Indium precursor for vapor deposition

Abstract

Disclosed are indium (In)-containing film-forming compositions including halogen-containing In(III)-containing precursors, methods for their synthesis, and methods for depositing indium-containing and / or indium-containing alloy films using them. The disclosed In(III)-containing precursors contain chlorine along with nitrogen-based ligands. In particular, the disclosed In(III)-containing precursors contain one or two amidinate ligands, one or two iminopyrrolidinate ligands, one or two amidoaminoalkane ligands, one or two μ-diketoiminate ligands, or silylamine ligands. The disclosed In(III)-containing precursors are suitable for vapor-phase deposition (e.g., ALD, CVD) of indium-containing and / or indium-containing alloy films.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims priority based on U.S. Patent Application No. 17 / 063,768, filed on October 6, 2020, which is hereby incorporated by reference in its entirety for all purposes.

[0002] The present invention relates to an indium(III) - containing film - forming composition comprising a halogen - containing In(III) - containing precursor, a method for synthesizing the same, and a method for using the same for the deposition of an indium - containing film and / or an indium - containing alloy film, and particularly relates to a chlorine - containing In(III) - containing precursor together with a nitrogen - based ligand suitable for vapor - phase deposition (e.g., ALD, CVD) of an indium - containing film and / or an indium - containing alloy film.

Background Art

[0003] Indium - containing alloys, thin films, and nanostructured materials are versatile optoelectronic materials widely used in research and industry, especially in the semiconductor industry, and are applied in many fields including electronics and photonics. For example, InGaAs is considered to be one of the promising candidates to replace silicon in future CMOS systems. In addition, InGaAs is a key component in optical fiber communication and serves as a high - speed and high - sensitivity photodetector. Despite the excellent physical properties of indium alloys and III - V alloys, these materials are hindered by two important issues. The synthesis of these materials is limited to slow - growth processes such as molecular beam epitaxy or metalorganic chemical vapor deposition, which requires a large amount of materials and difficult engineering to achieve throughput, uniformity, and reproducibility. The next issue is particularly relevant to the semiconductor industry. The combination of III - V semiconductors and silicon is very difficult and has hindered the rapid development of high - performance devices. Developing novel precursors for III - V alloys containing indium that are compatible with high - throughput production and ease of device integration is highly desirable for multiple industries.

[0004] Regarding the deposition process, homoleptic indium precursors have been studied. 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”, Chem. Eur. J. 2018, 24, 9525) disclose two new In complexes for the ALD of In2O3 containing tris(N,N’-diisopropylformamidinate)indium(III). The results are compared with homoleptic alkyl and aryl indium complexes, (CH3CH2)3In, (CH3)3In, and CpIn (Cp = cyclopentadienyl).

[0005] U.S. Patent Application Publication No. 20130273250 to Fujimura et al. discloses an (amidoaminoalkane) metal compound and a method for producing a metal-containing thin film using the metal compound, and a series of new homoleptic amidoaminoalkane metal complexes are used in chemical vapor deposition (CVD). The disclosed metal complexes include lithium, sodium, magnesium, manganese, iron, cobalt, nickel, zinc, yttrium, lanthanum, and indium complexes. Specific examples include those distilled under reduced pressure and isolated as a semi-solid wax (130 °C, 13.3 Pa) [Chemical formula] are mentioned.

[0006] Gebhard et al. disclose the synthesis of two homoleptic indium-tris-guanidinato complexes (“Indium-tris-guanidinates: A Promising Class of Precursors for Water Assisted Atomic Layer Deposition of In2O3 Films”, Dalton Trans, 2014, 43, 937). This compound was isolated as a solid and used in the ALD process of indium oxide.

[0007] McCarthy et al. (“Oxygen-Free Atomic Layer Deposition of Indium Sulfide”, ACS Appl. Mater. Interfaces 2014, 6, 12137) disclose indium(III) amidinate complexes used for ALD of indium sulfide using hydrogen sulfide.

[0008] Heteroleptic indium precursors have been studied for deposition processes. Examples of heteroleptic indium(III) precursors include alkyl ligands, acetate, and hydroxyl ligands. For example, low-temperature growth of indium oxide thin film by plasma-enhanced ALD using liquid dimethyl(N-ethoxy-2,2-dimethylpropanamido) indium for high-mobility thin film transistor application. Kim et al., ACS Appl. Mater. Interfaces 2016, 8, 40, 26924.

[0009] U.S. Patent Application Publication No. 2016017485 to Martinson et al. discloses an atomic layer deposition method of indium sulfide film using a synthesized indium precursor and hydrogen sulfide. U.S. Patent Application Publication No. 20160326008 to Koh et al. discloses details of the heteroleptic indium(III) precursors bis(trimethylsilyl)aminodiethylindium and dimethyl(3-dimethylaminopropyl)indium, which are liquids at room temperature.

[0010] Gebhard et al. (New amidinate complexes of indium(III): Promising CVD precursors for transparent and conductive In2O3 thin films, Dalton Trans., 2013, 00, 1 - 3) disclose the details of the synthesis of two new heteroleptic indium precursors: [InCl(amd)2] and [InMe(amd)2]. However, the chlorine-containing precursor was only synthesized and not used for deposition, nor were its thermal properties investigated.

[0011] International Publication No. 2017 / 083483 pamphlet to Curley et al. (U.S. Patent Application Publication No. 2017 / 0137360) discloses the details of the synthesis of a dicarboxylate monohydroxyl indium precursor. Several examples are provided where this precursor is used in the solution-phase synthesis of InP nanostructures.

[0012] 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) disclose the preparation of tin-doped In2O3 (ITO) films by dip-coating using an ethanol solution of indium diacetate monohydrate, In(OH)(CH3COO)2 and tin dichloride, SnCl2·2H2O with 2-aminoethanol (monoethanolamine), H2NC2H4OH.

[0013] Patton et al. (Chelating Diamide Group IV Metal Olefin Polymerization. Organometallics, 2002, 21, 10, 2145) disclose the synthesis of dichloroindium-tert-butyl-N,N'-diisopropylamidinate as an intermediate to indium-bridged chelating diamide titanium complexes used as catalysts for olefin polymerization. The indium amidinate compound was cleanly isolated in 48% yield and 1 H, 13 characterized using 1H, 13C NMR spectroscopy and HRMS.

[0014] International Publication No. 0146201A1 pamphlet to Campbell et al. (U.S. Patent Application Publication No. 20020098973A1) discloses a wide range of bridged Group 4 transition metal complexes. For those bridged Group 4 transition metal complexes containing indium, dichloroindium-tert-butyl-N,N'-diisopropylamidinate is synthesized as an intermediate.

[0015] Debnicke et al. (N,N,N'-tris(trimethylsilyl) as reagents in complex chemistry, J. Organomet. Chem, 1988, 352, (1-2), C1) disclose the synthesis of dichloroindium-phenyl-N,N'-bis(trimethylsilyl)amidinate during the screening of the reaction of N,N,N'-tris(trimethylsilyl)organoamidine with typical and transition metal halides. The isolation and characterization of the indium complex were not reported.

[0016] Kottmair-Maieron et al. (Monomeric dialkyl metal complexes of R2M(NR’)2XR type with M = aluminum, gallium, indium, thallium; X = sulfur, carbon and R, R’ = alkyl and silyl, Z. Anorg. Allg. Chem, 1991, 593, 111) disclosed a series of Group III compounds using an amidinate backbone. The synthesis of dichloroindium-methyl-N,N’-diisopropylamidinate was reported as a low melting solid and characterized by NMR and IR spectra; further applications of the molecule have not been reported.

[0017] Hwang et al. (J. Cryst. Growth, 1981, Vol. 55, Iss. 1, 116-124) disclosed that the indium trichloride acetonitrile adduct InCl3(NCCH3) (both dissolved in the acetonitrile solvent NCCH3) in combination with CuCl(NCCH3) as a copper source, and hydrogen sulfide H2S as a sulfur source, were applied as precursors for growing a CuInS2 layer on a GaP substrate by MOCVD. N2 was bubbled through the feed salts dissolved in acetonitrile to generate precursor vapor. n SUMMARY OF THE INVENTION MEANS FOR SOLVING THE PROBLEM

[0018] A method for forming an indium(III)-containing film on a substrate, comprising: exposing the substrate to the vapor of a film-forming composition containing an indium(III)-containing precursor; and depositing at least a portion of the indium(III)-containing precursor on the substrate by a vapor deposition process to form an indium(III)-containing film on the substrate. wherein the indium(III)-containing precursor has the formula:

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0019] Also, a method of forming an indium(III)-containing film on a substrate, comprising on the surface of the substrate a compound of the formula:

Chemical formula

Chemical formula

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[0020] Also, the formula:

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Chemical formula

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Chemical formula

[0021] Notation and nomenclature In the following detailed description and claims, many abbreviations, symbols, and terms well - known in the art are used. Specific abbreviations, symbols, and terms are used throughout the following description and claims and include the following:

[0022] As used herein, the indefinite article "a" or "an" means one or more.

[0023] As used herein, "about" or "substantially" or "approximately" in the text or in the claims means ± 10% of the recited value.

[0024] As used herein, "room temperature" in the text or in the claims means about 20°C to about 25°C.

[0025] The term "ambient temperature" refers to an environmental temperature of about 20°C to about 25°C.

[0026] The term "substrate" refers to one or more materials on which a process is performed. The substrate may refer to a wafer having one or more materials on which a process is performed. The substrate may be any suitable wafer used in the manufacture of semiconductor, solar cell, flat panel, or LCD-TFT devices. The substrate may also have one or more layers of different materials already deposited thereon from a previous manufacturing step. For example, the wafer may include a silicon layer (e.g., crystalline, amorphous, porous, etc.), a silicon-containing layer (e.g., SiO2, SiN, SiON, SiCOH, etc.), a metal-containing layer (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.), or a combination thereof. Further, the substrate may be flat or patterned. The substrate may be a photoresist film patterned with an organic material. The substrate may include a layer of oxide (e.g., a ZrO2-based material, an HfO2-based material, a TiO2-based material, a rare earth oxide-based material, a ternary oxide-based material, etc.) used as a dielectric material or a nitride-based film (e.g., TaN, TiN, NbN) used as an electrode in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications. Those skilled in the art will recognize that the terms "film" or "layer" as used herein refer to the thickness of any material disposed or extended on a surface, and that surface may be a trench or a line. Throughout this specification and the claims, the wafer and any associated layers thereon are referred to as the substrate.

[0027] The term "wafer" or "patterned wafer" means a wafer having a film stack on a substrate and having topographical features such that at least the topmost film was created in a step prior to the deposition of the indium-containing film.

[0028] The term "aspect ratio" means the ratio of the height of a trench (or opening) to the width of the trench (or the diameter of the opening).

[0029] In this specification, the terms "film" and "layer" may be used interchangeably. It is understood that a film may correspond to or be related to a layer, and a layer may refer to a film. Further, those skilled in the art will recognize that the term "film" or "layer" as used herein refers to the thickness of some material disposed or extended on a surface, and that surface may range in size from as large as an entire wafer to as small as a trench or line.

[0030] In this specification, the terms "aperture", "via", "hole", and "trench" may be used interchangeably to mean an opening formed in a semiconductor structure.

[0031] As used herein, the abbreviation "NAND" refers to a "Negative AND" or "Not AND" gate; the abbreviation "2D" refers to a two-dimensional gate structure on a flat substrate; and the abbreviation "3D" refers to a three-dimensional or vertical gate structure in which gate structures are stacked in the vertical direction.

[0032] In this specification, the terms "deposition temperature" and "substrate temperature" may be used interchangeably. It is understood that the substrate temperature may correspond to or be associated with the deposition temperature, and the deposition temperature may mean the substrate temperature.

[0033] In this specification, the terms "precursor", "deposition compound", and "deposition gas" may be used interchangeably when the precursor is in the gaseous state at room temperature and ambient pressure. It is understood that the precursor may correspond to or be associated with the deposition compound or deposition gas, and the deposition compound or deposition gas may mean the precursor.

[0034] Standard abbreviations for elements from the periodic table are used herein. It should be understood that elements may be referred to by these abbreviations (e.g., Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, H refers to hydrogen, F refers to fluorine, etc.).

[0035] To identify the specific molecules disclosed, the unique CAS Registry Number (i.e., "CAS") assigned by the Chemical Abstract Service is shown.

[0036] Note that silicon-containing films such as SiN and SiO are described throughout the specification and claims without reference to their exact stoichiometry. The silicon-containing films may include pure silicon (Si) layers such as crystalline Si, polysilicon (p-Si or polycrystalline Si), or amorphous silicon; silicon nitride (Si k N l ) layers; or silicon oxide (Si n O m ) layers; or mixtures thereof, where k, I, m, and n are inclusively in the range of 0.1 to 6. Preferably, the silicon nitride is S i kN l where k and I are each in the range of 0.5 to 1.5. More preferably, the silicon nitride is Si3N4. In this specification, SiN in the following description may be used to represent a Si k N l -containing layer. Preferably, the silicon oxide is Si n O m where n is in the range of 0.5 to 1.5 and m is in the range of 1.5 to 3.5. More preferably, the silicon oxide is SiO2. In this specification, SiO in the following description may be used to represent a Si n O m -containing layer. Also, the silicon-containing film may be an organic-based or silicon oxide-based low dielectric constant material such as the Black Diamond II or III materials of Applied Materials, Inc. having the formula SiOCH. The silicon-containing film may also include SiaObNc where a, b, c are in the range of 0.1 to 6. The silicon-containing film may contain dopants from groups III, IV, V, and VI such as B, C, P, As, and / or Ge.

[0037] As used herein, the term "hydrocarbon" means a saturated or unsaturated functional group containing only carbon and hydrogen atoms. As used herein, the term "alkyl group" means a saturated functional group containing only carbon and hydrogen atoms. An alkyl group is a type of hydrocarbon. Further, the term "alkyl group" means a straight-chain, branched, or cyclic alkyl group. Examples of straight-chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl groups, etc. Examples of branched alkyl groups include, but are not limited to, t-butyl. Examples of cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl groups, etc.

[0038] As used herein, the abbreviation "Me" means a methyl group; the abbreviation "Et" means an ethyl group; the abbreviation "Pr" means any propyl group (i.e., n-propyl or isopropyl); the abbreviation "iPr" means an isopropyl group; the abbreviation "Bu" means any butyl group (n-butyl, iso-butyl, tert-butyl, sec-butyl); the abbreviation "tBu" means a tert-butyl group; the abbreviation "sBu" means a sec-butyl group; the abbreviation "iBu" means an iso-butyl group; the abbreviation "Ph" means a phenyl group; the abbreviation "Am" means an amyl group (iso-amyl, sec-amyl, tert-amyl); the abbreviation "Cy" means a cyclic hydrocarbon group (cyclobutyl, cyclopentyl, cyclohexyl, etc.); the abbreviation "Ar" means an aromatic hydrocarbon group (phenyl, xylyl, mesityl, etc.).

[0039] As used herein, the formula,

Chem.

Chem.

Chemical formula

[0040] As used herein, the formula

Chemical formula

Chemical formula

[0041] As used herein, the formula

Chemical formula

Chemical formula

Chemical formula

[0042] As used herein, the formula

Chemical formula

Chemical formula

[0043] As used herein, the formula [(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-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 has the following structure: [Chemical formula] (wherein 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 are each independently selected from linear, branched or cyclic C1-C9 alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be -SiR 8 R 9 R 10 , and R 8 , R 9 , R 10 are each independently selected from linear, branched or cyclic C1-C9 alkyl, vinyl or aryl groups. For these In(III)-containing precursors, n = 1 or 2 provides either a 5-membered or 6-membered metallacycle. The groups R 6 and R 7 do not have to be the same for the structure where n = 2. Under certain conditions, when the disclosed In(III)-containing precursors have sufficiently small R 1 , R 2 and R 3 and n = 1, the structure can exist as 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).

[0044] As used herein, the formula [(R 2 R 3 )N-(CR 6R 7 ) n -C(R 4 R 5 )-N(R 1 )]2InX has the following structure:

Chemical formula

[0045] As used herein, the formula

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Chemical formula

[0046] As used herein, the formula

Chemical formula

Chemical formula

[0047] As used herein, the formula [N((SiR 1 R 2 R 3 )R 4 )]InX2 has the following structure:

Chemical formula

[0048] A range may be expressed herein as from about a particular value and / or to about another particular value. When such a range is expressed, it should be understood that another embodiment is from a particular value and / or to another particular value, together with all combinations within the range. Any range recited herein includes its endpoints (i.e., x = 1-4 or x ranges from 1-4 includes x = 1, x = 4, and any number in between), whether or not the term "including all" is used.

[0049] References to "one embodiment" or "an embodiment" in this specification mean that the particular features, structures, or characteristics described in connection with the embodiment can be included in at least one embodiment of the invention. The appearances of the phrase "in one embodiment" in various places in this specification are not necessarily all referring to the same embodiment, and another or alternative embodiment is not necessarily mutually exclusive of other embodiments. The same applies to the term "implementation".

[0050] As used herein, the term "independently" when used in connection with the description of R groups is to be understood to indicate that the R groups of interest are selected independently not only of another R group having the same or different subscripts or superscripts, but also of any additional types of that same R group. For example, in the formula MR 1 x (NR 2 R 3 ) (4-x) (where x is 2 or 3), two or three of the R 1 groups may or may not be the same as each other or as R 2 or R 3 , but need not be. Further, unless otherwise specified, the values of the R groups should be understood to be independent of each other when used in different formulas.

[0051] The term "exemplary" as used in this application is used in this specification to mean serving as an example, instance, or illustration. Aspects or designs described as "exemplary" in this specification should not necessarily be construed as being more preferred or advantageous than other aspects or designs. Rather, the use of the word exemplary is intended to present concepts in a concrete form.

[0052] Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". That is, unless otherwise specified or clear from the context, "X uses A or B" is intended to mean any of the natural inclusive permutations. That is, when X uses A, when X uses B, or when X uses both A and B; in any of the aforementioned cases, "X uses A or B" is satisfied. In addition, the articles "a" and "an" used in this application and the appended claims should be construed to mean "one or more" unless otherwise specified or clear from the context that they relate to the singular form.

[0053] "Comprising" in the claims is an open transitional term, meaning that the claimed elements that follow are a non-exclusive list (i.e., other things may be additionally included and remain within the scope of "comprising"). "Comprising" is defined herein as necessarily encompassing the more limiting transitional terms "consisting essentially of" and "consisting of". Thus, "comprising" may be replaced with "consisting essentially of" or "consisting of" and still remain within the explicitly defined scope of "comprising".

[0054] "Providing" in the claims is defined to mean equipping, supplying, making available, or preparing something. This step may be performed by any actor unless there is explicit language in the claims to the contrary.

[0055] For a further understanding of the nature and objects of the present invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings in which like or similar reference numerals have been assigned to like elements:

Brief Description of the Drawings

[0056]

Figure 1

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[0057] An indium (In)-containing film and / or an indium-containing alloy film forming composition containing an In(III)-containing precursor containing a halogen, a method for synthesizing the same, and a method for depositing an indium-containing film and / or an indium-containing alloy film using the same are disclosed.

[0058] There are several homoleptic indium precursors, but there is a lack of heteroleptic complexes containing halogen that can be used as precursors. The advantage of using heteroleptic compounds is that they can incorporate organic ligands and other reactive ligands such as halogen that can be beneficial for the desired surface chemistry. InCl3 has been used for deposition, but InCl3 has very low volatility (boiling point 800 °C, vapor pressure 1 torr at 310 °C) and is difficult to use for most applications. The disclosed In(III)-containing precursors not only contain at least one halogen but also contain organic ligands, and compared to InCl3, the vapor pressure of the disclosed In(III)-containing precursors is significantly increased to the point where it is sufficient for commercially viable vapor deposition (e.g., CVD and ALD) processes. The In(III)-containing precursors disclosed herein are indium(III)-containing precursors, which are referred to as In(III)-containing precursors throughout the patent application.

[0059] The disclosed In(III)-containing precursors contain one or two halogen ligands. More preferably, the disclosed In(III)-containing precursors contain chlorine together with a nitrogen-based ligand, which is suitable for the vapor deposition of indium-containing films and / or indium-containing alloy films.

[0060] The disclosed In(III)-containing precursors include the following classifications.

[0061] In a first embodiment, the disclosed In(III)-containing precursor has the formula:

Chemical formula

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[0062] Formula

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[0063] Examples of exemplary precursors having the formula [(R 1 )N = C(R 3 )-N(R 2 )]2InX include X = Cl, R 1 = R 2 = iPr, R 3 = nBu,

Chem.

[0064] When the disclosed In(III)-containing precursor is sufficiently small in R 1 , R 2 and R 3 have, under specific conditions, a structure that can exist as a dimer having the formula

Chemical formula

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[0065] In the second embodiment, the disclosed In(III)-containing compound has the formula

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[0066] The formula

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[0067] For the formula

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[0068] When the disclosed indium(III)-containing precursor is sufficiently small in R 1 , R 2 and R 3 have, its structure, under certain conditions, can exist as a dimer of the formula

Chemical formula

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[0069] In the third embodiment, the disclosed In(III)-containing compound has the formula [(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 )]InX2, [(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 )]2InX, [((R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 ))InX]2(μ-X)2, or

Chemical formula

[0070] Formula [(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 )]InX2, exemplary precursors include 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); 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); 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 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 is included.

[0071] Examples of the precursor having the formula [(R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 )]2InX include 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)); 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)); X = Cl, R 1 = R 2 = R3 =Me, R 4 =R 5 =R 6 =R 7 =H, n = 2, [(Me2)N-CH2-CH2-CH2-N(Me)]2InCl (bis-(1-methylamide-2-dimethylaminopropane-N,N’) indium(III) chloride)); 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)) is included.

[0072] The formula [((R 2 R 3 )N-(CR 6 R 7 ) n -C(R 4 R 5 )-N(R 1 ))InX]2(μ-X)2, exemplary precursors having this formula include 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; 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 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 is included.

[0073] In the fourth embodiment, the disclosed In(III)-containing compound has the formula

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[0074] Formula

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[0075] Formula [Chemistry] Exemplary precursors having X = Cl, R 1 = R 2 = R 3 = R 5 = Me, R 4= H, [Chemistry] (Bis-[N,N’-(1,3-dimethyl-1,3-propanediylidene)bis[methanaminato]indium(III) chloride); X = Cl, R 1 = R 2 = Ph, R 3 = R 5 = Me, R 4= H, [Chemistry] (Bis-[N,N’-(1,3-dimethyl-1,3-propanediylidene)bis[benzenaminato]indium(III) chloride); X = Cl, R 1 = R 2 = iPr, R 3 = R 5 = Me, R 4= H, [Chemistry] (Bis-[N,N’-(1,3-dimethyl-1,3-propanediylidene)bis[isopropylaminato]indium(III) chloride); and X = Cl, R 1 = R 2=tBu, R 3 =R 5 =Me, R 4= H,

Chem.

[0076] In the fifth embodiment, the disclosed In(III)-containing compound has the formula [N((SiR 1 R 2 R 3 )R 4 )]InX2 or

Chem.

[0077] Exemplary precursors having the formula [N((SiR 1 R 2 R 3 )R 4 )]InX2 include X = Cl, R 1 = R 2 = R 3 = Me, R4 = H, [N((SiMe3)H)]InCl2 ((trimethylsilyl)amino)indium(III) dichloride; X = Cl, R 1 = R 2 = R 3 = Et, R 4 = H, [N((SiEt3)H)]InCl2 ((triethylsilyl)amino)indium(III) dichloride; and X = Cl, R 1 = R 2 = Me, R 3 = H, R 4 = SiHMe2, [N(SiMe2H)2]InCl2 ((bis(dimethylsilyl)amino)indium(III) chloride is included.

Chemical formula

[0078] More preferably, the disclosed In(III)-containing precursor is

Chemical formula

Chemical formula

[0079] The disclosed In(III)-containing precursor is

Chemical formula

Chemical formula

[0080] The disclosed In(III)-containing precursor is

Chemical formula

[0081] The disclosed In(III)-containing precursor is [Chemical formula] and has the following structure: [Chemical formula] has

[0082] The disclosed In(III)-containing precursor is [Chemical formula] and has the following structure: [Chemical formula] has

[0083] [Chemical formula] Its vapor pressure is 1 torr at 145 °C. [Chemical formula] Its vapor pressure is 1 torr at 128 °C. [Chemical formula] Its vapor pressure is 1 torr at 155 °C. [Chemical formula] Its vapor pressure is 1 torr at 127 °C. See Table 1.

[0084] [Table 1]

[0085] The disclosed method for synthesizing the In(III)-containing precursor involves a salt metathesis reaction as shown in the following examples. The disclosed In(III)-containing precursor can be synthesized by a salt metathesis reaction by mixing 1 equivalent or 2 equivalents of a lithiated ligand with InX3 (X = Cl, Br, I). This reaction is carried out by loading a reaction flask with the desired nitrogen ligand in an ether solvent and cooling it to 0 °C or -78 °C. The necessary alkyllithium reagent is added to generate the reactive lithiated species of the ligand. This lithiated ligand is transferred at -78 °C or 0 °C to a suspension of the desired In(III) halide in an ether solvent. The reaction mixture is stirred for 12 hours. Then, the solution is filtered using celite as the filter aid, and subsequently, the solvent is removed in vacuo to isolate the product. For the lithiated amidinate ligand (e.g.,

Chemical formula

[0086] As a method for synthesizing the disclosed In(III)-containing precursor, as shown in the following examples, there is a ligand exchange reaction of In(III)Cl involving the formation of SiR3-X.

Chemical formula

[0087] The disclosed In(III)-containing precursor can be synthesized by a ligand exchange reaction by mixing 1 equivalent or 2 equivalents of a silylated ligand with InX3 (X = Cl, Br, I). This reaction is carried out by loading the desired In(III) halide into a reaction flask in an ether solvent at room temperature. The necessary silylated nitrogen ligand is added to the reaction mixture at room temperature and stirred for 2 - 12 hours. The solvent is removed in vacuo to isolate the product, which is extracted in a hydrocarbon solvent to remove the remaining indium(III) halide.

[0088] The disclosed In(III)-containing precursors can have the following characteristics that render them suitable for indium and indium alloy film deposition. In one aspect, the disclosed In(III)-containing precursors have a heteroleptic nature and a nitrogen ligand backbone, rendering the disclosed In(III)-containing precursors far more volatile than indium trichloride (InCl3) and having a sufficient vapor pressure at low temperatures. In another aspect, the presence of halogen (e.g., chloride) containing ligands in the disclosed In(III)-containing precursors enables the use of dehalosilylation chemistries to achieve ALD at low temperatures from room temperature to 500 °C, preferably 100 °C to 400 °C. The disclosed In(III)-containing precursors represent the possibility of new product lines in the semiconductor industry.

[0089] The disclosed In(III)-containing precursors have high thermal stability and can be used to form high-speed, high-sensitivity semiconductor layers, such as CMOS systems, 3D NAND channels, or in photodetectors. The disclosed In(III)-containing precursors and the disclosed film-forming compositions are suitable for their related uses regarding the deposition of corresponding element-containing films and the deposition of corresponding element-containing layers.

[0090] The disclosed In(III) precursors and the disclosed film-forming compositions are InGaAs, In used in the electronics field x O y(x = 0.5 to 1.5, y = 0.5 to 1.5), suitable for forming indium-containing thin films such as InSnO (ITO), InGaZnO (IGZO), InN, InP, InAs, InSb, In2S3. The disclosed In(III) precursors and the disclosed film-forming compositions are useful for displays, solar fuels, high-speed electronics (InN), optoelectronic components, high-speed electronics, photovoltaic (InP), infrared detectors, diode lasers (InAs), high-speed transistors, magnetic fields, thermal imaging detectors (InSb), optoelectronic devices, photoelectrochemical water splitting (In2S3), the production of indium tin oxide for LED applications, the production of copper indium gallium selenide (CIGS) for photovoltaic and optical applications, displays, semiconductors, the production of indium gallium zinc oxide (IGZO) in the logic and memory industries, etc.

[0091] This disclosure also includes a process for forming an indium-containing film and a method for forming an oxidized or oxygen-free indium-containing film by a vapor deposition method such as ALD or CVD using the disclosed In(III) precursors. Disclosed is a deposition process in which the disclosed In(III) precursors are used, which are introduced into a reaction chamber to form a film by ALD, CVD, spin-on, spray, dip coating, slit coating, or any other deposition technique in combination with one or more oxidizing agents (e.g., O2 and O3, or H2O and O3) introduced simultaneously and / or sequentially, or without an oxidizing agent, or in combination with one or more reducing agents or nitriding agents (e.g., H2 and NH3, N2 and NH3, or NH3 and N2H4). The disclosed deposition process using the disclosed In(III) precursors can be assisted by heating, light, direct or remote plasma, or combinations thereof.

[0092] When the object is a dielectric film, the co-reactant is an oxidizing gas, e.g., O2, O3, H2O, H2O2, NO, N2O, NO2, O - or OH -They can be oxygen-containing radicals such as, alcohols, silanols, amino alcohols, carboxylic acids such as formic acid, acetic acid, propionic acid, para-formaldehyde, 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 process, the co-reactant is plasma-treated oxygen, ozone, or a combination thereof. When using an oxidizing agent as the co-reactant, the resulting In(III)-containing film will also contain oxygen.

[0093] When the object is a conductive film, the co-reactants can be NH3, N2, H2 or N2 / H2, amines, diamines, cyanides, diimines, 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), pyrazoline, pyridine, radicals and plasma species, and mixtures thereof. The co-reactants may be primary amines, secondary amines, tertiary amines, trisilylamines, their radicals, and mixtures thereof. Preferably, the co-reactant is NH3 or H2. When using a reducing agent containing N, the resulting In(III)-containing film will also contain nitrogen.

[0094] 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, lanthanoids (such as Er), or combinations thereof, the co-reactant may include another precursor.

[0095] Furthermore, to decompose the reactants into their radical forms, the co-reactants can be treated by plasma, and when treated with plasma, at least one of H2, N2, and O2 can be utilized as a source gas for hydrogen, nitrogen, or oxygen, respectively. The plasma source can be an N2 plasma, an N2 / He plasma, an N2 / Ar plasma, an NH3 plasma, an NH3 / He plasma, an NH2 / Ar plasma, a He plasma, an Ar plasma, a H2 plasma, a H2 / He plasma, a H2 / organic amine plasma, and mixtures thereof. For example, the plasma can be generated with power in the range of about 10 W to about 1000 W, preferably about 50 W to about 500 W. The plasma can be generated or present inside the reactor itself. Alternatively, the plasma can be located at a position remote from the reactor, such as a remotely located plasma system. Those skilled in the art will recognize methods and apparatuses suitable for such plasma treatment.

[0096] For example, the co-reactants can be introduced into a direct plasma reactor where plasma is generated in the reaction chamber to produce reactants treated with plasma in the reaction chamber. The co-reactants can be introduced and maintained in the reaction chamber before plasma treatment. Alternatively, plasma treatment may be performed simultaneously with the introduction of the reactants.

[0097] Alternatively, the plasma-treated co-reactants can be generated outside the reaction chamber, such as a remote plasma for treating the co-reactants before passing through the reaction chamber.

[0098] Also disclosed is a method of forming an indium(III)-containing layer on a substrate using a vapor deposition process. Applicants believe that the disclosed film-forming compositions are suitable for ALD. More specifically, the disclosed film-forming compositions enable surface saturation, self-limiting growth per cycle, and complete step coverage with an aspect ratio in the range of about 2:1 to about 200:1, preferably about 60:1 to about 150:1. In addition, the disclosed film-forming compositions have a high decomposition temperature that exhibits good thermal stability to enable ALD. The high decomposition temperature enables ALD at higher temperatures, resulting in higher purity films. The disclosed method can be useful in the manufacture of semiconductors, solar cells, LCD-TFTs, flat panel type devices.

[0099] 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 chemical vapor deposition (CVD) or atomic layer deposition (ALD) with or without plasma enhancement. Exemplary ALD methods include thermal ALD, plasma-enhanced ALD (PEALD), spatial ALD, temporal ALD, selective or non-selective ALD, hot wire ALD (HWALD), radicals incorporated ALD, and combinations thereof. The deposition method is preferably ALD, PE-ALD, or spatial ALD to provide suitable step coverage and film thickness control. Exemplary CVD methods include metalorganic CVD (MOCVD), thermal CVD, pulsed CVD (PCVD), low pressure CVD (LPCVD), sub-atmospheric CVD (SACVD) or atmospheric CVD (APCVD), hot wire CVD or hot filament CVD (also known as cat-CVD where the hot wire functions as the energy source for the deposition process), hot wall CVD, cold wall CVD, aerosol assisted CVD, direct liquid injection CVD, combustion CVD, hybrid physical CVD, metalorganic CVD, rapid thermal CVD, photoinitiated CVD, laser CVD, radicals incorporated CVD, plasma-enhanced CVD (PECVD) including but not limited to flow-type PECVD, and combinations thereof.

[0100] The disclosed In(III)-containing film-forming composition contains any of its analogs or other reaction products in 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. This embodiment can provide better process reproducibility. This embodiment can be produced by purifying the In(III)-containing film-forming composition (e.g., distillation, sublimation, chromatography, etc.).

[0101] The purity of the disclosed film-forming composition is 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), 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 the purity can be determined by gas or liquid chromatography with NMR spectroscopy and mass spectrometry. The disclosed film-forming composition may contain the following impurities: pyrazole; pyridine; alkylamine; alkylimine; THF; ether; pentane; cyclohexane; heptane; benzene; toluene; metal chloride compounds; any of lithium, sodium, or potassium pyrazolyl. The total amount of these impurities is preferably less than 5% w / w (i.e., 0.0% w / w to 5.0% w / w), preferably less than 2% w / w (i.e., 0.0% w / w to 2.0% w / w), more preferably less than 1% w / w (i.e., 0.0% w / w to 1.0% w / w). The disclosed film-forming composition can be purified by recrystallization, sublimation, distillation, and / or passing a gas or liquid through a suitable adsorbent such as 4A molecular sieves.

[0102] By purifying the disclosed film-forming composition, the metal impurities can each independently be in the range of 0 ppbw to 1 ppmw, preferably at about 0 to about 500 ppbw (parts per billion) level, more preferably about 0 ppbw to about 100 ppbw, and even more preferably about 0 ppbw to about 10 ppbw. These metal 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).

[0103] Since the disclosed In(III)-containing film-forming composition may cause the decomposition of the indium(III) precursor to indium oxide (e.g., In2O3), care should be taken not to expose it to water.

[0104] The disclosed film-forming composition can be supplied either in neat form or as a blend with a suitable solvent such as ethylbenzene, xylene, mesitylene, decalin, decane, dodecane, etc. The disclosed precursors can be present in various concentrations in the solvent.

[0105] The neat blend film-forming composition is introduced into the reactor in vapor form by conventional means such as pipes and / or flow meters. The vapor form is produced by vaporizing the neat blend composition by direct vaporization, distillation, conventional vaporization steps by bubbling, or by using a sublimator such as that disclosed in International Publication No. WO 2009 / 087609 to Xu et al. The neat blend composition may be supplied in a liquid state to a vaporizer that vaporizes it before introducing it into the reactor. Alternatively, the neat blend composition can be vaporized by flowing a carrier gas through the container containing the composition and bubbling the carrier gas through the composition. Examples of the carrier gas include, but are not limited to, Ar, He, N2, and mixtures thereof. Bubbling of the carrier gas can also remove any dissolved oxygen present in the neat or blend composition solution. The carrier gas and the composition are then introduced into the reactor as vapor.

[0106] If necessary, the container containing the disclosed film-forming composition can be heated to a temperature at which the composition can have a sufficient vapor pressure. The container can be maintained at a temperature, for example, within 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 by well-known methods to control the amount of precursor to be vaporized.

[0107] The reactor can be any enclosure chamber in which the deposition method is carried out in an apparatus such as, but not limited to, a parallel plate reactor, a cold wall reactor, a hot wall reactor, a single wafer reactor, a multi-wafer reactor, or other types of deposition systems under conditions suitable for reacting compounds and forming layers. Those skilled in the art will recognize that any of these reactors can be used for either an ALD or a CVD deposition process.

[0108] The reactor houses one or more substrates on which a film is deposited. The substrate is generally defined as the material on which the process is carried out. The substrate can be any suitable substrate used in the manufacture of semiconductor, photovoltaic, flat panel, LCD-TFT devices. Examples of suitable substrates include wafers such as silicon, silica, glass, GaAs wafers. The wafer can have one or more layers of different materials deposited thereon in a previous manufacturing step. For example, the wafer can include a dielectric layer. Further, 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 oxide metal nitride layers (Ti, Ru, Ta, etc.) and combinations thereof. Further, the wafer can include copper layers, noble metal layers (e.g., platinum, palladium, rhodium, gold). The wafer can include barrier layers such as manganese, manganese oxide. Plastic layers such as poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) [PEDOT:PSS] can also be used. The layer can be planar or patterned. By the disclosed method, when a layer is formed directly or patterned on the wafer on the substrate, the layer can be deposited directly on one or more layers on the upper surface of the wafer. The patterned layer can be an alternating layer of two specific layers such as In2O3 and ZrO2 used in 3D NAND. Further, those skilled in the art will recognize that the terms "film" and "layer" as used herein mean a material of a certain thickness disposed or spread on a surface, and this surface can be a trench, a line. Throughout this specification and the claims, the wafer and any associated layers thereon are referred to as the substrate. For example, an indium oxide film can be deposited on a metal oxide layer such as a ZrO2 layer, an HfO2 layer, or a MoO2 layer.

[0109] The end use of the substrate is not limited to the present invention, but this technology can find particular advantages in the following types of substrates: silicon wafers, glass wafers and panels, beads, powders and nanopowders, monolithic porous media, printed circuit boards, plastic sheets, etc. Exemplary powder substrates include powders used in rechargeable battery technology. Non-limiting numbers of powder materials include NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials.

[0110] The temperature and pressure in the reactor are maintained at conditions suitable for deposition such as ALD and CVD. In other words, after the vaporized disclosed film-forming composition is introduced into the chamber, the conditions in the chamber are such that a portion of the precursor deposits on the substrate to form a layer. For example, the pressure in the reactor or deposition pressure can be maintained at about 10 -3 torr to about 100 torr, more preferably about 10 -2 torr to 10 torr as required in accordance with the deposition parameters. Similarly, the temperature in the reactor or deposition temperature can be maintained at about 100 °C to about 600 °C, preferably about 150 °C to about 500 °C. One skilled in the art will recognize that "at least a portion of the precursor deposits" means that a portion or all of the precursor reacts with or adheres to the substrate.

[0111] The temperature to achieve optimal film growth can be controlled by either controlling the temperature of the substrate holder. The apparatus used to heat the substrate is well known in the art. The substrate is heated to a temperature sufficient to obtain a desired film having the desired physical state and composition at a sufficient growth rate. Non-limiting and representative temperature ranges for heating the substrate can include from about 50 °C to about 600 °C. When a plasma deposition process is used, the deposition temperature can preferably be less than 400 °C. Instead, when a thermal process is performed, the deposition temperature can be in the range of about 100 °C to about 600 °C.

[0112] Alternatively, the substrate may be heated to a sufficient temperature to obtain a desired In(III)-containing film having a desired physical state and composition at a sufficient growth rate. Non-limiting exemplary temperature ranges at which the substrate can be heated include from room temperature to about 600 °C. Preferably, the temperature of the substrate remains below 500 °C.

[0113] The ALD conditions react the disclosed film-forming composition adsorbed or chemisorbed on the substrate surface to form a film on the substrate. In some embodiments, the applicants believe that a co-reactant having the energy required to react with the disclosed film-forming composition can be obtained by plasma treatment of the co-reactant. When the co-reactant is treated with plasma in this exemplary ALD process, the exemplary ALD process becomes an exemplary PEALD process. The co-reactant can be treated with plasma before and after introduction into the chamber.

[0114] The film-forming composition and the co-reactant can be introduced into a sequential reactor (ALD). The reactor can be purged with an inert gas between each introduction of the film-forming composition, any additional precursors, and the co-reactant. Another example is the continuous introduction of the co-reactant and the pulsed introduction of the film-forming composition while sequentially activating the co-reactant with plasma under conditions where the film-forming composition and the deactivated co-reactant do not substantially react under chamber temperature and pressure conditions (CW PEALD).

[0115] Each pulse of the disclosed film-forming composition can last for a time ranging from about 0.001 seconds to about 120 seconds, alternatively from about 1 second to about 80 seconds, alternatively from about 5 seconds to about 30 seconds. The co-reactant can also be pulsed into the reactor. In such embodiments, each pulse can last for a period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 second to about 30 seconds, alternatively from about 2 seconds to about 20 seconds. In another alternative, the vaporized film-forming composition and co-reactant can be sprayed simultaneously (without mixing of the composition and the reactant) from different sectors of a showerhead under which a susceptor holding several wafers rotates (spatial ALD).

[0116] Depending on certain process parameters, deposition can be carried out over various lengths of time. Generally, deposition can be continued for a desired necessary length to produce a film having the required properties. Typical film thicknesses can vary from a few angstroms to hundreds of microns, typically 1 nm to 100 nm, depending on the specific deposition process. The deposition process can also be carried out the number of times necessary to obtain the desired film.

[0117] The disclosed method for forming an In(III)-containing layer on a substrate includes placing the substrate in a reactor, delivering the vapor of the disclosed In(III)-containing film-forming composition into the reactor, and contacting / adsorbing the vapor with the substrate (typically directing the vapor towards 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 the vapor of the disclosed In(III)-containing film-forming composition and depositing an In(III)-containing layer on the surface of the substrate.

[0118] Generate the vapor of the In(III)-containing film-forming composition and then introduce it into the reaction chamber containing the substrate. The temperature and pressure in the reaction chamber, as well as the temperature of the substrate, are maintained at conditions appropriate for depositing at least a portion of the disclosed In(III)-containing precursor on the substrate. In other words, after introducing the vaporized composition into the reaction chamber, the conditions in the reaction chamber are adjusted such that at least a portion of the precursor deposits on the substrate to form an In(III)-containing layer. One of ordinary skill in the art will recognize that "at least a portion of the precursor deposits" means that a portion or all of the precursor reacts with or adheres to the substrate. In this specification, a co-reactant may be used to assist in the formation of the In(III)-containing layer.

[0119] The disclosed film-forming compositions and co-reactants can be introduced into the reactor simultaneously (CVD), sequentially (ALD), or in any different combinations thereof. The reactor may 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-reactant. Alternatively, the co-reactant and the film-forming composition can be mixed together to form a co-reactant / compound mixture, and then the mixture can be introduced into the reactor in the form of the mixture. Another example is to continuously introduce the co-reactant and introduce the disclosed film-forming composition by pulse (pulse CVD).

[0120] In a non-limiting exemplary ALD process for forming indium-containing films containing two elements such as In2O3, InN, InS, etc., the vapor phase of the disclosed film-forming composition, for example,

Chemical formula

[0121] Alternatively, when the desired indium-containing film contains three elements such as InGaN, the above two-step process (e.g., formation of an InN film) may be inserted by introducing the vapor of an additional precursor compound into the reactor (a three-step process). The additional precursor compound is selected according to the properties of the film to be deposited. The additional elements may include gallium (Ga), nitrogen (N), sulfur (S), phosphorus (P), tin (Sn), arsenic (As), antimony (Sb), zinc (Zn), and mixtures thereof. When an additional precursor compound is utilized, the resulting film deposited on the substrate contains indium and co-reactants in combination with the additional element. When the additional precursor and the In(III) precursor are used in two or more ALD supercycle sequences, a nanolaminated film is obtained. After introducing into the reactor, the additional precursor compound is brought into contact with or adsorbed onto the substrate. Thereafter, by purging and / or evacuating the reactor, the excess precursor compound is removed from the reactor. Depending on the requirements of the process, a co-reactant such as NH3 or an additional precursor may be introduced into the reactor to react with the indium precursor compound. By purging and / or evacuating the reactor, the excess co-reactant or precursor is removed from the reactor. In the final step of the cycle, the remaining co-reactant or precursor may be introduced into the reactor, and the excess remaining co-reactant or precursor is removed by purging and / or evacuating the reactor. The entire three-step process may be repeated until the desired film thickness is obtained. By alternately supplying the indium film-forming composition, the additional precursor compound, and the co-reactant, a film having the desired composition and thickness can be deposited.

[0122] Alternatively, when the desired indium-containing film contains four elements such as InGaZnO (IGZO), the above three-step process may be inserted by introducing the vapor of another additional precursor compound into the reactor (four-step process). The other additional precursor compounds are selected based on the properties of the film to be deposited. The additional elements may include gallium (Ga), nitrogen (N), sulfur (S), phosphorus (P), tin (Sn), arsenic (As), antimony (Sb), zinc (Zn), and mixtures thereof. When another additional precursor compound is utilized, the resulting film deposited on the substrate contains indium in combination with three additional elements. When two or more additional precursors and an In(III) precursor are used in two or more ALD supercycle sequences, a nanolaminate film is obtained. When forming an IGZO film, the precursors may include an indium precursor such as

Chem.

[0123] The indium-containing film obtained from the above process contains 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 a combination thereof, or a pure indium (In(0)) layer may be included. The indium-containing film may include 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 lanthanoids, or a combination thereof. Those skilled in the art will recognize that a desired film composition can be obtained by appropriate selection of the film-forming composition and co-reactants. The disclosed method is useful for the manufacture of semiconductor materials. For example, indium oxide is useful as a semiconductor material and forms heterojunctions with p-InP, n-GaAs, n-Si, and other materials. Thin films of indium oxide can be used as a diffusion barrier for semiconductors ("barrier metal") (e.g., to suppress diffusion between aluminum and silicon).

[0124] After obtaining the desired film thickness, the film can be subjected to further treatments such as thermal annealing, furnace annealing, rapid thermal annealing, UV, e-beam curing and / or plasma gas exposure. Those skilled in the art will recognize the systems and methods used to perform these further treatment steps. For example, an In2O3 film can be exposed to a temperature in the range of about 200°C to about 1000°C for a time in the range of 0.1 seconds to about 7200 seconds under an inert atmosphere, an O-containing atmosphere, and combinations thereof. Most preferably, under an inert atmosphere or an O-containing atmosphere, the temperature range is 350°C to 450°C for 3600 to 7200 seconds. The resulting film can contain fewer impurities and thus improve the density and leakage current. The annealing step may be performed in the same reaction chamber in which the deposition process is carried out. Alternatively, the substrate can be removed from the reaction chamber and the annealing / flash annealing process can be carried out in another apparatus. It has been found that any of the above post-treatment methods, especially thermal annealing, is effective in reducing the contamination of the In2O3 film by carbon and nitrogen. This thus tends to improve the resistivity of the film.

[0125] After annealing, the film deposited by any of the disclosed processes can have a bulk resistivity at room temperature of from about 50 μohm·cm to about 1,000 μohm·cm. Room temperature is from about 20 °C to about 25 °C depending on the season. Bulk resistivity is also known as volume resistivity. One of ordinary skill in the art will recognize that bulk resistivity is typically measured at room temperature for a film that is about 50 nm thick. Bulk resistivity typically increases for thinner films due to changes in the electron transport mechanism. Bulk resistivity also increases at higher temperatures.

Example

[0126] The following non-limiting examples are provided to further illustrate embodiments of the present invention. However, these examples are not intended to include everything, nor are they intended to limit the scope of the present invention as described herein.

[0127] Example 1:

Chemical formula

Chemical formula

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[0128] Example 2:

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[0129] Example 3:

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[0130] Example 4:

Chem.

Chem.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0131] Example 5: Synthesis of

Chemical formula

Chemical formula

[0132] Example 6: Synthesis of [Chemical formula] via a ligand exchange route [Chemical formula] of [Chemical formula] [Chemical formula] In a Schlenk flask under nitrogen, N,N'-diisopropyl-N-(trimethylsilyl)acetimidamide (1.4 equivalents, 0.31 mol, 66 grams) was dissolved in an ethereal solvent (500 mL), preferably tetrahydrofuran. In another Schlenk flask under nitrogen, indium(III) chloride (1.0 equivalent, 0.22 mol, 48.8 grams) was dissolved in an ethereal solvent (250 mL), preferably tetrahydrofuran. While stirring, the N,N'-diisopropyl-N-(trimethylsilyl)acetimidamide mixture was slowly added to the indium halide and stirred at room temperature for 12 hours. At this time, the solvent was removed under reduced pressure and the crude product was isolated. Soxhlet extraction was performed with 800 mL of pentane to isolate the desired product from trace amounts of residual indium(III) chloride. The solvent was removed, [Chemical formula] was isolated as a white solid (56.3 grams, 83% yield). By using a ligand exchange pathway, [Chemical formula] the yield of [Chemical formula] was significantly improved. Figure 13 shows the 1 1H NMR of

[0133] Predicted Example 1: [Chemical formula] Synthesis of [Chemical formula] In a Schlenk flask under nitrogen equipped with a dropping funnel, 1-tert-butyl-3-ethylcarbodiimide (2.0 equivalents, 0.08 mol, 10.10 g) is dissolved in an ethereal solvent (120 mL), preferably diethyl ether, and cooled to -78 °C. 1.6 M methyl lithium (2.0 equivalents, 0.08 mol, 50 mL) in diethyl ether is slowly added to the flask. The mixture is stirred for 2 hours and warmed to room temperature with stirring. In another Schlenk flask, a suspension of indium(III) chloride (1.0 equivalent, 0.040 mol, 8.87 g) in an ethereal solvent (200 mL), preferably dimethoxyethane, is placed and cooled to -78 °C. The lithium solution is slowly added to the suspension, the reaction is warmed to room temperature and stirred for 12 hours. At this time, the solvent is removed under reduced pressure, and then 250 mL of pentane is added. The reaction can be filtered through celite. After removing the solvent,

Chemical formula

[0134] Predictive Example 2:

Chemical formula

Chemical formula

[0135] Predictive Example 3: [Chemical formula] Synthesis of [Chemical formula] In a Schlenk flask under nitrogen equipped with a dropping funnel, isopropyl-imino-2,2-dimethylpyrrolidine (2.0 equivalents, 0.080 mol, 12.34 g) is dissolved in an ethereal solvent (120 mL), preferably diethyl ether, and cooled to -78 °C. 1.6 M methyl lithium (2.0 equivalents, 0.080 mol, 50 mL) in diethyl ether is slowly added to the flask. The mixture is stirred for 2 hours and warmed 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 ethereal solvent (200 mL) is placed and cooled to -78 °C. The lithium solution is slowly added to the suspension, the reaction is warmed to room temperature and stirred for 12 hours. At this time, the solvent is removed under reduced pressure, then 250 mL of pentane is added. The reaction is filtered through celite. After removing the solvent,

Chemical formula

[0136] Predictive Example 4: Synthesis of [(Et2)N-CH2-CH2-N(Et)]InCl2

Chemical formula

[0137] Predicted Example 5: Synthesis of [(Et2)N-CH2-CH2-N(Et)]2InCl

Chemical formula

[0138] Predictive Example 6: Precursors

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0139] Reference Example 7: Precursor

Chemical formula

Chemical formula

Chemical formula

[0140] Case Example 8: Precursor

Chemical formula

Chemical formula

Chemical formula

[0141] The subject matter described herein can be described in relation to an exemplary implementation for processing one or more computing application functions / operations for a computing application having user interaction components, but the subject matter is not limited to these specific embodiments. Rather, the techniques described herein can be applied to any suitable type of user interaction component execution management method, system, platform, and / or device.

[0142] It should be understood that many further variations of the details, materials, steps, and arrangements of parts described and illustrated herein to explain the nature of the present invention can be made by those skilled in the art without departing from the principles and scope of the present invention as set forth in the appended claims. Therefore, the present invention is not intended to be limited to the foregoing examples and / or specific embodiments in the accompanying drawings.

Claims

1. A method for forming an indium(III)-containing film on a substrate, comprising: exposing the substrate to a vapor of a film-forming composition containing an indium(III) precursor; and depositing at least a part of the indium(III) precursor on the substrate by a vapor deposition process to form the indium(III)-containing film on the substrate, wherein the indium(III) precursor is selected from 【Chemical 1】 、 【Chemical 2】 、 【Chemical Formula 3】 、 【Chemical Formula 5】 、 【Chemical Formula 6】 、 or 【Chemical Formula 10】 .

2. The method according to claim 1, wherein the indium(III) precursor is 【Chemical 11】 .

3. The method according to claim 1, wherein the indium(III) precursor is 【Chemical 12】 .

4. The method according to claim 1, wherein the indium(III) precursor is 【Chemical 13】 .

5. The method according to claim 1, wherein the indium(III) precursor is 【Chemical Formula 14】 .

6. The method according to claim 1, wherein the indium(III) precursor is 【Chemical Formula 15】 .

7. The method according to claim 1, wherein the indium(III) precursor is 【Chemical Formula 19】 .

8. The method according to claim 1, wherein the vapor deposition process is an ALD process or a CVD process.

9. The method according to claim 1, further comprising exposing the substrate to a co-reactant.

10. wherein the co-reactant is O ３ , O ２ , H ２ O, NO, N ２ O, NO ２ , H ２ O ２ , O radicals and combinations thereof, the method according to claim 9.

11. wherein the co-reactant is NH ３ , NO, N ２ O, hydrazine, N ２ plasma, N ２ / H ２ plasma, NH ３ plasma, amine, and combinations thereof, the method according to claim 9.

12. The method according to claim 1, wherein the indium(III)-containing film is an indium oxide film, or a binary, ternary, or quaternary indium alloy film.

13. 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, In ２ S ３ or In(OH) ３ The method according to claim 1

14. A method for forming an indium(III)-containing film on a substrate, comprising: forming a chemisorbed film and / or a physically adsorbed film of an indium(III) precursor on the surface of the substrate, wherein the indium(III) precursor is selected from 【Chemical 20】 、 【Chemical 21】 、 【Chemical 22】 、 【Chemical formula 24】 、 【Chemical 25】 、 or ​ .

15. The method according to claim 14, wherein the indium(III) precursor is selected from 【Chemical 30】 、 【Chemical Formula 31】 、 【Chemical 32】 、 【Chemical 33】 、 【Chemical 34】 , or 【Chemical 35】 .

16. The method according to claim 14, wherein the indium(III) precursor is selected from 【Chemical 39】 or 【Chemical Formula 40】 .

17. The method according to claim 14, further comprising chemically reacting the chemisorbed film and / or the physically adsorbed film containing the indium(III) precursor with a co-reactant.

18. The co-reactant is O ３ , O ２ , H ２ O, NO, N ２ O, NO ２ , H ２ O ２ , an oxygen radical, and combinations thereof, the method according to claim 17.

19. wherein the co-reactant is NH ３ , NO, N ２ O, hydrazine, N ２ plasma, N ２ / H ２ plasma, NH ３ plasma, amine, and combinations thereof, the method according to claim 17.

20. A film deposition composition comprising an indium(III) precursor selected from 【Chemical 41】 、 【Chemical 42】 、 【Chemical 43】 、 【Chemical 45】 、 【Chemical 46】 、 or 【Chemical Formula 50】 .

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