Reagents for removing oxygen from metal oxyhalide precursors in thin film deposition processes

Abstract

A method for vapor deposition of a metal or metal nitride film on a substrate surface includes reacting a metal oxy- or metal oxyhalide precursor with an oxyphilic reagent in a reactor containing the substrate to deoxygenate the metal oxy- or metal oxyhalide precursor, and forming the metal or metal nitride film on the substrate by a vapor deposition process. The substrate is exposed to the metal oxyhalide precursor and the oxyphilic reagent simultaneously or sequentially. After deoxygenation, the substrate is exposed to a reducing agent sequentially.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Patent Application No. 17 / 193,046, filed March 5, 2021, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to a method for deoxidizing metal halide precursors or removing oxygen from intermediate films formed by depositing metal halide precursors in ALD and CVD processes using highly oxyphilic compounds as reagents, and more specifically, to using such reagents to promote deoxidation to lower the temperature at which ALD or CVD occurs to produce metal or metal nitride films with low oxygen content.

[0004] background

[0005] Many transition metal halide oxides (such as W, Mo, Cr, V, etc.) are volatile and thermally stable and can be used as precursors in atomic layer deposition (ALD) and chemical vapor deposition (CVD) processes to deposit pure metal or metal nitride films by breaking MX and M=O bonds. Numerous examples include US 20170062224, US 20180286668, WO 2019209289, US 20200131628, US 20070049045A, US 20030022065A, US 10510590B2, US20190067003A, and US 4668528A. However, completely removing oxygen-containing substances (i.e., breaking M=O bonds) during ALD / CVD processes is challenging, and the properties of the deposited film depend heavily on the successful removal of surface impurities, such as oxygen atoms in this case.

[0006] Hydrogen and hydrides (especially hydrides of Si, B, P, and Al) are powerful reducing agents that can remove oxygen from metal halide oxides, producing water as a volatile byproduct. However, the reduction of M=O bonds by H2 or hydrides typically occurs at high temperatures (e.g., >500°C), which is incompatible with some applications where the substrates on which films are deposited cannot withstand such high temperatures. Furthermore, the reduction of transition metal halide oxides by hydrogen or hydrides results in the formation of hydrogen halides (e.g., HCl) and water, creating a highly corrosive gaseous environment for processing chambers and downstream equipment such as vacuum lines, pumps, pressure regulating valves, etc. Simultaneously, the water byproduct can react with surface metal halide oxides or metal halide intermediates, leaving behind oxygen contamination. Such effects are described by Davis (Davies M., Alloy Selection for Service in Chlorine, Hydrogen Chloride and Hydrochloric Acid, 2019, 2nd edition). Some metal or half-metal hydrides, such as AlH3, B2H6, PH3, SiH4, and Si2H6, are also strong reducing agents, but their reaction products with oxygen atoms usually lead to the formation of non-volatile metal or half-metal oxides (Al2O3, B2O3, SiO2, etc.). Thus, such metal or half-metal hydrides are not suitable as co-reactants with metal halide oxide precursors.

[0007] The application of Mo films has garnered attention for accelerating the deposition of some layers, particularly in middle-of-line (MOL) or backend-of-line (BEOL) processes requiring deposition of high-purity films at temperatures below 500°C. MoF6, MoCl5, MoOCl4, and MoO2Cl2 are known inorganic precursors for depositing pure Mo films when combined with reducing agents such as H2. MoO2Cl2 has been reported to be the least corrosive among these precursor groups and also has a higher vapor pressure. The minimum temperature for depositing Mo films from ALD MoO2Cl2 / H2 is at least 500°C, primarily due to the difficulty in removing the double bonds between oxygen and molybdenum.

[0008] US10533023 discloses the formation of a metal film from an "organic metal" precursor and a reducing agent, wherein a first compound having atoms in an oxidized state reacts with a bis(trimethylsilyl) six-membered ring system or related compounds to form a second compound having atoms in a reduced state relative to the first compound. The oxidized atoms are selected from groups 2-12 of the periodic table, the lanthanides, and the groups As, Sb, Bi, Te, Si, Ge, Sn, and Al.

[0009] WO 2020 / 023790 discloses depositing a pure metal film by using MoOCl4, MoO2Cl2, and H2 as a reducing gas at a ratio of 1:100 - 10000 at a high temperature of 500 °C to deposit Mo, where the residual oxygen is ≤ 1 atomic %. For the W film, WOF4, WOCl4, WO2Cl2, etc. are used.

[0010] US10510590 discloses a low - impedance metallization stack structure for logic and memory applications and a related manufacturing method, in which an Mo - containing layer is deposited on a W - containing layer by ALD / CVD. The Mo - containing layer is deposited by exposing the W - containing layer to a reducing agent and an Mo - containing precursor selected from: MoF6, MoCl5, MoO2Cl2, MoOCl4, and Mo(CO)6. The process temperature ranges from 300 °C to 700 °C.

[0011] Therefore, reducing the temperature of the deposition process is challenging. Summary of the Invention

[0012] Disclosed is a method for depositing a metal or metal nitride film on a substrate, the method comprising

[0013] reacting a metal oxyhalide precursor with an oxygen - philic reagent in a reactor containing the substrate to deoxygenate the metal oxyhalide precursor; and

[0014] forming the metal or metal nitride film on the substrate by a vapor deposition process. The disclosed method may include one or more of the following aspects:

[0015] · Further comprising simultaneously exposing the substrate to the metal oxyhalide precursor and the oxygen - philic reagent;

[0016] · Further comprising sequentially exposing the substrate to the metal oxyhalide precursor and the oxygen - philic reagent;

[0017] · Further comprising sequentially exposing the substrate to a reducing agent after deoxygenation;

[0018] · The metal oxyhalide precursor is M (a) X c O e , where M is Mo, W, V, Nb, Ta, and Cr; X is a halogen selected from Cl, Br, or I; a is the oxidation state of M and a is an integer ranging from 3 to 6; c is a number, 0 < c < 6; e is a number, 0 < e < 3; c + 2e = a;

[0019] · The oxygen - philic reagent is N (b) X d O fWhere N is a transition metal halide or halide oxide, or a Group 14 or Group 15 halide, halide oxide, or oxide; X is a halogen selected from Cl, Br, or I; b is the oxidation state of N and b is an integer ranging from 3 to 6; d is a number, 0 ≤ d < 6; f is a number, 0 <f<3;d+2f=b;

[0020] • N has a higher affinity for oxygen than M;

[0021] The metal halide oxide precursors are selected from the group consisting of MoO2Cl2, MoOCl4, WOCl4, WO2Cl2, NbOCl3, TaOCl3 and CrO2Cl2;

[0022] The precursor for metal halide oxides is MoO2Cl2;

[0023] Metal halide precursors are metal oxygen precursors;

[0024] • Metal halide oxide precursors are oxygen-containing metal precursors;

[0025] • Oxyphilic reagents and their oxidation products are volatile;

[0026] • Aerobic reagents are volatile;

[0027] The oxidation products of oxyphilic reagents are volatile;

[0028] • No traces of oxyphilic reagents and their oxidation products are left on the surface of the deposited film;

[0029] • The oxyphilic reagent is selected from halides, halide oxides or oxides containing Group 14 or Group 15;

[0030] • The oxyphilic reagent is selected from halides containing Group 14 or Group 15;

[0031] • The oxyphilic reagent is selected from halogen oxides containing Group 14 or Group 15;

[0032] • The oxyphilic reagent is selected from oxides containing Group 14 or Group 15;

[0033] • The oxyphilic reagent is selected from halides or halide oxides containing transition metals;

[0034] • The oxyphilic reagent is selected from halides containing transition metals;

[0035] • The oxyphilic reagent is selected from halide oxides containing transition metals;

[0036] • The oxygen-loving reagent is selected from:

[0037] a. Containing Group 14: CCl4; CBr4; COCl2; CO; RN=C=O, where R is H, or an alkyl group selected from Me, Et, iPr, nPr, iBu, tBu, sBu, nBu; or Si x R y X z Where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2; X is a halogen selected from Cl, Br, I; R is H, saturated or unsaturated hydrocarbon group, amino group, alkoxy group, or silyl group;

[0038] b. Including Group 15: NO, N2O, PCl3, PBr3, PI3; or

[0039] c. Containing transition metals: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4;

[0040] • Oxiphilic reagents are Si-containing oxophilic reagents, which have the general formula Si x R y X z Where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2; X is a halogen selected from Cl, Br, and I; R is H, saturated or unsaturated carbon-containing ligands, nitrogen-containing ligands, oxygen-containing ligands, and silicon-containing ligands;

[0041] • Oxiphilic reagents are Si-containing oxophilic reagents, which have the general formula Si x R y X z Where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2; X is a halogen selected from Cl, Br, I; R is H, saturated or unsaturated hydrocarbon group, amino group, alkoxy group, or silyl group;

[0042] • The Si-containing oxyphilic reagents are selected from Si2Cl6, Si2Cl5H, Si2Cl4Me2, Si2ClMe5, Si2Cl2Me4, Si2Br6, Si2Br5H, Si2Br4Me2, Si2BrMe5, Si2Br2Me4, Si2Br5H, Si2Me6, Si2I6, Si2I5H, Si2I4(Me)2, Si2(OMe)6, Si2(NR2)6 (where R = H, Me, Et), Si2(NMe2)5Cl, Si3Cl8, Si3Br8, Si3I8, or Si4(Me)9H;

[0043] The oxygen-loving reagent is Si2Cl6 (HCDS);

[0044] • The oxyphilic reagent is selected from the following halogen-free oxyphilic reagents:

[0045] Including Group 14: CO, RN=C=O, where R is H, or an alkyl group selected from Me, Et, iPr, nPr, iBu, tBu, sBu, nBu; or

[0046] Including Group 15: NO, N2O;

[0047] • The oxyphilic reagent is RN=C=O, where R is H, or an alkyl group selected from H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu, which leads to the formation of a metal nitride film;

[0048] • The oxygen-loving reagent is tBu-N=C=O;

[0049] • The oxyphilic reagent is a metal halide or metal halide oxide selected from VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4;

[0050] • The oxygen-loving reagent is WCl4, WCl5, or WCl6;

[0051] • Aerobic reagents are volatile;

[0052] The products of aerobic reagents are volatile;

[0053] The reducing agent is H2 or B2H6;

[0054] The reducing agent is H2;

[0055] The reducing agent is NH3;

[0056] The reducing agent is an oxyphilic reagent selected from CO, SiHCl3, SiHBr3, or SiHl3;

[0057] • Deposition temperature range from 50°C to 500°C;

[0058] • Deposition temperature range from 100°C to 500°C;

[0059] • Deposition temperature ranges from 150°C to 485°C;

[0060] • Deposition temperature below 500℃;

[0061] • Deposition temperature below 485℃;

[0062] • The purity in the metal or metal nitride film is greater than approximately 98.5%;

[0063] • The purity of the metal or metal nitride film is greater than approximately 99%;

[0064] • Oxygen impurities in the metal or metal nitride film are less than approximately 1%;

[0065] • The oxygen impurity content in the metal or metal nitride film is less than 1.5%;

[0066] • Silicon impurities in metal or metal nitride films are 0%;

[0067] • Silicon impurities in metal or metal nitride films are approximately 0%;

[0068] • The metal halide oxide precursors have purities ranging from approximately 93% w / w to approximately 100% w / w;

[0069] • The metal halide oxide precursors have purities ranging from approximately 99% w / w to approximately 99.999% w / w;

[0070] • Oxyphilic reagents have purities ranging from approximately 93% w / w to approximately 100% w / w;

[0071] • Oxyphilic reagents have purities ranging from approximately 99% w / w to approximately 99.999% w / w;

[0072] The reducing agent has a purity ranging from approximately 93% w / w to approximately 100% w / w;

[0073] The reducing agent has a purity ranging from approximately 99% w / w to approximately 99.999% w / w;

[0074] • Chemical vapor deposition is a thermal CVD process;

[0075] • Vapor deposition is a thermal ALD process;

[0076] • Vapor deposition is a plasma-enhanced CVD process;

[0077] • Vapor deposition process is plasma-enhanced ALD; and

[0078] • Vapor deposition is a spatial ALD process.

[0079] A method for removing oxygen from a metal halide oxide precursor or an intermediate film deposited from the metal halide oxide precursor to form a metal or metal nitride film on a surface is also disclosed, the method comprising:

[0080] The metal halide precursor or the intermediate film deposited from the metal halide precursor is reacted with an oxyphilic reagent to form a metal intermediate; and

[0081] The metal intermediate is reduced to a metal or metal nitride film on the surface by a reducing agent through a vapor deposition process.

[0082] in

[0083] The metal halide precursor is M(a) X c O e , where M is Mo, W, V, Nb, Ta, and Cr; X is a halogen selected from Cl, Br, or I; a is the oxidation state of M and a is an integer ranging from 3 to 6; c is a number, 0 < c < 6; e is a number, 0 < e < 3; c + 2e = a; and

[0084] The oxygenophilic reagent is N (b) X d O f , where N is a transition metal halide or haloxide, or a Group 14 or Group 15 halide, haloxide, or oxide; X is a halogen selected from Cl, Br, or I; b is the oxidation state of N and b is an integer ranging from 3 to 6; d is a number, 0 ≤ d < 6; f is a number, 0 < f < 3; d + 2f = b,

[0085] where the oxygenophilicity of N is higher than that of M,

[0086] where the oxygenophilic reagent and the oxidation product of the oxygenophilic reagent are volatile. The disclosed method may include one or more of the following aspects:

[0087] · The metal haloxide precursor is selected from MoO2Cl2, MoOCl4, WOCl4, WO2Cl2, NbOCl3, TaOCl3, and CrO2Cl2;

[0088] · The oxygenophilic reagent is selected from:

[0089] a. Containing Group 14: CCl4; CBr4; COCl2; CO; R-N = C = O, where R is H, or selected from

[0090] b. Alkyl groups of Me, Et, iPr, nPr, iBu, tBu, sBu, nBu; or Si x R y X z , where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2, X is a halogen selected from Cl, Br, I, R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group;

[0091] c. Containing Group 15: NO, N2O, PCl3, PBr3, PI3; or

[0092] d. Containing transition metals: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4;

[0093] · The oxygenophilic reagent is a Si-containing oxygenophilic reagent having the general formula Si x R y Xz Where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2; X is a halogen selected from Cl, Br, I; R is H, saturated or unsaturated hydrocarbon group, amino group, alkoxy group, or silyl group;

[0094] • The Si-containing oxyphilic reagents are selected from Si2Cl6, Si2Cl5H, Si2Cl4Me2, Si2ClMe5, Si2Cl2Me4, Si2Br6, Si2Br5H, Si2Br4Me2, Si2BrMe5, Si2Br2Me4, Si2Br5H, Si2Me6, Si2I6, Si2I5H, Si2I4(Me)2, Si2(OMe)6, Si2(NR2)6 (where R = H, Me, Et), Si2(NMe2)5Cl, Si3Cl8, Si3Br8, Si3I8, or Si4(Me)9H;

[0095] The oxygen-loving reagent is Si2Cl6 (HCDS);

[0096] • The oxyphilic reagent is selected from the following halogen-free oxyphilic reagents:

[0097] Including Group 14: CO, RN=C=O, where R is H, or an alkyl group selected from H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu; or

[0098] Including Group 15: NO, N2O;

[0099] • The oxyphilic reagent is RN=C=O, where R is H, or an alkyl group selected from H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu, which leads to the formation of a metal nitride film;

[0100] • The oxygen-loving reagent is tBu-N=C=O;

[0101] • The oxyphilic reagent is a metal halide or metal halide oxide selected from VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4;

[0102] • The oxygen-loving reagent is WCl4, WCl5, or WCl6;

[0103] • Aerobic reagents are volatile;

[0104] The products of aerobic reagents are volatile;

[0105] The reducing agent is H2 or B2H6;

[0106] The reducing agent is H2;

[0107] · The reducing agent is NH3;

[0108] · The reducing agent is an oxygenophilic reagent selected from CO, SiHCl3, SiHBr3, or SiHl3;

[0109] · The oxygen impurity in the metal or metal nitride film is less than about 1%;

[0110] · The vapor deposition process is thermal CVD or ALD, or plasma-enhanced CVD or ALD;

[0111] · The deposition temperature ranges from 50°C to 500°C;

[0112] · The deposition temperature ranges from 100°C to 500°C;

[0113] · The deposition temperature ranges from 150°C to 485°C;

[0114] · The deposition temperature is below 500°C; and

[0115] · The deposition temperature is below 485°C.

[0116] Also disclosed is a reagent for deoxidizing a metal oxyhalide precursor or an intermediate film deposited from the metal oxyhalide precursor to form a metal or metal nitride film in a vapor deposition process, the metal oxyhalide precursor having the following general formula: M (a) X c O e , where M is Mo, W, V, Nb, Ta, and Cr; X is a halogen selected from Cl, Br, or I; a is the oxidation state of M and a is an integer ranging from 3 to 6; c is a number, 0 < c < 6; e is a number, 0 < e < 3; c + 2e = a,

[0117] The reagent comprises:

[0118] An oxygenophilic reagent having the following general formula: N (b) X d O f , where N is a transition metal halide or oxyhalide, or a Group 14 or Group 15 halide, oxyhalide, or oxide; X is a halogen selected from Cl, Br, or I; b is the oxidation state of N and b is an integer ranging from 3 to 6; d is a number, 0 ≤ d < 6; f is a number, 0 < f < 3; d + 2f = b,

[0119] wherein the oxygenophilicity of N of the oxygenophilic reagent is higher than the oxygenophilicity of M of the metal oxyhalide precursor,

[0120] wherein the oxygenophilic reagent and the oxidation product of the oxygenophilic reagent are volatile. The disclosed reagent may include one or more of the following aspects:

[0121] The metal halide oxide precursors are selected from MoO2Cl2, MoOCl4, WOCl4, WO2Cl2, NbOCl3, TaOCl3 and CrO2Cl2;

[0122] • The oxygen-loving reagent is selected from:

[0123] a. Containing Group 14: CCl4; CBr4; COCl2; CO; RN=C=O, where R is H, or an alkyl group selected from Me, Et, iPr, nPr, iBu, tBu, sBu, nBu; or Si x R y X z Where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2, X is a halogen selected from Cl, Br, I, and R is H, saturated or unsaturated hydrocarbon group, amino group, alkoxy group, or silyl group;

[0124] b. Including Group 15: NO, N2O, PCl3, PBr3, PI3; or

[0125] c. Containing transition metals: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4;

[0126] • Oxiphilic reagents are Si-containing oxophilic reagents with the following general formula: Si x R y X z Where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2; X is a halogen selected from Cl, Br, I; R is H, saturated or unsaturated hydrocarbon group, amino group, alkoxy group, or silyl group;

[0127] • The Si-containing oxyphilic reagents are selected from Si2Cl6, Si2Cl5H, Si2Cl4Me2, Si2ClMe5, Si2Cl2Me4, Si2Br6, Si2Br5H, Si2Br4Me2, Si2BrMe5, Si2Br2Me4, Si2Br5H, Si2Me6, Si2I6, Si2I5H, Si2I4(Me)2, Si2(OMe)6, Si2(NR2)6 (where R = H, Me, Et), Si2(NMe2)5Cl, Si3Cl8, Si3Br8, Si3I8, or Si4(Me)9H;

[0128] The oxygen-loving reagent is Si₂Cl₆;

[0129] • The oxygen-loving reagent is WCl4, WCl5, or WCl6;

[0130] • The oxyphilic reagent is RN=C=O, where R is H, or an alkyl group selected from Me, Et, iPr, nPr, iBu, tBu, sBu, nBu, which leads to the formation of a metal nitride film;

[0131] • The oxygen-loving reagent is tBu-N=C=O;

[0132] • The oxyphilic reagent is a metal halide or metal halide oxide selected from VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4;

[0133] • Aerobic reagents are volatile;

[0134] The oxidation products of oxyphilic reagents are volatile;

[0135] • Oxyphilic reagents have purities ranging from approximately 93% w / w to approximately 100% w / w;

[0136] • Oxyphilic reagents have purities ranging from approximately 99% w / w to approximately 99.999% w / w; and

[0137] • The oxygen-loving reagent has less than 20 ppm of water impurities by weight.

[0138] Notation and naming conventions

[0139] The following detailed description and claims utilize many abbreviations, symbols, and terms commonly known in the art, and include:

[0140] As used in this article, the indefinite article “a or an” means one or more species.

[0141] As used herein, “about” or “around / approximately” in the text or claims means ±10% of the value.

[0142] As used herein, “room temperature” in the text or claims means from about 20°C to about 25°C.

[0143] 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.).

[0144] A unique CAS registry number (i.e., "CAS") assigned by the Chemical Abstracts Service is provided to help better identify the disclosed molecules.

[0145] As used in this article, the formula "M" (a) X cO e refers to a metal halide oxide precursor, where M is Mo, W, V, Nb, Ta, or Cr; X is a halogen selected from Cl, Br, or I; a is the oxidation state of M and a is an integer ranging from 3 to 6; c is a number, 0 < c < 6; e is a number, 0 < e < 3; c + 2e = a.

[0146] As used herein, the formula "N (b) X d O f " refers to an oxygenophilic reagent, where N is a transition metal halide or halide oxide, or a Group 14 or Group 15 halide, halide oxide, or oxide; X is a halogen selected from Cl, Br, or I; b is the oxidation state of N and b is an integer ranging from 3 to 6; d is a number, 0 ≤ d < 6; f is a number, 0 < f < 3; d + 2f = b.

[0147] As used herein, the formula "Si x R y Y z " refers to a Si-containing oxygenophilic reagent, where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2; X is a halogen selected from Cl, Br, I; R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group.

[0148] As used herein, the formula "M - X" refers to a metal halide, where M is a metal and X is a halogen element selected from Cl, Br, or I.

[0149] As used herein, the formula "MN x " refers to a metal nitride, where M is a metal, N is nitrogen, and x is a positive number in the range 0 < x ≤ 2, but not necessarily an integer.

[0150] As used herein, the formula "MO x " refers to a metal oxide, where M is a metal, O is oxygen, and x is a positive number in the range 0 < x ≤ 3, but not necessarily an integer.

[0151] As used herein, the formula "MO x X y " refers to a metal oxohalide, where M is a metal, O is oxygen, X is Cl, Br, or I, x is a number in the range 0 < x ≤ 3, y is a number in the range 0 < y ≤ 6, and 2x + y ≤ 6. x and y are not necessarily integers.

[0152] As used herein, the formula "R - N = C = O" refers to an isocyanate, where R is a saturated or unsaturated hydrocarbon group, such as an alkyl group, and preferably, R = H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu.

[0153] As used herein, the term "hydrocarbon group" refers to a saturated or unsaturated functional group containing only carbon and hydrogen atoms.

[0154] As used herein, the term "alkyl" refers to a saturated functional group containing only carbon and hydrogen atoms. An alkyl group is a type of hydrocarbon. Additionally, the term "alkyl" can refer 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.

[0155] As used in this article, the abbreviation "Me" refers to methyl; the abbreviation "Et" refers to ethyl; the abbreviation "Pr" refers to 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; and the abbreviation "Ph" refers to phenyl.

[0156] 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, gold, etc.), organic layers such as amorphous carbon, or photoresist, or combinations thereof. Furthermore, a substrate can be planar or patterned. The substrate may include an oxide layer used as a dielectric material (e.g., ZrO2-based materials, HfO2-based materials, TiO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, 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 quantity of material placed or spread on a surface of a certain thickness, 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.

[0157] It should be noted in this document that the terms "oxygen scavenger" and "deoxygenation" are used interchangeably. It should be understood that "oxygen scavenger" can correspond to or relate to deoxygenation or deoxygenation, and that deoxygenation or deoxygenation can refer to "oxygen scavenger".

[0158] 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 laid 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.

[0159] It should be noted in this article that the terms “aperture,” “gap,” “via,” “hole,” “opening,” “trench,” and “structure” are used interchangeably to refer to openings formed in a semiconductor substrate.

[0160] It should be noted in this document that the terms “deposition temperature,” “substrate temperature,” and “process temperature” are used interchangeably. It should be understood that substrate temperature may correspond to or be related to deposition temperature or process temperature, and deposition temperature or process temperature may refer to substrate temperature.

[0161] 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.

[0162] As used herein, the abbreviation “NAND” refers to a “Negated 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 gate structures are stacked in the vertical direction.

[0163] A range may be expressed herein 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 the range. Any and all ranges listed in the disclosed embodiments include their endpoints (i.e., x = 1 to 4 or x in the range from 1 to 4 includes x = 1, x = 4, and x = any value therebetween), regardless of whether the term "including endpoints" is used.

[0164] 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".

[0165] 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.

[0166] The word “comprising” in the claims is an open-ended transitional term, meaning that the subsequently defined 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.”

[0167] 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. Attached Figure Description

[0168] To further understand the nature and purpose of the 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:

[0169] Figure 1a The powder X-ray diffraction (PXRD) pattern and fit of the mixture of WCl6 and MoO2Cl2 before the reaction according to an exemplary embodiment of the present invention;

[0170] Figure 1b PXRD plot and fitting of a mixture of WCl6 and MoO2Cl2 after the reaction according to an exemplary embodiment of the present invention;

[0171] Figure 2a This is a flowchart of an ALD process using HCDS as a deoxidizer and H2 as a reducing agent according to an exemplary embodiment of the present invention.

[0172] Figure 2b This is according to an exemplary embodiment of the present invention. Figure 2a The X-ray photoelectron spectroscopy (XPS) of ALD at 485 °C using HCDS as an oxygen scavenger and H2 as a reducing agent is shown.

[0173] Figure 3a This is a flowchart of an ALD process using H2 as a reducing agent in the absence of HCDS as an oxygen scavenger, according to an exemplary embodiment of the present invention; and

[0174] Figure 3b This is according to an exemplary embodiment of the present invention. Figure 3a The XPS of ALD at 485°C is shown in the absence of HCDS as an oxygen scavenger and H2 as a reducing agent. Detailed Implementation

[0175] Methods for removing oxygen from metal-oxygen precursors (oxygen-containing metal precursors) or intermediate films formed by depositing metal-oxygen precursors in thin film deposition processes are disclosed. Methods for removing oxygen from metal-oxygen precursors or intermediate films formed by depositing metal-oxygen precursors in ALD and CVD processes using highly oxyphilic compounds as reagents are also disclosed. The disclosed metal-oxygen precursors include metal halide oxide precursors. More specifically, methods for removing oxygen from metal halide oxide precursors or intermediate films formed by depositing metal halide oxide precursors in halide-based ALD and CVD processes using highly oxyphilic compounds as reagents are disclosed.

[0176] The disclosed methods include using the disclosed oxyphilic reagent to facilitate the removal of oxygen from an intermediate film formed by depositing a metal halide oxide precursor, thereby reducing the process temperature during ALD or CVD to produce a metal or metal nitride film with low oxygen content or impurities. The disclosed methods include using the disclosed oxyphilic reagent to remove oxygen from an intermediate film or intermediate oxyhalide metal surface formed by depositing the disclosed metal halide oxide precursor in a halide-based ALD and CVD process, thereby reducing the temperature during ALD or CVD to produce a metal or metal nitride film with low oxygen content. The disclosed methods include using the disclosed oxyphilic reagent to remove oxygen from the disclosed metal halide oxide precursor, thereby forming a metal halide layer deposited on a surface by ALD and CVD processes. The metal halide can then be reduced to a metal or metal nitride film with low oxygen content by introducing a reducing agent. Furthermore, methods for forming metal or metal nitride films from metal oxygen precursors, more specifically metal halide oxide precursors, are disclosed, wherein an oxyphilic reagent is used, with or without the need for a reducing agent. The disclosed metal oxide precursor may be a metal halide oxide precursor. The term "metal halide oxide precursor" is used throughout the specification, but is not limited to it. Film-forming compositions comprising a metal halide oxide precursor, an oxyphilic agent, and a reducing agent are disclosed.

[0177] To reduce the process temperature, it can be assumed that an oxygen scavenger (an oxygen-loving agent or compound in this paper) can be used to promote the removal of oxygen, i.e., through deoxidation reduction, so that the deposition of metal films such as Mo films can be achieved.

[0178] The advantages of the disclosed method include: 1) fluorine-free reaction and process; 2) non-plasma or plasma process; 3) low temperature process, preferably deposition temperature below 500°C; 4) extremely low O- residue, preferably <1.5% oxygen remains in the deposited film after the reaction, more preferably <about 1% oxygen remains in the deposited film after the reaction.

[0179] Regarding oxophilicity, Kepp (Kepp, KP, A Quantitative Scale of Oxophilicity and Thiophilicity, Inorganic Chemistry, 2016, 55, 9461) provides a good summary of the oxophilicity of elements in the periodic table. In the disclosed methods, oxophilic reagents can be selected from those elements that have a higher oxophilicity than the metals that are the precursors of the metal halide oxides. For oxophilic reagents to function in the ALD / CVD process, the oxophilic reagents and their oxidation products must be volatile to facilitate transport and removal, so as not to leave traces of those elements on the surface of the deposited film.

[0180] Here, the disclosed oxygenophilic reagent can be a volatile compound containing an element with an oxygenophilicity higher than that of the metal of the metal halide oxide precursor.

[0181] The disclosed oxygenophilic reagent can be selected from compounds containing transition metals or main group elements to remove, exchange, scavenge, or transfer oxygen from the metal halide oxide precursor. The transition metal or main group element in the oxygenophilic reagent has an oxygenophilicity higher than that of the metal of the metal halide oxide precursor, which can correspond to the reduction of the metal center of the metal halide oxide precursor or remain in the oxidation state unchanged, i.e., ligand exchange.

[0182] The disclosed metal halide oxide precursor can have the following general formula:

[0183] M (a) X c O e ,

[0184] where M is Mo, W, V, Nb, Ta, and Cr; X is a halogen; a is the oxidation state of M and a is an integer ranging from 3 to 6; c is a number, 0 < c < 6; e is a number, 0 < e < 3; c + 2e = a. Preferably, X is selected from Cl, Br, or I. In one embodiment, the metal halide oxide precursor is selected from transition metal halide oxide precursors. Preferably, the metal halide oxide precursor is selected from MoO2Cl2, MoOCl4, WOCl4, WO2Cl2, NbOCl3, TaOCl3, CrO2Cl2, etc.

[0185] The disclosed oxygenophilic reagent can have the following general formula:

[0186] N (b) X d O f ,

[0187] where N is a transition metal halide or halide oxide, or a Group 14 or Group 15 halide, halide oxide, or oxide; X is a halogen; b is the oxidation state of N and b is an integer ranging from 3 to 6; d is a number, 0 ≤ d < 6; f is a number, 0 < f < 3; d + 2f = b. Preferably, X is selected from Cl, Br, or I.

[0188] Here, the oxygenophilicity of N in (b) X d O f should be greater than the oxygenophilicity of M in (a) X c O e For example, the oxygenophilicity Mo < W. Therefore, the oxygenophilic reagent N (b) X d O fOxiphilic reagents selected from those containing transition metal elements or elements from Group 14 or 15, wherein the oxophilicity of their principal element (i.e., transition metal elements or elements from Group 14 and 15) is higher than that of the metal in the metal halide precursor.

[0189] Preferably, the disclosed oxyphilic reagent can be selected from:

[0190] 14th clan:

[0191] Carbon-containing: CCl4, CBr4, COCl2, CO and RN=C=O, wherein R is a saturated or unsaturated hydrocarbon group, such as an alkyl group, preferably R=H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu;

[0192] Containing Si: Si x R y X z Where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2; X is a halogen selected from Cl, Br, I; R is H, saturated or unsaturated hydrocarbon group, amino group, alkoxy group, or silyl group;

[0193] Clan 15:

[0194] Nitrogen-containing: NO, N2O;

[0195] Containing P: PCl3, PBr3, PI3; or

[0196] Containing transition metals: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4.

[0197] Alternatively, the disclosed oxyphilic reagent may be a Si-containing oxyphilic reagent. x R y X zWhere x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2; X is a halogen selected from Cl, Br, and I; R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group. Exemplary Si-containing oxyphilic reagents include Si2Cl6, Si2Cl5H, Si2Cl4Me2, Si2ClMe5, Si2Cl2Me4, Si2Br6, Si2Br5H, Si2Br4Me2, Si2BrMe5, Si2Br2Me4, Si2Br5H, Si2Me6, Si2I6, Si2I5H, Si2I4(Me)2, Si2(OMe)6, Si2(NR2)6 (where R = H, Me, Et), Si2(NMe2)5Cl, Si3Cl8, Si3Br8, Si3I8, or Si4(Me)9H. Preferably, the Si-containing oxyphilic reagent is Si2Cl6 (HCDS).

[0198] Alternatively, the oxygen-loving reagent N (b) X d O f The precursors can be selected from those that do not contain halides (where d = 0), following similar criteria, i.e., their main element has a higher oxophilicity than the metal in the metal halide precursor. Preferably, those oxophilic reagents are selected from:

[0199] Group 14: CO and RN=C=O, where R is a saturated or unsaturated hydrocarbon group, such as an alkyl group, preferably R=H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu; or

[0200] Group 15: NO, N2O.

[0201] Alternatively, the oxygen-loving reagent N (b) X d O f The isocyanate can be of the formula RN=C=O, where R is a saturated or unsaturated hydrocarbon group, such as an alkyl group, preferably R=H, Me, Et, iPr, nPr, iBu, tBu, sBu, or nBu. When the isocyanate is used as an oxophile, the M=O bond of the metal halide precursor is replaced by an M=NR bond, resulting in the formation of a metal nitride film instead of a pure metal film. In this document, C and N elements have higher oxophilicity than the metal in the metal halide precursor. Preferably, the isocyanate is tBu-N=C=O. When tBu-N=C=O is used as an oxophile, the M=O bond of the metal halide precursor is replaced by an M=N-tBu bond, resulting in the formation of a metal nitride film instead of a pure metal film.

[0202] Alternatively, the oxygen-loving reagent N (b) X d O fIt can be a transition metal halide or a halogen oxide. Exemplary transition metal-containing halides or halogen oxides include VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, and WCl4.

[0203] In one embodiment, in addition to the oxygenophilic reagent N (b) X d O f in addition, a reducing agent can be used to convert the deposited film into a metal film. The reducing agent can be H2, B2H6, HCl, etc., for forming the metallic form. The reducing agent can be NH3, for forming a metal nitride film.

[0204] Alternatively, the oxygenophilic reagent itself can also act as a reducing agent capable of reducing the metal halogen oxide precursor to a metal. In this case, the oxygenophilic reagent acts as both an oxygen scavenger and a reducing agent. For example, CO can act as both an oxygen scavenger and a reducing agent.

[0205] Generally, as described below, there are three general reaction schemes or equations for deoxygenation reactions or deoxidation from metal halogen oxide precursors.

[0206] Equation I: The oxidation state of the metal in the metal halogen oxide precursor does not change:

[0207] M (a) X c O e +N (b) X d O f →M (a) X c+2 O e-1 +N (b) X d-2 O f+1 (I)

[0208] Where

[0209] M (a) X c O e is a metal halogen oxide precursor, where M is Mo, W, V, Nb, Ta, and Cr; X is a halogen; a is the oxidation state of M and a is an integer ranging from 3 to 6; c is a number, 0 < c < 6; e is a number, 0 < e < 3; c + 2e = a;

[0210] N (b) X d O fIt is an oxophilic reagent, where N is a transition metal halide or halide oxide, or a group 14 or 15 halide, halide oxide, or oxide; X is a halogen; b is the oxidation state of N and b is an integer from 3 to 6; d is a number, 0 ≤ d < 6; f is a number, 0 <f<3;d+2f=b;

[0211] The premise is N (b) X d O f The oxygen affinity of N is greater than that of M. (a) X c O e The oxygen-loving nature of M, and N (b) X d O f and N (b) X d-2 O f+1 It is volatile. Preferably, X is selected from Cl, Br or I.

[0212] Examples of Equation I:

[0213] 1) The metal halide oxide precursor is MoO2Cl2, and the oxyphilic reagent is WCl6, which removes oxygen in the following sequence:

[0214] Mo (VI) Cl2O2+W (VI) Cl6→Mo (VI) Cl4O+W (VI) Cl4O

[0215] Mo (VI) Cl4O+W (VI) Cl6→Mo (VI) Cl6+W (VI) Cl4O

[0216] Among them W (VI) Cl6 and W (VI) Cl4O is volatile.

[0217] 2) Two M=O atoms are removed in a single step, with the metal halide precursor being MoO2Cl2 and the oxyphilic reagent being WCl6:

[0218] Mo (VI) Cl2O2+2W (VI) Cl6→Mo (VI) Cl6+2W (VI) Cl4O

[0219] Among them W (VI) Cl6 and W (VI) Cl4O is volatile.

[0220] 3) The reaction product Mo in 1) and 2)(VI) Cl6 is unstable and undergoes further reactions:

[0221] Mo (VI) Cl6 → Mo (IV) Cl4 + Cl2

[0222] Mo (VI) Cl4 + 2H2 → Mo (0) + 4HCl

[0223] Wherein, Mo (VI) Cl4 can be reduced by H2 to Mo and HCl, or decomposed by heating to Mo and Cl2.

[0224] Equation II: The oxidation state of the metal in the metal halide oxide precursor changes by two valence:

[0225] M (a) X c O e + N (b) X d O f → M (a-2) X c O e-1 + N (b+2) X d O f+1 (II)

[0226] Wherein

[0227] M (a) X c O e is a metal halide oxide precursor, where M is Mo, W, V, Nb, Ta, and Cr; X is a halogen; a is the oxidation state of M and a is an integer ranging from 3 to 6; c is a number, 0 < c < 6; e is a number, 0 < e < 3; c + 2e = a;

[0228] N (b) X d O f is an oxygenophilic reagent, where N is a transition metal halide or halide oxide, or a Group 14 or Group 15 halide, halide oxide, or oxide; X is a halogen; b is the oxidation state of N and b is an integer ranging from 3 to 6; d is a number, 0 ≤ d < 6; f is a number, 0 < f < 3; d + 2f = b;

[0229] Provided that N (b) X d O f the oxygenophilicity of N in (a) X c O e should be greater than the oxygenophilicity of M in (b) Xd O f and N (b+2) X d O f+1 is volatile. Preferably, X is selected from Cl, Br, or I.

[0230] Example of Equation II: The metal halo - oxide precursor is MoO2Cl2, and the oxygenophilic reagent is WCl4:

[0231] Mo (VI) Cl2O2+W (IV) Cl4→Mo (IV) Cl4+W (VI) Cl2O2

[0232] Mo (IV) Cl4+2H2→Mo (0) +4HCl

[0233] wherein, Mo (IV) Cl4 can be reduced by H2 to Mo and HCl, or decomposed by heating to Mo and Cl2; W (IV) Cl4 and W (VI) Cl2O2 are volatile.

[0234] Equation III: The oxidation state of the metal in the metal halo - oxide precursor changes by one valence:

[0235] M (a) X c O e +N (b) X d O f >→M (a-1) X c+1 O e-1 +N (b+1) X d-1 O f+1 (III)

[0236] wherein

[0237] M (a) X c O e is the metal halo - oxide precursor, where M is Mo, W, V, Nb, Ta, and Cr; X is a halogen; a is the oxidation state of M and a is an integer ranging from 3 to 6; c is a number, 0 < c < 6; e is a number, 0 < e < 3; c + 2e = a;

[0238] N (b) X d O fIt is an oxophilic reagent, where N is a transition metal halide or halide oxide, or a group 14 or 15 halide, halide oxide, or oxide; X is a halogen; b is the oxidation state of N and b is an integer from 3 to 6; d is a number, 0 ≤ d < 6; f is a number, 0 <f<3;d+2f=b;

[0239] The premise is N (b) X d O f The oxygen affinity of N should be greater than that of M. (a) X c O e The oxygen-loving nature of M, and N (b) X d O f and N (b+1) X d- 1O f+1 It is volatile. Preferably, X is selected from Cl, Br or I.

[0240] Example of Equation III:

[0241] 1) The metal halide precursor is MoO2Cl2, and the oxyphilic reagent is WCl5:

[0242] Mo (VI) Cl2O2+W (V) Cl5→Mo (V) Cl3O+W (VI) Cl4O

[0243] Mo (V) Cl3O+W (V) Cl5→Mo (IV) Cl4+W (VI) Cl4O

[0244] Mo (IV) Cl4 + 2H2 → Mo (0) +4HCl

[0245] Among them Mo (IV) Cl4 can be reduced to Mo and HCl by H2, or decomposed into Mo and Cl2 by heating; W (V) Cl5 and W (VI) Cl4O is volatile.

[0246] 2) Removing the two M=O atoms, the metal halide precursor is MoO2Cl2, and the oxyphilic reagent is WCl5:

[0247] Mo (VI) Cl2O2+W (V) Cl5→Mo (V) Cl5+W (VI) Cl2O2

[0248] 2Mo (V) Cl5 + 5H2 → 2Mo (0) +10HCl

[0249] Among them Mo (IV) Cl4 can be reduced to Mo and HCl by H2, or decomposed into Mo and Cl2 by heating; W (V) Cl5 and W (VI) Cl2O2 is volatile.

[0250] The selection criteria for the disclosed oxyphilic reagent should be i) regarding oxyphilicity, the major element of the oxyphilic reagent (e.g., C, N, P, Si, transition metals V, W, Nb, Ta) should be greater than the oxyphilicity of the metal halide precursor metal; and ii) the oxyphilic reagent and its reaction products (e.g., products in the M=O form) are volatile. Table I lists exemplary promising elements that can be used as oxyphilic reagents before and after reacting with oxygen in the metal halide precursor, along with their oxyphilicity, volatility, and volatile oxidation products.

[0251] Table I

[0252]

[0253] Unless otherwise stated, the volatility value is the boiling point at ambient pressure.

[0254] □ See Gaggler, HW, Online Gas Chemistry Experiments with TransActinide Elements, J. Radioanalytical. Nucl. Chem., 1994, 183, 261-271.

[0255] In this paper, not all transition metals used as oxophiles meet the selection criteria. For example, TiCl4, ZrCl4, HfCl4, LaCl3, and CeCl3 do not meet the selection criteria because no literature reports the existence of their halide oxides and that they are sufficiently volatile, despite their much higher oxophilicity than Mo. Similarly, CrCl3 is too non-volatile to be used as an oxygen scavenger.

[0256] When silicon compounds are used as oxyphilic agents, although there are no known stable and volatile halide oxides, deoxygenation can occur by forming siloxane compounds that can be volatile. Thus, silanes, and especially polyhalogenated polysilanes such as Si₂Cl₆ or Si₂HCl₅, are particularly good candidates for removing O from metal halide oxides. Similarly, polysilanes such as Si₂Cl₆, Si₂HCl₅, and Si₂Me₆ are particularly suitable candidates for removing O from metal halide oxide precursors.

[0257] For example, when the metal halide oxide precursor is MoO2Cl2, possible oxophilic reagents containing oxophilic elements can be selected from:

[0258] Group 14: Carbon-containing: CCl4, CBr4, COCl2, CO and RN=C=O, wherein R is a saturated or unsaturated hydrocarbon group, such as an alkyl group, preferably R=H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu;

[0259] Containing Si: Si x R y X z Where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2; X is a halogen selected from Cl, Br, I; R is H, saturated or unsaturated hydrocarbon group, amino, alkoxy, or silyl group, such as Si2Cl6, Si2Cl5H, Si2Cl4Me2, Si2ClMe5, Si2Cl2Me4, Si2Br6, Si2Br5H, Si2Br4Me2, Si2BrMe5, Si2Br2Me4, Si2Br5H, Si2Me6, Si2I6, Si2I5H, Si2I4(Me)2, Si2(OMe)6, Si2(NR2)6 (where R = H, Me, Et), Si2(NMe2)5Cl, Si3Cl8, Si3Br8, Si3I8, or Si4(Me)9H;

[0260] Group 15: Nitrogen-containing compounds: NO, N2O;

[0261] Containing P: PCl3, PBr3, PI3; or

[0262] Transition metals: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, WCl4.

[0263] Similar methods can be applied to deoxygenation or deoxidation of other metal halide precursors. For example, CrO₂Cl₂ is highly volatile and can be used as a precursor for Cr-deposited metal halide oxides using a method similar to that used for MoO₂Cl₂. For this purpose, oxophilic agents can be used to facilitate the clean removal of oxygen, and these can be selected from:

[0264] Group 14: CCl4, CBr4, COCl2, CO and RN=C=O, wherein R is a saturated or unsaturated hydrocarbon group, such as an alkyl group, preferably R=H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu;

[0265] Si x R y X z Where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2; X is a halogen selected from Cl, Br, I; R is H, saturated or unsaturated hydrocarbon group, amino, alkoxy, or silyl; such as Si2Cl6, Si2Cl5H, Si2Cl4Me2, Si2ClMe5, Si2Cl2Me4, Si2Br6, Si2Br5H, Si2Br4Me2, Si2BrMe5, Si2Br2Me4, Si2Br5H, Si2Me6, Si2I6, Si2I5H, Si2I4(Me)2, Si2(OMe)6, Si2(NR2)6 (where R = H, Me, Et), Si2(NMe2)5Cl, Si3Cl8, Si3Br8, Si3I8, or Si4(Me)9H;

[0266] Group 15: NO, N₂O, PCl₃, PBr₃, PI₃; or

[0267] Transition metals: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, WCl4.

[0268] In CVD or ALD processes, the removal of oxygen from metal halide precursors or intermediate films formed by depositing metal halide precursors using oxyphilic agents can typically be supplemented by the complete reduction of the metal center (metal intermediate MX) to form a metal film. Thus, the oxyphilic agent can be used in combination with a complementary reducing agent such as H2 to convert MX to M and HX, where X = Cl, Br, or I, and M = the metal from the metal halide precursor. However, once oxygen has been removed from the film, other hydrogen reducing agents can be used, such as AlH3, AlH3:L (where L is a neutral ligand such as diethyl ether, tetrahydrofuran, diethyl sulfide, trimethylamine, triethylamine, etc.), SiH4, Si2H6, B2H6, PH3, etc.

[0269] To avoid reduction of the oxyphilic reagent by the supplemental reducing agent, the method is preferably performed in ALD or pulsed CVD mode, wherein the substrate is sequentially exposed to the metal halide precursor, the oxyphilic reagent, and the supplemental reducing agent. The order of the sequence can vary depending on the selected chemical properties. For example, the sequence order could be: i) metal halide precursor (M...(a) X c O e ii) Adsorption of the precursor on the substrate; iii) Reduction reaction or deoxidation of the adsorbed metal halide precursor; iv) Supplemental reducing agent (reduction of the metal intermediate obtained in the deoxidation reaction to the metal). An alternative sequence could be i) metal halide precursor plus oxophilic agent (reduction reaction or deoxidation of the metal halide precursor); ii) addition of supplemental reducing agent (reduction of the metal intermediate obtained in the deoxidation reaction to the metal).

[0270] Oxiphilic reagents can also act as reducing agents. For example, CO can be both an oxophile (CO→CO2) and a reducing agent (CO→COCl2). Similarly, HSiCl3 can remove MO. x X y The O in the metal halide precursor (M is a metal, X is Cl, Br or I, and x and y are integers) can be reduced from the metal intermediate obtained by the deoxidation reaction that forms SiCl3-O-SiCl3 and 2HX as byproducts to break the MX bond.

[0271] In order to form metal nitrides (MN) x Metal nitride films can be produced by replacing the reducing agent with a nitride reagent (such as NH3). In metal nitride film applications, alkyl or silyl isocyanates such as tert-butyl isocyanate can be used as oxyphiles to remove oxygen from metal halide oxides. The tBu-imino group is bonded to the metal center of the intermediate in place of the M=O bond to form two tBu-imino bonds, which will produce a metal nitride film (Equation IV).

[0272] -M=O+tBu-N=C=O→-M=N-tBu+CO2 (IV)

[0273] In one embodiment, the disclosed method / process may be a CVD process. The CVD process may or may not be plasma-enhanced CVD. Preferably, the CVD process is not a plasma process. More preferably, the CVD is thermal CVD.

[0274] Alternatively, the disclosed method / process can be an ALD process, in which a surface is sequentially exposed to reactants, such as a metal halide oxide precursor, an oxyphilic agent, and a reducing agent, wherein the oxyphilic agent reacts with the metal halide oxide precursor to form a metal intermediate; the metal intermediate reacts with a complementary reducing agent, such as H2, to form a pure metal film. The ALD conditions within the chamber allow the disclosed metal halide oxide precursor, adsorbed or chemisorbed onto the substrate surface, to react and form a film on the substrate. In some embodiments, the metal halide oxide precursor can be plasma-treated. In this case, the ALD process becomes a PEALD process. Therefore, the ALD process may or may not be a plasma-enhanced ALD process, preferably not a plasma-enhanced ALD process. The ALD process can be thermal ALD or spatial ALD.

[0275] Alternatively, the disclosed method may be the ALD method, in which the surface is sequentially exposed to reactants (precursor / oxyphilic agent / reducing agent), wherein the oxyphilic agent forms an M=N-tBu bond with M=O; and the reducing agent is selected as NH3 to form a nitride film.

[0276] The disclosed metal halide oxide precursor, oxyphilic agent, and reducing agent can be introduced into the reactor simultaneously (CVD) or sequentially (ALD). The reactor can be purged with an inert gas (e.g., N2, Ar, Kr, Xe) between the introduction of the metal halide oxide precursor, oxyphilic agent, and reducing agent. Alternatively, the metal halide oxide precursor and oxyphilic agent can be mixed together to form a metal halide oxide precursor and oxyphilic agent mixture, and then introduced into the reactor as a mixture. The reactor can be purged with an inert gas (such as N2, Ar, Kr, Xe) between the introduction of each film-forming component or the mixture of metal halide oxide precursor and oxyphilic agent.

[0277] The disclosed film-forming components or the disclosed metal halide oxides, oxyphilic agents, and reducing agents have 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 compositions may contain any of the following impurities: THF; ethers; pentane; cyclohexane; heptane; benzene; toluene; halided metal compounds; etc. 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). Preferably, the water content or impurities in each film-forming composition are less than 20 ppm by weight. The purified disclosed film-forming composition can be obtained by recrystallization, sublimation, distillation, and / or by passing the gas or liquid through a suitable adsorbent (such as...). Molecular sieve purification.

[0278] The disclosed film-forming compositions can be supplied in pure form or as blends with suitable solvents such as ethylbenzene, xylene, mesitylene, naphthane, decane, and dodecane. The disclosed metal halide precursors and oxyphilic agents can be present in the solvent at different concentrations.

[0279] The pure, blended film-forming composition disclosed herein 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 or 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 WO2009 / 087609 granted to Xu et al.). The pure or blended composition can be fed as a liquid into a vaporizer, vaporized therein, and then introduced into the reactor. Alternatively, the pure or 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.

[0280] 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.

[0281] 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.

[0282] The reaction chamber may contain one or more substrates. For example, the reaction chamber may contain 1 to 200 silicon wafers with diameters ranging from 25.4 mm to 450 mm. 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, Ge, SiGe, GeSn, InGaAs, GaSb, InP, or GaAs wafers. From previous manufacturing steps, the wafer will have multiple films or layers thereon, including silicon-containing films or layers. These layers may be patterned or unpatterned. For example, the wafer may include a dielectric layer. Furthermore, the wafer may 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. In addition, the wafer may include copper layers and noble metal layers (e.g., platinum, palladium, rhodium, gold). The wafer may include barrier layers such as manganese, manganese oxide, etc. Plastic layers, such as poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) [PEDOT:PSS], may also be used. These layers may be planar or patterned. When patterned layers are formed on a substrate, the disclosed process may deposit the layers directly on the wafer or directly on top of one or more layers on the wafer. The patterned layer may be an alternating layer of two specific layers (e.g., 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 may be trenches or lines. Throughout the specification and claims, the wafer and any associated layers thereon are referred to as a substrate.

[0283] 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 -2 The 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 500°C, preferably between about 150°C and about 485°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 the substrate and adheres to the substrate.

[0284] 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 500°C. When using a plasma deposition process, the deposition temperature can be less than about 500°C, preferably less than about 400°C. Alternatively, when performing a thermal process, the deposition temperature range can be from about 100°C to about 500°C.

[0285] Alternatively, the substrate can be heated to a sufficient temperature to obtain a desired metal film with a sufficient growth rate and the desired physical state and composition. Non-limiting exemplary temperature ranges to which the substrate can be heated include from room temperature to approximately 500°C. Preferably, the temperature of the substrate is maintained at less than or equal to 500°C.

[0286] The duration of each pulse of the disclosed film-forming composition ranges 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. Oxyphilic reagents can also be pulsed into the reactor. In such embodiments, the duration of each substance's pulse ranges 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 the oxygen-loving reagent (without mixing the composition and reactants) can be simultaneously sprayed from different portions of a spray head, while a substrate of several wafers is kept rotating under the spray head (space ALD).

[0287] 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.

[0288] The disclosed method for depositing a metal or metal nitride film on a substrate includes the following steps: reacting a metal halide oxide precursor with an oxyphilic agent in a reactor containing the substrate to deoxygenate the metal halide oxide precursor; and forming a metal or metal nitride film on the substrate by a vapor deposition process. In this document, the substrate may be simultaneously exposed to the metal halide oxide precursor and the oxyphilic agent. Alternatively, the substrate may be sequentially exposed to the metal halide oxide precursor and the oxyphilic agent. After the step of reacting the metal halide oxide with the oxyphilic agent, the substrate may be sequentially exposed to a reducing agent to form a metal or metal nitride film.

[0289] Alternatively, the disclosed method for depositing a metal film on a substrate includes: placing the substrate in a reactor, delivering a vapor of a metal halide precursor into the reactor, contacting / adsorbing the vapor with the surface of the substrate (and typically directing the vapor to the substrate) to form a metal halide layer on the surface of the substrate, introducing a vapor of an oxyphilic reagent into the reactor to react with the metal halide on the surface of the substrate to form a metal halide on the surface, and introducing a reducing agent to reduce the metal halide to a metal.

[0290] Alternatively, the disclosed method for depositing a metal film on a substrate includes: placing the substrate in a reactor, delivering a vapor of a mixture of a metal halide precursor and an oxyphilic agent into the reactor, contacting / adsorbing the vapor with the surface of the substrate (and typically directing the vapor to the substrate) to form a metal halide layer on the surface of the substrate, wherein the oxyphilic agent reacts with the metal halide on the surface of the substrate to form a metal halide on the surface, and introducing a reducing agent to reduce the metal halide to a metal.

[0291] The disclosed method for depositing a metal nitride film on a substrate includes: placing the substrate in a reactor, delivering a vapor of a metal halide precursor into the reactor, contacting / adsorbing the vapor with the substrate (and typically directing the vapor to the substrate) to form a metal halide layer on the surface of the substrate, introducing a vapor of an oxyphilic reagent containing CN bonds (such as tBu-N bonds) into the reactor to react with the metal halide on the surface of the substrate to form a metal nitride halide intermediate on the surface, and introducing a reducing agent (such as NH3) to reduce the metal nitride halide to a metal nitride film.

[0292] Alternatively, the disclosed method for depositing a metal nitride film on a substrate includes: placing the substrate in a reactor, delivering a vapor of a mixture of a metal halide precursor and an oxyphilic reagent containing CN bonds (such as tBu-N bonds) into the reactor, contacting / adsorbing the vapor onto the substrate (and typically directing the vapor onto the substrate) to form a metal halide layer on the surface of the substrate, wherein the oxyphilic reagent reacts with the metal halide on the surface of the substrate to form a metal nitride halide on the surface, and introducing a reducing agent (such as NH3) to reduce the metal nitride halide to a metal nitride film.

[0293] The purity of the metal or metal nitride film produced according to the disclosed method may be > about 98.5%, preferably > about 99%, and the oxygen content or impurities in the produced metal or metal nitride film may be <1.5%, preferably < about 1%.

[0294] Example

[0295] The following non-limiting examples are provided to further illustrate embodiments of the invention. However, these examples are not intended to cover all cases, nor are they intended to limit the scope of the invention described herein.

[0296] Example 1

[0297] The chemical properties from the condensed phase were tested to validate the concept and reactivity. To experimentally confirm that the reaction between the metal halide precursor and the oxyphilic reagent is advantageous at or below the target vapor deposition process temperature, solid / liquid phase experiments were performed by mixing the metal halide precursor and the oxyphilic reagent and analyzing the reaction products. This was to confirm the transfer of oxygen atoms to the oxyphilic reagent through the cleavage of M=O from the metal halide precursor.

[0298] The results using MoO₂Cl₂ (CAS No.: 13637-68-8) as the test precursor and WCl₆, WCl₅, WCl₄, WOCl₄, or NbCl₅ as the oxyphilic reagent are summarized below. The experiments were conducted at 120℃–240℃ for several hours. Additionally, MoO₃ was tested to demonstrate that metals in their oxide form can be removed in a similar manner to form volatile substances. In summary, prior analysis of the reaction mixtures of MoO₂Cl₂ and WCl₆, WCl₅, WCl₄, WOCl₄, NbCl₅, VCl₄, VCl₃, PI₃, Me₃SiCl, or HSiCl₃ showed the presence of Mo=O bonds and MCl₂. x or MCl xFollowing the reaction at elevated temperatures, PXRD patterns, Raman spectra (not shown), and GC spectra (if liquid reagents or products (not shown) are observed) showing the complete disappearance of Mo=O bonds and MoO₂Cl₂. M=O bonds appear when using oxophilic reagents such as WCl₆, WCl₅, WOCl₄, and NbCl₅, and MOM bonds appear when using Si-based oxophilic reagents. With the oxophilic reagent WOCl₄, lower reactivity and incomplete removal of Mo=O bonds are observed. Higher reaction temperatures (e.g., <500 °C) will drive the reaction to completion. Table II shows the results of reactions with various oxophilic reagents using MoO₂Cl₂ as a metal halide precursor and MoO₃ as an oxide, as representative examples.

[0299] Figure 1a The image shows the powder X-ray diffraction (PXRD) pattern and fitting of the mixture of WCl6 and MoO2Cl2 before the reaction. Figure 1b The PXRD pattern and fitting are shown for a mixture of 2WCl6 and MoO2Cl2 after heating at 235℃ for 8 hours. By comparing the PXRD patterns before and after the reaction, it is determined that oxygen was completely removed from MoO2Cl2 to form MoCl2. x Furthermore, the oxyphilic reagent WCl6 is converted into WOCl4.

[0300] Table II

[0301]

[0302] *MoCl x The identification of MoI3 was not fully confirmed; MoCl6 decomposes into MoCl4 at the reaction temperature.

[0303] & Due to VOCl x The instability at the reaction temperature has not been fully confirmed.

[0304] ^VOCl2 thermally decomposes at elevated temperatures to form VO x Due to the relatively low reactivity and high melting point of VCl3, the reaction is incomplete. Increasing the reaction temperature to 350℃-500℃ should drive the reaction to completion.

[0305] The reaction of MoO₂Cl₂ or MoO₃ with SiHCl₃ proceeds at a relatively low temperature of 120°C, resulting in partial deoxygenation from MoO₂Cl₂ or MoO₃ to form MoOCl₃. By increasing the reaction temperature, it is expected that oxygen will be removed from MoOCl₃, leaving MoCl₃. x .

[0306] The reaction between MoO3 and SiMe3Cl was carried out at an excessively low temperature of 120°C. Increasing the reaction temperature is expected to remove oxygen from MoO3, leaving behind MoCl. x .

[0307] Example 2

[0308] As described above, the biggest challenge in reducing MoO2Cl2 to Mo metal is the deoxidation step. Therefore, using deoxidizing agents other than H2 can facilitate the reduction process. A small pool of candidates for deoxidizing agents is considered, such as HCDS.

[0309] The ALD of Mo using MoO2Cl2 at temperatures below 500°C (where the first step is deoxygenation via an oxophilic reagent) is represented by Equation I. The subsequent interaction of the deoxygenated metal halide precursor with a second reducing agent under low-pressure conditions to deposit Mo material (e.g., a Mo layer) can be pure (e.g., at least 95%, 98%, 99%, 99.5%, or 99.9% (atomic) Mo).

[0310] For example, an ALD process (T = 485°C, total P = 10 Torr) using a SiO2 substrate under the following conditions and sequence: Figure 2a As shown, a mixture of MoO2Cl2 / HCDS (hexachlorodisilane, Si2Cl6, CAS No.: 13465-77-5) was pulsed into the reactor for 2.5 seconds (1.01 / 11.3 sccm) using argon as the carrier gas (100 sccm), followed by argon purging for 5 seconds (10 sccm), H2 pulse for 5 seconds (500 sccm), and argon purging for 5 seconds (10 sccm) to deposit a high-purity Mo film of 98.5%. Oxygen impurities were <1.5%. The expected chemical reactions are as follows.

[0311] Mo (VI) O2Cl2+2Si (III) 2Cl6→Mo (II) Cl2+2OSi (IV) 2Cl6

[0312] Mo (II) Cl2 + H2 → Mo (0) +2HCl

[0313] Figure 2bThis is an X-ray photoelectron spectroscopy (XPS) method using HCDS as an oxygen scavenger and H2 as a reducing agent. As a comparative example, the same process was performed under the same conditions in the absence of HCDS: T = 485℃, total P = 10 Torr, MoO2Cl2 2.5 s (1.01 sccm), argon as carrier gas (100 sccm), argon purging for 5 s (10 sccm), H2 pulse for 5 s (500 sccm) and argon purging for 5 s (10 sccm). Figure 3a As shown in the figure. Film characterization by XPS shows substrates without Mo and those with only SiO2. Figure 3b This is a typical ALD XPS using H2 at 485°C in the absence of HCDS as an oxygen scavenger.

[0314] Therefore, HCDS can act as an oxygen scavenger, functioning in conjunction with MoO2Cl2 under Ar purging and H2 reduction conditions, respectively. (See reference) Figure 2b Using HCDS, the Mo film exhibits ultra-high purity (Mo > 98.5%, O < 1.5%, Si 0%). At the same temperature without HCDS, no Mo deposition occurs, as per reference. Figure 3b .

[0315] While the subject matter described herein can be described in the context of illustrative implementations to address one or more computing application features / operations of a computing application with user interaction components, 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 methods, systems, platforms, and / or devices.

[0316] 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.

[0317] Although embodiments of the invention have been shown and described, those skilled in the art can modify them without departing from the spirit or teachings of the invention. The embodiments described herein are exemplary and not limiting. Many variations and modifications of the compositions and methods are possible and are within the scope of the invention. Therefore, the scope of protection is not limited to the embodiments described herein, but is defined only by the following claims, the scope of which should include all equivalents of the subject matter of the claims.

Claims

1. A method for depositing a metal or metal nitride film on a substrate, the method comprising: The metal halide oxide precursor is reacted with an oxyphilic reagent in a reactor containing the substrate to deoxygenate the metal halide oxide precursor; After deoxidation, the substrate was sequentially exposed to a reducing agent; and The metal or metal nitride film is formed on the substrate by a vapor phase deposition process. in, The metal oxyhalide precursor is M (a) X c O e wherein M is Mo, W, V, Nb, Ta and Cr; X is a halogen selected from Cl, Br or I; a is the oxidation state of M and a is an integer ranging from 3 to 6; c is a number, 0 < c < 6; e is a number, 0 < e < 3; c + 2e = a; and The aerophilic reagent is N. (b) X d O f Where N is a transition metal halide or halide oxide, or a Group 14 or Group 15 halide, halide oxide, or oxide; X is a halogen selected from Cl, Br, or I; b is the oxidation state of N and b is an integer ranging from 3 to 6; d is a number, 0 ≤ d < 6; f is a number, 0 <f<3;d+2f=b, N has a higher affinity for oxygen than M. The aerophilic reagent and its product are volatile.

2. The method of claim 1, further comprising: The substrate is simultaneously or sequentially exposed to the metal halide precursor and the oxyphilic reagent.

3. The method of claim 1, wherein the reducing agent is selected from H2, HCl, B2H6, NH3, CO, SiHCl3, SiHBr3, or SiHl3.

4. The method of claim 1, wherein, The metal halide precursors are selected from MoO2Cl2, MoOCl4, WOCl4, WO2Cl2, NbOCl3, TaOCl3 and CrO2Cl2.

5. The method of claim 1, wherein, The aerophilic reagent is selected from: a. Containing Group 14: CCl4; CBr4; COCl2; CO; RN=C=O, where R is H, or an alkyl group selected from Me, Et, iPr, nPr, iBu, tBu, sBu, nBu; or Si x R y X z Where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2, X is a halogen selected from Cl, Br, I, and R is H, saturated or unsaturated hydrocarbon group, amino group, alkoxy group, or silyl group; b. Including Group 15: NO, N2O, PCl3, PBr3, PI3; or c. Containing transition metals: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4.

6. The method of claim 1, wherein, This oxygen-containing reagent is a Si-containing oxygen-containing reagent with the following general formula: Si x R y X z Where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2; X is a halogen selected from Cl, Br, I; R is H, saturated or unsaturated hydrocarbon group, amino group, alkoxy group, or silyl group.

7. The method of claim 6, wherein, The Si-containing oxyphilic reagent is selected from Si2Cl6, Si2Cl5H, Si2Cl4Me2, Si2ClMe5, Si2Cl2Me4, Si2Br6, Si2Br5H, Si2Br4Me2, Si2BrMe5, Si2Br2Me4, Si2Me6, Si2I6, Si2I5H, Si2I4(Me)2, Si2(OMe)6, Si2(NR2)6, where R = H, Me, Et, Si2(NMe2)5Cl, Si3Cl8, Si3Br8, Si3I8, or Si4(Me)9H.

8. The method according to any one of claims 1 to 6, wherein, The oxyphilic reagent is Si2Cl6.

9. The method according to any one of claims 1 to 7, wherein, The oxyphilic reagent is RN=C=O, where R is H, or an alkyl group selected from Me, Et, iPr, nPr, iBu, tBu, sBu, nBu; or a metal halide or metal halide selected from VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4.

10. The method according to any one of claims 1 to 7, wherein, The vapor deposition process is either thermal CVD or ALD, or plasma-enhanced CVD or ALD, at a deposition temperature of less than 485°C.

11. A method for removing oxygen from a metal halide oxide precursor or an intermediate film deposited from the metal halide oxide precursor to form a metal or metal nitride film on a surface, the method comprising: The metal halide precursor or the intermediate film deposited from the metal halide precursor is reacted with an oxyphilic reagent to form a metal intermediate; and The metal intermediate is reduced to a metal or metal nitride film on the surface by a reducing agent through a vapor deposition process. in The metal halide oxide precursor is M (a) X c O e , where M is Mo, W, V, Nb, Ta, and Cr; X is a halogen selected from Cl, Br, or I; a is the oxidation state of M and a is an integer ranging from 3 to 6; c is a number, 0 < c < 6; e is a number, 0 < e < 3; c + 2e = a; and The aerophilic reagent is N. (b) X d O f Where N is a transition metal halide or halide oxide, or a Group 14 or Group 15 halide, halide oxide, or oxide; X is a halogen selected from Cl, Br, or I; b is the oxidation state of N and b is an integer ranging from 3 to 6; d is a number, 0 ≤ d < 6; f is a number, 0 <f<3;d+2f=b, N has a higher affinity for oxygen than M. The aerophilic reagent and its product are volatile.

12. The method of claim 11, wherein, The metal halide precursor is selected from MoO₂Cl₂, MoOCl₄, WOCl₄, WO₂Cl₂, NbOCl₃, TaOCl₃, and CrO₂Cl₂; and The aerophilic reagent is selected from: a. Containing Group 14: CCl4; CBr4; COCl2; CO; RN=C=O, where R is H, or an alkyl group selected from Me, Et, iPr, nPr, iBu, tBu, sBu, nBu; or Si x R y X z Where x = 1 to 5, y and z = 0 to 12, y + z ≤ 2x + 2, X is a halogen selected from Cl, Br, I, and R is H, saturated or unsaturated hydrocarbon group, amino group, alkoxy group, or silyl group; b. Including Group 15: NO, N2O, PCl3, PBr3, PI3; or c. Containing transition metals: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4.

13. The method according to any one of claims 11 to 12, wherein, The vapor deposition process is either thermal CVD or ALD, or plasma-enhanced CVD or ALD, at a deposition temperature of less than 485°C.

14. A reagent for deoxygenating a metal halide oxide precursor or an intermediate film deposited from the metal halide oxide precursor to form a metal or metal nitride film in a vapor deposition process, the metal halide oxide precursor having the following general formula: M (a) X c O e , where M is Mo, W, V, Nb, Ta, and Cr; X is a halogen selected from Cl, Br, or I; a is the oxidation state of M and a is an integer ranging from 3 to 6; c is a number, 0 < c < 6; e is a number, 0 < e < 3; c + 2e = a, The reagent includes: Oxyphilic reagents with the following general formula: N (b) X d O f Where N is a transition metal halide or halide oxide, or a Group 14 or Group 15 halide, halide oxide, or oxide; X is a halogen selected from Cl, Br, or I; b is the oxidation state of N and b is an integer ranging from 3 to 6; d is a number, 0 ≤ d < 6; f is a number, 0 <f<3;d+2f=b, The oxygen-loving property of N in this oxygen-loving reagent is higher than that of M in the metal halide precursor. The oxyphilic reagent and its oxidation product are volatile.

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