Tin-containing precursors for the deposition of tin-containing thin films and their corresponding deposition processes - Patents.com

Abstract

[Solution] A method for forming a tin-containing film on a substrate includes exposing the substrate to a vapor or liquid of a film-forming composition including a tin-containing precursor having the general formula: (RSn)NR', ​​where R and R' are each independently H, a C1-C6 linear, branched, or cyclic alkyl group, or a C1-C4 linear, branched, or cyclic saturated hydrofluorocarbon group, and depositing at least a portion of the tin-containing precursor on the substrate using a deposition method to form a tin-containing film. Exemplary tin-containing precursors include (MeSn)NMe, (MeSn)NEt, (MeSn)N(nPr), (MeSn)N(nBu), and (MeSn)N(CH2CF3).

Description

[Technical field]

[0001] The present invention relates to a film-forming composition comprising a tin-containing precursor and a method of using the same to deposit a tin-containing film by chemical vapor deposition (CVD) or atomic layer deposition (ALD), and in particular to a compound having the general formula: (R3Sn)2NR' wherein R and R' are independently H, a C1-C6 straight chain, branched or cyclic alkyl group, or a C1-C4 straight chain, branched or cyclic saturated hydrofluorocarbon group. [Background technology]

[0002] Transparent Conductive Oxides (TCOs) have been widely investigated in both academia and industry for many front-running technologies, including liquid crystal displays, organic light-emitting diodes (OLEDs), touch screens, and solar cells. Among all TCOs, indium tin oxide (ITO), indium zinc oxide (IZO), and InO xIndium oxide, including In, has been established as a key component in the aforementioned applications due to its remarkable conductivity and electrical properties. For example, ITO is most utilized in the form of an oxygen-saturated composition with a formulation of 74% In, 18% O2, and 8% Sn, and is readily utilized as a component in liquid crystal displays, OLED displays, touch panels, and solar cells. In fact, the global market revenue for ITO exceeds US$1.5 billion and is expected to continue growing until at least 2025. However, despite the growing demand, the scarcity and high cost of indium have been a bottleneck in reducing the cost of indium-containing materials. Thus, there has been intensive development efforts to explore alternative TCOs that are composed of abundant resources and use less indium, especially tin-based materials such as SnO, SnO2, zinc tin oxide (ZTO), and fluorine-doped tin oxide (FTO). Indeed, for example, SnO2 is a chemically and thermally stable transparent n-type semiconducting oxide with high direct and indirect optical bandgaps of about 3.6 eV and about 2.6 eV, respectively. Its excellent electrical, optical and electrochemical properties have led to its use in thin-film solar cells, as a catalyst support material, in solid-state chemical sensors and for high-capacity lithium storage. Another material that has attracted much attention is ZrO2, whose thin films exhibit a wide band gap (~3.6 eV) and a valence band gap (~4 × 10 -3 and about 10 -3 Low electrical resistivity of Ωcm and approximately 10-15cm 2 V -1 s -1ZTO is an n-type semiconductor with the main crystal structures of ZnSnO3 and Zn2SnO4 consisting of ZnSnO3 and Zn2SnO4, which have high electron mobility of 100 nm. Due to such impressive properties, ZTO is considered as a cheap alternative to ITO and has been intensively studied as a building block for large-area flexible OLEDs, active materials in gas sensors, buffer layers in solar cells, and passivation layers in indium gallium zinc oxide (IGZO) thin-film transistors (TFTs). Nevertheless, the electrical properties of ZTO are not comparable to those of leading TCO materials such as ITO, mainly due to the difficulty in producing single-crystalline oxides and the localized disorder of tin in polycrystalline ZTO.

[0003] British Patent No. 1,043,609 to Oakes discloses that dialkyltin salts of organic acids are prepared by grinding together a dialkyltin oxide and an acid anhydride.

[0004] US Pat. No. 8,334,016 to Gordon et al. discloses that metal silicates or phosphates are deposited on a heated substrate by reaction of alkoxysilanol or alkylphosphate vapors with reactive metal amides, alkyls, or alkoxides.

[0005] U.S. Patent Application Publication No. 2018 / 0334471 to Park et al. discloses metal precursors having improved thermal stability and volatility and the use of the metal precursors to produce metal oxide thin films.

[0006] U.S. Patent Application Publication No. 2019 / 144472 to Ryu et al. discloses tin compounds, tin precursor compounds for ALD, methods for forming tin-containing material films, and methods for synthesizing tin compounds, the tin compounds having the chemical formula (I): [ka] (In the formula, R 1 , R 2 , Q 1 , Q 2 , Q 3 , and Q4 are each independently a C1 to C4 linear or branched alkyl group.

[0007] U.S. Patent Application Publication No. 2020 / 0231610 to Ryu et al. discloses tin compounds, tin precursor compounds for forming tin-containing layers, and methods for forming thin layers, wherein the tin compound has the formula (I): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently a straight chain alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 or 4 carbon atoms).

[0008] U.S. Patent Application Publication No. 2019 / 0390341 to Singhal et al. discloses ALD configured to deposit a metal oxide layer onto an organic photoresist on a substrate using organometallic precursors that are metalorganic tin precursors, such as aminotin-type precursors or methoxy-type precursors. Examples of aminotin-type precursors include dimethylaminodimethyltin (Me2Sn(NMe2)2), dimethylaminotrimethyltin (Me3Sn(MMe2), tetrakisdimethylaminotin (Sn(NMe2)4) or tetrakisdiethylaminotin (Sn(NEt2)4). Examples of methoxy-type precursors include dibutyldimethoxytin (Bu2Sn(OMe)2) or (b) aminotin and methoxy metalorganic tin precursors.

[0009] U.S. Patent Application Publication No. 2020 / 0223877 to Odedra discloses compounds useful for depositing high purity tin oxide. Such compounds have the formula: Rx-Sn-A 4-x where A is (Y a R' zeach R group is selected from the group consisting of alkyl or aryl groups having 1 to 10 carbon atoms; each R' group is independently selected from the group consisting of alkyl, acyl, or aryl groups having 1 to 10 carbon atoms; x is an integer from 0 to 4; a is an integer from 0 to 1; Y is selected from the group consisting of N, O, S, and P; and when Y is O, S or Y is absent, z is 1, and when Y is N or P, z is 2.

[0010] U.S. Patent Application Publication No. 2020 / 0002814 to Knisley et al. discloses tin-containing precursors and methods for forming tin-containing thin films. The tin precursors have tin-diazadiene bonds and are homoleptic or heteroleptic.

[0011] Kozima et al. (“Formation of an Organotin-Nitrogen Bond. II.1 Syntheses of Tris(trialkyltin)amines”, J. Org. Soc. 1964, 29, 907) disclose the preparation of tris(trialkyltin)amines (R3Sn)3N by reaction of lithium or sodium amide with triaryltin halides.

[0012] Jones et al. ("Amino-derivatives of Metals and Metalloids. Part I. Preparation of Aminostannanes, Stannylamines, and Stannazanes", J. Chem. Soc. 1965, 1944) have synthesized the aminostannanes RnSn(NR'2) 4-n discloses the preparation of amino derivatives of tin(IV), including stannylamine R3Sn·NHR and (R2Sn)3N, distannazanes (R3Sn)2NR', and cyclic tristannazanes (R2SnR)3.

[0013] Dimer et al. disclose the following ("Synthesis and Structure of Bis(trimethylstannyl)- and Bis(dimethylhalogenstannyl)amines: in the Roll of Stickstoff-Electron Devices", Chem. Ber. 1992, 125, 389).

[0014] Neumann et al. disclose the following ("New Building Blocks in Amide Chemistry-N-Lithiobis(trimethylstannyl)amine and N-Lithiotrimethylstannyl(trimethylsilyl)amine", Angew. Chem. Int. Ed. 2001, 40, 3405).

[0015] Elam et al. disclose the following ("Atomic Layer Deposition of Indium Tin Oxide Thin Films Using Nonhalogenated Precursors", J. Phys. Chem. C 2008, 112, 1938).

[0016] Elam et al. disclose the following ("Atomic layer deposition of tin oxide films using tetrakis(dimethylamino)tin", J. Vac. Sci. Technol. 2008, 26, 244).

[0017] Choi discloses the following ("The Fabrication of Tin Oxide Films by Atomic Layer Deposition using Tetrakis(Ethylmethylamino)Tin Precursor", Trans. Electr. Electron. Mater. 2009, 10, 200).

[0018] Choi discloses the following ("Effects of Seed Layer and Thermal Treatment on Atomic Layer Deposition-Grown Tin Oxide", Trans. Electr. Electron. Mater. 2010, 11, 222).

[0019] Prasittichai et al. disclose the following ("Surface Modification of SnO2 Photoelectrodes in Dye-Sensitized Solar Cells: Significant Improvements in Photovoltage via Al2O3 Atomic Layer Deposition", J. Phys. Chem. Lett. 2010, 1, 1611).

[0020] Mullings et al. disclose the following ("Tin oxide atomic layer deposition from tetrakis(dimethylamino)tin and water", J. Vac. Sci. Technol. A 2013, 31, 061503).

[0021] Choi et al. disclose the following ("Highly conductive SnO2 thin films deposited by atomic layer deposition using tetrakis-dimethyl-amine-tin precursor and ozone reactant", Surf. Coat. Technol. 2014, 259, 238).

[0022] Das et al. disclose the following ("SnO2: A comprehensive review on structures and gas sensors", Ceram. Int. 2019, 45, 5124).

[0023] It is important to emphasize that the above tin-containing materials are commonly utilized in the form of thin films, especially for display and coating applications. It is therefore desirable to establish techniques that minimize the deposition temperature of tin-containing thin films with sufficient conformality and crystallinity.

[0024] Strategies to incorporate tin into thin-film materials have progressed rapidly over the past decades, especially through dry physical methods such as chemical vapor deposition (CVD) and atomic layer deposition (ALD). In fact, numerous tin precursors have been developed so far, many of which consist of Sn centers in the +IV oxidation state. In particular, tetrakis(dimethylamino)tin (TDMASn, ((CH3)2N)4Sn, CAS number 1066-77-9) can be synthesized at temperatures below 100 °C upon reaction with H2O, O3, or H2O2 with or without plasma support. n O x It has been widely studied in both academia and industry, as it is one of the few liquid precursors capable of producing thin films of TDMASn. The process at low temperatures is particularly attractive for applications, for example, in coating displays and transparent devices, since too high a process temperature can destroy the underlying architecture. Despite its outstanding speciality, TDMASn has some notable drawbacks. For example, TDMASn is inconvenient for large-scale production, since it requires four molecules of dimethylaminolithium (Me2NLi), a pyrophoric organometallic reagent that is usually prepared by the reaction of dimethylamine with n-butyllithium, to synthesize one molecule. In addition, the volatility of TDMASn is rather low (0.1 Torr at 50 °C), which consequently limits its use, especially in large-scale supply. The limited volatility of TDMASn is due to its size as well as its high symmetry (point group = T d Attempts to improve the volatility of tetrakisamidotin derivatives have been made previously by desymmetrization through the incorporation of asymmetric amide ligands, i.e., ethylmethylamide groups, but this instead resulted in a worsening of volatility (0.4 Torr at 100 °C), presumably because the overall symmetry was still sufficiently high (point group = D 3d) Desymmetrization can also be achieved by preparing tetrakisamidotin complexes bearing two or more amide ligands, but no straightforward method for synthesizing such tin compounds has been developed to date. It is also worth noting that Me2HN is a gas that requires special handling.

[0025] There are several other tin precursors that are compatible with low-temperature deposition processes but have tin centers primarily in the +II oxidation state. For example, bis(hexamethyldisilylamino)tin (Sn(hmds)2), one of the rare stable diaminostannylenes, was found to yield tin oxide thin films at temperatures as low as 80°C and 100°C using O3 and H2O as reactive gases, respectively. Meanwhile, tin oxide thin films fabricated by using H2O as reactive gas were typically mixtures of SnO and SnO2, while those produced using O3 suffered from Si contamination resulting from the decomposition of hexamethyldisilazane (HMDS). In addition, Sn(hmds)2 has a low melting point of 37°C but is poorly volatile, recording only 0.05 torr at 112°C. In the case of bis(N-ethoxy-2,2-dimethylpropanamido)tin (Sn(edpa)2), a liquid Sn(II) precursor that does not contain silicon in its ligands, treatment with H2O at temperatures between 70 and 180 °C led to the formation of thin films of amorphous SnO without significant carbon and nitrogen contaminants. The aforementioned process is one of the rare examples that allows the production of SnO in the presence of only small amounts of Sn(IV) impurities. Alternatively, under the same temperature range, it is possible to produce pure polycrystalline SnO2 thin films by using O2 plasma as a co-reactant. Nevertheless, the volatility of Sn(edpa)2 is still insufficient (0.1 torr at 90 °C) and further improvements are needed.

[0026] Overall, there remains a need to develop new liquid Sn ALD precursors that are both sufficiently reactive and volatile at low temperatures. Summary of the Invention [Means for solving the problem]

[0027] A method for forming a tin-containing film on a substrate is disclosed, the method comprising: The substrate may be a compound having the general formula: (R3Sn)2NR' wherein R and R' are each independently H, a C1-C6 linear, branched or cyclic alkyl group, or a C1-C4 linear, branched or cyclic saturated hydrofluorocarbon group; and depositing at least a portion of the tin-containing precursor on the substrate using a chemical vapor deposition method to form a tin-containing film. The disclosed method may include one or more of the following features: Chemical vapor deposition includes ALD, CVD, MLD, SOD, SOC, mist coating, dip coating, slit coating, spray coating; Chemical vapor deposition is ALD; Chemical vapor deposition is CVD; Chemical vapor deposition is MLD; Chemical Vapor Deposition SOD; Chemical vapor deposition is SOC; Chemical vapor deposition is a mist coating; Chemical vapor deposition is dip coating; Chemical vapor deposition is slit coating; Chemical vapor deposition is a spray coating; · The deposition process may be assisted by heat, light, direct or remote plasma, or a combination thereof; · The deposition method may be unassisted by heat, light, direct or remote plasma, or a combination thereof; The deposition temperature for chemical vapor deposition is about 100°C or less; The deposition temperature for chemical vapor deposition is about 80°C or less; · The tin-containing precursor is liquid at ambient temperature; · The tin-containing precursor is volatile at temperatures below about 100°C; · Tin-containing precursors are volatile at temperatures below about 80°C; The tin-containing precursor is (Me3Sn)2NMe; The tin-containing precursor is (Me3Sn)2NEt; The tin-containing precursor is (Me3Sn)2N(nPr); The tin-containing precursor is (Me3Sn)2N(nBu); · The tin-containing precursor is (Me3Sn)2N(CH2CF3); · further comprising exposing the substrate to a co-reactant; · the co-reactant is an oxidizing agent selected from O2, O3, H2O, H2O2, NO, N2O, NO2, O radical, alcohol, silanol, aminoalcohol, carboxylic acid, para-formaldehyde, or mixtures thereof; · The coreactant is O3; · The coreactant is O2; · The coreactant is H2O2; · The coreactant is H2O; · The oxidant is O3; · The oxidant is O2; · The oxidizing agent is H2O2; The oxidant is H2O; · the co-reactant is a nitrogen-containing reducing agent selected from NH3, N2, H2, N2 / H2, H2 and NH3, N2 and NH3, NH3 and N2H4, NO, N2O, amines, diamines, cyanides, diimines, hydrazines, organic amines, pyrazolines, pyridines, primary amines such as methylamine, ethylamine, tertbutylamine, secondary amines such as dimethylamine, diethylamine, di-isopropylamine, ethylmethylamine, tertiary amines such as pyrrolidine, trimethylamine, triethylamine, trisilylamine, or mixtures thereof; The nitrogen-containing reductant is NH3; The tin-containing film is SnO2, InSnO (ITO), ZnSnO (ZTO), SnN, SnP, SnAs, SnSb or Sn2S3; · The tin-containing film is SnO2; · The tin-containing film is InSnO (ITO); The tin-containing film is ZnSnO (ZTO); · Tin-containing films are SnN; The tin-containing film is SnP; The tin-containing film is SnAs; The tin-containing film is SnSb; · The tin-containing film is Sn2S3; the tin-containing film contains a second element selected from Zn, In, Ga, N, S, P, As, Sb, B, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, Bi, Pb, Co, one or more lanthanides, or mixtures thereof; The substrate is a powder; and The powder includes one or more of NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode active materials.

[0028] Also, the general formula: (R3Sn)2NR' Disclosed are film-forming compositions for vapor deposition processes comprising a tin-containing precursor having the formula: wherein R and R' are each independently H, a C1-C6 linear, branched or cyclic alkyl group, or a C1-C4 linear, branched or cyclic saturated hydrofluorocarbon group. The disclosed compositions can include one or more of the following features: the tin-containing precursor is selected from the group consisting of (Me3Sn)2NMe, (Me3Sn)2NEt, (Me3Sn)2N(nPr), (Me3Sn)2N(nBu) and (Me3Sn)2N(CH2CF3); · The purity of the tin-containing precursor is greater than 99%; the tin-containing precursor is liquid at ambient temperature; and · Tin-containing precursors are volatile at temperatures below about 100°C.

[0029] Notation and Terminology The following detailed description and claims utilize a number of abbreviations, symbols, and terms that are commonly known in the art. Certain abbreviations, symbols, and terms are used throughout the following description and claims, including the following:

[0030] As used herein, the indefinite articles "a" or "an" mean one or more.

[0031] As used herein, in the text or claims, "about" or "approximately" or "approximately" means ±10% of the stated value.

[0032] As used herein, "room temperature" in the text and claims means about 20°C to about 25°C.

[0033] The term "ambient temperature" refers to an environmental temperature of about 20°C to about 25°C.

[0034] The term "substrate" refers to one or more materials on which a process is performed. A substrate may refer to a wafer having one or more materials on which a process is performed. The substrate may be any suitable wafer used in the manufacture of semiconductors, solar cells, flat panels, or LCD-TFT devices. The substrate may also have one or more layers of different materials already deposited thereon from a previous manufacturing step. For example, the wafer may include a silicon layer (e.g., crystalline, amorphous, porous, etc.), a silicon-containing layer (e.g., SiO2, SiN, SiON, SiCOH, etc.), a metal-containing layer (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.), or a combination thereof. Furthermore, the substrate may be flat or patterned. The substrate may be an organic patterned photoresist film. The substrate may include a layer of oxide (e.g., ZrO2-based material, HfO2-based material, TiO2-based material, rare earth oxide-based material, ternary oxide-based material, etc.) used as a dielectric material in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications, or a nitride-based film (e.g., TaN, TiN, NbN) used as an electrode. Those skilled in the art will recognize that the term "film" or "layer" as used herein refers to a thickness of any material disposed or extending over a surface, which may be a trench or line. Throughout this specification and claims, the wafer and any associated layers thereon are referred to as the substrate.

[0035] The term "wafer" or "patterned wafer" refers to a wafer having a stack of films on a substrate, with at least the topmost film having topographical features created in a step prior to the deposition of an indium-containing film.

[0036] The term "aspect ratio" refers to the ratio of the height of a trench (or aperture) to the width of the trench (diameter of the aperture).

[0037] It should be noted that, as used herein, the terms "film" and "layer" may be used interchangeably. It is understood that a film may correspond to or relate to a layer, and a layer may refer to a film. Furthermore, one of ordinary skill in the art will recognize that the terms "film" or "layer" as used herein refer to a thickness of any material disposed or spread over a surface, which may be as large as an entire wafer or as small as a trench or line.

[0038] It should be noted that the terms "aperture," "via," "hole," and "trench" may be used interchangeably herein and refer to openings formed in a semiconductor structure.

[0039] As used herein, the abbreviation "NAND" refers to a "Negative AND" or "Not AND" gate; the abbreviation "2D" refers to a two-dimensional gate structure on a flat substrate; and the abbreviation "3D" refers to a three-dimensional or vertical gate structure in which the gate structures are stacked vertically.

[0040] It should be noted that, in this specification, the terms "deposition temperature" and "substrate temperature" may be used interchangeably. It is understood that substrate temperature may correspond to or be related to deposition temperature, and deposition temperature may refer to substrate temperature.

[0041] The term "film-forming composition" refers to a composition used for deposition of a film. The film-forming composition may include, but is not limited to, a precursor, a solvent, and / or a carrier gas. Additionally, the film-forming composition may include, but is not limited to, a precursor, an optional solvent, an optional carrier gas, and optionally one or more co-reactants. Herein, the precursor may be provided either in neat form or in a blend with a suitable solvent. The precursor may be present in the solvent at various concentrations. Alternatively, the precursor may be vaporized by passing a carrier gas through a vessel containing the precursor or by bubbling the carrier gas through the precursor. The carrier gas and precursor are then introduced into the reactor as described above. The co-reactant may be an oxidizing agent, a reducing agent, a diluent gas, an additive, an additional or secondary precursor, etc. to aid in the formation of the film. Herein, an inert gas selected from N2, Ar, Kr, Xe may be used as a carrier gas and / or a diluent gas.

[0042] It should be noted that, in this specification, the terms "precursor" and "deposition compound" and "deposition gas" can be used interchangeably when the precursor is in a gaseous state at room temperature and ambient pressure. It is understood that a precursor can correspond to or be associated with a deposition compound or deposition gas, and a deposition compound or deposition gas can refer to a precursor.

[0043] Standard abbreviations of elements from the periodic table are used herein. It should be understood that elements can be referred to by these abbreviations (e.g., Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, H refers to hydrogen, F refers to fluorine, etc.).

[0044] Unique CAS Registry Numbers assigned by the Chemical Abstract Service (ie, "CAS") are provided to identify the particular molecules disclosed.

[0045] It should be noted that silicon-containing films such as SiN and SiO are recited throughout this specification and claims without reference to their appropriate stoichiometry. Silicon-containing films include pure silicon (Si) layers such as crystalline Si, polysilicon (p-Si or polycrystalline Si), or amorphous silicon; silicon nitride (Si k N l ) layer; or silicon oxide (Si n O m ) layer; or a mixture thereof, where k, l, m, and n are in the range of 0.1 to 6 inclusive. Preferably, the silicon nitride is Si k N l where k and l are each in the range of 0.5 to 1.5. More preferably, the silicon nitride is Si3N4. In the following description of this specification, SiN is Si k N l It can be used to represent the containing layer. Preferably, silicon oxide is Si n O m Here, n is in the range of 0.5 to 1.5, and m is in the range of 1.5 to 3.5. More preferably, the silicon oxide is SiO2. In the following description, SiO means Si n O m It can be used to represent a containing layer. The silicon-containing film can also be a silicon oxide-based dielectric material, such as an organic-based or silicon oxide-based low-k material, for example, Black Diamond II or III material by Applied Materials, Inc., which has the formula SiOCH. The silicon-containing film can also be Si a O b N c where a, b, and c range from 0.1 to 6. The silicon-containing film may also include dopants from groups III, IV, V, and VI, such as B, C, P, As, and / or Ge.

[0046] Deposited films or layers such as silicon oxide or silicon nitride may be recited throughout this specification and claims without reference to their appropriate stoichiometry (i.e., SiO, SiO2, Si3N4). The layers may be pure (Si) layers, carbide (Si o C p ) layer, nitride (Si k N l ) layer, oxide (Si n O m ) layers, or mixtures thereof, where k, l, m, n, o, and p range from 1 to 6, inclusive. For example, silicon oxide can be represented by the formula: Si n O m where n is in the range of 0.5 to 1.5, and m is in the range of 1.5 to 3.5. More preferably, the silicon oxide layer is SiO or SiO2. The silicon oxide layer can be a silicon oxide-based dielectric material, such as an organic-based or silicon oxide-based low-k material, for example, Black Diamond II or III material by Applied Materials, Inc., which has the formula SiOCH. Alternatively, any silicon-containing layer mentioned may be pure silicon. Any silicon-containing layer may also include dopants, such as B, C, P, As and / or Ge.

[0047] As used herein, the term "hydrocarbon" refers to a saturated or unsaturated functional group that contains exclusively carbon and hydrogen atoms. As used herein, the term "alkyl group" refers to a saturated functional group that contains exclusively carbon and hydrogen atoms. An alkyl group is a type of hydrocarbon. Furthermore, the term "alkyl group" refers to a straight-chain, branched, or cyclic alkyl group. Examples of straight-chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, and the like. Examples of branched alkyl groups include, but are not limited to, t-butyl. Examples of cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, and the like.

[0048] As used herein, the abbreviation "Me" refers to a methyl group; the abbreviation "Et" refers to an ethyl group; the abbreviation "Pr" refers to any propyl group (i.e., n-propyl or isopropyl); the abbreviation "iPr" refers to an isopropyl group; the abbreviation "Bu" refers to any butyl group (n-butyl, iso-butyl, tert-butyl, sec-butyl); the abbreviation "tBu" refers to a tert-butyl group; the abbreviation "sBu" refers to a sec-butyl group; the abbreviation "iBu" refers to an iso-butyl group; the abbreviation "Ph" refers to a phenyl group; the abbreviation "Am" refers to any amyl group (iso-amyl, sec-amyl, tert-amyl); the abbreviation "Cy" refers to a cyclic hydrocarbon group (cyclobutyl, cyclopentyl, cyclohexyl, etc.); and the abbreviation "Ar" refers to an aromatic hydrocarbon group (phenyl, xylyl, mesityl, etc.).

[0049] Ranges may be expressed herein as from about one particular value and / or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and / or to the other particular value, along with all combinations within said ranges. All ranges recited herein include their endpoints (i.e., x=1-4 or x is a range from 1-4 includes x=1, x=4, and x=any number therebetween), regardless of whether the term "inclusive" is used.

[0050] References herein to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of the invention. The appearances of the phrase "in one embodiment" in various places in the specification do not necessarily all refer to the same embodiment, and alternative or alternate embodiments are not necessarily mutually exclusive of other embodiments. The same applies to the term "implementation."

[0051] As used herein, the term "independently" when used in reference to a description of an R group should be understood to mean that the R group in question is selected independently not only from other R groups having the same or different subscripts or superscripts, but also from any additional species of the same R group. For example, the formula MR 1 x (NR 2 R 3 ) (4-x) (wherein x is 2 or 3), 1 The groups may be mutually or mutually 2 Or R 3 It is to be further understood that unless specifically stated otherwise, the values ​​of R groups are independent of each other when used in different formulas.

[0052] As used in this application, the term "exemplary" is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete form.

[0053] Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless expressly stated otherwise or clear from the context, "X uses A or B" is intended to mean any of the natural inclusive permutations. That is, if X uses A, if X uses B, or if X uses both A and B; in any of the foregoing cases, "X uses A or B" is satisfied. In addition, the articles "a" and "an" as used in this application and the appended claims should generally be construed to mean "one or more" unless expressly stated otherwise or clear from the context to refer to the singular form.

[0054] "Comprising" in the claims is an open transitional term meaning that the claim elements identified thereafter are a non-exclusive list (i.e., other elements may additionally be included and remain within the scope of "comprising"). "Comprising" may be replaced by the more restrictive transitional terms "consisting essentially of" or "consisting of" and remain within the expressly defined scope of "comprising."

[0055] "Providing" in the claims is defined to mean modifying, supplying, making available, or preparing something. Steps, to the contrary, may be performed in any relationship in the absence of specific language in the claims.

[0056] For a further understanding of the nature and objects of the present invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings, in which like elements are given the same or similar reference numerals and in which: [Brief description of the drawings]

[0057]

Figure 1

Figure 2

Figure 3

Figure 4

[0058] Disclosed is a film-forming composition comprising a tin-containing precursor and a method of using the same to deposit tin-containing films by chemical vapor deposition (CVD) or atomic layer deposition (ALD) for applications in electronics, displays and coatings. The tin-containing films include tin oxide films, S n O x (where x varies from 1 to 2 inclusive), and indium tin oxide In 2-y Sn y O3 (ITO) (wherein indium and tin are in various concentrations and y varies from 0 to 1, preferably from 0 to 0.2), zinc tin oxide ZnSnO (ZTO) (wherein Sn and Zn are in various concentrations and preferably Zn:Sn is in a 1:1 ratio), fluorine tin oxide SnO2:F (FTO) (wherein part of the oxygen in tin(IV) oxide is replaced by fluorine). Disclosed is the development of tin-based precursors for the formation of tin-containing thin films by other chemical vapor deposition methods such as CVD, ALD or MLD, SOD, SOC, mist coating, dip coating, slit coating, spray coating, particularly at low temperatures such as 100°C or less, preferably 80°C or less. The tin-containing precursors disclosed herein likely meet such characteristics and can be a good replacement for existing tin-containing precursors currently utilized. Typical applications of the deposited tin-containing films include liquid crystal displays (LCDs), flat panel displays, smart windows, transparent electrodes, antistatic coatings, thin film solar cells, glass coatings, solar cells, transistors, gas sensors, heat shields, etc.

[0059] As mentioned above, TDMASn is a moisture-sensitive molecule that decomposes rapidly in air to produce Me2NH and SnO2. This high reactivity arises from the presence of labile Sn-N bonds that play a key role in facilitating chemisorption on the target substrate. In fact, many of the tin-containing precursors suitable for low-temperature ALD of Sn-containing films tend to have multiple Sn-N bonds, regardless of the oxidation state of the metal center.

[0060] The tin-containing precursors disclosed are a class of amines having two stannyl groups, namely distannazanes, which have the general formula: (R3Sn)2NR' where R and R' are each independently H, a C1-C6 linear, branched or cyclic alkyl group, or a C1-C4 linear, branched or cyclic saturated hydrofluorocarbon group. Results of several previously synthesized and characterized distannazanes have shown that (Me3Sn)2NR' (where R' = Me or Et) are liquids at ambient temperature with excellent volatility (e.g., 4 Torr at 64°C for (Me3Sn)2NMe and 15 Torr at 93°C for (Me3Sn)2NEt). The distannazanes disclosed herein can be used as volatile precursors, as an alternative to TDMASn, to obtain films, including thin films, of Sn-containing materials such as SnO2, ITO, and ZTO by chemical vapor deposition methods, including but not limited to CVD and ALD.

[0061] The advantage of this family of chemicals is that the thermal properties can be tuned by simply replacing the substituents on the nitrogen center, typically alkyl groups. Such substituents can be easily varied by utilizing the corresponding secondary amines, many of which are inexpensive and commercially available. Furthermore, the synthesis of all of the tin-containing precursors disclosed herein is accomplished in either a one-step or two-step synthesis, demonstrating the convenience for large-scale production.

[0062] Illustrative examples of the disclosed tin-containing precursors are as follows: [ka]

[0063] The above disclosed tin-containing precursors are all liquid at ambient temperature with excellent volatility and thermal stability, and therefore easily purified by distillation, and are suitable for use as precursors for chemical vapor deposition such as CVD, ALD, or other chemical vapor deposition methods such as MLD, SOD, SOC, mist coating, dip coating, slit coating, spray coating, especially at low temperatures such as below 100° C., preferably below 80° C.

[0064] Furthermore, disclosed tin-containing precursors for the deposition of tin-containing thin films include (Me3Sn)2N(Cyclo-Pr), (Me3Sn)2N(sBu), (Me3Sn)2N(Cyclo-Bu), (Me3Sn)2N(1-Pen), (Me3Sn)2N(2-Pen), (Me3Sn)2N(3-Pen), (Me3Sn)2N(tPen), (Me3Sn)2N(Neo-Pen), (Me3Sn)2N(Cyclo-Pen), (Me3Sn)2N(2-Hex), (Me3Sn)2N(3-Hex), (Me3Sn)2N(tHex), (Me3Sn)2N(Neo-Hex), (Me3Sn)2N(Cyclo-Hex), (Me3Sn)2N(CH2CF2CF3), (Me3Sn)2N(CH(CF3)2), (Me3Sn)2N(CH2(CF2)2CF3), (Me3Sn)2N(SiHMe2), (Me3Sn)2N(SiEtMe2), (Me3Sn)2N(SiEt2Me), (Me3Sn)2N(SiEt3), (Et3Sn)2NMe, (Et3Sn)2NEt, (Et3Sn)2N(nPr), (Et3Sn)2N(iPr), (Et3Sn)2N(Cyclo-Pr), (Et3Sn)2N(nBu), (Et3Sn)2N(sBu), (Et3Sn)2N(iBu), (Et3Sn)2N(tBu), (Et3Sn)2N(CH2CF3), (Et3Sn)2N(CH2CF2CF3), (Et3Sn)2N(Cyclo-Bu), (Et3Sn)2N(1-Pen), (Et3Sn)2N(2-Pen), (Et3Sn)2N(3-Pen), (Et3Sn)2N(tPen), (Et3Sn)2N(Neo-Pen), (Et3Sn)2N(Cyclo-Pen), (Et3Sn)2N(1-Hex), (Et3Sn)2N(2-Hex), (Et3Sn)2N(3-Hex), (Et3Sn)2N(tHex), (Et3Sn)2N(Neo-Hex), (Et3Sn)2N(Cyclo-Hex), (Et3Sn)2N(allyl), (Et3Sn)2N(CH(CF3)2), (Et3Sn)2N(CH2(CF2)2CF3), (Et3Sn)2N(SiMe3), (Et3Sn)2N(SiHMe2), (Et3Sn)2N(SiEtMe2), (Et3Sn)2N(SiEt2Me), (Et3Sn)2N(SiEt3), (nPr3Sn)2NMe, (nPr3Sn)2NEt, (nPr3Sn)2N(nPr),<h2 style=";text-align:left;direction:ltr">(nPr3Sn)2N(iPr)、(nPr3Sn)2N(iPr)、(nPr3Sn)2N(nBu)、(nPr3Sn)2N(sBu)、(nPr3Sn)2N(tBu)、(nPr3Sn)2N(iPen)、(nPr3Sn)2N(1Pen)、(nP r3Sn)2N(2-Pen)、(nPr3Sn)2N(3-Pen)、(nPr3Sn)2N(tPen)、(nPr3Sn)2N(Ti-Pen)、(nPr3Sn)2N(Ti-Pen)、(nPr3Sn)2N(Ti-Pen)、(nPr3Sn)2N(1-Hex)、(nPr3Sn)2N(2-Hex )、(nPr3Sn)2N(3-Hex)、(nPr3Sn)2N(tHex)、(nPr3Sn)2N(ネオ-Hex)、(nPr3 Sn)2N(シクロ-Hex)、(nPr3Sn)2N(アリル)、(nPr3Sn)2N(CH2CF3)、(nPr3Sn)2N(C) H2CF3CF3)、(nPr3Sn)2N(CH(CF3)2)、(nPr3Sn)2N(CH2(CF2)2CF3)、(nPr3Sn)2N(SiMe3)、(nPr3Sn)2N(SiHMe2)、(nPr3Sn)2N(SiEtMe2)、(nPr3Sn)2N( SiEt2Me)、(nPr3Sn)2N(SiEt3)、(nPr3Sn)2NH、(nBu3Sn)2NMe、(nBu3Sn)2NEt、(nBu3Sn)2NMe、(nBu3Sn)2N(nPr)、(nBu3Sn)2N(iPr)、(nBu3Sn)2N(Ni (Pr)、(nBu3Sn)2N(nBu)、(nBu3Sn)2N(sBu)、(nBu3Sn)2N(tBu)、(nBu3Sn)2N(tBu)、(nBu3Sn)2N(1-Pen)、(nBu3Sn)2N(2-Pen)、(nBu3Sn)2N(3-Pe) n)、(nBu3Sn)2N(tPen)、(nBu3Sn)2N(ネオ-Pen)、(nBu3Sn)2N(シクロ-Pen)、(n Bu3Sn)2N(1-Hex)、(nBu3Sn)2N(2-Hex)、(nBu3Sn)2N(3-Hex)、(nBu3Sn)2N (tHex)、(nBu3Sn)2N(tHex)、(nBu3Sn)2N(tHex)、(nBu3Sn)2N(tHex)、(nBu3Sn)2N(tHex)、(nBu3Sn)2N(CH2CF3)、(nBu3Sn)2N(CH(CF3)2)、<h2 style=";text-align:left;direction:ltr">(nBu3Sn)2N(CH2(CF2)2CF3)、 (nBu3Sn)3N, (nBu3Sn)2N(SiMe3), (nBu3Sn)2N(SiHMe2), (nBu3Sn)2N(SiEtMe2), (nBu3Sn)2N(SiEt2Me), (nBu3Sn)2N(SiEt3), (nBu3Sn)2N(SiEt3), (nBu3Sn)2N(SiEt3), (nBu3Sn)2NH, (nPen3Sn)2NMe, (nPen3Sn)2NEt, (nPen3Sn)2N(nPr), (nPen3Sn)2N(iPr), (nPen3Sn)2N(Pr), (nPen3Sn)2N(nBu), (nPen3Sn) )2N(sBu)、(nPen3Sn)2N(tBu)、(nPen3Sn)2N(Bu)、(nPen3Sn)2N(1-Pen)、(nPen3Sn)2N(2-Pen)、(nPen3Sn)2N(3-Pen)、(nPen3Sn)2N(tPen)、(nPen3Sn)2N(Ti-Pen)、(nPen3Sn)2N(1-Hex)、(nPen3Sn)2N(2-Hex)、(nPen3Sn)2N(3-Hex)、(nPen3 Sn)2N(tHex)、(nPen3Sn)2N(SiMe3)、(nPen3Sn)2N(SiHMe2)、(nPen3Sn)2N(SiHMe2)、(nPen3Sn)2N(SiHMe2)、(nPen3Sn)2N(SiHMe2) iEtMe2)、(nPen3Sn)2N(SiEt2Me)、(nPen3Sn)2N(SiEt3)、(nPen3Sn)2NH、(nHex3Sn)2NMe、(nHex3Sn)2NEt、(nHex3Sn)2NMe、(nHex3Sn)2NEt、(nHex3Sn)2N(nPr)、(nHex3Sn)2N(iPr)、(nHex3Sn)2N(NiPr)、(nHex3Sn)2N(nBu)、(nHex3Sn)2N(sBu)、(nHex3Sn)2N(tBu)、(n、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">Hex3Sn)2N(Bu-Bu)、(nHex3Sn)2N(1-Pen)、(nHex3Sn)2N(2-Pen)、(nHex3Sn)2N(3-Pen)、(nHex3Sn)2N(tPen)、(nHex3Sn)2N(Bu-Pen)、(nHex3Sn)2N (シクロ-Pen)、(nHex3Sn)2N(1-Hex)、(nHex3Sn)2N(2-Hex)、(nHex3Sn)2N(3- Hex)、(nHex3Sn)2N(tHex)、(nHex3Sn)2N(ネオ-Hex)、(nHex3Sn)2N(シクロ-Hex) (nHex3Sn)2N(His)、(nHex3Sn)2N(CH2CF3)、(nHex3Sn)2N(CH2CF3)、(nHex3Sn)2N(CH(CF3)2)、(nHex3Sn)2N(CH2(CF2)2CF3)、(nHex3Sn)3N、(nHe x3Sn)2N(SiMe3)、(nHex3Sn)2N(SiHMe2)、(nHex3Sn)2N(SiEtMe2)、(nHex3Sn)2N(SiEt2Me)、(nHex3Sn)2N(SiEt3)、(nHex3Sn)2NH、(EtMe2Sn)2NMe、(E tMe2Sn)2NEt、(EtMe2Sn)2NMe、(EtMe2Sn)2NEt、(EtMe2Sn)2N(nPr)、(EtMe2Sn)2N(iPr)、(EtMe2)2N(Ni-Pr)、(EtMe2)2N(nBu)、(EtMe2Sn)2N(sBu)、 (EtMe2Sn)2N(tBu)、(EtMe2)2N(Bu-Bu)、(EtMe2Sn)2N(1-Pen)、(EtMe2Sn)2N(2-Pen)、(EtMe2Sn)2N(3-Pen)、(EtMe2Sn)2N(tPen)、(EtMe2Sn)2N(Ki- Pen)、(EtMe2Sn)2N(Pen-Pen)、(EtMe2Sn)2N(1-Hex)、(EtMe2Sn)2N(2-Hex)、(EtMe2Sn)2N(3-Hex)、(EtMe2Sn)2N(tHex)、(EtMe2Sn)2N(Shin-Hex)、(EtM e2Sn)2N(Hydroxy-Hex)、(EtMe2Sn)2N(Hydroxy-Hex)、(EtMe2Sn)2N(CH2CF3)、(EtMe2Sn)2N(CH2CF3)CF3)、(EtMe2Sn)2N(CH(CF3)2)、(EtMe2Sn)2N(CH2(CF2)2CF3)、<h2 style=";text-align:left;direction:ltr">(EtMe2Sn)3N、(EtMe2Sn)2N(SiMe3)、(EtMe2Sn)2N(SiHMe2)、(EtMe2Sn)2N(SiEtMe2)、(EtMe2Sn)2N(SiEt2Me)、(EtMe2Sn)2N(SiEt3)、(EtMe2Sn)2NH (nPrMe2Sn)2NMe, (nPrMe2Sn)2NEt, (nPrMe2Sn)2NMe, (nPrMe2Sn)2NEt, (nPrMe2Sn)2N(nPr), (nPrMe2Sn)2N(iPr), (nPrMe2)2N(iPr), (nPrMe2)2 N(nBu)、(nPrMe2Sn)2N(sBu)、(nPrMe2Sn)2N(tBu)、(nPrMe2)2N(tBu)、(nPrMe2)2N(1-Pen)、(nPrMe2Sn)2N(2-Pen)、(nPrMe2Sn)2N(3-Pen)、(n PrMe2Sn)2N(tPen)、(nPrMe2Sn)2N(ネオ-Pen)、(nPrMe2Sn)2N(シクロ-Pen)、(n PrMe2Sn)2N(1-Hex)、(nPrMe2Sn)2N(2-Hex)、(nPrMe2Sn)2N(3-Hex)、(nPrM e2Sn)2N(tHex)、(nPrMe2Sn)2N(ネオ-Hex)、(nPrMe2Sn)2N(シクロ-Hex)、(nPrM e2Sn)2N(アリル)、(nPrMe2Sn)2N(CH2CF3)、(nPrMe2Sn)2N(CH2CF3CF3)、(nPr Me2Sn)2N(CH(CF3)2)、(nPrMe2Sn)2N(CH2(CF2)2CF3)、(nPrMe2Sn)3N、(nPrMe2Sn)2N(SiMe3)、(nPrMe2Sn)2N(SiHMe2)、(nPrMe2Sn)2N(SiEtMe2)、(nPrMe2Sn)2N(SiEt2Me)、(nPrMe2Sn)2N(SiEt3)、(nPrMe2Sn)2NH、(iPrMe2Sn)2NMe、(iPrMe2Sn)2NEt、(iPrMe2Sn)2N(nPr)、(iPrMe2Sn)2N(iPr)、(iPrM e2)2N(Pr-Pr)、(iPrMe2)2N(nBu)、(iPrMe2Sn)2N(sBu)、(iPrMe2Sn)2N(tBu)、(iPrMe2)2N(Pr-Bu)、(iPrMe2Sn)2N(1-Pen)、(iPrMe2Sn)2N(2-Pen)、<h2 style=";text-align:left;direction:ltr">(iPrMe2Sn)2N(3-Pen)、(iPrMe2Sn)2N(tPen)、(iPrMe2Sn)2N(ネオ-Pen)、(i PrMe2Sn)2N(シクロ-Pen)、(iPrMe2Sn)2N(1-Hex)、(iPrMe2Sn)2N(2-Hex)、(i PrMe2Sn)2N(3-Hex)、(iPrMe2Sn)2N(tHex)、(iPrMe2Sn)2N(ネオ-Hex)、(iPr Me2Sn)2N(シクロ-Hex)、(iPrMe2Sn)2N(アリル)、(iPrMe2Sn)2N(CH2CF3)、(iPrMe 2Sn)2N(CH2CF3CF3)、(iPrMe2Sn)2N(CH(CF3)2)、(iPrMe2Sn)2N(CH2(CF2)2CF3)、(iPrMe2Sn)2N(SiMe3)、(iPrMe2Sn)2N(SiHMe2)、(iPrMe2Sn)2N(SiEtMe2)、(iPrMe2Sn)2N(SiEt2Me)、(iPrMe2Sn)2N(SiEt3)、(iPrMe2Sn)2NH、(nBuMe2Sn)2NMe、(nBuMe2Sn)2NEt、(nBuMe2Sn)2NMe、(nBuMe2Sn)2NEt、(nB uMe2Sn)2N(nPr)、(nBuMe2Sn)2N(iPr)、(nBuMe2)2N(iPr)、(nBuMe2)2N(nBu)、(nBuMe2Sn)2N(sBu)、(nBuMe2Sn)2N(tBu)、(nBuMe2)2N(iBu)、(n BuMe2Sn)2N(1-Pen)、(nBuMe2Sn)2N(2-Pen)、(nBuMe2Sn)2N(3-Pen)、(nBuMe2Sn)2N(tPen)、(nBuMe2Sn)2N(Single-Pen)、(nBuMe2Sn)2N(Single-Pen)、(nBuM e2Sn)2N(1-Hex)、(nBuMe2Sn)2N(2-Hex)、(nBuMe2Sn)2N(3-Hex)、(nBuMe2 Sn)2N(tHex)、(nBuMe2Sn)2N(ネオ-Hex)、(nBuMe2Sn)2N(シクロ-Hex)、(nBuMe2S n)2N(BuMe2Sn)2N(CH2CF3)、(nBuMe2Sn)2N(CH2CF3)、(nBuMe2Sn)2N(CH(CF3)2)、(nBuMe2Sn)2N(CH2(CF2)2CF3)、(nBuMe2Sn)3N、(nBuMe、<h2 style=";text-align:left;direction:ltr">2Sn)2N(SiMe3)、(nBuMe2Sn)2N(SiHMe2)、(nBuMe2Sn)2N(SiEtMe2)、(nBuMe2Sn)2N(SiEt2Me)、(nBuMe2Sn)2N(SiEt3)、(nBuMe2Sn)2NH、(sBuMe2Sn)2NMe、(sBuMe2Sn)2NEt、(sBuMe2Sn)2NMe、(sBuMe2Sn)2NEt、(sBuMe2Sn)2N(nPr)、(sBuMe2Sn)2N(iPr)、(sBuMe2)2N(Pr)、(sBuMe2)2N(nBu)、(sBu (Me2Sn)2N(sBu)、(sBuMe2Sn)2N(tBu)、(sBuMe2)2N(sBu-Bu)、(sBuMe2Sn)2N(1-Pen)、(sBuMe2Sn)2N(2-Pen)、(sBuMe2Sn)2N(3-Pen)、(sBuMe2Sn)2N( tPen)、(sBuMe2Sn)2N(ネオ-Pen)、(sBuMe2Sn)2N(シクロ-Pen)、(sBuMe2Sn)2N( 1-Hex)、(sBuMe2Sn)2N(2-Hex)、(sBuMe2Sn)2N(3-Hex)、(sBuMe2Sn)2N(tHe x)、(sBuMe2Sn)2N(Hex-Hex)、(sBuMe2Sn)2N(Hex-Hex)、(sBuMe2Sn)2N(Hex)、(sBuMe2Sn)2N(Hex)、(sBuMe2Sn)2N(CH2CF3)、(sBuMe2Sn)2N(CH2CF3CF3)、(sBuMe2Sn)2N(CH(CF3)2)、(sBuMe2Sn)2N(CH2(CF2)2CF3)、(sBuMe2Sn)3N、(sBuMe2Sn)2N(SiMe3)、(sBuMe2Sn)2N(SiHMe2)、(sBuMe2Sn)2N(SiEtMe2)、(sBuMe2Sn)2N( (SiEt2Me)、(sBuMe2Sn)2N(SiEt3)、(sBuMe2Sn)2NH、(tBuMe2Sn)2NMe、(tBuMe2Sn)2NEt、(tBuMe2Sn)2NMe、(tBuMe2Sn)2NEt、(tBuMe2Sn)2N(nPr)、(tB uMe2Sn)2N(iPr)、(tBuMe2)2N(iPr)、(tBuMe2)2N(nBu)、(tBuMe2Sn)2N(sBu)、(tBuMe2Sn)2N(tBu)、(tBuMe2)2N(iPen)、<h2 style=";text-align:left;direction:ltr">(tBuMe2Sn)2N(2-Pen)、(tBuMe2Sn)2N(3-Pen)、(tBuMe2Sn)2N(tPen)、(tB uMe2Sn)2N(ネオ-Pen)、(tBuMe2Sn)2N(シクロ-Pen)、(tBuMe2Sn)2N(1-Hex)、(tB uMe2Sn)2N(2-Hex)、(tBuMe2Sn)2N(3-Hex)、(tBuMe2Sn)2N(tHex)、(tBuMe 2Sn)2N(ネオ-Hex)、(tBuMe2Sn)2N(シクロ-Hex)、(tBuMe2Sn)2N(アリル)、(tBuMe2S n)2N(CH2CF3)、(tBuMe2Sn)2N(CH2CF3CF3)、(tBuMe2Sn)2N(CH(CF3)2)、(tBuMe2Sn)2N(CH2(CF2)2CF3)、(tBuMe2Sn)3N、(tBuMe2Sn)2N(SiMe3)、(tBuMe2Sn)2N(SiHMe2)、(tBuMe2Sn)2N(SiEtMe2)、(tBuMe2Sn)2N(SiEt2Me)、(tBuMe2Sn)2N(SiEt3)、(tBuMe2Sn)2NH、(Me2HSn)2NMe、(Me2HSn)2NEt、(Me2H Sn)2N(nPr)、(Me2HSn)2N(iPr)、(Me2HSn)2N(Sn-Pr)、(Me2HSn)2N(nBu)、(Me2HSn)2N(sBu)、(Me2HSn)2N(iBu)、(Me2HSn)2N(tBu)、(Me2HSn)2N(Sn- Bu)、(Me2HSn)2N(1-Pen)、(Me2HSn)2N(2-Pen)、(Me2HSn)2N(3-Pen)、(Me2HSn)2N(tPen)、(Me2HSn)2N(Shin-Pen)、(Me2HSn)2N(Shin-Pen)、(Me2HSn)2N( 1-Hex)、(Me2HSn)2N(2-Hex)、(Me2HSn)2N(3-Hex)、(Me2HSn)2N(tHex)、(M e2HSn)2N(ネオ-Hex)、(Me2HSn)2N(シクロ-Hex)、(Me2HSn)2N(アリル)、(Me2HSn)2N (CH2CF3)、(Me2HSn)2N(CH2CF2CF3)、(Me2HSn)2N(CH(CF3)2)、(Me2HSn)2N(CH2(CF2)2CF3)、(Me2HSn)3N、(Me2HSn)2N(SiMe3)、(Me2HSn)2N(SiHMe2)、<h2 style=";text-align:left;direction:ltr">(Me2HSn)2N(SiEtMe2)、(Me2HSn)2N(SiEt2Me)、(Me2HSn)2N(SiEt3)、(Me2HSn)2NH、(Me2HSn)3N、(MeH2Sn)2NMe、(MeH2Sn)2NEt、(MeH2Sn)2N(n Pr)、(MeH2Sn)2N(iPr)、(MeH2Sn)2N(Pr-Pr)、(MeH2Sn)2N(nBu)、(MeH2Sn)2N(sBu)、(MeH2Sn)2N(tBu)、(MeH2Sn)2N(Pr-Bu)、(MeH2Sn)2N(1- Pen)、(MeH2Sn)2N(2-Pen)、(MeH2Sn)2N(3-Pen)、(MeH2Sn)2N(tPen)、(MeH2Sn)2N(MeH2Sn-Pen)、(MeH2Sn)2N(MeH2Sn-Pen)、(MeH2Sn)2N(1-Hex ... 2Sn)2N(2-Hex)、(MeH2Sn)2N(3-Hex)、(MeH2Sn)2N(tHex)、(MeH2Sn)2N(ネオ-Hex)、(MeH2Sn)2N(シクロ-Hex)、(MeH2Sn)2N(アリル)、(MeH2Sn)2N(CH2CF) 3)、(MeH2Sn)2N(CH2CF3CF3)、(MeH2Sn)2N(CH(CF3)2)、(MeH2Sn)2N(CH2(CF2)2CF3)、(MeH2Sn)3N、(MeH2Sn)2N(SiMe3)、(MeH2Sn)2N(SiHMe2)、(MeH2Sn)2N(SiEtMe2)、(MeH2Sn)2N(SiEt2Me)、(MeH2Sn)2N(SiEt3)、(MeH2Sn)2NH、(H3Sn)2NMe、(H3Sn)2NEt、(H3Sn)2N(nPr)、(H3Sn)2N(iPr)、 (H3Sn)2N(Pr-Pr)、(H3Sn)2N(nBu)、(H3Sn)2N(sBu)、(H3Sn)2N(tBu)、(H3Sn)2N(Pr-Bu)、(H3Sn)2N(1-Pen)、(H3Sn)2N(2-Pen)、(H3Sn)2N(3- Pen)、(H3Sn)2N(tPen)、(H3Sn)2N(ネオ-Pen)、(H3Sn)2N(シクロ-Pen)、(H3Sn) )2N(1-Hex)、(H3Sn)2N(2-Hex)、(H3Sn)2N(3-Hex)、(H3Sn)2N(tHex)、(、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">H3Sn)2N(Hex), (H3Sn)2N(Hex), (H3Sn)2N(Hex), (H3Sn)2N(Hex), (H3Sn)2N(CH2CF3), (H3Sn)2N(CH2CF3CF3), (H3Sn)2N(CH(CF3)2), (H3Sn)2N(CH2(CF2)2CF3), (H3Sn)3N, (H3Sn)2N(SiMe3), (H3Sn)2N(SiHMe2), (H<h2 style=";text-align:left;direction:ltr"> 32<h2 style=";text-align:left;direction:ltr">Sn)2N(SiEtMe2)、(H3Sn)2N(SiEt2Me)、(H3Sn)2N(SiEt3)、(Et2HSn)2NMe、(Et2HSn)2NEt、(Et2HSn)2N(nPr)、(Et2HSn)2N(Ni-Pr)、(Et2HSn)2N(nBu )、(Et2HSn)2N(sBu)、(Et2HSn)2N(tBu)、(Et2HSn)2N(See-Bu)、(Et2HSn)2N(1-Pen)、(Et2HSn)2N(2-Pen)、(Et2HSn)2N(3-Pen)、(Et2HSn)2N(tPen)、( Et2HSn)2N(Hi-Pen)、(Et2HSn)2N(Hi-Pen)、(Et2HSn)2N(1-Hex)、(Et2HSn)2N(2-Hex)、(Et2HSn)2N(3-Hex)、(Et2HSn)2N(tHex)、(Et2HSn)2N(Hi-Hex) x)、(Et2HSn)2N(SiMe3)、(Et2HSn)2N(SiMe3)、(Et2HSn)2N(CH(CF3)2)、(Et2HSn)2N(CH2(CF2)2CF3)、(Et2HSn)3N、(Et2HSn)2N(SiMe3)、(Et2HSn)2N( SiHMe2)、(Et2HSn)2N(SiEtMe2)、(Et2HSn)2N(SiEt2Me)、(Et2HSn)2N(SiEt3)、(Et2HSn)2NH、(EtH2Sn)2NMe、(EtH2Sn)2NEt、(EtH2Sn)2N(nPr)、(EtH 2Sn)2N(iPr)、(EtH2Sn)2N(Pr-Pr)、(EtH2Sn)2N(nBu)、(EtH2Sn)2N(sBu)、(EtH2Sn)2N(tBu)、(EtH2Sn)2N(Pen-Bu)、(EtH2Sn)2N(1-Pen)、(EtH2Sn)2 N(2-Pen)、(EtH2Sn)2N(3-Pen)、(EtH2Sn)2N(tPen)、(EtH2Sn)2N(ネオ-Pen) 、(EtH2Sn)2N(シクロ-Pen)、(EtH2Sn)2N(1-Hex)、(EtH2Sn)2N(2-Hex)、(EtH2S n)2N(3-Hex)、(EtH2Sn)2N(tHex)、(EtH2Sn)2N(ネオ-Hex)、(EtH2Sn)2N(シクロ-Hex)、(EtH2Sn)2N(アリル)、(EtH2Sn)2N(CH2CF3)、(EtH2Sn)2N(CH2CF3CF3)、Examples include, but are not limited to, (EtH2Sn)2N(CH(CF3)2), (EtH2Sn)2N(CH2(CF2)2CF3), (EtH2Sn)3N, (EtH2Sn)2N(SiMe3), (EtH2Sn)2N(SiHMe2), (EtH2Sn)2N(SiEtMe2), (EtH2Sn)2N(SiEt2Me), (EtH2Sn)2N(SiEt3) and (EtH2Sn)2NH.

[0065] The disclosed tin-containing precursors and the disclosed film-forming compositions are suitable for the deposition of corresponding element-containing films and their associated uses for the deposition of corresponding element-containing layers. The disclosed tin-containing precursors and the disclosed film-forming compositions are suitable for forming tin-containing thin films, such as tin oxide, SnO2, InSnO (ITO), ZnSnO (ZTO), SnN, SnP, SnAs, SnSb, SnS2, etc., used in the electronics field.

[0066] The disclosed tin-containing precursors can be useful for the production of tin dioxide for a variety of applications including gas sensors, solar cells, CMOS, high capacity electrode materials, catalysts, LED applications, optical applications, ITO and ZTO components in displays, semiconductor, logic, memory industries, etc.

[0067] Also disclosed are processes for forming tin-containing deposits, such as tin-containing films, tin-containing dots, or continuous, partially continuous, and non-continuous tin-containing films, using the disclosed tin-containing precursors in combination with or without one or more co-reactants through chemical vapor deposition. The disclosed processes are deposition processes in which the disclosed tin-containing precursors are used in combination with or without one or more oxidizing agents (e.g., O2 and O3, or H2O and O3) or in combination with or without one or more reducing or nitriding agents (e.g., H2 and NH3, N2 and NH3, or NH3 and NH2H4) or in combination with or without reducing or nitriding agents, which are simultaneously and / or sequentially introduced into the reaction chamber to form a film by CVD, ALD, molecular layer deposition (MLD), spin-on dielectric (SOD), mist coating, dip coating, slit coating, spin-on coating (SOC), spray coating, or any other deposition technique. The disclosed deposition processes using the disclosed tin-containing precursors can be assisted by heat, light, direct or remote plasma, or combinations thereof.

[0068] The co-reactant may be an oxygen source, an oxygen-containing gas, or an oxidant or oxidizing agent. The oxygen-containing gas includes, but is not limited to, O2, O3, H2O, H2O2, NO, N2O, NO2, O radicals, oxidizing agents such as alcohols, silanols, aminoalcohols, carboxylic acids, paraformaldehyde, other nitrogen-oxygen molecules, or combinations thereof. Preferably, the oxygen-containing gas is O3 or O2. Alternatively, the co-reactant may be an N source, a nitrogen-containing gas, or a reducing gas. Nitrogen-containing gases include, but are not limited to, NH3, N2, H2, N2 / H2, H2 and NH3, N2 and NH3, NH3 and N2H4, NO, N2O, amines, diamines, cyanides, diimines, hydrazines, organic amines, primary amines such as pyrazolines, pyridines, methylamines, ethylamines, tertbutylamines, etc.; secondary amines such as dimethylamine, diethylamine, diisopropylamine, ethylmethylamine, pyrrolidine, etc.; tertiary amines such as trimethylamine, triethylamine, trisilylamine, etc., or mixtures thereof. Preferably, the nitrogen-containing gas is NH3. Alternatively, the co-reactant may be a P source such as PH3. Alternatively, the co-reactant may be a S source such as H2S, mercaptans, and combinations thereof. For example, the process may be assisted by heating the substrate using direct or remote plasma, and / or irradiation with light having a wavelength of 120-800 nm. Such a process would result in the formation of a tin-containing thin film having a non-uniformity of less than 4% in the temperature range of 50-400°C.

[0069] If the target deposited film is a conductive film, the co-reactant can be H2, H2CO, N2H4, NH3, primary amines, secondary amines, tertiary amines, trisilylamine, radicals thereof, and mixtures thereof. Preferably, the co-reactant is H2 or NH3. Alternatively, if the target deposited film is a dielectric film, the co-reactant can be an oxidizing gas, such as one of O2, O3, H2O, H2O2, NO, N2O, NO2, oxygen-containing radicals (such as O-OH-), carboxylic acids, formic acid, acetic acid, propionic acid, and mixtures thereof. Preferably, the oxidizing gas is selected from the group consisting of O3, H2O2, and H2O.

[0070] Additionally, the co-reactant can be treated with plasma to break down the reactant into its radical form, and when treated with plasma, at least one of H2, N2, and O2 can be utilized as a source gas for hydrogen, nitrogen, or oxygen, respectively. The plasma source can be N2 plasma, N2 / He plasma, N2 / Ar plasma, NH3 plasma, NH3 / He plasma, NH2 / AR plasma, He plasma, Ar plasma, H2 plasma, H2 / He plasma, H2 / organic amine plasma, and mixtures thereof. For example, the plasma can be generated at a power ranging from about 10 W to about 1000 W, preferably from about 50 W to about 500 W. The plasma can be generated and present within the reaction chamber itself. Alternatively, the plasma can be located away from the reaction chamber, typically, for example, a remotely located plasma system. For example, the co-reactant can be introduced into a direct plasma reaction chamber that generates plasma within the reaction chamber, producing a plasma-treated reactant within the reaction chamber. Alternatively, the plasma treatment can be performed simultaneously with the introduction of the reactants.

[0071] Alternatively, a plasma treated co-reactant can be generated outside the reaction chamber, for example a remote plasma to treat the co-reactant prior to passing into the reaction chamber.

[0072] Also disclosed is a method of forming a tin-containing layer on a substrate using a deposition process. Applicants believe that the disclosed film-forming compositions are suitable for ALD. More specifically, the disclosed film-forming compositions are capable of surface saturation, self-limiting growth per cycle, and complete step coverage at aspect ratios ranging from about 2:1 to about 200:1, preferably about 20:1 to about 100:1. In addition, the disclosed film-forming compositions have high decomposition temperatures that exhibit good thermal stability to enable ALD. The high decomposition temperatures allow ALD at higher temperatures (e.g., about 600° C.) resulting in films of higher purity. The disclosed methods can be useful in the manufacture of semiconductor, solar cell, LCD-TFT, and flat panel type devices.

[0073] The disclosed film-forming compositions can be used to deposit films using any deposition method known to those skilled in the art. Examples of suitable deposition methods include CVD and ALD. Exemplary CVD methods include thermal CVD, plasma-assisted CVD (PECVD), pulsed CVD (PCVD), low pressure CVD (LPCVD), subatmospheric pressure CVD (SACVD), atmospheric pressure CVD (APCVD), hot wire CVD (HWCVD, also known as cat-CVD, where a hot wire serves as the energy source for the deposition process), radical-incorporated CVD, and combinations thereof. Exemplary ALD methods include thermal ALD, plasma-assisted ALD (PEALD), spatial ALD, hot wire ALD (HWALD), radical-incorporated ALD, and combinations thereof. Supercritical fluid deposition such as molecular layer deposition (MLD), spin-on deposition (SOD), spin-on coating (SOC), mist coating, dip coating, slit coating, spray coating, etc. may also be used. The deposition method is preferably ALD, PE-ALD, spatial ALD to provide adequate step coverage and film thickness control. The disclosed film-forming compositions can be used to deposit films using any deposition method known to one of ordinary skill in the art, especially at low temperatures such as below 100° C., preferably below 80° C.

[0074] The purity of the disclosed film-forming compositions is greater than 95% w / w (i.e., 95.0% w / w to 100.0% w / w), preferably greater than 98% w / w (i.e., 98.0% w / w to 100.0% w / w), and more preferably greater than 99% w / w (i.e., 99.0% w / w to 100.0% w / w). One skilled in the art will recognize that purity can be determined by H NMR or gas-liquid chromatography with mass spectrometry. The disclosed film-forming compositions may contain any of the following impurities: pyrazole; pyridine; alkylamines; alkylimines; THF; ethers; pentane; cyclohexane; heptane; benzene; toluene; chlorinated metal compounds; lithium, sodium, or potassium pyrazolyl. The total amount of these impurities is preferably less than 5% w / w (i.e., 0.0% w / w to 5.0% w / w), preferably less than 2% w / w (i.e., 0.0% w / w to 2.0% w / w), more preferably less than 1% w / w (i.e., 0.0% w / w to 1.0% w / w). The disclosed film forming compositions can be purified by recrystallization, sublimation, distillation, and / or passing the gas or liquid through a suitable adsorbent such as 4A molecular sieves.

[0075] Purification of the disclosed film-forming compositions may also result in metal impurities at levels of 0 ppbw to 1 ppmw, preferably 0 to 500 ppbw (parts per billion by weight), which may include, but are not limited to, aluminum (Al), arsenic (As), barium (Ba), beryllium (Be), bismuth (Bi), cadmium (Cd), calcium (Ca), chromium (Cr), cobalt (Co), copper (Cu), gallium (Ga), germanium (Ge), hafnium (Hf), zirconium (Zr), iron (Fe), lead (Pb), lithium (Li), magnesium (Mg), manganese (Mn), tungsten (W), nickel (Ni), potassium (K), sodium (Na), strontium (Sr), thorium (Th), indium (In), and titanium (Ti).

[0076] The disclosed film-forming compositions can be supplied either in neat form or in blends with a suitable solvent, such as ethylbenzene, xylene, mesitylene, decalin, decane, dodecane, etc. The disclosed precursors can be present in various concentrations in the solvent.

[0077] The neat or mixed film-forming composition is introduced into the reaction chamber in vapor form by conventional means such as piping and / or flow meters. The vapor form can be obtained by vaporizing the neat or mixed composition by a conventional vaporization step, such as direct vaporization, distillation, bubbling, or by using a sublimator. If vaporized before being introduced into the reaction chamber, the neat or mixed composition can be provided to the vaporizer in a liquid state. Alternatively, the neat or mixed composition can be vaporized by bubbling the carrier gas into the composition by flowing the carrier gas into a vessel containing the composition. The carrier gas can include, but is not limited to, Ar, He, N2, and mixtures thereof. Bubbling the carrier gas can also remove any dissolved oxygen present in the neat or mixed composition solution. The carrier gas and the composition are then introduced into the reaction chamber as vapor.

[0078] If necessary, the vessel containing the disclosed film-forming composition can be heated to a temperature at which the composition can be in its liquid phase and have sufficient vapor pressure. The vessel can be maintained at a temperature within the range of, for example, about 0° C. to about 200° C. One skilled in the art will recognize that the temperature of the vessel can be adjusted in known manner to control the amount of precursor vaporized.

[0079] The reaction chamber can be any enclosure chamber in which the deposition process takes place, such as, but not limited to, a parallel plate reaction chamber, a cold wall reaction chamber, a hot wall reaction chamber, a single wafer reaction chamber, a multi-wafer reaction chamber, or other type of deposition system, under appropriate conditions to react the compounds and form a layer. One of skill in the art will recognize that any of these reaction chambers can be used for either ALD or CVD deposition processes.

[0080] The reaction chamber contains one or more substrates on which the film is deposited. The substrate is generally defined as the material on which the process is performed. The substrate can be any suitable substrate used in the manufacture of semiconductor, photovoltaic, flat panel, LCD-TFT devices. Examples of suitable substrates include silicon, silica, glass, etc. wafers, GaAs wafers. The wafer can have one or more layers of different materials deposited thereon in previous manufacturing steps. For example, the wafer can include a dielectric layer. Additionally, the wafer can include a silicon layer (crystalline, amorphous, porous, etc.), a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, a carbon-doped silicon oxide (SiCOH) layer, a metal, a metal oxide metal nitride layer (Ti, Ru, Ta, etc.), and combinations thereof. Additionally, the wafer can include a copper layer, a noble metal layer (e.g., platinum, palladium, rhodium, gold). The wafer can include a barrier layer, such as manganese, manganese oxide, etc. Plastic layers can also be used. The layers can be planar or patterned. The disclosed method can deposit a layer directly on the wafer or directly on one or more layers on the top surface of the wafer when a patterned layer is formed on a substrate. The patterned layer can be alternating layers of two specific layers, such as SiO and SiN, used in 3D NAND. Furthermore, those skilled in the art will recognize that the terms "film" and "layer" as used herein refer to a material of a certain thickness that is disposed and spread on a surface, which may be a trench, a line. Throughout this specification and claims, the wafer and any associated layers thereon are referred to as a substrate. For example, an indium oxide film can be deposited on a metal oxide layer, such as a ZrO2 layer, a HfO2 layer, a MoO2 layer, etc.

[0081] While the end use of the substrate is not limited to the present invention, this technology may find particular benefit with the following types of substrates: silicon wafers, glass wafers and panels, beads, powders and nanopowders, monolithic porous media, printed circuit boards, plastic sheets, etc. Exemplary powder substrates include powders used in rechargeable battery technology. A non-limiting number of powder materials include NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials.

[0082] The temperature and pressure in the reactor are maintained at conditions suitable for deposition, such as ALD and CVD. In other words, after introducing the vaporized disclosed film-forming composition into the chamber, the conditions in the chamber are such that a portion of the precursor deposits on the substrate to form a layer. For example, the pressure in the reactor or deposition pressure can be about 10 to 2000 psi, as needed, in accordance with the deposition parameters. -3 Torr to about 100 Torr, more preferably about 10 -2 Torr to about 100 Torr. Similarly, the temperature within the reactor or deposition temperature can be maintained at room temperature to about 600° C., preferably room temperature to about 500° C., more preferably room temperature to about 200° C., and even more preferably room temperature to about 100° C. One of ordinary skill in the art will recognize that "at least a portion of the precursor deposits" means that some or all of the precursor reacts with or adheres to the substrate.

[0083] The temperature of the reactor can be controlled either by controlling the temperature of the substrate holder or by controlling the temperature of the reactor walls. The equipment used to heat the substrate is well known in the art. The reactor walls are heated to a temperature sufficient to obtain the desired film having the desired physical state and composition at a sufficient growth rate. Non-limiting representative temperature ranges to which the reactor walls can be heated include room temperature to about 600°C. If a plasma deposition process is used, the deposition temperature can range from room temperature to about 500°C, preferably from room temperature to about 200°C, and more preferably from room temperature to about 100°C. Alternatively, if a thermal process is performed, the deposition temperature can range from room temperature to about 600°C, preferably from room temperature to about 500°C, more preferably from room temperature to about 200°C, and even more preferably from room temperature to about 100°C.

[0084] The ALD conditions react the disclosed film-forming compositions adsorbed or chemisorbed on the substrate surface to form a film on the substrate. In some embodiments, applicants believe that plasma treatment of the co-reactant can provide the co-reactant with the necessary energy to react with the disclosed film-forming composition. When the co-reactant is treated with plasma in this exemplary ALD process, the exemplary ALD process becomes an exemplary PEALD process. The co-reactant can be treated with plasma before or after introduction into the chamber.

[0085] The film-forming composition and the co-reactant may be introduced into the reactor sequentially (ALD). The reactor may be purged with an inert gas between each introduction of the film-forming composition, any additional precursors and the co-reactant. Another example is the continuous introduction of the co-reactant and the pulsed introduction of the film-forming composition while sequentially activating the co-reactant with a plasma, provided that the film-forming composition and the non-activated co-reactant do not substantially react at the chamber temperature and pressure conditions (CW PEALD).

[0086] Each pulse of the disclosed film-forming composition can last for a time period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 second to about 80 seconds, alternatively from about 5 seconds to about 30 seconds. The co-reactant can also be delivered in a pulse into the reactor. In such an embodiment, each pulse can last for a time period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 second to about 30 seconds, alternatively from about 2 seconds to about 20 seconds. In another alternative, the vaporized film-forming composition and the co-reactant can be sprayed simultaneously (without mixing of the composition and the reactants) from different sectors of a showerhead under which a susceptor holding several wafers rotates (spatial ALD).

[0087] Depending on the particular process parameters, deposition may be carried out for various lengths of time. In general, deposition may continue as long as desired to produce a film having the required properties. Typical film thicknesses may vary from a few angstroms to hundreds of microns, typically 2 nm to 100 nm, depending on the specific deposition process. The deposition process may be carried out as many times as necessary to obtain the desired film.

[0088] The disclosed film-forming composition and co-reactant can be introduced into the reactor either simultaneously (CVD), sequentially (ALD), or in different combinations thereof. The reactor may be purged with an inert gas (e.g., N2, Ar, Kr, Xe) between the introduction of the film-forming composition and the introduction of the co-reactant. Alternatively, the co-reactant and the film-forming composition can be mixed together to form a co-reactant / compound mixture and then introduced into the reactor in the form of a mixture. Another example is to introduce the co-reactant sequentially and introduce the disclosed film-forming composition by pulses (pulsed CVD).

[0089] For the deposition of ITO and ZTO films, the disclosed tin-containing precursors may be used in combination with indium and zinc precursors with one or more oxygen-containing reactant gases, such as, but not limited to, O2, O3, H2O, H2O2, NO, NO2, and N2O. Common indium and zinc precursors have the general formulas InR3 and ZnR2, respectively, where R=C1-C4 alkyl groups may be used. To form ITO and ZTO films, however, it is preferred to utilize the tin-containing precursors disclosed herein with non-pyrophoric indium and zinc precursors. Suitable Zn precursors include ZnR 1 2[R 2 O(CH2) x OR 3 ], ZnR 1 2[R 2 O(CHR 4 )(CH2)OR 3 ], ZnR 1 2[R 2 O(CHR 4 )(CH2)2OR 3 ], ZnR 1 2[R 2 O(CH2)(CHR 4 )(CH2)OR 3 ], and ZnR 5 2[(R 6 R 7 )2N(CH2) x N(R 8 R 9 )2], ZnR 5 2[(R 6 R 7 )2N(CHR 10 )(CH2)N(R 8 R 9 )2], ZnR 5 2[(R 6 R 7 )2N(CHR 10 )(CH2)2N(R 8 R 9 )2] and ZnR 5 2[(R 6 R 7 )2N(CH2)(CHR 10 )(CH2)N(R 8 R 9 )2](where R1 ~R 10 are independently selected from C1 to C4 alkyl groups). 1 )2In[R 2 N(R 3 ) CNR 5 ](wherein, R 1 ~R 5 are independently selected from C1-C4 linear or branched alkyl groups. Another class of In precursors are non-pyrophoric cyclopentadienyl indium derivatives, particularly those of the formula (RCp)In, where R=H or C1-C 10 Monocyclopentadienyl indium(I) compounds having alkyl groups (linear or branched alkyl chains) may be considered.

[0090] When forming tin-containing films, particularly ITO, the limited tin content can be fine-tuned through appropriate ALD sequences to optimize optical and electrical properties. For example, 3:1, 9:1, and 19:1 indium to zinc precursor sequences result in tin contents of approximately 5%, 2%, and 1%, respectively.

[0091] In a non-limiting exemplary ALD-type process for forming a tin-containing film, the disclosed film-forming composition, e.g., Me3Sn)2N(nPr), is introduced into a reaction chamber where it contacts a suitable substrate. Excess composition can then be removed from the reaction chamber by purging and / or evacuating the reaction chamber, i.e., by purging the reaction chamber with an inert gas (e.g., N2, Ar, Kr, Xe) or by passing the substrate through an area under high vacuum and / or a carrier gas curtain. A co-reactant (e.g., O3) is introduced into the reaction chamber where it reacts in a self-limiting manner with the adsorbed film-forming composition. Any excess co-reactant is removed from the reaction chamber by purging and / or evacuating the reaction chamber. If the desired deposited film is an oxide, e.g., SnO2, this two-step process can provide a desired film thickness and can be repeated until a film having the required thickness is obtained. By alternately feeding the tin film-forming composition and the co-reactant, a film of the desired composition and thickness can be deposited.

[0092] Alternatively, if the desired deposited film includes tin and a second element, then after the two-step process described above, vapor of an additional precursor compound can be introduced into the reaction chamber (three-step process). The additional precursor compound is selected based on the nature of the film to be deposited. The second element can include Zn, In, Ga, N, S, P, As, Sb, B, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, Bi, Pb, Co, one or more lanthanides, or mixtures thereof. When an additional precursor compound is utilized, the resulting film deposited on the substrate includes tin in combination with the additional element. Nanolaminate films are obtained when the additional precursor and the tin-containing precursor are used in two or more ALD super cycle sequences. After introduction into the reaction chamber, the additional precursor compound contacts or is adsorbed onto the substrate. Any excess additional precursor compound is then removed from the reaction chamber by purging and / or evacuation of the reaction chamber. Again, a co-reactant can be introduced into the reaction chamber to react with the tin-containing precursor compound. Excess co-reactant is removed from the reaction chamber by purging and / or evacuating the reaction chamber. Once the desired film thickness is achieved, the process can be terminated. However, if a thicker film is desired, the entire three-step process can be repeated. By alternating the supply of the tin film-forming composition, the additional precursor compound, and the co-reactant, a film of the desired composition and thickness can be deposited. For example, if the additional precursor is an indium precursor, ITO is formed. For example, if the additional precursor is a zinc precursor, ZTO is formed.

[0093] The tin-containing films resulting from the above-mentioned process can include tin oxide (SnO2), InSnO (ITO), ZnSnO (ZTO), SnN, SnP, SnAs, SnSb, Sn2S3. Those skilled in the art will recognize that by selecting the appropriate film-forming composition and co-reactants, the desired film composition can be obtained. The tin-containing films can provide suitable step coverage for capacitor electrodes in DRAM, gate metals in 3D flash memory devices, heating elements in phase change memories, electromigration barrier layers, gate metals and contact layers in logic devices.

[0094] After obtaining the desired film thickness, the film may undergo further processing such as thermal annealing, furnace annealing, rapid thermal annealing, UV, e-beam curing and / or plasma gas exposure. Those skilled in the art will recognize the systems and methods used to perform these further processing steps. For example, the SnO2 film may be exposed to a temperature ranging from about 200°C to about 1000°C under an inert atmosphere, or an O2-containing atmosphere, or a combination thereof, for a time ranging from 0.1 seconds to about 7200 seconds. Most preferably, the temperature is 400°C for 3600 seconds under an inert atmosphere or an O2-containing atmosphere. The resulting film may contain fewer impurities, thus improving the density and improving the leakage current. The annealing step may be performed in the same reaction chamber as the deposition is performed, or may be performed in a separate apparatus. Any of the above post-processing methods, particularly thermal annealing, have been found to be effective in reducing carbon and nitrogen contamination of the SnO2 film, which therefore tends to improve the resistivity of the film.

[0095] After annealing, the tin-containing films deposited by any of the disclosed processes may have a bulk resistivity at room temperature of about 50 μohm.cm to about 1,000 μohm.cm. Room temperature is about 20°C to about 28°C depending on the season. Bulk resistivity is also known as volume resistivity. Those skilled in the art will recognize that bulk resistivity is typically measured at room temperature for a film that is about 50 nm thick. Bulk resistivity typically increases for thinner films due to changes in electron transport mechanisms. Bulk resistivity also increases at higher temperatures. EXAMPLES

[0096] The following non-limiting examples are provided to further illustrate embodiments of the present invention, but are not intended to be all-inclusive and are not intended to limit the scope of the invention described herein.

[0097] Example 1: Synthesis of (Me3Sn)2NEt In a three-necked 1 L round-bottom flask equipped with a reflux condenser and a 200 mL addition funnel, a 2.0 M solution of EtNH2 in THF (100 mL, 200 mmol) and 300 mL of hexane were added and the mixture was cooled to -78 °C. The addition funnel was charged with 1.59 M nBuLi in hexane (126 mL, 200 mmol), which was then added dropwise to the EtNH2 solution over a period of 45 min, during which a white precipitate formed. After stirring for 30 min, the cooling bath was removed and the mixture was stirred at room temperature for an additional hour. Under vacuum, all volatiles were removed and the flask was filled with 300 mL of hexane and the corresponding suspension was cooled to -78 °C. In another 500 mL three-necked round-bottom flask, a solution of Me3SnCl (39.46 g, 198 mmol) dissolved in 300 mL of Et2O was prepared in a glove box. The Me3SnCl / Et2O solution was transferred via cannula to the EtNHLi suspension over 45 min and the resulting mixture was stirred at -78 °C for 15 min. After removing the cooling bath, the mixture was allowed to warm to ambient temperature and stirred for an additional 15 min. The white suspension was then refluxed at 70 °C for 2 h. The reaction mixture was cooled to ambient temperature and all solids were filtered off over Celite under N2 atmosphere to give a pale yellow solution. Most of the volatiles were removed in vacuum at 5 kPa and the residue was transferred to a 100 mL two-neck flask, which was then equipped with a fractional distillation apparatus. Impurities were removed at 25-75 °C at 2 kPa and (Me3Sn)2NEt (21.88 g, 59 mmol) was isolated as a colorless oil in 59% yield at 90-110 °C at 0.1 kPa. 1 H NMR (C6D6, 400MHz): δ 3.29(q;2H, 2 J H-Sn =33.8Hz, 3 J H-H =6.9Hz,N-CH2),1.05(t;3H, 3 J H-H =6.9Hz,N-CH2-CH3),0.18(s;18H, 117 About Sn 2 J H-Sn =51.8Hz, 119 About Sn 2 J H-Sn =54.3Hz). 13C{ 1 H}NMR (C6D6, 100MHz): δ 47.4(N-CH2),25.9(N-CH2-CH3),-4.4(Sn-CH3, 117 About Sn 1 J C-Sn =354.0Hz, 119 About Sn 1 J C-Sn =370.5Hz). 119 Sn NMR (C6D6, 149MHz): δ 74.4.

[0098] Thermogravimetry (TG) and differential thermal analysis (DTA) measurements shown in Figure 1 were performed under the following measurement conditions: sample weight: 24.007 mg, atmosphere: N2 at 1 atm, and temperature increase rate: 10.0 °C / min. >99% of the compound's mass was evaporated at 171 °C (residue <1%), and T(50%) = 134 °C.

[0099] Example 2: Synthesis of (Me3Sn)2N(nPr) In a 1 L three-necked round-bottom flask equipped with a reflux condenser and a 200 mL addition funnel, nPrNH2 (19.74 g, ca. 27.5 mL, 334 mmol) and 300 mL of hexane were added and the mixture was cooled to -78 °C. The addition funnel was charged with 1.59 M nBuLi in hexane (200 mL, 318 mmol), which was then added dropwise over 30 min into the nPrNH2 solution, during which a white precipitate formed. After stirring for 30 min, the cooling bath was removed and the mixture was stirred at ambient temperature for an additional 30 min. Under vacuum, all volatiles were removed and the flask was filled with 400 mL of hexane and the nPrNHLi suspension was cooled to -78 °C. In a separate 500 mL three-necked round-bottom flask, a solution of Me3SnCl (63.37 g, 318 mmol) dissolved in 400 mL of Et2O was prepared in a glove box. The Me3SnCl / Et2O solution was added slowly to the nPrNHLi suspension using a cannula over 30 min. After stirring at -78 °C for 1 h, the cooling bath was removed and the mixture was allowed to warm to ambient temperature. The white suspension was then refluxed at 75 °C for 2 h. After cooling to ambient temperature, all solids were filtered off over Celite under N2 atmosphere to give a pale yellow solution. Most of the volatiles were removed in vacuum at 5 kPa total pressure and the residue was transferred to a 200 mL two-neck flask which was then equipped with a distillation apparatus. Impurities were removed at 50 °C at 0.1 kPa and (Me3Sn)2N(nPr) (49.80 g, 129 mmol) was isolated as a colorless oil in 82% yield at 100-130 °C at 0.1 kPa. 1 H NMR (C6D6, 400MHz): δ 3.23(dt;2H, 117 About Sn 3 J H-Sn =32.7Hz, 119 About Sn 3 J H-Sn =34.1Hz, 3 J H-H =3.1Hz, 4 J H-H =1.5Hz, N-CH2), 1.39 (pseudo tq; 2H, 3 J H-H =3.1Hz,N-CH2-CH2),0.88(t;3H, 3 JH-H =7.3Hz,CH2-CH3),0.19(s;18H, 117 About Sn 2 J H-Sn =52.1Hz, 119 About Sn 2 J H-Sn =54.3Hz). 13 C{ 1 H}NMR (C6D6, 100MHz): δ 55.4(N-CH2),32.9(N-CH2-CH2),11.7(CH2-CH3),-4.4(Sn-CH3, 117 About Sn 1 J C-Sn =354.4Hz, 119 About Sn 1 J C-Sn =371.1Hz). 119 Sn NMR (C6D6, 149MHz): δ 75.5.

[0100] The TG and DTA measurements shown in Figure 2 were carried out under the following measurement conditions: sample weight: 20.173 mg, atmosphere: N2 at 1 atm, and temperature increase rate: 10.0 °C / min. >99% of the compound's mass was evaporated at 165 °C (residue <1%), and T(50%) = 142 °C.

[0101] Example 3: Synthesis of (Me3Sn)2N(nBu) In a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a 100 mL addition funnel, nBuNH2 (7.24 g, ca. 9.9 mL, 100 mmol) and 200 mL of hexane were added and the mixture was cooled to -78 °C. The addition funnel was charged with 1.57 M nBuLi in hexane (63.9 mL, 100 mmol), which was then added dropwise over 30 min into the nBuNH2 solution, during which a white precipitate formed. After stirring for 30 min, the cooling bath was removed and the mixture was stirred at ambient temperature for another 30 min. Under vacuum, all volatiles were removed, the flask was filled with 200 mL of hexane, and the nBuNHLi suspension was cooled again to -78 °C. In another 200 mL two-necked round-bottom flask, a solution of Me3SnCl (19.98 g, 100 mmol) dissolved in 100 mL of Et2O was prepared in a glove box. The Me3SnCl / Et2O solution was slowly added to the nBuNHLi suspension using a cannula over 20 min. After stirring at -78 °C for 1 h, the cooling bath was removed and the mixture was allowed to warm to ambient temperature. The white suspension was then refluxed at 75 °C for 2 h. After cooling to ambient temperature, all solids were filtered off over Celite under N2 atmosphere to give a pale yellow solution. Most of the volatiles were removed in vacuum at 5 kPa total pressure and the residue was transferred to a 100 mL two-neck flask which was then equipped with a distillation apparatus. Impurities were removed at 50 °C at 0.1 kPa and (Me3Sn)2N(nBu) (15.76 g, 39.5 mmol) was isolated as a colorless oil in 79% yield at 0.1 kPa at 100-130 °C. 1 H NMR (C6D6, 400MHz): δ 3.28(t;2H, 117 About Sn 3 J H-Sn =33.3Hz, 119 About Sn 3 J H-Sn =34.1Hz, 3 J H-H =7.2Hz),1.40(m;2H,N-CH2-CH2),1.33(m;2H,N-CH2-CH2-CH2),0.93(t;3H, 3 J H-H =7.2Hz,CH2-CH3),0.21(s;18H, 117About Sn 2 J H-Sn =53.2Hz, 119 About Sn 2 J H-Sn =54.3Hz). 13 C{ 1 H}NMR (C6D6, 100MHz): δ 52.9(N-CH2),42.4(N-CH2-CH2),20.8(N-CH2-CH2-CH2),15.2(CH2-CH3),-4.3(Sn-CH3, 117 About Sn 1 J C-Sn =354.1Hz, 119 About Sn 1 J C-Sn =370.8Hz). 119 Sn NMR (C6D6, 149MHz): δ 75.4.

[0102] The TG and DTA measurements shown in Figure 3 were carried out under the following measurement conditions: sample weight: 18.389 mg, atmosphere: N2 at 1 atm, and temperature increase rate: 10.0 °C / min. >99% of the compound's mass was evaporated at 189 °C (residue <1%), and T(50%) = 164 °C.

[0103] Example 4: Synthesis of (Me3Sn)2N(CH2CF3) In a glove box, a 100 mL J. Young tube was charged with Me3SnNEt2 (25.06 g, 106.2 mmol) and CF3CH2NH2 (5.25 g, 53.0 mmol) at room temperature. After stirring for 2 h, the progress of the reaction was monitored by NMR spectroscopy. If Me3SnNEt2 still remained, an appropriate amount of CF3CH2NH2 was further added to the reaction mixture. The resulting colorless reaction mixture was then stirred overnight. The reaction setup was removed from the glove box and then equipped with a fractional distillation apparatus. After removal of volatile by-products at 50-75 °C and 2 kPa, pure (Me3Sn)2N(CH2CF3) (15.38 g, 36.2 mmol) was collected as a colorless oil in 68% yield at 90-110 °C and 0.1 kPa. 1 H NMR (C6D6, 400MHz):δ 3.53(q;2H, 3 J H-F =9.5Hz, 117 About Sn 3 J H-Sn =31.7Hz, 119 About Sn 3 J H-Sn =33.0Hz,N-CH2),0.15(s;18H, 2 J H-Sn =54.7Hz,Sn-CH3). 13 C{ 1 H}NMR (C6D6, 100 MHz): N-CH2 signal was combined with the reference signal, 53.6 (q; 2 J C-F =30.5Hz, 2 J C-Sn =10.1Hz,N-CH2),-4.4(Sn-CH3, 117 About Sn 1 J C-Sn =362.7Hz, 119 About Sn 1 J C-Sn =380.0Hz). 13 C{ 1 H}NMR(ppm, CDCl3): 127.1(q; 1 J C-F =281.3Hz,CH2-CF3),52.8(q; 2 J C-F =30.7Hz, 2 J C-Sn =11.0Hz,N-CH2),-4.8(Sn-CH3, 117 About Sn 1 J C-Sn =362.7Hz, 119 About Sn 1 J C-Sn =380.0Hz). 19 F NMR (C6D6, 376MHz): -74.9 (t; 3 J F-H =9.5Hz). 119 Sn NMR(C6D6,149MHz):94.6.

[0104] The TG and DTA measurements shown in Figure 4 were carried out under the following measurement conditions: sample weight: 19.728 mg, atmosphere: N2 at 1 atm, and temperature increase rate: 10.0 °C / min. >99% of the compound's mass was evaporated at 156 °C (residue <1%), and T(50%) = 134 °C.

[0105] Example 5: SnO using (Me3Sn)2N(nPr)+O3 at 50°C x CVD of films Under the experimental conditions shown below, SnO was synthesized by CVD using (Me3Sn)2N(nPr) and O3 as the tin and oxygen sources, respectively. x The deposition of the film was carried out: Reaction chamber temperature: 50°C Reaction chamber pressure: 1 torr Carrier gas N2 flow rate: 350sccm Precursor canister pressure: 40 torr N2 bubbling of precursor: 40sccm Precursor flow rate: approx. 0.26 sccm O3 flow rate: 100sccm (concentration >200g / m 3 ) Deposition duration: 30 minutes

[0106] Based on the thickness measurements made by the ellipsometer, we extrapolate the results for films on Si substrates as follows: Thickness: 28nm Growth rate: 0.94nm / min Refractive index: 1.92

[0107] Based on X-ray photoelectron spectroscopy (XPS) analysis, the film composition data is estimated as follows: Sn: 43.1%, O: 40.5%, C: 12%, N: 1.7 at 50 °C.

[0108] Example 6: SnO using (Me3Sn)2N(nPr)+O3 at 100°C x CVD of films Under the experimental conditions shown below, SnO was synthesized by CVD using (Me3Sn)2N(nPr) and O3 as the tin and oxygen sources, respectively. xThe deposition of the film was carried out: Reaction chamber temperature: 100°C Reaction chamber pressure: 1 torr Carrier gas N2 flow rate: 350sccm Precursor canister temperature: RT Precursor canister pressure: 40 torr N2 bubbling of precursor: 40sccm Precursor flow rate: approx. 0.26 sccm O3 flow rate: 100sccm (concentration >200g / m 3 ) Deposition duration: 30 minutes

[0109] Based on the thickness measurements made by the ellipsometer, we extrapolate the results for films on Si substrates as follows: Thickness: 14nm Growth rate: 0.46nm / min Refractive index: 1.92

[0110] Based on the XPS analysis, the film composition data is estimated as follows: Sn: 41.2%, O: 46.6%, C: 6.6%, N: 1.2 at 100°C.

[0111] Example 7: SnO using (Me3Sn)2N(nPr)+O3 at 200°C x CVD of films Under the experimental conditions shown below, SnO was synthesized by CVD using (Me3Sn)2N(nPr) and O3 as the tin and oxygen sources, respectively. x The deposition of the film was carried out: Reaction chamber temperature: 200°C Reaction chamber pressure: 1 torr Carrier gas N2: 350sccm Precursor canister temperature: room temperature Precursor canister pressure: 40 torr N2 bubbling of precursor: 40sccm Precursor flow rate: approx. 0.26 sccm O3 flow rate: 100sccm (concentration >200g / m 3 ) Deposition duration: 30 minutes

[0112] Based on the thickness measurements made by the ellipsometer, we extrapolate the results for films on Si substrates as follows: Thickness: 12nm Growth rate: 0.41nm / min Refractive index: 1.92

[0113] Based on the XPS analysis, the film composition data is estimated as follows: Sn: 42.9%, O: 57.1%, C: <DL、N:200℃で<DL。

[0114] Example 8: SnO using (Me3Sn)2N(nPr)+O3 at 300°C x CVD of films Under the experimental conditions shown below, SnO was synthesized by CVD using (Me3Sn)2N(nPr) and O3 as the tin and oxygen sources, respectively. x The deposition of the film was carried out: Reaction chamber temperature: 300℃ Reaction chamber pressure: 1 torr Carrier gas N2: 350sccm Precursor canister temperature: room temperature Precursor canister pressure: 40 torr N2 bubbling of precursor: 40sccm Precursor flow rate: approx. 0.26 sccm O3 flow rate: 100sccm (concentration >200g / m 3 ) Duration: 30 minutes

[0115] Based on the thickness measurements made by the ellipsometer, we extrapolate the results for films on Si substrates as follows: Thickness: 28nm Growth rate: 0.94nm / min Refractive index: 1.92

[0116] Based on the XPS analysis, the film composition data is estimated as follows: Sn: 41.7%, O: 58.3%, C: <DL、N:300℃で<DL

[0117] Example 9: SnO using (Me3Sn)2N(nPr)+O3 at 400°C x CVD of films Under the experimental conditions shown below, SnO was synthesized by CVD using (Me3Sn)2N(nPr) and O3 as the tin and oxygen sources, respectively. x The deposition of the film was carried out: Reaction chamber temperature: 400℃ Reaction chamber pressure: 1 torr Carrier gas N2: 350sccm Precursor canister temperature: room temperature Precursor canister pressure: 40 torr N2 bubbling of precursor: 40sccm Precursor flow rate: approx. 0.26 sccm O3 flow rate: 100sccm (concentration >200g / m 3 ) Deposition duration: 30 minutes

[0118] Based on the thickness measurements made by the ellipsometer, we extrapolate the results for films on Si substrates as follows: Thickness: 28nm Growth rate: 0.94nm / min Refractive index: 1.92

[0119] Based on the XPS analysis, the film composition data is estimated as follows: Sn: 38.7%, O: 54.3%, C: <3.6, N: 0.9 at 400°C.

[0120] Example 10: SnO using (Me3Sn)2N(nPr)+O3 at 300°C x ALD of films (P=1 torr) Under the following experimental conditions, alternating pulses of (Me3Sn)2N(nPr) and O3, separated by a purge time between the two pulses, were used to produce SnO x The deposition of the films was carried out in a tubular reaction chamber: Reaction chamber temperature: 300℃ Reaction chamber pressure: 1 torr Canister temperature: 26℃ Canister pressure: 40 torr N2 bubble flow rate: 40 sccm N2 carrier flow rate: 350 sccm Number of cycles: 300 Pulse sequence: (Me3Sn)2N(nPr) (1 sccm): 5 seconds N2 flow (purge): 5 seconds O3 (100 sccm): 5 seconds N2 flow (purge): 5 seconds

[0121] Based on thickness measurements performed by an ellipsometer, the results of the film on the Si substrate are estimated as follows: Substrate: Si (pretreated with HF) Average thickness: 3.0 nm Growth per cycle: 0.10 Å / cycle Refractive index: 1.82

[0122] Based on the atomic ratio profile estimated by XPS, the SnO x film was composed of a 1:4 Sn:O ratio with <DL and about 6% C and N contamination, respectively.

[0123] Example 11: ALD of SnO x film using "(Me3Sn)2N(nPr) + O3" at 400 °C Under the following experimental conditions, the SnO x film was deposited in a tubular reaction chamber by alternating pulses of (Me3Sn)2N(nPr) and O3 separated by a purge time between two pulses: Reaction chamber temperature: 400 °C Reaction chamber pressure: 1 torr Canister temperature: 26 °C Canister pressure: 40 torr N2 bubble flow rate: 40 sccm N2 carrier flow rate: 350 sccm Number of cycles: 300 Pulse sequence: (Me3Sn)2N(nPr) (1 sccm): 5 seconds N2 flow (purge): 5 seconds O3 (100 sccm): 5 seconds N2 flow (purge): 5 seconds

[0124] Based on the thickness measurements performed by ellipsometer, the results of the film on the Si substrate are estimated as follows: Substrate: Si (pretreated with HF) Average thickness: 5.4 nm Growth per cycle: 0.18 Å / cycle Refractive index: 1.91

[0125] Based on the atomic ratio profile estimated by XPS, the SnO film formed by this method x was composed of a Sn:O ratio of 1:1.7 with <DL and <3% C and N contamination respectively.

[0126] Example 12: ALD of SnO film using "(Me3Sn)2N(nPr) + O3" at 500 °C x (P = 1 torr) Under the following experimental conditions, the deposition of the SnO film was carried out in a tubular reaction chamber by alternating pulses of (Me3Sn)2N(nPr) and O3 separated by the purge time between two pulses: x Reaction chamber temperature: 500 °C Reaction chamber pressure: 1 torr Canister temperature: 26 °C Canister pressure: 40 torr N2 bubble flow rate: 40 sccm N2 carrier flow rate: 350 sccm Number of cycles: 300 Pulse sequence: (Me3Sn)2N(nPr) (1 sccm): 5 seconds N2 flow (purge): 5 seconds O3 (100 sccm): 5 seconds N2 flow (purge): 5 seconds ​

[0127] Based on the thickness measurements performed by an ellipsometer, the results of the film on the Si substrate are estimated as follows: Substrate: Si (pretreated with HF) Average thickness: 6.9 nm Growth per cycle: 0.23 Å / cycle Refractive index: 1.92

[0128] Based on the atomic ratio profile estimated by XPS, the SnO formed by this method x film was composed of a Sn:O ratio of 1:1.6 with <DL and <2% C and N contamination, respectively.

[0129] Example 13: SnO using "(Me3Sn)2N(nPr) + O3" at 80 °C x High-pressure ALD (P = 100 torr) of the film Under the following experimental conditions, the SnO x film was deposited in a tubular reaction chamber by alternating pulses of (Me3Sn)2N(nPr) and O3 separated by the purge time between two pulses: Reaction chamber temperature: 80 °C Reaction chamber pressure: 100 torr Canister temperature: 52 °C Canister pressure: 130 torr N2 bubble flow rate: 130 sccm N2 carrier flow rate: 350 sccm Number of cycles: 300 Pulse sequence: (Me3Sn)2N(nPr) (4 sccm): 10 seconds N2 flow (purge): 60 seconds O3 (100 sccm): 30 seconds N2 flow (purge): 60 seconds

[0130] Based on the thickness measurements performed by an ellipsometer, the results of the film on the Si substrate are estimated as follows: Substrate: Si (pretreated with HF) Average thickness: 13.9 nm Growth amount per cycle: 0.49 Å / cycle Refractive index: 1.87

[0131] Based on the atomic ratio profile estimated by XPS, the SnO formed by this method x The film consisted of a Sn:O ratio of 1:1.89.

[0132] Example 14: SnO using (Me3Sn)2N(nPr)+O3 at 80°C x High-pressure ALD of films (P=200 torr) Under the following experimental conditions, alternating pulses of (Me3Sn)2N(nPr) and O3, separated by a purge time between the two pulses, were used to produce SnO x The deposition of the films was carried out in a tubular reaction chamber: Reaction chamber temperature: 80°C Reaction chamber pressure: 200 torr Canister temperature: 52℃ Canister pressure: 230 torr N2 bubble flow rate: 230sccm N2 carrier flow rate: 700sccm Number of cycles: 300 Pulse sequence: (Me3Sn)2N(nPr)(4sccm): 10 seconds N2 flow (purge): 60 seconds O3(100sccm):30 seconds N2 flow (purge): 60 seconds

[0133] Based on the thickness measurements made by the ellipsometer, we extrapolate the results for films on Si substrates as follows: Substrate: Si (pretreated with HF) Average thickness: 15.1 nm Growth amount per cycle: 0.50 Å / cycle Refractive index: 1.87

[0134] Based on the atomic ratio profile estimated by XPS, the SnO formed by this method x The film consisted of a Sn:O ratio of 1:1.9.

[0135] Example 15: SnO using (Me3Sn)2N(nPr)+O3 at 80°C x High-pressure ALD of films (P=350 torr) Under the following experimental conditions, alternating pulses of (Me3Sn)2N(nPr) and O3, separated by a purge time between the two pulses, were used to produce SnO x The deposition of the films was carried out in a tubular reaction chamber: Reaction chamber temperature: 80°C Reaction chamber pressure: 350 torr Canister temperature: 52℃ Canister pressure: 400 torr N2 bubble flow rate: 400sccm N2 carrier flow rate: 1225sccm Number of cycles: 300 Pulse sequence: (Me3Sn)2N(nPr)(4sccm): 10 seconds N2 flow (purge): 60 seconds O3(100sccm):30 seconds N2 flow (purge): 60 seconds

[0136] Based on the thickness measurements made by the ellipsometer, we extrapolate the results for films on Si substrates as follows: Substrate: Si (pretreated with HF) Average thickness: 8.7 nm Growth amount per cycle: 0.29 Å / cycle Refractive index: 1.78

[0137] Based on the atomic ratio profile estimated by XPS, the SnO formed by this method x The film consisted of a Sn:O ratio of 1:1.83.

[0138] Example 16: SnO using "(Me3Sn)2N(nPr)+O2 plasma" at 80°C x PEALD OF MEMBRANE Under the following experimental conditions, alternating pulses of (Me3Sn)2N(nPr) and O2 direct plasma separated by a purge time between the two pulses produced SnO x The film deposition was performed on a Beneq tool: Reaction chamber temperature: 80°C Canister temperature: 52℃ Reaction chamber pressure: 1.0mbar (Me3Sn)2N(nPr) pulse pressure: 10.0mbar N2 carrier flow rate: 300sccm Number of cycles: 200 Pulse sequence: (Me3Sn)2N(nPr): 1 sec N2 flow (purge): 4 seconds O2 plasma: 4 seconds N2 flow (purge): 4 seconds Plasma Settings: Type: Direct plasma O2 flow rate: 100sccm Ar flow rate: 100sccm RF power: 200W

[0139] Based on the thickness measurements made by the ellipsometer, we extrapolate the results for films on Si substrates as follows: Thickness_Average: 22.6nm Growth rate: 1.13 Å / cycle Std. Non-uniformity (NU): 1.2% Refractive index: 1.99

[0140] Alternatively, when a H2O pulse was added between the precursor (Me3Sn)2N(nPr) pulse and the O2 direct plasma pulse separated by a purge time between each two pulses, no deposition film was observed in the following experimental conditions: Reaction chamber temperature: 80°C Canister temperature: 52℃ Reaction chamber pressure: 1.0mbar (Me3Sn)2N(nPr) pulse pressure: 10.0mbar H2O pulse pressure: 11.0mbar O2 pulse pressure: 20.0mbar O2 flow rate: 540sccm N2 carrier flow rate: 300sccm Number of cycles: 200 Pulse sequence: (Me3Sn)2N(nPr): 1 sec N2 flow (purge): 4 seconds H2O: 2 seconds N2 flow (purge): 2 seconds O2:2 seconds N2 flow (purge): 2 seconds

[0141] Based on thickness measurements made by ellipsometer, no film was observed to be deposited.

[0142] Although the subject matter described herein may be described in relation to example implementations for processing one or more computing application functions / operations for a computing application having a user-interactive component, the subject matter is not limited to these particular embodiments. Rather, the techniques described herein may be applied to any suitable type of user-interactive component execution management method, system, platform, and / or device.

[0143] It will be understood that many further modifications of the details, materials, steps and arrangements of parts described and illustrated herein to explain the nature of the invention may be made by those skilled in the art without departing from the principles and scope of the invention as set forth in the appended claims.Accordingly, it is not intended that the invention be limited to the specific embodiments in the foregoing examples and / or accompanying drawings.

[0144] Although embodiments of the present invention have been shown and described, modifications thereof may be made by those skilled in the art without departing from the spirit or teaching of the present invention. The embodiments described herein are illustrative only and not limiting. Many variations and modifications of the compositions and methods are possible and are within the scope of the present invention. Thus, the scope of protection is not limited to the embodiments described herein, but only by the claims, which shall include all equivalents of the subject matter of the claims.

Claims

1. 1. A method for forming a tin-containing film on a substrate, the method comprising: The substrate is formed of a compound having the general formula: (R) ３ (S) ２ NR' (Wherein, R and R′ are each independently H, C １ ~C ６ A linear, branched or cyclic alkyl group, or C １ ~C ４ exposing the film-forming composition to a vapor or liquid of a tin-containing precursor having a tin-containing group, the tin-containing group being a linear, branched or cyclic saturated hydrofluorocarbon group; and depositing at least a portion of the tin-containing precursor onto the substrate using a chemical vapor deposition process to form the tin-containing film.

2. 2. The method of claim 1, wherein the chemical vapor deposition process includes ALD, CVD, MLD, SOD, SOC, mist coating, dip coating, slit coating, spray coating, which may or may not be assisted by heat, light, direct or remote plasma, or combinations thereof.

3. The method of claim 1 , wherein the deposition temperature for the chemical vapor deposition process is about 100° C. or less.

4. The method of claim 1 , wherein the deposition temperature for the chemical vapor deposition process is about 80° C. or less.

5. The method of claim 1 , wherein the tin-containing precursor is a liquid at ambient temperature.

6. The method of claim 1 , wherein the tin-containing precursor is volatile at a temperature of about 100° C. or less.

7. The tin-containing precursor is ３ Sn) ２ N(cyclo-Pr), (Me ３ Sn) ２ N(sBu), (Me ３ Sn) ２ N(cyclo-Bu), (Me ３ Sn) ２ N(1-Pen), (Me ３ Sn) ２ N (2-Pen), (Me ３ Sn) ２ N (3-Pen), (Me ３ Sn) ２ N(tPen), (Me ３ Sn) ２ N (Neo-Pen), (Me ３ Sn) ２ N(Cyclo-Pen), (Me ３ Sn) ２ N(2-Hex), (Me ３ Sn) ２ N(3-Hex), (Me ３ Sn) ２ N(tHex), (Me ３ Sn) ２ N (Neo-Hex), (Me ３ Sn) ２ N(cyclo-Hex), (Me ３ Sn) ２ N (CH ２ CF ２ CF ３ ), (Me ３ Sn) ２ N(CH(CF ３ ) ２ ), (Me ３ Sn) ２ N (CH ２ (CF ２ ) ２ CF ３ ), (Me ３ Sn) ２ N(SiHMe ２ ), (Me ３ Sn) ２ N(SiEtMe ２ ), (Me ３ Sn) ２ N(SiEt ２ Me) ３ (S) ２ N(SiEt ３ ), (Et) ３ (S) ２ NỮMễ, (Et) ３ (S) ２ NEt、(Et ３ (S) ２ N(nPr), (Et ３ (S) ２ N(iPr), (Et ３ (S) ２ N(シクロ-Pr), (Et ３ (S) ２ N(nBu), (Et ３ (S) ２ N(sBu), (Et ３ (S) ２ N(iBu), (Et ３ (S) ２ N(tBu), (Et ３ (S) ２ N(CH ２ CF ３ ), (Et) ３ (S) ２ N(CH ２ CF ２ CF ３ ), (Et) ３ (S) ２ N(シクロ-Bu), (Et ３ (S) ２ N(1-Ppen), (Et ３ (S) ２ N(2-Ppen), (Et ３ (S) ２ N(3-Ppen), (Et ３ (S) ２ N(tPpen), (Et ３ (S) ２ N(ネオ-Ppen), (Et ３ (S) ２ N(シクロ-Ppen), (Et ３ (S) ２ N(1-Hex), (Et ３ (S) ２ N(2-Hex), (Et ３ (S) ２ N(3-Hex), (Et ３ (S) ２ N(tHex)、(Et ３ (Sn) ２ N(ネオ-Hex)、(Et ３ (Sn) ２ N(シクロ-Hex)、(Et ３ (Sn) ２ N(アリル)、(Et ３ (Sn) ２ N(CH(CF ３ ) ２ (), (Et) ３ (Sn) ２ N(CH ２ (CF ２ ) ２ CF ３ (), (Et) ３ (Sn) ２ N(SiMe ３ (), (Et) ３ (Sn) ２ N(SiHMe ２ (), (Et) ３ (Sn) ２ N(SiEtMe ２ (), (Et) ３ (Sn) ２ N(SiEt ２ (Me), (Et) ３ (Sn) ２ N(SiEt ３ ()、(nPr) ３ (Sn) ２ 1920s, 1930s ３ (Sn) ２ NEt、(nPr ３ (Sn) ２ N(nPr), nPr ３ (Sn) ２ N(iPr)、(nPr ３ (Sn) ２ N(シクロ-Pr)、(nPr ３ (Sn) ２ N(nBu)、(nPr ３ (Sn) ２ N(sBu)、(nPr ３ (Sn) ２ N(tBu)、(nPr ３ (Sn) ２ N(シクロ-Bu)、(nPr ３ (Sn) ２ N(1-Pen)、(nPr ３ (Sn) ２ N(2-Pen)、(nPr ３ (Sn) ２ N(3-Pen)、(nPr ３ (Sn) ２ N(tPen)、(nPr ３ (Sn) ２ N(ネオ-Pen)、(nPr ３ (Sn) ２ N(シクロ-Pen)、(nPr ３ (Sn) ２ N(1-Hex)、(nPr ３ (Sn) ２ N(2-Hex)、(nPr ３ (Sn) ２ N(3-Hex)、(nPr ３ (Sn) ２ N(tHex)、(nPr ３ (Sn) ２ N(ネオ-Hex)、(nPr ３ (Sn) ２ N(シクロ-Hex)、(nPr ３ (Sn) ２ N(アリル)、(nPr ３ (Sn) ２ N(CH ２ CF ３ ()、(nPr) ３ (Sn) ２ N(CH ２ CF ３ CF ３ ()、(nPr) ３ (Sn) ２ N(CH(CF ３ ) ２ ()、(nPr) ３ (Sn) ２ N(CH ２ (CF ２ ) ２ CF ３ ()、(nPr) ３ (Sn) ２ N(SiMe ３ ()、(nPr) ３ (Sn) ２ N(SiHMe ２ ()、(nPr) ３ (Sn) ２ N(SiEtMe ２ ()、(nPr) ３ (Sn) ２ N(SiEt ２ Me), (nPr ３ (Sn) ２ N (SiEt) ３ ), (nrr ３ (Sn) ２ NH, (nBu) ３ (Sn) ２ NMe, (nBu) ３ (Sn) ２ NET, (nBu) ３ (Sn) ２ NMe, (nBu) ３ (Sn) ２ N(nPr), (ｮBu ３ (Sn) ２ N(iPr), (NBu ３ (Sn) ２ N (シロロ-Pr), (nBu ３ (Sn) ２  ( Bu), ( Bu ３ (Sn) ２ N(sBu), (nBu ３ (Sn) ２ N(~Bu), (･Bu ３ (Sn) ２ N (cyclo-Bu), (nBu ３ (Sn) ２ N(1-P), (NBu ３ (Sn) ２ N(2-P), (NBu ３ (Sn) ２ (3-PPen), (nBu ３ (Sn) ２ N(~PPen), (NBu ３ (Sn) ２ N (ネオ-Pen), (nBu ３ (Sn) ２ N (シロロ-Pen), (nBu ３ (Sn) ２ N(1-+･), (nBu ３ (Sn) ２ N(2-+･), (nBu ３ (Sn) ２ N(3-M･), (nBu ３ (Sn) ２ N(tHex), (ｮBu ３ (Sn) ２ N(ネオ-Hex), (nBu ３ (Sn) ２ N(シクロ-Hex)、(nBu ３ Sn) ２ N(アリル)、(nBu ３ Sn) ２ N(CH ２ CF ３ )、(nBu ３ Sn) ２ N(CH ２ CF ３ CF ３ )、(nBu ３ Sn) ２ N(CH(CF ３ ) ２ )、(nBu ３ Sn) ２ N(CH ２ (CF ２ ) ２ CF ３ )、 (nBu ３ Sn) ３ N、(nBu ３ Sn) ２ N(SiMe ３ )、(nBu ３ Sn) ２ N(SiHMe ２ )、(nBu ３ Sn) ２ N(SiEtMe ２ )、(nBu ３ Sn) ２ N(SiEt ２ Me)、(nBu ３ Sn) ２ N(SiEt ３ )、(nBu ３ Sn) ２ NH、(nPen ３ Sn) ２ 2015-04-2016 ３ Sn) ２ 2015-2016 ３ Sn) ２ N(nPr)、(nPen ３ Sn) ２ N(iPr)、(nPen ３ Sn) ２ N(シクロ-Pr)、(nPen ３ Sn) ２ N(nBu)、(nPen ３ Sn) ２ N(sBu), (nPen ３ Sn) ２ N(tBu), (nPen ３ Sn) ２ N(cyclo-Bu), (nPen ３ Sn) ２ N(1-Pen), (nPen ３ Sn) ２ N(2-Pen), (nPen ３ Sn) ２ N(3-Pen), (nPen ３ Sn) ２ N(tPen), (nPen ３ Sn) ２ N (Neo-Pen), (nPen ３ Sn) ２ N (cyclo-Pen), (nPen ３ Sn) ２ N(1-Hex), (nPen ３ Sn) ２ N(2-Hex), (nPen ３ Sn) ２ N(3-Hex), (nPen ３ Sn) ２ N(tHex), (nPen ３ Sn) ２ N (Neo-Hex), (nPen ３ Sn) ２ N(cyclo-Hex), (nPen ３ Sn) ２ N (allyl), (nPen ３ Sn) ２ N (CH ２ CF ３ ), (nPen ３ Sn) ２ N (CH ２ CF ３ CF ３ ), (nPen ３ Sn) ２ N(CH(CF ３ ) ２ ), (nPen ３ Sn) ２ N (CH ２ (CF ２ ) ２ CF ３ ), (nPen ３ Sn) ３ N、(nPen ３ (S) ２ N (SiM) ３ ), (nPpen ３ (S) ２ N(SiHM% ２ ), (nPpen ３ (S) ２ N(SiEtMe ２ ), (nPpen ３ (S) ２ N(SiEt ２ Me), (nPpen ３ (S) ２ N(SiEt ３ ), (nPpen ３ (S) ２ NH、(n･ex) ３ (S) ２ NMe、(n･ex ３ (S) ２ NEt、(n･ex) ３ (S) ２ NMe、(n･ex ３ (S) ２ NEt、(n･ex) ３ (S) ２ N(nPr), (nHex ３ (S) ２ N(iPr), (nHex ３ (S) ２ N(シクロ-Pr), (nHex ３ (S) ２ N(nBu), (nHex ３ (S) ２ N(sBu), (nHex ３ (S) ２ N(tBu), (nHex ３ (S) ２ N (シ クロ-Bu)(nHex ３ (S) ２ N(1-Ppen), (nHex ３ (S) ２ N(2-Ppen), (nHex ３ (S) ２ N(3-Ppen), (nHex ３ (S) ２ N(tPP), (nHex ３ (S) ２ N(ネオ-Ppen), (nHex ３ (S) ２ N(シクロ-Ppen), (nHex ３ (S) ２ N(1-Hex), (nHex ３ (S) ２ N(2-Hex), (nHex ３ (S) ２ N(3-Hex), (nHex ３ (S) ２ N(tHex), (nHex ３ (S) ２ N(ネオ-Hex), (nHex ３ (S) ２ N(シクロ-Hex), (nHex ３ (S) ２ N(アリル), (nHex ３ (S) ２ N(CH) ２ CF ３ ), (n･ex) ３ (S) ２ N(CH) ２ CF ３ CF ３ ), (n･ex) ３ (S) ２ N(CH(CF ３ ) ２ ), (n･ex) ３ (S) ２ N(CH) ２ (CF) ２ ) ２ CF ３ ), (n･ex) ３ (S) ３ N、(nｭex) ３ (S) ２ N (SiM) ３ ), (n･ex) ３ (S) ２ N(SiHMe ２ )、(nHex ３ Sn) ２ N(SiEtMe ２ )、(nHex ３ Sn) ２ N(SiEt ２ Me)、(nHex ３ Sn) ２ N(SiEt ３ )、(nHex ３ Sn) ２ NH、(EtMe ２ Sn) ２ NMe、(EtMe ２ Sn) ２ NEt、(EtMe ２ Sn) ２ NMe、(EtMe ２ Sn) ２ NEt、(EtMe ２ Sn) ２ N(nPr)、(EtMe ２ Sn) ２ N(iPr)、(EtMe ２ ) ２ N(シクロ-Pr)、(EtMe ２ ) ２ N(nBu)、(EtMe ２ Sn) ２ N(sBu)、(EtMe ２ Sn) ２ N(tBu)、(EtMe ２ ) ２ N(シクロ-Bu)、(EtMe ２ Sn) ２ N(1-Pen)、(EtMe ２ Sn) ２ N(2-Pen)、(EtMe ２ Sn) ２ N(3-Pen)、(EtMe ２ Sn) ２ N(tPen)、(EtMe ２ Sn) ２ N(ネオ-Pen)、(EtMe ２ Sn) ２ N(シクロ-Pen)、(EtMe ２ Sn) ２ N(1-Hex)、(EtMe ２ Sn) ２ N(2-Hex)、(EtMe ２ Sn) ２ N(3-Hex)、(EtMe ２ Sn) ２ N(tHex)、(EtMe ２ Sn) ２ N(ネオ-Hex)、(EtMe ２ Sn) ２ N(シクロ-Hex)、(EtMe ２ Sn) ２ N(アリル)、(EtMe ２ Sn) ２ N(CH ２ CF ３ )、(EtMe ２ Sn) ２ N(CH ２ CF ３ CF ３ )、(EtMe ２ Sn) ２ N(CH(CF ３ ) ２ )、(EtMe ２ Sn) ２ N(CH ２ (CF ２ ) ２ CF ３ )、(EtMe ２ Sn) ３ N、(EtMe ２ Sn) ２ N(SiMe ３ )、(EtMe ２ Sn) ２ N(SiHMe ２ )、(EtMe ２ Sn) ２ N(SiEtMe ２ )、(EtMe ２ Sn) ２ N(SiEt ２ Me)、(EtMe ２ Sn) ２ N(SiEt ３ )、(EtMe ２ Sn) ２ NH、(nPrMe ２ Sn) ２ NMe、(nPrMe ２ Sn) ２ NEt、(nPrMe ２ Sn) ２ NMe, (nPrMe ２ Sn) ２ NEt, (nPrMe ２ Sn) ２ N(nPr), (nPrMe ２ Sn) ２ N(iPr), (nPrMe ２ ) ２ N(cyclo-Pr), (nPrMe ２ ) ２ N (nBu), (nPrMe ２ Sn) ２ N(sBu), (nPrMe ２ Sn) ２ N(tBu), (nPrMe ２ ) ２ N(cyclo-Bu), (nPrMe ２ Sn) ２ N(1-Pen), (nPrMe ２ Sn) ２ N(2-Pen), (nPrMe ２ Sn) ２ N(3-Pen), (nPrMe ２ Sn) ２ N(tPen), (nPrMe ２ Sn) ２ N (Neo-Pen), (nPrMe ２ Sn) ２ N(cyclo-Pen), (nPrMe ２ Sn) ２ N(1-Hex), (nPrMe ２ Sn) ２ N(2-Hex), (nPrMe ２ Sn) ２ N(3-Hex), (nPrMe ２ Sn) ２ N(tHex), (nPrMe ２ Sn) ２ N (neo-Hex), (nPrMe ２ Sn) ２ N(cyclo-Hex), (nPrMe ２ Sn) ２ N(allyl), (nPrMe ２ Sn) ２ N (CH ２ CF ３ ()、(nPrMe) ２ (Sn) ２ N(CH ２ CF ３ CF ３ ()、(nPrMe) ２ (Sn) ２ N(CH(CF ３ ) ２ ()、(nPrMe) ２ (Sn) ２ N(CH ２ (CF ２ ) ２ CF ３ ()、(nPrMe) ２ (Sn) ３ N、(nPrMe ２ (Sn) ２ N(SiMe ３ ()、(nPrMe) ２ (Sn) ２ N(SiHMe ２ ()、(nPrMe) ２ (Sn) ２ N(SiEtMe ２ ()、(nPrMe) ２ (Sn) ２ N(SiEt ２ Me)、(nPrMe ２ (Sn) ２ N(SiEt ３ ()、(nPrMe) ２ (Sn) ２ NH!(iPrMee ２ (Sn) ２ NMe、(iPrMe ２ (Sn) ２ NEt、(iPrMe ２ (Sn) ２ N(nPr) and (iPrMe ２ (Sn) ２ N(iPr)、(iPrMe ２ ) ２ N(シクロ-Pr)、(iPrMe ２ ) ２ N(nBu)、(iPrMe ２ (Sn) ２ N(sBu)、(iPrMe ２ (Sn) ２ N(tBu)、(iPrMe ２ ) ２ N(シクロ-Bu), (iPrMe ２ (S) ２ N (1-Pen), (iPrｭe ２ (S) ２ N (2-Pen), (iPrｭe ２ (S) ２ N (3-Pen), (iPrｭe ２ (S) ２ N(tPe), (iPrMe ２ (S) ２ N(ネオ-Ppen), (iPrMe ２ (S) ２ N(シクロ-Pen), (iPrMe ２ (S) ２ N(1-Hex), (iPrMe ２ (S) ２ N(2-Hex), (iPrMe ２ (S) ２ N(3-Hex), (iPrMe ２ (S) ２ N(tHex), (iPrMe ２ (S) ２ N(ネオ-Hex), (iPrMe ２ (S) ２ N(シクロ-Hex), (iPrMe ２ (S) ２ N(アリル),(iPrMe ２ (S) ２ N(CH) ２ CF ３ ), (iｰrｭe ２ (S) ２ N(CH) ２ CF ３ CF ３ ), (inrrｭe ２ (S) ２ N(CH(CF ３ ) ２ ), (iｰrｭe ２ (S) ２ N(CH) ２ (CF) ２ ) ２ CF ３ ), (iｰrｭe ２ (S) ２ N (SiM) ３ ), (iｰrｭe ２ (S) ２ N (SiHMe) ２ ), (iPrMe) ２ (Sn) ２ N (Si Et Me) ２ ), (iPrMe) ２ (Sn) ２ N (SiEt) ２ Me), (iPPMe ２ (Sn) ２ N (SiEt) ３ ), (iPrMe) ２ (Sn) ２ NH, (nBuMe) ２ (Sn) ２ NMe、(ｮBuMe ２ (Sn) ２ NEt、(NBuMe ２ (Sn) ２ NMe、(ｮBuMe ２ (Sn) ２ NEt、(NBuMe ２ (Sn) ２ N(nPr), (nBuMe ２ (Sn) ２ N(iPr), (NBuMe ２ ) ２ N (シロロ-Pr), (nBuMe ２ ) ２ N (nBu), (nBuMe ２ (Sn) ２ N(sBu), (nBuMe ２ (Sn) ２ N(~Bu), (ｮBuMe ２ ) ２ N (cyclo-Bu), (nBuMe ２ (Sn) ２ N(1-PPen), (NBuMe ２ (Sn) ２ N(2-P), (NBuMe ２ (Sn) ２ N(3-PPen), (nBuMe ２ (Sn) ２ N(~PP), (NBuMe ２ (Sn) ２ N(ネオ-Pen), (nBuMe ２ (Sn) ２ N (シロロ-Pen), (nBuMe ２ (Sn) ２ N(1-Hex), (&BuMe ２ Sn) ２ N(2-Hex)、(nBuMe ２ Sn) ２ N(3-Hex)、(nBuMe ２ Sn) ２ N(tHex)、(nBuMe ２ Sn) ２ N(ネオ-Hex)、(nBuMe ２ Sn) ２ N(シクロ-Hex)、(nBuMe ２ Sn) ２ N(アリル)、(nBuMe ２ Sn) ２ N(CH ２ CF ３ )、(nBuMe ２ Sn) ２ N(CH ２ CF ３ CF ３ )、(nBuMe ２ Sn) ２ N(CH(CF ３ ) ２ )、(nBuMe ２ Sn) ２ N(CH ２ (CF ２ ) ２ CF ３ )、(nBuMe ２ Sn) ３ N、(nBuMe ２ Sn) ２ N(SiMe ３ ), (nBuｭe ２ (S) ２ N(SiHM%) ２ ), (nBuｭe ２ (S) ２ N(SiEtMe ２ ), (nBuｭe ２ (S) ２ N(SiEt ２ Me), (nBuMe ２ (S) ２ N(SiEt ３ ), (nBuｭe ２ (S) ２ NH、(s｢uｭe ２ (S) ２ NMe、(sBuMe ２ (S) ２ NEt、(sBuMe ２ (S) ２ NMe、(sBuMe ２ (S) ２ NEt、(sBuMe ２ (S) ２ N(nPr), (sBuMe ２ (S) ２ N(iPr), (sBuMe ２ ) ２ N(シクロ-Pr), (sBuMe ２ ) ２ N(nBu), (sBuMe ２ (S) ２ N(sBu), (sBuMe ２ (S) ２ N(tBu), (sBuMe ２ ) ２ N(シクロ-Bu), (sBuMe ２ (S) ２ N(1-PP),(sBuMe ２ (S) ２ N(2-PP), (sBuMe ２ (S) ２ N(3-PP),(sBuMe ２ (S) ２ N(tPen),(sBuMe ２ (S) ２ N(ネオ-PP), (sBuMe ２ (S) ２ N(シクロ-Pen)、(sBuMe ２ Sn) ２ N(1-Hex)、(sBuMe ２ Sn) ２ N(2-Hex)、(sBuMe ２ Sn) ２ N(3-Hex)、(sBuMe ２ Sn) ２ N(tHex)、(sBuMe ２ Sn) ２ N(ネオ-Hex)、(sBuMe ２ Sn) ２ N(シクロ-Hex)、(sBuMe ２ Sn) ２ N(アリル)、(sBuMe ２ Sn) ２ N(CH ２ CF ３ )、(sBuMe ２ Sn) ２ N(CH ２ CF ３ CF ３ )、(sBuMe ２ Sn) ２ N(CH(CF ３ ) ２ )、(sBuMe ２ Sn) ２ N(CH ２ (CF ２ ) ２ CF ３ )、(sBuMe ２ Sn) ３ N、(sBuMe ２ Sn) ２ N(SiMe ３ )、(sBuMe ２ Sn) ２ N(SiHMe ２ )、(sBuMe ２ Sn) ２ N(SiEtMe ２ )、(sBuMe ２ Sn) ２ N(SiEt ２ Me)、(sBuMe ２ Sn) ２ N(SiEt ３ )、(sBuMe ２ Sn) ２ NH, (tBuMe ２ Sn) ２ NMe, (tBuMe ２ Sn) ２ NEt, (tBuMe ２ Sn) ２ NMe, (tBuMe ２ Sn) ２ NEt, (tBuMe ２ Sn) ２ N(nPr), (tBuMe ２ Sn) ２ N(iPr), (tBuMe ２ ) ２ N(cyclo-Pr), (tBuMe ２ ) ２ N (nBu), (tBuMe ２ Sn) ２ N(sBu), (tBuMe ２ Sn) ２ N(tBu), (tBuMe ２ ) ２ N(cyclo-Bu), (tBuMe ２ Sn) ２ N(1-Pen), (tBuMe ２ Sn) ２ N(2-Pen), (tBuMe ２ Sn) ２ N(3-Pen), (tBuMe ２ Sn) ２ N(tPen), (tBuMe ２ Sn) ２ N (Neo-Pen), (tBuMe ２ Sn) ２ N(cyclo-Pen), (tBuMe ２ Sn) ２ N(1-Hex), (tBuMe ２ Sn) ２ N(2-Hex), (tBuMe ２ Sn) ２ N(3-Hex), (tBuMe ２ Sn) ２ N(tHex), (tBuMe ２ Sn) ２ N (Neo-Hex), (tBuMe ２ Sn) ２ N(cyclo-Hex), (tBuMe ２ Sn) ２ N(アリル)、(tBuMe ２ Sn) ２ N(CH ２ CF ３ )、(tBuMe ２ Sn) ２ N(CH ２ CF ３ CF ３ )、(tBuMe ２ Sn) ２ N(CH(CF ３ ) ２ )、(tBuMe ２ Sn) ２ N(CH ２ (CF ２ ) ２ CF ３ )、(tBuMe ２ Sn) ３ N、(tBuMe ２ Sn) ２ N(SiMe ３ )、(tBuMe ２ Sn) ２ N(SiHMe ２ )、(tBuMe ２ Sn) ２ N(SiEtMe ２ )、(tBuMe ２ Sn) ２ N(SiEt ２ Me)、(tBuMe ２ Sn) ２ N(SiEt ３ )、(tBuMe ２ Sn) ２ NH、(Me ２ HSn) ２ NMe、(Me ２ HSn) ２ NEt、(Me ２ HSn) ２ N(nPr)、(Me ２ HSn) ２ N(iPr)、(Me ２ HSn) ２ N(シクロ-Pr)、(Me ２ HSn) ２ N(nBu)、(Me ２ HSn) ２ N(sBu)、(Me ２ HSn) ２ N(iBu)、(Me ２ HSn) ２ N(tBu)、(Me ２ HSn) ２ N(シクロ-Bu)、(Me ２ HSn) ２ N(1-Pen)、(Me ２ HSn) ２ N(2-Pen)、(Me ２ HSn) ２ N(3-Pen)、(Me ２ HSn) ２ N(tPen)、(Me ２ HSn) ２ N(ネオ-Pen)、(Me ２ HSn) ２ N(シクロ-Pen)、(Me ２ HSn) ２ N(1-Hex)、(Me ２ HSn) ２ N(2-Hex)、(Me ２ HSn) ２ N(3-Hex)、(Me ２ HSn) ２ N(tHex)、(Me ２ HSn) ２ N(ネオ-Hex)、(Me ２ HSn) ２ N(シクロ-Hex)、(Me ２ HSn) ２ N(アリル)、(Me ２ HSn) ２ N(CH ２ CF ３ )、(Me ２ HSn) ２ N(CH ２ CF ２ CF ３ )、(Me ２ HSn) ２ N(CH(CF ３ ) ２ )、(Me ２ HSn) ２ N(CH ２ (CF ２ ) ２ CF ３ )、(Me ２ HSn) ３ 9、(7e ２ 200) ２ 8(3)71 ３ )、(7e ２ 200) ２ 8(3i27e ２ )、(7e ２ 200) ２ 8(3iEtte ２ )、(7e ２ 200) ２ 8(3iEt ２ Me)、(Me ２ 200) ２ 8(3iEt ３ )、(7e ２ 200) ２ 8、(7e ２ 200) ３ 9、(712) ２ 3n) ２ <e、(Meeｨ ２ 3n) ２ 8Et、Meｨ ２ 3n) ２ <(nPr)、(7eeｨ ２ 3n) ２ 8(iPrr)、(7eeｨ ２ 3n) ２ The ２ 3n) ２ <(nBuu)、(7eeｨ ２ 3n) ２ <(sBuu)、(7eeｨ ２ 3n) ２ <(tBuu)、(7eeｨ ２ 3n) ２ 8(シクロ-3〕)、(7ヅ2 ２ 3n) ２ 8(101)、(71) ２ 3n) ２ 8(201)、(71) ２ 3n) ２ 8(3-101)、(71) ２ 3n) ２ <(tPenn)、(7eeｨ ２ 3n) ２ <(ネオ-Pennn)、(7eeｨ ２ 3n) ２ The ２ 3n) ２ N(1-Hex)、(MeH ２ (Sn) ２ N(2-Hex)、(MeH ２ (Sn) ２ N(3-Hex)、(MeH ２ (Sn) ２ N(tHex)、(MeH ２ (Sn) ２ N(ネオ-Hex)、(MeH ２ (Sn) ２ N(シクロ-Hex)、(MeH ２ (Sn) ２ N(アリル)、(MeH ２ (Sn) ２ N(CH ２ CF ３ (), (MeH) ２ (Sn) ２ N(CH ２ CF ３ CF ３ (), (MeH) ２ (Sn) ２ N(CH(CF ３ ) ２ (), (MeH) ２ (Sn) ２ N(CH ２ (CF ２ ) ２ CF ３ (), (MeH) ２ (Sn) ３ N,(Me) ２ (Sn) ２ N(SiMe ３ (), (MeH) ２ (Sn) ２ N(SiHMe ２ (), (MeH) ２ (Sn) ２ N(SiEtMe ２ (), (MeH) ２ (Sn) ２ N(SiEt ２ (Me), (MeH) ２ (Sn) ２ N(SiEt ３ (), (MeH) ２ (Sn) ２ () ３ (Sn) ２ (NMe、(H ３ (Sn) ２ NEt, (H ３ Sn) ２ N(nPr), (H ３ Sn) ２ N(iPr), (H ３ Sn) ２ N(cyclo-Pr), (H ３ Sn) ２ N(nBu), (H ３ Sn) ２ N(sBu), (H ３ Sn) ２ N(tBu), (H ３ Sn) ２ N(cyclo-Bu), (H ３ Sn) ２ N (1-Pen), (H ３ Sn) ２ N (2-Pen), (H ３ Sn) ２ N (3-Pen), (H ３ Sn) ２ N(tPen), (H ３ Sn) ２ N (Neo-Pen), (H ３ Sn) ２ N(cyclo-Pen), (H ３ Sn) ２ N(1-Hex), (H ３ Sn) ２ N(2-Hex), (H ３ Sn) ２ N(3-Hex), (H ３ Sn) ２ N(tHex), (H ３ Sn) ２ N (Neo- ()、(() ３ )) ２ (シクロ-Hex)、(; ３ )) ２ (アリル)、(); ３ )) ２ !!(|) ２ .. ３ )、() ３ )) ２ !!(|) ２ .. ３ .. ３ )、() ３ )) ２ !!(|(). ３ ) ２ )、() ３ )) ２ !!(|) ２ (|) ２ ) ２ .. ３ )、() ３ )) ３ 、(): ３ )) ２ *()) ** ３ )、() ３ )) ２ #())||| ２ )、() ３２ )) ２ #(3)##| ２ )、() ３ )) ２ ())t ２ **)、() ３ )) ２ ())t ３ )、(#] ２ _)) ２ #||、(#| ２ _)) ２ ##、(#] ２ _)) ２ (#)、(#) ２ _)) ２ シクロ!Pr)、(!44 ２ _)) ２ #(||)、(#] ２ _)) ２ #(#|)、(#] ２ _)) ２ #(#|)、(#] ２ _)) ２ N (シクロ-Bu), (Et ２ HSn) ２ N(1-P), (E｣ ２ HSn) ２ N(2-P), (Et ２ HSn) ２ N(3-P), (E｣ ２ HSn) ２ N (tP), (･t ２ HSn) ２ N (ネオ-P), (E｣ ２ HSn) ２ N (シクロ-P), (Et ２ HSn) ２ N(1-Hex), (Et ２ HSn) ２ N(2-Hex), (Et ２ HSn) ２ N(3-Hex), (Et ２ HSn) ２ N(tHex), (･t ２ HSn) ２ N(ネオ-Hex), (Et ２ HSn) ２ N (シクロ-Hex), (Et ２ HSn) ２ N (アリル), (Et ２ HSn) ２ N (CH (CF) ３ ) ２ ), (Et ２ HSn) ２ N (CH) ２ (CF) ２ ) ２ CF ３ ), (Et ２ HSn) ３ N, (Et) ２ HSn) ２ N (SiMe) ３ ), (Et ２ HSn) ２ N (SiHMe) ２ ), (Et ２ HSn) ２ N (SiEtMe) ２ ), (Et ２ HSn) ２ N (SiEt) ２ Me), (Et ２ HSn) ２ N(SiEt ３ )、(Et ２ HSn) ２ NH、(EtH ２ Sn) ２ NMe、(EtH ２ Sn) ２ NEt、(EtH ２ Sn) ２ N(nPr)、(EtH ２ Sn) ２ N(iPr)、(EtH ２ Sn) ２ N(シクロ-Pr)、(EtH ２ Sn) ２ N(nBu)、(EtH ２ Sn) ２ N(sBu)、(EtH ２ Sn) ２ N(tBu)、(EtH ２ Sn) ２ N(シクロ-Bu)、(EtH ２ Sn) ２ N(1-Pen)、(EtH ２ Sn) ２ N(2-Pen)、(EtH ２ Sn) ２ N(3-Pen)、(EtH ２ Sn) ２ N(tPen)、(EtH ２ Sn) ２ N(ネオ-Pen)、(EtH ２ Sn) ２ N(シクロ-Pen)、(EtH ２ Sn) ２ N(1-Hex)、(EtH ２ Sn) ２ N(2-Hex)、(EtH ２ Sn) ２ N(3-Hex)、(EtH ２ Sn) ２ N(tHex)、(EtH ２ Sn) ２ N(ネオ-Hex)、(EtH ２ Sn) ２ N(シクロ-Hex)、(EtH ２ Sn) ２ N(アリル)、(EtH ２ Sn) ２ N (CH ２ CF ３ ), (EtH ２ Sn) ２ N (CH ２ CF ３ CF ３ ), (EtH ２ Sn) ２ N(CH(CF ３ ) ２ ), (EtH ２ Sn) ２ N (CH ２ (CF ２ ) ２ CF ３ ), (EtH ２ Sn) ３ N, (EtH ２ Sn) ２ N(SiMe ３ ), (EtH ２ Sn) ２ N(SiHMe ２ ), (EtH ２ Sn) ２ N(SiEtMe ２ ), (EtH ２ Sn) ２ N(SiEt ２ Me), (EtH ２ Sn) ２ N(SiEt ３ ), (EtH ２ Sn) ２ NH, or combinations thereof.

8. The tin precursor is (Me ３ Sn) ２ 2. The method of claim 1, wherein the .alpha.-methyl.beta.-propanediol is NEt.

9. The tin precursor is (Me ３ Sn) ２ 2. The method of claim 1 , wherein N(nPr) is N(nPr).

10. The tin precursor is (Me ３ Sn) ２ 2. The method of claim 1 , wherein N(nBu).

11. The tin precursor is (Me ３ Sn) ２ N (CH ２ CF ３ 2. The method of claim 1 , wherein

12. The substrate is ２ , O ３ , H ２ O, H ２ O ２ , NO, N ２ O, NO ２ an oxidizing agent selected from O radicals, alcohols, silanols, aminoalcohols, carboxylic acids, paraformaldehyde, or mixtures thereof, or NH ３ , N ２ , H ２ , N ２ / H ２ , H ２ and N.H. ３ , N ２ and N.H. ３ , N.H. ３ and N ２ H ４ , NO, N ２ 10. The method of claim 1, further comprising exposing to a co-reactant comprising a nitrogen-containing reducing agent selected from: primary amines such as O, amines, diamines, cyanides, diimines, hydrazines, organic amines, pyrazolines, pyridines, methylamines, ethylamines, tertbutylamines, etc.; secondary amines such as dimethylamine, diethylamine, diisopropylamine, ethylmethylamine, pyrrolidine, etc.; trimethylamine, triethylamine, trisilylamine, or mixtures thereof.

13. The coreactant is O ３ , O ２ , H ２ O ２ Or H ２ The method of claim 12, wherein

14. The tin-containing film is SnO ２ , InSnO (ITO), ZnSnO (ZTO), SnN, SnP, SnAs, SnSb or Sn ２ S ３ The method according to any one of claims 1 to 13, wherein

15. 14. The method of any one of claims 1 to 13, wherein the tin-containing film comprises a second element selected from Zn, In, Ga, N, S, P, As, Sb, B, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, Bi, Pb, Co, one or more lanthanides, or mixtures thereof.

16. 14. The method of any one of claims 1 to 13, wherein the substrate is a powder comprising one or more of NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode active materials.

17. 1. A film-forming composition for a vapor deposition process, comprising the general formula: (R) ３ (S) ２ NR' (Wherein, R and R′ are each independently H, C １ ~C ６ A linear, branched or cyclic alkyl group, or C １ ~C ４ A film-forming composition comprising a tin-containing precursor having a tin-containing group, the tin-containing group being a linear, branched or cyclic saturated hydrofluorocarbon group.

18. The tin-containing precursor is ３ Sn) ２ NEt, (Me ３ Sn) ２ N(nPr), (Me ３ Sn) ２ N(nBu) and (Me ３ Sn) ２ N (CH ２ CF ３ 20. The film-forming composition of claim 17, wherein the film-forming composition is selected from the group consisting of:

19. 19. The film-forming composition of claim 17 or 18, wherein the purity of the tin-containing precursor is greater than 99%.

20. 19. The film-forming composition of claim 17 or 18, wherein the tin-containing precursor is liquid at ambient temperature and volatile at temperatures below about 100°C.

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