Precursors and related methods

Abstract

To form silicon-containing films, we provide a silicon precursor that can exhibit at least one of the following: high growth / cycle (GPC), high thermal stability, or any combination thereof. [Solution] A precursor is provided that includes a precursor for gas-phase deposition. The precursor comprises an aliphatic hydrocarbon and at least one disilylamine group. At least one disilylamine group is bonded to the aliphatic hydrocarbon. At least one disilylamine group does not contain a silanide group. Some embodiments relate to a method for preparing the precursor. This method involves reacting a polyamine compound and a silyl halide compound in the presence of a base to form a precursor useful for gas-phase deposition. Some embodiments relate to a method for forming a silicon-containing film using the precursor.

Description

[Technical Field]

[0001] Priority This disclosure claims priority to U.S. Provisional Patent Application No. 63 / 291,119, filed on 17 December 2021, which is incorporated herein by reference.

[0002] This disclosure relates, in general terms, to precursors and related methods for gas-phase deposition. [Background technology]

[0003] In the manufacturing process of semiconductor devices, silicon source reagents are used in the vapor deposition process for forming silicon films. One example of a silicon source reagent is tetraethyl orthosilicate (TEOS). To form a silicon film from TEOS, TEOS is vaporized and deposited onto a substrate. [Overview of the Initiative]

[0004] Some embodiments relate to precursors. In some embodiments, the precursor comprises an aliphatic hydrocarbon and at least one disilylamine group. In some embodiments, the at least one disilylamine group is bonded to the aliphatic hydrocarbon. In some embodiments, the at least one disilylamine group does not contain a silanide group.

[0005] In some embodiments, aliphatic hydrocarbons are C1-C 10 Contains alkanes.

[0006] In some embodiments, aliphatic hydrocarbons are straight-chain C1-C1 10 Contains alkanes.

[0007] In some embodiments, aliphatic hydrocarbons are branched C1-C 10 Contains alkanes.

[0008] In some embodiments, at least one disilylamine group has the following chemical formula: TIFF2026067856000002.tif54170[wherein, R 1 、R 2 and R 3 are each independently hydrogen, C1 - C 10 linear alkyl, C3 - C 10 branched alkyl, C3 - C8 cycloalkyl, aryl, or benzyl] has.

[0009] In some embodiments, the precursor further comprises at least one silylamine group bonded to an aliphatic hydrocarbon.

[0010] In some embodiments, the at least one silylamine group has the following chemical formula: TIFF2026067856000003.tif39170[wherein, R 1 、R 2 and R 3 are each independently hydrogen, C1 - C 10 linear alkyl, C3 - C 10 branched alkyl, C3 - C8 cycloalkyl, aryl, or benzyl] has.

[0011] In some embodiments, the precursor has the following formula: TIFF2026067856000004.tif125170[wherein, n is from 0 to 10; R 1 、R 2 and R 3 are each independently hydrogen, C1 - C 10 linear alkyl, C3 - C 10 branched alkyl, C3 - C8 cycloalkyl, aryl, or benzyl] is a compound of.

[0012] In some embodiments, the precursor is a reaction product of a polyamine compound and a silyl halide compound.

[0013] In some embodiments, the precursor is a compound of the following formula. TIFF2026067856000005.tif109170

[0014] In some embodiments, the precursor is liquid at room temperature.

[0015] Some embodiments relate to methods for forming silicon-containing films. In some embodiments, the method for forming a silicon-containing film includes one or more of the following steps: obtaining a precursor comprising an aliphatic hydrocarbon and at least one disilylamine group, wherein at least one disilylamine group is bonded to an aliphatic hydrocarbon and at least one disilylamine group does not contain a silanide group; vaporizing the precursor to obtain a vaporized precursor; and contacting the vaporized precursor with a substrate under gas-phase deposition conditions to form a silicon-containing film on the substrate.

[0016] In some embodiments, the gas phase deposition conditions include atomic layer deposition conditions.

[0017] In some embodiments, the vapor phase deposition conditions include plasma-enhanced atomic layer deposition conditions.

[0018] In some embodiments, the gas phase deposition conditions include thermal atomic layer deposition conditions.

[0019] In some embodiments, the silicon-containing film comprises at least one of SiO, SiN, SiOC, SiCN, SiCN, or any combination thereof.

[0020] In some embodiments, the precursor is given by the following formula: TIFF2026067856000006.tif55170[In the formula, n is between 0 and 10; R 1 , R 2 and R 3 These are, independently, hydrogen, C1~C 10 Linear alkyl, C3~C 10 [Containing branched alkyl, C3-C8 cycloalkyl, aryl, or benzyl elements] It is a compound of [the compound].

[0021] In some embodiments, the precursor is given by the following formula: TIFF2026067856000007.tif55170[In the formula, n is between 0 and 10; R 1 , R 2 and R 3 These are, independently, hydrogen, C1~C 10 Linear alkyl, C3~C 10 [Containing branched alkyl, C3-C8 cycloalkyl, aryl, or benzyl elements] It is a compound of [the compound].

[0022] In some embodiments, the precursor is a compound of the following formula. TIFF2026067856000008.tif113170

[0023] Some embodiments relate to methods for producing precursors. In some embodiments, the method for producing a precursor comprises one or more of the following steps: reacting a polyamine compound with a silyl halogenated compound in the presence of a base to form a precursor comprising an aliphatic hydrocarbon and at least one disilylamine group, wherein at least one disilylamine group is bonded to the aliphatic hydrocarbon and at least one disilylamine group does not contain a silanide group.

[0024] Refer to the drawings which constitute part of this disclosure and illustrate embodiments in which the materials and methods described herein may be carried out. [Brief explanation of the drawing]

[0025] [Figure 1] This is a flowchart of a method for producing a precursor according to some embodiments. [Figure 2] This is a flowchart of a method for producing a silicon-containing film according to some embodiments. [Figure 3]This figure shows a proton nuclear magnetic resonance (1H NMR) spectrum from one embodiment. [Modes for carrying out the invention]

[0026] definition As used herein, the term “aliphatic hydrocarbon” refers to a monovalent or polyvalent aliphatic hydrocarbon group. This term includes, for example, at least one of a monovalent alkyl group, a polyvalent alkyl group, a monovalent alkenyl group, a polyvalent alkenyl group, a monovalent alkynyl group, a polyvalent alkynyl group, or any combination thereof. The term “polyvalent” includes, for example, at least one of other polyvalent groups, such as a divalent group, a trivalent group, a tetravalent group, or any combination thereof. Non-limiting examples of aliphatic hydrocarbons include at least one of a monovalent alkyl group, a divalent alkyl group, a trivalent alkyl group, or a tetravalent alkyl group. In some embodiments, the aliphatic hydrocarbon does not contain heteroatoms. In some embodiments, the aliphatic hydrocarbon does not contain cyclic compounds such as cycloalkanes, for example, but not limited to cycloalkanes.

[0027] As used herein, the term "alkyl" refers to a monovalent or polyvalent hydrocarbon chain group having 1 to 30 carbon atoms. An alkyl group having n carbon atoms is called "C n It may be specified as "alkyl". For example, "C3 alkyl" may include n-propyl and isopropyl. For example, alkyls having a range of carbon atoms such as 1 to 30 carbon atoms are C1 to C 30 It may be specified as alkyl. In some embodiments, alkyl is linear. In some embodiments, alkyl is branched. In some embodiments, alkyl is substituted. In some embodiments, alkyl is unsubstituted. In some embodiments, alkyl is C1-C 10 Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C2-C 10 Alkyl, C3~C 10Alkyl, C4~C 10 Alkyl, C5~C 10 Alkyl, C6~C 10 Alkyl, C7~C 10 Alkyl, C8~C 10 The alkyl group comprises, consists of, is essentially composed of, or is selected from the group comprising at least one of alkyl, C2-C9 alkyl, C2-C8 alkyl, C2-C7 alkyl, C2-C6 alkyl, C2-C5 alkyl, C3-C5 alkyl, or any combination thereof. In some embodiments, the alkyl group comprises, consists of, is essentially composed of, or is selected from the group comprising at least one of methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, isobutyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, isopentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof.

[0028] As used herein, the term “cycloalkyl” refers to a non-aromatic carbocyclic group having 3 to 8 carbon atoms in the ring, linked by a single bond. This term includes monocyclic and polycyclic non-aromatic carbocyclic groups. For example, to obtain a polycyclic non-aromatic carbocyclic group, two or more cycloalkyls may be condensed, crosslinked, or condensed and crosslinked. In some embodiments, the cycloalkyl comprises, consists of, essentially consists of, or is comprised of, at least one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or any combination thereof.

[0029] As used herein, the term "aryl" refers to an aromatic ring containing carbon and hydrogen atoms. Examples of aryls include, but are not limited to, phenyl, biphenyl, and naphthyl.

[0030] As used herein, the terms “growth per cycle” or “GPC” refer to the increment in film thickness per cycle of deposition.

[0031] As used herein, the term “silicon-containing film” refers to a film comprising at least one of silicon, silicon nitride, silicon oxynitride, silicon oxide, silicon dioxide, silicon carbide, silicon carbonitride, silicon oxynitride, carbon-doped silicon nitride, carbon-doped silicon oxide, carbon-doped silicon oxynitride, or any combination thereof. For example, a silicon-containing film may comprise at least one of an SiO film, a SiN film, an SiOC film, a SiCN film, an SiOCN film, or any combination thereof. In some embodiments, the silicon-containing film has a thickness of 20 Å to 2000 Å.

[0032] Consideration Some embodiments relate to precursors and related methods. At least some of these embodiments relate to precursors useful for the manufacture of microelectronic devices, including semiconductor devices. For example, precursors can be used to form silicon-containing films by one or more deposition methods. Examples of deposition methods, but are not limited to, chemical vapor deposition (CVD) processes, digital or pulsed chemical vapor deposition processes, plasma-enhanced periodic chemical vapor deposition (PECCVD), fluid chemical vapor deposition (FCVD), atomic layer deposition (ALD) processes, thermal atomic layer deposition, plasma-enhanced atomic layer deposition (PEALD) processes, metal-organic chemical vapor deposition (MOCVD) processes, plasma-enhanced chemical vapor deposition (PECVD) processes, or any combination thereof.

[0033] In some embodiments, for example, silicon precursors are provided. Silicon precursors can exhibit many advantages over conventional silicon precursors. For example, precursors can exhibit at least one of high growth / cycle (GPC), high thermal stability, or any combination thereof. At least one advantage of precursors is that high GPC in deposition processes such as atomic layer deposition increases with increasing number of silyl groups bonded to the nitrogen of the amine. At least another advantage is that the strength of the silicon-nitrogen bond of the silylamine and / or disilylamine groups confers high thermal stability to the silicon precursor, while the amine groups increase the reactivity of silicon. Furthermore, precursors can be provided in liquid form (e.g., as liquid silicon precursors). These advantages are not limiting, as numerous other advantages are described herein or otherwise evident from this disclosure.

[0034] The precursor comprises, consists of, or essentially comprises an aliphatic hydrocarbon, at least one silylamine group, at least one disilylamine group, or any combination thereof. In some embodiments, the precursor comprises, consists of, or essentially comprises an aliphatic hydrocarbon bonded to at least one disilylamine group. The number of disilylamine groups bonded to the aliphatic hydrocarbon is not particularly limited. For example, 1 to 20 disilylamine groups may be bonded to the aliphatic hydrocarbon. In some embodiments, the aliphatic hydrocarbon has at least one silylamine group bonded to it, or more. The number of silylamine groups bonded to the aliphatic hydrocarbon is not particularly limited. For example, 1 to 20 silylamine groups may be bonded to the aliphatic hydrocarbon, or more. In some embodiments, at least one silylamine group and / or at least one disilylamine group are terminal groups in which a nitrogen atom is bonded to the terminal carbon atom of the aliphatic hydrocarbon.

[0035] In some embodiments, the disilylamine group has the following chemical formula: TIFF2026067856000009.tif55170[where, R 1 , R 2 and R 3 Each of them independently consists of hydrogen, C1~C 10 Linear alkyl, C3~C 10 [Includes branched alkyl, C3-C8 cycloalkyl, aryl, benzyl, or any combination thereof] It is represented as follows.

[0036] In some embodiments, the silylamine group has the following chemical formula: TIFF2026067856000010.tif39170[where, R 1 , R 2 and R 3 Each of them independently consists of hydrogen, C1~C 10 Linear alkyl, C3~C 10 [Includes branched alkyl, C3-C8 cycloalkyl, aryl, benzyl, or any combination thereof] It is represented as follows.

[0037] In some embodiments, the precursor is given by the following formula TIFF2026067856000011.tif125170[In the formula, n is between 0 and 10; R 1 , R 2 and R 3 Each of them independently consists of hydrogen, C1~C 10 Linear alkyl, C3~C 10 [Includes branched alkyl, C3-C8 cycloalkyl, aryl, benzyl, or any combination thereof] It contains, consists of, or is essentially composed of the compounds of.

[0038] In some embodiments, the precursor is a reaction product of an amine compound and a silyl halogenated compound.

[0039] In some embodiments, the amine compound is a primary amine, a secondary amine, or a tertiary amine. In some embodiments, the amine compound is at least one of diamines, triamines, tetraamines, pentaamines, or any combination thereof. In some embodiments, the amine compound is a polyamine compound. In some embodiments, the polyamine compound includes, consists of, essentially consists of, or is selected from the group including at least one of ethylenediamine, propylenediamine, trimethylenediamine, triethylenediamine, methylpentanediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,2,3-triaminopropane, hydrazine, tetra(aminomethyl)methane, or any combination thereof. In some embodiments, the polyamine compound comprises, consists of, is essentially derived from, or is selected from the group comprising N-methylethylenediamine, N,N-dimethylethylenediamine, trimethylethylenediamine, N-ethylethylenediamine, N,N-diethylethylenediamine, triethylethylenediamine, or any combination thereof. In some embodiments, the polyamine compound comprises, consists of, is essentially derived from, or is selected from the group comprising tris(2-aminoethyl)amine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, heptaethyleneoctamine, nonaethylenedecamine, N′,N′-bis(2-aminoethyl)ethane-1,2-diamine, or any combination thereof.In some embodiments, the polyamine compound includes at least one of the following: 1,2-ethanediamine; 1,2-propanediamine; 1,3-propanediamine; 1,4-butanediamine; 1,6-hexanediamine; 2-methyl-1,5-pentanediamine; 2,2(4),4-trimethylhexanediamine; 2,2,4-trimethyl-1,6-hexanediamine; 2,4,4-trimethyl-1,6-hexanediamine; or any combination thereof.

[0040] In some embodiments, the silyl halogenated compound is given by the following formula: TIFF2026067856000012.tif34170[In the formula, X is a halogen (e.g., F, Cl, Br, or I); R 1 , R 2 and R 3 Each of them independently consists of hydrogen, C1~C 10 Linear alkyl, C3~C 10 [Containing branched alkyl, C3-C8 cycloalkyl, aryl, or benzyl elements] It is a compound of [the compound].

[0041] In some embodiments, the silyl halogenated compound comprises, consists of, is essentially derived from, or is selected from the group comprising dialkylsilyl halogenated compounds, trialkylsilyl halogenated compounds, monoalkyldiarylsilyl halogenated compounds, triarylsilyl halogenated compounds, or any combination thereof. In some embodiments, the silyl halogenated compound comprises, consists of, is essentially derived from, or is selected from the group comprising dichlorosilane, trichlorosilane, triethylsilyl chloride, tert-butyldimethylsilyl chloride, trimethylsilane, trimethylchlorosilane, tetramethylsilyl chloride, triphenylsilyl chloride, tert-butyldiphenylsilyl chloride, or any combination thereof.

[0042] In some embodiments, the precursor is at least one compound of the following formula. TIFF2026067856000013.tif101170

[0043] The precursor can have a purity level of 95% or higher. For example, in some embodiments, the precursor has a purity level of 95%-100%, 96%-100%, 97%-100%, 98%-100%, 99%-100%, 99.9%-100%, 99.99%-100%, 99.999%-100%, or 99.9999%-100%.

[0044] Figure 1 is a flowchart of a method for preparing a precursor according to some embodiments. As shown in Figure 1, the method for preparing a precursor may include, consist of, or essentially consist of, one or more of the following steps: step 102 for obtaining an amine compound, step 104 for obtaining a silyl halide compound, and step 106 for reacting the amine compound with the silyl halide compound to obtain a precursor. In some embodiments, the reaction proceeds by contacting the amine compound with the silyl halide compound in the presence of a base. In some embodiments, the reaction proceeds by contacting the amine compound with the silyl halide compound in a solvent containing a base.

[0045] The amine compound may include, consist of, or be essentially composed of, compounds containing one or more amine groups. In some embodiments, the amine compound may contain multiple amine groups. For example, the amine compound may be a polyamine compound. In some embodiments, the polyamine compound may include, consist of, or be essentially composed of, or be composed of, ethylenediamine, propylenediamine, trimethylenediamine, triethylenediamine, methylpentanediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,2,3-triaminopropane, hydrazine, tetra(aminomethyl)methane, or any combination thereof. In some embodiments, the polyamine compound comprises, consists of, is essentially derived from, or is selected from the group comprising at least one of N-methylethylenediamine, N,N-dimethylethylenediamine, trimethylethylenediamine, N-ethylethylenediamine, N,N-diethylethylenediamine, triethylethylenediamine, or any combination thereof. In some embodiments, the polyamine compound comprises, consists of, is essentially derived from, or is selected from the group comprising at least one of tris(2-aminoethyl)amine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, heptaethyleneoctamine, nonaethylenedecamine, N′,N′-bis(2-aminoethyl)ethane-1,2-diamine, or any combination thereof. In some embodiments, the polyamine compound includes at least one of 1,2-ethanediamine; 1,2-propanediamine; 1,3-propanediamine; 1,4-butanediamine; 1,6-hexanediamine; 2-methyl-1,5-pentanediamine; 2,2(4),4-trimethylhexanediamine; 2,2,4-trimethyl-1,6-hexanediamine; 2,4,4-trimethyl-1,6-hexanediamine; or any combination thereof.

[0046] Silyl halogenated compounds are, formula: TIFF2026067856000014.tif34170[In the formula, X is a halogen (e.g., F, Cl, Br, or I); R 1 , R 2 and R 3 Each of them independently consists of hydrogen, C1~C 10 Linear alkyl, C3~C 10 [Containing branched alkyl, C3-C8 cycloalkyl, aryl, or benzyl elements] It may contain, consist of, or essentially consist of the following compounds.

[0047] In some embodiments, the silyl halogenated compound comprises, consists of, is essentially derived from, or is selected from the group comprising dialkylsilyl halogenated compounds, trialkylsilyl halogenated compounds, monoalkyldiarylsilyl halogenated compounds, triarylsilyl halogenated compounds, or any combination thereof. In some embodiments, the silyl halogenated compound comprises, consists of, is essentially derived from, or is selected from the group comprising dichlorosilane, trichlorosilane, triethylsilyl chloride, tert-butyldimethylsilyl chloride, trimethylsilane, trimethylchlorosilane, tetramethylsilyl chloride, triphenylsilyl chloride, tert-butyldiphenylsilyl chloride, or any combination thereof.

[0048] The base may include compounds that can deprotonate the amine in an amine compound and substitute the halogen in a silyl halide compound. For example, the base may contain, consist of, or essentially consist of non-nucleophilic organic amines. In some embodiments, the base includes, consists of, essentially consists of, or is made from, at least one of the following: trimethylamine; triethylamine; diisopropylethylamine; pyrrolidine; tetramethylguanidine; 1,4-diazabicyclo[2.2.2]octane (DABCO); 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) (CAS No. 3001-72-7); 4-dimethylaminopyridine (DMAP) (CAS No. 1122-58-3); 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD) (CAS No. 5807-14-7); 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU), (CAS No. 6674-22-2) or any combination thereof.

[0049] The solvent may include polar aprotic solvents that do not participate in the reaction or do not otherwise interfere with it. The solvent may include, consist of, or essentially consist of at least one of tetrahydrofuran (THF), diethyl ether (Et2O), toluene, dichloromethane (CH2Cl2), n-hexane, ethyl acetate (RINKAN), or any combination thereof.

[0050] In some embodiments, the silicon precursor is reacted in the following way: TIFF2026067856000015.tif31170[In the formula, n is between 0 and 10. R 1 , R 2 and R 3 Each of them independently consists of hydrogen, C1~C 10 Linear alkyl, C3~C 10 Containing branched alkyl, C3-C8 cycloalkyl, aryl, or benzyl, X is F, Cl, Br, or I. The bases include at least one of the following: trimethylamine; triethylamine; diisopropylethylamine; pyrrolidine; tetramethylguanidine; 1,4-diazabicyclo[2.2.2]octane (DABCO); 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) (CAS No. 3001-72-7); 4-dimethylaminopyridine (DMAP) (CAS No. 1122-58-3); 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD) (CAS No. 5807-14-7); 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU) (CAS No. 6674-22-2); or any combination thereof. The solvent comprises at least one of tetrahydrofuran (THF), diethyl ether (Et2O), toluene, dichloromethane (CH2Cl2), n-hexane, ethyl acetate (RINKAN), or any combination thereof. rt is room temperature (e.g., ambient temperature, e.g., a temperature of 20°C to 30°C (e.g., approximately 25°C)). It is prepared according to the following.

[0051] In some embodiments, the silicon precursor is reacted in the following way: TIFF2026067856000016.tif31170[In the formula, n is between 0 and 10; R 1 , R 2 and R 3 Each of them independently consists of hydrogen, C1~C 10 Linear alkyl, C3~C 10 Containing branched alkyl, C3-C8 cycloalkyl, aryl, or benzyl; X is F, Cl, Br, or I; The base includes at least one of the following: trimethylamine; triethylamine; diisopropylethylamine; pyrrolidine; tetramethylguanidine; 1,4-diazabicyclo[2.2.2]octane (DABCO); 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) (CAS No. 3001-72-7); 4-dimethylaminopyridine (DMAP) (CAS No. 1122-58-3); 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD) (CAS No. 5807-14-7); 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU) (CAS No. 6674-22-2); or any combination thereof. The solvent comprises at least one of tetrahydrofuran (THF), diethyl ether (Et2O), toluene, dichloromethane (CH2Cl2), n-hexane, ethyl acetate (RINKAN), or any combination thereof; rt is room temperature (e.g., ambient temperature, e.g., a temperature of 20°C to 30°C (e.g., approximately 25°C)). It is prepared according to the following.

[0052] Figure 2 is a flowchart of a method for producing a silicon-containing film according to some embodiments. As shown in Figure 2, the method for producing a silicon-containing film includes, consists of, or essentially consists of, one or more of the following steps: a step 202 for obtaining a precursor; a step 204 for obtaining at least one co-reactant precursor; a step 206 for volatilizing the precursor to obtain a vaporized precursor; a step 208 for volatilizing at least one co-reactant precursor to obtain at least one vaporized co-reactant precursor; and a step 210 for forming a silicon-containing film on a substrate by contacting at least one of the vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof, with the substrate under gas-phase deposition conditions.

[0053] Step 202 may include, consist of, or be essentially derived from, a precursor. The precursor may include, consist of, or be essentially derived from any one or more of the precursors disclosed herein. Obtaining may include obtaining a container or other vessel containing the precursor. In some embodiments, the precursor may be obtained in a container or other vessel in which the precursor is vaporized.

[0054] Step 204 may include, consist of, or be essentially derived from, at least one co-reactant precursor. In some embodiments, the at least one co-reactant precursor may consist of, consist of, or be essentially derived from, at least one of oxidizing gases, reducing gases, hydrocarbons, or any combination thereof. The at least one co-reactant precursor may be selected to obtain a particular silicon-containing film. In some embodiments, the at least one co-reactant precursor may consist of, consist of, or be essentially derived from, at least one of N2, H2, NH3, N2H4, CH3HNNH2, CH3HNNHCH3, NCH3H2, NCH3CH2H2, N(CH3)2H, N(CH3CH2)2H, N(CH3)3, N(CH3CH2)3, Si(CH3)2NH, pyrazoline, pyridine, ethylenediamine, their groups, or any combination thereof. In some embodiments, the at least one co-reactant precursor may consist of, be composed of, or be essentially composed of, at least one of H2, O2, O3, H2O, H2O2, NO, N2O, NO2, CO, CO2, carboxylic acids, alcohols, diols, their groups, or any combination thereof. In some embodiments, the at least one co-reactant precursor may consist of, be composed of, or be essentially composed of, at least one of methane, ethane, ethylene, acetylene, or any combination thereof. Obtaining may involve obtaining a container or other vessel containing the at least one co-reactant precursor. In some embodiments, the at least one co-reactant precursor may be obtained in a container or other vessel in which the at least one co-reactant precursor is vaporized. In some embodiments, the method further includes an inert gas, such as at least one of argon, helium, nitrogen, or any combination thereof.

[0055] Step 206 may include, consist of, or be essentially of, volatilizing the precursor to obtain a vaporized precursor. Volatilization may include, consist of, or be essentially of, heating the precursor sufficiently to obtain a vaporized precursor. In some embodiments, volatilization may include, consist of, or be essentially of, heating a container containing the precursor. In some embodiments, volatilization may include, consist of, or be essentially of, heating the precursor in a deposition chamber in which the gas-phase deposition process is carried out. In some embodiments, volatilization may include, consist of, or be essentially of, heating a conduit for delivering the precursor, the vaporized precursor, or any combination thereof to, for example, the deposition chamber. In some embodiments, volatilization may include, consist of, or be essentially of, activating a vapor delivery system containing the precursor. In some embodiments, volatilization may include, consist of, or be essentially of, heating the precursor to a temperature sufficient to vaporize it to obtain a vaporized precursor. In some embodiments, volatilization may involve, consist of, or be essentially of, heating the precursor, the vaporized precursor, or any combination thereof to a temperature below the decomposition temperature of at least one of them. In some embodiments, the precursor may be present in the gas phase, in which case step 206 is optional and not required. For example, the precursor may include, consist of, or be essentially of the vaporized precursor.

[0056] Step 208 may include, consist of, or be essentially of, volatilizing at least one co-reactant precursor to obtain at least one evaporated co-reactant precursor. In some embodiments, volatilization may include, consist of, or be essentially of, heating at least one co-reactant precursor to obtain at least one vaporized co-reactant precursor. In some embodiments, volatilization may include, consist of, or be essentially of, heating a container containing at least one co-reactant precursor. In some embodiments, volatilization may include, consist of, or be essentially of, heating at least one co-reactant precursor in a deposition chamber in which the gas-phase deposition process is carried out. In some embodiments, volatilization may include, consist of, or be essentially of, heating a conduit for delivering at least one co-reactant precursor, at least one vaporized co-reactant precursor, or any combination thereof to, for example, the deposition chamber. In some embodiments, volatilization may include, consist of, or be essentially of, operating a vapor delivery system containing at least one co-reactant precursor. In some embodiments, volatilization may include, consist of, or be essentially of, heating at least one co-reactant precursor to a temperature sufficient to vaporize it in order to obtain at least one vaporized co-reactant precursor. In some embodiments, volatilization may include, consist of, or be essentially of, heating at least one of the co-reactant precursors, at least one vaporized co-reactant precursor, or any combination thereof to a temperature below the decomposition temperature of at least one. In some embodiments, at least one co-reactant precursor may be present in the gas phase, in which case step 108 is optional and not required. For example, at least one co-reactant precursor may include, consist of, or be essentially of at least one vaporized co-reactant precursor.

[0057] Step 210 may include, consist of, or be essentially of, contacting the vaporized precursor and at least one vaporized co-reactant precursor with the substrate under vapor deposition conditions sufficient to form a silicon-containing film on the substrate surface. The contact may be carried out in any system, apparatus, device, assembly, chamber, or component thereof suitable for a vapor deposition process, including, but not limited to, a deposition chamber. The vaporized precursor and at least one co-reactant precursor may be contacted with the substrate simultaneously or at different times. For example, the vaporized precursor, at least one vaporized co-reactant precursor, and the substrate may each be present in the deposition chamber at the same time. That is, in some embodiments, the contact may include simultaneous or concurrent contact between the vaporized precursor and at least one vaporized co-reactant precursor and the substrate. Alternatively, the vaporized precursor and at least one vaporized co-reactant precursor may each be present in the deposition chamber at different times. In other words, in some embodiments, the contact may include alternating and / or sequential contacts in which a vaporized precursor is brought into contact with the substrate in one or more cycles, followed by contact with at least one vaporized co-reactant precursor.

[0058] The vapor deposition conditions may include, consist of, or be essentially of the deposition temperature. The deposition temperature may be below the thermal decomposition temperature of at least one of the vaporized precursors, at least one vaporized co-reactant precursor, or any combination thereof. The deposition temperature may be sufficiently high to reduce or avoid condensation of at least one of the vaporized precursors, at least one vaporized co-reactant precursor, or any combination thereof. In some embodiments, the substrate may be heated to the deposition temperature. In some embodiments, the chamber or other container into which the substrate is brought into contact with the vaporized precursors and at least one vaporized co-reactant precursor is heated to the deposition temperature. In some embodiments, at least one of the vaporized precursors, at least one vaporized co-reactant precursor, or any combination thereof may be heated to the deposition temperature.

[0059] The deposition temperature may be between 200°C and 2500°C. In some embodiments, the deposition temperature may be between 500°C and 700°C. For example, in some embodiments, the deposition temperature may be between 500°C and 680°C, 500°C and 660°C, 500°C and 640°C, 500°C and 620°C, 500°C and 600°C, 500°C and 580°C, 500°C and 560°C, 500°C and 540°C, 500°C and 520°C, 520°C and 700°C, 540°C and 700°C, 560°C and 700°C, 580°C and 700°C, 600°C and 700°C, 620°C and 700°C, 640°C and 700°C, 660°C and 700°C, or 680°C and 700°C. In other embodiments, the deposition temperature is, for example, not limited to, 400°C to 2000°C, 500°C to 2000°C, 550°C to 2400°C, 600°C to 2400°C, 625°C to 2400°C, 650°C to 2400°C, 675°C to 2400°C, 700°C to 2400°C, 725°C to 2400°C, 750°C to 2400°C, 775°C to 2400°C, and 800°C to 2400°C. 00℃, 825℃~2400℃, 850℃~2400℃, 875℃~2400℃, 900℃~2400℃, 925℃~2400℃, 950℃~2400℃, 975℃~2400℃, 1000℃~2400℃, 1025℃~2400℃, 1050℃~2400℃, 1075℃~2400℃, 1100℃~2400℃, 1200℃~2400℃, 13 00℃~2400℃, 1400℃~2400℃, 1500℃~2400℃, 1600℃~2400℃, 1700℃~2400℃, 1800℃~2400℃, 1900℃~2400℃, 2000℃~2400℃, 2100℃~2400℃, 2200℃~2400℃, 2300℃~2400℃, 500℃~2000℃, 500℃~1900℃, 500 Temperatures exceeding 200°C to 2500°C are also acceptable, such as ℃~1800°C, 500°C~1700°C, 500°C~1600°C, 500°C~1500°C, 500°C~1400°C, 500°C~1300°C, 500°C~1200°C, 500°C~1100°C, 500°C~1000°C, 500°C~1000°C, 500°C~900°C, or 500°C~800°C.

[0060] The gas phase deposition conditions may include, consist of, or be essentially derived from, the deposition pressure. In some embodiments, the deposition pressure may include, consist of, or be essentially derived from, the vapor pressure of at least one of the vaporized precursors, at least one vaporized co-reactant precursor, or any combination thereof. In some embodiments, the deposition pressure may include, consist of, or be essentially derived from, the chamber pressure.

[0061] The deposition pressure may be between 0.001 Torr and 100 Torr. For example, in some embodiments, the deposition pressure may be between 1 Torr and 30 Torr, 1 Torr and 25 Torr, 1 Torr and 20 Torr, 1 Torr and 15 Torr, 1 Torr and 10 Torr, 5 Torr and 50 Torr, 5 Torr and 40 Torr, 5 Torr and 30 Torr, 5 Torr and 20 Torr, or 5 Torr and 15 Torr. In other embodiments, the deposition pressure is 1 Torr~100 Torr, 5 Torr~100 Torr, 10 Torr~100 Torr, 15 Torr~100 Torr, 20 Torr~100 Torr, 25 Torr~100 Torr, 30 Torr~100 Torr, 35 Torr~100 Torr, 40 Torr~100 Torr, 45 Torr~100 Torr, 50 Torr~100 Torr, 55 Torr~100 Torr, 60 Torr~10 The pressure may be 0 Torr, 65 Torr to 100 Torr, 70 Torr to 100 Torr, 75 Torr to 100 Torr, 80 Torr to 100 Torr, 85 Torr to 100 Torr, 90 Torr to 100 Torr, 95 Torr to 100 Torr, 1 Torr to 95 Torr, 1 Torr to 90 Torr, 1 Torr to 85 Torr, 1 Torr to 80 Torr, 1 Torr to 75 Torr, or 1 Torr to 70 Torr. In other further embodiments, the deposition pressure may be a pressure of 1mTorr~100mTorr, 1mTorr~90mTorr, 1mTorr~80mTorr, 1mTorr~70mTorr, 1mTorr~60mTorr, 1mTorr~50mTorr, 1mTorr~40mTorr, 1mTorr~30mTorr, 1mTorr~20mTorr, 1mTorr~10mTorr, 100mTorr~300mTorr, 150mTorr~300mTorr, 200mTorr~300mTorr, or 150mTorr~250mTorr, or 150mTorr~225mTorr.

[0062] The substrate may contain, consist of, or be essentially composed of at least one of Si, Co, Cu, Al, W, WN, WC, TiN, Mo, MoC, SiO2, W, SiN, WCN, Al2O3, AlN, ZrO2, La2O3, TaN, RuO2, IrO2, Nb2O3, Y2O3, hafnium oxide, or any combination thereof. In some embodiments, the silicon-containing film may contain, consist of, or be essentially composed of at least one of silicon, silicon nitride, silicon oxynitride, silicon oxide, silicon dioxide, silicon carbide, silicon carbonitride, silicon oxycarbonitride, carbon-doped silicon nitride, carbon-doped silicon oxide, carbon-doped silicon oxynitride, or any combination thereof. In some embodiments, the substrate may include other silicon-based substrates, such as one or more of polysilicon substrates, metal substrates, and dielectric substrates.

[0063] Some embodiments relate to silicon-containing films on the surface of a substrate. In some embodiments, the silicon-containing film includes any film formed according to the methods disclosed herein. In some embodiments, the silicon-containing film includes any film prepared from precursors disclosed herein.

[0064] manner Various embodiments are described below. Please understand that one or more of the features described in the embodiments below can be combined with one or more other embodiments.

[0065] Embodiment 1. The precursor comprises an aliphatic hydrocarbon and at least one disilylamine group, wherein at least one disilylamine group is bonded to the aliphatic hydrocarbon and at least one disilylamine group does not contain a silanide group.

[0066] Apparatus 2. Aliphatic hydrocarbons are C1-C 10 A precursor according to embodiment 1, comprising an alkane.

[0067] Embodiment 3. Aliphatic hydrocarbons are straight-chain C1-C 10A precursor according to embodiments 1 to 2, comprising an alkane.

[0068] Appearance 4. Aliphatic hydrocarbons are branched C1-C 10 A precursor according to embodiments 1 to 3, comprising an alkane.

[0069] Embodiment 5. At least one disilylamine group having the following chemical formula: TIFF2026067856000017.tif54170[In the formula, R 1 , R 2 and R 3 Each of them independently consists of hydrogen, C1~C 10 Linear alkyl, C3~C 10 [Containing branched alkyl, C3-C8 cycloalkyl, aryl, or benzyl elements] A precursor according to embodiments 1 to 4, having the characteristics described herein.

[0070] Embodiment 6. The precursor according to Embodiments 1 to 5, further comprising at least one silylamine group bonded to an aliphatic hydrocarbon.

[0071] Embodiment 7. At least one silylamine group having the following chemical formula: TIFF2026067856000018.tif39170[In the formula, R 1 , R 2 and R 3 Each of them independently consists of hydrogen, C1~C 10 Linear alkyl, C3~C 10 [Containing branched alkyl, C3-C8 cycloalkyl, aryl, or benzyl elements] A precursor according to embodiments 1 to 6, having the characteristics described herein.

[0072] Apparatus 8. The precursor is given by the following formula: TIFF2026067856000019.tif125170[In the formula, n is between 0 and 10; R 1 , R 2 and R 3 Each of them independently consists of hydrogen, C1~C10 linear alkyl, C3-C 10 branched alkyl, C3-C8 cycloalkyl, aryl, or benzyl] The precursor according to any one of aspects 1 to 7, which is a compound of.

[0073] Aspect 9. The precursor according to any one of aspects 1 to 8, wherein the precursor is a reaction product of a polyamine compound and a silyl halide compound.

[0074] Aspect 10. The precursor according to any one of aspects 1 to 9, wherein the precursor is a compound of the following formula: TIFF2026067856000020.tif109170

[0075] Aspect 11. The precursor according to any one of aspects 1 to 10, wherein the precursor is liquid at room temperature.

[0076] Aspect 12. A method for forming a silicon-containing film, comprising obtaining a precursor comprising an aliphatic hydrocarbon and at least one disilylamine group, wherein at least one disilylamine group is bonded to the aliphatic hydrocarbon and at least one disilylamine group does not contain a silanide group; vaporizing the precursor to obtain a vaporized precursor; and contacting the vaporized precursor with a substrate under vapor deposition conditions to form a silicon-containing film on the substrate.

[0077] Aspect 13. The method according to aspect 12, wherein the vapor deposition conditions include atomic layer deposition conditions.

[0078] <00…​​​​​​​​​​​ Aspect 17. The precursor has the following formula: TIFF2026067856000021.tif55170[wherein, n is from 0 to 10; R 1 and R 2 and R 3 each independently is hydrogen, C1-C 10 linear alkyl, C3-C 10 branched alkyl, C3-C8 cycloalkyl, aryl, or benzyl] The method according to any one of Aspects 12 to 16, which is a compound of.

[0082] Aspect 18. The precursor has the following formula: TIFF2026067856000022.tif55170[wherein, n is from 0 to 10; R 1 and R 2 and R 3 each independently is hydrogen, C1-C 10 linear alkyl, C3-C 10 branched alkyl, C3-C8 cycloalkyl, aryl, or benzyl] The method according to any one of Aspects 12 to 17, which is a compound of.

[0083] Aspect 19. The precursor has the following formula: TIFF2026067856000023.tif113170 The method according to any one of Aspects 12 to the compound of 18.

[0084] Aspect 20. A method for preparing a precursor, comprising reacting a polyamine compound with a silyl halide compound in the presence of a base to form a precursor for vapor deposition comprising an aliphatic hydrocarbon and at least one disilylamine group, wherein at least one disilylamine group is bonded to the aliphatic hydrocarbon and at least one disilylamine group does not contain a silanide group.

Example

[0085] Silicon Precursor 1 To prepare silicon precursor 1 (above), triethylamine (TEA, 276.8 mL, 2.0 mol) and ethylenediamine (33.4 mL, 0.5 mol) were added to a flame-dried container filled with dichloromethane (1.5 L). Chlorodimethylsilane (CDMS, 217.7 mL, 2.0 mol) was then slowly added dropwise. The reaction mixture was refluxed at 50°C under an N2 atmosphere for 16 hours. A white precipitate formed as a result of the reaction, and the reaction was stopped by filtering with n-hexane through a Celite pad. The filtrate was concentrated at 50°C at 250 torr. The target product (118 g, yield 81%) was obtained as a colorless liquid by fractional distillation at 80°C at 1 torr. 1 H NMR (CDCl3): δ 4.44 - 4.41 (m, 4H), 2.73 (s, 4H), 0.16 (d, J = 0.1 Hz, 24H) ppm. See Figure 3.

Claims

1. A precursor comprising an aliphatic hydrocarbon and at least one disilylamine group, At least one disilylamine group is bonded to an aliphatic hydrocarbon, At least one disilylamine group does not contain a silanide group. Precursor.

2. Aliphatic hydrocarbons are C １ ~C １０ The precursor according to claim 1, comprising an alkane.

3. Aliphatic hydrocarbons are straight-chain carbon １ ~C １０ The precursor according to claim 1, comprising an alkane.

4. Aliphatic hydrocarbons are branched C １ ~C １０ The precursor according to claim 1, comprising an alkane.

5. At least one disilylamine group is in the following chemical formula: [In the formula, R １ , R ２ and R ３ are each independently hydrogen, C １ -C １０ linear alkyl, C ３ -C １０ branched alkyl, C ３ -C ８ cycloalkyl, aryl, or benzyl]. A precursor according to claim 1, having the following characteristics.

6. The precursor according to claim 1, further comprising at least one silylamine group bonded to an aliphatic hydrocarbon.

7. At least one silylamine group is in the following chemical formula: [In the formula, R １ , R ２ and R ３ Hydrogen and C are independent of each other. １ ~C １０ Linear alkyl, C ３ ~C １０ Branched alkyl, C ３ ~C ８ [Containing cycloalkyl, aryl, or benzyl compounds] A precursor according to claim 6, having the following characteristics.

8. The precursor is given by the following formula: [In the formula, n is between 0 and 10; R １ , R ２ and R ３ Hydrogen and C are independent of each other. １ ~C １０ Linear alkyl, C ３ ~C １０ Branched alkyl, C ３ ~C ８ [Containing cycloalkyl, aryl, or benzyl compounds] The precursor according to claim 1, which is a compound of the above.

9. The precursor according to claim 1, wherein the precursor is a reaction product of a polyamine compound and a silyl halogenated compound.

10. The precursor is given by the following formula The precursor according to claim 1, which is a compound of the above.

11. The precursor according to claim 1, wherein the precursor is a liquid at room temperature.

12. A method for forming a silicon-containing film, The objective is to obtain a precursor comprising an aliphatic hydrocarbon and at least one disilylamine group, At least one disilylamine group is bonded to an aliphatic hydrocarbon, At least one disilylamine group does not contain a silanide group. To obtain a precursor; The process involves vaporizing a precursor to obtain a vaporized precursor; The process involves bringing a vaporized precursor into contact with a substrate under gas-phase deposition conditions to form a silicon-containing film on the substrate, Methods that include...

13. The method according to claim 12, wherein the gas phase deposition conditions include atomic layer deposition conditions.

14. The method according to claim 12, wherein the gas phase deposition conditions include plasma-enhanced atomic layer deposition conditions.

15. The method according to claim 13, wherein the gas phase deposition conditions include thermal atomic layer deposition conditions.

16. The method according to claim 12, wherein the silicon-containing film comprises at least one of SiO, SiN, SiOC, SiCN, SiOCN, or any combination thereof.

17. The precursor is given by the following formula [In the formula, n is between 0 and 10; R １ , R ２ and R ３ Hydrogen and C are independent of each other. １ ~C １０ Linear alkyl, C ３ ~C １０ Branched alkyl, C ３ ~C ８ [Containing cycloalkyl, aryl, or benzyl compounds] The method according to claim 12, wherein the compound is [the compound].

18. The precursor is given by the following formula: [In the formula, n is between 0 and 10; R １ , R ２ and R ３ Hydrogen and C are independent of each other. １ ~C １０ Linear alkyl, C ３ ~C １０ Branched alkyl, C ３ ~C ８ [Containing cycloalkyl, aryl, or benzyl compounds] The method according to claim 12, wherein the compound is [the compound].

19. The precursor is given by the following formula: The method according to claim 12, wherein the compound is [the compound].

20. A method for producing a precursor, The process involves reacting a polyamine compound with a silyl halogenated compound in the presence of a base to form a precursor for gas-phase deposition containing an aliphatic hydrocarbon and at least one disilylamine group, At least one disilylamine group is bonded to an aliphatic hydrocarbon, At least one disilylamine group does not contain a silanide group. A method comprising forming a precursor.

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