Indium precursors for vapor deposition

Abstract

Indium(In)-containing film-forming compositions comprising In(III)-containing precursors containing halogen, methods of synthesizing the same, and methods of using the same to deposit indium-containing films and / or indium-containing alloy films are disclosed. The disclosed In(III)-containing precursors contain chlorine with nitrogen-based ligands. In particular, the disclosed In(III)-containing precursors contain 1 or 2 amidinate ligands, 1 or 2 imidazolylpyrrolidinato ligands, 1 or 2 amidoaminoalkane ligands, 1 or 2 μ-bis-ketimine ligands, or silylamide ligands. The disclosed In(III)-containing precursors are suitable for vapor deposition (e.g., ALD, CVD) of indium-containing films and / or indium-containing alloy films.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Application No. 17 / 063,768, filed October 6, 2020, which is incorporated herein by reference in its entirety for all purposes. Technical Field

[0003] The present invention relates to indium(III) film-forming compositions comprising halogen-containing In(III) precursors, methods for their synthesis, and methods for using them to deposit indium-containing films and / or indium-containing alloy films, particularly to chlorine-containing In(III) precursors having nitrogen-based ligands suitable for vapor deposition (e.g., ALD, CVD) of indium-containing films and / or indium-containing alloy films. Background Technology

[0004] Indium-containing alloys, thin films, and nanostructured materials are highly versatile optoelectronic materials, widely used in research and industry, particularly in the semiconductor industry, and applied in many fields, including electronics and photonics. For example, InGaAs is considered one of the strong contenders to replace silicon in future CMOS systems. InGaAs is also a key component in fiber optic communications, used as a high-speed, high-sensitivity photodetector. Despite the impressive physical properties of indium alloys and virtually all Group III-V alloys, these materials are hampered by two key challenges. The synthesis of these materials is limited to slow growth processes, such as molecular beam epitaxy, or by metal-organic chemical vapor deposition, which requires large quantities of materials and challenging engineering to achieve throughput, uniformity, and reproducibility. The next challenge specifically relates to the semiconductor industry. Combining Group III-V semiconductors with silicon is extremely challenging and has hindered the rapid development of high-performance devices. Developing new precursors for Group III-V alloys, including indium, that are compatible with high-throughput production and easy device integration is highly desirable for multiple industries.

[0005] Homogeneous indium precursors have been studied for use in deposition processes. For example, Kim et al. (“Obtaining a Low and Wide Atomic Layer Deposition Window (150–275 °C) for In₂O₃ Films Using an In…”) III Amidinate and H2O [using amidoyl In] III[“Low and wide atomic layer deposition window (150℃-275℃) for In2O3 films obtained with H2O”, Chem. Eur. J [European Journal of Chemistry]. 2018, 24, 9525] discloses two new In complexes for ALD of In2O3, including tris(N,N'-diisopropylformamidinyl)indium(III). The results are compared with homogeneous alkyl and aryl indium complexes (CH3CH2)3In, (CH3)3In, and CpIn (Cp = cyclopentadienyl).

[0006] US Patent 20130273250 by Fujimura et al. discloses (amide-aminoalkane) metal compounds and a method for fabricating metal-containing thin films using said metal compounds, wherein a series of novel homogeneous amide-aminoalkane metal complexes are used for chemical vapor deposition (CVD). The disclosed metal complexes include lithium, sodium, magnesium, manganese, iron, cobalt, nickel, zinc, yttrium, lanthanum, and indium complexes.

[0007] Specific examples include

[0008]

[0009] It was distilled under reduced pressure (130℃, 13.3Pa) to separate it as a semi-solid wax.

[0010] Gebhard et al. disclosed the synthesis of two homogeneous indium-tris-guanidinates (“Indium-tris-guanidinates: A Promising Class of Precursors for Water Assisted Atomic Layer Deposition of In2O3 Films”, Dalton Trans, 2014, 43, 937). The compounds were isolated as solids and used in the indium oxide ALD process.

[0011] McCarthy et al. (“Oxygen-Free Atomic Layer Deposition of Indium Sulfide”, ACS Appl. Mater. Interfaces, 2014, 6, 12137) disclosed an amidine-indium(III) complex for use indium sulfide ALD using hydrogen sulfide.

[0012] Hybrid indium precursors have been investigated for use in deposition processes. Examples of hybrid indium(III) precursors include alkyl ligands, acetates, and hydroxyl ligands. For example, low-temperature growth of indium oxide films via plasma-enhanced ALD using liquid dimethyl(N-ethoxy-2,2-dimethylpropionamide)indium is used for high-mobility thin-film transistor applications. Kim et al., ACS Appl. Mater. Interfaces, 2016, 8, 40, 26924.

[0013] Martinson et al.'s US 2016017485 discloses a method for atomic layer deposition of indium sulfide films using synthetic indium precursors and hydrogen sulfide. Koh et al.'s US 20160326008 details the heterojunction indium(III) precursors bis(trimethylsilyl)aminodiethylindium and dimethyl(3-dimethylaminopropyl)indium, which are liquid at room temperature.

[0014] Gebhard et al. (Novel indium(III) amidine salt complexes: Promising CVD precursors for transparent and conductive In2O3 thin films, Dalton Trans., 2013, 00, 1-3) detailed the synthesis of two novel heterojunction indium precursors: [InCl(amd)2] and [InMe(amd)2]. However, only the chloride-containing precursors were synthesized, and they were not used for deposition or their thermal properties were investigated.

[0015] Curley et al.'s WO 2017083483 (US 20170137360) details the synthesis of a dicarboxylic acid monohydroxyindium precursor. Several examples of this precursor for solution-phase synthesis of InP nanostructures are provided.

[0016] Seki et al. (Indium tin oxide thin films prepared by dip-coating of indium diacetate monohydroxide and tin dichloride, Thin Solid Films, 2001, 388, 22-26) disclosed the preparation of tin-doped In2O3 (ITO) films by dip-coating an ethanol solution of indium diacetate monohydroxide (In(OH)(CH3COO)2) and tin dichloride (SnCl2·2H2O) with 2-aminoethanol (monoethanolamine) H2NC2H4OH.

[0017] Patton et al. (Chelating Diamide Group IV Metal Olefin Polymerization. Organometallics, 2002, 21, 10, 2145) disclosed the synthesis of indium dichloro-tert-butyl-N,N'-diisopropylamidine salt as an intermediate in the process, yielding an indium-bridged chelate diamide titanium complex, which was used as a catalyst for olefin polymerization. The amidine indium compound was cleanly isolated in 48% yield and used... 1 H, 13 C10 NMR spectroscopy and HRMS characterization.

[0018] Campbell et al.'s WO 0146201A1 (US 20020098973A1) discloses a wide range of bridged Group 4 transition metal complexes. For those indium-containing bridged Group 4 transition metal complexes, dichloroindium-tert-butyl-N,N'-diisopropylamidine salt was synthesized as an intermediate.

[0019] Debnicke et al. (N,N,N'-tris(trimethylsilyl) as reagents in complex chemistry) J. Organomet. Chem, 1988, 352, (1-2), C1) disclosed that dichloroindium-phenyl-N,N'-bis(trimethylsilyl)amidine salts were synthesized during screening reactions of N,N,N'-tris(trimethylsilyl)organamidines with group and transition metal halides. The isolation or characterization of indium complexes was not reported.

[0020] Kottmair-Maieron et al. (R2M(NR')2XR type monomeric dialkyl metal complexes, where M = aluminum, gallium, indium, thallium; x = sulfur, carbon and R, R' = alkyl and silyl, Z. Anorg. Allg. Chem [Journal of Inorganic and General Chemistry], 1991, 593, 111) disclosed a series of Group III compounds using the reported amidine skeleton. The synthesis of indium dichloromethyl-N,N'-diisopropylamidinium salt was reported as a low-melting-point solid and characterized by NMR and IR spectroscopy; no further applications of the molecule were reported.

[0021] Hwang et al. (J. Cryst. Growth, 1981, Vol. 55, No. 1, pp. 116-124) disclosed the reaction of indium trichloride acetonitrile adduct InCl3 (NCCH3) with CuCl (NCCH3) as a copper source. n Both (both dissolved in acetonitrile solvent, NCCH3) and hydrogen sulfide (H2S) as a sulfur source are combined and applied as precursors for growing CuInS2 layers on GaP substrates via MOCVD. Precursor vapor is generated by bubbling N2 through a source dissolved in acetonitrile. Summary of the Invention

[0022] A method for forming an indium (III)-containing film on a substrate is disclosed, the method comprising the following steps:

[0023] Expose the substrate to vapors containing a film-forming composition with an indium(III) precursor; and

[0024] At least a portion of the indium(III) precursor is deposited on the substrate by vapor deposition to form the indium(III) film on the substrate.

[0025] The indium(III)-containing precursor has the following formula:

[0026] (a)

[0027] or

[0028]

[0029] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 and R 2 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups or -SiR groups. 4 R 5 R 6 , where R 4 R 5 R 6 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 3 Selected from H or straight-chain, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or -NR 7 R 8 , where R 7 and R 8 Each is independently selected from H or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R 1 R 2and R 3 When the structure can function as a dimer, it can be considered a dimeric structure. exist,

[0030] (b)

[0031] or

[0032]

[0033] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 It can also be -SiR 8 R 9 R 10 , where R 8 R 9 R 10 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R... 1 R 2 and R 3 When the structure can function as a dimer, it can be considered a dimeric structure. exist,

[0034] (c)[(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 InX2,

[0035] [(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 )]2InX, or

[0036] [((R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 ))InX]2(μ-X)2,

[0037] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 It can also be -SiR 8 R 9 R 10 , where R 8 R 9 R 10 Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. For these In(III)-containing precursors, n=1 or 2 will provide 5-membered or 6-membered metal ring compounds, respectively. For structures where n=2, the R group on each C is... 6 and R 7 Identities are not required. Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R... 1 R 2 and R 3 And when n=1, the structure can be considered a dimer structure [((R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 [InX]2(μ-X)2 exists.

[0038] (d) or

[0039]

[0040] Where X is a halogen, preferably chlorine; R 1 R 2 R 3 R 4 and R 5 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 and R 5 It can also be -SiR 6 R 7 R 8 , where R 6 R 7 R 8 Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Group R 1 R 2 R 3 and R 5 It can also be selected from fluorinated straight-chain or aromatic groups (e.g., CF3, m-(CF3)2-C6H3, etc.). Group R 4 It can also be selected from halogens, such as F.

[0041] as well as

[0042] (e)[N((SiR 1 R 2 R 3 )R 4 InX2

[0043] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 and R 3 Each is independently selected from hydrogen or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups, R 4 It is hydrogen or a straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl group or -SiR 5 R 6 R 7 Group, wherein R 5 R 6 and R 7 Each group is independently selected from hydrogen or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups.

[0044] The disclosed methods may include one or more of the following:

[0045] X is a chloride;

[0046] The indium(III) precursor is

[0047] The indium(III) precursor is or

[0048] The indium(III) precursor is

[0049] The indium(III) precursor is

[0050] • The indium (III)-containing film is an indium oxide film, or a binary, ternary, or quaternary indium alloy film;

[0051] • The indium (III) film is, but is not limited to, the following layers: InGaAs, In x O y (x = 0.5 to 1.5, y = 0.5 to 1.5), InSnO (ITO), InGaZnO (IGZO), InN, InP, InAs, InSb, In2S3, or In(OH)3;

[0052] • The indium(III) film is a pure indium (In(0)) layer;

[0053] • The indium-containing film contains a second element selected from the following: P, N, S, Ga, As, B, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co, Zn, one or more lanthanides, or a combination thereof;

[0054] • The vapor deposition method is the ALD method, the CVD method, or a combination thereof;

[0055] • The vapor deposition method is either the PEALD method or the spatial ALD method;

[0056] The method further includes the step of exposing the substrate to the co-reactant;

[0057] • The co-reactants are selected from O3, O2, H2O, NO, N2O, NO2, H2O2, O free radicals and their combinations;

[0058] • The co-reactant is O3 or O2;

[0059] • The co-reactants are selected from NH3, NO, N2O, hydrazine, N2 plasma, N2 / H2 plasma, NH3 plasma, amines and combinations thereof;

[0060] The co-reactant is NH3;

[0061] • The co-reactant is N2 plasma;

[0062] • The co-reactant is treated with plasma;

[0063] The substrate is a powder;

[0064] The powder contains one or more of NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials;

[0065] • Deposition pressure remains at approximately 10 -3 Between approximately 100 and 100 tots;

[0066] • Deposition pressure remains at approximately 10 -2 Between 100 and 100 tots;

[0067] The deposition temperature was maintained between approximately 100°C and approximately 600°C.

[0068] The deposition temperature was maintained between approximately 150°C and approximately 500°C; and

[0069] • The walls of the deposition reactor are heated from approximately 50°C to approximately 600°C.

[0070] A method for forming an indium(III) film on a substrate is also disclosed, the method comprising the following steps:

[0071] A chemisorption and / or physisorption film having the following formula is formed on the surface of the substrate:

[0072] (a)

[0073] or

[0074]

[0075] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 and R 2 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups or -SiR groups. 4 R 5 R 6 , where R 4 R 5 R 6 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 3 Selected from H or straight-chain, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or -NR 7 R 8 , where R 7 and R8 Each is independently selected from H or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R 1 R 2 and R 3 When the structure can function as a dimer, it can be considered a dimeric structure. exist,

[0076] (b)

[0077]

[0078]

[0079] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 It can also be -SiR 8 R 9 R 10 , where R 8 R 9 R 10 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R... 1 R 2 and R 3 When the structure can function as a dimer, it can be considered a dimeric structure. exist,

[0080] (c)[(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 InX2,

[0081] [(R 2 R 3 )N-(CR6 R 7 ) n -C(R 4 R 5 )-N(R 1 )]2InX, or

[0082] [((R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 ))InX]2(μ-X)2,

[0083] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 It can also be -SiR 8 R 9 R 10 , where R 8 R 9 R 10 Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. For In(III) precursors, n=1 or 2 provides 5- or 6-membered metal ring compounds, respectively. For structures where n=2, the R group... 6 and R 7 Identities are not required. Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R... 1 R 2 and R 3 And when n=1, the structure can be considered a dimer structure [((R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 [InX]2(μ-X)2 exists.

[0084] (d) or

[0085]

[0086] Where X is a halogen, preferably chlorine; R 1 R 2 R 3 R 4 and R 5 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 and R 5 It can also be -SiR 6 R 7 R 8 , where R 6 R 7 R 8 Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Group R 1 R 2 R 3 and R 5 It can also be selected from fluorinated straight-chain or aromatic groups (e.g., CF3, m-(CF3)2-C6H3, etc.). Group R 4 It can also be selected from halogens, such as F.

[0087] as well as

[0088] (e)[N((SiR 1 R 2 R 3 )R 4 InX2

[0089] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 and R 3 Each is independently selected from hydrogen or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups, R 4 It is hydrogen or a straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl group or -SiR 5 R 6 R 7 Group, wherein R 5 R 6 and R 7 Each group is independently selected from hydrogen or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups.

[0090] The disclosed methods may include one or more of the following:

[0091] The method further includes the step of chemically reacting the membrane containing the indium(III) precursor, which is chemically adsorbed and / or physically adsorbed, with the co-reactant;

[0092] • The co-reactant reacts with the indium(III) precursor in the chemisorbed and / or physisorbed film to generate a reaction product, which forms the indium(III) film on the surface of the substrate.

[0093] • The co-reactants are selected from O3, O2, H2O, NO, N2O, NO2, H2O2, O radicals, and combinations thereof; and

[0094] • The co-reactants are selected from NH3, NO, N2O, hydrazine, N2 plasma, N2 / H2 plasma, NH3 plasma, amines and combinations thereof.

[0095] A composition for depositing a film comprising an indium(III) precursor having the following formula is also disclosed:

[0096] (a)

[0097] or

[0098]

[0099] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 and R 2 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups or -SiR groups. 4 R 5 R 6 , where R 4 R 5 R 6 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 3 Selected from H or straight-chain, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or -NR 7 R 8 , where R 7 and R 8 Each is independently selected from H or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R 1 R 2 and R 3 When the structure can function as a dimer, it can be considered a dimeric structure. exist,

[0100] (b)

[0101] or

[0102]

[0103] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 It can also be -SiR 8 R 9 R 10 , where R 8 R 9 R 10 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R... 1 R 2 and R 3 When the structure can function as a dimer, it can be considered a dimeric structure. exist,

[0104] (c)[(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 InX2,

[0105] [(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 )]2InX, or

[0106] [((R 2 R 3)N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 ))InX]2(μ-X)2,

[0107] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 It can also be -SiR 8 R 9 R 10 , where R 8 R 9 R 10 Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. For these In(III)-containing precursors, n=1 or 2 will provide 5-membered or 6-membered metal ring compounds, respectively. For structures where n=2, the group R 6 and R 7 Identities are not required. Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R... 1 R 2 and R 3 And when n=1, the structure can be considered a dimer structure [((R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 [InX]2(μ-X)2 exists.

[0108] (d) or

[0109]

[0110] Where X is a halogen, preferably chlorine; R 1 R 2 R 3R 4 and R 5 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 and R 5 It can also be -SiR 6 R 7 R 8 , where R 6 R 7 R 8 Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Group R 1 R 2 R 3 and R 5 It can also be selected from fluorinated straight-chain or aromatic groups (e.g., CF3, m-(CF3)2-C6H3, etc.). Group R 4 It can also be selected from halogens, such as F.

[0111] as well as

[0112] (e)[N((SiR 1 R 2 R 3 )R 4 InX2

[0113] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 and R 3 Each is independently selected from hydrogen or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups, R 4 It is hydrogen or a straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl group or -SiR 5 R 6 R 7 Group, wherein R 5 R 6 and R 7 Each group is independently selected from hydrogen or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups.

[0114] The disclosed methods may include one or more of the following:

[0115] X is a chloride;

[0116] The indium(III) precursor was selected from or

[0117] The indium(III) precursor is

[0118] The indium(III) precursor is

[0119] The indium(III) precursor is

[0120] The indium(III) precursor is

[0121] The indium(III) precursor has a purity ranging from approximately 93% w / w to approximately 100% w / w; and

[0122] The indium(III) precursor has a purity ranging from about 99% w / w to about 99.999% w / w.

[0123] Symbols and nomenclature

[0124] The following detailed description and claims utilize many abbreviations, symbols, and terms commonly known in the art. Specific abbreviations, symbols, and terms are used throughout the following description and claims, and include:

[0125] As used in this article, the indefinite article “a or an” means one or more species.

[0126] As used herein, “about” or “around or approximately” in the text or claims means ±10% of the stated value.

[0127] As used herein, “room temperature” in the text or claims means from about 20°C to about 25°C.

[0128] The term "ambient temperature" refers to the ambient temperature, which is approximately 20°C to approximately 25°C.

[0129] The term "substrate" refers to one or more materials on which processes are performed. A substrate can refer to a wafer having one or more materials on which processes are performed. A substrate can be any suitable wafer used in the manufacture of semiconductor, photovoltaic, flat panel, or LCD-TFT devices. A substrate can also have one or more different material layers deposited thereon from previous manufacturing steps. For example, a wafer can include silicon layers (e.g., crystalline, amorphous, porous, etc.), silicon-containing layers (e.g., SiO2, SiN, SiON, SiCOH, etc.), metal-containing layers (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.), or combinations thereof. Furthermore, a substrate can be planar or patterned. A substrate can be an organically patterned photoresist film. The substrate may include an oxide layer used as a dielectric material (e.g., ZrO2-based, HfO2-based, TiO2-based, rare earth oxide-based, ternary oxide-based, etc.) 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 terms "film" or "layer" as used herein refer to a material of a certain thickness placed or spread on a surface, and that surface may be trenches or lines. Throughout the specification and claims, the wafer and any associated layers thereon are referred to as a substrate.

[0130] 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 morphological features that have been generated in a step prior to the deposition of an indium-containing film.

[0131] The term "aspect ratio" refers to the ratio of the height of a groove (or hole) to the width of the groove (or the diameter of the hole).

[0132] It should be noted in this document that the terms “film” and “layer” are used interchangeably. It should be understood that a film can correspond to or be associated with a layer, and a layer can refer to a film. Furthermore, those skilled in the art will recognize that, as used herein, the terms “film” or “layer” refer to a material of a certain thickness placed or spread on a surface, and that surface can range from as large as an entire wafer to as small as a trench or line.

[0133] It should be noted in this article that the terms “aperture,” “via,” “hole,” and “trench” are used interchangeably to refer to openings formed in semiconductor structures.

[0134] As used herein, the abbreviation “NAND” refers to a “Negative AND or Not AND” gate; the abbreviation “2D” refers to a 2D gate structure on a planar substrate; and the abbreviation “3D” refers to a 3D or vertical gate structure in which the gate structures are stacked in the vertical direction.

[0135] It should be noted in this document that the terms "deposition temperature" and "substrate temperature" are used interchangeably. It should be understood that substrate temperature can correspond to or be related to deposition temperature, and deposition temperature can refer to substrate temperature.

[0136] It should be noted in this document that when the precursor is in a gaseous state at room temperature and ambient pressure, the terms "precursor," "deposited compound," and "deposited gas" are used interchangeably. It should be understood that a precursor can correspond to, or be associated with, a deposited compound or deposited gas, and a deposited compound or deposited gas can refer to a precursor.

[0137] This article uses standard abbreviations of elements from the periodic table. It should be understood that elements may be referred to by these abbreviations (e.g., Si for silicon, N for nitrogen, O for oxygen, C for carbon, H for hydrogen, F for fluorine, etc.).

[0138] A unique CAS registry number (“CAS”) assigned by the Chemical Abstracts Service is provided to identify the specific molecule disclosed.

[0139] Please note that silicon-containing films, such as SiN and SiO, are listed throughout this specification and claims without mentioning their proper stoichiometry. Silicon-containing films may include pure silicon (Si) layers, such as crystalline Si, polycrystalline silicon (p-Si or polycrystalline Si), or amorphous silicon; silicon nitride (SiO2)... k N l ) layer; or silicon dioxide (Si) n O m The silicon nitride is a layer; or a mixture thereof, wherein k, l, m, and n range from 0.1 to 6 (inclusive of the endpoints). Preferably, the silicon nitride is Si. k N l Where k and I each range from 0.5 to 1.5. More preferably, silicon nitride is Si3N4. In this document, SiN as described below can be used to represent Si-containing silicon. k N l The layer. Preferably, the silicon oxide is Si. n O m Where n ranges from 0.5 to 1.5 and m ranges from 1.5 to 3.5. More preferably, the silicon oxide is SiO2. In this document, SiO as described below can be used to represent Si-containing... n Om The silicon-containing film may also be a silicon oxide-based dielectric material, such as an organic-based or silicon oxide-based low-k dielectric material, such as Applied Materials, Inc.'s Black Diamond II or III materials (with the formula SiOCH). The silicon-containing film may also include 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.

[0140] As used herein, the term "alkyl group" refers to a saturated or unsaturated functional group containing only carbon and hydrogen atoms. As used herein, the term "alkyl group" refers to a saturated functional group containing only carbon and hydrogen atoms. An alkyl group is a hydrocarbon group. Additionally, the term "alkyl" 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, etc. Examples of branched alkyl groups include, but are not limited to, tert-butyl. Examples of cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, etc.

[0141] As used in this article, the abbreviation "Me" refers to methyl; the abbreviation "Et" refers to ethyl; the abbreviation "Pr" refers to any propyl (i.e., n-propyl or isopropyl); the abbreviation "iPr" refers to isopropyl; the abbreviation "Bu" refers to any butyl (n-butyl, isobutyl, tert-butyl, sec-butyl); the abbreviation "tBu" refers to tert-butyl; the abbreviation "sBu" refers to sec-butyl; the abbreviation "iBu" refers to isobutyl; the abbreviation "Ph" refers to phenyl; the abbreviation "Am" refers to any pentyl (isopentyl, sec-pentyl, tert-pentyl); the abbreviation "Cy" refers to cyclic hydrocarbons (cyclobutyl, cyclopentyl, cyclohexyl, etc.); and the abbreviation "Ar" refers to aromatic hydrocarbons (phenyl, xylyl, mesityl, etc.).

[0142] As used in this article, the formula or It can be represented by the following structure:

[0143]

[0144] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 and R 2 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups or -SiR groups. 4 R 5 R 6 , where R 4 R 5 R 6Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl groups; R 3 Selected from H or straight-chain, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or -NR 7 R 8 , where R 7 and R 8 Each is independently selected from H or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R 1 R 2 and R 3 When the structure can function as a dimer, it can be considered a dimeric structure. exist.

[0145] As used in this article, the formula It can be represented by the following structure:

[0146]

[0147] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 and R 2 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups or -SiR groups. 4 R 5 R 6 , where R 4 R 5 R 6 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 3 Selected from H or straight-chain, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or -NR 7 R 8 , where R 7 and R 8 Each group is independently selected from H or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups.

[0148] As used in this article, the formula or It can be represented by the following structure:

[0149]

[0150] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 R 3 R 4 R 5 R 6 and R 7Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 It can also be -SiR 8 R 9 R 10 , where R 8 R 9 R 10 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R... 1 R 2 and R 3 When the structure can function as a dimer, it can be considered a dimeric structure. exist,

[0151] As used in this article, the formula It can be represented by the following structure:

[0152]

[0153] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 It can also be -SiR 8 R 9 R 10 , where R 8 R 9 R 10 Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups.

[0154] As used in this article, the formula [(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R5 )-N(R 1 )]InX2 or [((R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 InX]2(μ-X)2 is represented by the following structure:

[0155]

[0156] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 It can also be -SiR 8 R 9 R 10 , where R 8 R 9 R 10 Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. For these In(III)-containing precursors, n=1 or 2 will provide 5-membered or 6-membered metal ring compounds, respectively. For structures where n=2, the group R 6 and R 7 Identities are not required. Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R... 1 R 2 and R 3 And when n=1, the structure can be considered a dimer structure [((R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 ))InX]2(μ-X)2 exists.

[0157] As used in this article, the formula [(R 2 R3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 ]2InX is represented by the following structure:

[0158]

[0159] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 It can also be -SiR 8 R 9 R 10 , where R 8 R 9 R 10 Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups.

[0160] As used in this article, the formula It can be represented by the following structure:

[0161]

[0162] Where X is a halogen, preferably chlorine; R 1 R 2 R 3 R 4 and R 5 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 and R 5 It can also be -SiR 6 R 7 R 8 , where R 6 R 7 R 8Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Group R 1 R 2 R 3 and R 5 It can also be selected from fluorinated straight-chain or aromatic groups (e.g., CF3, m-(CF3)2-C6H3, etc.). Group R 4 It can also be selected from halogens, such as F.

[0163] As used in this article, the formula It can be represented by the following structure:

[0164]

[0165] Where X is a halogen, preferably chlorine; R 1 R 2 R 3 R 4 and R 5 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 and R 5 It can also be -SiR 6 R 7 R 8 , where R 6 R 7 R 8 Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Group R 1 R 2 R 3 and R 5 It can also be selected from fluorinated straight-chain or aromatic groups (e.g., CF3, m-(CF3)2-C6H3, etc.). Group R 4 It can also be selected from halogens, such as F.

[0166] As used in this article, the formula [N((SiR)] 1 R 2 R 3 )R 4 InX2 is represented by the following structure:

[0167]

[0168] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 and R 3 Each is independently selected from hydrogen or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups, R4 It is hydrogen or a straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl group or -SiR 5 R 6 R 7 Group, wherein R 5 R 6 and R 7 Each group is independently selected from hydrogen or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups.

[0169] In this document, a range may be expressed as from about one specific value and / or to about another specific value. When such a range is expressed, it should be understood that another embodiment is from one specific value and / or to another specific value, together with all combinations within said range. Any and all ranges listed herein include their endpoints (i.e., x = 1 to 4, or x in the range from 1 to 4, including x = 1, x = 4, and x = any number in between), regardless of whether the term "inclusive" is used.

[0170] In this document, references to "an embodiment" or "embodiment" mean that a particular feature, structure, or characteristic described with respect to that embodiment may be included in at least one embodiment of the invention. The phrase "in an embodiment" appearing in different places in the specification does not necessarily refer to the same embodiment in all instances, and individual or alternative embodiments are not necessarily mutually exclusive with other embodiments. The foregoing also applies to the term "implementation".

[0171] As used herein, when used in the context of describing an R group, the term "independently" should be understood to mean that the subject R group is chosen independently not only relative to other R groups with the same or different subscripts or superscripts, but also relative to any additional kind of the same R group. For example, in the formula MR 1 x (NR 2 R 3 ) (4-x) In the case where x is 2 or 3, two or three R 1 Groups may (but need not) be identical to each other or with R 2 Or R 3 The same. Furthermore, it should be understood that, unless otherwise specified, the values ​​of the R group are independent of each other when used in different formulas.

[0172] As used herein, the term “exemplary” is used to mean serving as an instance, example, or illustration. Any aspect or design described herein as “exemplary” is not necessarily to be construed as superior to or advantageous to other aspects or designs. Rather, the use of the term “exemplary” is intended to present the concept in a concrete manner.

[0173] Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". That is, unless otherwise stated or clear from the context, "X adopts A or B" is intended to mean any natural inclusive arrangement. That is, if X adopts A; X adopts B; or X adopts both A and B, then "X adopts A or B" is satisfied in any of the foregoing cases. Additionally, the article "a / an" as used in this application and the appended claims should generally be interpreted as meaning "one or more" unless otherwise stated or clearly indicated from the context to the singular form.

[0174] The term “comprising” in the claims is an open-ended transitional term, meaning that the subsequently determined claim elements are a non-exclusive list (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” is defined herein as necessary to encompass the more restrictive transitional terms “substantially consists of” and “consisting of”; therefore, “comprising” can be replaced by “substantially consists of” or “consisting of” and remain within the clearly defined scope of “comprising”.

[0175] In the claims, "provide" is defined as supplying, providing, making available, or preparing something. The steps can, conversely, be performed by any actor even if not explicitly stated in the claims. Attached Figure Description

[0176] To further understand the nature and purpose of the present invention, reference should be made to the following detailed description in conjunction with the accompanying drawings, in which similar elements are given the same or similar reference numerals, and in the drawings:

[0177] Figure 1 yes The results of vacuum thermogravimetric analysis (TGA);

[0178] Figure 2 yes Differential scanning calorimetry (DSC) results;

[0179] Figure 3 yes In C6D6 1 H NMR;

[0180] Figure 4 yes The TGA results;

[0181] Figure 5 yes DSC results;

[0182] Figure 6 yes In THF-d81 H NMR;

[0183] Figure 7 yes The TGA results;

[0184] Figure 8 yes DSC results;

[0185] Figure 9 yes In C6D6 1 H NMR;

[0186] Figure 10 yes The TGA results;

[0187] Figure 11 yes In C6D6 1 H NMR;

[0188] Figure 12 yes The TGA results; and

[0189] Figure 13 yes In C6D6 1 H NMR. Detailed Implementation

[0190] Film-forming compositions comprising indium (In) films and / or indium alloys containing halogen-containing In(III) precursors are disclosed, as well as methods for their synthesis and methods for using them to deposit indium-containing films and / or indium alloy films.

[0191] While some homopolymeric indium precursors exist, there is a lack of halogen-containing heteropolymeric complexes that can be used as precursors. The advantage of using heteropolymeric compounds is the ability to incorporate organic ligands and other reactive ligands, such as halogens, which may be beneficial to the desired surface chemistry. InCl3 has been used for deposition; however, its very low volatility (boiling point 800 °C, vapor pressure 1 Torr at 310 °C) makes it unsuitable for most applications. The disclosed In(III)-containing precursors not only include at least one halogen but also an organic ligand that significantly increases volatility relative to InCl3, making the vapor pressure of the disclosed In(III)-containing precursors sufficient for commercially viable vapor deposition (e.g., CVD and ALD) methods. The In(III)-containing precursors disclosed herein are indium(III)-containing precursors that will be referred to as In(III)-containing precursors throughout the patent application.

[0192] The disclosed In(III)-containing precursor contains one or two halogen ligands. More preferably, the disclosed In(III)-containing precursor contains chlorine with a nitrogen-based ligand, which is suitable for vapor deposition of indium-containing films and / or indium-containing alloy films.

[0193] The disclosed In(III)-containing precursors include the following categories.

[0194] In the first embodiment, the disclosed In(III)-containing precursor contains one or two amidine ligands having the following formula:

[0195]

[0196]

[0197]

[0198] or

[0199]

[0200] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 and R 2 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups or -SiR groups. 4 R 5 R 6 , where R 4 R 5 R 6 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 3 Selected from H or straight-chain, branched or cyclic C1 to C8 alkyl, vinyl or aryl groups or -NR 7 R 8 , where R 7 and R 8 Each group is independently selected from H or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups.

[0201] Having a style Exemplary precursors include:

[0202] X = Cl, R 1 =R 2 =iPr,R 3 =tBu, (N,N'-Diisopropyl-tert-butylformamidinyl)indium(III)dichloride);

[0203] X = Cl, R 1 =Et,R 2 =tBu,R 3=Me, (N-tert-butyl-N'-ethylacetamidine)indium(III) dichloride);

[0204] X = Cl, R 1 =Et,R 2 =R 3 =tBu, (N-tert-butyl-N'-ethylbutylformamidinyl)indium(III)dichloride);

[0205] X = Cl, R 1 =R 2 =Ph,R 3 =Me, (N,N'-Diphenylacetamidine)indium(III)dichloride);

[0206] X = Cl, R 1 =R 2 =iPr,R 3 =NEt2, (N,N'-diisopropyl-2-diethylamino-guanidin)indium dichloride); and

[0207] X = Cl, R 1 =Et,R 2 =tBu,R 3 =NEt2, (N-tert-butyl-N'-ethyl-2-diethylamino-guanidin)indium dichloride.

[0208] Having the formula [(R 1 N = C(R) 3 )-N(R 2 Exemplary precursors for 2InX include:

[0209] X = Cl, R 1 =R 2 =iPr,R 3 =nBu, (bis-(N,N'-diisopropylbutylformamidinyl)indium(III)chloride));

[0210] X = Cl, R 1 =R 2 =iPr,R 3 =H, (bis-(N,N'-diisopropylformamidinyl)indium(III)chloride));

[0211] X = Cl, R 1 =Et,R 2 =tBu,R 3 =Me, (bis-(N-tert-butyl-N'-ethylacetamidine)indium(III)chloride));

[0212] X = Cl, R 1 =Et,R 2 =tBu,R 3 =nBu, (bis-(N-tert-butyl-N'-ethylbutylformamidinyl)indium(III)chloride));

[0213] X = Cl, R 1 =R 2 =Ph,R 3 =Me, (bis-(N,N'-diphenylacetamidine)indium(III) chloride);

[0214] X = Cl, R 1 =R 2 =iPr,R 3 =NEt2, (bis-(N,N'-diisopropyl-2-diethylamino-guanidinyl))indium(III) chloride); and

[0215] X = Cl, R 1 =Et,R 2 =tBu,R 3 =NEt2, (bis-(N-tert-butyl-N'-ethyl-2-diethylamino-guanidinyl)indium chloride)).

[0216] Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R 1 R 2 and R 3 At that time, the structure can be used as a formula The dimer exists. It has the formula... Exemplary precursors include:

[0217] X = Cl,

[0218] X = Cl, (N,N'-Dimethyl-acetamidine)indium(III) dichloride);

[0219] X = Cl, R 1 =R 2 =Me,R 3 =H, (N,N'-Dimethylformamidinyl)indium(III)dichloride);

[0220] X = Cl, R 1 =R2 =Et,R 3 =H, (N,N'-diethylmethylammonium)indium(III)dichloride); and

[0221] X = Cl, R 1 =R 2 =iPr,R 3 =H, (N,N'-Diisopropylformamidinyl)indium(III)dichloride);

[0222] In the second embodiment, the disclosed In(III)-containing compound contains one or two iminopyrrolidine ligands having the following formula:

[0223]

[0224]

[0225]

[0226] or

[0227]

[0228] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 It can also be -SiR 8 R 9 R 10 , where R 8 R 9 R 10 Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups.

[0229] have Exemplary precursors include:

[0230] R 1 =tBu,R 2 =R 3 =Me,R 4 =R5 =R 6 =R 7 =H, (tert-butyl-imino-2,2-dimethylpyrrolidine-N,N')indium(III) dichloride;

[0231] X = Cl, R 1 =tBu,R 2 =R 3 =Et,R 4 =R 5 =R 6 =R 7 =H, (tert-butyl-imino-2,2-diethylpyrrolidine-N,N')indium(III) dichloride; and

[0232] X = Cl, R 1 =tBu,R 2 =Et,R 3 =Me,R 4 =R 5 =R 6 =R 7 =H, (tert-butyl-imino-2-ethyl-2-methylpyrrolidine-N,N')indium(III) dichloride.

[0233] Having a style Exemplary precursors include:

[0234] X = Cl, R 1 =iPr,R 2 =R 3 =Me,R 4 =R 5 =R 6 =R 7 =H, (bis-(isopropyl-imino-2,2-dimethylpyrrolidine-N,N')indium(III))chloride;

[0235] X = Cl, R 1 =tBu,R 2 =R 3 =Me,R 4 =R 5 =R 6 =R 7 =H, (bis-(tert-butyl-imino-2,2-dimethylpyrrolidine-N,N')indium(III))chloride;

[0236] X = Cl, R 1 =tBu,R 2 =R3 =Et,R 4 =R 5 =R 6 =R 7 =H, (bis-(tert-butyl-imino-2,2-diethylpyrrolidine-N,N')indium(III) chloride; and

[0237] X = Cl, R 1 =tBu,R 2 =Et,R 3 =Me,R 4 =R 5 =R 6 =R 7 =H, (bis-(tert-butyl-imino-2-ethyl-2-methylpyrrolidine-N,N')indium(III) chloride.

[0238] Under certain conditions, when the disclosed In(III)-containing precursor has a sufficiently small R 1 R 2 and R 3 At that time, the structure can be used as a formula The dimer exists. It has the formula... Exemplary precursors include:

[0239] X = Cl, R 1 =R 2 =R 3 =R 4 =R 5 =R 6 =R 7 =H,

[0240] X = Cl, R 1 =R 2 =R 3 =Me,R 4 =R 5 =R 6 =R 7 =H,

[0241] X = Cl, R 1 =Me,R 2 =R 3 =R 4 =R 5 =R 6 =R 7 =H, as well as

[0242] X = Cl, R 1 =iPr,R2 =R 3 =R 4 =R 5 =R 6 =R 7 =H,

[0243] In the third embodiment, the disclosed In(III)-containing precursor contains one or two amide-aminoalkane ligands having the following formula:

[0244] [(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 InX2,

[0245] [(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 )]2InX,

[0246] [((R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 ))InX]2(μ-X)2,

[0247] or

[0248]

[0249] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 R 5 R 6 and R7 It can also be -SiR 8 R 9 R 10 , where R 8 R 9 R 10 Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. For these In(III)-containing precursors, n=1 or 2 will provide 5-membered or 6-membered metal ring compounds, respectively. For structures where n=2, the group R 6 and R 7 They do not have to be the same.

[0250] Having the formula [(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 Exemplary precursors for InX2 include:

[0251] X = Cl, R 1 =R 2 =R 3＝ iPr, R 4 =R 5 =R 6 =R 7 =H, n=1, [(iP2)N-CH2-CH2-N(iPr)]InCl2(1-isopropylamide-2-diisopropylaminoethane-N,N')indium(III)dichloride);

[0252] X = Cl, R 1 =tBu,R 2 =R 3 =Me,R 4 =R 5 =R 6 =R 7 =H, n=1, [(Me2)N-CH2-CH2-N(tBu)]InCl2(1-tert-butylamide-2-dimethylaminoethane-N,N')indium(III)dichloride);

[0253] X = Cl, R 1 =tBu,R 2 =R 3 =Me,R 4 =R 5 =R 6 =R 7=H, n=2, [(Me2)N-CH2-CH2-CH2-N(tBu)]InCl2(1-tert-butylamide-3-dimethylaminopropane-N,N')indium(III)dichloride); and

[0254] X = Cl, R 1 =tBu,R 2 =R 3 =R 4 =Me,R 5 =R 6 =R 7 =H, n=1, [(Me2)N-CH2-CH2-CH2-N(tBu)]InCl2(1-tert-butylamide-2-dimethylaminopropane-N,N')indium(III)dichloride).

[0255] Having the formula [(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 Exemplary precursors for 2InX include:

[0256] X = Cl, R 1 =iPr,R 2 =R 3 =Me,R 4 =R 5 =R 6 =R 7 =H, n=1, [(Me2)N-CH2-CH2-N(iPr)]2InCl(bis-(1-isopropylamide-2-dimethylaminoethane-N,N')indium(III)chloride));

[0257] X = Cl, R 1 =R 2 =R 3 =Et,R 4 =R 5 =R 6 =R 7 =H, n=1, [(Et2)N-CH2-CH2-N(Et)]2InCl(bis-(1-ethylamide-2-diethylaminoethane-N,N')indium(III)chloride));

[0258] X = Cl, R 1 =R 2 =R 3 =Me,R 4 =R 5 =R6 =R 7 =H, n=2, [(Me2)N-CH2-CH2-CH2-N(Me)]2InCl(bis-(1-methylamido-2-dimethylaminopropane-N,N')indium(III)chloride));

[0259] X = Cl, R 1 =tBu,R 2 =R 3 =Me,R 4 =R 5 =R 6 =R 7 =H, n=2, [(Me2)N-CH2-CH2-CH2-N(tBu)]2InCl(bis-(1-tert-butylamide-2-dimethylaminopropane-N,N')indium(III)chloride)).

[0260] Having the formula [((R) 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 Exemplary precursors of [InX]2(μ-X)2 include:

[0261] X = Cl, R 1 =Me,R 2 =R 3 =H,R 4 =R 5 =R 6 =R 7 =H, n=1, [((H2)N-CH2-CH2-N(Me))InCl]2(μ-Cl)2;

[0262] X = Cl, R 1＝ R 2 =R 3 =Me,R 4 =R 5 =R 6 =R 7 =H, n=1, [((Me2)N-CH2-CH2-N(Me))InCl]2(μ-Cl)2; and

[0263] X = Cl, R 1＝ R 2 =R 3 =Et,R 4 =R 5 =R 6 =R 7=H, n=1, [((Et2)N-CH2-CH2-N(Et))InCl]2(μ-Cl)2.

[0264] In the fourth embodiment, the disclosed In(III)-containing precursor contains one or two μ-dienone imine ligands having the following formula:

[0265]

[0266] or

[0267]

[0268] Where X is a halogen, preferably chlorine. R 1 R 2 R 3 R 4 and R 5 Each is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups; R 1 R 2 R 3 R 4 and R 5 It can also be -SiR 6 R 7 R 8 , where R 6 R 7 R 8 Each group is independently selected from straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups. Group R 1 R 2 R 3 and R 5 It can also be selected from fluorinated straight-chain or aromatic groups (e.g., CF3, m-(CF3)2-C6H3, etc.). Group R 4 It can also be selected from halogens, such as F.

[0269] Having a style Exemplary precursors include:

[0270] X = Cl, R 1 =R 2 =R 3 =R 5 =Me,R 4 =H, ([N,N'-(1,3-dimethyl-1,3-propanediyl)bis[methylamino]indium(III) chloride);

[0271] X = Cl, R 1 =R 2=Me,R 3 =R 5 =CF 3 R 4 =H, ([N,N'-(1,3-bis(trifluoromethyl)-1,3-propanediyl)bis[methylamino]indium(III) chloride);

[0272] X = Cl, R 1 =R 2 =Ph,R 3 =R 5 =Me,R 4 =H, ([N,N'-(1,3-dimethyl-1,3-propanediyl)bis[aniline]indium(III) chloride);

[0273] X = Cl, R 1 =R 2 =iPr,R 3 =R 5 =Me,R 4 =H, ([N,N'-(1,3-dimethyl-1,3-propanediyl)bis[isopropylamino]indium(III) chloride); and

[0274] X = Cl, R 1 =R 2 =tBu,R 3 =R 5 =Me,R 4 =H, ([N,N'-(1,3-dimethyl-1,3-propanediyl)bis[tert-butylamino]indium(III) chloride).

[0275] Having a style Exemplary precursors include:

[0276] X = Cl, R 1 =R 2 =R 3 =R 5 =Me,R 4 =H, (bis-[N,N'-(1,3-dimethyl-1,3-propanediyl)bis[methylamino]indium(III) chloride);

[0277] X = Cl, R 1 =R 2 =Ph,R3 =R 5 =Me,R 4 =H, (bis-[N,N'-(1,3-dimethyl-1,3-propanediyl)bis[anilino]indium(III) chloride);

[0278] X = Cl, R 1 =R 2 =iPr,R 3 =R 5 =Me,R 4 =H, (bis-[N,N'-(1,3-dimethyl-1,3-propanediyl)bis[isopropylamino]indium(III) chloride); and

[0279] X = Cl, R 1 =R 2 =tBu,R 3 =R 5 =Me,R 4 =H, (bis-[N,N'-(1,3-dimethyl-1,3-propanediyl)bis[tert-butylamino]indium(III) chloride).

[0280] In the fifth embodiment, the disclosed In(III)-containing precursor contains a silylamine ligand having the following formula:

[0281] [N((SiR 1 R 2 R 3 )R 4 InX2

[0282] or

[0283]

[0284] Where X is selected from chlorine, bromine, and iodine, preferably chlorine; R 1 R 2 and R 3 Each is independently selected from hydrogen or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups, R 4 It is hydrogen or a straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl group or -SiR 5 R 6 R 7 Group, wherein R 5 R 6 and R 7Each group is independently selected from hydrogen or straight-chain, branched, or cyclic C1 to C9 alkyl, vinyl, or aryl groups.

[0285] Having the formula [N((SiR 1 R 2 R 3 )R 4 Exemplary precursors for InX2 include:

[0286] X = Cl, R 1 =R 2 =R 3 =Me,R 4 =H, [N((SiMe3)H)]InCl2(trimethylsilyl)amino)indium(III)dichloride;

[0287] X = Cl, R 1 =R 2 =R 3 =Et,R 4 =H, [N((SiEt3)H)]InCl2(triethylsilyl)amino)indium(III) dichloride; and

[0288] X = Cl, R 1 =R 2 =Me,R 3 =H,R 4 =SiHMe2,[N(SiMe2H)2]InCl2(bis(dimethylsilyl)amino)indium(III) chloride.

[0289]

[0290] More preferably, the disclosed In(III)-containing precursor has the following structure

[0291]

[0292] The disclosed In(III)-containing precursors have the following structure depending on given conditions. or

[0293]

[0294] The disclosed In(III)-containing precursor has the following structure

[0295]

[0296] The disclosed In(III)-containing precursor has the following structure

[0297]

[0298] The disclosed In(III)-containing precursor has the following structure

[0299]

[0300] The vapor pressure at 145°C is 1 Torr. The vapor pressure at 128°C is 1 Torr. The vapor pressure at 155°C is 1 Torr. The vapor pressure at 127°C is 1 Torr. See Table 1.

[0301] Table 1. Precursors containing In(III)

[0302]

[0303] The disclosed method for synthesizing the disclosed In(III)-containing precursor includes a salt metathesis reaction as illustrated in the following examples. The disclosed In(III)-containing precursor can be synthesized via a salt metathesis reaction by mixing one or two equivalents of a lithium-ionized ligand with InX3 (where X = Cl, Br, I). The reaction is carried out by charging the desired nitrogen ligand in an ether solvent in a reaction flask and cooling it to 0°C or -78°C. The desired alkyllithium reagent is added to produce a reactive lithiumized form of the ligand. The lithium-ionized ligand is then transferred to a suspension of the desired In(III) halide in an ether solvent at -78°C or 0°C. The reaction is stirred for 12 hours. The solution is then filtered using diatomaceous earth as a filter, followed by vacuum removal of the solvent to separate the product. The lithium-ionized amidine ligand (e.g., In this case, the desired starting material is the corresponding carbodiimide [(R 1 N = C = N(R) 2 Furthermore, the alkyllithium reagent is LiR. 3 .

[0304] The disclosed methods for synthesizing the disclosed In(III)-containing precursors include a ligand exchange reaction of In(III)Cl to produce SiR3-X, as illustrated in the following examples.

[0305]

[0306] The disclosed In(III)-containing precursor can be synthesized via a ligand exchange reaction by mixing one or two equivalents of a silylated ligand with InX3 (where X = Cl, Br, I). The reaction is carried out at room temperature by charging the desired In(III) halide in an ether solvent in a reaction flask. The desired silylated nitrogen ligand is added to the reaction at room temperature and stirred for 2 to 12 hours. The solvent is removed under vacuum to separate the product, followed by extraction in a hydrocarbon solvent to remove any residual indium(III) halide.

[0307] The disclosed In(III)-containing precursors possess the following characteristics that make them suitable for indium and indium alloy film deposition. On one hand, the disclosed In(III)-containing precursors have heteroligand properties and a nitrogen-ligand framework, making them more volatile than indium trichloride (InCl3) and possessing sufficient vapor pressure at lower temperatures. On the other hand, the presence of halogenated (e.g., chlorine) ligands in the disclosed In(III)-containing precursors allows for the use of dehalogenated silylation chemicals to achieve ALD at low temperatures ranging from room temperature to 500°C, preferably 100°C–400°C. The disclosed In(III)-containing precursors represent a potential new product line for the semiconductor industry.

[0308] The disclosed In(III)-containing precursors can exhibit high thermal stability and can be used to form high-speed, high-sensitivity semiconductor layers, such as in CMOS systems, 3D NAND channels, or photodetectors. The disclosed In(III)-containing precursors and the disclosed film-forming compositions are suitable for depositing films containing the corresponding element and for their related applications in depositing layers containing the corresponding element.

[0309] The disclosed In(III) precursor and the disclosed film-forming composition are suitable for forming indium-containing thin films, such as InGaAs and In... x O y (x=0.5-1.5,y=0.5-1.5), InSnO (ITO), InGaZnO (IGZO), InN, InP, InAs, InSb, In2S3, etc. The disclosed In(III) precursors and the disclosed film-forming compositions can be used in the manufacture of indium tin oxide in displays, solar fuels, high-speed electronic devices (InN), optoelectronic components, high-speed electronic devices, photovoltaics (InP), infrared detectors, diode lasers (InAs), fast transistors, magnetic fields, thermal imaging detectors (InSb), optoelectronic devices, photoelectrochemical water splitting (In2S3), LED applications, the manufacture of copper indium gallium selenide (CIGS) in photovoltaic and optical applications, and the manufacture of indium gallium zinc oxide (IGZO) in the display, semiconductor, logic and memory industries, etc.

[0310] This disclosure also includes methods for forming indium-containing films and methods for forming oxidized or oxygen-free indium-containing films using the disclosed In(III) precursor via vapor deposition methods such as ALD or CVD. The disclosed deposition method involves using the disclosed In(III) precursor and introducing it into a reaction chamber to deposit a film to form a film via ALD, CVD, spin coating, spraying, dip coating, slot coating, or any other deposition technique, with or without combination with one or more oxidizing agents (e.g., O2 and O3, or H2O and O3), or with one or more reducing agents or nitriding agents (e.g., H2 and NH3, N2 and NH3, or NH3 and N2H4) introduced simultaneously and / or sequentially. The disclosed deposition method using the disclosed In(III) precursor can be assisted by heating, light, direct or remote plasma, or a combination thereof.

[0311] When the target is a dielectric film, the co-reactant can be an oxidizing gas, such as one of the following: O2, O3, H2O, H2O2, NO, N2O, NO2, oxygen-containing free radicals such as O· or OH·, alcohols, silanols, amino alcohols, carboxylic acids such as formic acid, acetic acid, propionic acid, paraformaldehyde, other oxidizing compounds, and mixtures thereof. Preferably, the oxidizing gas is selected from the group consisting of O2, O3, H2O2, and H2O. Preferably, when performing the ALD method, the co-reactant is plasma-treated oxygen, ozone, or a combination thereof. When an oxidant is used as the co-reactant, the resulting In(III)-containing film will also contain oxygen.

[0312] When the target is a conductive film, the co-reactants can be NH3, N2, H2 or N2 / H2, amines, diamines, cyanides, diimides, hydrazines (e.g., N2H4, MeHNNH2, MeHNNHMe), organic amines (e.g., H2N(CH3), H2N(CH2CH3), H2NC(CH3)3, N(CH3)H2, N(C2H5)H2, N(CH3)2H, N(C2H5)2H, N(CH3)3, N(C2H5)3, (SiMe3)2NH), pyrazolines, pyridines, free radicals and plasma substances, and mixtures thereof. The co-reactants can be primary amines, secondary amines, tertiary amines, trimethylsilylamines, their groups, and mixtures thereof. Preferably, the co-reactant is NH3 or H2. When using a nitrogen-containing reducing agent, the resulting In(III)-containing film will also contain nitrogen.

[0313] When the desired In(III)-containing film also contains another element, such as, but not limited to, P, Ga, As, B, Ge, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, Sb, Bi, Sn, Pb, Co, lanthanides (such as Er), or combinations thereof, the co-reactant may include another precursor.

[0314] Furthermore, co-reactants can be treated with plasma to decompose them into their free radical forms. When treated with plasma, at least one of H2, N2, and O2 can be used as the hydrogen, nitrogen, or oxygen source gas, 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, 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 or present within the reactor itself. Alternatively, the plasma can typically be located remotely from the reactor, for example, in a remotely positioned plasma system. Those skilled in the art will recognize methods and apparatus suitable for such plasma treatment.

[0315] For example, co-reactants can be introduced into a direct plasma reactor (which generates plasma in a reaction chamber) to produce plasma-treated reactants within the reaction chamber. The co-reactants can be introduced and held in the reaction chamber prior to plasma processing. Alternatively, plasma processing can occur simultaneously with the introduction of the reactants.

[0316] Alternatively, plasma-treated co-reactants can be generated outside the reaction chamber, for example, by remotely plasma-treating the co-reactants before they are introduced into the reaction chamber.

[0317] A method for forming an indium (III)-containing layer on a substrate using a vapor deposition process is also disclosed. The applicants believe that the disclosed film-forming composition is suitable for ALD (Alternating Current Deposition). More specifically, the disclosed film-forming composition is capable of surface saturation, self-limiting growth per cycle, and perfect stepped coverage in an aspect ratio ranging from about 2:1 to about 200:1, and preferably from about 60:1 to about 150:1. Furthermore, the disclosed film-forming composition has a high decomposition temperature, indicating good thermal stability that enables ALD. The high decomposition temperature allows for ALD at higher temperatures, resulting in films with high purity. The disclosed method can be used to manufacture semiconductors, photovoltaics, LCD-TFTs, and flat panel devices.

[0318] The disclosed In(III)-containing film-forming compositions can be used to deposit In(III)-containing films using any deposition method known to those skilled in the art. Examples of suitable deposition methods include plasma-enhanced chemical vapor deposition (CVD) or atomic layer deposition (ALD), with or without plasma. Exemplary ALD methods include thermal ALD, plasma-enhanced ALD (PEALD), spatially isolated ALD, time-isolated ALD, selective or non-selective ALD, hot-wire ALD (HWALD), radical-binding ALD, and combinations thereof. The deposition method is preferably ALD, PE-ALD, or spatial ALD to provide suitable stepped coverage and film thickness control. Exemplary CVD methods include metal-organic CVD (MOCVD), thermal CVD, pulsed CVD (PCVD), low-pressure CVD (LPCVD), subatmospheric pressure CVD (SACVD) or atmospheric pressure CVD (APCVD), hot wire CVD or hot filament CVD (also known as cat-CVD, where the hot wire is used as the energy source for the deposition method), hot-wall CVD, cold-wall CVD, aerosol-assisted CVD, direct liquid jet CVD, combustion CVD, hybrid physical CVD, metal-organic CVD, rapid thermal CVD, photo-initiated CVD, laser CVD, radical-binding CVD, plasma-enhanced CVD (PECVD) including but not limited to flowable PECVD, and combinations thereof.

[0319] The disclosed In(III)-containing film-forming composition contains less than 5% v / v, preferably less than 1% v / v, more preferably less than 0.1% v / v, and even more preferably less than 0.01% v / v of its analogues or other reaction products. This embodiment provides better process reproducibility. This embodiment can be prepared by purifying (e.g., distillation, sublimation, chromatography, etc.) the In(III)-containing film-forming composition.

[0320] The disclosed film-forming composition has a purity greater than 93% 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 about 99.999% w / w or 99.0% w / w to 100.0% w / w). Those skilled in the art will recognize that purity can be determined by NMR spectroscopy and gas or liquid chromatography combined with mass spectrometry. The disclosed film-forming composition may contain any of the following impurities: pyrazole; pyridine; alkylamine; alkylimine; THF; ether; pentane; cyclohexane; heptane; benzene; toluene; chlorinated metal compounds; lithium pyrazolium, sodium pyrazolium, potassium pyrazolium. 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), and more preferably less than 1% w / w (i.e., 0.0% w / w to 1.0% w / w). The disclosed film-forming composition can be obtained by recrystallization, sublimation, distillation, and / or by passing the gas or liquid through a suitable adsorbent (e.g., Molecular sieve purification.

[0321] Purification of the disclosed film-forming composition may also result in metallic impurities, each independently ranging from 0 ppbw to 1 ppmw, preferably from about 0 to about 500 ppbw (parts per billion by weight), more preferably from about 0 ppbw to about 100 ppbw, and even more preferably from about 0 ppbw to about 10 ppbw. These metallic or metalloid impurities 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), tin (Sn), titanium (Ti), uranium (U), vanadium (V), and zinc (Zn).

[0322] Care should be taken to prevent the disclosed film-forming compositions containing In(III) from being exposed to water, as this may cause the In(III)-containing precursors to decompose into indium oxide (e.g., In2O3).

[0323] The disclosed film-forming compositions may be supplied in pure form or as blends with suitable solvents such as ethylbenzene, xylene, mesitylene, naphthane, decane, and dodecane. The disclosed precursors may be present in solvents at different concentrations.

[0324] The pure, blended film-forming composition is introduced into the reactor in vapor form using conventional means such as piping systems and / or flow meters. This vapor form can be generated by vaporizing the pure, blended composition via conventional vaporization steps (such as direct vaporization, distillation), by bubbling, or by using a sublimator (such as the sublimator disclosed in PCT disclosure WO 2009 / 087609 granted to Xu et al.). The pure, blended composition can be fed as a liquid into a vaporizer, vaporized therein, and then introduced into the reactor. Alternatively, the pure, blended composition can be vaporized by bubbling a carrier gas into the composition, which is then passed to a container containing the composition. The carrier gas can include, but is not limited to, Ar, He, N2, and mixtures thereof. Bubbling with a carrier gas also removes any dissolved oxygen present in the pure or blended composition. The carrier gas and composition are then introduced into the reactor as vapor.

[0325] If necessary, the container holding the disclosed film-forming composition may be heated to a temperature that allows the composition to have sufficient vapor pressure. The container may be maintained at a temperature, for example, in the range of about 0°C to about 200°C. Those skilled in the art will recognize that the temperature of the container can be adjusted in known ways to control the amount of the vaporized precursor.

[0326] The reactor can be any accessory chamber within the apparatus in which the deposition method takes place, such as, but not limited to: parallel plate reactors, cold-wall reactors, hot-wall reactors, single-wafer reactors, multi-wafer reactors, and other types of deposition systems under conditions suitable for inducing the reaction of the compounds and the formation of a layer. Those skilled in the art will recognize that any of these reactors can be used for ALD or CVD deposition processes.

[0327] The reactor contains one or more substrates on which a film will be deposited. A substrate is generally defined as the material on which the method is performed. The substrate can be any suitable substrate used in the manufacture of semiconductor, photovoltaic, flat panel, and LCD-TFT devices. Examples of suitable substrates include wafers such as silicon, silicon dioxide, glass, and GaAs wafers. The wafer can have one or more layers of different materials deposited thereon from previous manufacturing steps. For example, the wafer can include a dielectric layer. Furthermore, the wafer can include silicon layers (crystalline, amorphous, porous, etc.), silicon oxide layers, silicon nitride layers, silicon oxynitride layers, carbon-doped silicon oxide (SiCOH) layers, metals, metal oxides, metal nitride layers (Ti, Ru, Ta, etc.), and combinations thereof. Additionally, the wafer can include copper layers and noble metal layers (e.g., platinum, palladium, rhodium, gold). The wafer can include barrier layers such as manganese, manganese oxide, etc. Plastic layers, such as poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) [PEDOT:PSS], can also be used. These layers can be planar or patterned. When a patterned layer is formed on a substrate, the disclosed process can deposit the layer directly onto the wafer, or directly onto one or more layers on top of the wafer. The patterned layer can be an alternating layer of two specific layers (such as In₂O₃ and ZrO₂ 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 laid or spread on a surface, and the surface can be trenches or lines. Throughout the 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, HfO₂ layer, or MoO₂ layer).

[0328] The final applications of the substrate are not limited to this invention, but this technology can be particularly beneficial for substrates such as silicon wafers, glass wafers and glass panels, beads, powders and nanopowders, monolithic porous media, printed circuit boards, plastic sheets, etc. Exemplary powder substrates include powders used in rechargeable battery technology. An unlimited number of powder materials include NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials.

[0329] The temperature and pressure within the reactor are maintained under conditions suitable for vapor deposition (such as ALD and CVD). In other words, after the vaporized, disclosed film-forming composition is introduced into the chamber, the conditions within the chamber are such that at least a portion of the precursor is deposited onto the substrate to form a layer. For example, the pressure in the reactor, or the deposition pressure, can be maintained at approximately 10 °C, as required by the deposition parameters. -3 Between 100 and approximately 100, more preferably between 10 -2The temperature is between 10 Torr and 10 Torr. Similarly, the temperature in the reactor or the deposition temperature can be maintained between about 100°C and about 600°C, preferably between about 150°C and about 500°C. Those skilled in the art will recognize that "depositing at least part of the precursor" means that some or all of the precursor reacts with or adheres to the substrate.

[0330] The optimal temperature for film growth can be controlled by adjusting the temperature of the substrate support. Apparatus for heating the substrate is known in the art. The substrate is heated to a sufficient temperature to obtain the desired film at a sufficient growth rate and with the desired physical state and composition. Non-limiting exemplary temperature ranges to which the substrate can be heated include from about 50°C to about 600°C. When using plasma deposition methods, the deposition temperature is preferably less than 400°C. Alternatively, when performing thermal processes, the deposition temperature range can be from about 100°C to about 600°C.

[0331] Alternatively, the substrate can be heated to a sufficient temperature to obtain the desired In(III)-containing film at a sufficient growth rate and with the desired physical state and composition. Non-limiting exemplary temperature ranges to which the substrate can be heated include from room temperature to approximately 600°C. Preferably, the substrate temperature is maintained at less than or equal to 500°C.

[0332] The ALD conditions within the chamber allow the disclosed film-forming composition, adsorbed or chemisorbed onto the substrate surface, to react and form a film on the substrate. In some embodiments, the applicants believe that plasma treatment of the co-reactants can provide the co-reactants with the energy required to react with the disclosed film-forming composition. When the co-reactants in this exemplary ALD process are treated with plasma, the exemplary ALD process becomes an exemplary PEALD process. The co-reactants can be treated with plasma before or after introduction into the chamber.

[0333] The film-forming composition and co-reactants can be introduced sequentially into the reactor (ALD). Between the introduction of each film-forming composition, any additional precursors, and the co-reactants, the reactor can be purged with an inert gas. Another example is the continuous introduction of the co-reactants and the introduction of the film-forming composition via pulses, while the co-reactants are sequentially activated with plasma, provided that the film-forming composition and the unactivated co-reactants do not substantially react under the chamber temperature and pressure conditions (CW PEALD).

[0334] The duration of each pulse of the disclosed film-forming composition can range from about 0.001 seconds to about 120 seconds, alternatively from about 1 second to about 80 seconds, or alternatively from about 5 seconds to about 30 seconds. Co-reactants can also be pulsed into the reactor; in such embodiments, the pulse of each co-reactant can last from about 0.01 seconds to about 120 seconds, alternatively from about 1 second to about 30 seconds, or alternatively from about 2 seconds to about 20 seconds. In another alternative, the vaporized film-forming composition and co-reactants (without mixing the composition and reactants) can be simultaneously sprayed from different portions of a spray head, while a substrate of several wafers is rotated under the spray head (space ALD).

[0335] Depending on the specific process parameters, deposition may take varying durations. Typically, deposition can continue for the length necessary to produce a film with the desired properties. Depending on the specific deposition process, typical film thicknesses can range from a few angstroms to hundreds of micrometers, and typically vary from 1 to 100 nm. The deposition process can also be repeated multiple times as needed to obtain the desired film.

[0336] The disclosed method for forming an In(III)-containing layer on a substrate includes: placing the substrate in a reactor, delivering a vapor of the disclosed In(III)-containing film-forming composition into the reactor, and contacting / adsorbing the vapor with the substrate (and typically directing the vapor to the substrate) to form an In(III)-containing layer on the surface of the substrate. Alternatively, the disclosed method for forming an In(III)-containing layer on a substrate includes: exposing the substrate to a vapor of the disclosed In(III)-containing film-forming composition and depositing an In(III)-containing layer on the surface of the substrate.

[0337] A vapor of an In(III)-containing film-forming composition is generated and then introduced into a reaction chamber containing a substrate. The temperature and pressure within the reaction chamber, and the temperature of the substrate, are maintained under conditions suitable for depositing at least a portion of the disclosed In(III)-containing precursor onto the substrate. In other words, after the vaporized composition is introduced into the reaction chamber, the conditions within the reaction chamber are adjusted such that at least a portion of the precursor is deposited onto the substrate to form an In(III)-containing layer. Those skilled in the art will recognize that “depositing at least a portion of the precursor” means that some or all of the precursor reacts with or adheres to the substrate. Co-reactants may also be used herein to aid in the formation of the In(III)-containing layer.

[0338] The disclosed film-forming composition and co-reactants can be introduced into the reactor simultaneously (CVD), sequentially (ALD), or in different combinations thereof. The reactor can be purged with an inert gas (e.g., N2 or Ar) between the introduction of the film-forming composition and the introduction of the co-reactants. Alternatively, the co-reactants and film-forming composition can be mixed together to form a co-reactant / compound mixture, and then introduced into the reactor as a mixture. Another example is the continuous introduction of the co-reactants and the introduction of the disclosed film-forming composition via pulsed (pulsed CVD).

[0339] In a non-limiting exemplary ALD method for forming an indium-containing film (such as In₂O₃, InN, InS, etc.) containing two elements, the disclosed film-forming composition (e.g., The vapor phase of the indium is introduced into the reactor, where it is brought into contact with a suitable substrate and chemisorbed or physicosorbed onto the substrate. Excess composition is then removed from the reactor by purging and / or evacuating the reactor, i.e., by purging the reactor with an inert gas (e.g., N2, Ar, Kr, or Xe) or by passing the substrate through a high-vacuum section and / or a carrier gas curtain. A co-reactant (e.g., O3 or NH3) is introduced into the reactor, where it reacts with the adsorbed film-forming composition in a self-limiting manner. Any excess co-reactant is removed from the reactor by purging and / or evacuating the reactor. If the desired film is an oxide, such as In2O3, this two-step process can be repeated until a film with the desired thickness has been obtained to provide the desired film thickness. By alternately providing the indium film-forming composition and co-reactant, films with the desired composition and thickness can be deposited.

[0340] Alternatively, if the desired indium-containing film contains three elements, such as InGaN, the above two-step process (e.g., forming an InN film) can be inserted (three-step process) by introducing the vapor of an additional precursor compound into the reactor. The additional precursor compound is selected based on the properties of the deposited film. The additional elements can include gallium (Ga), nitrogen (N), sulfur (S), phosphorus (P), tin (Sn), arsenic (As), antimony (Sb), zinc (Zn), and mixtures thereof. When using an additional precursor compound, the resulting film deposited on the substrate contains indium and co-reactants in combination with the additional elements. When an additional precursor and an In(III) precursor are used in more than one ALD supercycle sequence, a nanolayer film is obtained. After introduction into the reactor, the additional precursor compound is brought into contact with or adsorbed onto the substrate. Subsequently, any excess precursor compound is removed from the reactor by purging and / or evacuating the reactor. Depending on process requirements, co-reactants such as NH3 or additional precursors can be introduced into the reactor to react with the indium precursor compound. Excess co-reactants or precursors are removed from the reactor by purging and / or evacuating the reactor. In the final step of the cycle, any remaining co-reactants or precursors can be introduced into the reactor and removed by purging and / or evacuating the reactor. The entire three-step process can be repeated until the desired film thickness is achieved. By alternately providing the indium film-forming composition, additional precursor compounds, and co-reactants, films with the desired composition and thickness can be deposited.

[0341] Alternatively, if the desired indium-containing film contains four elements such as InGaZnO (IGZO), the above three-step (four-step) process can be inserted by introducing the vapor of another precursor compound into the reactor. The other precursor compound will be selected based on the properties of the deposited film. Other elements may include gallium (Ga), nitrogen (N), sulfur (S), phosphorus (P), tin (Sn), arsenic (As), antimony (Sb), zinc (Zn), and mixtures thereof. When another precursor compound is used, the resulting film deposited on the substrate contains indium in combination with the other three elements. When two other precursors and an In(III) precursor are used in more than one ALD supercycle sequence, a nanolayer film is obtained. In the case of forming an IGZO film, the precursor may include an indium precursor combined with the co-reactant O3, such as... Ga precursors such as GaCl3 or Ga(NO3)3, and Zn precursors such as Zn(NO3)2. By alternately providing indium film-forming compositions, additional precursor compounds, another additional precursor, and co-reactants, films with desired compositions and thicknesses can be deposited.

[0342] The indium-containing film obtained by the above method may include In x O y(x = 0.5 to 1.5, y = 0.5 to 1.5), InSnO (ITO), InGaZnO (IGZO), InN, InP, InAs, InSb, In2S3, or combinations thereof, or a pure indium (In(0)) layer. The indium-containing film may contain a second element selected from: P, N, S, Ga, As, B, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co, Zn, one or more lanthanides, or combinations thereof. Those skilled in the art will recognize that desired film compositions can be obtained through appropriate selection of the film-forming composition and co-reactants. The disclosed methods can be used to manufacture semiconductor materials, for example, indium oxide can be used as a semiconductor material to form heterojunctions with p-InP, n-GaAs, n-Si, and other materials. Thin films of indium oxide can be used as diffusion barriers (“barrier metals”) in semiconductors (e.g., to suppress diffusion between aluminum and silicon).

[0343] Once the desired film thickness is obtained, the film can be subjected to further processing, such as thermal annealing, furnace annealing, rapid thermal annealing, UV curing, electron beam curing, and / or plasma gas exposure. Those skilled in the art will recognize the systems and methods used to perform these additional processing steps. For example, in an inert atmosphere, an O-containing atmosphere, and combinations thereof, the In2O3 film can be exposed to temperatures ranging from about 200°C to about 1000°C for durations ranging from about 0.1 seconds to about 7200 seconds. Most preferably, in an inert or O-containing atmosphere, the temperature range is 350°C to 450°C for 3600–7200 seconds. The resulting film may contain fewer impurities and therefore may have improved density, resulting in improved leakage current. The annealing step can be performed in the same reaction chamber in which the deposition process takes place. Alternatively, the substrate can be removed from the reaction chamber, and the annealing / rapid annealing process can be performed in a separate device. Any of the above post-treatment methods, but especially thermal annealing, has been found to effectively reduce carbon and nitrogen contamination of the In2O3 film. This, in turn, tends to improve the resistivity of the membrane.

[0344] Following annealing, films deposited by any of the disclosed methods can have a bulk resistivity of approximately 50 μohm·cm to approximately 1,000 μohm·cm at room temperature. Room temperature is approximately 20°C to approximately 25°C, depending on the season. Bulk resistivity is also known as volume resistivity. Those skilled in the art will recognize that bulk resistivity is measured at room temperature on films typically approximately 50 nm thick. For thinner films, bulk resistivity typically increases due to changes in electron transport mechanisms. Bulk resistivity also increases at higher temperatures.

[0345] Example

[0346] The following non-limiting examples are provided to further illustrate embodiments of the invention. These examples are not intended to be exhaustive, nor are they intended to limit the scope of the invention described herein.

[0347] Example 1: Synthesis

[0348]

[0349] Under nitrogen atmosphere, in a Schlenk flask equipped with a feeding funnel, 1-tert-butyl-3-ethylcarbodiimide (0.95 equivalents, 0.038 mol, 4.79 g) was dissolved in an ether solvent (120 mL), preferably diethyl ether, and cooled to -78°C. Methyllithium (1.6 M, 0.97 equivalents, 0.039 mol, 24.3 mL) in diethyl ether was slowly added to the flask. The mixture was stirred for 2 hours and heated to room temperature with stirring. In a separate Schlenk flask, a suspension of indium(III) chloride (1.0 equivalents, 0.040 mol, 8.87 g) in an ether solvent (200 mL), preferably dimethoxyethane, was cooled to -78°C. The lithium solution was slowly added to the suspension, and the mixture was heated to room temperature and stirred for 12 hours. The solvent was then removed under reduced pressure, followed by the addition of 250 mL of pentane. The reactants were filtered through diatomaceous earth and the volume was reduced under vacuum. Cool the remaining solution and crystallize the desired product from the solution at -20°C. Separate the product. (5.84 g, 45% yield), it is a white solid that melts at 88°C. 1 H-NMR (benzene-d6, δ (ppm): 0.94 (3H, t, 7.2Hz), 1.30 (9H, s), 1.57 (3H, s), 3.29 (2H, q, 7.0Hz). Figure 1 It shows Vacuum TGA results show a single-step evaporation process, in which... At 220°C, <3% residue remained. For comparative purposes, vacuum TGA results for InCl3 were also added. As shown, The volatility of the precursor increases relative to that of InCl3. Figure 2 It shows The DSC results. It has a vapor pressure of 1 Torr at 145°C. Figure 3 yes In C6D6 1 H NMR.

[0350] Example 2: or Synthesis

[0351]

[0352] The same procedure was followed for Example 1. The reagents used were N,N'-bis(1-methylethyl)methylimine (0.95 equivalents, 0.039 mol, 5.00 g), lithium methyl (0.97 equivalents, 0.040 mol, 24.9 mL), and indium(III) chloride (1.0 equivalents, 0.041 mol, 9.09 g). The product (6.10 g, 50% yield) was isolated as a white solid that melted at 91 °C. 1 H-NMR (THF-d8, δ (ppm)): 1.16 (12H, d, 6.5Hz), 3.57 (2H, spt, 6.5Hz), 7.69 (1H, s). Figure 4 It shows The TGA results show a single-step evaporation, in which <5% residue remained at 210°C. For comparative purposes, vacuum TGA results for InCl3 were also added. As shown, The volatility of the precursor increases relative to that of InCl3. (Based on the method used to obtain...) 1 The characteristics of the solvent in the 1H NMR spectrum were observed, indicating its role as a monomer. or dimer The structure. Figure 5 It shows The DSC results. It has a vapor pressure of 1 Torr at 128°C. Figure 6 yes In THF-d8 1 H NMR.

[0353] Example 3: Synthesis

[0354]

[0355] The same procedure was followed for Example 1. The reagents used were N,N'-diisopropylcarbodiimide (0.95 equivalents, 0.046 mol, 5.75 g), n-butyllithium (0.97 equivalents, 0.047 mol, 29.1 ml), and indium(III) chloride (1.0 equivalents, 0.048 mol, 10.64 g). The precursor, which was a viscous liquid, was separated. (12.91g, 73% yield). 1H-NMR (benzene-d6, δ (ppm): 0.80 (3H, t, 7.3Hz), 1.19 (2H, m), 1.27 (12H, d, 6.5Hz), 1.33 (2H, m), 1.35 (2H, m), 2.05 (2H, m), 3.60 (2H, quint, 6.2Hz). Figure 7 It shows The TGA results show a single-step evaporation, in which At 250°C, <3% residue remained. For comparative purposes, vacuum TGA results for InCl3 were also added. As shown, The volatility of the precursor increases relative to that of InCl3. Figure 8 It shows The DSC results. It has a vapor pressure of 1 Torr at 155°C. Figure 9 yes In C6D6 1 H NMR.

[0356] Example 4: Synthesis

[0357]

[0358] The same procedure was followed for Example 1. The reagents used were 1-tert-butyl-3-ethylcarbodiimide (0.95 equivalents, 0.048 mol, 5.99 g), n-butyllithium (0.97 equivalents, 0.049 mol, 30.3 ml), and indium(III) chloride (1.0 equivalents, 0.05 mol, 11.09 g). The precursor, which was a viscous liquid, was separated. (12.18g, 66% yield). 1 H-NMR (benzene-d6, δ (ppm): 0.77 (3H, t, 7.3Hz), 1.10 (3H, t, 7.2Hz), 1.16 (2H, m), 1.30 (2H, m), 1.38 (9H, s), 2.17 (2H, m), 3.11 (2H, q, 7.0Hz). Figure 10 It shows The TGA results show a single-step evaporation, in which <8% residue remained at 240°C. For comparative purposes, vacuum TGA results for InCl3 were also added. As shown, The volatility of the precursor increases relative to that of InCl3. Figure 11 yes In C6D6 1 H NMR.

[0359] Example 5: Synthesis via the amidine-lithium pathway

[0360]

[0361] The same procedure was followed for Example 1. The reagents used were diisopropylcarbodiimide (0.95 equivalents, 0.14 mol, 22.7 mL), methyllithium (0.97 equivalents, 0.15 mol, 90.9 mL), and indium(III) chloride (1.0 equivalents, 0.15 mol, 33.3 g). The product was separated (25.1 g, 51% yield), which was a white solid that melted at 110 °C. 1 ¹H-NMR (benzene-d6, δ (ppm): 1.20 (¹³H, d, 6.5 Hz), 1.41 (³H, s), 3.46 (²H, spt, 6.5 Hz). Figure 12 It shows The TGA results show a single-step evaporation, in which At 200°C, <5% residue remained. For comparative purposes, vacuum TGA results for InCl3 were also added. As shown, The volatility of the precursor increases relative to that of InCl3.

[0362] Example 6: Synthesis via ligand exchange pathway

[0363]

[0364] Under nitrogen atmosphere, in a Schlenk flask, N,N'-diisopropyl-N-(trimethylsilyl)ethyliminoamide (1.4 equivalents, 0.31 mol, 66 g) was dissolved in an ether solvent (500 mL), preferably tetrahydrofuran. Under nitrogen atmosphere, in a separate Schlenk flask, indium(III) chloride (1.0 equivalents, 0.22 mol, 48.8 g) was dissolved in an ether solvent (250 mL), preferably tetrahydrofuran. The N,N'-diisopropyl-N-(trimethylsilyl)ethyliminoamide mixture was slowly added to the indium halide with stirring, and the mixture was stirred at room temperature for 12 hours. The solvent was then removed under reduced pressure to separate the crude product. Soxhlet extraction was performed with 800 mL of pentane to separate the desired product from trace amounts of remaining indium(III) chloride. After solvent removal, the product was separated as a white solid. (56.3 g, 83% yield). The use of the ligand exchange pathway significantly improved... The yield. Figure 13 yes In C6D6 1 H NMR.

[0365] Predictive Example 1: Synthesis

[0366]

[0367] Under nitrogen atmosphere, in a Schlenk flask equipped with a feeding funnel, 1-tert-butyl-3-ethylcarbodiimide (2.0 equivalents, 0.08 mol, 10.10 g) was dissolved in an ether solvent (120 mL), preferably diethyl ether, and cooled to -78°C. Methyllithium (2.0 equivalents, 0.08 mol, 50 mL) in diethyl ether was slowly added to the flask at 1.6 M. The mixture was stirred for 2 hours and heated to room temperature with stirring. In a separate Schlenk flask, a suspension of indium(III) chloride (1.0 equivalents, 0.040 mol, 8.87 g) in an ether solvent (200 mL), preferably dimethoxyethane, was cooled to -78°C. The lithium solution was slowly added to the suspension, and the reaction was heated to room temperature and stirred for 12 hours. The solvent was then removed under reduced pressure, followed by the addition of 250 mL of pentane. The reaction could be filtered through diatomaceous earth. After solvent removal, Further purification can be achieved through crystallization or sublimation (for solid materials) or distillation (for liquid materials).

[0368] Predictive Example 2: Synthesis

[0369]

[0370] Under nitrogen atmosphere, in a Schlenk flask equipped with a feeding funnel, isopropylimino-2,2-dimethylpyrrolidine (1.0 equivalent, 0.040 mol, 6.17 g) was dissolved in an ether solvent (120 mL), preferably diethyl ether, and cooled to -78 °C. Methyllithium (1.0 equivalent, 0.040 mol, 25 mL) in diethyl ether was slowly added to the flask at 1.6 M. The mixture was stirred for 2 hours and heated to room temperature with stirring. In a separate Schlenk flask, a suspension of indium(III) chloride (1.0 equivalent, 0.040 mol, 8.87 g) in an ether solvent (200 mL) was cooled to -78 °C. The lithium solution was slowly added to the suspension, and the reaction was heated to room temperature and stirred for 12 hours. The solvent was then removed under reduced pressure, followed by the addition of 250 mL of pentane. The reaction was filtered through diatomaceous earth. After solvent removal, Further purification can be achieved through crystallization or sublimation (for solid materials) or distillation (for liquid materials).

[0371] Predictive Example 3: Synthesis

[0372]

[0373] Under nitrogen atmosphere, in a Schlenk flask equipped with a feeding funnel, isopropylimino-2,2-dimethylpyrrolidine (2.0 equivalents, 0.080 mol, 12.34 g) was dissolved in an ether solvent (120 mL), preferably diethyl ether, and cooled to -78 °C. Methyllithium (2.0 equivalents, 0.080 mol, 50 mL) in diethyl ether was slowly added to the flask at 1.6 M. The mixture was stirred for 2 hours and heated to room temperature with stirring. In a separate Schlenk flask, a suspension of indium(III) chloride (1.0 equivalents, 0.040 mol, 8.87 g) in an ether solvent (200 mL) was cooled to -78 °C. The lithium solution was slowly added to the suspension, and the reaction was heated to room temperature and stirred for 12 hours. The solvent was then removed under reduced pressure, followed by the addition of 250 mL of pentane. The reaction was filtered through diatomaceous earth. After solvent removal, Further purification can be achieved through crystallization or sublimation (for solid materials) or distillation (for liquid materials).

[0374] Predictive Example 4: Synthesis of [(Et2)N-CH2-CH2-N(Et)]InCl2

[0375]

[0376] Under nitrogen atmosphere, in a Schlenk flask equipped with a feeding funnel, N,N,N'-triethylethylenediamine (1.0 equivalent, 0.040 mol, 5.77 g) was dissolved in an ether solvent (120 mL), preferably diethyl ether, and cooled to -78 °C. Methyllithium (1.0 equivalent, 0.040 mol, 25 mL) in diethyl ether was slowly added to the flask at 1.6 M. The mixture was stirred for 2 hours and heated to room temperature with stirring. In a separate Schlenk flask, a suspension of indium(III) chloride (1.0 equivalent, 0.040 mol, 8.87 g) in an ether solvent (200 mL) was cooled to -78 °C. The lithium solution was slowly added to the suspension, and the reaction was heated to room temperature and stirred for 12 hours. The solvent was then removed under reduced pressure, followed by the addition of 250 mL of pentane. The reaction was filtered through diatomaceous earth. After removing the solvent, [(Et2)N-CH2-CH2-N(Et)]InCl2 can be further purified by crystallization or sublimation (for solid materials) or distillation (for liquid materials).

[0377] Predictive Example 5: Synthesis of [(Et2)N-CH2-CH2-N(Et)]2InCl

[0378]

[0379] Under nitrogen atmosphere, in a Schlenk flask equipped with a feeding funnel, N,N,N'-triethylethylenediamine (1.0 equivalent, 0.080 mol, 11.54 g) was dissolved in an ether solvent (120 mL), preferably diethyl ether, and cooled to -78 °C. Methyllithium (1.0 equivalent, 0.080 mol, 50 mL) in diethyl ether was slowly added to the flask at 1.6 M. The mixture was stirred for 2 hours and heated to room temperature with stirring. In a separate Schlenk flask, a suspension of indium(III) chloride (1.0 equivalent, 0.040 mol, 8.87 g) in an ether solvent (200 mL) was cooled to -78 °C. The lithium solution was slowly added to the suspension, and the reaction was heated to room temperature and stirred for 12 hours. The solvent was then removed under reduced pressure, followed by the addition of 250 mL of pentane. The reaction was filtered through diatomaceous earth. After removing the solvent, [(Et2)N-CH2-CH2-N(Et)]InCl2 can be further purified by crystallization or sublimation (for solid materials) or distillation (for liquid materials).

[0380] Predictive Example 6: Using Precursors ALD of In2O3 membrane

[0381] Used in ALD reactors Alternating exposure to O3 and N2 carrier gas was used to perform In2O3 ALD. The steam is fed into the ALD reactor. The ALD sequence is represented as the precursor. The process involved exposure to the precursor, followed by purging, then exposure to the co-reactant O3, and finally purging after exposure to O3. In2O3 ALD films could be deposited on 2cm x 2cm Si(100) and glass substrates. The deposition temperature at 1 Torr could be 250°C. SEM images of the resulting In2O3 films were acquired. Elemental analysis was performed using an energy-dispersive X-ray spectroscopy (EDAX) detector. AFM, XRD, and ellipsometric measurements were performed on the resulting In2O3 films deposited on the Si(100) surface. Various other characterization techniques, such as atomic absorption (AA), MS-GC, NMR, FT-IR, neutron activation analysis (NAA), energy-dispersive X-ray spectroscopy (EDAX), Rutherford backscattering analysis (RBS), and X-ray analysis, were used to aid in understanding the underlying mechanisms of the resulting In2O3 films.

[0382] Predictive Example 7: Using Precursors Thermal ALD of InP film

[0383] P(SiMe3)3 and P(SiMe3)3 were used as the In source and P source, respectively. N2 was used as the carrier gas for precursor delivery during film deposition. A sufficiently long purging step occurred after each precursor was added to the thermal ALD reactor. A precursor is added to the reactor to initiate the cycle. P(SiMe3)3 is then introduced into the reactor to shut down the cycle. The precursor is adsorbed onto the substrate surface by being transported to it. The reactive material then diffuses to a preferred location on the surface and reacts in a heterogeneous phase to form an InP film. Deposition can be catalyst-free and can be performed on various substrates such as thin Si or oxide substrates. The substrate temperature is maintained at approximately 150°C. The resulting InP film can then be subjected to further processing, such as a thermal annealing step. The InP film is characterized using various techniques such as atomic absorption (AA), MS-GC, NMR, FT-IR, neutron activation analysis (NAA), energy-dispersive X-ray analysis (EDAX), Rutherford backscattering analysis (RBS), and X-ray diffraction, which helps to understand the fundamental mechanism of ALD growth.

[0384] Predictive Example 8: Using Precursors Thermal ALD of InGaAs films

[0385] GaCl3 and As(SiMe3)3 were used as In, Ga, and As sources, respectively. Film deposition was performed using an ACBC-type supercycle, with N2 used as the carrier gas for precursor delivery. A sufficiently long purging step occurred after each precursor was fed into the thermal ALD reactor. The cycle is initiated by adding a precursor to the reactor. As(SiMe3)3 is introduced into the reactor. Then, GaCl3 is added to the chamber. Finally, As(SiMe3)3 is added to shut down the cycle. The precursor is adsorbed onto the substrate surface by being delivered to it. Therefore, the reactive material diffuses to a preferred location on the surface and reacts in a heterogeneous phase to form an InGaAs film. This cycle can be used to provide InGaAs films. 0.5 Ga 0.5 The film is composed of As1. The thermal ALD process of InGaAs can also be tuned to provide films with different compositions. Deposition can be catalyst-free and can be performed on a variety of substrates such as thin Si or oxide substrates. The substrate temperature is maintained at approximately 150°C. The resulting InGaAs film can then be subjected to further processing, such as thermal annealing. The InGaAs film is characterized using various techniques such as atomic absorption (AA), MS-GC, NMR, FT-IR, neutron activation analysis (NAA), energy-dispersive X-ray analysis (EDAX), Rutherford backscattering analysis (RBS), and X-ray analysis, which helps to understand the fundamental mechanism of ALD growth.

[0386] While the subjects described herein can be described in the context of illustrative implementations to handle one or more computing application features / operations of a computing application with user interaction components, the subjects are not limited to these specific embodiments. Rather, the techniques described herein can be applied to any suitable type of user interaction component execution management methods, systems, platforms, and / or devices.

[0387] It should be understood that many additional changes in details, materials, steps, and arrangements of parts that have been described and elucidated to explain the nature of the invention can be made by those skilled in the art within the principles and scope of the invention as set forth in the appended claims. Therefore, the invention is not intended to be limited to the specific embodiments given above and / or in the drawings.

Claims

1. A method for forming an indium (III)-containing film on a substrate, the method comprising the following steps: The substrate was exposed to vapors containing a film-forming composition with an indium(III) precursor; as well as At least a portion of the indium(III) precursor is deposited on the substrate by vapor deposition to form the indium(III) film on the substrate. The indium(III) precursor is selected from: [(Et)N C(Me) N( t Bu)]In(III)Cl2, [( i Pr)N CH N( i Pr)]In(III)Cl2or [(( iPr )N C(H) N( iPr ))InCl]2( -Cl)2, [(And)N C( n Bu) N( t Bu)]In(III)Cl2, [( i Pr)N C(Me) N( i Pr)]In(III)Cl2, or [( i Pr)N C( n This) N( i Pr)]In(III)Cl2。 2. The method as described in claim 1, wherein, The indium(III)-containing precursor is [(Et)N C(Me) N( t Bu)]In(III)Cl2.

3. The method as described in claim 1, wherein, The indium(III)-containing precursor is [( i Pr)N CH N( i Pr)]In(III)Cl2 or [(( iPr )N C(H) N( iPr ))InCl]2(μ-Cl)2.

4. The method of claim 1, wherein, The indium(III)-containing precursor is [(Et)N C( n Bu) N( t Bu)]In(III)Cl2.

5. The method of claim 1, wherein, The indium(III)-containing precursor is [( i Pr)N C( n Bu) N( i Pr)]In(III)Cl2.

6. The method of claim 1, wherein, The indium(III)-containing precursor is [( i Pr)N C(Me) N( i Pr)]In(III)Cl2.

7. The method of claim 1, wherein, The indium (III) film is an indium oxide film, or a binary, ternary, or quaternary indium alloy film.

8. The method of claim 1, wherein, The indium (III) containing film is InGaAs, In x O y where x = 0.5 to 1.5, y = 0.5 to 1.5, InSnO (ITO), InGaZnO (IGZO), InN, InP, InAs, InSb, In2S3, or In(OH)3.

9. The method of claim 1, wherein, The vapor deposition method is either ALD or CVD.

10. The method of any one of claims 1 to 9, further comprising the step of exposing the substrate to the co-reactant.

11. The method of claim 10, wherein, The co-reactants are selected from O3, O2, H2O, NO, N2O, NO2, H2O2, O free radicals and their combinations.

12. The method of claim 10, wherein, The co-reactants are selected from NH3, NO, N2O, hydrazine, N2 plasma, N2 / H2 plasma, NH3 plasma, amines and combinations thereof.

13. A composition for depositing a film, wherein the composition comprises an indium(III) precursor selected from: [(And)N C(Me) N( t Bu)]In(III)Cl2, [( i (Pr)N CH N( i (Pr)]In(III)Cl2 or [(( iPr ))N C(H) N( iPr ))InCl]2( -Cl)2, [(And)N C( n Bu) N( t Bu)]In(III)Cl2, [( i Pr)N C(Me) N( i Pr)]In(III)Cl2, or [( i Pr)N C( n This) N( i Pr)]In(III)Cl2。 14. A method for forming an indium(III)-containing film on a substrate, the method comprising the steps of: A film containing an indium(III) precursor, formed by chemical adsorption and / or physical adsorption, is formed on the surface of the substrate, wherein the indium(III) precursor is selected from: [(And)N C(Me) N( t Bu)]In(III)Cl2, [( i (Pr)N CH N( i (Pr)]In(III)Cl2 or [(( iPr )N C(H) N( iPr ))InCl]2( -Cl)2, [(And)N C( n Bu) N( t Bu)]In(III)Cl2, [( i Pr)N C(Me) N( i Pr)]In(III)Cl2, or [( i Pr)N C( n This) N( i Pr)]In(III)Cl2。 15. The method of claim 14, further comprising the step of chemically reacting the membrane containing the indium(III) precursor with the co-reactant.

16. The method of claim 15, wherein, The co-reactant reacts with the indium(III) precursor in the chemisorbed and / or physisorbed film to generate a reaction product, which forms the indium(III) film on the surface of the substrate.

17. The method of any one of claims 15 to 16, wherein, The co-reactants are selected from O3, O2, H2O, NO, N2O, NO2, H2O2, O free radicals and their combinations.

18. The method of any one of claims 15 to 16, wherein, The co-reactants are selected from NH3, NO, N2O, hydrazine, N2 plasma, N2 / H2 plasma, NH3 plasma, amines and combinations thereof.

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