Thin film forming raw material, thin film manufacturing method, and novel compound

Abstract

The present invention aims to provide a thin film formation raw material for a CVD method, a method for manufacturing a thin film using the same, and a novel compound used as a thin film formation raw material, which are excellent in safety, handling, and productivity. To achieve the above object, the present invention is a thin film formation raw material containing a compound represented by the following general formula (1), a method for manufacturing a thin film using the same, and a novel compound represented by general formula (2) in the specification. [In formula (1), X represents a halogen atom, and R represents a primary alkyl group or a secondary butyl group having 1 to 5 carbon atoms.]

Description

TECHNICAL FIELD

[0001] The present application relates to a raw material for forming a thin film, a method for manufacturing a thin film using the raw material for forming a thin film, and a novel compound. BACKGROUND

[0002] As a gate insulating film in a semiconductor storage material, a thin film containing titanium oxide is applied. In addition, a thin film containing titanium carbide is used for a cutting tool, a wiring and an electrode for an electronic material, and for example, application to a semiconductor storage material, an electrode for a lithium-air battery, and the like is also studied.

[0003] As the manufacturing method of the above-described thin film, there are, for example, a sputtering method, an ion plating method, a coating thermal decomposition method, a sol-gel method, and the like MOD (Metal Organic Deposition) method; a chemical vapor deposition method (hereinafter, sometimes simply referred to as a CVD (Chemical Vapor Deposition) method). However, among the above-described manufacturing methods, the CVD method has many advantages such as excellent composition controllability and step coverage, suitability for mass production, and ability to mix and integrate, and thus the CVD method including an ALD (Atomic Layer Deposition) method is the best manufacturing process.

[0004] In Patent Literature 1 and Patent Literature 2, as a titanium-containing thin film forming raw material using an ALD method, Ti(C5Me5)(Me)3 (Me represents a methyl group) is disclosed. However, since Ti(C5Me5)(Me)3 has poor thermal stability, there is a problem that residual carbon components as an organic substance are mixed in a thin film, and a high-quality thin film cannot be formed.

[0005] In addition, in Patent Literature 3, as a zirconium compound and a hafnium compound that can be applied to a CVD method and an ALD method, MCl3(R1R2R3R4R5Cp) (M represents hafnium or zirconium, R1 to R5 represent an alkyl group, and Cp represents a cyclopentadienyl group) is disclosed. According to Table 1 of Patent Literature 3, it is disclosed that, in the case where the alkyl group bonded to the cyclopentadienyl group is an alkyl group having 3 carbon atoms, the melting point is lower when the alkyl group is an isopropyl group than when the alkyl group is a n-propyl group, and in the case where the alkyl group bonded to the cyclopentadienyl group is an alkyl group having 4 carbon atoms, the melting point is lower when the alkyl group is a tert-butyl group than when the alkyl group is a n-butyl group. From this, it is known that, in the compound represented by MCl3(R1R2R3R4R5Cp), in the case where M is hafnium, there is a tendency that the melting point is lower when the alkyl group bonded to the cyclopentadienyl group is a bulky alkyl group.

[0006] Moreover, in Non-Patent Literature 1 and Non-Patent Literature 2, tetrakis neopentyl titanium is disclosed as a titanium source used when a titanium carbide thin film is manufactured by a MOCVD (Metal-Organic Chemical Vapor Deposition) method. However, in the case where tetrakis neopentyl titanium is used to manufacture a titanium carbide thin film by a MOCVD method, the carbon component concentration in the titanium carbide becomes lower than the theoretical amount, and a high-quality titanium carbide thin film cannot be manufactured. Furthermore, in the case where film formation is performed at a high temperature in order to stabilize the quality, since tetrakis neopentyl titanium has poor thermal stability, the carbon component of the organic matter is mixed in the thin film, and it is difficult to form a high-quality titanium carbide thin film.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 2006-310865

[0010] Patent Document 2: Japanese Patent Application Laid-Open (JP-A) No. 2009-545135

[0011] Patent Document 3: International Publication No. 2011 / 057114

[0012] Non-Patent Literature

[0013] Non-Patent Literature 1: Journal of American Chemical Society. 1987, vol. 109, p. 1579-1580 (USA)

[0014] Non-Patent Literature 2: Journal of American Ceramic Society. 2013, vol. 96, No. 4, p. 1060-1062 (USA) SUMMARY

[0015] PROBLEMS TO BE SOLVED BY THE INVENTION

[0016] What is required for a manufacturing method of a titanium atom-containing thin film using a CVD method is that the raw material for thin film formation has no spontaneous ignition property, and can safely form a thin film; the raw material for thin film formation has a low melting point, and can be transported in a liquid state; furthermore, the raw material for thin film formation has good thermal decomposability and / or reactivity with a reactive gas, and is excellent in productivity. Moreover, it is also required that in the obtained titanium atom-containing thin film, the residual carbon component as an organic matter is less mixed, and the quality is high. In the past, there has been no raw material for thin film formation and a manufacturing method of a thin film that can sufficiently satisfy these aspects.

[0017] Solution to the problem

[0018] As a result of repeated research, the present inventors have found the following fact, thereby completing the present application: a thin film forming raw material containing a specific compound and a method for manufacturing a titanium atom-containing thin film using the thin film forming raw material can solve the above problems.

[0019] The present application provides a thin film forming raw material containing a compound represented by the following general formula (1) and a method for manufacturing a thin film using the raw material.

[0020]

[0021] (In the formula, X represents a halogen atom, and R represents a primary alkyl group or a secondary butyl group having 1 to 5 carbon atoms.)

[0022] Further, the present application provides a compound represented by the following general formula (2).

[0023]

[0024] (In the formula, L represents a primary alkyl group or a secondary butyl group having 2 to 5 carbon atoms.)

[0025] Effects of the Invention

[0026] According to the present application, a low-melting-point thin film forming raw material for forming a titanium atom-containing thin film, which is suitable for chemical vapor deposition, can be provided, which becomes a liquid at 30°C under normal pressure or by slight heating. Furthermore, a titanium atom-containing thin film having excellent productivity, which is excellent in quality and has little mixing of residual carbon components as an organic substance, can be safely manufactured. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 is a schematic diagram showing one example of a chemical vapor deposition apparatus used in the method for manufacturing a titanium atom-containing thin film of the present application.

[0028] Figure 2 is a schematic diagram showing another example of a chemical vapor deposition apparatus used in the method for manufacturing a titanium atom-containing thin film of the present application.

[0029] Figure 3 is a schematic diagram showing another example of a chemical vapor deposition apparatus used in the method for manufacturing a titanium atom-containing thin film of the present application.

[0030] Figure 4 is a schematic diagram showing another example of a chemical vapor deposition apparatus used in the method for manufacturing a titanium atom-containing thin film of the present application. DETAILED DESCRIPTION

[0031] The raw material for forming a thin film of the present application is a raw material for forming a thin film containing the compound represented by the above general formula (1), and is suitable as a precursor for a thin film production method having a vaporization step such as a CVD method, and can also be used to form a thin film using an ALD method.

[0032] In the above general formula (1), X represents a halogen atom. As the halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, and the like can be exemplified, and in the case where X is a chlorine atom or a bromine atom, the effect of being able to produce a titanium atom-containing thin film having less mixing of a residual carbon component as an organic substance is good, and thus is preferred.

[0033] Further, in the above general formula (1), R represents a primary alkyl group having 1 to 5 carbon atoms or a secondary butyl group. As the primary alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group can be exemplified.

[0034] In the above general formula (1), in the case where X is a chlorine atom, the melting point is low when R is a secondary butyl group or a primary alkyl group having 3 to 5 carbon atoms, and thus is preferred. Among them, a secondary butyl group, an n-propyl group, or an n-butyl group is more preferred, and a secondary butyl group or an n-butyl group is particularly preferred.

[0035] In the above general formula (1), in the case where X is a bromine atom, the melting point is low when R is a secondary butyl group or a primary alkyl group having 2 to 4 carbon atoms, and thus is preferred. Among them, in the case where R is a secondary butyl group or an ethyl group, the vapor pressure is high, and thus is preferred, and in the case where R is an ethyl group, the melting point is particularly low, and thus is preferred.

[0036] As preferred specific examples of the compound represented by general formula (1), for example, the compounds represented by the following Compound Nos. 1 to 12 can be exemplified. Note that in the following Compound Nos. 1 to 12, "Me" represents a methyl group, "Et" represents an ethyl group, "Pr" represents an n-propyl group, "Bu" represents an n-butyl group, "sBu" represents a secondary butyl group, and "Am" represents an n-pentyl group.

[0037]

[0038] The compound represented by the above general formula (1) is not particularly limited in the manufacturing method thereof, and can be manufactured by using a well-known reaction. As the manufacturing method, for example, in the case where X is a chlorine atom and R is an ethyl group, it can be obtained by reacting titanium tetrachloride with trimethyl(3-ethyl-2,4-cyclopentadien-l-yl)silane at room temperature, followed by distillation purification. In the case where X is a chlorine atom and R is a n-propyl group, it can be obtained by reacting titanium tetrachloride with trimethyl(3-propyl-2,4-cyclopentadien-l-yl)silane at room temperature, followed by distillation purification. In the case where X is a chlorine atom and R is a n-butyl group, it can be obtained by reacting titanium tetrachloride with trimethyl(3-butyl-2,4-cyclopentadien-l-yl)silane at room temperature, followed by distillation purification. In the above method, titanium tetrachloride can be changed to titanium tetrabromide to manufacture a substance in which X is a bromine atom.

[0039] The raw material for thin film formation of the present application is a substance in which the compound represented by general formula (1) is used as a precursor for CVD method for forming a thin film containing a titanium atom, and the form thereof varies depending on the manufacturing process in which the raw material for thin film formation is used. For example, in the case of manufacturing a thin film containing a titanium atom, the raw material for thin film formation of the present application does not contain a metal compound and a metalloid compound other than the compound represented by general formula (1) described above. On the other hand, in the case of manufacturing a thin film containing a metal and / or a metalloid other than a titanium atom as well as a titanium atom, the raw material for thin film formation of the present application contains, in addition to the compound represented by general formula (1) described above, a compound containing a metal other than a titanium atom and / or a compound containing a metalloid (hereinafter, also referred to as other precursor). As described later, the raw material for thin film formation of the present application can also contain an organic solvent and / or a nucleophilic reagent. As the raw material for thin film formation of the present application, as described above, the physical properties of the compound represented by general formula (1) as a precursor are suitable for CVD method and ALD method, and therefore, particularly, it is useful as a raw material for chemical vapor deposition (hereinafter, sometimes referred to as CVD raw material).

[0040] The form of the raw material for thin film formation of the present application can be appropriately selected depending on the method such as the delivery and supply method of the CVD method used.

[0041] As the above-mentioned delivery method, there are a gas delivery method in which a CVD raw material is vaporized by heating and / or reducing pressure in a container (hereinafter, sometimes simply referred to as a raw material container) storing the raw material to produce a vapor, and the vapor is introduced into a film formation chamber provided with a substrate together with a carrier gas such as argon, nitrogen, helium, or the like as needed. Further, there is a liquid delivery method in which a CVD raw material is delivered in a liquid or solution state to a vaporization chamber, and is vaporized by heating and / or reducing pressure in the vaporization chamber to produce a vapor, and the vapor is introduced into the film formation chamber. In the case of the gas delivery method, the compound represented by the above general formula (1) itself can be used as the CVD raw material. In the case of the liquid delivery method, the compound represented by the above general formula (1) itself or a solution in which the compound is dissolved in an organic solvent can be used as the CVD raw material. These CVD raw materials can further contain other precursors, nucleophilic reagents, or the like.

[0042] Further, in the CVD method of a multi-component system, there are a method in which each component is independently vaporized and a CVD raw material is delivered (hereinafter, sometimes referred to as a single source method), and a method in which a multi-component raw material is preliminarily mixed in a desired composition, and the mixed raw material is vaporized and delivered (hereinafter, sometimes referred to as a cocktail source method). In the case of the cocktail source method, a mixture of the compound represented by the above general formula (1) and other precursors or a mixed solution in which the mixture is dissolved in an organic solvent can be used as the CVD raw material. The mixture or the mixed solution can further contain nucleophilic reagents or the like.

[0043] As the organic solvent described above, there is no particular limitation, and a generally known organic solvent can be used. As the organic solvent, for example, alcohols such as methanol, ethanol, isopropanol, n-butanol, and the like; acetates such as ethyl acetate, butyl acetate, methoxyethyl acetate, and the like; ethers such as tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, dioxane, and the like; ketones such as methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, methylcyclohexanone, and the like; hydrocarbons such as hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, toluene, xylene, and the like; hydrocarbons having a cyano group such as 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, 1,4-dicyanobenzene, and the like; pyridine, dimethylpyridine, and the like can be exemplified. These organic solvents can be used alone or two or more kinds thereof can be used in mixture, according to the solubility of the solute, the relationship between the use temperature and the boiling point, the flash point, and the like. In the case where these organic solvents are used, the amount of the entire precursors in the CVD raw material which is a solution of the precursors dissolved in the organic solvent is 0.01 mol / L to 2.0 mol / L, and particularly preferably 0.05 mol / L to 1.0 mol / L. In the case where the thin film forming raw material of the present application does not contain a metal compound and a metalloid compound other than the compound represented by the general formula (1) described above, the amount of the entire precursors refers to the amount of the compound represented by the general formula (1) described above, and in the case where the thin film forming raw material of the present application contains a compound containing a metal and / or a compound containing a metalloid other than the compound represented by the general formula (1) described above (other precursors), the amount of the entire precursors refers to the total amount of the compound represented by the general formula (1) described above and the other precursors.

[0044] Further, in the case of the CVD method of a multi-component system, as the other precursors used together with the compound represented by the general formula (1) described above, there is no particular limitation, and a generally known precursor used in the CVD raw material can be used. A substance in which the ligand used in the precursor does not contain an oxygen atom in the structure can reduce the amount of oxygen mixed in the obtained thin film containing a titanium atom, and thus is particularly preferable.

[0045] As the other precursors described above, one or more kinds selected from the group consisting of a compound using an alcohol compound, a diol compound, a β-diketone compound, a cyclopentadiene compound, an organic amine compound, and the like as an organic ligand, and a compound of silicon, a metal (except for titanium), can be exemplified. Further, as the kind of the metal of the precursor, magnesium, calcium, strontium, barium, vanadium, niobium, tantalum, aluminum, manganese, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, zirconium, hafnium, gallium, indium, germanium, tin, lead, antimony, bismuth, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium can be exemplified.

[0046] As the alcohol compound used as the organic ligand of the other precursors described above, methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, tert-butanol, pentanol, isopentanol, tert-pentanol, and the like alkyl alcohols; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-methoxy-l-methylethanol, 2-methoxy-l,l-dimethylethanol, 2-ethoxy-l,l-dimethylethanol, 2-isopropoxy-l,l-dimethylethanol, 2-butoxy-l,l-dimethylethanol, 2-(2-methoxyethoxy)-l,l-dimethylethanol, 2-propoxy-l,l-diethylethanol, 2-s-butoxy-l,l-diethylethanol, 3-methoxy-l,l-dimethylpropanol, and the like ether alcohols can be exemplified.

[0047] As the diol compound used as the organic ligand of the other precursors described above, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2,4-hexanediol, 2,2-dimethyl-l,3-propanediol, 2,2-diethyl-l,3-propanediol, 1,3-butanediol, 2,4-butanediol, 2,2-diethyl-l,3-butanediol, 2-ethyl-2-butyl-l,3-propanediol, 2,4-pentanediol, 2-methyl-l,3-propanediol, 2-methyl-2,4-pentanediol, 2,4-hexanediol, 2,4-dimethyl-2,4-pentanediol, and the like can be exemplified.

[0048] Further, as the β-diketone compounds, there can be mentioned acetylacetone, hexane-2,4-dione, 5-methylhexane-2,4-dione, heptane-2,4-dione, 2-methylheptane-3,5-dione, 5-methylheptane-2,4-dione, 6-methylheptane-2,4-dione, 2,2-dimethylheptane-3,5-dione, 2,6-dimethylheptane-3,5-dione, 2,2,6-trimethylheptane-3,5-dione, 2,2,6,6-tetramethylheptane-3,5-dione, octane-2,4-dione, 2,2,6-trimethyloctane-3,5-dione, 2,6-dimethyloctane-3,5-dione, 2,9-dimethylnonane-4,6-dione, 2-methyl-6-ethyldecane-3,5-dione, 2,2-dimethyl-6-ethyldecane-3,5-dione, and the like alkyl-substituted β-diketones; 1,1,1-trifluoropentane-2,4-dione, 1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione, 1,1,1,5,5,5-hexafluoropentane-2,4-dione, 1,3-bisperfluorohexylpropane-1,3-dione, and the like fluorine-substituted alkyl β-diketones; 1,1,5,5-tetramethyl-1-methoxyhexane-2,4-dione, 2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dione, 2,2,6,6-tetramethyl-1-(2-methoxyethoxy)heptane-3,5-dione, and the like ether-substituted β-diketones.

[0049] Further, as the cyclopentadiene compounds, there can be mentioned cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, tetramethylcyclopentadiene, and the like. Also, as the organic amine compounds used as the above-mentioned organic ligands, there can be mentioned methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine, isopropylmethylamine, and the like.

[0050] The above-mentioned other precursors are substances known in the technical field, and the manufacturing methods thereof are also known. If one example of the manufacturing method is mentioned, for example, in the case where an alcohol compound is used as the organic ligand, the precursor can be manufactured by reacting the above-mentioned inorganic salt of a metal or a hydrate thereof with an alkali metal alcoholate of the alcohol compound. Here, as the inorganic salt of a metal or a hydrate thereof, there can be mentioned halides, nitrate salts, and the like of a metal, and as the alkali metal alcoholate, there can be mentioned sodium alcoholate, lithium alcoholate, potassium alcoholate, and the like.

[0051] For the other precursors described above, in the case of the single source method, compounds similar to the compound represented by the general formula (1) described above are preferred in terms of the behavior of thermal and / or oxidative decomposition. In addition, in the case of the mixed source method, substances that do not cause deterioration due to chemical reactions upon mixing are preferred in addition to the similarity in the behavior of thermal and / or oxidative decomposition.

[0052] Further, for the raw material for thin film formation of the present application, a nucleophilic reagent can be contained as necessary to impart stability to the raw material. As the nucleophilic reagent, glyme, diglyme, triglyme, tetraglyme, and the like can be exemplified as glycol ethers; 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, dibenzo-24-crown-8, and the like can be exemplified as crown ethers; ethylenediamine, N,N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, triethoxytriethylenylamine, and the like can be exemplified as polyamines; cyclam, cyclen, and the like can be exemplified as cyclic polyamines; pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, thiazole, oxathiolane, and the like can be exemplified as heterocyclic compounds; methyl acetoacetate, ethyl acetoacetate, 2-methoxyethyl acetoacetate, and the like can be exemplified as β-keto esters; or acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, di-tert-amylmethane, and the like can be exemplified as β-diketones. The amount of use of these nucleophilic reagents is preferably in the range of 0.1 to 10 moles, and more preferably 1 to 4 moles, relative to 1 mole of the compound represented by the general formula (1) described above. In addition, in the case of using these nucleophilic reagents, substances that do not contain an oxygen atom in the structure of the nucleophilic reagent are preferred, and substances that contain a nitrogen atom in the structure are particularly preferred.

[0053] In the raw material for film formation of the present application, impurity metal element components, impurity halogen components such as impurity chlorine, and impurity organic components other than the components constituting the raw material are preferably not contained. The impurity metal element components are preferably 100 ppb or less, more preferably 10 ppb or less, per element, and 1 ppm or less, more preferably 100 ppb or less, in total. In particular, in the case of use as a gate insulating film, a gate film, and a barrier layer for LSI (Large Scale Integration), it is necessary to reduce the content of alkali metal elements, alkaline earth metal elements, and similar elements which have an influence on the electrical properties of the resulting film. The impurity halogen components are preferably 100 ppm or less, more preferably 10 ppm or less, and further preferably 1 ppm or less. The impurity organic components are preferably 500 ppm or less, more preferably 50 ppm or less, and further preferably 10 ppm or less, in total. Furthermore, since moisture is a cause of particle generation in the raw material for CVD and particle generation during film formation, it is desirable to remove moisture as much as possible before use in order to reduce the moisture content of the precursors, organic solvents, and nucleophilic reagents. The moisture content of each of the precursors, organic solvents, and nucleophilic reagents is preferably 10 ppm or less, and further preferably 1 ppm or less.

[0054] Furthermore, in order to reduce or prevent particle contamination of the film formed, the raw material for film formation of the present application preferably does not contain particles as much as possible. Specifically, in particle measurement by a light scattering type liquid particle detector in a liquid phase, the number of particles of 0.3 μm or more is preferably 100 or less per 1 ml of the liquid phase, more preferably the number of particles of 0.2 μm or more is 1000 or less per 1 ml of the liquid phase, and further preferably the number of particles of 0.2 μm or more is 100 or less per 1 ml of the liquid phase.

[0055] The apparatus for producing a film containing a titanium atom using the raw material for film formation of the present application can use a well-known chemical vapor deposition apparatus. As examples of specific apparatuses, there can be mentioned: Figure 1 an apparatus capable of supplying a precursor by bubbling, such as Figure 2 an apparatus having a vaporization chamber. Furthermore, there can be mentioned: Figure 3 and Figure 4 an apparatus capable of plasma processing of a reactive gas. Not limited to Figure 1 , Figure 2 , Figure 3 and Figure 4 a single wafer type apparatus, an apparatus capable of simultaneously processing a plurality of pieces using a batch furnace can also be used.

[0056] The thin film containing a titanium atom manufactured using the raw material for thin film formation of the present application can be used for cutting tools, wiring and electrodes for electronic materials, for example, and can be used for semiconductor storage materials, electrodes for lithium air batteries, and the like.

[0057] The method for manufacturing the thin film of the present application is a method realized by a CVD method in which a vapor of a compound represented by the above general formula (1) gasified and a reactive gas used as necessary are introduced into a film formation chamber provided with a substrate, and then a precursor is caused to decompose and / or chemically react on the substrate and / or in the film formation chamber and / or in the vicinity of a gas introduction port to grow and deposit a thin film containing a titanium atom on the surface of the substrate. The method of supplying and feeding the raw material, the deposition method, the manufacturing conditions, the manufacturing apparatus, and the like are not particularly limited, and general conditions and methods well known can be used.

[0058] As the reactive gas used as necessary described above, for example, as an oxidizing substance, oxygen, ozone, nitrogen dioxide, nitric oxide, water vapor, hydrogen peroxide, formic acid, acetic acid, acetic anhydride, and the like can be listed, and as a reducing substance, hydrogen; silane, disilane, and the like silane compounds; diborane and the like boron compounds; phosphine and the like phosphorus compounds can be listed. In addition, as the reactive gas, as a substance for manufacturing nitride, organic amine compounds such as monoalkyl amine, dialkyl amine, trialkyl amine, and alkylene diamine; hydrazine; ammonia and the like can be used, and one or two or more kinds thereof can be used. In addition, plasma treatment can be performed in advance before causing the above reactive gas to react with the precursor.

[0059] In addition, as the method of supplying and feeding described above, the above gas supply method, liquid supply method, single source method, mixed source method, and the like can be listed.

[0060] In addition, as the deposition method described above, thermal CVD in which a raw material gas or a raw material gas and a reactive gas are caused to react by heat alone to deposit a thin film; plasma CVD using heat and plasma; photo CVD using heat and light; photo plasma CVD using heat, light, and plasma; ALD in which a deposition reaction of CVD is divided into elementary processes to deposit in stages at a molecular level can be listed.

[0061] As the material of the substrate described above, for example, silicon; indium arsenide, indium gallium arsenide, silicon oxide, silicon nitride, silicon carbide, titanium nitride, tantalum oxide, tantalum nitride, titanium oxide, titanium nitride, ruthenium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, gallium nitride, and the like ceramics; glass; platinum, ruthenium, aluminum, copper, nickel, cobalt, tungsten, molybdenum, and the like metals can be listed. As the shape of the substrate, a plate shape, a spherical shape, a fibrous shape, a scale shape can be listed, and the substrate surface can be a flat surface, or a three-dimensional structure such as a trench structure.

[0062] Further, as the above-mentioned manufacturing conditions, reaction temperature (substrate temperature), reaction pressure, deposition rate, etc. can be exemplified. As for the reaction temperature, it is preferable to be 100°C or higher of a temperature at which the compound represented by the above-mentioned general formula (1) sufficiently reacts, and more preferable to be 150°C to 400°C. Further, as for the reaction pressure, in the case of thermal CVD, photo CVD, it is preferable to be 10 Pa to atmospheric pressure, and in the case of using plasma, it is preferable to be 10 Pa to 2000 Pa. Further, as for the deposition rate, it can be controlled by the supply conditions of the raw material (vaporization temperature, vaporization pressure), reaction temperature, reaction pressure. If the deposition rate is large, sometimes the properties of the obtained thin film deteriorate, and if the deposition rate is small, sometimes the productivity becomes a problem, and therefore, it is preferable to be 0.01 nm / min to 100 nm / min, and more preferable to be 1 nm / min to 50 nm / min. Further, in the case of the ALD method, in order to obtain a desired film thickness, the number of cycles is controlled.

[0063] As the above-mentioned manufacturing conditions, the temperature and pressure at the time of vaporizing the raw material for thin film formation to make a vapor can also be exemplified. The process of vaporizing the raw material for thin film formation to make a vapor can be performed in a raw material container or in a vaporization chamber. In either case, the raw material for thin film formation used in the thin film manufacturing method of the present application is preferably evaporated at 0°C to 150°C. Further, in the case of vaporizing the raw material for thin film formation to make a vapor in a raw material container or in a vaporization chamber, the pressure in the raw material container and the pressure in the vaporization chamber are each preferably 1 Pa to 10000 Pa.

[0064] The thin film manufacturing method of the present application employs the ALD method, and in addition to the raw material introduction process of vaporizing the raw material for thin film formation to make a vapor by the above-mentioned transport supply method and introducing the vapor into a film formation chamber, it can also have: a precursor thin film film-formation process of forming a precursor thin film on the surface of the above-mentioned substrate from the compound represented by the above-mentioned general formula (1) in the vapor; an exhaust process of exhausting the unreacted compound represented by the above-mentioned general formula (1) gas; and a titanium atom-containing thin film formation process of causing the precursor thin film to chemically react with a reactive gas to form a thin film containing titanium atoms on the surface of the substrate.

[0065] Hereinafter, as an example of forming a thin film containing titanium atoms by the ALD method, each of the above-mentioned processes will be described in detail. In the case of forming a thin film containing titanium atoms by the ALD method, first, the above-mentioned raw material introduction process is performed. The preferable temperature and pressure at the time of vaporizing the raw material for thin film formation to make a vapor are the same as those described above. Next, a precursor thin film is formed on the surface of the substrate from the compound represented by the above-mentioned general formula (1) introduced into the film formation chamber (precursor thin film film-formation process). At this time, heating can be applied by heating the substrate or heating the film formation chamber.

[0066] The precursor thin film formed in this process is a thin film in which the compound represented by the above general formula (1) is adsorbed on the surface of the substrate or a thin film generated by decomposition and / or reaction of the compound or a part of the compound, and has a different composition from the target titanium atom-containing thin film. The temperature of the substrate during this process is preferably room temperature to 600°C, and more preferably 150°C to 400°C. The pressure of the system (in the film formation chamber) during this process is preferably 1 Pa to 10,000 Pa, and more preferably 10 Pa to 1,000 Pa.

[0067] Next, the unreacted compound gas represented by the above general formula (1) and the by-produced gas are discharged from the film formation chamber (discharge process). It is desirable that the unreacted compound gas represented by the above general formula (1) and the by-produced gas be completely discharged from the film formation chamber, but it is not necessary to be completely discharged. As the discharge method, there can be mentioned a method in which the system is purged with an inert gas such as nitrogen, helium, or argon; a method in which the system is depressurized to discharge the gas; a method in which these are combined; and the like. In the case where the system is depressurized, the degree of depression is preferably 0.01 Pa to 300 Pa, and more preferably 0.01 Pa to 100 Pa.

[0068] Next, a reactive gas is introduced into the film formation chamber, and a thin film containing a titanium atom is formed from the precursor thin film obtained in the preceding precursor thin film formation process by the action of the reactive gas or the reactive gas and heat (titanium atom-containing thin film formation process). In the case where heat is allowed to act in this process, the temperature is preferably room temperature to 600°C, and more preferably 150°C to 400°C. The pressure of the system (in the film formation chamber) during this process is preferably 1 Pa to 10,000 Pa, and more preferably 10 Pa to 1,000 Pa.

[0069] In the method for manufacturing a thin film of the present application, in the case where the ALD method is employed as described above, the deposition of the thin film achieved by a series of operations including the above-described raw material introduction process, the precursor thin film formation process, the discharge process, and the titanium atom-containing thin film formation process can be set as one cycle, and this cycle can be repeated a plurality of times until a thin film having a desired film thickness is obtained. In this case, it is preferable that, after one cycle is performed, the unreacted compound gas represented by the above general formula (1) and the reactive gas, and further the by-produced gas be discharged from the film formation chamber in the same manner as the above-described discharge process, and then the next cycle be performed.

[0070] Further, in the method for manufacturing the thin film of the present application, in the case where the ALD method is employed as described above, energy such as plasma, light, voltage, etc. can be applied, and a catalyst can be used. The timing of applying these energies is not particularly limited, and for example, it can be at the time of introduction of the compound gas in the raw material introduction step, at the time of heating in the precursor thin film formation step or the titanium atom-containing thin film formation step, at the time of evacuation in the system in the evacuation step, at the time of introduction of the reactive gas in the titanium atom-containing thin film formation step, or between the above steps. Further, the reactive gas can be subjected to these energies before the introduction of the reactive gas.

[0071] Further, in the method for manufacturing the thin film of the present application, in the case where the plasma ALD method is employed as described above, the reactive gas can be continuously flowed into the film formation chamber during all steps in the manufacturing method, or a gas subjected to plasma treatment can be introduced into the film formation chamber only at the time of the titanium atom-containing thin film formation step. If the high frequency (hereinafter, sometimes referred to as RF) output is too low, a good film containing titanium atoms is not easily obtained, and if the high frequency output is too high, damage to the substrate is large, and therefore, it is preferably 0 to 1500 W, and more preferably 50 W to 600 W. In the manufacturing method of the present application, in the case where the plasma ALD method is employed, a thin film containing titanium atoms having a very high quality can be obtained, and therefore, it is preferable.

[0072] Further, in the method for manufacturing the thin film of the present application, after the deposition of the thin film, in order to obtain a more excellent electrical property, an annealing treatment can be performed in an inert atmosphere, and in the case where step embedding is required, a reflow step can be provided. The temperature in this case is 200°C to 1000°C, and is preferably 250°C to 500°C.

[0073] Note that the compound represented by General Formula (2) in the above-mentioned raw material for thin film formation is also novel. The novel compound of the present application has a low melting point, and is a particularly preferable compound which can be applied to the ALD method, and is particularly preferable as a precursor for a thin film manufacturing method having a vaporization step such as a CVD method.

[0074] In the above General Formula (2), L represents a primary alkyl group or a secondary butyl group having 2 to 5 carbon atoms. As the primary alkyl group having 2 to 5 carbon atoms, for example, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group can be mentioned.

[0075] In the above General Formula (2), in the case where L is an ethyl group, the melting point is particularly low, and therefore, it is preferable.

[0076] The compound represented by the above general formula (2) is not particularly limited in its production method, and can be produced by using a well-known reaction. As the production method, for example, in the case where L is ethyl, it can be obtained by reacting titanium tetrabromide with trimethyl (3-ethyl-2, 4-cyclopentadien-1-yl) silane at room temperature, followed by distillation purification. In the case where L is propyl, it can be obtained by reacting titanium tetrabromide with trimethyl (3-propyl-2, 4-cyclopentadien-1-yl) silane at room temperature, followed by distillation purification. In the case where L is butyl, it can be obtained by reacting titanium tetrabromide with trimethyl (3-butyl-2, 4-cyclopentadien-1-yl) silane at room temperature, followed by distillation purification.

[0077] As specific examples of the novel compound represented by general formula (2), for example, the compounds represented by the above compound Nos. 8 to 12 can be given.

[0078] Examples

[0079] Hereinafter, the present application will be further explained in detail by examples and evaluation examples. However, the present application is not limited to any of the following examples, etc.

[0080] [Production Example 1] Synthesis of Compound No. 3

[0081] Into a 1000 mL four-necked flask, 36.80 g of titanium tetrabromide and 268.13 g of dehydrated toluene were added under an Ar atmosphere, and mixed well. After the mixture was cooled to 10°C, trimethyl (3-propyl-2, 4-cyclopentadien-1-yl) silane was added dropwise while stirring. After stirring at room temperature overnight, desolvation was performed under reduced pressure at 65°C of an oil bath. The flask containing the resulting titanium complex was connected to a distillation purification apparatus, and distillation purification was performed at 145°C of an oil bath and 7 Pa, to obtain 36.36 g of compound No. 3 as a red-orange solid. The melting point of the compound was 49°C.

[0082] (Analysis)

[0083] (1) Atmospheric pressure TG-DTA (quartz pan)

[0084] Temperature at which the mass decreased by 50%: 242°C (Ar flow rate: 100 mL / minute, temperature increase: 10°C / minute, sample amount: 9.552 mg)

[0085] (2) Reduced pressure TG-DTA (quartz pan)

[0086] Temperature at which the mass decreased by 50%: 152°C (Ar flow rate: 50 mL / minute, temperature increase: 10°C / minute, sample amount: 9.960 mg)

[0087] (3)1H-NMR (C6D6)

[0088] 0.596 ppm (t, 3H), 1.154 ppm (m, 2H), 2.296 ppm (t, 2H), 5.991 ppm (m, 4H)

[0089] (4) Elemental analysis (Metal analysis: ICP-AES, CHN analysis: CHN analyzer, Chlorine analysis: TOX analyzer)

[0090] Ti: 18.3 mass%, C: 36.8 mass%, H: 4.0 mass%, CI: 40.8 mass% (theoretical value; Ti: 18.31 mass%, C: 36.76 mass%, H: 4.24 mass%, CI: 40.69 mass%)

[0091] [Production Example 2] Synthesis of Compound No. 4

[0092] Into a 500 mL four-necked flask, 35.77 g of titanium tetrachloride and 246.54 g of dehydrated toluene were added under an Ar atmosphere and mixed well. After the mixture was cooled to 10°C, trimethyl(3-butyl-2,4-cyclopentadien-l-yl)silane was added dropwise while stirring. After stirring at room temperature overnight, desolvation was performed under reduced pressure at an oil bath temperature of 89°C. The flask containing the resulting titanium complex was connected to a distillation purification apparatus and subjected to distillation purification at an oil bath temperature of 136°C and 12 Pa to obtain 44.09 g of Compound No. 4 as a red-orange liquid.

[0093] (Analysis value)

[0094] (1) Normal pressure TG-DTA (quartz pan)

[0095] Temperature at which mass decreased by 50%: 250°C (Ar flow rate: 100 mL / minute, temperature increase: 10°C / minute, sample amount: 9.919 mg)

[0096] (2) Reduced pressure TG-DTA (quartz pan)

[0097] Temperature at which mass decreased by 50%: 159°C (Ar flow rate: 50 mL / minute, temperature increase: 10°C / minute, sample amount: 9.917 mg)

[0098] (3)1H-NMR (C6D6)

[0099] 0.744 ppm (t, 3H), 1.029 ppm (m, 2H), 1.188 ppm (m, 2H), 2.400 ppm (t, 2H), 6.092 ppm (m, 4H)

[0100] (4) Elemental analysis (Metal analysis: ICP-AES, CHN analysis: CHN analyzer, Chlorine analysis: TOX analyzer)

[0101] Ti: 17.2 mass%, C: 39.5 mass%, H: 4.5 mass%, CI: 38.3 mass% (theoretical value; Ti: 17.38 mass%, C: 39.25 mass%, H: 4.76 mass%, CI: 38.61 mass%)

[0102] [Production Example 3] Synthesis of Compound No. 5

[0103] To a 200 mL four-necked flask was added 9.76 g of titanium tetrachloride and 71.09 g of dehydrated toluene under an Ar atmosphere, and the mixture was thoroughly mixed. After the mixture was cooled to 10°C, trimethyl(3-sec-butyl-2,4-cyclopentadien-l-yl)silane was added dropwise while stirring. After stirring at room temperature overnight, desolvation was performed under reduced pressure at 70°C of an oil bath. The flask containing the resulting titanium complex was connected to a distillation purification apparatus, and distillation purification was performed at 145°C of an oil bath and 11 Pa, to obtain 9.07 g of Compound No. 5 as a red-orange liquid.

[0104] (analysis value)

[0105] (1) Normal pressure TG-DTA (quartz pan)

[0106] Temperature at which mass decreased by 50%: 246°C (Ar flow rate: 100 mL / minute, temperature increase: 10°C / minute, sample amount: 10.172 mg)

[0107] (2) Reduced pressure TG-DTA (quartz pan)

[0108] Temperature at which mass decreased by 50%: 157°C (Ar flow rate: 50 mL / minute, temperature increase: 10°C / minute, sample amount: 10.404 mg)

[0109] (3)1H-NMR (C6D6)

[0110] 0.552 ppm (t, 3H), 0.936 ppm (d, 3H), 1.061 ppm (m, IH), 1.264 ppm (m, IH), 2.717 ppm (m, IH), 5.962 ppm (m, IH), 6.026 ppm (m, IH), 6.141 ppm (m, 2H)

[0111] (4) Elemental analysis (Metal analysis: ICP-AES, CHN analysis: CHN analyzer, Chlorine analysis: TOX analyzer)

[0112] Ti: 17.2 mass%, C: 39.3 mass%, H: 4.6 mass%, CI: 38.2 mass% (theoretical value; Ti: 17.38 mass%, C: 39.25 mass%, H: 4.76 mass%, CI: 38.61 mass%)

[0113] [Example 1] Synthesis of Compound No. 8

[0114] Into a 100 mL three-necked flask was added 3.00 g of titanium tetrabromide and 30.00 g of dehydrated toluene under an Ar atmosphere, and the mixture was thoroughly mixed. After the mixture was cooled to 10°C, trimethyl(3-ethyl-2,4-cyclopentadien-l-yl)silane was added dropwise while stirring. After stirring at room temperature overnight, desolvation was performed under reduced pressure at 75°C in an oil bath. The flask containing the resulting titanium complex was connected to a distillation purification apparatus, and distillation purification was performed to obtain Compound No. 8 as a red solid. The melting point of the compound was 70°C.

[0115] (analytical value)

[0116] (1) Normal pressure TG-DTA (quartz pan)

[0117] Temperature at which the mass decreased by 50%: 261°C (Ar flow rate: 100 mL / minute, temperature increase: 10°C / minute, sample amount: 9.877 mg)

[0118] (2) Reduced pressure TG-DTA (quartz pan)

[0119] Temperature at which the mass decreased by 50%: 168°C (Ar flow rate: 50 mL / minute, temperature increase: 10°C / minute, sample amount: 10.192 mg)

[0120] (3)1H-NMR (C6D6)

[0121] 0.784 ppm (t, 3H), 2.283 ppm (q, 2H), 6.081 ppm (m, 4H)

[0122] (4) Elemental analysis (metal analysis: ICP-AES, CHN analysis: CHN analyzer, bromine analysis: TOX analyzer)

[0123] Ti: 12.5 mass%, C: 22.1 mass%, H: 2.5 mass%, Br: 62.6 mass% (theoretical value; Ti: 12.57 mass%, C: 22.08 mass%, H: 2.38 mass%, Br: 62.96 mass%)

[0124] [Example 2] Synthesis of Compound No. 10

[0125] To a 100 mL three-necked flask was added 3.00 g of titanium tetrabromide and 30.00 g of dehydrated toluene under an argon atmosphere, and the mixture was stirred well. After the mixture was cooled to 10°C, trimethyl(3-butyl-2,4-cyclopentadien-l-yl)silane was added dropwise while stirring. After stirring at room temperature overnight, desolvation was performed under reduced pressure at 75°C in an oil bath. The flask containing the resulting titanium complex was connected to a distillation purification apparatus, and distillation purification was performed to obtain compound No. 10 as a red solid. The melting point of the compound was 51°C.

[0126] (analytical value)

[0127] (1) Normal pressure TG-DTA (aluminum pan)

[0128] Temperature at which the mass decreased by 50%: 280°C (Ar flow rate: 100 mL / minute, temperature increase: 10°C / minute, sample amount: 10.368 mg)

[0129] (2) Reduced pressure TG-DTA (aluminum pan)

[0130] Temperature at which the mass decreased by 50%: 171°C (Ar flow rate: 50 mL / minute, temperature increase: 10°C / minute, sample amount: 10.005 mg)

[0131] (3)1H-NMR (C6D6)

[0132] 0.737 ppm (t, 3H), 1.013 ppm (m, 2H), 1.177 ppm (m, 2H), 2.376 ppm (t, 2H), 6.146 ppm (m, 4H)

[0133] (4) Elemental analysis (metal analysis: ICP-AES, CHN analysis: CHN analyzer, bromine analysis: TOX analyzer)

[0134] Ti: 11.4 mass%, C: 26.5 mass%, H: 3.0 mass%, Br: 58.6 mass% (theoretical value; Ti: 11.71 mass%, C: 26.44 mass%, H: 3.21 mass%, Br: 58.64 mass%)

[0135] [Example 1] Evaluation of spontaneous ignition property

[0136] The presence or absence of spontaneous ignition property was confirmed by leaving the above-described compounds Nos. 3, 4, 5, 8 and 10 in the atmosphere. The results are shown in Table 1.

[0137] [Table 1]

[0138] Compound Ignition property Compound No. 3 None Compound No. 4 None Compound No. 5 None Compound No. 8 None Compound No. 10 None

[0139] From the results of Table 1, it was found that the compounds No. 3, 4, 5, 8 and 10 did not show spontaneous ignition property, and could be safely used as a raw material for chemical vapor deposition even in the atmosphere.

[0140] [Example 2] Melting point evaluation

[0141] With respect to the compounds No. 3, 4, 5, 8 and 10 and the following comparative compounds 1, 2, 3 and 4, the state of each compound at normal pressure at 30°C was observed by visual observation, and with respect to the solid compounds, the melting point was measured using a micro melting point measuring device. The results are shown in Table 2. Note that in the following comparative compounds 1 to 4, "Me" represents a methyl group.

[0142] [Table 2]

[0143]

[0144]

[0145] From the results of Table 2, it was found that the compounds No. 3, 4, 5, 8 and 10 showed a lower melting point than the comparative compounds 1 to 4. Among them, it was found that the compounds No. 3, 4, 5 and 10 had a low melting point, and the compounds No. 4 and 5 had a particularly low melting point and were excellent. It was confirmed that the trend of the melting point obtained from the results of Table 2 was contrary to the findings obtained from the above-described Patent Document 3, and that the melting point was higher for the tert-butyl group having a large alkyl volume compared to the n-butyl group (compound No. 4) or the sec-butyl group (compound No. 5) bonded to the cyclopentadienyl group.

[0146] [Example 3] Production of titanium carbide thin film

[0147] The compound No. 3 was used as a raw material for ALD method, and a titanium carbide thin film was produced on a silicon wafer using the device shown in Figure 3 by the ALD method under the following conditions. With respect to the obtained thin film, film thickness measurement by X-ray reflectance method, and confirmation of the structure and composition of the thin film by X-ray diffraction method and X-ray photoelectron spectroscopy were performed, and as a result, the film thickness was 7.6 nm, the film composition was a titanium carbide thin film, and the carbon content was 51 atom% (theoretical amount 50 atom%). No residual carbon component as an organic substance was detected. The film thickness obtained in each cycle was 0.15 nm.

[0148] (Conditions) Reaction temperature (substrate temperature): 250°C, reactive gas: hydrogen

[0149] (Procedure) A series of procedures including the following (1) to (4) was set as one cycle, and 50 cycles were repeated.

[0150] (1) The vapor of the chemical vapor deposition raw material, which was gasified under the conditions of a raw material container temperature of 90°C and a raw material container pressure of 0.8 Torr (106 Pa), was introduced into the film formation chamber, and was deposited on the surface of a silicon wafer for 10 seconds under a system pressure of 0.6 Torr (80 Pa).

[0151] (2) The unreacted raw material was removed by argon purge for 20 seconds.

[0152] (3) The reactive gas was introduced, and was allowed to react for 10 seconds under a system pressure of 0.6 Torr (80 Pa). At this time, the plasma was generated by applying a high frequency output of 13.56 MHz and 100 W to the reactive gas.

[0153] (4) The unreacted raw material was removed by argon purge for 15 seconds.

[0154] [Example 4] Production of titanium carbide thin film

[0155] The production of the titanium carbide thin film was performed under the same conditions as in Example 3, except that Compound No. 4 was used as the ALD method raw material.

[0156] The obtained thin film was subjected to film thickness measurement by X-ray reflectance method, and confirmation of the thin film structure and thin film composition by X-ray diffraction method and X-ray photoelectron spectroscopy, and as a result, the film thickness was 7.5 nm, the film composition was titanium carbide thin film, and the carbon content was 52 atom% (theoretical amount 50 atom%). No residual carbon component as an organic substance was detected. The film thickness obtained per one cycle was 0.15 nm.

[0157] [Example 5] Production of titanium carbide thin film

[0158] The production of the titanium carbide thin film was performed under the same conditions as in Example 3, except that Compound No. 5 was used as the ALD method raw material.

[0159] The obtained thin film was subjected to film thickness measurement by X-ray reflectance method, and confirmation of the thin film structure and thin film composition by X-ray diffraction method and X-ray photoelectron spectroscopy, and as a result, the film thickness was 7.8 nm, the film composition was titanium carbide thin film, and the carbon content was 52 atom% (theoretical amount 50 atom%). No residual carbon component as an organic substance was detected. The film thickness obtained per one cycle was 0.16 nm.

[0160] [Example 6] Production of titanium carbide thin film

[0161] The production of the titanium carbide thin film was performed under the same conditions as in Example 3, except that Compound No. 8 was used as the ALD method raw material.

[0162] The obtained thin film was subjected to film thickness measurement by X-ray reflectance method, and confirmation of film structure and film composition by X-ray diffraction method and X-ray photoelectron spectroscopy, as a result, the film thickness was 7.2 nm, the film composition was titanium carbide film, and the carbon content was 50 atom% (theoretical amount 50 atom%). No residual carbon component as an organic substance was detected. The film thickness obtained per cycle was 0.14 nm.

[0163] [Example 7] Production of titanium carbide film

[0164] The production of a titanium carbide film was performed under the same conditions as in Example 3, except that Compound No. 10 was used as the raw material for the ALD method.

[0165] The obtained thin film was subjected to film thickness measurement by X-ray reflectance method, and confirmation of film structure and film composition by X-ray diffraction method and X-ray photoelectron spectroscopy, as a result, the film thickness was 7.0 nm, the film composition was titanium carbide film, and the carbon content was 51 atom% (theoretical amount 50 atom%). No residual carbon component as an organic substance was detected. The film thickness obtained per cycle was 0.14 nm.

[0166] [Comparative Example 1] Production of titanium carbide film

[0167] The production of a titanium carbide film was performed under the same conditions as in Example 1, except that titanium tetra-isoamyl was used as the raw material for the ALD method.

[0168] The obtained thin film was subjected to film thickness measurement by X-ray reflectance method, and confirmation of film structure and film composition by X-ray diffraction method and X-ray photoelectron spectroscopy, as a result, the film thickness was 1.0 nm, the film composition was titanium carbide, and the carbon content was 40 atom% (theoretical amount 50 atom%). A residual carbon component as an organic substance of 10 atom% or more was detected. The film thickness obtained per cycle was 0.12 nm.

[0169] From the results of Examples 1 to 4, it was found that, in the case where the raw material for film formation of the present application was used, the content of the residual carbon component as an organic substance was very small, and a high-quality titanium carbide film containing a carbon component close to the theoretical amount could be formed; on the other hand, in Comparative Example 1, a large amount of the residual carbon component as an organic substance was mixed into the film, and a poor-quality titanium carbide film with a carbon content less than the theoretical amount was obtained.

Claims

1. A method for producing a thin film containing a titanium atom, comprising: a step of vaporizing a raw material for forming a thin film containing a compound represented by general formula (1); a step of introducing a vapor containing the compound represented by general formula (1) thus obtained into a processing atmosphere; and a step of allowing the compound to decompose and / or chemically react to deposit on a surface of a substrate, wherein general formula (1) is ###0001### wherein X represents a halogen atom, and R represents an ethyl group, an n-propyl group, an n-pentyl group, or a sec-butyl group.

2. The method according to claim 1, wherein X is a chlorine atom or a bromine atom.

3. The method according to claim 1 or 2, wherein X is a chlorine atom, and R is an n-propyl group, an n-pentyl group, or a sec-butyl group.

4. The method according to claim 1 or 2, wherein X is a bromine atom, and R is a primary alkyl group having 2 to 4 carbon atoms or a sec-butyl group. ​ ​ ​ ​ ​ ​ ​

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