Titanium Complex, Method for Producing the Same, and Method for Producing Titanium-Containing Thin Film

Abstract

The present invention provides a titanium complex useful for producing a titanium-containing film under low-temperature film-forming conditions without using an oxidizing gas. The above titanium complex is represented by the general formula (1) (wherein, R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms, and may optionally bond to each other to form a ring. X represents CR3 or an N atom. Y represents CR4 or an N atom. Z represents CR5 or an N atom. R3, R4 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 3.). #imgabs0#

Description

Technical Field

[0001] The present invention relates to a titanium complex useful as a raw material for manufacturing semiconductor elements, a method for manufacturing the same, and a method for manufacturing a titanium-containing film by using the titanium complex as a material. Background Art

[0002] In current semiconductor element manufacturing, methods for forming thin films for wiring barrier layers, capacitor dielectrics, and electrodes mainly utilize physical vapor deposition methods (PVD methods) based on sputtering. However, in semiconductor manufacturing after the next generation, it is required to form a uniform and thin film on the surface of a complex three-dimensional structure of miniaturized elements. Therefore, the PVD method, which is difficult to form a uniform film on a surface with unevenness, is inappropriate. Therefore, recently, research has been conducted on thin film formation methods based on chemical vapor deposition (CVD) methods in which a raw material gas is decomposed to deposit a film, or atomic layer deposition (ALD) methods in which a raw material adsorbed on the surface of a substrate is decomposed to deposit a film. In addition, in order to form a uniform thin film with excellent continuity, low-temperature film formation (200 °C) has become a necessary condition.

[0003] For manufacturing raw materials for forming thin films by CVD or ALD methods, raw materials having an appropriate vapor pressure and thermal stability and capable of being vaporized at a stable supply rate are selected. In addition, in order to be stably vaporized at a constant supply rate, a liquid is preferred.

[0004] As materials for capacitor electrodes, gate electrodes of transistors, and copper wiring barrier layers of semiconductor elements after the next generation, titanium, titanium nitride, and silicon-containing titanium nitride can be cited as candidates. If these titanium-containing films are oxidized, problems such as poor conduction with transistors due to an increase in resistance value will occur.

[0005] In Non-Patent Document 1, as compounds having a structure similar to the titanium complex represented by the general formula (1) of the present invention (hereinafter also referred to as titanium complex (1)) in terms of having a pyrazolate ligand, dimethylbis(3,5-di-tert-butylpyrazolate)titanium and isopropylimidebis(3,5-di-tert-butylpyrazolate)(pyridine)titanium are described, but they are different from the titanium complex of the present invention in terms of having an alkyl ligand and an imide ligand. Moreover, using these titanium complexes as raw materials for CVD and ALD methods is not described.

[0006] In Non-Patent Document 2, as compounds having a structure similar to the titanium complex (1) of the present invention in terms of having a pyrazolate ligand, trichloro(3,5-di-tert-butylpyrazolate)titanium and tetra(3,5-dimethylpyrazolate)titanium are described, but they are different from the titanium complex of the present invention in terms of having a chlorine ligand or having four pyrazolate ligands. In addition, using these titanium complexes as raw materials for CVD and ALD methods is not described.

[0007] In Non-Patent Document 3, although tris(3,5-di-tert-butylpyrazolato)(3,5-dimethyl-1,2,4-triazolato)titanium etc. are described, they are different from the titanium complex of the present invention in that they have four nitrogen-containing heterocyclic ligands. Further, there is no description of using these titanium complexes as raw materials for the CVD method or the ALD method.

[0008] Under the above circumstances, there is a desire to provide a material for producing a titanium-containing film under low-temperature film-forming conditions without using an oxidizing gas such as oxygen or ozone as a reaction gas.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Non-Patent Documents

[0012] Non-Patent Document 1: Organometallics, Vol. 18, p. 1168 (1999)

[0013] Non-Patent Document 2: Inorganic Chemistry, Vol. 38, p. 1871 (1999)

[0014] Non-Patent Document 3: Inorganic Chemistry, Vol. 40, p. 6451 (2001) Summary of the Invention

[0015] Problems to be Solved by the Invention

[0016] An object of the present invention is to provide a titanium complex useful for producing a titanium-containing film under low-temperature film-forming conditions without using an oxidizing gas.

[0017] Means for Solving the Problems

[0018] The present inventors conducted intensive studies to solve the above problems, and as a result, found that a titanium complex represented by the general formula (1) is useful as a material for producing a titanium-containing film under low-temperature film-forming conditions without using an oxidizing gas, particularly under low-temperature film-forming conditions using a reducing gas, thereby completing the present invention.

[0019] That is, the present invention includes the following embodiments.

[0020] [1] A titanium complex represented by the general formula (1),

[0021] [Chemical Formula 1]

[0022]

[0023] In the formula, R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms, optionally bonding to each other to form a ring, X represents CR3 or an N atom, Y represents CR4 or an N atom, Z represents CR5 or an N atom, R3, R4 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3.

[0024] [2] The titanium complex according to [1] above, wherein

[0025] R1 and R2 are each independently an alkyl group having 1 to 4 carbon atoms, R3, R4 and R5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is 2 or 3.

[0026] [3] The titanium complex according to [1] or [2] above, wherein

[0027] R1 and R2 are each independently methyl or ethyl, R3, R4 and R5 are each independently a hydrogen atom or methyl, and n is 3.

[0028] [4] A method for producing the titanium complex according to any one of [1] to [3] above, the method comprising:

[0029] reacting an amide complex represented by the general formula (2) with an unsaturated cyclic amine represented by the general formula (3),

[0030] [Chemical formula 2]

[0031]

[0032] In formula (2), R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms, optionally bonding to each other to form a ring,

[0033] [Chemical formula 3]

[0034]

[0035] In formula (3), X represents CR3 or an N atom, Y represents CR4 or an N atom, Z represents CR5 or an N atom, and R3, R4 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0036] [5] A method for producing a titanium-containing film, the method comprising:

[0037] using the titanium complex represented by the general formula (1) in a chemical vapor deposition method,

[0038] [Chemical formula 4]

[0039]

[0040] In the formula, R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms, optionally bonding to each other to form a ring, X represents CR3 or an N atom, Y represents CR4 or an N atom, Z represents CR5 or an N atom, R3, R4 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3.

[0041] [6] The method for manufacturing a titanium-containing film according to [5] above, wherein

[0042] The vapor deposition method based on a chemical reaction is a chemical vapor deposition method.

[0043] [7] The method for manufacturing a titanium-containing film according to [5] or [6] above, wherein

[0044] A reaction gas is used in the vapor deposition method based on a chemical reaction.

[0045] [8] The method for manufacturing a titanium-containing film according to [7] above, wherein

[0046] A reducing gas is used as the reaction gas.

[0047] [9] The method for manufacturing a titanium-containing film according to any one of [5] to [8] above, wherein

[0048] The titanium-containing film is a titanium nitride film.

[0049] Effects of the Invention

[0050] By using the titanium complex (1) of the present invention as a material, a titanium-containing film can be manufactured under low-temperature film formation conditions without using an oxidizing gas. Description of the Drawings

[0051] Figure 1 It is a chart of DSC of tris(dimethylamide)(3,5-dimethylpyrazolato)titanium(1-8) in Evaluation Example 1.

[0052] Figure 2 It is a chart of DSC of tris(ethylmethylamide)(3-methylpyrazolato)titanium(1-20) in Evaluation Example 2.

[0053] Figure 3 It is a chart of DSC of tetrakis(dimethylamide)titanium in Comparative Example 1.

[0054] Figure 4 It is a chart of DSC of tetrakis(ethylmethylamide)titanium in Comparative Example 2.

[0055] Figure 5 It is a chart of DSC of tetrakis(diethylamide)titanium in Comparative Example 3.

[0056] Figure 6 This is a diagram showing the outline of the CVD apparatus used in Example 14 and Comparative Example 4.

[0057] Symbol Explanation

[0058] 1 Material container

[0059] 2 Constant temperature bath

[0060] 3 Reaction chamber

[0061] 4 Substrate

[0062] 5 Reaction gas inlet

[0063] 6 Diluent gas inlet

[0064] 7 Carrier gas inlet

[0065] 8 Mass flow controller

[0066] 9 Mass flow controller

[0067] 10 Mass flow controller

[0068] 11 Oil rotary pump

[0069] 12 Exhaust Detailed Description of the Invention

[0070] Hereinafter, the present invention will be described in more detail. First, considering that the titanium complex (1) of the present invention has a vapor pressure and thermal stability that are preferable as raw materials for forming a thin film by CVD method or ALD method (hereinafter, these will also be referred to as CVD materials or ALD materials), X, Y, and Z in the general formula (1) are preferably CR3, CR4, and CR5, respectively.

[0071] Next, the definitions of R1, R2, R3, R4 and R5 in the general formula (1) will be described. The alkyl group having 1 to 6 carbon atoms represented by R1, R2, R3, R4 and R5 can be any of linear, branched or cyclic alkyl groups. Specific examples include: methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclobutylmethyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, cyclohexyl, cyclopentylmethyl, 1-cyclobutylethyl, 2-cyclobutylethyl, etc. The group formed by the bonding of the alkyl groups having 1 to 6 carbon atoms of R1 and R2 to each other to form a ring can be any group in linear or branched form. Examples include: 1,2-ethylene, 1-methyl-1,2-ethylene, 1,1-dimethyl-1,2-ethylene, 1,2-dimethyl-1,2-ethylene, 1,3-trimethylene, 1-methyl-1,3-trimethylene, 2-methyl-1,3-trimethylene, 1,1-dimethyl-1,3-trimethylene, 1,2-dimethyl-1,3-trimethylene, 1,3-dimethyl-1,3-trimethylene, 2,2-dimethyl-1,3-trimethylene, 1,4-tetramethylene, 1-methyl-1,4-tetramethylene, 2-methyl-1,4-tetramethylene, 1,5-pentamethylene, 1-methyl-1,5-pentamethylene, 2-methyl-1,5-pentamethylene, 3-methyl-1,5-pentamethylene, 1,6-hexamethylene, 1-methyl-1,6-hexamethylene, 2-methyl-1,6-hexamethylene, 3-methyl-1,6-hexamethylene, etc. From the aspect that the titanium complex (1) of the present invention has a vapor pressure and thermal stability preferable as a CVD material and an ALD material, R1 and R2 are each independently preferably an alkyl group having 1 to 4 carbon atoms, more preferably methyl or ethyl. In addition, from the aspect that the titanium complex (1) of the present invention has a vapor pressure and thermal stability preferable as a CVD material and an ALD material, R3, R4 and R5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or methyl.

[0072] Next, the definition of n in the general formula (1) will be described. n represents an integer of 1 to 3. From the aspect that the titanium complex (1) of the present invention has a vapor pressure and thermal stability preferable as a CVD material and an ALD material, n is preferably 2 or 3, more preferably 3.

[0073] It should be noted that the pyrazole ligand in the titanium complex (1) of the present invention is as shown below and can be η 1-coordination and η 2 -coordination, but in this specification, it is represented by η 2 -coordination.

[0074] [Chemical Formula 5]

[0075]

[0076] (In the formula, R1, R2, X, Y, Z and n have the same meanings as described above.)

[0077] As specific examples of the titanium complex (1) of the present invention, the following titanium complexes etc. can be cited.

[0078] [Chemical Formula 6]

[0079]

[0080] [Chemical Formula 7]

[0081]

[0082] [Chemical Formula 8]

[0083]

[0084] [Chemical Formula 9]

[0085]

[0086] Among them, from the aspect of having a vapor pressure and thermal stability preferably as a CVD material and an ALD material, the titanium complexes represented by (1-1), (1-2), (1-6) to (1-8), (1-10), (1-19), (1-20), (1-24) to (1-26), (1-28), (1-37), (1-38), (1-42) to (1-44), (1-46), (1-55), (1-56), (1-60) to (1-62), (1-64), (1-66), (1-67), (1-71) to (1-73), (1-75), (1-77), (1-80), (1-88) are preferred, and the titanium complexes represented by (1-1), (1-2), (1-6), (1-8), (1-19), (1-20), (1-24), (1-26), (1-37), (1-38), (1-42), (1-44) are more preferred.

[0087] Next, the manufacturing method of the titanium complex (1) of the present invention will be described.

[0088] The titanium complex (1) can be manufactured by the following manufacturing method 1.

[0089] Production method 1 of the present invention is a production method of a titanium complex (1) in which the amide complex represented by the above general formula (2) (hereinafter also referred to as amide complex (2)) reacts with an unsaturated cyclic amine represented by the general formula (3) (hereinafter also referred to as unsaturated cyclic amine (3)).

[0090] Production method 1

[0091] [Chemical formula 10]

[0092]

[0093] (In the formula, R1, R2, X, Y, Z and n have the same meanings as above.)

[0094] Examples of the amide complex (2) that can be used in Production method 1 of the present invention include the following amide complexes and the like.

[0095] [Chemical formula 11]

[0096]

[0097] From the aspect of good yield of the titanium complex (1) of the present invention, amide complexes represented by (2-1), (2-2), (2-7), (2-14) or (2-15) are preferred, and amide complexes represented by (2-1), (2-2) or (2-7) are more preferred.

[0098] The amide complex (2) that can be used in Production method 1 of the present invention can be obtained by purchasing commercially available products or by the methods described in European Polymer journal, Volume 7, page 289 (1971), Organometallics, Volume 24, page 5383 (2005), Journal of the Chemical Society, page 3857 (1960), etc.

[0099] Examples of the unsaturated cyclic amine (3) that can be used in Production method 1 of the present invention include the following unsaturated cyclic amines and the like.

[0100] [Chemical formula 12]

[0101]

[0102] From the aspect of good yield of the titanium complex (1) of the present invention, unsaturated cyclic amines represented by (3-1), (3-2), (3-7) to (3-9), (3-12) are preferred, and unsaturated cyclic amines represented by (3-1), (3-2), (3-7), (3-9) are more preferred.

[0103] As a method for obtaining the unsaturated cyclic amine (3) that can be used in the production method 1 of the present invention, it can be obtained by purchasing commercially available products or by the methods described in CN106316956A, Bulletin of the Chemical Society of Japan, Vol. 64, p. 719 (1991), etc.

[0104] The molar ratio of the amide complex (2) and the unsaturated cyclic amine (3) in the implementation of the production method 1 of the present invention will be described. When n in the formula (1) is 1, from the aspect of good yield of the titanium complex (1) of the present invention, relative to 1 molar equivalent of the amide complex (2), the unsaturated cyclic amine (3) is preferably 2.5 to 3.5 molar equivalents, more preferably 2.9 to 3.1 molar equivalents. When n in the formula (1) is 2, from the aspect of good yield of the titanium complex (1) of the present invention, relative to 1 molar equivalent of the amide complex (2), the unsaturated cyclic amine (3) is preferably 1.5 to 2.5 molar equivalents, more preferably 1.9 to 2.1 molar equivalents. When n in the formula (1) is 3, from the aspect of good yield of the titanium complex (1) of the present invention, relative to 1 molar equivalent of the amide complex (2), the unsaturated cyclic amine (3) is preferably 0.8 to 1.5 molar equivalents, more preferably 0.9 to 1.1 molar equivalents.

[0105] From the aspect of good yield of the titanium complex (1) of the present invention, the production method 1 of the present invention is preferably carried out in an inert gas atmosphere. As such an inert gas, helium, neon, argon, krypton, xenon, nitrogen, etc. can be specifically exemplified. From the aspect of low cost, nitrogen or argon is preferred.

[0106] From the aspect of good yield of the titanium complex (1) of the present invention, the production method 1 of the present invention is preferably carried out in an organic solvent. The type of the organic solvent that can be used is not particularly limited as long as it does not hinder the reaction. Examples of the organic solvent that can be used include: aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, butylbenzene, 2-methylpropylbenzene, 1-methylpropylbenzene, tert-butylbenzene, 1,3,5-trimethylbenzene (mesitylene), ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), cyclopentyl ethyl ether (CPEE), tert-butyl methyl ether (MTBE), THF, di alkane, 1,2-dimethoxyhexane, etc. These organic solvents can be used alone or in combination of multiple kinds at any ratio. From the aspect of good yield of the titanium complex (1) of the present invention, as the organic solvent, hexane, heptane, toluene or ether is preferred, and hexane is more preferred.

[0107] In the manufacturing method 1 of the present invention, the reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for manufacturing organometallic complexes. As a specific example, the titanium complex (1) of the present invention can be manufactured in good yield by appropriately selecting a reaction temperature in the range of -80°C to 120°C and a reaction time appropriately selected in the range of 10 minutes to 120 hours.

[0108] Those skilled in the art can purify the titanium complex (1) of the present invention manufactured by the manufacturing method 1 of the present invention by appropriately selecting and using general purification methods for purifying organometallic complexes. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, etc.

[0109] Next, a manufacturing method of a titanium-containing film using the titanium complex (1) of the present invention for a chemical reaction-based vapor deposition method will be described in detail. In this specification, the chemical reaction-based vapor deposition method refers to a method of manufacturing a titanium-containing film by decomposing the vaporized titanium complex (1) on a substrate. As the chemical reaction-based vapor deposition method, specific examples include CVD methods such as thermal CVD method, plasma CVD method, photo CVD method, or ALD method. The CVD method is particularly preferred in terms of good film formation rate, and the ALD method is particularly preferred in terms of good step coverage. For example, in the case of manufacturing a titanium-containing film by the CVD method or ALD method, the titanium complex (1) can be vaporized, supplied to a reaction chamber, and decomposed on a substrate provided in the reaction chamber to manufacture a titanium-containing film on the substrate. As a method of decomposing the titanium complex (1), examples include general technical means used by those skilled in the art when manufacturing metal-containing films. Specific examples include a method of reacting the titanium complex (1) with a reaction gas, or a method of applying heat, plasma, light, etc. to the titanium complex (1).

[0110] In the case of using a reactive gas, examples of the reactive gas that can be used include a reducing gas or an oxidizing gas. As the reactive gas, a reducing gas is preferred in terms of preventing deterioration of the substrate when forming a film on a substrate made of a material such as a metal or a metal nitride that is easily oxidized. Specific examples of the reducing gas include: ammonia, hydrogen, monosilane, hydrazine, formic acid, borane-amine complexes such as borane-dimethylamine complex or borane-trimethylamine complex, 1-butene, 2-butene, 2-methylpropene, 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 2-methyl-2-pentene, 4-methyl-2-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-methyl-2-pentene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2,3-dimethyl-2-butene, 3,3-dimethyl-1-butene, buta-1,3-diene, penta-1,3-diene, penta-1,4-diene, 2-methylbuta-1,3-diene, hexa-1,3-diene, hexa-2,4-diene, 2-methylpenta-1,3-diene, 3-methylpenta-1,3-diene, 4-methylpenta-1,3-diene, 2-ethylbuta-1,3-diene, 3-methylpenta-1,4-diene or 2,3-dimethylbuta-1,3-diene and other linear unsaturated hydrocarbons, cyclohex-1,3-diene, cyclohex-1,4-diene, 1-methylcyclohex-1,3-diene, 2-methylcyclohex-1,3-diene, 5-methylcyclohex-1,3-diene, 3-methylcyclohex-1,4-diene, α-phellandrene, β-phellandrene, α-terpinene, β-terpinene, γ-terpinene or limonene and other cyclic unsaturated hydrocarbons. Multiple reactive gases can be used simultaneously. In terms of less limitation due to the specifications of the film-forming apparatus and easy handling, as the reducing gas, ammonia, hydrogen, formic acid, cyclohex-1,3-diene, cyclohex-1,4-diene, α-terpinene, β-terpinene, γ-terpinene, gas are preferred. In addition, in terms of being able to form a titanium nitride film described later, it is preferred to use ammonia gas. The flow rate of the reactive gas is appropriately adjusted according to the reactivity of the material and the capacity of the reaction chamber. For example, when the capacity of the reaction chamber is 1 to 10 L, the flow rate of the reactive gas is not particularly limited, and for economic reasons, it is preferably 1 to 10000 sccm. It should be noted that in this specification, sccm refers to the unit representing the flow rate of a gas. If 1 sccm is converted into an ideal gas, it means that the gas moves at a speed of 2.68 mmol / h.

[0111] In the case of manufacturing a titanium-containing thin film by CVD method or ALD method, by appropriately selecting and using these decomposition methods, a titanium-containing thin film can be manufactured. Multiple decomposition methods can also be used in combination. As a method for supplying the titanium complex (1) to the reaction chamber, for example, methods commonly used by those skilled in the art such as a bubbling method in which the above titanium complex is placed in a heated constant temperature bath and a carrier gas is blown to gasify it, a liquid vaporization supply system, etc. are not particularly limited. A dilution gas can also be appropriately introduced into the reaction chamber together.

[0112] As the carrier gas and dilution gas when manufacturing a titanium-containing thin film by CVD method or ALD method, noble gases such as helium, neon, argon, krypton, xenon or nitrogen are preferred, and nitrogen or argon is further preferred for economic reasons. The flow rates of the carrier gas and dilution gas are appropriately adjusted according to the capacity of the reaction chamber, etc. For example, when the capacity of the reaction chamber is 1 to 10 L, the flow rate of the carrier gas is not particularly limited, and for economic reasons, it is preferably 1 to 10000 sccm.

[0113] The substrate temperature when manufacturing a titanium-containing thin film by CVD method or ALD method is appropriately selected according to the presence or absence of use of heat, plasma, light, etc., the type of reaction gas, etc. For example, when light and plasma are not used in combination and ammonia is used as the reaction gas, the substrate temperature is not particularly limited, and for economic reasons, it is preferably 50°C to 1000°C. From the aspect of good film formation rate, it is preferably 100°C to 300°C, and for forming a uniform thin film with excellent continuity, it is further preferably 150°C to 250°C. In addition, by appropriately using light, plasma, hydrazine, etc., a titanium-containing thin film can further be manufactured in a low temperature region.

[0114] From the aspects of film thickness uniformity, step-coverage, and good film quality, the film formation pressure when manufacturing a titanium-containing thin film by CVD method or ALD method is preferably under reduced pressure conditions, preferably 1 to 100 Torr, and further preferably 1 to 10 Torr.

[0115] Examples of the titanium-containing film obtained by the method for manufacturing a titanium-containing film of the present invention include a metallic titanium film, a titanium nitride film, a silicon-containing titanium nitride film, a titanium silicide film, and the like. Further, after manufacturing the metallic titanium film, the substrate may be heat-treated at an arbitrary temperature to obtain a titanium-containing composite film. For example, a titanium-containing composite film may be obtained by combining with other metal materials. For example, a titanium silicide film is obtained by using the titanium complex (1) of the present invention in combination with a silicon material. Examples of the silicon material include monosilane, disilane, trisilane, tetraethoxysilane, dimethyldimethoxysilane, bis(tert-butylamino)silane, bis(diethylamino)silane, tris(dimethylamino)silane, and the like. Further, a titanium-containing composite film containing these metal elements is obtained by using a metal material containing a typical metal such as aluminum and germanium, a transition metal such as zirconium, hafnium, niobium, tantalum, and tungsten, or a rare earth metal such as lanthanum and neodymium in combination with the titanium complex (1) of the present invention. In addition, when manufacturing a titanium-containing composite film by the CVD method or the ALD method, the titanium complex (1) of the present invention and other metal materials may be separately supplied into the reaction chamber, or may be supplied after mixing.

[0116] By using the titanium-containing film of the present invention as a constituent member, a high-performance semiconductor device with improved reliability and responsiveness can be manufactured. Examples of the semiconductor device include semiconductor memory devices such as DRAM, FeRAM, PRAM, MRAM, ReRAM, and flash memory, and field effect transistors. Examples of their constituent members include capacitor electrodes, gate electrodes of transistors, copper wiring barrier layers, and the like.

[0117] Examples

[0118] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. The manufacture of the compounds described in Reference Examples 1 to 4 and Examples 1 to 13 was all carried out in an argon atmosphere. The hexane and tetrahydrofuran (THF) used were dehydrated products manufactured by Kanto Chemical Co., Inc. Dimethylamine, ethylmethylamine, and pyrrolidine were purchased from Tokyo Chemical Industry Co., Ltd., and diethylamine was purchased from Fujifilm Wako Pure Chemical Corporation.

[0119] Reference Example 1

[0120] [Chemical Formula 13]

[0121]

[0122] At -78 °C, a hexane solution (245 mL, 1.59 mol / L, 389.6 mmol) of butyllithium was added to a THF solution (200.0 mL, 2.00 mol / L, 400.0 mmol) of dimethylamine. After stirring the mixture at 25 °C for 1 hour, a hexane (50 mL) solution of titanium tetrachloride (17.3 g, 91.2 mmol) was added at -78 °C. The mixture was stirred at 25 °C for 18 hours. After filtering the suspension, the solvent was removed by distillation under reduced pressure from the filtrate. By distilling the remaining liquid (heating temperature 60 °C / back pressure 49 Pa), 15.7 g of titanium tetrakis(dimethylamide) (2-1) as a yellow liquid was obtained. The yield was 77%. 1 H-NMR (400 MHz, C6D6, δ): 3.11 (s, 24H).

[0123] Reference Example 2

[0124] [Chemical Formula 14]

[0125]

[0126] At -78 °C, a hexane solution (266.0 mL, 1.59 mol / L, 422.3 mmol) of butyllithium was added to a hexane (120 mL) solution of ethylmethylamine (36.3 mL, 422.5 mmol). After stirring the mixture at 25 °C for 1 hour, a hexane (40 mL) solution of titanium tetrachloride (19.0 g, 100.2 mmol) was added at -78 °C. The mixture was stirred at 25 °C for 18 hours. After filtering the suspension, the solvent was removed by distillation under reduced pressure from the filtrate. By distilling the remaining liquid (heating temperature 90 °C / back pressure 19 Pa), 22.4 g of titanium tetrakis(ethylmethylamide) (2-2) as an orange liquid was obtained. The yield was 80%.

[0127] 1 H-NMR (400 MHz, C6D6, δ): 3.47 (q, 8H), 3.13 (s, 12H), 1.12 (t, 12H).

[0128] Reference Example 3

[0129] [Chemical Formula 15]

[0130]

[0131] To a solution of 43.7 mL (422.7 mmol) of diethylamine in 120 mL of hexane was added 266.0 mL of a hexane solution of butyllithium (1.59 mol / L, 422.3 mmol) at -78 °C. After the mixture was stirred at 25 °C for 1 hour, a solution of 19.0 g (100.2 mmol) of titanium tetrachloride in 40 mL of hexane was added at -78 °C. The mixture was stirred at 25 °C for 18 hours. After the suspension was filtered, the solvent was removed by distillation under reduced pressure from the filtrate. By distilling the remaining liquid (heating temperature 120 °C / back pressure 42 Pa), 18.9 g of titanium tetrakis(diethylamide) (2-7) was obtained as a red liquid. The yield was 56%.

[0132] 1 H-NMR (400 MHz, C6D6, δ): 3.59 (q, 16H), 1.12 (t, 24H).

[0133] Reference Example 4

[0134] [Chemical Formula 16]

[0135]

[0136] To a solution of 23.0 g (323.4 mmol) of pyrrolidine in 50 mL of hexane was added 220.0 mL of a hexane solution of butyllithium (1.59 mol / L, 349.8 mmol) at -78 °C. After the mixture was stirred at 25 °C for 1 hour, a solution of 15.4 g (81.2 mmol) of titanium tetrachloride in 25 mL of hexane was added at -78 °C. The mixture was stirred at 25 °C for 18 hours. After the suspension was filtered, the solvent was removed by distillation under reduced pressure from the filtrate. By distilling the remaining liquid (heating temperature 160 °C / back pressure 68 Pa), 13.5 g of titanium tetrakis(pyrrolidino) (2-14) was obtained as a yellow liquid. The yield was 51%.

[0137] 1 H-NMR (400 MHz, C6D6, δ): 3.79 (t, 16H), 1.56 (t, 16H).

[0138] Example 1

[0139] [Chemical Formula 17]

[0140]

[0141] To a solution of 1.0 g (4.5 mmol) of tetra(dimethylamido)titanium(2-1) synthesized in Reference Example 1 in 33 mL of THF was added a solution of 0.31 g (4.6 mmol) of pyrazole in 16 mL of THF at -78°C. The solution was stirred at 25°C for 1 hour, and the solvent was removed by distillation under reduced pressure. By sublimating the remaining solid (heating temperature 100°C / back pressure 32 Pa), 0.4 g of tris(dimethylamido)(pyrazolato)titanium(1-1) as a red solid was obtained. The yield was 36%.

[0142] 1 H-NMR (400 MHz, C6D6, δ): 7.75 (d, 2H), 6.54 (t, 1H), 3.24 (s, 18H).

[0143] Example 2

[0144] [Chemical formula 18]

[0145]

[0146] To a solution of 1.3 g (5.8 mmol) of tetra(dimethylamido)titanium(2-1) synthesized in Reference Example 1 in 40 mL of THF was added a solution of 0.46 g (5.7 mmol) of 3-methylpyrazole in 20 mL of THF at -78°C. The solution was stirred at 25°C for 1 hour, and the solvent was removed by distillation under reduced pressure. By distilling the remaining liquid (heating temperature 80°C / back pressure 30 Pa), 0.4 g of tris(dimethylamido)(3-methylpyrazolato)titanium(1-2) as a red liquid was obtained. The yield was 28%.

[0147] 1 H-NMR (400 MHz, C6D6, δ): 7.68 (s, 1H), 6.33 (s, 1H), 3.26 (s, 18H), 2.30 (s, 3H).

[0148] Example 3

[0149] [Chemical formula 19]

[0150]

[0151] A solution of 0.39 g (4.0 mmol) of 3,5-dimethylpyrazole in THF (15 mL) was added to a solution of 0.9 g (4.0 mmol) of tetrakis (dimethylamide) titanium (2-1) synthesized in Reference Example 1 in THF (30 mL) at -78°C. The solution was stirred at 25°C for 1 hour, and the solvent was distilled off under reduced pressure. By distilling the remaining liquid (heating temperature 100°C / back pressure 25 Pa), 0.2 g of tris (dimethylamide) (3,5-dimethylpyrazol) titanium (1-8) was obtained as a red liquid. The yield was 21%.

[0152] 1 H-NMR (400MHz, C6D6, δ): 6.11(s,1H), 3.28(s,18H), 2.28(s,6H).

[0153] 13 C-NMR (400MHz, C6D6, δ): 146.58, 111.88, 46.24, 13.12.

[0154] Example 4

[0155] [Chemical formula 20]

[0156]

[0157] To a THF (47 mL) solution of 1.8 g (6.4 mmol) of tetrakis (ethylmethylamide) titanium (2-2) synthesized in Reference Example 2 was added a THF (24 mL) solution of 0.44 g (6.5 mmol) of pyrazole at -78°C. The solution was stirred at 25°C for 1 hour, and the solvent was distilled off under reduced pressure. By distilling the remaining liquid (heating temperature 90°C / back pressure 19 Pa), 0.7 g of tris (ethylmethylamide) (pyrazol) titanium (1-19) was obtained as a red liquid. The yield was 37%.

[0158] 1 H-NMR (400MHz, C6D6, δ): 7.76 (d, 2H), 6.54 (t, 1H), 3.59 (q, 6H), 3.28 (s, 9H), 1.07 (t, 9H).

[0159] 13 C-NMR (400MHz, C6D6, δ): 135.82, 111.77, 53.05, 42.13, 15.16.

[0160] Example 5

[0161] [Chemical formula 21]

[0162]

[0163] At -78 °C, a solution of 3.5 g (42.8 mmol) of 3-methylpyrazole in THF (90 mL) was added to a solution of 12.0 g (42.9 mmol) of tetra(ethylmethylamide)titanium(2-2) synthesized in Reference Example 2 in THF (190 mL). The solution was stirred at 25 °C for 1 hour, and the solvent was removed by distillation under reduced pressure. By distilling the remaining liquid (heating temperature 103 °C / back pressure 38 Pa), 9.6 g of tris(ethylmethylamide)(3-methylpyrazolato)titanium(1-20) as a red liquid was obtained. The yield was 74%.

[0164] 1 H-NMR (400 MHz, C6D6, δ): 7.69 (d, 1H), 6.33 (d, 1H), 3.62 (q, 6H), 3.30 (s, 9H), 2.31 (s, 3H), 1.08 (t, 9H).

[0165] 13 C-NMR (400 MHz, C6D6, δ): 145.86, 136.52, 111.67, 53.14, 42.20, 15.23, 12.90.

[0166] Example 6

[0167] [Chemical formula 22]

[0168]

[0169] At -78 °C, a solution of 0.71 g (7.4 mmol) of 3,5-dimethylpyrazole in THF (27 mL) was added to a solution of 2.1 g (7.5 mmol) of tetra(ethylmethylamide)titanium(2-2) synthesized in Reference Example 2 in THF (54 mL). The solution was stirred at 25 °C for 1 hour, and the solvent was removed by distillation under reduced pressure. By distilling the remaining liquid (heating temperature 110 °C / back pressure 18 Pa), 1.2 g of tris(ethylmethylamide)(3,5-dimethylpyrazolato)titanium(1-26) as a red liquid was obtained. The yield was 51%.

[0170] 1 H-NMR (400 MHz, C6D6, δ): 6.12 (s, 1H), 3.64 (q, 6H), 3.32 (s, 9H), 2.30 (s, 6H), 1.10 (t, 9H).

[0171] 13 C-NMR (400 MHz, C6D6, δ): 146.43, 111.62, 53.22, 42.27, 15.30, 13.07.

[0172] Example 7

[0173] [Chemical formula 23]

[0174]

[0175] At -78 °C, a solution of 1.00 g (14.7 mmol) of pyrazole in THF (54 mL) was added to a solution of 4.9 g (14.6 mmol) of titanium(2-7) tetra(diethylamide) synthesized in Reference Example 3 in THF (108 mL). The solution was stirred at 25 °C for 1 hour, and the solvent was removed by distillation under reduced pressure. By distilling the remaining liquid (heating temperature 120 °C / back pressure 20 Pa), 3.2 g of tris(diethylamide)(pyrazolato)titanium(1-37) as a red liquid was obtained. The yield was 66%.

[0176] 1 H-NMR (400 MHz, C6D6, δ): 7.76 (d, 2H), 6.55 (t, 1H), 3.69 (q, 12H), 1.07 (t, 18H).

[0177] 13 C-NMR (400 MHz, C6D6, δ): 135.84, 111.45, 47.82, 15.49.

[0178] Example 8

[0179] [Chemical formula 24]

[0180]

[0181] At -78 °C, a solution of 0.23 g (2.8 mmol) of 3-methylpyrazole in THF (10 mL) was added to a solution of 0.9 g (2.8 mmol) of titanium(2-7) tetra(diethylamide) synthesized in Reference Example 3 in THF (20 mL). The solution was stirred at 25 °C for 1 hour, and the solvent was removed by distillation under reduced pressure. By distilling the remaining liquid (heating temperature 120 °C / back pressure 38 Pa), 0.3 g of tris(diethylamide)(3-methylpyrazolato)titanium(1-38) as a red liquid was obtained. The yield was 33%.

[0182] 1 H-NMR (400 MHz, C6D6, δ): 7.69 (d, 1H), 6.33 (d, 1H), 3.71 (q, 12H), 2.32 (s, 3H), 1.08 (t, 18H).

[0183] Example 9

[0184] [Chemical formula 25]

[0185]

[0186] At -78 °C, a solution of 0.47 g (4.9 mmol) of 3,5-dimethylpyrazole in 18 mL of THF was added to a solution of 1.7 g (5.0 mmol) of titanium(IV) bis(diethylamide)2-7 synthesized in Reference Example 3 in 36 mL of THF. The solution was stirred at 25 °C for 1 hour, and the solvent was removed by distillation under reduced pressure. By distilling the remaining liquid (heating temperature: 130 °C / back pressure: 22 Pa), 0.7 g of tris(diethylamide)(3,5-dimethylpyrazolato)titanium(IV)(1-44) as a red liquid was obtained. The yield was 40%.

[0187] 1 H-NMR (400 MHz, C6D6, δ): 6.12 (s, 1H), 3.74 (q, 12H), 2.31 (s, 6H), 1.10 (t, 18H).

[0188] 13 C-NMR (400 MHz, C6D6, δ): 146.29, 111.37, 48.01, 15.61, 13.03.

[0189] Example 10

[0190] [Chemical formula 26]

[0191]

[0192] At -78 °C, a solution of 0.32 g (3.9 mmol) of 3-methylpyrazole in 10 mL of THF was added to a solution of 1.3 g (4.0 mmol) of titanium(IV) tetrakis(pyrrolidide)(2-14) synthesized in Reference Example 4 in 20 mL of THF. The solution was stirred at 25 °C for 1 hour, and the solvent was removed by distillation under reduced pressure. By distilling the remaining liquid (heating temperature: 114 °C / back pressure: 28 Pa), 0.3 g of tris(pyrrolidide)(3-methylpyrazolato)titanium(IV)(1-56) as a red liquid was obtained. The yield was 24%.

[0193] 1 H-NMR (400 MHz, C6D6, δ): 7.74 (d, 1H), 6.38 (d, 1H), 4.00 (t, 12H), 2.34 (s, 3H), 1.53 (t, 12H).

[0194] Example 11

[0195] [Chemical formula 27]

[0196]

[0197] To a solution of 1.0 g (4.6 mmol) of titanium tetrakis(dimethylamide) (2-1) synthesized in Reference Example 1 in 35 mL of THF was added a solution of 0.63 g (9.2 mmol) of pyrazole in 35 mL of THF at -78 °C. The solution was stirred at 25 °C for 1 hour, and the solvent was removed by distillation under reduced pressure. Bis(dimethylamide)bis(pyrazolato)titanium (1-77) was obtained as a dark red liquid. The yield was 48%.

[0198] 1 H-NMR (400 MHz, C6D6, δ): 7.81 (d, 4H), 6.59 (t, 2H), 3.28 (s, 12H).

[0199] Example 12

[0200] [Chemical formula 28]

[0201]

[0202] To a solution of 0.9 g (4.0 mmol) of titanium tetrakis(dimethylamide) (2-1) synthesized in Reference Example 1 in 30 mL of THF was added a solution of 0.79 g (8.2 mmol) of 3,5-dimethylpyrazole in 30 mL of THF at -78 °C. The solution was stirred at 25 °C for 1 hour, and the solvent was removed by distillation under reduced pressure. Bis(dimethylamide)bis(3,5-dimethylpyrazolato)titanium (1-80) was obtained as a dark red liquid. The yield was 51%.

[0203] 1 H-NMR (400 MHz, C6D6, δ): 6.09 (s, 2H), 3.47 (s, 12H), 2.23 (s, 12H).

[0204] Example 13

[0205] [Chemical formula 29]

[0206]

[0207] To a solution of 1.1 g (3.3 mmol) of titanium tetrakis(diethylamide) (2-7) synthesized in Reference Example 3 in 25 mL of THF was added a solution of 0.62 g (6.45 mmol) of 3,5-dimethylpyrazole in 25 mL of THF at -78 °C. The solution was stirred at 25 °C for 1 hour, and the solvent was removed by distillation under reduced pressure. Bis(diethylamide)bis(3,5-dimethylpyrazolato)titanium (1-88) was obtained as a dark red liquid. The yield was 56%.

[0208] 1H-NMR (400 MHz, C6D6, δ): 6.10 (s, 2H), 3.89 (q, 8H), 2.25 (s, 12H), 0.99 (t, 12H).

[0209] Evaluation Example 1

[0210] Thermal Analysis of Tris(dimethylamide)(3,5-dimethylpyrazolato)titanium(1-8)

[0211] In differential scanning calorimetry (DSC), 8.3 mg of tris(dimethylamide)(3,5-dimethylpyrazolato)titanium(1-8) synthesized in Example 3 was used as a sample.

[0212] The results of DSC measured at a heating rate of 10 °C / min in a sealed container under an argon atmosphere are shown in Figure 1 . According to DSC, the onset temperature of thermal decomposition is 152 °C.

[0213] Evaluation Example 2

[0214] Thermal Analysis of Tris(ethylmethylamide)(3-methylpyrazolato)titanium(1-20)

[0215] In differential scanning calorimetry (DSC), 5.8 mg of tris(ethylmethylamide)(3-methylpyrazolato)titanium(1-20) synthesized in Example 5 was used as a sample.

[0216] The results of DSC measured at a heating rate of 10 °C / min in a sealed container under an argon atmosphere are shown in Figure 2 . According to DSC, the onset temperature of thermal decomposition is 147 °C.

[0217] Comparative Example 1

[0218] Thermal Analysis of Tetrakis(dimethylamide)titanium

[0219] In DSC, as Comparative Example 1, 2.5 mg of tetrakis(dimethylamide)titanium(2-1) synthesized in Reference Example 1, which is not the titanium complex (1) of the present invention, was used as a sample.

[0220] The results of DSC measured at a heating rate of 10 °C / min in a sealed container under an argon atmosphere are shown in Figure 3 . According to DSC, the onset temperature of thermal decomposition is 229 °C.

[0221] Comparative Example 2

[0222] Thermal Analysis of Tetrakis(ethylmethylamide)titanium

[0223] In DSC, as Comparative Example 2, 4.4 mg of titanium tetra(ethylmethylamide) (2-2) synthesized in Reference Example 2, which is not the titanium complex (1) of the present invention, was used as a sample.

[0224] The results of DSC measured at a heating rate of 10 °C / min in a sealed container under an argon atmosphere are shown in Figure 4 . According to DSC, the thermal decomposition start temperature is 242 °C.

[0225] Comparative Example 3

[0226] Thermal analysis of titanium tetra(diethylamide)

[0227] In DSC, as Comparative Example 3, 3.0 mg of titanium tetra(diethylamide) (2-7) synthesized in Reference Example 3, which is not the titanium complex (1) of the present invention, was used as a sample.

[0228] The results of DSC measured at a heating rate of 10 °C / min in a sealed container under an argon atmosphere are shown in Figure 5 . According to DSC, the thermal decomposition start temperature is 232 °C.

[0229] From the results of Evaluation Examples 1 and 2 and Comparative Examples 1 to 3, it can be seen that the titanium complex (1) of the present invention has a lower thermal decomposition start temperature compared to titanium tetra(dimethylamide), titanium tetra(diethylamide), and titanium tetra(ethylmethylamide), and is a more suitable complex for low-temperature film formation.

[0230] Example 14

[0231] Tris(ethylmethylamide)(3-methylpyrazolato)titanium (1-20) synthesized in Example 5 was used as a material, and a titanium-containing film was fabricated by thermal CVD method. The outline of the apparatus used for film fabrication is shown in Figure 6 . The film fabrication conditions are as follows.

[0232] Carrier gas flow rate: 20 sccm, ammonia flow rate: 40 sccm, dilution gas flow rate: 140 sccm, substrate material: SiO2, film formation time: 60 minutes, total pressure in reaction chamber: 1.3 kPa, temperature of material container: 50 °C, total pressure inside material container: 6.7 kPa, material supply rate: 0.01 sccm, substrate temperature: 200 °C. Argon was used as the carrier gas and dilution gas. The fabricated film was confirmed by fluorescence X-ray analysis, and characteristic X-rays based on titanium were detected. The film thickness was calculated based on the intensity of the detected X-rays to be 53 nm.

[0233] According to the results of Example 14, the titanium complex (1) of the present invention is a material capable of producing a titanium-containing film at a low temperature of 200 °C even without using an oxidizing gas and without combining light or plasma.

[0234] Comparative Example 4

[0235] Using tetra(dimethylamido)titanium (2-1) synthesized in Reference Example 1 as a material, a titanium-containing thin film was produced by thermal CVD method. The outline of the apparatus used for producing the thin film is shown in Figure 6 . The thin film production conditions are as described below.

[0236] Carrier gas flow rate: 20 sccm, ammonia flow rate: 40 sccm, dilution gas flow rate: 140 sccm, substrate material: SiO2, film formation time: 60 minutes, total pressure in reaction chamber: 1.3 kPa, material container temperature: 40 °C, total pressure in material container: 13.3 kPa, material supply rate: 0.064 sccm, substrate temperature: 200 °C. Argon was used as the carrier gas and dilution gas. The produced thin film was confirmed by fluorescence X-ray analysis, and as a result, characteristic X-rays based on titanium were detected. Based on the intensity of the detected X-rays, the film thickness was calculated to be 36 nm.

[0237] According to the results of Example 14 and Comparative Example 4, the titanium complex (1) of the present invention has a faster film formation rate at 200 °C although the material supply rate is lower than that of tetra(dimethylamido)titanium, and is a complex suitable for film formation of titanium-containing thin films at low temperatures.

[0238] Although the present invention has been described in detail with reference to specific embodiments, it is obvious to those skilled in the art that various changes and modifications can be made without departing from the essence and scope of the present invention.

[0239] It should be noted that the entire contents of the specification, claims, drawings, and the specification of Japanese Patent Application No. 2020-117772 filed on July 8, 2020 are hereby incorporated by reference as the disclosure content of the specification of the present invention.

Claims

1. A titanium complex represented by the general formula (1), wherein R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms, optionally bonding to each other to form a ring, X represents CR3 or an N atom, Y represents CR4 or an N atom, Z represents CR5 or an N atom, R3, R4 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3.

2. The titanium complex according to claim 1, wherein R1 and R2 are each independently an alkyl group having 1 to 4 carbon atoms, R3, R4 and R5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is 2 or 3.

3. The titanium complex according to claim 1 or 2, wherein R1 and R2 are each independently methyl or ethyl, R3, R4 and R5 are each independently a hydrogen atom or methyl, and n is 3.

4. A method for producing the titanium complex according to any one of claims 1 to 3, the method comprising: reacting an amide complex represented by the general formula (2) with an unsaturated cyclic amine represented by the general formula (3), in the formula (2), R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms, optionally bonding to each other to form a ring, in the formula (3), X represents CR3 or an N atom, Y represents CR4 or an N atom, Z represents CR5 or an N atom, and R3, R4 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

5. A method for producing a titanium-containing film, the method comprising: using the titanium complex represented by the general formula (1) in a chemical reaction-based vapor deposition method, in the formula, R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms, optionally bonding to each other to form a ring, X represents CR3 or an N atom, Y represents CR4 or an N atom, Z represents CR5 or an N atom, R3, R4 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3.

6. The method for producing a titanium-containing film according to claim 5, wherein the chemical reaction-based vapor deposition method is a chemical vapor deposition method.

7. The method for producing a titanium-containing film according to claim 5 or 6, wherein a reaction gas is used in the chemical reaction-based vapor deposition method.

8. The method for producing a titanium-containing film according to claim 7, wherein a reducing gas is used as the reaction gas.

9. The method for producing a titanium-containing film according to any one of claims 5 to 8, wherein the titanium-containing film is a titanium nitride film.

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