Reagent for removing oxygen from metal oxyhalide precursors in the thin film deposition process

Abstract

A method for gas-phase deposition of a metal or metal nitride film on the surface of a substrate comprises the steps of: reacting a metal-oxo or metal oxyhalide precursor with an oxyphilic reagent in a reactor containing the substrate to deoxygenate the metal-oxo or metal oxyhalide precursor; and forming a metal or metal nitride film on the substrate through 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 sequentially exposed to a reducing agent.

Description

Technology Field

[0001] Cross-reference of related applications

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

[0003] Technology field

[0004] The present invention relates to a method of using a highly oxyphilic compound as a reagent for deoxygenating a metal oxyhalide precursor in an ALD and CVD process or for removing oxygen from an intermediate film formed by the deposition of a metal oxyhalide precursor, and more specifically, to the use of such a reagent to produce a metal or metal nitride film having a low oxygen content by promoting deoxygenation and reducing the temperature at which ALD or CVD occurs. Background Technology

[0005] Many transition metal (e.g., W, Mo, Cr, V…) oxyhalides are volatile and thermally stable and can be used as precursors for atomic layer deposition (ALD) and chemical vapor deposition (CVD) processes to deposit pure metal or metal nitride films through the cleavage of MX and M=O bonds. Numerous examples are shown in US 20170062224, US 20180286668, WO 2019209289, US 20200131628, US 20070049045A, US 20030022065A, US 10510590B2, US 20190067003A, and US 4668528A. However, the complete removal of oxygen-containing species during the ALD / CVD process, that is, the breaking of M=O bonds, is a difficult task, and in this case, the properties of the deposited film depend largely on the successful removal of surface impurities such as oxygen atoms.

[0006] Hydrogen and hydride compounds (particularly hydrides of Si, B, P, and Al) are powerful reducing agents capable of removing oxygen from metal oxyhalides and generating water as a volatile byproduct. However, since the reduction of M=O bonds by H2 or hydrides typically occurs at high temperatures (e.g., > 500°C), they cannot be used in certain applications where the substrate on which the film is deposited cannot withstand such high temperatures. Additionally, the reduction of transition metal oxyhalides by hydrogen or hydrides results in the formation of hydrogen halides (e.g., HCl) and water, which creates a highly corrosive gas environment for process chambers and downstream equipment such as vacuum lines, pumps, and pressure regulating valves. At the same time, water as a byproduct can react with surface metal oxyhalides or metal halide intermediates, leaving behind oxygen contaminants. Davis's literature [Davies M., Alloy Selection for Service in Chlorine, Hydrogen Chloride and Hydrochloric Acid, 2019, 2 nd Such effects are described in [Edition]. Some metal or semi-metal hydrides, such as AlH3, B2H6, PH3, SiH4, and Si2H6, are also strong reducing agents, but the reaction products with oxygen atoms generally lead to the formation of non-volatile metal or semi-metal oxides (Al2O3, B2O3, SiO2…). Therefore, such metal or semi-metal hydrides are not suitable as co-reagents with metal oxyhalide precursors.

[0007] In particular, the application of Mo films to replace some layers in middle-of-line (MOL) or backend-of-the-line (BEOL) processes, which require processes below 500°C while depositing very pure films, is receiving increasing interest. MoF6, MoCl5, MoOCl4, and MoO2Cl2 are well-known inorganic precursors that deposit pure Mo films when combined with reducing agents such as H2. Among this group of precursors, MoO2Cl2 has been reported to be less corrosive and have a higher vapor pressure. The minimum temperature for depositing Mo films by ALD MoO2Cl2 / H2 is usually at least 500°C, due to the difficulty in removing the double bond between oxygen and molybdenum.

[0008] US 10533023 discloses forming a metal film from a “metal-organic” 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 a related compound to form a second compound having atoms in a reduced state relative to the first compound. The atoms in the oxidized state are selected from the group consisting of Groups 2 through 12 of the periodic table, the lanthanides, As, Sb, Bi, Te, Si, Ge, Sn, and Al.

[0009] WO 2020 / 023790 discloses the deposition of a pure metal film having an oxygen residue of ≤ 1 atomic% by depositing Mo using MoOCl4 or MoO2Cl2 as a reducing agent with H2 at a high temperature of 500°C in a ratio of 1:100 to 10000. For the W film, WOF4, WOCl4, WO2Cl2, etc. are used.

[0010] US 10510590 discloses a low-resistance metallized stack structure for logic and memory applications and a related manufacturing method, wherein a Mo-containing layer is deposited on a W-containing layer using ALD / CVD. The Mo-containing layer is deposited by exposing the W-containing layer to a reducing agent and a Mo-containing precursor selected from MoF6, MoCl5, MoO2Cl2, MoOCl4, and Mo(CO)6. The process temperature is in the range of 300°C to 700°C.

[0011] Therefore, lowering the temperature of the deposition process remains a difficult task. means of solving the problem

[0012] A method for depositing a metal or metal nitride film on a substrate is disclosed, and the method

[0013] A step of deoxygenating the metal oxyhalogen precursor by reacting it with an oxygenophilic reagent in a reactor accommodating the substrate; and

[0014] A step of forming the metal or metal nitride film on the substrate through a vapor deposition process.

[0015] Includes. The disclosed method may include one or more of the following embodiments:

[0016] ● An embodiment further comprising the step of simultaneously exposing a substrate to a metal oxyhalogen precursor and an oxygen-philic reagent;

[0017] ● An embodiment further comprising the step of sequentially exposing a substrate to a metal oxyhalogen precursor and an oxygen-philic reagent;

[0018] ● An embodiment further comprising the step of sequentially exposing the substrate to a reducing agent after deoxygenation;

[0019] ● The metal oxyhalogenate precursor is M (a) X c O eand, 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 in the range of 3 to 6; c is a number such that 0 < c < 6; e is a number such that 0 < e < 3; and a modality in which c + 2e = a;

[0020] ● Oxophilic reagents are N (b) X d O f and, 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 in the range of 3 to 6; d is a number 0 ≤ d < 6; f is a number 0 < f < 3; and an embodiment in which d + 2f = b;

[0021] ● An aspect where the oxygen-philicity of N is greater than the oxygen-philicity of M;

[0022] ● The metal oxyhalide precursor is an embodiment selected from the group consisting of MoO2Cl2, MoOCl4, WOCl4, WO2Cl2, NbOCl3, TaOCl3, and CrO2Cl2;

[0023] ● An embodiment in which the metal oxyhalogenate precursor is MoO2Cl2;

[0024] ● The metal oxyhalogenate precursor is a metal-oxo precursor;

[0025] ● A mode in which the metal oxyhalogenate precursor is an oxygen-containing metal precursor;

[0026] ● The oxygen-friendly reagent and its oxidized product are volatile;

[0027] ● Oxyphilic reagents are volatile;

[0028] ● The oxidized product of an oxygen-friendly reagent is volatile;

[0029] ● An embodiment in which no residual amount of the element of the oxygen-friendly reagent and its oxidized product remains on the surface of the deposited film;

[0030] ● The oxygen-philic reagent is an embodiment selected from group 14-containing or group 15-containing halides, oxyhalides, or oxides;

[0031] ● The oxygen-philic reagent is an embodiment selected from group 14-containing or group 15-containing halides;

[0032] ● The oxygen-philic reagent is an embodiment selected from Group 14-containing or Group 15-containing oxyhalides;

[0033] ● The oxygen-philic reagent is an embodiment selected from group 14-containing or group 15-containing oxides;

[0034] ● The oxygen-philic reagent is an embodiment selected from transition metal-containing halides or oxyhalides;

[0035] ● The oxygen-friendly reagent is an embodiment selected from transition metal-containing halides;

[0036] ● The oxygen-philic reagent is an embodiment selected from transition metal-containing oxyhalides;

[0037] ● The oxygen-philic reagent is selected from the following modes:

[0038] a. Group 14-containing: 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 (wherein x is 1 to 5, y and z are 0 to 12, y + z ≤ 2x+2; X is a halogen selected from Cl, Br, and I; and R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group);

[0039] b. Group 15-containing: NO, N2O, PCl3, PBr3, PI3; or

[0040] c. Transition metal-containing: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4 or WCl4;

[0041] ● The general chemical formula for oxygen-philic reagents is Si x R y X z An embodiment of a Si-containing oxygen-philic reagent having (wherein x is 1 to 5, y and z are 0 to 12, y + z ≤ 2x+2; X is a halogen selected from Cl, Br, and I; and R is H, a saturated or unsaturated carbon-containing ligand, a nitrogen-containing ligand, an oxygen-containing ligand, or a silicon-containing ligand);

[0042] ● The general chemical formula for oxygen-philic reagents is Si x R y X z An embodiment of a Si-containing oxygen-philic reagent having (wherein x is 1 to 5, y and z are 0 to 12, y + z ≤ 2x+2; X is a halogen selected from Cl, Br, and I; and R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group);

[0043] ● The Si-containing oxygen-philic reagent is an embodiment 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;

[0044] ● An embodiment in which the oxygen-friendly reagent is Si2Cl6(HCDS);

[0045] ● An embodiment in which the oxygen-philic reagent is a non-halogen-containing oxygen-philic reagent selected from the following:

[0046] Group 14-containing: CO, RN=C=O(wherein R is H, or an alkyl group selected from Me, Et, iPr, nPr, iBu, tBu, sBu, nBu); or

[0047] Group 15 - Contains: NO, N2O;

[0048] ● An oxygen-friendly reagent is RN=C=O (wherein R is H, or an alkyl group selected from Me, Et, iPr, nPr, iBu, tBu, sBu, nBu), and thereby a mode in which a metal nitride film is formed;

[0049] ● The oxygen-philic reagent is in the form tBu-N=C=O;

[0050] ● An embodiment in which the oxygen-friendly reagent is a metal halide or metal oxyhalide selected from VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4;

[0051] ● An embodiment in which the oxygen-friendly reagent is WCl4, WCl5, or WCl6;

[0052] ● Oxyphilic reagents are volatile;

[0053] ● The product of the oxygen-philic reagent is volatile;

[0054] ● The reducing agent is H2 or B2H6;

[0055] ● The reducing agent is H2;

[0056] ● The reducing agent is NH3;

[0057] ● An embodiment in which the reducing agent is an oxygen-philic reagent selected from CO, SiHCl3, SiHBr3, or SiHl3;

[0058] ● An embodiment in which the deposition temperature is in the range of 50℃ to 500℃;

[0059] ● An embodiment in which the deposition temperature is in the range of 100℃ to 500℃;

[0060] ● An embodiment in which the deposition temperature is in the range of 150℃ to 485℃;

[0061] ● An embodiment in which the deposition temperature is less than 500℃;

[0062] ● An embodiment in which the deposition temperature is less than 485℃;

[0063] ● An embodiment in which the purity of the metal or metal nitride film is approximately greater than 98.5%;

[0064] ● An embodiment in which the purity of the metal or metal nitride film is approximately over 99%;

[0065] ● An embodiment in which oxygen impurities in the metal or metal nitride film are approximately less than 1%;

[0066] ● An embodiment in which oxygen impurities in the metal or metal nitride film are less than 1.5%;

[0067] ● An embodiment in which silicon impurities in a metal or metal nitride film are 0%;

[0068] ● An embodiment in which silicon impurities in the metal or metal nitride film are approximately 0%;

[0069] ● A metal oxyhalide precursor having a purity in the range of approximately 93% w / w to approximately 100% w / w;

[0070] ● A metal oxyhalogenate precursor having a purity in the range of approximately 99% w / w to approximately 99.999% w / w;

[0071] ● An embodiment in which the oxygen-philic reagent has a purity in the range of approximately 93% w / w to approximately 100% w / w;

[0072] ● An oxygen-friendly reagent in an embodiment having a purity in the range of approximately 99% w / w to approximately 99.999% w / w;

[0073] ● The reducing agent is in an embodiment having a purity in the range of approximately 93% w / w to approximately 100% w / w;

[0074] ● The reducing agent is an embodiment having a purity in the range of approximately 99% w / w to approximately 99.999% w / w;

[0075] ● The vapor deposition process is a thermal CVD mode;

[0076] ● The vapor deposition process is a thermal ALD mode;

[0077] ● The vapor deposition process is a plasma-enhanced CVD mode;

[0078] ● The vapor deposition process is a plasma-enhanced ALD mode; and

[0079] ● The vapor deposition process is a spatial ALD mode.

[0080] Additionally, a method for forming a metal or metal nitride film on a surface by removing oxygen from a metal oxyhalogenate precursor or an intermediate film deposited by a metal oxyhalogenate precursor is disclosed, and the method comprises:

[0081] A step of forming a metal intermediate by reacting the metal oxyhalogen precursor or the intermediate film deposited by the metal oxyhalogen precursor with an oxygenophilic reagent; and

[0082] A step of reducing the metal intermediate to a metal or metal nitride film on the surface using a reducing agent through a vapor deposition process.

[0083] Includes,

[0084] The above metal oxyhalogenate precursor is M (a) X c O e and, 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 in the range of 3 to 6; c is a number such that 0 < c < 6; e is a number such that 0 < e < 3; and c + 2e = a;

[0085] The above-mentioned oxygen-friendly reagent is N (b) X d O fand, 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 in the range of 3 to 6; d is a number such that 0 ≤ d < 6; f is a number such that 0 < f < 3; and d + 2f = b;

[0086] The oxygen-philicity of N is greater than the oxygen-philicity of M;

[0087] The above-mentioned oxygenophilic reagent and the oxygenation product of the above-mentioned oxygenophilic reagent are volatile. The disclosed method may include one or more of the following embodiments:

[0088] ● The metal oxyhalide precursor is an embodiment selected from MoO2Cl2, MoOCl4, WOCl4, WO2Cl2, NbOCl3, TaOCl3, and CrO2Cl2;

[0089] ● The oxygen-philic reagent is selected from the following modes:

[0090] a. Group 14-containing: CCl4; CBr4; COCl2; CO; RN=C=O (where R is H, or b. an alkyl group selected from Me, Et, iPr, nPr, iBu, tBu, sBu, nBu); or Si x R y X z (wherein x is 1 to 5, y and z are 0 to 12, y + z ≤ 2x+2, X is a halogen selected from Cl, Br, and I, and R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group);

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

[0092] d. Transition metal-containing: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4 or WCl4;

[0093] ● The general chemical formula for oxygen-philic reagents is Si x R y X z An embodiment of a Si-containing oxygen-philic reagent having (wherein x is 1 to 5, y and z are 0 to 12, y + z ≤ 2x+2; X is a halogen selected from Cl, Br, and I; and R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group);

[0094] ● The Si-containing oxygen-philic reagent is an embodiment 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] ● An embodiment in which the oxygen-friendly reagent is Si2Cl6(HCDS);

[0096] ● An embodiment in which the oxygen-philic reagent is a non-halogen-containing oxygen-philic reagent selected from the following:

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

[0098] Group 15 - Contains: NO, N2O;

[0099] ● An oxygen-friendly reagent is RN=C=O (wherein R is H, or an alkyl group selected from H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu), and thereby a mode in which a metal nitride film is formed;

[0100] ● The oxygen-philic reagent is in the form tBu-N=C=O;

[0101] ● An embodiment in which the oxygen-friendly reagent is a metal halide or metal oxyhalide selected from VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4;

[0102] ● An embodiment in which the oxygen-friendly reagent is WCl4, WCl5, or WCl6;

[0103] ● Oxyphilic reagents are volatile;

[0104] ● The product of the oxygen-philic reagent is volatile;

[0105] ● The reducing agent is H2 or B2H6;

[0106] ● The reducing agent is H2;

[0107] ● The reducing agent is NH3;

[0108] ● An embodiment in which the reducing agent is an oxygen-philic reagent selected from CO, SiHCl3, SiHBr3, or SiHl3;

[0109] ● An embodiment in which oxygen impurities in the metal or metal nitride film are approximately less than 1%;

[0110] ● The vapor deposition process is in the form of thermal CVD or ALD, or plasma-enhanced CVD or ALD;

[0111] ● An embodiment in which the deposition temperature is in the range of 50℃ to 500℃;

[0112] ● An embodiment in which the deposition temperature is in the range of 100℃ to 500℃;

[0113] ● An embodiment in which the deposition temperature is in the range of 150℃ to 485℃;

[0114] ● An embodiment in which the deposition temperature is less than 500℃; and

[0115] ● An embodiment in which the deposition temperature is less than 485℃.

[0116] Additionally, a reagent is disclosed for deoxygenating a metal oxyhalogen precursor or an intermediate film deposited by said metal oxyhalogen precursor to form a metal or metal nitride film in a vapor deposition process, wherein said metal oxyhalogen precursor has the general chemical formula: M (a) X c O e having, 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 in the range of 3 to 6; c is a number such that 0 < c < 6; e is a number such that 0 < e < 3; and c + 2e = a,

[0117] The above reagent has the general chemical formula: N (b) X d O f It comprises an oxygen-philic reagent having, wherein 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 in the range of 3 to 6; d is a number such that 0 ≤ d < 6; f is a number such that 0 < f < 3; and d + 2f = b, and

[0118] The oxygenophilicity of N of the above oxygenophilic reagent is greater than the oxygenophilicity of M of the metal oxyhalogen precursor, and

[0119] The above-mentioned oxygenophilic reagent and the oxygenation product of the above-mentioned oxygenophilic reagent are volatile. The disclosed reagent may include one or more of the following embodiments:

[0120] ● The metal oxyhalide precursor is an embodiment selected from MoO2Cl2, MoOCl4, WOCl4, WO2Cl2, NbOCl3, TaOCl3, and CrO2Cl2;

[0121] ● The oxygen-philic reagent is selected from the following modes:

[0122] a. Group 14-containing: 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 (wherein x is 1 to 5, y and z are 0 to 12, y + z ≤ 2x+2, X is a halogen selected from Cl, Br, and I, and R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group);

[0123] b. Group 15-containing: NO, N2O, PCl3, PBr3, PI3; or

[0124] c. Transition metal-containing: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4 or WCl4;

[0125] ● The general chemical formula for oxygen-philic reagents is Si x R y X z An embodiment of a Si-containing oxygen-philic reagent having (wherein x is 1 to 5, y and z are 0 to 12, y + z ≤ 2x+2; X is a halogen selected from Cl, Br, and I; and R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group);

[0126] ● The Si-containing oxygen-philic reagent is an embodiment 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;

[0127] ● An embodiment in which the oxygen-friendly reagent is Si2Cl6;

[0128] ● An embodiment in which the oxygen-friendly reagent is WCl4, WCl5, or WCl6;

[0129] ● An oxygen-friendly reagent is RN=C=O (wherein R is H, or an alkyl group selected from Me, Et, iPr, nPr, iBu, tBu, sBu, nBu), and thereby a mode in which a metal nitride film is formed;

[0130] ● The oxygen-philic reagent is in the form tBu-N=C=O;

[0131] ● An embodiment in which the oxygen-friendly reagent is a metal halide or metal oxyhalide selected from VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4;

[0132] ● Oxyphilic reagents are volatile;

[0133] ● The oxygenation product of an oxygen-friendly reagent is volatile;

[0134] ● An embodiment in which the oxygen-philic reagent has a purity in the range of approximately 93% w / w to approximately 100% w / w;

[0135] ● An oxygen-friendly reagent in an embodiment having a purity in the range of approximately 99% w / w to approximately 99.999% w / w; and

[0136] ● An embodiment of the oxygen-friendly reagent having less than 20 ppm of water impurities by weight.

[0137] Notation and Naming

[0138] The following detailed description and claims use numerous abbreviations, symbols, and terms commonly known in the art, and include the following:

[0139] As used herein, the singular form means one or more.

[0140] As used herein, "about, around" or "approximately" in the text or claims means ±10% of the stated value.

[0141] As used herein, "room temperature" in the text or claims means approximately 20°C to approximately 25°C.

[0142] Standard abbreviations for elements from the periodic table are used herein. It should be understood that an element may be referred to by its abbreviation (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, and so on).

[0143] A unique CAS registration number (i.e., "CAS") assigned by the Chemical Identification Service is provided to help better identify the disclosed molecule.

[0144] As used herein, the chemical formula "M (a) X c O e " refers to a metal oxyhalogenate precursor, 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, a is an integer in the range of 3 to 6; c is a number in the range 0 < c < 6; e is a number in the range 0 < e < 3; and c + 2e = a.

[0145] As used herein, the chemical formula "N (b) X d O f" refers to an oxygen-philic reagent, where N is a transition metal halide or oxyhalide, or a group 14 or 15 halide, oxyhalide, or oxide; X is a halogen selected from Cl, Br, or I; b is the oxidation state of N, b is an integer in the range of 3 to 6; d is a number 0 ≤ d < 6; f is a number 0 < f < 3; and d + 2f = b.

[0146] As used herein, the chemical formula "Si x R y Y z " refers to a Si-containing oxygen-philic reagent, where x is 1 to 5, y and z are 0 to 12, y + z ≤ 2x+2; X is a halogen selected from Cl, Br, and I; and R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group.

[0147] As used herein, the chemical formula “MX” refers to a metal halide, where M is a metal and X is a halogen element selected from Cl, Br or I.

[0148] As used herein, the chemical formula "MN" x " refers to a metal nitride, where M is a metal, N is nitrogen, and x is a positive integer in the range 0 < x ≤ 2, but does not necessarily have to be an integer.

[0149] As used herein, the chemical formula "MO" x " refers to a metal oxide, where M is a metal, O is oxygen, and x is a positive integer in the range 0 < x ≤ 3, but does not necessarily have to be an integer.

[0150] As used herein, the chemical formula "MO" x X y" refers to a metal oxygen halide, 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.

[0151] As used herein, the chemical formula "RN=C=O" refers to an isocyanate, where R is a saturated or unsaturated hydrocarbon group, such as an alkyl group, and preferably R is H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu.

[0152] As used herein, the term "hydrocarbon" refers to a saturated or unsaturated functional group containing only carbon and hydrogen atoms.

[0153] As used herein, the term "alkyl group" refers to a saturated functional group containing only carbon and hydrogen atoms. An alkyl group is a type of hydrocarbon. Additionally, the term "alkyl group" refers to a linear, branched, or cyclic alkyl group. Examples of linear alkyl groups include, without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyl groups include, without limitation, t-butyl. Examples of cyclic alkyl groups include, without limitation, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, etc.

[0154] As used herein, the abbreviation "Me" refers to a methyl group; the abbreviation "Et" refers to an ethyl group; the abbreviation "Pr" refers to a propyl group (i.e., n-propyl or isopropyl); the abbreviation "iPr" refers to an isopropyl group; the abbreviation "Bu" refers to any butyl group (n-butyl, iso-butyl, tert-butyl, sec-butyl); the abbreviation "tBu" refers to a tert-butyl group; the abbreviation "sBu" refers to a sec-butyl group; the abbreviation "iBu" refers to an iso-butyl group; and the abbreviation "Ph" refers to a phenyl group.

[0155] The term "substrate" refers to the material or materials on which the process is performed. The substrate may refer to a wafer having the material or materials on which the process is performed. The substrate may be any suitable wafer used in the manufacture of semiconductors, photovoltaics, flat panel, or LCD-TFT devices. The substrate may also have one or more layers of different materials already deposited on the substrate in 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, gold, etc.), an organic layer, such as amorphous carbon, or a photoresist or a combination thereof. Additionally, the substrate may be planar or patterned. The substrate may comprise a layer of oxide (e.g., ZrO2-based materials, HfO2-based materials, TiO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc.) used as a dielectric material in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications, or a nitride-based film (e.g., TaN, TiN, NbN) used as an electrode. Those skilled in the art will recognize that as used herein, the terms “film” or “layer” refer to a portion of material of a certain thickness placed on or diffused over a surface, and that said surface may be a trench or a line. Throughout this specification and claims, a wafer and any related layer on the wafer are referred to as a substrate.

[0156] It is noted herein that the terms "oxygen scavenging," "oxygen removal," and "deoxygenation" may be used interchangeably. Oxygen scavenging corresponds to or may be related to oxygen removal or deoxygenation, and oxygen removal or deoxygenation is understood to refer to oxygen scavenging.

[0157] It is noted herein that 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 that a layer may refer to a film. Furthermore, those skilled in the art will recognize that the terms “film” or “layer” as used herein refer to a portion of material of a certain thickness placed on or diffused over a surface, and that said surface may range from large enough to be an entire wafer to small enough to be a trench or a line.

[0158] It is noted that in this document, the terms "opening," "gap," "via," "hole," "opening," "trench," and "structure" may be used interchangeably to refer to an opening formed in a semiconductor substrate.

[0159] It is noted herein that the terms "deposition temperature," "substrate temperature," and "process temperature" may be used interchangeably. It is understood that the substrate temperature may correspond to or be related to the deposition temperature or the process temperature, and that the deposition temperature or the process temperature may refer to the substrate temperature.

[0160] It is noted herein that the terms "precursor," "deposited compound," and "deposited gas" may be used interchangeably when the precursor is in a gaseous state at room temperature and ambient pressure. It is understood that the precursor may correspond to or be related to the deposited compound or the deposited gas, and that the deposited compound or the deposited gas may refer to the precursor.

[0161] As used herein, the abbreviation "NAND" refers to a "Non-AND" or "Non-AND" gate; the abbreviation "2D" refers to a two-dimensional gate structure on a planar substrate; and the abbreviation "3D" refers to a three-dimensional or vertical gate structure, wherein the gate structures are stacked in a vertical direction.

[0162] A range may be expressed herein as approximately from one specific value and / or approximately from another specific value. When such a range is expressed, another embodiment should be understood as being from one specific value and / or another specific value, together with all combinations within said range. Any and all ranges mentioned in the disclosed embodiments include their endpoints, regardless of whether the term "inclusively" is used (i.e., x = 1 to 4 or the x range of 1 to 4 includes x = 1, x = 4, and x = any number in between).

[0163] References to “one embodiment” or “an embodiment” herein mean that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of the present invention. Wherever the phrase “in one embodiment” appears in this specification, it does not necessarily refer to the same embodiment, nor does it necessarily refer to a separate or alternative embodiment that is mutually exclusive from other embodiments. The same applies to the term “an embodiment.”

[0164] As used in this application, the word "exemplary" is used to mean that it functions as an example, case, or illustration. Any mode or design described herein as "exemplary" is not to be interpreted as being more desirable or advantageous than any other mode or design. Rather, the use of the word "exemplary" is intended to provide the concept in a concrete manner.

[0165] The term “comprising” within the claim is an open transitional term, meaning that the elements of the claim identified prior to it are a non-exclusive list, that is, any other may additionally be included and maintained within the scope of “comprising”. “Comprising” is defined herein as essentially including the more restrictive transitional terms “essentially composed of” and “composed of”; and “comprising” may, accordingly, be replaced by “essentially composed of” or “composed of” and maintained within the explicitly defined scope of “comprising”.

[0166] Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless otherwise specified or evident from the context, "X uses A or B" is intended to mean any natural inclusive permutation. In other words, if X uses A, X uses B, or X uses both A and B, "X uses A or B" is satisfied in any of these cases. Additionally, the singular form used in this application and the appended claims should generally be deemed to mean "one or more" unless otherwise specified or clearly indicated by the context. Brief explanation of the drawing

[0167] To better understand the features and purposes of the present invention, reference will be made to the following detailed description in conjunction with the accompanying drawings, in which similar components are given the same or similar reference numbers: Fig. 1a is the powder X-ray diffraction (PXRD) pattern and fitting of a mixture of WCl6 and MoO2Cl2 before reaction according to an exemplary embodiment of the present invention; Fig. 1bis the PXRD pattern and fitting of a mixture of WCl6 and MoO2Cl2 after reaction according to an exemplary embodiment of the present invention; Fig. 2a is a flowchart of an ALD process using HCDS as an oxygen scavenger and H2 as a reducing agent according to an exemplary embodiment of the present invention; Fig. 2b According to an exemplary embodiment of the present invention, HCDS is used as an oxygen scavenger and H2 as a reducing agent. Fig. 2a This is the X-ray photoelectron spectroscopy (XPS) of the ALD at 485°C shown in Figure 1; Fig. 3a 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; Fig. 3b According to an exemplary embodiment of the present invention, H2 is used as a reducing agent in the absence of HCDS as an oxygen scavenger. Fig. 3a This is the XPS of the ALD at 485℃ shown in [figure]. Specific details for implementing the invention

[0168] A method is disclosed for using a reagent to remove oxygen from an intermediate film formed by the deposition of a metal-oxo precursor (oxygen-containing metal precursor) or a metal-oxo precursor in a thin film deposition process. A method is disclosed for using a highly oxyphilic compound as a reagent to remove oxygen from an intermediate film formed by the deposition of a metal-oxo precursor or a metal-oxo precursor in an ALD and CVD process. The disclosed metal-oxo precursor includes a metal oxyhalide precursor. More specifically, a method is disclosed for using a highly oxyphilic compound as a reagent to remove oxygen from an intermediate film formed by the deposition of a metal oxyhalide precursor or a metal oxyhalide precursor in an oxyhalide-based ALD and CVD process.

[0169] The disclosed method includes the use of the disclosed oxyphilic reagent to produce a metal or metal nitride film having a low oxygen content or impurities by promoting oxygen removal from an intermediate film formed by the deposition of a metal oxyhalide precursor, thereby reducing the process temperature at which ALD or CVD occurs. The disclosed method includes a method for producing a metal or metal nitride film having a low oxygen content by reducing the temperature at which ALD or CVD occurs, by removing oxygen from an intermediate film or an intermediate oxo-halide metal surface formed by the deposition of a disclosed metal oxyhalide precursor using the disclosed oxyphilic reagent in oxyhalide-based ALD and CVD processes. The disclosed method includes a method for forming a metal halide layer deposited on a surface via ALD and CVD processes by removing oxygen from a disclosed metal oxyhalide precursor using the disclosed oxyphilic reagent. Subsequently, the metal halide can be reduced to a metal or metal nitride film having a low oxygen content by introducing a reducing agent. Additionally, a method is disclosed for forming a metal or metal nitride film from a metal-oxo precursor, more specifically a metal oxyhalide precursor, using an oxygenophilic reagent with or without the need for a reducing agent. The disclosed metal-oxo precursor may be a metal oxyhalide precursor. Hereinafter, throughout this specification, metal oxyhalide precursors are used, but are not limited thereto. A film-forming composition comprising a metal oxyhalide precursor, an oxygenophilic reagent, and a reducing reagent is disclosed.

[0170] It can be assumed that, in order to lower the process temperature, the deposition of a metal film, such as a Mo film, can be achieved by applying an oxygen scavenger (in the present invention, an oxygen-friendly reagent or compound) to promote the removal of oxygen, that is, reduction by deoxygenation.

[0171] Advantages of the disclosed method include: 1) fluorine-free reaction and process; 2) non-plasma or plasma process; 3) low temperature process, preferably a deposition temperature of less than 500°C; 4) very low O-residual impurities, preferably < 1.5% oxygen remaining in the film deposited after the reaction, more preferably approximately < 1% oxygen remaining in the film deposited after the reaction.

[0172] Regarding oxygenophilicity, the oxygenophilicity of periodic table elements is well summarized in Kepp's literature [Kepp, KP, A Quantitative Scale of Oxophilicity and Thiophilicity, Inorganic Chemistry, 2016, 55, 9461]. In the disclosed method, an oxygenophilic reagent can be selected from elements having higher oxygenophilicity than the metal of the metal oxyhalide precursor. To operate the oxygenophilic reagent in the ALD / CVD process, the oxygenophilic reagent and its oxidized products must be volatile to facilitate transfer and removal, so that no residue of such elements remains on the surface of the deposited film.

[0173] Here, the disclosed oxygen-friendly reagent may be a volatile compound containing an element having higher oxygen-friendliness than the metal of the metal oxyhalide precursor.

[0174] The disclosed oxygenophilic reagent may be selected from transition metal-containing or main group element-containing compounds to remove, exchange, scavenge, or transfer oxygen from a metal oxyhalide precursor. In the oxygenophilic reagent, the transition metal or main group element has higher oxygenophilicity than the metal of the metal oxyhalide precursor, which may correspond to the reduction of the metal center of the metal oxyhalide precursor or maintain the oxidation state (i.e., ligand exchange).

[0175] The disclosed metal oxyhalogenate precursor may have the following general chemical formula:

[0176] M (a) X c O e

[0177] In the formula, 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 in the range of 3 to 6; c is a number in the range 0 < c < 6; e is a number in the range 0 < e < 3; and c + 2e = a. Preferably, X is selected from Cl, Br, or I. In one embodiment, the metal oxyhalide precursor is selected from transition metal oxyhalide precursors. Preferably, the metal oxyhalide precursor is selected from MoO2Cl2, MoOCl4, WOCl4, WO2Cl2, NbOCl3, TaOCl3, CrO2Cl2, etc.

[0178] The disclosed oxygen-philic reagent may have the following general chemical formula:

[0179] N (b) X d O f

[0180] In the formula, N is a transition metal halide or oxyhalide, or a Group 14 or Group 15 halide, oxyhalide, or oxide; X is a halogen; b is the oxidation state of N, and b is an integer in the range of 3 to 6; d is a number of 0 ≤ d < 6; f is a number of 0 < f < 3; and d + 2f = b. Preferably, X is selected from Cl, Br, or I.

[0181] Here, N (b) X d O f The oxygen-philicity of N in M (a) X c O e It must be greater than the oxygenophilicity of M. For example, oxygenophilicity is Mo < W. Therefore, the oxygenophilic reagent N (b) X d O fis selected from an oxygenophilic reagent containing an element of a transition metal or an element from Group 14 or Group 15, and the oxygenophilicity of the major element (i.e., transition metal or Group 14 and 15 element) in the oxygenophilic reagent is higher than the oxygenophilicity of the metal in the metal oxyhalide precursor.

[0182] Preferably, the disclosed oxygen-friendly reagent may be selected from the following:

[0183] 14th foot:

[0184] C-containing: CCl4, CBr4, COCl2, CO and RN=C=O (wherein R is a saturated or unsaturated hydrocarbon group, e.g., an alkyl group, and preferably R is H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu);

[0185] Si-containing: Si x R y X z (wherein x is 1 to 5, y and z are 0 to 12, y + z ≤ 2x+2; X is a halogen selected from Cl, Br, and I; and R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group);

[0186] 15th group:

[0187] N-containing: NO, N2O;

[0188] P-containing: PCl3, PBr3, PI3; or

[0189] Transition metal-containing: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4.

[0190] Alternatively, the disclosed oxygen-philic reagent is a Si-containing oxygen-philic reagent Si x R y X zIt may be, where x is 1 to 5, y and z are 0 to 12, y + z ≤ 2x+2; X is a halogen selected from Cl, Br, and I; and R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group. Exemplary Si-containing oxygen-philic 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 oxygen-philic reagent is Si2Cl6(HCDS).

[0191] Alternatively, oxygen-friendly reagent N (b) X d O f can be selected from non-halogenated containing precursors (d = 0) based on criteria similar to the major element having higher oxygenophilicity than the metal in the metal oxyhalide precursor. Preferably, such an oxygenophilic reagent is selected from the following:

[0192] Group 14: CO, and RN=C=O (wherein R is a saturated or unsaturated hydrocarbon group, e.g., an alkyl group, preferably R is H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu); or

[0193] 15th group: NO, N2O.

[0194] Alternatively, oxygen-friendly reagent N (b) X d O fmay be an isocyanate having the chemical formula RN=C=O, where R is a saturated or unsaturated hydrocarbon group, e.g., an alkyl group, and preferably, R is H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu. When the isocyanate is used as an oxygenophilic reagent, the M=O bond of the metal oxyhalide precursor will be replaced by an M=NR bond, which leads to the formation of a metal nitride film rather than a pure metal film. In the above, the C and N elements have higher oxygenophilicity than the metal of the metal oxyhalide precursor. Preferably, the isocyanate is tBu-N=C=O. When tBu-N=C=O is used as an oxygenophilic reagent, the M=O bond of the metal oxyhalide precursor will be replaced by an M=N-tBu bond, which leads to the formation of a metal nitride film rather than a pure metal film.

[0195] Alternatively, oxygen-friendly reagent N (b) X d O f It may be a transition metal halide or an oxyhalide. Exemplary transition metal-containing halides or oxyhalides include VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, and WCl4.

[0196] In one embodiment, the oxygen-friendly reagent N (b) X d O f In addition, the deposited film can be converted into a metal film using a reducing agent. The reducing agent for forming the metal form may be H2, B2H6, HCl, etc. The reducing agent for forming the metal nitride film may be NH3.

[0197] Alternatively, the oxyphilic reagent itself may also act as a reducing agent capable of reducing metal oxyhalide precursors to metals. In such cases, the oxyphilic 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.

[0198] Generally, as described below, there are three general reaction schemes or reaction formulas for the oxygen removal reaction or deoxygenation from metal oxyhalide precursors.

[0199] Reaction Equation I: The oxidation state of the metal in the metal oxyhalogenate precursor does not change:

[0200] [Reaction Equation I]

[0201] 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

[0202] During the meal,

[0203] M (a) X c O e is a metal oxyhalide precursor, where M is Mo, W, V, Nb, Ta, and Cr; X is a halogen; a is the oxidation state of M, where a is an integer in the range of 3 to 6; c is a number such that 0 < c < 6; e is a number such that 0 < e < 3; and c + 2e = a;

[0204] N (b) X d O fis an oxygen-philic reagent, where N is a transition metal halide or oxyhalide, or a Group 14 or Group 15 halide, oxyhalide, or oxide; X is a halogen; b is the oxidation state of N, and b is an integer in the range of 3 to 6; d is a number such that 0 ≤ d < 6; f is a number such that 0 < f < 3; and d + 2f = b, wherein;

[0205] However, N (b) X d O f The oxygen-philicity of N in M (a) X c O e At, greater than the oxygen-philicity of M, and N (b) X d O f and N (b) X d-2 O f+1 is volatile. Preferably, X is selected from Cl, Br, or I.

[0206] Reaction Equation I Example of:

[0207] 1) The metal oxyhalide precursor is MoO2Cl2, the oxygenophilic reagent is WCl6, and oxygen is removed in sequential steps:

[0208] Mo (VI) Cl2O2+ W (VI) Cl6→ Mo (VI) Cl4O + W (VI) Cl4O

[0209] Mo (VI) Cl4O + W (VI) Cl6→ Mo (VI) Cl6+ W (VI) Cl4O

[0210] During the meal, W (VI) Cl6 and W (VI) Cl4O is volatile.

[0211] 2) Two M=O groups are removed in a single step, the metal oxyhalide precursor is MoO2Cl2, and the oxygen-philic reagent is WCl6:

[0212] Mo(VI) Cl2O2+ 2W (VI) Cl6→ Mo (VI) Cl6+ 2W (VI) Cl4O

[0213] During the meal, W (VI) Cl6 and W (VI) Cl4O is volatile.

[0214] 3) Reaction product Mo in 1) and 2) (VI) Cl6 is unstable and undergoes the following additional reactions:

[0215] Mo (VI) Cl6→ Mo (IV) Cl4+ Cl2

[0216] Mo (VI) Cl4 + 2 H2 → Mo (0) + 4 HCl

[0217] During the meal, Mo (VI) Cl4 can be reduced to Mo and HCl by H2, or decomposed into Mo and Cl2 by heating.

[0218] Reaction Equation II: The oxidation state of the metal in the metal oxyhalogenate precursor changed by 2:

[0219] [Reaction Equation II]

[0220] 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

[0221] During the meal,

[0222] M (a) X c O eis a metal oxyhalide precursor, where M is Mo, W, V, Nb, Ta, and Cr; X is a halogen; a is the oxidation state of M, where a is an integer in the range of 3 to 6; c is a number such that 0 < c < 6; e is a number such that 0 < e < 3; and c + 2e = a;

[0223] N (b) X d O f is an oxygen-philic reagent, where N is a transition metal halide or oxyhalide, or a Group 14 or Group 15 halide, oxyhalide, or oxide; X is a halogen; b is the oxidation state of N, and b is an integer in the range of 3 to 6; d is a number such that 0 ≤ d < 6; f is a number such that 0 < f < 3; and d + 2f = b, wherein;

[0224] However, N (b) X d O f The oxygen-philicity of N in M (a) X c O e It must be greater than the oxygen-philicity of M, and N (b) X d O f and N (b+2) X d O f+1 is volatile. Preferably, X is selected from Cl, Br, or I.

[0225] Reaction Equation II Example: The metal oxyhalide precursor is MoO2Cl2, and the oxygenophilic reagent is WCl4:

[0226] Mo (VI) Cl2O2+ W (IV) Cl4→ Mo (IV) Cl4+ W (VI) Cl2O2

[0227] Mo (IV) Cl4 + 2 H2 → Mo (0) + 4 HCl

[0228] During the meal, Mo (IV)Cl4 can be reduced to Mo and HCl by H2, or decomposed into Mo and Cl2 by heating; W (IV) Cl4 and W (VI) Cl2O2 is volatile.

[0229] Reaction Equation III : The oxidation state of the metal in the metal oxyhalogenate precursor changed by 1:

[0230] [Chemical Formula III]

[0231] 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

[0232] During the meal,

[0233] M (a) X c O e is a metal oxyhalide precursor, where M is Mo, W, V, Nb, Ta, and Cr; X is a halogen; a is the oxidation state of M, where a is an integer in the range of 3 to 6; c is a number such that 0 < c < 6; e is a number such that 0 < e < 3; and c + 2e = a;

[0234] N (b) X d O f is an oxygen-philic reagent, where N is a transition metal halide or oxyhalide, or a Group 14 or Group 15 halide, oxyhalide, or oxide; X is a halogen; b is the oxidation state of N, and b is an integer in the range of 3 to 6; d is a number such that 0 ≤ d < 6; f is a number such that 0 < f < 3; and d + 2f = b, wherein;

[0235] However, N (b) X d O f The oxygen-philicity of N in M (a)X c O e It must be greater than the oxygen-philicity of M, and N (b) X d O f and N (b+1) X d-1 O f+1 is volatile. Preferably, X is selected from Cl, Br, or I.

[0236] Reaction Equation III Example of:

[0237] 1) The metal oxyhalide precursor is MoO2Cl2, and the oxygen-philic reagent is WCl5:

[0238] Mo (VI) Cl2O2+ W (V) Cl5→ Mo (V) Cl3O + W (VI) Cl4O

[0239] Mo (V) Cl3O + W (V) Cl5→ Mo (IV) Cl4+ W (VI) Cl4O

[0240] Mo (IV) Cl4 + 2 H2 → Mo (0) + 4 HCl

[0241] During the meal, 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.

[0242] 2) Two M=O groups are removed, the metal oxyhalide precursor is MoO2Cl2, and the oxygen-philic reagent is WCl5:

[0243] Mo (VI) Cl2O2+ W (V) Cl5→ Mo (V) Cl5+ W (VI) Cl2O2

[0244] 2 Mo (V) Cl5 + 5 H2 → 2 Mo (0) + 10 HCl

[0245] During the meal, 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.

[0246] The selection criteria for the disclosed oxygen-friendly reagent are i) with respect to oxygen-friendliness, the major element of the oxygen-friendly reagent (e.g., C, N, P, Si, transition metal V, W, Nb, Ta) must be greater than that of the metal of the metal oxyhalide precursor; and ii) the oxygen-friendly reagent and its reaction product (e.g., a product of the form M=O) must be volatile. Table I It is an exemplary promising element and its oxygen-friendly, volatile oxygenation product that can be used as an oxygen-friendly reagent before and after reaction with oxygen in metal oxyhalide precursors.

[0247] [Table I]

[0248]

[0249] Here, not all transition metals satisfy the selection criteria for oxygen-friendly reagents. For example, TiCl4, ZrCl4, HfCl4, LaCl3, and CeCl3 do not satisfy the selection criteria because, despite their oxygen-friendliness being much higher than that of Mo, there is no literature record indicating that their oxyhalides exist and are sufficiently volatile. Similarly, CrCl3 is not sufficient for use as an oxygen removal reagent because it is very non-volatile.

[0250] In the case of silicon compounds used as oxyphilic reagents, stable and volatile oxyhalides are not known, but deoxygenation may occur through the formation of siloxane compounds that may be volatile. Therefore, silanes, particularly polyhalo-polysilanes such as Si2Cl6 or Si2HCl5, are particularly useful candidate materials for removing O from metal oxyhalides. Thus, polysilanes such as Si2Cl6, Si2HCl5, and Si2Me6 are particularly suitable candidate materials for removing O from metal oxyhalide precursors.

[0251] For example, when the metal oxyhalide precursor is MoO2Cl2, possible oxygen-philic reagents containing an oxygen-philic element can be selected from the following:

[0252] 14th foot:

[0253] C-containing: CCl4, CBr4, COCl2, CO and RN=C=O (wherein R is a saturated or unsaturated hydrocarbon group, e.g., an alkyl group, and preferably R is H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu);

[0254] Si-containing: Si x R y X z (where x is 1 to 5, y and z are 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, e.g. 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);

[0255] 15th group:

[0256] N-containing: NO, N2O;

[0257] P-containing: PCl3, PBr3, PI3; or

[0258] Transition metal-containing: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, WCl4.

[0259] A similar approach may be applied to the oxygen removal or deoxygenation of other metal oxyhalide precursors. For example, CrO2Cl2 is highly volatile and can be used as a metal oxyhalide precursor for Cr deposition in a manner similar to MoO2Cl2. To this end, an oxyphilic reagent can be used to facilitate the complete removal of oxygen, which may be selected from the following:

[0260] 14th foot:

[0261] CCl4, CBr4, COCl2, CO and RN=C=O (wherein R is a saturated or unsaturated hydrocarbon group, e.g., an alkyl group, and preferably R is H, Me, Et, iPr, nPr, iBu, tBu, sBu, nBu);

[0262] Si x R y X z(where x is 1 to 5, y and z are 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, e.g. 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);

[0263] Group 15: NO, N2O, PCl3, PBr3, PI3; or

[0264] Transition metals: VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, WCl4.

[0265] In CVD or ALD processes, the removal of oxygen from a metal oxyhalide precursor or from an intermediate film formed by the deposition of a metal oxyhalide precursor by an oxyphilic reagent can generally be complemented by the complete reduction of a metal center (metal intermediate MX) to form a metallic film. Thus, an oxyphilic reagent can be used in combination with a complementary reducing reagent, such as H2, to convert MX (where X is Cl, Br, or I, and M is a metal from the metal oxyhalide precursor) to M and HX. However, when oxygen is removed from the film, other hydrogen reducing agents, 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., may be used.

[0266] To avoid the reduction of the oxyphilic reagent by the complementary reducing reagent, this method is performed in ALD or pulsed CVD mode, primarily by sequentially exposing the substrate to a metal oxyhalide precursor, an oxyphilic reagent, and a complementary reducing agent. The order may vary depending on the selected chemical. For example, the order is i) metal oxyhalide precursor (M on the substrate (a) X c O e It may be i) adsorption of the precursor; ii) an oxyphilic reagent (reduction or deoxygenation of the adsorbed metal oxyhalide precursor); iii) a complementary reducing agent (reduction of the metal intermediate obtained from the deoxygenation reaction to the metal). An alternative sequence may be i) metal oxyhalide precursor + oxyphilic reagent (reduction or deoxygenation of the metal oxyhalide precursor); ii) addition of a complementary reducing reagent (reduction of the metal intermediate obtained from the deoxygenation reaction to the metal).

[0267] Oxophilic reagents can also act as reducing agents. For example, CO can be both an oxygenophilic agent (CO → CO2) and a reducing agent (CO → COCl2). Similarly, HSiCl3 is MO x X y O is removed from a metal oxyhalide precursor (M is a metal, X is Cl, Br, or I, and x and y are integers), and can be reduced to break the MX bond from a metal intermediate obtained from a deoxygenation reaction while forming SiCl3-O-SiCl3 and 2 HX as byproducts.

[0268] Metal nitride (MN) xTo form the film, the reducing agent can be replaced with a nitride reagent, such as NH3, to produce a metal nitride film. In metal nitride film applications, alkyl or silyl isocyanates, such as tert-butyl isocyanate, can be used as an oxyphilic reagent to remove oxygen from the metal oxyhalides. The tBu-imido bonds to the metal center of the intermediate, replacing the M=O bond to form two tBu-imido bonds, which will lead to the metal nitride film. Reaction Equation IV ).

[0269] [Reaction Equation IV]

[0270] -M=O + tBu-N=C=O → -M=N-tBu + CO2

[0271] 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.

[0272] Alternatively, the disclosed method / process may be an ALD process that sequentially exposes a surface to reagents such as a metal oxyhalide precursor, an oxyphilic agent, and a reducing agent, wherein the oxyphilic reagent reacts with the metal oxyhalide precursor to form a metal intermediate; and the metal intermediate reacts with a complementary reducing reagent, e.g., H2, to form a pure metal film. ALD conditions within a chamber cause the disclosed metal oxyhalide precursor, which is adsorbed or chemo-adsorbed on the substrate surface, to react to form a film on the substrate. In some embodiments, the metal oxyhalide precursor may be plasma-treated. In such cases, the ALD process becomes a PEALD process. Thus, the ALD process may or may not be a plasma-enhanced ALD process, and preferably, the ALD process is not a plasma-enhanced ALD process. The ALD process may be thermal ALD or spatial ALD.

[0273] Alternatively, the disclosed process may be an ALD process in which the surface is sequentially exposed to reagents (precursor / oxyphilic agent / reducing agent), wherein the oxygenphilic reagent forms M=N-tBu bonds with M=O; and NH3 is selected as the reducing reagent to form a nitride film.

[0274] The disclosed metal oxyhalogen precursor, oxygenophilic reagent, and reducing agent may be introduced into the reactor simultaneously (CVD) or sequentially (ALD). The reactor may be purged with an inert gas (e.g., N2, Ar, Kr, Xe) between the introduction of the metal oxyhalogen precursor, oxygenophilic reagent, and reducing agent. Alternatively, the metal oxyhalogen precursor and the oxygenophilic reagent may be mixed together to form a mixture of the metal oxyhalogen precursor and the oxygenophilic reagent, which may then be introduced into the reactor in the form of the mixture. The reactor may be purged with an inert gas, such as N2, Ar, Kr, Xe, between the introduction of each film-forming composition or the mixture of the metal oxyhalogen precursor and the oxygenophilic reagent.

[0275] The purity of the disclosed film-forming composition, or the disclosed metal oxyhalide, oxygenophilic reagent, and reducing agent 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 approximately 99.999% w / w or 99.0% w / w to 100.0% w / w). Those skilled in the art will recognize that purity may be determined by gas or liquid chromatography and NMR spectroscopy in combination with mass spectrometry. The disclosed film-forming composition may contain any of the following impurities: THF; ether; pentane; cyclohexane; heptane; benzene; toluene; metal halide 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), 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 disclosed purified film-forming compositions can be purified by recrystallization, sublimation, distillation, and / or by passing a gas or liquid through a suitable adsorbent such as a 4Å molecular sieve.

[0276] The disclosed film-forming composition may be supplied in a clean (neat) form or as a blend with a suitable solvent such as ethylbenzene, xylene, mesitylene, decalin, decane, and dodecane. The disclosed metal oxyhalide precursor and the oxyphilic reagent may be present in the solvent at various concentrations.

[0277] The disclosed blended pure film-forming composition is introduced into a reactor in vapor form by conventional means such as tubing and / or a flow meter. The vapor form may be produced by vaporizing the pure blended composition through a conventional vaporization step such as direct vaporization or distillation, or by bubbling, or by using a sublimator such as that disclosed in PCT Publication WO2009 / 087609 (Xu et al.). The pure blended composition may be supplied to the vaporizer in a liquid state, where it is vaporized before being introduced into the reactor. Alternatively, the pure blended composition may be vaporized by passing a carrier gas through a vessel containing the composition by bubbling a carrier gas into the composition. The carrier gas may include, but is not limited to, Ar, He, N2, and mixtures thereof. Bubbling with a carrier gas may also remove any dissolved oxygen present in the pure blended composition. The carrier gas and the composition are then introduced into the reactor as vapor.

[0278] If necessary, a container containing 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, for example, at a temperature in the range of approximately 0°C to approximately 200°C. Those skilled in the art recognize that the amount of precursor vaporized can be controlled by adjusting the temperature of the container in a known manner.

[0279] The reactor may be any enclosure chamber within the apparatus where the deposition method is performed, such as a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, or other types of deposition systems, without limitation, under conditions suitable for the compound to react to form a layer. Those skilled in the art will recognize that any of these reactors may be used in either an ALD or CVD deposition process.

[0280] The reaction chamber may contain one or more than one substrate. For example, the reaction chamber may contain 1 to 200 silicon wafers having a diameter of 25.4 mm to 450 mm. A substrate is generally defined as the material on which the process is performed. The substrate may be any suitable wafer used in the manufacture of semiconductors, photovoltaics, flat panel, or LCD-TFT devices. Examples of suitable substrates include wafers such as silicon, silica, glass, Ge, SiGe, GeSn, InGaAs, GaSb, InP, or GaAs wafers. The wafer will have a number of films or layers on the wafer from a previous manufacturing step, which include silicon-containing films or layers. The layers may or may not be patterned. For example, the wafer may include a dielectric layer. In addition, the wafer may comprise a silicon layer (crystalline, amorphous, porous, etc.), a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, a carbon-doped silicon oxide (SiCOH) layer, a metal, a metal oxide, a metal nitride layer (Ti, Ru, Ta, etc.), and combinations thereof. Additionally, the wafer may comprise a copper layer and a precious metal layer (e.g., platinum, palladium, rhodium, gold). The wafer may comprise a barrier layer such as manganese, manganese oxide, etc. A plastic layer such as poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) [PEDOT:PSS] may also be used. The layer may be planar or patterned. The disclosed process may deposit the layer directly onto the wafer or directly deposit the patterned layer onto one or more layers on top of the wafer when the layer is formed on the substrate. The patterned layer may be an alternating layer of two specific layers, such as In2O3 and ZrO2 used in 3D NAND. Additionally, those skilled in the art will recognize that the terms “film” and “layer” as used herein refer to a certain thickness of a material placed on or diffused over a surface, and that said surface may be a trench or a line.Throughout this specification and claims, a wafer and any related layer on the wafer are referred to as a substrate.

[0281] The temperature and pressure within the reactor are maintained at conditions suitable for vapor deposition, such as ALD and CVD. In other words, after the disclosed vaporized film-forming composition is introduced into the chamber, the conditions within the chamber cause at least a portion of the precursor to be deposited on the substrate to form a layer. For example, the pressure within the reactor or the deposition pressure is about 10 as required by the deposition parameters. -3 torr to about 100 torr, more preferably about 10 -2 It may be maintained at torr to 10 torr. Likewise, the temperature in the reactor or the deposition temperature may be maintained at about 100°C to about 500°C, preferably about 150°C to about 485°C. Those skilled in the art will recognize that “at least a portion of the precursor is deposited” means that some or all of the precursor reacts with the substrate or adheres to the substrate.

[0282] The temperature for achieving optimal film growth can be controlled by controlling the temperature of the substrate holder. Devices used to heat the substrate are known in the art. The substrate is heated to a temperature sufficient to obtain a desired film of the desired physical state and composition at a sufficient growth rate. Non-limiting exemplary temperature ranges in which the substrate may be heated include approximately 50°C to approximately 500°C. If a plasma deposition process is used, the deposition temperature may be approximately less than 500°C, preferably approximately less than 400°C. Alternatively, if a thermal process is performed, the deposition temperature may be in the range of approximately 100°C to approximately 500°C.

[0283] Alternatively, the substrate may be heated to a temperature sufficient to obtain a desired metal film of a desired physical state and composition at a sufficient growth rate. Non-limiting exemplary temperature ranges in which the substrate may be heated include room temperature to approximately 500°C. Preferably, the temperature of the substrate is maintained at 500°C or lower.

[0284] Each pulse of the disclosed film-forming composition may be sustained for a period ranging 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. An oxygen-friendly reagent may also be pulsed into the reactor. In such an embodiment, each pulse may be sustained for a period ranging 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-friendly reagent may be sprayed simultaneously from different sectors of a showerhead (without mixing the composition and the reagent), where a susceptor employing multiple wafers is rotated beneath the showerhead (space ALD).

[0285] Depending on specific process parameters, deposition can occur for varying lengths of time. Generally, deposition can be continued as long as needed to produce a film with the required properties. Typical film thicknesses can vary from a few angstroms to hundreds of micrometers, and typically from 1 nm to 100 nm, depending on the specific deposition process. The deposition process can also be performed multiple times as needed to obtain the desired film.

[0286] A disclosed method for depositing a metal or metal nitride film on a substrate comprises the steps of: reacting a metal oxyhalogen precursor with an oxyphilic reagent in a reactor containing said substrate to deoxygenate said metal oxyhalogen precursor; and forming a metal or metal nitride film on said substrate through a vapor deposition process. Herein, the substrate may be exposed to the metal oxyhalogen precursor and the oxyphilic reagent simultaneously. Alternatively, the substrate may be exposed to the metal oxyhalogen precursor and the oxyphilic reagent sequentially. After the step of reacting the metal oxyhalogen with the oxyphilic reagent, the substrate may be sequentially exposed to a reducing agent to form a metal or metal nitride film.

[0287] Alternatively, a disclosed method for depositing a metal film on a substrate comprises the steps of placing the substrate in a reactor, delivering vapor of a metal oxyhalogen precursor into the reactor, contacting / adsorbing the vapor with the surface of the substrate (and typically directing the vapor toward the substrate) to form a metal oxyhalogen layer on the surface of the substrate, introducing vapor of an oxyphilic reagent into the reactor to react with the metal oxyhalogen on the surface of the substrate, forming the metal halide on the surface, and introducing a reducing agent to reduce the metal halide to a metal.

[0288] Alternatively, a disclosed method for depositing a metal film on a substrate comprises the steps of placing the substrate in a reactor, delivering vapor of a mixture of a metal oxyhalogen precursor and an oxyphilic reagent into the reactor, contacting / adsorbing the vapor with the surface of the substrate (and typically directing the vapor toward the substrate) to form a metal oxyhalogen layer on the surface of the substrate, reacting the oxyphilic reagent with the metal oxyhalogen on the surface of the substrate, forming the metal halide on the surface, and introducing a reducing agent to reduce the metal halide to a metal.

[0289] A disclosed method for depositing a metal nitride film on a substrate comprises the steps of placing the substrate in a reactor, delivering vapor of a metal oxyhalide precursor into the reactor, contacting / adsorbing the vapor with the substrate (and typically directing the vapor toward the substrate) to form a metal oxyhalide layer on the surface of the substrate, introducing vapor of an oxyphilic reagent containing a CN bond, e.g., a tBu-N bond, into the reactor to react with the metal oxyhalide on the surface of the substrate, forming a metal nitride halide intermediate on the surface, and introducing a reducing agent (e.g., NH3) to reduce the metal nitride halide to a metal nitride film.

[0290] Alternatively, a disclosed method for depositing a metal nitride film on a substrate comprises the steps of placing the substrate in a reactor; delivering vapor of a mixture of a metal oxyhalide precursor and an oxyphilic reagent containing a CN bond, e.g., a tBu-N bond, into the reactor; contacting / adsorbing the vapor with the substrate (and typically directing the vapor toward the substrate) to form a metal oxyhalide layer on the surface of the substrate, and the oxyphilic reagent reacting with the metal oxyhalide on the surface of the substrate; forming a metal nitride halide on the surface; and introducing a reducing agent (e.g., NH3) to reduce the metal nitride halide to a metal nitride film.

[0291] The purity of the metal or metal nitride film produced according to the disclosed method may be approximately > 98.5%, preferably approximately > 99%, and the oxygen content or impurities in the produced metal or metal nitride film may be < 1.5%, preferably approximately < 1%.

[0292] Examples

[0293] The following non-limiting examples are provided to further illustrate embodiments of the present invention. However, the examples are not intended to be all-encompassing, nor are they intended to limit the scope of the invention as described herein.

[0294] Example 1

[0295] The concept and reactivity were verified by testing chemicals from the condensed phase. To experimentally confirm that the reaction between the metal oxyhalide precursor and the oxyphilic reagent is favorable at or below the target gas phase deposition process temperature, solid / liquid phase experiments were performed by mixing the metal oxyhalide precursor and the oxyphilic reagent, and the reaction products were analyzed to confirm that oxygen atoms are transferred from the metal oxyhalide precursor to the oxyphilic reagent by the splitting of M=O.

[0296] The results using MoO2Cl2 (CAS No.: 13637-68-8) as a test precursor and WCl6, WCl5, WCl4, WOCl4, or NbCl5 as an oxygenophilic reagent are summarized below. Experiments were conducted at 120 to 240°C for several hours. Additionally, MoO3 was tested to demonstrate that its oxidized metal form can be removed in a similar manner to form volatile species. In summary, prior to the reaction, analysis of reaction mixtures such as MoO2Cl2 and WCl6, WCl5, WCl4, WOCl4, NbCl5, VCl4, VCl3, PI3, Me3SiCl, or HSiCl3 revealed the Mo=O bond and MCl, respectively. x or MCl x The presence of [the substance] was demonstrated. After the reaction at elevated temperatures, the PXRD pattern, Raman spectrum (not shown), and GC spectrum (not shown) in the case of liquid reagents or products showed that the Mo=O bond and MoO2Cl2 were completely extinguished, and instead, when using oxygen-friendly reagents, e.g., WCl6, WCl5, WOCl4, and NbCl5, M=O bonds, e.g., W=O, Nb=O bonds, or when using Si-based oxygen-friendly reagents, MOM bonds appeared. In the case of the oxygen-friendly reagent WOCl4, weak reactivity and incomplete elimination of the Mo=O bond were observed. Higher reaction temperatures (e.g., < 500°C) would induce the reaction to complete. Table IIThis is the result of reacting MoO2Cl2 as a metal oxyhalide precursor and MoO3 as a representative oxide with various oxyphilic reagents.

[0297] Fig. 1a is the powder X-ray diffraction (PXRD) pattern and fitting of the mixture of WCl6 and MoO2Cl2 before the reaction. Fig. 1b Figure 2 shows the PXRD pattern and fitting of a mixture of 2 WCl6 and MoO2Cl2 after heating at 235°C for 8 hours. Comparing the PXRD patterns before and after the reaction, oxygen is completely removed from MoO2Cl2, and MoCl x was formed, and the oxygen-friendly reagent WCl6 was converted to WOCl4.

[0298] [Table II]

[0299]

[0300] Example 2

[0301] As described above, the most difficult task in reducing MoO2Cl2 to Mo metal is the deoxygenation step. Therefore, the reduction process can be accelerated by using oxygen removal reagents other than H2. Several candidate oxygen scavengers, for example, HCDS, have been considered.

[0302] The ALD of Mo using MoO2Cl2 at less than 500℃ as the first step of removing oxygen by an oxygen-friendly reagent Reaction Equation I This is shown in [figure]. Subsequent interaction of the already deoxygenated metal oxyhalide precursor reacts with a second reducing agent under low pressure conditions to deposit a Mo material (e.g., a Mo layer), which can be pure (e.g., at least 95, 98, 99, 99.5 or 99.9% (atomic) Mo).

[0303] For example, an ALD process consisting of the following conditions and sequence was performed using a SiO2 substrate (T = 485 o C, total P = 10 torr): Fig. 2aAs shown in [figure], a pulse of 2.5 seconds (1.01 / 11.3 sccm) of a mixture of MoO2Cl2 / HCDS (hexachlorodisilane, Si2Cl6, CAS No.: 13465-77-5) was introduced into the reactor using argon as the carrier gas (100 sccm), followed by an argon purge of 5 seconds (10 sccm), an H2 pulse of 5 seconds (500 sccm), and an argon purge of 5 seconds (10 sccm), after which a very pure Mo film of 98.5% was deposited. Oxygen impurities were < 1.5%. The chemical reaction is expected to be as follows.

[0304] Mo (VI) O2Cl2+ 2 Si (III) 2Cl6→ Mo (II) Cl2+ 2 OSi (IV) 2Cl6

[0305] Mo (II) Cl2 + H2 → Mo (0) + 2 HCl

[0306] Fig. 2b X-ray photoelectron spectroscopy (XPS) using HCDS as an oxygen scavenger and H2 as a reducing agent. As a comparative example, the same process was performed in the absence of HCDS under the same process conditions of T=485℃ and total P=10 torr. Fig. 3a As shown in [figure], MoO2Cl2 2.5 seconds (1.01 sccm), argon as carrier gas (100 sccm), argon purge 5 seconds (10 sccm), H2 pulse 5 seconds (500 sccm), and argon purge 5 seconds (10 sccm). Film characterization by XPS indicated that there was no Mo and only the SiO2 substrate was present. Fig. 3b It is a conventional ALD XPS using H2 at 485°C in the absence of HCDS as an oxygen scavenger.

[0307] Therefore, HCDS can act as an oxygen removal reagent for MoO2Cl2 while separately using Ar purge and H2 reduction. Fig. 2bReferring to [the source], the Mo film has ultra-high purity (Mo > 98.5%, O < 1.5%, Si 0%) by HCDS. Fig. 3b Referring to [the source], Mo deposition did not occur at the same temperature in the absence of HCDS.

[0308] The subject matter of the claims described herein may be described in the context of exemplary implementations for handling one or more computing application features / behaviors for a computing application having a user-interactive component, but the subject matter of the claims is not limited to these specific embodiments. Rather, the technology described herein may be applied to any suitable type of user-interactive component execution management method, system, platform and / or device.

[0309] It will be understood that many additional modifications to the details, materials, steps, and arrangements of parts described and illustrated herein to illustrate the characteristics of the invention may be made by those skilled in the art within the principles and scope of the invention as expressed in the appended claims. Accordingly, the invention is not intended to be limited to specific embodiments of the examples given above and / or the appended drawings.

[0310] Although embodiments of the present invention have been presented and described, modifications may be made by those skilled in the art without departing from the spirit or teachings of the present invention. The embodiments described herein are illustrative only and are not limited. Many changes and modifications to the composition and method are possible within the scope of the present invention. Accordingly, the scope of protection is not limited to the embodiments described herein, but is limited only by the following claims, the scope of which includes all equivalents to the subject matter of the claims.

Claims

Claim 1 A method for depositing a metal or metal nitride film on a substrate, comprising the steps of: reacting a metal oxyhalogenate precursor with an oxyphilic reagent in a reactor containing the substrate to deoxygenate the metal oxyhalogenate precursor; sequentially exposing the substrate to a reducing agent after deoxygenation; and forming the metal or metal nitride film on the substrate through a vapor deposition process, wherein the metal oxyhalogenate precursor is M (a) X c O e and, 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 in the range of 3 to 6; c is a number such that 0 < c < 6; e is a number such that 0 < e < 3; c + 2e = a; and the oxygenophilic reagent is N (b) X d O f A method wherein N is a transition metal, or an element of group 14 or 15; X is a halogen selected from Cl, Br, or I; b is the oxidation state of N, and b is an integer in the range of 3 to 6; d is a number of 0 ≤ d ≤ 6; f is a number of 0 ≤ f < 3; d + 2f = b; the oxygenophilicity of N is greater than the oxygenophilicity of M; and the oxygenophilic reagent and the product of the oxygenophilic reagent are volatile. Claim 2 A method according to claim 1, further comprising the step of exposing the substrate to the metal oxyhalogen precursor and the oxygen-friendly reagent simultaneously or sequentially. Claim 3 In claim 1, the reducing agent is selected from H2, HCl, B2H6, NH3, CO, SiHCl3, SiHBr3, or SiHl3. Claim 4 The method of claim 1, wherein the metal oxyhalogenate precursor is selected from MoO2Cl2, MoOCl4, WOCl4, WO2Cl2, NbOCl3, TaOCl3, and CrO2Cl2. Claim 5 In claim 1, the oxygen-philic reagent is a. containing Group 14: CCl4; CBr4; COCl2; CO; or Si x R y X z (wherein x is 1 to 5, y is 0, z is 0 to 6, y + z ≤ 2x+2, X is a halogen selected from Cl, Br, and I, and R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group); b. Group 15-containing: NO, N2O, PCl3, PBr3, PI3; or c. Transition metal-containing: selected from VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4 or WCl4, method. Claim 6 In claim 1, the oxygen-philic reagent is of the general chemical formula Si x R y X z A method comprising a Si-containing oxygen-philic reagent having (wherein x is 1 to 5, y is 0, z is 0 to 6, y + z ≤ 2x+2; X is a halogen selected from Cl, Br, and I; and R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group). Claim 7 In claim 6, the method wherein the Si-containing oxygen-philic reagent is selected from Si2Cl6, Si2Br6, or Si2I6. Claim 8 A method according to any one of claims 1 to 7, wherein the oxygen-friendly reagent is Si2Cl6. Claim 9 A method according to any one of claims 1 to 5, wherein the oxygen-friendly reagent is a metal halide or metal oxyhalide selected from VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4, or WCl4. Claim 10 A method according to any one of claims 1 to 7, wherein the vapor deposition process is thermal CVD or ALD at a deposition temperature of less than 485°C, or plasma-enhanced CVD or ALD. Claim 11 A method for forming a metal or metal nitride film on a surface by removing oxygen from a metal oxyhalogen precursor or an intermediate film deposited by said metal oxyhalogen precursor, comprising the steps of: reacting said metal oxyhalogen precursor or said intermediate film deposited by said metal oxyhalogen precursor with an oxyphilic reagent to form a metal intermediate; and reducing said metal intermediate to a metal or metal nitride film on said surface using a reducing agent through a vapor deposition process, wherein the metal oxyhalogen precursor is M (a) X c O e and, 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 in the range of 3 to 6; c is a number such that 0 < c < 6; e is a number such that 0 < e < 3; c + 2e = a; and the oxygenophilic reagent is N (b) X d O f and, where N is a transition metal, or an element of group 14 or 15; X is a halogen selected from Cl, Br, or I; b is the oxidation state of N, and b is an integer in the range of 3 to 6; d is a number 0 ≤ d ≤ 6; f is a number 0 ≤ f < 3; d + 2f = b; the oxygenophilicity of N is greater than the oxygenophilicity of M; and the oxygenophilic reagent and the product of the oxygenophilic reagent are volatile, method. Claim 12 In claim 11, the metal oxyhalogenate precursor is selected from MoO2Cl2, MoOCl4, WOCl4, WO2Cl2, NbOCl3, TaOCl3, and CrO2Cl2; and the oxygenophilic reagent is a. containing Group 14: CCl4; CBr4; COCl2; CO; or Si x R y X z (wherein x is 1 to 5, y is 0, z is 0 to 6, y + z ≤ 2x+2, X is a halogen selected from Cl, Br, and I, and R is H, a saturated or unsaturated hydrocarbon group, an amino group, an alkoxy group, or a silyl group); b. Group 15-containing: NO, N2O, PCl3, PBr3, PI3; or c. Transition metal-containing: selected from VCl4, VCl3, NbCl5, TaCl5, WCl6, WCl5, WOCl4 or WCl4, method. Claim 13 A method according to claim 11 or 12, wherein the vapor deposition process is thermal CVD or ALD at a deposition temperature of less than 485°C, or plasma-enhanced CVD or ALD. Claim 14 As a reagent for deoxygenating a metal oxyhalogenate precursor or an intermediate film deposited by said metal oxyhalogenate precursor to form a metal or metal nitride film in a vapor deposition process, said metal oxyhalogenate precursor is of the general formula M (a) X c O e having, 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 in the range of 3 to 6; c is a number such that 0 < c < 6; e is a number such that 0 < e < 3; c + 2e = a; and the above reagent has the general chemical formula: N (b) X d O f A reagent comprising an oxygenophilic reagent having, wherein N is a transition metal or an element of Group 14 or 15; X is a halogen selected from Cl, Br, or I; b is an oxidation state of N, and b is an integer in the range of 3 to 6; d is a number of 0 ≤ d ≤ 6; f is a number of 0 ≤ f < 3; d + 2f = b; the oxygenophilicity of N of the oxygenophilic reagent is greater than the oxygenophilicity of M of the metal oxyhalide precursor; and the oxygenation product of the oxygenophilic reagent and the oxygenation product of the oxygenophilic reagent are volatile. Claim 15 delete

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