a francium cation, a beryllium cation, a magnesium cation, a calcium cation, a strontium cation, a barium cation, a radium cation, a scandium cation, a titanium cation, a vanadium cation, a chromium cation, a manganese cation, an iron cation, a cobalt cation, a nickel cation, a copper cation, a zinc cation, a yttrium cation, a zirconium cation, a niobium cation, a molybdenum cation, a technetium cation, a ruthenium cation, a rhodium cation, a palladium cation, a silver cation, a cadmium cation, a hafnium cation, a tantalum cation, a tungsten cation, a rhenium cation, an osmium cation, an iridium cation, a platinum cation, a gold cation, a mercury cation, an aluminum cation, a gallium cation, an indium cation, a tin cation, a thallium cation, a lead cation, a bismuth cation, or a polonium cation. The charge of the metal cation is known and is not repeated here for simplicity; however, it should be understood that the metal cation can have any known charge. For example, in some embodiments, the metal cation includes Li + 、Na + , K + , Rb + , Cs + Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ 、Zn 2+ Sn 2+ or Sn 4+ In some embodiments, the metal cation is Sn 2+ In some embodiments, the metal cation is Sn 4+ .

[0031] Some embodiments relate to precursors and related methods. At least some of these embodiments relate to precursors that can be used to make microelectronic devices (including semiconductor devices, etc.). For example, the precursors can be used to form silicon-containing films by one or more deposition processes. Examples of deposition processes include, but are not limited to, at least one of the following: chemical vapor deposition (CVD) process, digital or pulsed chemical vapor deposition process, plasma enhanced cyclic chemical vapor deposition process (PECCVD), flow chemical vapor deposition process (FCVD), atomic layer deposition (ALD) process, thermal atomic layer deposition, plasma enhanced atomic layer deposition (PEALD) process, metal organic chemical vapor deposition (MOCVD) process, plasma enhanced chemical vapor deposition (PECVD) process, or any combination thereof.

[0032] Some embodiments relate to compounds such as compounds used in applications for tin oxide film growth, extreme ultraviolet lithography, plastics or radiation sensitive films. The compounds include precursors useful in the production of photoresists, such as photoresists in processes associated with the electronics industry.

[0033] Some embodiments relate to compounds for use in applications such as extreme ultraviolet lithography applications. The compounds include precursors targeting extreme ultraviolet lithography applications (e.g., extreme ultraviolet hard mask applications). The disclosed compounds can be used as precursors to materials to be used as hard mask materials in extreme ultraviolet lithography applications.

[0034] In some embodiments, the present disclosure comprises Formula I: A n M(X) 4-n In some embodiments, M is Sn, and n is 0, 1, 2, 3, or 4. In some embodiments, "A" is an alkyl, alkenyl, alkynyl, formate, enolate, ester, imide, alkoxide, cyclopentadienyl, ether, nitrile, cyano, isocyanate, or a combination thereof.

[0035] In some embodiments, the compound is one selected from the following:

[0036]

[0037] In some embodiments, A of Formula I is an enolate. In some embodiments, the enolate comprises the following structure:

[0038]

[0039] In some embodiments, M may include a metal in solid form. For example, in some embodiments, M may include a metal in powder, granule, or ingot form. In some embodiments, M is Sn.

[0040] In some embodiments, R is hydrogen or C1-C6 alkyl. For example, in some embodiments, the alkyl is saturated (e.g., a single bond). In some embodiments, the alkyl is unsaturated (e.g., a double bond and / or a triple bond). 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 may include, consist of, consist essentially of, or be selected from the group consisting of C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, C1 alkyl, fluorine-substituted C1-C6 alkyl, or any combination thereof.

[0041] In some embodiments, A is the same as X. For example, A and X can be the same class / family of ligands. In some embodiments, A and X are both alkyl, alkenyl, alkynyl, formates, enolates, esters, imides, alkoxides, cyclopentadienyl, ethers, or combinations thereof (i.e., A and X are the same combination of the foregoing compounds).

[0042] In some embodiments, A of Formula I is a of cyclopentadienyl.

[0043] In some embodiments, each R 1 -R 5 In some embodiments, the alkyl radical is independently selected from hydrogen or C1-C6 alkyl. In some embodiments, the C1-C6 alkyl radical is branched or unbranched (straight chain). In some embodiments, the C1-C6 alkyl radical is substituted or unsubstituted. For example, in some embodiments, the alkyl radical is saturated (e.g., a single bond). In some embodiments, the alkyl radical is unsaturated (e.g., a double bond and / or a triple bond). In some embodiments, the alkyl radical may include, consist of, or consist essentially of, at least one of a C1-C6 alkyl radical, a C1-C5 alkyl radical, a C1-C4 alkyl radical, a C1-C3 alkyl radical, a C1-C2 alkyl radical, a C1 alkyl radical, or any combination thereof, or may be selected from a group consisting of.

[0044] In some embodiments, n of Formula I is 1. In some embodiments, (X) of Formula I 4-n is (NR2)3, (OR)3, (CCR)3, (CRCR2)3, or H3. In some embodiments, R is hydrogen or a C1-C6 alkyl group. In some embodiments, X may comprise a halide, such as a fluoride (F - ), fluoride (Cl - ), bromide (Br - ) and iodide (I - ). In some embodiments, X of Formula I is NR2, OR, CCR, CRCR2, F, Cl, Br, I, or H. In some embodiments, R is hydrogen or C1-C6 alkyl. In some embodiments, R is hydrogen, C1-C6 alkyl, or fluorinated C1-C6 alkyl. In some embodiments, fluorinated C1-C6 alkyl is CH2CF3.

[0045] In some embodiments, X is a ligand. In some embodiments, the ligand is a cyclopentadienyl, a nitrile, or a cyanide.

[0046] In some embodiments, A comprises a substituted fluorinated group. In some embodiments, the substituted fluorinated group comprises -OCH2CF3, -OCH(CF3)2, -O2CCF3, or -OC(CF3)CH2.

[0047] In some embodiments, A having a substituted fluorinated group comprises a fluorinated ether, a fluorinated carboxylate, or a fluorinated alkoxide.

[0048] Figure 1 FIG. 1 is a flow chart of a method 100 for producing a monosubstituted tin silicon alkoxide compound according to some embodiments. Figure 1 , a method 100 of producing a mono-substituted tin silanolate compound includes one or more of the following steps: obtaining 102 a mono-substituted tin (IV) compound, obtaining 104 a silanolate reactant; and contacting 106 the mono-substituted tin (IV) compound with the silanolate reactant to form the mono-substituted tin silanolate compound.

[0049] At step 102, method 100 includes obtaining a monosubstituted tin (IV) compound. In some embodiments, the monosubstituted tin (IV) compound includes a compound of the formula:

[0050] RSnQ3,

[0051] in:

[0052] 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, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof; and

[0053] Q is independently at least one of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, silanolate, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof.

[0054] In some embodiments, R is at least one of -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.

[0055] In some embodiments, R is at least one of -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, or any combination thereof. In some embodiments, R is 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.

[0056] In some embodiments, Q is independently -H, -Cl, -Br, -F, -I, -NR 1 2. -OR 1 、-C≡CR 1 、-OSiR 1 3 or any combination thereof, wherein R 1 The alkyl radicals are independently at least one of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, silanolate, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof.

[0057] In some embodiments, Q is independently at least one of -Cl, -Br, -F, -I, or any combination thereof.

[0058] In some embodiments, Q is independently -H, -NR 1 2. -OR 1 、-C≡CR 1 or at least one of any combination thereof, wherein R 1 The alkyl radicals are independently at least one of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, silanolate, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof.

[0059] In some embodiments, Q is -OSiR 1 3, where R 1The alkyl radicals are independently at least one of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, silanolate, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof.

[0060] 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≡C at least one of CH3, -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; Q is independently -H, -Cl, -Br, -F, -I, -NR 1 2. -OR 1 、-C≡CR 1 、-OSiR 1 3 or any combination thereof, wherein R 1 The alkyl radicals are independently at least one of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, silanolate, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof.

[0061] In some embodiments, R is different from Q. In some embodiments, R is the same as Q. In some embodiments, R is different from at least one Q. In some embodiments, R is the same as at least one Q.

[0062] At step 104, method 100 includes obtaining a silicon alkoxide reactant. In some embodiments, the silicon alkoxide reactant includes a compound of the formula:

[0063] M(OSiR 2 3) n ,

[0064] in:

[0065] M is an alkali metal cation, an alkaline earth metal cation, a transition metal cation or a post-transition metal cation;

[0066] R 2 is independently at least one of hydrogen, halide, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkaryl, haloalkyl, or any combination thereof; and

[0067] n is 1 to 4.

[0068] In some embodiments, R 2 are independently hydrogen, C1-C 12 Alkyl, C1-C 12 Alkenyl, C1-C 12 The invention further comprises at least one of alkynyl, phenyl, fluorine, chlorine, bromine, iodine or any combination thereof.

[0069] In some embodiments, R is isopropyl; Q is chloro; M is Na + ; and R 2 In some embodiments, R is vinyl; X is chlorine; M is Na + ; and R 2 It is methyl.

[0070] At step 106 , method 100 includes contacting a mono-substituted tin(IV) compound with a silicon alkoxide reactant to form a mono-substituted tin silicon alkoxide compound.

[0071] In some embodiments, the at least one leaving group Q is removed by a substitution reaction (eg, from -OSiR 2 3 substitution reaction) to form a mono-substituted tin siliconate compound. In some embodiments, contacting includes reacting the mono-substituted tin (IV) compound with a siliconate reactant. In some embodiments, contacting includes mixing the mono-substituted tin (IV) compound and the siliconate reactant. In some embodiments, contacting includes stirring the mono-substituted tin (IV) compound and the siliconate reactant. In some embodiments, contacting includes adding the mono-substituted tin (IV) compound and the siliconate reactant to a reaction vessel. In some embodiments, contacting includes dissolving the mono-substituted tin (IV) compound and the siliconate reactant. In some embodiments, contacting includes combining the mono-substituted tin (IV) compound and the siliconate reactant. In some embodiments, contacting is performed in a solution.

[0072] In some embodiments, the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0073] RSn(OSiR 2 3)3,

[0074] in:

[0075] 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, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof; and

[0076] R 2 is independently at least one of hydrogen, halide, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkaryl, haloalkyl, or any combination thereof.

[0077] In some embodiments, R is at least one of -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.

[0078] In some embodiments, R is at least one of -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, or any combination thereof. In some embodiments, R is 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.

[0079] In some embodiments, R 2 are independently hydrogen, C1-C 12 Alkyl, C1-C 12 Alkenyl, C1-C12 The invention further comprises at least one of alkynyl, phenyl, fluorine, chlorine, bromine, iodine or any combination thereof.

[0080] In some embodiments, the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0081]

[0082] in:

[0083] 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(C6H 5), -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 or -Si(CH3)3.

[0084] In some embodiments, the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0085]

[0086] In some embodiments, the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0087]

[0088] Some embodiments relate to a composition. In some embodiments, the composition includes a monosubstituted tin silicon alkoxide compound. In some embodiments, the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0089] RSn(OSiR 2 3)3,

[0090] in:

[0091] 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, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof; and

[0092] R 2is independently at least one of hydrogen, halide, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkaryl, haloalkyl, or any combination thereof.

[0093] In some embodiments, R is at least one of -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.

[0094] In some embodiments, R is at least one of -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, or any combination thereof. In some embodiments, R is 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.

[0095] In some embodiments, R 2 are independently hydrogen, C1-C 12 Alkyl, C1-C 12 Alkenyl, C1-C 12 The invention further comprises at least one of alkynyl, phenyl, fluorine, chlorine, bromine, iodine or any combination thereof.

[0096] In some embodiments, the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0097]

[0098] in:

[0099] 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(C6H 5), -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 or -Si(CH3)3.

[0100] In some embodiments, the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0101]

[0102] In some embodiments, the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0103]

[0104] In some embodiments, the mono-substituted tin siliconate compound has a purity of at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, at least 99.9%, at least 99.99%, at least 99.999%, at least 99.9999%, or greater. In some embodiments, the mono-substituted tin siliconate compound has a purity of 70% to 95%, 75% to 95%, 80% to 95%, 85% to 95%, 90% to 95%, 70% to 90%, 70% to 85%, 70% to 80%, 70% to 75%, or any range or sub-range between 70% and 95%. In some embodiments, the mono-substituted tin silanol compound has a purity of 95% to 99.9999%, 95% to 99.999%, 95% to 99.99%, 95% to 99.9%, 95% to 99%, 95% to 99%, 95% to 98%, 95% to 97%, 95% to 96%, 96% to 99.9999%, 97% to 99.9999%, 98% to 99.9999%, 99% to 99.9999%, 99.9% to 99.9999%, 99.99% to 99.9999%, 99.999% to 99.9999%, or any range or sub-range between 95% and 99.9999%.

[0105] In some embodiments, the impurity includes a compound of the formula:

[0106] R a Sn(OSiR 2 3) b ,

[0107] in:

[0108] a is 2, 3 or 4;

[0109] b is 0, 1, or 2; and

[0110] R and R 2 is as defined above.

[0111] Figure 2 A schematic cross-sectional view of a non-limiting embodiment of an ampoule 200 according to some embodiments is depicted. In an inner chamber 204 of the ampoule 200, the ampoule 200 contains a tray assembly 202. The inner chamber 204 has an inner wall surface 206. The tray assembly 202 includes trays 208, each tray being configured to contain a vaporizable precursor. In some embodiments, the vaporizable precursor includes any one or more compositions disclosed herein, including a composition containing a monosubstituted silanol tin compound. Each tray 208 of the tray assembly 202 includes a portion 210 configured to contact (e.g., thermal contact, physical contact, etc.) the inner wall surface 206 of the ampoule 200. The surface-to-surface contact of the portion 210 with the inner wall surface 206 enhances heat transfer from the ampoule 200 to each tray 208 and thereby from each tray 208 to the vaporizable precursor on each tray 208. Different fluid flow paths are defined within the interior chamber 204 of the ampoule 200, allowing the fluid to flow upward, downward, or both through the ampoule 200. The ampoule 200 is shown as having a generally cylindrical interior chamber. However, it should be understood that the interior chamber 204 of the ampoule may have other shapes without departing from the scope of the present disclosure.

[0112] Example 1

[0113] Synthesis of iPrSn(OSi(CH3)3)3

[0114] In a nitrogen-filled glove box, iPrSnCl3 (20.0 g, 74.5 mmol) (CAS#27440-55-7) was loaded into a 500 mL round-bottom flask equipped with a magnetic stirring bar and diluted with 400 mL of hexane. NaOSi(CH3)3 (26.2 g, 234 mmol) (CAS#18027-10-6) was added directly to the stirred solution using a conical addition funnel over a one-hour period, thereby achieving an exotherm and presenting a thick white mixture. After the addition was completed, the flask was equipped with a reflux condenser cooled to -4°C and the reaction solution was stirred at 60°C for 12 hours. The reaction solution was cooled to room temperature, the resulting thick white mixture was filtered through a disposable polyethylene filter frit, the frit was washed with 50 mL of hexane, and the combined organic fractions were dried under reduced pressure to produce iPrSn(OSi(CH3)3)3 in the form of a colorless liquid. Mass: 19.27 g, 60.1% yield. The product was loaded into a 50 mL Schlenk flask equipped with a magnetic stirring bar and placed on a Schlenk line under N2 working gas, and equipped with a short path distillation head equipped with a thermometer and a 50 mL collection flask. The distillation apparatus was placed under reduced pressure, the condenser was warmed to 25°C, and an ice bath was used to cool the collection flask. The product was purified by distillation at 40-42°C and 100-110 mTorr pressure to produce iPrSn(O(Si(CH3)3)3 in the form of a colorless liquid. The mass of the distilled product: 15.11 g, 47.3% distillation yield. 1 H- and 119 Sn-NMR purity>99.9%. 1 H{ 13 C}-NMR (400MHz, C6D6, 298K): 0.21 (s, 27H); 1.12 (d, 6H); 1.63 (sept, 1H) ppm; 13 C{ 1 H}-NMR (100MHz, C6D6, 298K): 3.34; 19.65; 26.84ppm; 119 Sn{ 1 H}-NMR(149MHz,C6D6,298K):-267.60ppm. 29 Si 1 H}-NMR (79MHz, C6D6, 298K): 12.08ppm. Figure 3 3 is a thermogravimetric analysis (TGA) of iPrSn(OSi(CH3)3)3 according to some embodiments.

[0115] Example 2

[0116] Synthesis of Vinyl Sn(OSi(CH3)3)3

[0117] In a nitrogen-filled glove box, vinyl SnCl3 (1.0 g, 3.96 mmol) was placed in a 40 mL amber vial equipped with a stirring bar and dissolved in 10 mL hexane. NaOSi (CH3) 3 (1.34 g, 12.0 mmol) (CAS# 18027-10-6) was added over 5 minutes. Exothermic and solid were observed. The reaction mixture was then stirred overnight at 60 ° C. The next day, the thick reaction mixture was filtered through a disposable polyethylene (PE) glaze and the solid was washed with 5 mL hexane. The solvent was then removed from the filtrate and washed under vacuum. A transparent colorless oil was obtained and some crystalline material was observed after overnight. A minimum amount of hexane was added to dissolve the solid and the solution was placed in a -35 ° C freezer. White crystalline material was observed. The solution was decanted and the crystalline solid was washed with 2 mL cold hexane, and then dried under vacuum. Vinyl Sn (OSi (CH3) 3) 3 (1.2 g, 73% yield, was collected in the form of a crystalline white solid. 119 Sn purity: 83%). 1 H{ 13 C}-NMR (400MHz, C6D6, 298K): 0.23 (s, 27H); 5.76 (2H); 5.8-6.6 (1H)ppm; 13 C{ 1 H}-NMR (100MHz, C6D6, 298K): 3.24; 131.07; 139.99ppm; 119 Sn{ 1 H}-NMR (149MHz, C6D6, 298K): -300.8ppm. Figure 4 3 is a thermogravimetric analysis (TGA) of vinyl Sn(OSi(CH3)3)3 according to some embodiments.

[0118] aspect

[0119] Different aspects are described below. It should be understood that any one or more of the recited features in the following aspects may be combined with any one or more of the other aspects.

[0120] Aspect 1. A formula I: A n M(X) 4-n (I) a compound wherein: M is Sn; n is 0, 1, 2, 3 or 4; and A is alkyl, alkenyl, alkynyl, formate, enolate, ester, imide, alkoxide, cyclopentadienyl, ether, nitrile, cyano, isocyanate or a combination thereof.

[0121] Aspect 2. The compound according to aspect 1, wherein A is an enolate.

[0122] Aspect 3. The compound according to aspect 2, wherein the enolate comprises the structure Where M is Sn.

[0123] Aspect 4. The compound according to aspect 3, wherein R is hydrogen or C1-C6 alkyl.

[0124] Aspect 5. The compound according to aspect 1, wherein A is a compound having the formula of cyclopentadienyl.

[0125] Aspect 6. The compound according to aspect 5, wherein each R 1 -R 5 Independently selected from hydrogen or C1-C6 alkyl.

[0126] Aspect 7. The compound according to Aspect 6, wherein the C1-C6 alkyl group is branched or unbranched.

[0127] Aspect 8. The compound according to Aspect 6, wherein the C1-C6 alkyl group is substituted or unsubstituted.

[0128] Aspect 9. The compound according to any one of the preceding aspects, wherein n is 1.

[0129] Aspect 10. The compound according to Aspect 9, wherein (X) 4-n It is (NR2)3, (OR)3, (CCR)3, (CRCR2)3 or H3.

[0130] Aspect 11. The compound according to aspect 10, wherein R is hydrogen or C1-C6 alkyl.

[0131] Aspect 12. The compound according to any one of the preceding aspects, wherein X is NR2, OR, CCR, CRCR2, F, Cl, Br, I or H.

[0132] Aspect 13. The compound according to aspect 12, wherein R is hydrogen, C1-C6 alkyl, or C1-C6 alkyl substituted with fluorine.

[0133] Aspect 14. The compound according to aspect 13, wherein the fluorine-substituted C1-C6 alkyl is CH2CF3.

[0134] Aspect 15. The compound according to any one of aspects 1 to 11, wherein X is a ligand.

[0135] Aspect 16. The compound according to aspect 15, wherein the ligand is cyclopentadienyl, nitrile or cyanide.

[0136] Aspect 17. The compound according to any one of the preceding aspects, wherein A comprises a substituted fluorinated group.

[0137] Aspect 18. The compound according to aspect 17, wherein A having the substituted fluorinated group comprises -OCH2CF3, -OCH(CF3)2, -O2CCF3 or -OC(CF3)CH2.

[0138] Aspect 19. The compound according to aspect 17, wherein A having the substituted fluorinated group comprises a fluorinated ether, a fluorinated carboxylic acid ester, or a fluorinated alkoxide.

[0139] Aspect 20. The compound according to aspect 1, wherein the compound is one selected from the following:

[0140]

[0141] Where M is Sn.

[0142] Aspect 21. A method comprising:

[0143] contacting a monosubstituted tin(IV) compound with a silicon alkoxide reactant to form a monosubstituted tin silicon alkoxide compound;

[0144] The monosubstituted tin (IV) compound comprises a compound of the following formula:

[0145] RSnQ3,

[0146] in:

[0147] 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, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof;

[0148] Q is independently at least one of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, silanolate, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof;

[0149] The silicon alkoxide reactant comprises a compound of the formula:

[0150] M(OSiR 2 3) n ,

[0151] in:

[0152] M is an alkali metal cation, an alkaline earth metal cation, a transition metal cation or a post-transition metal cation;

[0153] R 2 is independently at least one of hydrogen, halide, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkaryl or haloalkyl;

[0154] n is 1 to 4.

[0155] Aspect 22. The method according to aspect 21, wherein R is at least one of -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, or any combination thereof.

[0156] Aspect 23. A method according to any one of aspects 21 to 22, wherein R is 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.

[0157] Aspect 24. The method according to any one of aspects 21 to 23, wherein Q is independently -H, -Cl, -Br, -F, -I, -NR 1 2. -OR 1 、-C≡CR 1 、-OSiR 1 3 or at least one of any combination thereof,

[0158] in:

[0159] R 1 The alkyl radicals are independently at least one of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, silanolate, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof.

[0160] Aspect 25. The method according to any one of aspects 21 to 24, wherein:

[0161] R is isopropyl;

[0162] Q is chlorine;

[0163] M is Na + ;and

[0164] R 2 It is methyl.

[0165] Aspect 26. The method according to any one of aspects 21 to 25, wherein:

[0166] R is vinyl;

[0167] X is chlorine;

[0168] M is Na + ;and

[0169] R 2 It is methyl.

[0170] Aspect 27. The method according to any one of aspects 21 to 26, wherein:

[0171] M is Li + 、Na + , K + , Rb + , Cs + Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ 、Zn 2+ Sn 2+ or Sn 4+ .

[0172] Aspect 28. The method according to any one of aspects 21 to 27, wherein:

[0173] M is Sn 4+ .

[0174] Aspect 29. The method according to any one of aspects 21 to 28, wherein R 2 are independently hydrogen, C1-C 12 Alkyl, C1-C 12 Alkenyl, C1-C 12 The invention further comprises at least one of alkynyl, phenyl, fluorine, chlorine, bromine, iodine or any combination thereof.

[0175] Aspect 30. The method according to any one of aspects 21 to 29, wherein the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0176] RSn(OSiR 2 3)3,

[0177] in:

[0178] 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, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof; and

[0179] R 2 and independently at least one of hydrogen, halide, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkaryl or haloalkyl.

[0180] Aspect 31. The method according to any one of aspects 21 to 30, wherein the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0181]

[0182] in:

[0183] 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(C6H 5), -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 or -Si(CH3)3.

[0184] Aspect 32. The method according to any one of aspects 21 to 31, wherein the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0185]

[0186] Aspect 33. The method according to any one of aspects 21 to 32, wherein the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0187]

[0188] Aspect 34. A composition comprising:

[0189] The monosubstituted tin silicon alkoxide compound of the following formula:

[0190] RSn(OSiR 23)3,

[0191] in:

[0192] 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, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof; and

[0193] R 2 and independently at least one of hydrogen, halide, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkaryl or haloalkyl.

[0194] Aspect 35. The composition according to aspect 34, wherein the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0195]

[0196] in:

[0197] 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(C6H 5), -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 or -Si(CH3)3.

[0198] Aspect 36. The composition according to any one of aspects 34 to 35, wherein the monosubstituted tin silicon alkoxide compound is a compound of the formula:

[0199]

[0200] Aspect 37. The composition of aspect 36, wherein the mono-substituted tin silanol compound has a purity of at least 99.9%.

[0201] Aspect 38. The composition according to any one of aspects 34 to 37, wherein the mono-substituted tin siliconate compound is a siliconate compound of the formula:

[0202]

[0203] Aspect 39. The composition of aspect 38, wherein the mono-substituted tin silanol compound has a purity of at least 80%.

[0204] Aspect 40. The composition of any one of aspects 34 to 39, wherein the mono-substituted tin silanol compound has a purity of at least 99.9%.

[0205] It is to be understood that changes may be made in detail, particularly as to the construction materials employed and the shape, size and arrangement of parts without departing from the scope of the present disclosure.This specification and described embodiments are examples, with the true scope and spirit of the disclosure being indicated by the following claims.

Claims

1. A method comprising: contacting a monosubstituted tin(IV) compound with a silicon alkoxide reactant to form a monosubstituted tin silicon alkoxide compound; The monosubstituted tin (IV) compound comprises a compound of the following formula: RSnQ3, in: R is at least one of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amide, halide, imide, cyanate, nitrile, alkoxide, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof; Q is independently at least one of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, silanolate, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amide, halide, imide, cyanate, nitrile, alkoxide, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof; The silicon alkoxide reactant comprises a compound of the formula: M(OSiR 2 3) n , in: M is an alkali metal cation, an alkaline earth metal cation, a transition metal cation or a post-transition metal cation; R 2 is independently at least one of hydrogen, halide, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkaryl or haloalkyl; n is 1 to 4.

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

3. The method according to claim 1, wherein R is -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, At least one of -CH2Si(CH3)3, -Si(CH3)3, or any combination thereof.

4. The method according to claim 1, wherein Q is independently -H, -Cl, -Br, -F, -I, -NR 1 2. -OR 1 , -C≡CR 1 、-OSiR 1 3 or any combination thereof, in: R 1 The alkyl radicals are independently at least one of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, silyl, silylalkyl, silanolate, aminoalkyl, alkoxyalkyl, aralkyl, fluoroalkyl, haloalkyl, silylated alkoxide, ether, amine, halide, imide, cyanate, nitrile, alkoxide, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof.

5. The method according to claim 1, wherein: R is isopropyl; Q is chlorine; M is Na + ;and R 2 It is methyl.

6. The method according to claim 1, wherein: R is vinyl; X is chlorine; M is Na + ;and R 2 It is methyl.

7. The method according to claim 1, wherein: M is Li + 、Na + , K + , Rb + , Cs + Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ 、Zn 2+ Sn 2+ or Sn 4+ .

8. The method according to claim 1, wherein: M is Sn 4+ .

9. The method according to claim 1, wherein R 2 are independently hydrogen, C1-C 12 Alkyl, C1-C 12 Alkenyl, C1-C 12 The invention further comprises at least one of alkynyl, phenyl, fluorine, chlorine, bromine, iodine or any combination thereof.

10. The method according to claim 1, wherein the monosubstituted tin silicon alkoxide compound is a compound of the following formula: RSn(OSiR 2 3)3, in: 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, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof; and R 2 and independently at least one of hydrogen, halide, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkaryl or haloalkyl.

11. The method according to claim 1, wherein the monosubstituted tin silicon alkoxide compound is a compound of the following formula: in: R is -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, -CH2CN, -CN, -CH3, -CH2CH3, -CH 2CH2CH3, -CH(CH3)2, -CH(CH3)CH2CH3, -CH2CH(CH3)2, -C(CH3)3, -(CH2)3CH3, -C6H5, -CH 2(C6H5), -CH=CH2, -C≡CCH3, -CH2C≡CH, -CH2C≡CCH3, -C(CH3)=CH2, -HC=CHCH3, -CH2CH=CH 2. -CH2N(CH3)2, -(CH2)3N(CH3)2, -CH2CH2OCH3, -CH(CH2)2O, -CH2Si(CH3)3 or -Si(CH3)3.

12. The method according to claim 1, wherein the monosubstituted tin silicon alkoxide compound is a compound of the following formula:

13. The method according to claim 1, wherein the monosubstituted tin silicon alkoxide compound is a compound of the following formula:

14. A composition comprising: The monosubstituted tin silicon alkoxide compound of the following formula: RSn(OSiR 2 3)3, in: 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, carboxylate, enolate, ester, cyclopentadienyl, or any combination thereof; and R 2 and independently at least one of hydrogen, halide, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkaryl or haloalkyl.

15. The composition according to claim 14, wherein the monosubstituted tin silicon alkoxide compound is a compound of the formula: in: 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(C6H 5), -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 or -Si(CH3)3.

16. The composition according to claim 14, wherein the monosubstituted tin silicon alkoxide compound is a compound of the formula:

17. The composition of claim 16, wherein the mono-substituted tin siliconate compound has a purity of at least 99.9%.

18. The composition of claim 14, wherein the mono-substituted tin silicon alkoxide compound is a silicon alkoxide compound of the formula:

19. The composition of claim 18, wherein the mono-substituted tin silanol compound has a purity of at least 80%.

20. The composition of claim 14, wherein the mono-substituted tin siliconate compound has a purity of at least 99.9%.

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