Organic-inorganic hybrid film and method for producing same

Abstract

Provided is a method for producing an organic-inorganic hybrid film, wherein an organic-inorganic hybrid film is formed using a first thin film forming raw material containing a metallic material and a second thin film forming raw material containing an organic material, and both conditions (A) and (B) described in the present specification are satisfied.

Description

Organic-inorganic hybrid film and method for producing the same

[0001] This disclosure relates to an organic-inorganic hybrid film formed using molecular layer deposition (MLD) and a method for producing the same.

[0002] Atomic layer deposition (ALD) is a technique that allows for the deposition of ultrathin layers of metallic materials onto a substrate. Because strong covalent bonds are formed between the metallic material and the substrate, the layer exhibits high adhesion to the substrate, and layers of desired thickness can be formed by repeating the deposition process. ALD offers advantages such as easy film control even on substrates with high aspect ratios and the formation of continuous films without voids such as pinholes. Recently, attempts have been made to apply ALD to form organic-inorganic hybrid films, including ultrathin polymer coatings.

[0003] The above-mentioned organic-inorganic hybrid film is not merely a mixture like a composite material, but rather a structure in which a metal layer formed from a metal material and an organic layer formed from an organic material are three-dimensionally bonded to each other at the nanoscale or molecular level, representing a form in which the metal layer and organic layer are formed alternately and become a single, integrated entity.

[0004] The development of organic-inorganic hybrid films that combine the advantages of both organic and metallic materials is anticipated. For example, Patent Document 1 proposes a method using molecular layer deposition (MLD) to alternately stack layers of two or more components based on bifunctional or higher-order functional reactions. Patent Document 2 proposes a method to form a patterned radiation-sensitive film by depositing a metal-containing layer using a metal precursor and depositing an organic layer containing a photosensitive organic portion using an organic precursor.

[0005] Special table 2010-509501 publication Special table 2023-535349 publication

[0006] However, successful examples of organic-inorganic hybrid film manufacturing are limited. Conventional manufacturing methods have the problem that the polymerization reaction between organic and metal materials is extremely slow, or the polymerization reaction stops after several reaction cycles, because it is difficult for the reactants obtained in one reaction cycle to generate new functional groups that can be used in the next reaction cycle. Therefore, there has been a need for a manufacturing method that allows for a good polymerization reaction between organic and metal materials and enables the stable production of organic-inorganic hybrid films.

[0007] The present inventors, after diligently studying to solve the above problems, have found that the above problems can be solved by a method for manufacturing thin films using specific materials, and have completed this disclosure. Specifically, this disclosure provides a method for manufacturing an organic-inorganic hybrid film using a first thin-film forming raw material containing a metal material and a second thin-film forming raw material containing an organic material, and is characterized by satisfying both of the following conditions (A) and (B).

[0008] Condition (A) is that the first thin film forming raw material contains a compound having a structure in which a metal atom M and a ligand L that coordinates to the metal atom M are present as a metallic material.

[0009]

[0010] In general formula (1), M represents a metal atom, L represents a ligand that bonds to the metal atom represented by M, and there may be two or more ligands. t represents the number of metal atoms represented by M, which is between 1 and 5, u represents the number of ligands that bond to the metal atom represented by M, and at least one of the ligands represented by L is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms (*-OR 1 ), monoalkylamino group (*-NHR 1 ), dialkylamino group (*-NR 1 R 2 ), alkylene amino group (*-(CR 4 R 5 ) m -NR 6R 7 ), alkyl(alkyleneamino)amino group (*-NR 1 ((CR 4 R 5 ) m -NR 6 R 7 )), trialkylsilyl group (*-SiR 1 R 2 R 3 ), alkylenetrialkylsilyl group (*-(CH2) m -SiR 1 R 2 R 3 ), alkyl(trimethylsilyl)amino group (*-NR 1 -SiMe3), bis(trialkylsilyl)amino group (*-N(SiR 1 R 2 R 3 )2), alkylimide group (*=NR 1 ), acetonitrile group (*-NC-CH3), carbonyl group (*=C=O), nitroso group (*-N=O), an aryl group having 6 to 20 carbon atoms, a cyclopentadiene compound, a diketonate structure (*-O-C(R 4 )=C(R 5 )-C(=O)-R 6 ), a ketoiminato structure (*-N(R 4 )-C(R 5 )=C(R 6 )-C(=O)-R 7 ), a diiketiminato structure (*-N(R 4 )-C(R 5 )=C(R 6 )-C(=NR 7 )-R 8 ), an amidinate structure (*-N(R 4 )-C(R 5 )=NR 6 ) and an amino alcohol structure (*-O-(CR 4 R 5 ) m -NR 6 R 7 ), which is a group selected from the group consisting of; R 1 , R 2 and R 3Each of these independently represents an alkyl group having 1 to 10 carbon atoms, and R 4 , R 5 , R 6 , R 7 and R 8 Each of the following independently represents a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, m represents an integer between 1 and 10, and if m is 2 or more, there are multiple R 4 , R 5 (These may be the same or different, and * represents the bonding position with the metal atom represented by M.)

[0011] Condition (B) is that the second thin film forming raw material contains, as an organic material, a compound represented by the following general formula (2-1), a compound represented by the following general formula (2-2), a compound represented by the following general formula (2-3), 4-isocyanatophenol, alkyl isocyanatoacetate, or phenylethylene glycol.

[0012]

[0013] In general formula (2-1), A represents a direct bond, a divalent aliphatic group having 1 to 20 carbon atoms, a divalent aromatic group having 6 to 20 carbon atoms, or a divalent heterocyclic group having 2 to 20 carbon atoms, X 1 This represents a monovalent hydrocarbon group or trialkylsilyl group having 1 to 10 carbon atoms, Y 1 -O-, -S-, -OCO-, -COO- and -N(X 2 ) - represents a divalent group selected from the group, Y 1 X in 2 This represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a trialkylsilyl group.

[0014]

[0015] In general formula (2-2), X 2 and X 3 Each of these independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a trialkylsilyl group, Z 1This represents a monovalent aliphatic group having 1 to 20 carbon atoms, a monovalent aromatic group having 6 to 20 carbon atoms, or a monovalent heterocyclic group having 2 to 20 carbon atoms. 2 This represents a direct bond or -O-.

[0016]

[0017] (In general formula (2-3), A 2 This represents a divalent aliphatic group with 1 to 20 carbon atoms, a divalent aromatic group with 6 to 20 carbon atoms, or a heterocyclic group or carbonyl group with 2 to 20 carbon atoms. 3 -O-, -OCO-, -COO- and -N(X 5 ) - represents a divalent group selected from the group, X 4 and X 5 Each of these independently represents a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 4 carbon atoms, or a trialkylsilyl group, and n represents 0 or 1. However, as described above, A 2 A divalent aliphatic group with 1 to 20 carbon atoms, represented by A, represents a group in which at least one methylene group is substituted with a thioether, thioester, dithioester, or trithioester, or at least one hydrogen atom is substituted with a halogen atom, or at least one heteroatom is contained. 2 A divalent aromatic group having 6 to 20 carbon atoms, represented by , has at least one methylene group substituted with a thioether, thioester, dithioester, or trithioester, or at least one hydrogen atom is a halogen atom or -(Y 3 ) n -X 4 Represents a group that is substituted with or contains at least one heteroatom, and A 2 A heterocyclic group having 2 to 20 carbon atoms, represented by [the symbol], represents a group in which at least one methylene group is substituted with a thioether, thioester, dithioester, or trithioester, or in which at least one hydrogen atom is substituted with a halogen atom.

[0018] This disclosure provides an organic-inorganic hybrid film manufactured using the above-described method for manufacturing an organic-inorganic hybrid film.

[0019] This disclosure demonstrates that organic-inorganic hybrid films can be easily formed using metallic and organic materials, and that their thickness can be controlled to a desired level.

[0020] This is a schematic diagram showing an example of an ALD apparatus used in the method for manufacturing an organic-inorganic hybrid film according to this disclosure. This is a schematic diagram showing another example of an ALD apparatus used in the method for manufacturing an organic-inorganic hybrid film according to this disclosure. This is a schematic diagram showing yet another example of an ALD apparatus used in the method for manufacturing an organic-inorganic hybrid film according to this disclosure. This is a schematic diagram showing yet another example of an ALD apparatus used in the method for manufacturing an organic-inorganic hybrid film according to this disclosure.

[0021] The method for producing the organic-inorganic hybrid film described herein will be explained below. First, the raw materials for forming the thin film used in the method for producing the organic-inorganic hybrid film described herein will be explained.

[0022] A. Raw materials for forming thin films The manufacturing method disclosed herein uses a first raw material for forming thin films containing a metal material and a second raw material for forming thin films containing an organic material as raw materials for forming thin films.

[0023] A1. First Thin Film Forming Raw Materials The first thin film forming raw materials include a metal material. The metal material can be used without particular limitations as long as it is a precursor that can form a metal layer and is usable in the MLD method. The first thin film forming raw materials may include one or more of the metal materials.

[0024] (1) Metallic material The precursor as the metallic material is a compound composed of metal atoms and ligands. Examples of the metal atoms include Group 1 elements such as lithium (Li), sodium (Na), potassium (K), and cesium (Cs); and Group 2 elements such as magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra); Transition elements such as scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au); aluminum (Al), gallium (Ga), indigo Examples include poor metals such as um (In), tin (Sn), thallium (Tl), lead (Pb), bismuth (Bi), and polonium (Po); metalloids such as boron (B), silicon (Si), germanium (Ge), antimony (Sb), and tellurium (Te); and lanthanides such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).

[0025] The above-mentioned metal material may have multiple metal atoms in a single molecule. In this disclosure, from the viewpoint of significantly enhancing the effects of the invention, the above-mentioned metal atoms are preferably selected from the group consisting of transition elements, poor metals, metalloids, and lanthanides, and are particularly preferably selected from the group consisting of cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), molybdenum (Mo), hafnium (Hf), aluminum (Al), gallium (Ga), indium (In), tin (Sn), bismuth (Bi), and antimony (Sb).

[0026] The ligand constituting the metal material is not particularly limited, and examples of the ligand include a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms (*-OR 1 ), a monoalkylamino group (*-NHR 1 ), a dialkylamino group (*-NR 1 R 2 ), an alkyleneamino group (*-(CR 4 R 5 ) m -NR 6 R 7 ), an alkyl(alkyleneamino)amino group (*-NR 1 ((CR 4 R 5 ) m -NR 6 R 7 )), a trialkylsilyl group (*-SiR 1 R 2 R 3 ), an alkylenetrialkylsilyl group (*-(CH2) m -SiR 1 R 2 R 3 ), an alkyl(trimethylsilyl)amino group (*-NR 1 -SiMe3), a bis(trialkylsilyl)amino group (*-N(SiR 1 R 2 R 3 )2), an alkylimido group (*=NR 1 ), an acetonitrile group (*-NC-CH3), a carbonyl group (*=C=O), a nitroso group (*-N=O), an aryl group having 6 to 20 carbon atoms, a cyclopentadiene compound, a diketonate structure (*-O-C(R 4 )=C(R 5 )-C(=O)-R 6 ), a ketoiminate structure (*-N(R 4 )-C(R 5 )=C(R 6 )-C(=O)-R 7 ), a diiminato structure (*-N(R 4 )-C(R 5 )=C(R 6 )-C(=NR7 )-R 8 ), amidinate structure (*-N(R 4 )-C(R 5 ) = NR 6 ) and amino alcohol structure (*-O-(CR 4 R 5 ) m -NR 6 R 7 A metallic material containing a group selected from the above is preferred, because the effects of the invention are more pronounced.

[0027] The above R 1 , R 2 and R 3 Each of these independently represents an alkyl group having 1 to 10 carbon atoms, and R 4 , R 5 , R 6 , R 7 and R 8 Each of the following independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, m represents an integer between 1 and 10, and if m is 2 or more, there are multiple R 4 , R 5 These elements may be the same or different, and * indicates the bonding position with the above metal atom.

[0028] If the above-mentioned metallic material has multiple ligands in a single molecule, the ligands may have different structures or may have the same structure.

[0029] Examples of halogen atoms used as ligands include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0030] Examples of alkyl groups having 1 to 10 carbon atoms as ligands include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, tert-amyl group, n-hexyl group, isohexyl group, n-heptyl group, 2-heptyl group, 3-heptyl group, tert-heptyl group, n-octyl group, 2-ethylhexyl group, tert-octyl group, n-nonyl group, isononyl group, 3,5,5-trimethylhexyl group, n-decyl group, and isodecyl group.

[0031] The alkyl group described above may have some or all of its hydrogen atoms replaced by fluorine atoms. Examples of alkyl groups having 1 to 10 carbon atoms in which some or all of its hydrogen atoms are replaced by fluorine atoms include monofluoromethyl groups, difluoromethyl groups, trifluoromethyl groups, and pentafluoroethyl groups.

[0032] From the viewpoint of facilitating the production of organic-inorganic hybrid films, alkyl groups having 1 to 5 carbon atoms are more preferred, alkyl groups having 1 to 3 carbon atoms are even more preferred, and methyl or ethyl groups are particularly preferred.

[0033] Examples of alkoxy groups having 1 to 10 carbon atoms as ligands include methoxy, ethoxy, propoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy, tert-amyloxy, and hexyloxy groups.

[0034] The above-mentioned alkoxy group may have some or all of its hydrogen atoms replaced with fluorine atoms. Examples of alkoxy groups having 1 to 10 carbon atoms in which some or all of its hydrogen atoms are replaced with fluorine atoms include monofluoromethoxy groups, difluoromethoxy groups, trifluoromethoxy groups, and pentafluoroethoxy groups.

[0035] In this disclosure, from the viewpoint of facilitating the production of organic-inorganic hybrid films, alkoxy groups having 1 to 8 carbon atoms are more preferred, alkoxy groups having 2 to 7 carbon atoms are even more preferred, and alkoxy groups having 3 to 6 carbon atoms are particularly preferred.

[0036] The above ligand is a monoalkylamino group (*-NHR 1 ) R 1 This can be a group similar to the alkyl group having 1 to 10 carbon atoms used as a ligand.

[0037] The above ligand is a dialkylamino group (*-NR 1 R 2 ) in R 1 and R 2 R can be a group similar to the alkyl group having 1 to 10 carbon atoms as the ligand described above. In this disclosure, R in the dialkylamino group 1 and R 2 From the viewpoint of facilitating the production of organic-inorganic hybrid films, alkyl groups having 1 to 5 carbon atoms are more preferred, alkyl groups having 1 to 3 carbon atoms are even more preferred, and methyl or ethyl groups are particularly preferred.

[0038] The alkylene amino group as the ligand (*-(CR 4 R 5 ) m -NR 6 R 7 ) R 4 , R 5 , R 6 and R 7 R independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In this disclosure, R in the alkylene amino group 6 and R 7From the viewpoint of facilitating the production of organic-inorganic hybrid films, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is more preferable, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is even more preferable, and a methyl group or an ethyl group is particularly preferable. From the viewpoint of facilitating the production of organic-inorganic hybrid films, m in the alkylene amino group is more preferably an integer between 1 and 5, even more preferably an integer between 1 and 4, and particularly preferably 2 to 4. When m is 2 or more, multiple R 4 or R 5 These may be the same group or very different groups, but it is preferable that they be the same group, R 4 and R 5 It is particularly preferable that both are hydrogen atoms.

[0039] The alkyl (alkyleneamino)amino group (*-NR) as the ligand mentioned above 1 ((CR 4 R 5 ) m -NR 6 R 7 )) R 1 As such, it can be a group similar to the alkyl group having 1 to 10 carbon atoms as the ligand mentioned above. R in the alkyl(alkyleneamino)amino group mentioned above 1 From the viewpoint of facilitating the production of organic-inorganic hybrid films, alkyl groups having 1 to 5 carbon atoms are more preferred, alkyl groups having 1 to 3 carbon atoms are even more preferred, and methyl or ethyl groups are particularly preferred. In the above alkyl (alkylene amino) amino group, R 4 , R 5 , R 6 , R 7 and m are R in the alkylene amino group above. 4 , R 5 , R 6 , R 7 It can be a base similar to m.

[0040] The above ligand is a trialkylsilyl group (*-SiR 1 R 2 R 3 ) R 1 , R 2and R 3 R can be a group similar to the alkyl group having 1 to 10 carbon atoms used as a ligand. 1 , R 2 and R 3 From the viewpoint of facilitating the production of organic-inorganic hybrid films, it is more preferable that the alkyl group has 1 to 3 carbon atoms, and even more preferable that the alkyl group has 1 to 2 carbon atoms. 1 , R 2 and R 3 It is particularly preferable that they are the same group.

[0041] The alkylenthryalkylsilyl group (*-(CH2)) as the ligand mentioned above m -SiR 1 R 2 R 3 ) R 1 , R 2 and R 3 The R of the above trialkylsilyl group 1 , R 2 and R 3 It can be a group similar to the above. From the viewpoint of facilitating the production of organic-inorganic hybrid films, the above alkylentrialkylsilyl group is more preferably m is 1 to 10, even more preferably m is 1 to 5, and particularly preferably m is 1 to 3.

[0042] The alkyl(trimethylsilyl)amino group (*-NR) as the ligand mentioned above 1 - R in SiMe3) 1 R in the alkyl(trimethylsilyl)amino group can be the same group as the alkyl group having 1 to 10 carbon atoms as the ligand described above. 1 From the viewpoint of facilitating the production of organic-inorganic hybrid films, alkyl groups having 1 to 5 carbon atoms are more preferred, alkyl groups having 1 to 3 carbon atoms are even more preferred, and methyl or ethyl groups are particularly preferred.

[0043] The above ligand is a bis(trialkylsilylamino) group (*-N(SiR 1 R 2 R3 ) 2) R 1 , R 2 and R 3 The R of the above trialkylsilyl group 1 , R 2 and R 3 It can be used as a similar base.

[0044] The alkylimide group as the ligand (* = NR 1 ) R 1 R in the alkylimide group can be the same group as the alkyl group having 1 to 10 carbon atoms as the ligand described above. 1 From the viewpoint of facilitating the production of organic-inorganic hybrid films, alkyl groups having 1 to 6 carbon atoms are more preferred, alkyl groups having 2 to 5 carbon atoms are even more preferred, and tert-butyl groups are particularly preferred.

[0045] The above-mentioned aryl group having 6 to 20 carbon atoms as a ligand may include monocyclic aromatic ring groups such as phenyl and tolyl groups (hereinafter sometimes referred to as "monocyclic aromatic ring groups"), fused aromatic ring groups such as naphthyl, anthracenyl, phenentryl, fluorenyl, and pyrenyl groups (hereinafter sometimes referred to as "fused aromatic ring groups"), monocyclic aromatic ring groups such as biphenyl and benzophenyl groups, or groups in which a fused aromatic ring group is bonded to another monocyclic or fused aromatic ring group via a single bond or a divalent group such as -O-, -S-, -OCO-, and -COO-. In addition, hydrogen atoms in the monocyclic or fused aromatic ring group may be substituted with alkyl groups, such as the tolyl group. The above-mentioned alkyl group may be the same as the alkyl group having 1 to 10 carbon atoms as a ligand. Some or all of the hydrogen atoms in the above-mentioned aryl group having 6 to 20 carbon atoms may be substituted with halogen atoms.

[0046] The cyclopentadiene compound used as the ligand has a five-membered ring of cyclopentadiene and may be substituted with an alkyl group. The alkyl group can be the same as the alkyl group having 1 to 10 carbon atoms used as the ligand. Examples of the cyclopentadiene compound include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, n-butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, tetramethylcyclopentadiene, and pentamethylcyclopentadiene. From the viewpoint of facilitating the production of organic-inorganic hybrid films, the above cyclopentadiene compounds are more preferably unsubstituted cyclopentadiene compounds or cyclopentadiene compounds substituted with alkyl groups having 1 to 5 carbon atoms, even more preferably unsubstituted cyclopentadiene compounds or cyclopentadiene compounds substituted with alkyl groups having 1 to 5 carbon atoms, and particularly preferably unsubstituted cyclopentadiene compounds or cyclopentadiene compounds substituted with alkyl groups having 1 to 4 carbon atoms.

[0047] The diketonate structure (*-O-C(R) used as the ligand above 4 ) = C(R 5 )-C(=O)-R 6 ) is synonymous with the structure represented by the following general formula (4).

[0048]

[0049] In general formula (4), * represents the bonding position with the metal atom, and R 4 , R 5 and R 6 R in the above diketnate structure represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, independently of each other. 4 and R 6From the viewpoint of facilitating the production of organic-inorganic hybrid films, alkyl groups having 1 to 6 carbon atoms are preferred, alkyl groups having 1 to 5 carbon atoms are more preferred, and alkyl groups having 1 to 4 carbon atoms are particularly preferred. R in the above diketnate structure 5 From the viewpoint of facilitating the production of organic-inorganic hybrid films, hydrogen atoms or alkyl groups having 1 to 3 carbon atoms are preferred, hydrogen atoms or methyl groups are more preferred, and hydrogen atoms are particularly preferred.

[0050] The above ligand is a ketoimaginate structure (*-N(R 4 )-C(R 5 ) = C(R 6 )-C(=O)-R 7 ) is synonymous with the structure represented by the following general formula (5).

[0051]

[0052] In general formula (5), * represents the bonding position with the metal atom, and R 4 , R 5 , R 6 and R 7 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0053] The diketiminate structure (*-N(R) used as the ligand above 4 )-C(R 5 ) = C(R 6 ) - C (= NR 7 )-R 8 ) is synonymous with the structure represented by the following general formula (6).

[0054]

[0055] In the above general formula (6), * represents the bonding position with the metal atom, and R 4 , R 5 , R 6 , R 7 and R 8 R in the above diketiminate structure represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, independently of each other. 4 and R 7From the viewpoint of facilitating the production of organic-inorganic hybrid films, alkyl groups having 3 to 6 carbon atoms are more preferred, branched alkyl groups having 3 to 6 carbon atoms are even more preferred, and branched alkyl groups having 3 to 5 carbon atoms are particularly preferred. R in the above diketiminate structure 5 and R 8 From the viewpoint of facilitating the production of organic-inorganic hybrid films, alkyl groups having 1 to 4 carbon atoms are more preferred, alkyl groups having 1 to 3 carbon atoms are even more preferred, and methyl or ethyl groups are particularly preferred. In the above diketiminate structure, R 6 From the viewpoint of facilitating the production of organic-inorganic hybrid films, hydrogen atoms or alkyl groups having 1 to 4 carbon atoms are more preferred, hydrogen atoms or alkyl groups having 1 to 3 carbon atoms are even more preferred, and hydrogen atoms are particularly preferred.

[0056] The amidinate structure (*-N(R) used as the ligand above 4 )-C(R 5 ) = NR 6 ) is synonymous with the structure represented by the following general formula (7).

[0057]

[0058] In general formula (7), * represents the bonding position with the metal atom, and R 4 , R 5 and R 6 R in the above amidinate structure represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, independently of each other. 5 From the viewpoint of facilitating the production of organic-inorganic hybrid films, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferred, a hydrogen atom, a methyl group or an ethyl group is even more preferred, and a hydrogen atom or a methyl group is particularly preferred. R in the above amidinate structure 4 and R 6 From the viewpoint of facilitating the production of organic-inorganic hybrid films, alkyl groups having 1 to 8 carbon atoms are more preferred, alkyl groups having 2 to 8 carbon atoms are even more preferred, and branched alkyl groups having 3 to 8 carbon atoms are particularly preferred.

[0059] The amino alcohol structure used as the ligand above (*-O-(CR 4 R 5 ) m -NR 6 R 7 ) is synonymous with the structure represented by the following general formula (8).

[0060]

[0061] In the above general formula (8), * represents the bonding position with the metal atom, and R 4 , R 5 , R 6 and R 7 Each of the following independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m represents an integer having 1 to 10 carbon atoms. In the above amino alcohol structure, m is more preferably 2 to 4, even more preferably 2 to 3, and particularly preferably 2, from the viewpoint of facilitating the production of organic-inorganic hybrid films. When m is 2 or more, multiple R 4 or R 5 The R of the carbon atom bonded to the oxygen atom may be the same group or different groups, but from the viewpoint of facilitating the production of organic-inorganic hybrid films, 4 and R 5 These are different groups, and the R of the carbon atom that is linked to the nitrogen atom. 4 and R 5 It is preferable that both are hydrogen atoms. In the above amino alcohol structure, R 6 and R 7 From the viewpoint of facilitating the production of organic-inorganic hybrid films, alkyl groups having 1 to 5 carbon atoms are more preferred, alkyl groups having 1 to 3 carbon atoms are even more preferred, and methyl or ethyl groups are particularly preferred.

[0062] In the manufacturing method of this disclosure, preferred metal materials include, for example, the compounds described in the following general formula (1).

[0063]

[0064] In the above general formula (1), M represents a metal atom, L represents a ligand that bonds to the metal atom represented by M, and there may be two or more ligands. t represents the number of metal atoms represented by M, which is between 1 and 5, u represents the number of ligands that bond to the metal atom represented by M, and at least one of the ligands represented by L is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms (*-OR 1 ), monoalkylamino group (*-NHR 1 ), dialkylamino group (*-NR 1 R 2 ), alkylene amino group (*-(CR 4 R 5 ) m -NR 6 R 7 ), alkyl (alkylene amino) amino group (*-NR 1 ((CR 4 R 5 ) m -NR 6 R 7 )), trialkylsilyl group (*-SiR 1 R 2 R 3 ), alkylenthryalkylsilyl group (*-(CH2) m -SiR 1 R 2 R 3 ), alkyl (trimethylsilyl) amino group (*-NR 1 -SiMe3), bis(trialkylsilyl)amino group (*-N(SiR 1 R 2 R 3 ) 2) Alkylimide group (* = NR 1 ), acetonitrile group (*-NC-CH3), carbonyl group (*=C=O), nitroso group (*-N=O), aryl group with 6 to 20 carbon atoms, cyclopentadiene compound, diketnate structure (*-O-C(R 4 ) = C(R 5 )-C(=O)-R 6 ), ketoimaginate structure (*-N(R 4 )-C(R 5 ) = C(R 6)-C(=O)-R 7 ), dikethiminate structure (*-N(R 4 )-C(R 5 ) = C(R 6 ) - C (= NR 7 )-R 8 ), amidinate structure (*-N(R 4 )-C(R 5 ) = NR 6 ) and amino alcohol structure (*-O-(CR 4 R 5 ) m -NR 6 R 7 ) includes a group selected from the group consisting of R 1 , R 2 and R 3 Each of these independently represents an alkyl group having 1 to 10 carbon atoms, and R 4 , R 5 , R 6 , R 7 and R 8 Each of the following independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, m represents an integer between 1 and 10, and if m is 2 or more, there are multiple R 4 , R 5 These may be the same or different, and * represents the bonding position with the metal atom represented by M.

[0065] The above t is the number of metal atoms represented by M contained in one molecule, and is between 1 and 5. However, in this disclosure, from the viewpoint of facilitating the production of organic-inorganic hybrid films, t is more preferably between 1 and 3, even more preferably between 1 and 2, and particularly preferably 1.

[0066] The number of ligands that bond to the metal atom represented by M in the above u is, for example, when A is a trivalent ligand, B is a divalent ligand, and C is a monovalent ligand, then the following seven compounds are examples of metal material structures in which M has two trivalent Al metal atoms and can be composed of ligands A, B, or C: Al2A2, Al2ABC, Al2AC3, Al2B3, Al2BC4, Al2B2C2, and Al2C6. In other words, u is a number that changes in relation to the valence and number of metal atoms in the metal material and the valence of each ligand that bonds to the metal atom. In this disclosure, the total number of ligands that bond to the metal atom represented by M is preferably 1 or more and 10 or less, more preferably 2 or more and 8 or less, and particularly preferably 2 or more and 6 or less, from the viewpoint of facilitating the manufacture of organic-inorganic hybrid films.

[0067] A specific example of a preferred metallic material in which the metal atom represented by M is a bismuth atom or an antimony atom is, for example, a ligand represented by L being a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group (*-OR) having 1 to 10 carbon atoms. 1 ), monoalkylamino group (*-NHR 1 ), dialkylamino group (*-NR 1 R 2 ), aryl group having 6 to 20 carbon atoms, bis(trialkylsilylamino) group (*-N(SiR 1 R 2 R 3 ) 2) Alkylsilylamino group (*-NR 1 -SiMe 3 ), alkylenthryalkylsilyl group (*-(CH2)n-SiR 1 R 2 R 3 ), diketnate structure (*-O-C(R 4 ) = C(R 5 )-C(=O)-R 6 ), ketoimaginate structure (*-N(R 4 )-C(R 5 ) = C(R 6 )-C(=O)-R 7 ), dikethiminate structure (*-N(R 4 )-C(R 5) = C(R 6 ) - C (= NR 7 )-R 8 ), amidinate structure (*-N(R 4 )-C(R 5 ) = NR 6 Examples of compounds include those containing a group selected from the group consisting of ) and cyclopentadiene compounds.

[0068] Specific examples of preferred metallic materials in which the metal atom represented by M is a cobalt atom, a nickel atom, a copper atom, or a zinc atom include, for example, a material in which the ligand represented by L is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms (*-OR 1 ), monoalkylamino group (*-NHR 1 ), dialkylamino group (*-NR 1 R 2 ), alkylene amino group (*-(CR 4 R 5 ) m -NR 6 R 7 ), bis(trialkylsilylamino) group (*-N(SiR 1 R 2 R 3 )2), aryl group having 6 to 20 carbon atoms, cyclopentadiene compound, diketnate structure (*-O-C(R 4 ) = C(R 5 )-C(=O)-R 6 ), ketoimaginate structure (*-N(R 4 )-C(R 5 ) = C(R 6 )-C(=O)-R 7 ), dikethiminate structure (*-N(R 4 )-C(R 5 ) = C(R 6 ) - C (= NR 7 )-R 8 ), amidinate structure (*-N(R 4 )-C(R 5 ) = NR 6 ) and amino alcohol structure (*-O-(CR 4 R 5 ) m -NR 6 R7 Examples of compounds include those containing a group selected from the group consisting of ).

[0069] A specific example of a preferred metallic material in which the metal atom represented by M above is a tin atom is, for example, a material in which the ligand represented by L above is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms (*-OR 1 ), monoalkylamino group (*-NHR 1 ), dialkylamino group (*-NR 1 R 2 ), bis(trialkylsilylamino) group (*-N(SiR 1 R 2 R 3 )2), aryl group having 6 to 20 carbon atoms, cyclopentadiene compound, diketnate structure (*-O-C(R 4 ) = C(R 5 )-C(=O)-R 6 ), ketoimaginate structure (*-N(R 4 )-C(R 5 ) = C(R 6 )-C(=O)-R 7 ), dikethiminate structure (*-N(R 4 )-C(R 5 ) = C(R 6 ) - C (= NR 7 )-R 8 ) and amidinate structure (*-N(R 4 )-C(R 5 ) = NR 6 Examples of compounds include those containing a group selected from the group consisting of ).

[0070] A preferred specific example of a metallic material in which the metal atom represented by M is a titanium atom, a zirconium atom, or a hafnium atom is, for example, a ligand represented by L being a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group (*-OR) having 1 to 10 carbon atoms. 1 ), monoalkylamino group (*-NHR 1 ), dialkylamino group (*-NR 1 R 2 ), alkylenthryalkylsilyl group (*-(CH2)n-SiR 1 R2 R 3 ), bis(trialkylsilyl)amino group (*-N(SiR 1 R 2 R 3 2) Examples include compounds containing a group selected from the group consisting of an aryl group having 6 to 20 carbon atoms and a cyclopentadiene compound.

[0071] A preferred specific example of a metallic material in which the metal atom represented by M is an aluminum atom, a gallium atom, or an indium atom is, for example, a ligand represented by L being a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms (*-OR 1 ), monoalkylamino group (*-NHR 1 ), dialkylamino group (*-NR 1 R 2 ), alkylene amino group (*-(CR 4 R 5 ) m -NR 6 R 7 ), alkyl (alkylene amino) amino group (*-NR 1 ((CR 4 R 5 ) m -NR 6 R 7 )), bis(trialkylsilylamino) group (*-N(SiR 1 R 2 R 3 )2), aryl group having 6 to 20 carbon atoms, cyclopentadiene compound, diketnate structure (*-O-C(R 4 ) = C(R 5 )-C(=O)-R 6 ), ketoimaginate structure (*-N(R 4 )-C(R 5 ) = C(R 6 )-C(=O)-R 7 ), dikethiminate structure (*-N(R 4 )-C(R 5 ) = C(R 6 ) - C (= NR 7 )-R 8 ) and amidinate structure (*-N(R 4 )-C(R5 ) = NR 6 Examples of compounds include those containing a group selected from the group consisting of ).

[0072] A specific example of a preferred metallic material in which the metal atom represented by M is a molybdenum atom is, for example, a ligand represented by L being a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a monoalkylamino group (*-NHR 1 ), dialkylamino group (*-NR 1 R 2 ), alkylene amino group (*-(CR 4 R 5 ) m -NR 6 R 7 ), bis(trialkylsilylamino) group (*-N(SiR 1 R 2 R 3 ) 2) Alkylimide group (* = NR 1 ), acetonitrile group (*-NC-CH3), carbonyl group (*=C=O), nitroso group (*-N=O), aryl group with 6 to 20 carbon atoms, cyclopentadiene compound, diketnate structure (*-O-C(R 4 ) = C(R 5 )-C(=O)-R 6 ), ketoimaginate structure (*-N(R 4 )-C(R 5 ) = C(R 6 )-C(=O)-R 7 ), dikethiminate structure (*-N(R 4 )-C(R 5 ) = C(R 6 ) - C (= NR 7 )-R 8 ) and amidinate structure (*-N(R 4 )-C(R 5 ) = NR 6 Examples of compounds include those containing a group selected from the group consisting of ).

[0073] A specific example of a preferred metallic material in which the metal atom represented by M is a tungsten atom is, for example, a ligand represented by L being a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a monoalkylamino group (*-NHR1 ), dialkylamino group (*-NR 1 R 2 ), bis(trialkylsilylamino) group (*-N(SiR 1 R 2 R 3 ) 2) Alkylimide group (* = NR 1 ), acetonitrile group (*-NC-CH3), carbonyl group (*=C=O), aryl group with 6 to 20 carbon atoms, cyclopentadiene compound, diketnate structure (*-O-C(R 4 ) = C(R 5 )-C(=O)-R 6 ), ketoimaginate structure (*-N(R 4 )-C(R 5 ) = C(R 6 )-C(=O)-R 7 ), and dikethiminate structure (*-N(R 4 )-C(R 5 ) = C(R 6 ) - C (= NR 7 )-R 8 Examples of compounds include those containing a group selected from the group consisting of ).

[0074] A specific example of a preferred metallic material in which the metal atom represented by M above is a tellurium atom is, for example, a ligand represented by L above which is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group (*-OR) having 1 to 10 carbon atoms. 1 ), aryl groups having 6 to 20 carbon atoms and trialkylsilyl groups (*-SiR 1 R 2 R 3 Examples of compounds include those containing a group selected from the group consisting of ).

[0075] Preferred specific examples of the compounds represented by the above general formula (1) include, for example, the compounds No. 1-1 to No. 1-578 listed below. However, the manufacturing method of the present disclosure is not limited to these compounds. In the following chemical formulas, "R" is an alkyl group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the alkyl group may be substituted with halogen atoms. "X" is a halogen atom, "SiMe3" represents a trimethylsilyl group, "m" is the number of repeating units of the methylene group, a number from 1 to 10, and "n" is the number of substituents, a number from 0 to 5.

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096] In this disclosure, from the viewpoint of facilitating the formation of organic-inorganic hybrid films, the first thin film forming raw material is No. 1-1, No. 1-3, No. 1-21, No. 1-34, No. 1-117, No. 1-169, No. 1-221, No. 1-254, No. 1-284, No. 1-322, No. 1-345, No. 1-346, No. 1-367, No. 1-389, No. 1-391, No. 1-428, No. 1-446, No. 1-475, No. 1-524, No. 1-527, No. 1-539, No. 1-554 or No. It is particularly preferable that the compound contains compounds 1-572.

[0097] In this disclosure, when the first thin film forming raw material contains a compound represented by the general formula (1), the content of the compound represented by the general formula (1) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more, especially preferably 90 parts by mass or more, and most preferably 99 parts by mass or more, from the viewpoint of facilitating the production of organic-inorganic hybrid films.

[0098] (2) Other components In this disclosure, the first thin film forming raw material may include a nucleophile as a component other than the metal material.

[0099] (a) Nucleophile The first thin film forming raw material may contain a nucleophile to stabilize the metal material. Examples of the nucleophile include ethylene glycol ethers such as glyme, diglyme, triglyme and tetraglyme; crown ethers such as 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8 and dibenzo-24-crown-8; ethylenediamine, N,N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine and Examples include polyamines such as riethoxytriethyleneamine; cyclic polyamines such as cyclam and cyclene; heterocyclic compounds such as pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, thiazole and oxathiolane; β-ketoesters such as methyl acetoacetate, ethyl acetoacetate and 2-methoxyethyl acetoacetate; and β-diketones such as acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione and dipivaloylmethane.

[0100] When the first thin film forming raw material contains the nucleophile, the amount of the nucleophile is preferably in the range of 0.1 moles to 10 moles, and more preferably in the range of 1 mole to 4 moles, per mole of the total amount of precursor. This is because it makes it easier to stabilize the metal material. The total amount of precursor refers to the total amount of precursor contained in the first thin film forming raw material, and the precursor contained in the first thin film forming raw material refers to the metal material.

[0101] (b) Impurities It is desirable that the first raw material for forming the thin film contains as few impurities as possible, except for the metal material and the nucleophile, such as impurity metal elements, impurity halogens, and impurity organics.

[0102] The above-mentioned impurity metal elements include metal elements different from the above-mentioned metal material or nucleophile. The content of the impurity metal elements in the first thin-film forming raw material is preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less, in terms of elemental content.

[0103] Examples of the above-mentioned impurity halogens include compounds containing halogen atoms that are different from the above-mentioned metal material and nucleophile. The content of the impurity halogens in the first thin-film forming raw material is preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less.

[0104] The above-mentioned impurity organic components include organic compounds containing carbon and oxygen, excluding carbon monoxide and carbon dioxide, and excluding the above-mentioned metal materials and nucleophiles. The total amount of impurity organic components in the above-mentioned first thin film forming raw material is preferably 500 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less.

[0105] Furthermore, since moisture can cause particle generation in the first thin film forming raw material and during thin film formation, it is preferable to remove moisture from the metal material and the nucleophile before use in order to reduce their respective moisture content. The moisture content of the metal material and the nucleophile is preferably 10 ppm or less, and more preferably 1 ppm or less.

[0106] Furthermore, the first thin film forming raw material described above preferably contains as few particles as possible in order to reduce or prevent particle contamination of the formed thin film. Specifically, in particle measurement using a light scattering type liquid particle detector in the liquid phase, it is preferable that the number of particles larger than 0.3 μm is 100 or less per 1 ml of liquid phase, and it is more preferable that the number of particles larger than 0.2 μm is 100 or less per 1 ml of liquid phase.

[0107] (3) First thin film forming raw material The first thin film forming raw material is useful for the MLD method, but can also be used as a thin film forming raw material for ALD. In this disclosure, from the viewpoint of facilitating the production of organic-inorganic hybrid films, the content of the metal material in the first thin film forming raw material is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more, especially preferably 90 parts by mass or more, and most preferably 99 parts by mass or more.

[0108] A2. Second thin film forming raw material The second thin film forming raw material includes an organic material. The organic material can be used without particular limitations as long as it can form an organic layer and is a precursor that can be used in the MLD method. The second thin film forming raw material may include one or more of the organic materials in combination.

[0109] (1) Organic material The above organic material is a compound that does not contain metal atoms and has ligands. Examples of ligands constituting the above organic material include alkyl groups, alkynyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups, amino groups, acrylate groups, vinyl ester groups, carboxylic acid structures, diacid structures, triacid structures, cyclic anhydride moieties, hydroxyl groups, carboxyl groups, amino groups, oxo groups, trialkylsilyl groups, or combinations thereof.

[0110] The second thin-film forming raw material described above may contain one or more of the above-mentioned organic materials in combination. In this disclosure, the above-mentioned organic material is preferably a compound whose thermal decomposition temperature and / or oxidative decomposition behavior are similar to that of the metal material used in the first thin-film forming raw material, from the viewpoint of facilitating the formation of an organic-inorganic hybrid film. When the second thin-film forming raw material described above contains a mixture of two or more precursors as the organic material, it is preferable that the organic material in the mixture is a compound whose thermal decomposition temperature and / or oxidative decomposition behavior are similar to that of the metal material used in the first thin-film forming raw material, and also a compound that does not undergo alteration due to chemical reactions after mixing.

[0111] In this disclosure, from the viewpoint of facilitating the production of organic-inorganic hybrid films, it is preferable that the second thin-film forming raw material contains, as an organic material, a compound represented by the following general formula (2-1), a compound represented by the following general formula (2-2), a compound represented by the following general formula (2-3), 4-isocyanatophenol, alkyl isocyanatoacetate, or phenylethylene glycol.

[0112]

[0113] In general formula (2-1), A represents a direct bond, a divalent aliphatic group having 1 to 20 carbon atoms, a divalent aromatic group having 6 to 20 carbon atoms, or a divalent heterocyclic group having 2 to 20 carbon atoms, and X 1 Y represents a monovalent hydrocarbon group or trialkylsilyl group having 1 to 10 carbon atoms. 1 -O-, -S-, -OCO-, -COO- and -N(X 2 ) - represents a divalent group selected from the group, Y 1 X in 2 This represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a trialkylsilyl group.

[0114]

[0115] In general formula (2-2), X 2 and X 3 Each of these independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 4 carbon atoms, or a trialkylsilyl group, Z 1 This represents a monovalent aliphatic group having 1 to 20 carbon atoms, a monovalent aromatic group having 6 to 20 carbon atoms, or a monovalent heterocyclic group having 2 to 20 carbon atoms. 2 This represents a direct bond or -O-.

[0116]

[0117] (In general formula (2-3), A 2 This represents a divalent aliphatic group with 1 to 20 carbon atoms, a divalent aromatic group with 6 to 20 carbon atoms, or a heterocyclic group or carbonyl group with 2 to 20 carbon atoms.3 -O-, -OCO-, -COO- and -N(X 5 ) - represents a divalent group selected from the group, X 4 and X 5 Each of these independently represents a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 4 carbon atoms, or a trialkylsilyl group, and n represents 0 or 1. However, as described above, A 2 A divalent aliphatic group with 1 to 20 carbon atoms, represented by A, represents a group in which at least one methylene group is substituted with a thioether, thioester, dithioester, or trithioester, or at least one hydrogen atom is substituted with a halogen atom, or at least one heteroatom is contained. 2 A divalent aromatic group having 6 to 20 carbon atoms, represented by , has at least one methylene group substituted with a thioether, thioester, dithioester, or trithioester, or at least one hydrogen atom is a halogen atom or -(Y 3 ) n -X 4 Represents a group that is substituted with or contains at least one heteroatom, and A 2 A heterocyclic group having 2 to 20 carbon atoms, represented by [the symbol], represents a group in which at least one methylene group is substituted with a thioether, thioester, dithioester, or trithioester, or in which at least one hydrogen atom is substituted with a halogen atom.

[0118] (a) Compounds represented by general formula (2-1) In the above general formula (2-1), the divalent aliphatic group having 1 to 20 carbon atoms represented by A is a divalent group that does not contain aromatic rings or heterocycles. Examples of divalent aliphatic groups that do not contain aromatic rings or heterocycles include divalent linear saturated aliphatic groups having 1 to 20 carbon atoms, divalent linear unsaturated aliphatic groups having 2 to 20 carbon atoms, or divalent alicyclic aliphatic groups having 3 to 20 carbon atoms.

[0119] The above-mentioned divalent chain-like saturated aliphatic group having 1 to 20 carbon atoms represents a group having 1 to 20 carbon atoms that does not contain alicyclic hydrocarbons and does not contain carbon-carbon unsaturated bonds. Examples of the above-mentioned divalent chain-like saturated aliphatic group having 1 to 20 carbon atoms include alkylene groups having 1 to 20 carbon atoms, such as methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, sec-butylene group, and tert-butylene group.

[0120] The above-mentioned divalent chain-like unsaturated aliphatic group having 2 to 20 carbon atoms includes groups obtained by abstracting one or more hydrogen atoms from the above-mentioned divalent chain-like saturated aliphatic group having 1 to 20 carbon atoms. Examples of the above-mentioned divalent chain-like unsaturated aliphatic group having 2 to 20 carbon atoms include alkenyl groups such as vinylene group, ethenyl group, 2-propenyl group, 1,1-dimethyl-2-propenyl group, 2-methyl-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, and 2-methyl-3-butenyl group.

[0121] The above-mentioned divalent alicyclic-containing aliphatic group having 3 to 20 carbon atoms is a group having an alicyclic hydrocarbon in its molecule, for example, a group from which two hydrogen atoms have been removed from an alicyclic hydrocarbon, a group in which some hydrogen atoms of a divalent linear saturated aliphatic group or a divalent linear unsaturated aliphatic group are substituted with an alicyclic hydrocarbon, or a group in which some methylene groups of a divalent linear saturated aliphatic group or a divalent linear unsaturated aliphatic group are substituted with an alicyclic hydrocarbon, and represents a group having 3 to 20 carbon atoms.

[0122] The alicyclic hydrocarbon in the above-mentioned divalent alicyclic-containing aliphatic group having 3 to 20 carbon atoms may be a saturated alicyclic, an unsaturated alicyclic, a monocyclic structure, a polycyclic structure having multiple rings, or a spiro structure in which two rings share some carbon atoms of the rings. The above-mentioned divalent alicyclic-containing aliphatic group having 3 to 20 carbon atoms may have one or more alicyclic hydrocarbons.

[0123] Examples of the saturated alicyclic compounds mentioned above include monocyclic cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane; polycyclic cycloalkanes such as decahydronaphthalene, norbornane, norcalane, hausan, basquetan, iaisan, bicycloundecane, adamantane, and isobornane; and spirocyclic cycloalkanes such as spiro[5.5]undecane. A polycyclic structure refers to a polycyclic structure in which the constituent rings share one or more atoms, or two or more atoms.

[0124] The above-mentioned unsaturated alicyclic rings include those in which one or more hydrogen atoms are extracted from the above-mentioned saturated alicyclic ring, resulting in the presence of unsaturated bonds in the ring structure.

[0125] The above divalent aliphatic group having 1 to 20 carbon atoms may be a group in which some of the methylene groups are substituted with -O-, -CO-, -OCO- or -COO-, and some of the hydrogen atoms are [-Y 1 -X 1 It may be substituted with a group represented by ].

[0126] In the above general formula (2-1), the divalent aromatic group having 6 to 20 carbon atoms represented by A represents a group having 6 to 20 carbon atoms that includes an aromatic ring but does not include a heterocycle. Examples of the above divalent aromatic group having 6 to 20 carbon atoms include a group from which two hydrogen atoms have been extracted from one aromatic ring, a group in which some hydrogen atoms of the above divalent linear saturated aliphatic group or divalent linear unsaturated aliphatic group are substituted with an aromatic ring, and a group in which some methylene groups of the divalent linear saturated aliphatic group or divalent linear unsaturated aliphatic group are substituted with an aromatic ring, and which have 6 to 20 carbon atoms.

[0127] The aromatic ring is not particularly limited as long as it is an aromatic ring, and examples include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, pyrene rings, etc. In this disclosure, it is preferable that the aromatic ring is a benzene ring from the viewpoint of facilitating the formation of organic-inorganic hybrid films.

[0128] The above divalent aromatic group having 6 to 20 carbon atoms is a group in which some methylene groups (excluding carbon atoms constituting the aromatic ring) are substituted with -O-, -CO-, -OCO-, or -COO-, and some hydrogen atoms are [-Y 1 -X 1 It may be substituted with a group represented by ].

[0129] The above-mentioned divalent heterocyclic group having 2 to 20 carbon atoms represents a group having a heterocyclic group in its molecule, for example, a group from which two hydrogen atoms have been extracted from one heterocyclic group, a group in which some of the hydrogen atoms of the above-mentioned divalent linear saturated aliphatic group or divalent linear unsaturated aliphatic group are substituted with a heterocyclic group, or a group in which some of the methylene groups of the above-mentioned divalent linear saturated aliphatic group or divalent linear unsaturated aliphatic group are substituted with a heterocyclic group, and represents a group having 2 to 20 carbon atoms.

[0130] The above heterocycle is a ring structure containing carbon atoms and heteroatoms, and examples of heteroatoms constituting the above heterocycle include sulfur atoms, nitrogen atoms, or oxygen atoms. Examples of the above heterocycle include thiophene, thiane, dithiane, thiazole, dithiolane, pyrrole, imidazole, purine, pyridine, pyrimidine, piperidine, piperazine, pyrazine, triazine, furan, tetrahydrofuran, pyran, tetrahydrofuran, dioxane, morpholine, and the like.

[0131] In this disclosure, fused rings of heterocyclic and aromatic rings, such as quinoline, quinazoline, benzofuran, carbazole, indole, and benzimidazole, are also included as heterocycles. Furthermore, in this disclosure, rings containing a structure in which two carbonyl groups are linked to an ether group, and rings containing a structure in which two carbonyl groups are linked to an imide group are also included as heterocycles. Examples of rings containing a structure in which two carbonyl groups are linked to an ether group include dihydrofuran-2,5-dione, isobenzofuran-1,3-dione, dihydro-2H-pyran-2,6(3H)-dione, isochroman-1,3-dione, and oxepane-2,7-dione. Examples of rings containing a structure in which two carbonyl groups are linked to the above-mentioned imide group include pyrrolidine-2,5-dione, isoindoline-1,3-dione, piperidine-2,6-dione, isoquinoline-1,3(2H,4H)-dione, and azepane-2,7-dione.

[0132] The above divalent heterocyclic group having 2 to 20 carbon atoms may be a group in which some of the methylene groups are substituted with -O-, -CO-, -OCO- or -COO-, and some of the hydrogen atoms are [-Y 1 -X 1 It may be substituted with a group represented by ].

[0133] In this disclosure, A in the above general formula (2-1) is more preferably a directly bonded alkylene group having 1 to 5 carbon atoms, even more preferably a directly bonded alkylene group having 1 to 4 carbon atoms, and particularly preferably a directly bonded alkylene group having 1 to 3 carbon atoms, from the viewpoint of facilitating the formation of organic-inorganic hybrid films.

[0134] In the above general formula (2-1), X 1 Examples of monovalent hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and alkynyl groups having 2 to 10 carbon atoms.

[0135] The above X 1The alkyl group having 1 to 10 carbon atoms represented by is R as described in the section "A1. First raw material for forming thin film" above. 1 It can be an alkyl group having 1 to 10 carbon atoms represented by [formula], or a similar group.

[0136] The above X 1 Examples of alkenyl groups with 2 to 10 carbon atoms represented by this formula include vinyl groups, propenyl groups, 2-propenyl groups, 2-methylpropenyl groups, and butenyl groups.

[0137] Examples of the alkynyl group having 2 to 10 carbon atoms include the ethynyl group, propynyl group, 2-propynyl group, and butynyl group.

[0138] The monovalent hydrocarbon group having 1 to 10 carbon atoms may be a group in which some or all of the hydrogen atoms are replaced by fluorine atoms.

[0139] In the above general formula (2-1), X 1 The trialkylsilyl group represented by can be the same as the trialkylsilyl group described in section "A1. First thin film forming raw material".

[0140] In this disclosure, the above X 1 From the viewpoint of facilitating the formation of organic-inorganic hybrid films, it is more preferable that the group is a monovalent hydrocarbon group or trialkylsilyl group having 1 to 4 carbon atoms, even more preferable that it is an alkyl group or trialkylsilyl group having 1 to 3 carbon atoms, and particularly preferable that it is a methyl group, ethyl group, isopropyl group, or trialkylsilyl group.

[0141] Preferred specific examples of the compound represented by the above general formula (2-1) include, for example, the compounds No. 2-1 to No. 2-11 and No. 2-15 to No. 2-48 listed below. However, the manufacturing method of this disclosure is not limited to these compounds.

[0142]

[0143]

[0144] In this disclosure, when the second thin film forming raw material contains a compound represented by general formula (2-1), it is particularly preferable that the second thin film forming raw material contains compounds No. 2-1, No. 2-2, No. 2-3, No. 2-4, No. 2-5, No. 2-7, No. 2-8, No. 2-9, No. 2-11, No. 2-15, No. 2-20, No. 2-24, No. 2-28, No. 2-32, No. 2-37, No. 2-38, No. 2-42, or No. 2-46, from the viewpoint of facilitating the production of organic-inorganic hybrid films.

[0145] In this disclosure, when the second thin film forming raw material contains a compound represented by general formula (2-1), the content of the compound represented by general formula (2-1) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more, especially preferably 90 parts by mass or more, and most preferably 99 parts by mass or more, from the viewpoint of facilitating the production of organic-inorganic hybrid films.

[0146] (b) Compound represented by general formula (2-2) In the above general formula (2-2), X 2 and X 3 A monovalent hydrocarbon group having 1 to 10 carbon atoms, represented by the above general formula (2-1), is X 1 It can be a group similar to a monovalent hydrocarbon group having 1 to 10 carbon atoms represented by .

[0147] In the above general formula (2-2), Z 1 The monovalent aliphatic group represented by is a monovalent aliphatic group having 1 to 20 carbon atoms, which does not contain aromatic rings or heterocycles. Examples include monovalent linear saturated aliphatic groups having 1 to 20 carbon atoms, monovalent linear unsaturated aliphatic groups having 2 to 20 carbon atoms, or monovalent alicyclic aliphatic groups having 3 to 20 carbon atoms.

[0148] The above-mentioned monovalent linear saturated aliphatic group having 1 to 20 carbon atoms represents a group that does not contain an alicyclic structure and does not contain carbon-carbon unsaturated bonds. Examples of the above-mentioned monovalent linear saturated aliphatic group having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group.

[0149] The above-mentioned monovalent linear unsaturated aliphatic group having 2 to 20 carbon atoms includes groups obtained by abstracting one or more hydrogen atoms from the above-mentioned monovalent linear saturated aliphatic group having 1 to 20 carbon atoms. Examples of the above-mentioned monovalent linear unsaturated aliphatic group having 2 to 20 carbon atoms include alkenyl groups having 2 to 20 carbon atoms, such as vinyl groups, ethenyl groups, 2-propenyl groups, 1,1-dimethyl-2-propenyl groups, 2-methyl-butenyl groups, 3-methyl-2-butenyl groups, 3-methyl-3-butenyl groups, and 2-methyl-3-butenyl groups.

[0150] The above-mentioned monovalent alicyclic-containing aliphatic group having 3 to 20 carbon atoms is a group having an alicyclic hydrocarbon in its molecule, for example, a group from which one hydrogen atom has been removed from an alicyclic hydrocarbon, a monovalent linear saturated aliphatic group or a monovalent linear unsaturated aliphatic group in which some of the hydrogen atoms have been replaced by an alicyclic hydrocarbon, or a group in which some of the methylene groups of a monovalent linear saturated aliphatic group or a monovalent linear unsaturated aliphatic group have been replaced by an alicyclic hydrocarbon, and represents a group having 3 to 20 carbon atoms.

[0151] The alicyclic hydrocarbons in the monovalent alicyclic-containing aliphatic group having 3 to 20 carbon atoms mentioned above are the same as those in the divalent alicyclic-containing aliphatic group having 3 to 20 carbon atoms represented by A in the general formula (2-1) above.

[0152] The above monovalent aliphatic group having 1 to 20 carbon atoms may be a group in which some of the methylene groups are substituted with -O-, -CO-, -OCO-, or -COO-.

[0153] In the above general formula (2-2), X 2The monovalent aromatic group having 6 to 20 carbon atoms represented by contains a ring having aromaticity, does not contain a heterocycle, and represents a group having 6 to 20 carbon atoms. Examples of the monovalent aromatic group having 6 to 20 carbon atoms include a group obtained by removing one hydrogen atom from one aromatic ring, a group obtained by substituting an aromatic ring for some hydrogen atoms of the monovalent chain saturated aliphatic group or monovalent chain unsaturated aliphatic group, and a group obtained by substituting an aromatic ring for some methylene groups of the monovalent chain saturated aliphatic group or monovalent chain unsaturated aliphatic group, which is a group having 6 to 20 carbon atoms.

[0154] The aromatic ring in the above-mentioned monovalent aromatic group having 6 to 20 carbon atoms is the same as the aromatic ring in the divalent aromatic group having 6 to 20 carbon atoms represented by A in the above general formula (2-1). The above-mentioned monovalent aromatic group having 6 to 20 carbon atoms may be a group in which some methylene groups are substituted with -O-, -CO-, -OCO- or -COO-.

[0155] The above-mentioned monovalent heterocycle-containing group having 2 to 20 carbon atoms is a group having a heterocycle in the molecule, and examples include a group obtained by removing one hydrogen atom from the heterocycle, a group obtained by substituting a heterocycle for some hydrogen atoms of the monovalent chain saturated aliphatic group or monovalent chain unsaturated aliphatic group, and a group obtained by substituting a heterocycle for some methylene groups of the monovalent chain saturated aliphatic group or monovalent chain unsaturated aliphatic group, which is a group having 2 to 20 carbon atoms.

[0156] The heterocycle in the above-mentioned monovalent heterocycle-containing group having 2 to 20 carbon atoms is the same as the heterocycle in the divalent heterocycle-containing group having 2 to 20 carbon atoms represented by A in the above general formula (2-1). The above-mentioned monovalent heterocycle-containing group having 2 to 20 carbon atoms may be a group in which some methylene groups are substituted with -O-, -CO-, -OCO- or -COO-.

[0157] In the present disclosure, the above X 2 is more preferably a monovalent aromatic group having 6 to 20 carbon atoms, and particularly preferably a benzene ring, from the viewpoint of facilitating the formation of an organic-inorganic hybrid film.

[0158] Preferable specific examples of the compound represented by the above general formula (2-2) include, for example, the following compounds No. 2-12 to No. 2-14. However, the production method of the present disclosure is not limited by these compounds.

[0159]

[0160] In the present disclosure, when the second raw material for thin film formation contains a compound represented by general formula (2-2), from the viewpoint of facilitating production of an organic-inorganic hybrid film, it is particularly preferable that the second raw material for thin film formation contains the compound of No. 2-12.

[0161] In the present disclosure, when the second raw material for thin film formation contains a compound represented by general formula (2-2), from the viewpoint of facilitating production of an organic-inorganic hybrid film, the content of the compound represented by general formula (2-2) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, still more preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more, even more particularly preferably 90 parts by mass or more, and most preferably 99 parts by mass or more, per 100 parts by mass of the second raw material for thin film formation.

[0162] (c) Compound represented by general formula (2-3) The compound represented by the above general formula (2-3) does not contain the compound represented by the above general formula (2-1).

[0163] In the above general formula (2-3), A 2 Examples of the divalent aliphatic group having 1 to 20 carbon atoms represented by include groups in which, in the divalent aliphatic group having 1 to 20 carbon atoms represented by A in the above general formula (2-1), some methylene groups are substituted with thioether, thioester, dithioester or trithioester, at least one hydrogen atom is substituted with a halogen atom, or the group contains at least one heteroatom.

[0164] In the above general formula (2-3), A 2Examples of divalent aromatic groups having 6 to 20 carbon atoms, represented by the above general formula (2-1), include divalent aromatic groups having 6 to 20 carbon atoms, represented by A in the above general formula (2-1), in which some methylene groups are substituted with thioethers, thioesters, dithioesters, or trithioesters, or at least one hydrogen atom is substituted with a halogen atom, or a group containing at least one heteroatom.

[0165] In the above general formula (2-3), A 2 Examples of heterocyclic groups having 2 to 20 carbon atoms, represented by the above general formula (2-1), include heterocyclic groups having 2 to 20 carbon atoms, represented by A in the above general formula (2-1), in which some methylene groups are substituted with thioethers, thioesters, dithioesters, or trithioesters, or in which at least one hydrogen atom is substituted with a halogen atom.

[0166] The above X 4 and X 5 A monovalent hydrocarbon group having 1 to 4 carbon atoms, represented by the above general formula (2-1), is X 1 Examples include monovalent hydrocarbon groups with 1 to 10 carbon atoms, where the number of carbon atoms is the same.

[0167] In this disclosure, the above X 4 From the viewpoint of facilitating the formation of organic-inorganic hybrid films, the group is preferably a hydroxyl group, a hydrocarbon group having 1 to 3 carbon atoms, or a trialkylsilyl group; more preferably a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or a trimethylsilyl group or triethylsilyl group; and even more preferably a hydroxyl group, a methyl group, or a trimethylsilyl group.

[0168] Preferred specific examples of compounds represented by the above general formula (2-3) include, for example, the compounds represented by No. 2-49 to No. 2-110 below. However, the manufacturing method of this disclosure is not limited to these compounds.

[0169]

[0170]

[0171]

[0172] In this disclosure, when the second thin film forming raw material contains a compound represented by general formula (2-3), from the viewpoint of facilitating the production of organic-inorganic hybrid films, the second thin film forming raw material is No. 2-49, No. 2-52, No. 2-53, No. 2-54, No. 2-55, No. 2-56, No. 2-60, No. 2-64, No. 2-67, No. 2-71, No. 2-80, No. 2-81, No. 2-82, No. 2-83, No. 2-84, No. 2-85, No. 2-86, No. 2-87, No. 2-89, No. 2-94, No. 2-96, No. 2-97, No. It is particularly preferable to include compounds 2-98, No. 2-102, No. 2-106, or No. 2-110.

[0173] In this disclosure, when the second thin film forming raw material contains a compound represented by general formula (2-3), the content of the compound represented by general formula (2-3) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more, especially preferably 90 parts by mass or more, and most preferably 99 parts by mass or more, from the viewpoint of facilitating the production of organic-inorganic hybrid films.

[0174] (d) Other Compounds In this disclosure, the second thin film forming raw material may include other compounds other than those represented by the general formulas (2-1) to (2-3). Examples of other compounds include the compounds No. 2-111 to No. 2-113 listed below.

[0175]

[0176] In this disclosure, if the second thin film forming raw material contains the other compounds, the content of the other compounds is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more, especially preferably 90 parts by mass or more, and most preferably 99 parts by mass or more, from the viewpoint of facilitating the production of organic-inorganic hybrid films, per 100 parts by mass of the second thin film forming raw material.

[0177] (2) Other components In this disclosure, the second raw material for forming a thin film may include a nucleophile as a component other than the organic material.

[0178] (a) Nucleophile The second thin film forming raw material may contain a nucleophile in order to stabilize the organic material. The nucleophile may be a compound similar to the nucleophile that can be used in the first thin film forming raw material.

[0179] When the second thin film forming raw material contains the nucleophile, the amount of the nucleophile is preferably in the range of 0.1 moles to 10 moles, and more preferably in the range of 1 mole to 4 moles, per mole of the total amount of precursor. This is because it makes it easier to stabilize the organic material. Here, the total amount of precursor refers to the total amount of precursor contained in the second thin film forming raw material.

[0180] (b) Impurities It is desirable that the second raw material for forming the thin film contains as few impurities as possible, except for the organic material and the nucleophile, such as impurity metal elements, impurity halogens, and impurity organics.

[0181] The above-mentioned impurity metal elements include metal elements different from those of the nucleophile. The content of the impurity metal elements in the second thin-film forming raw material is preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less, in terms of elemental content.

[0182] Examples of the above-mentioned impurity halogens include compounds containing halogen atoms that are different from the above-mentioned organic material or nucleophile. The content of the impurity halogens in the second thin-film forming raw material is preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less.

[0183] The above-mentioned impurity organic components include compounds containing carbon and oxygen, excluding carbon monoxide and carbon dioxide, and organic compounds excluding the above-mentioned organic materials and nucleophiles. The content of impurity organic components in the second thin film forming raw material is preferably 500 ppm or less in total, more preferably 50 ppm or less, and even more preferably 10 ppm or less.

[0184] Furthermore, since moisture can cause particle generation in the second thin film forming raw material and during thin film formation, it is preferable to remove moisture from the metal material and the nucleophile before use in order to reduce their respective moisture content. The moisture content of the metal material and the nucleophile is preferably 10 ppm or less, and more preferably 1 ppm or less.

[0185] Furthermore, the second thin film forming raw material described above is preferably made to contain as few particles as possible in order to reduce or prevent particle contamination of the formed thin film. Specifically, in particle measurement using a light scattering type liquid particle detector in the liquid phase, it is preferable that the number of particles larger than 0.3 μm is 100 or less per 1 ml of liquid phase, and it is more preferable that the number of particles larger than 0.2 μm is 100 or less per 1 ml of liquid phase.

[0186] (3) Second thin film forming raw material The second thin film forming raw material described above is useful for the MLD method, but can also be used as a thin film forming raw material for the ALD method.

[0187] A3. Raw Material for Thin Film Formation In the production method of the present disclosure, the raw material for thin film formation is characterized by satisfying both of the following conditions (A) or (B). Condition (A): the metal material includes a compound represented by the above general formula (1). Condition (B): the organic material includes a compound represented by the above general formula (2-1), a compound represented by the above general formula (2-2), the above general formula (2-3), 4-isocyanatophenol, alkyl isocyanatoacetate or a compound represented by phenylethylene glycol.

[0188] From the perspective of facilitating the production of an organic-inorganic hybrid film in the production method of the present disclosure, it is preferable that the first raw material for thin film formation includes the compound represented by the above general formula (1), and the second raw material for thin film formation includes the compound represented by the above general formula (2-1) or the compound represented by the above general formula (2-3).

[0189] B. Film Forming Process Next, the film forming process in the production method of the present disclosure will be described. A well-known ALD apparatus can be used as the apparatus used in the production method of the present disclosure. Examples of specific apparatuses include an apparatus capable of supplying a precursor by bubbling as shown in Fig. 1 and Fig. 3, and an apparatus having a vaporization chamber 102 as shown in Fig. 2 and Fig. 4. Further, as shown in Fig. 3 and Fig. 4, there may be mentioned an apparatus capable of performing plasma treatment on the film forming chamber 100. The apparatus is not limited to a single-wafer apparatus provided with the film forming chamber 100 as shown in Fig. 1 to Fig. 4, and an apparatus capable of simultaneously processing a plurality of wafers using a batch furnace can also be used. These apparatuses can also be used as CVD apparatuses.

[0190] The production method of the present disclosure relates to a method for producing an organic-inorganic hybrid film, which uses a molecular layer deposition (MLD) method and forms the organic-inorganic hybrid film by using the first raw material for thin film formation and the second raw material for thin film formation.

[0191] In some embodiments, the manufacturing method of the present disclosure includes, for example, a metal layer formation step of introducing a first raw material gas obtained by vaporizing the first thin film forming raw material into a film formation chamber in which a substrate has been previously placed, and depositing a metal material contained in the first raw material gas onto the surface of the substrate to form a metal layer, and an organic layer formation step of introducing a second raw material gas obtained by vaporizing the second thin film forming raw material into a film formation chamber, and depositing an organic material contained in the second raw material gas onto the surface of the substrate on which the metal layer has been formed to form an organic layer.

[0192] In another embodiment, the process includes an organic layer formation step in which a second raw material gas obtained by vaporizing the second thin film forming raw material is introduced into a film formation chamber in which a substrate has been previously installed, and an organic material contained in the second raw material gas is deposited on the surface of the substrate to form an organic layer, and a metal layer formation step in which a first raw material gas obtained by vaporizing the first thin film forming raw material is introduced into a film formation chamber, and a metal material contained in the first raw material gas is deposited on the surface of the substrate on which the organic layer has been formed to form a metal layer.

[0193] The steps of the manufacturing method described herein will be explained below with reference to Figures 1 to 4.

[0194] B1. Metal layer formation process In this process, a first raw material gas obtained by vaporizing a first thin film formation raw material M1 containing a metal material is introduced into the film formation chamber 100, and the metal material in the first raw material gas is deposited on the surface of the substrate S or the organic layer described later to form a metal layer.

[0195] (1) Substrate The substrate S is not particularly limited as long as it can support the metal layer. The substrate S may be any known substrate, for example, an organic compound or an inorganic compound. Examples of materials for the substrate S include silicon; ceramics such as silicon nitride, titanium nitride, tantalum nitride, titanium oxide, molybdenum oxide, zirconium oxide, hafnium oxide, and lanthanum oxide; glass; and metals such as metallic cobalt, metallic molybdenum, molybdenum sulfide, molybdenum selenide, tungsten sulfide, or tungsten selenide. Examples of substrate shapes include plate-like shapes such as flakes, flat plates or discs, fibrous shapes, cylindrical shapes, prismatic shapes, tubular shapes, spiral shapes, spherical shapes, ring shapes, or three-dimensional structures such as trench structures.

[0196] The above-mentioned surface of the substrate includes not only the surface of the substrate S, but also the surface of the metal layer, organic layer, or organic-inorganic hybrid film formed by each step of the manufacturing method described later.

[0197] (2) Introduction of the first raw material gas The first raw material gas is obtained by vaporizing the first thin film forming raw material M1 which contains the metal material. A method for obtaining the first raw material gas is, for example, a method of heating and / or reducing the pressure of the first thin film forming raw material M1.

[0198] Methods for heating the first thin film forming raw material M1 include, for example, heating the first thin film forming raw material in the raw material container 101 of the ALD apparatus shown in Figure 1 or Figure 3 using a heater 103 or the like, or heating the first thin film forming raw material in the vaporization chamber 102 of the ALD apparatus shown in Figure 2 or Figure 4. The temperature range for heating the first thin film forming raw material M1 is preferably 130°C or lower, more preferably 40°C to 120°C, and even more preferably 80°C to 100°C, from the viewpoint of preventing thermal decomposition of the first thin film forming raw material M1, enabling a fast film formation rate, and facilitating the formation of a high-purity organic-inorganic hybrid film with uniform film thickness.

[0199] As a method for reducing the pressure of the first thin film forming raw material M1 described above, for example, a method of reducing the pressure of the first thin film forming raw material in the raw material container 101 of the ALD apparatus described in Figure 1 or Figure 3, or a method of reducing the pressure of the first thin film forming raw material in the vaporization chamber 102 of the ALD apparatus described in Figure 2 or Figure 4. As for the above pressure reduction (vacuum level) conditions, from the viewpoint of facilitating the formation of organic-inorganic hybrid films, for example, it is preferable to be in the range of 1 Pa to 10,000 Pa, more preferably in the range of 10 Pa to 5,000 Pa, and even more preferably in the range of 20 Pa to 1,000 Pa.

[0200] Methods for introducing the first raw material gas into the film deposition chamber 100 include gas transport and liquid transport. For example, as shown in Figures 1 and 3, the first thin-film forming raw material M1 is heated and / or vaporized in the raw material container 101 to produce the first raw material gas, and this gas is introduced into the film deposition chamber 100 along with a carrier gas 201 such as argon, nitrogen, or helium, as needed. For example, as shown in Figures 2 and 4, the first thin-film forming raw material M1 is transported in liquid or solution form to the vaporization chamber 102, where it is heated and / or depressurized to produce the first raw material gas, and this gas is introduced into the film deposition chamber 100 along with a carrier gas 201 such as argon, nitrogen, or helium, as needed. The flow rate of each gas is controlled by a mass flow controller (MFC) 104. Furthermore, if the first thin-film forming raw material M1 contains the other precursors mentioned above, the first raw material gas can be introduced into the film formation chamber 100, for example, using a single-source method.

[0201] (3) Formation of a metal layer In the metal layer formation step described above, as stated above, a metal material from the first raw material gas introduced into the film formation chamber 100 is deposited on the surface of a substrate S that has been previously placed in the film formation chamber 100 to form a metal layer. In this disclosure, "deposit" refers to a concept that includes the chemical adsorption of a compound on the surface of the substrate S.

[0202] In this process, it is preferable to heat either the film deposition chamber 100 or the substrate S. The heating temperature of the film deposition chamber 100 or the substrate S can be appropriately selected depending on the type of metal material, but from the viewpoint of facilitating the deposition of organic-inorganic hybrid films, it is preferable to heat between 25°C and 250°C, more preferably between 25°C and 200°C, even more preferably between 25°C and 150°C, and particularly preferably between 25°C and 100°C.

[0203] In this process, the heating of the first raw material gas is preferably carried out in a non-oxygen atmosphere, and more preferably in an inert gas atmosphere such as nitrogen gas or argon gas, from the viewpoint of facilitating the formation of the organic-inorganic hybrid film. Furthermore, the heating reaction may be carried out under any of the following conditions: under pressure, under reduced pressure, at normal pressure, or at atmospheric pressure. However, in this process, it is preferable to carry it out under reduced pressure (20 Pa to 1,000 Pa) from the viewpoint of facilitating the formation of the organic-inorganic hybrid film.

[0204] B2. Organic Layer Formation Process In this process, a second raw material gas obtained by vaporizing a second thin film forming raw material M2 containing an organic material is introduced into the film formation chamber 100, and the organic layer contained in the second raw material gas is deposited on the surface of the substrate to form an organic layer. In this process, the substrate can be the same as the substrate described in section B1. Metal Layer Formation Process, and a metal layer, an organic layer, or an organic-inorganic hybrid film may be formed on the surface of the substrate.

[0205] (1) Introduction of the second raw material gas In the manufacturing method of the present disclosure, the second raw material gas is obtained by vaporizing the second thin film forming raw material M2 which contains an organic material. As for the method of obtaining the second raw material gas, in the section "(2) Introduction of the first raw material gas" in "B1. Metal layer formation process", the first thin film forming raw material M1 which contains the metal material is replaced with the second thin film forming raw material M2 which contains the organic material, and the first raw material gas is replaced with the second raw material gas, so the explanation is omitted here. In this process, from the viewpoint of facilitating the production of organic-inorganic hybrid films, for example, in the ALD apparatus shown in Figures 1 to 4, it is preferable not to supply the metal material and the organic material to the film formation chamber 100 at the same time, and to separate the supply lines for the first gas and the second gas from the raw material container 101 to the film formation chamber 100, so as not to bring the first thin film forming raw material M1 which contains the metal material and the second thin film forming raw material M2 which contains the organic material into direct contact.

[0206] (2) Formation of the organic layer In this step, as described above, an organic layer is formed by depositing the organic material contained in the second raw material gas introduced into the film formation chamber 100 onto the surface of the substrate S which has been previously placed inside the film formation chamber 100. In this step, it is preferable to heat either the inside of the film formation chamber 100 or the substrate S, from the viewpoint that heating the second raw material gas promotes the formation of the organic layer, but the heating temperature of the inside of the film formation chamber 100 or the substrate S may be the same as in "B1. Metal layer formation step".

[0207] This step may also involve forming an organic layer using a second thin-film forming raw material containing the compound represented by the general formula (2-1), the compound represented by the general formula (2-2), the compound represented by the general formula (2-3), 4-isocyanatophenol, alkyl isocyanatoacetate, or phenylethylene glycol, and then further forming an organic layer using a second thin-film forming raw material containing a compound other than the one used to form the organic layer, from among the compounds represented by the general formula (2-1), the compound represented by the general formula (2-2), the compound represented by the general formula (2-3), 4-isocyanatophenol, alkyl isocyanatoacetate, or phenylethylene glycol.

[0208] B3. Reactive gas introduction step The manufacturing method of the present disclosure may include a reactive gas introduction step in which a reactive gas 202 is introduced into the film formation chamber 100 and the reactive gas is brought into contact with the metal layer or organic layer.

[0209] (1) Reactive gas The type of reactive gas 202 is not limited, but from the viewpoint of facilitating the formation of organic-inorganic hybrid films, a reactive gas comprising at least one selected from the group consisting of water vapor, oxygen, ozone, hydrogen, halogens, hydrogen halides, and monovalent or divalent alcohols having 1 to 10 carbon atoms is preferred.

[0210] Examples of halogens used as reactive gases include fluorine gas, chlorine gas, bromine gas, or iodine gas.

[0211] Examples of the hydrogen halides used as reactive gases include hydrofluoric acid gas, hydrochloric acid gas, hydrogen bromide gas, and hydrogen iodide gas.

[0212] Examples of monohydric or dihydric alcohols having 1 to 10 carbon atoms as the reactive gas include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, pentyl alcohol, isopentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, cyclopentanol, cyclohexanol, and other monohydric alcohols; and dihydric alcohols such as ethylene glycol and propylene glycol. Furthermore, the above monohydric or dihydric alcohols may be substituted with an ether group, such as 2-methoxyethanol.

[0213] (2) Introduction of reactive gas The reactive gas 202 can be introduced into the film deposition chamber 100 together with a carrier gas 201 such as argon, nitrogen, or helium, as needed. As for the method of introducing the reactive gas, the first raw material gas can be replaced with the reactive gas in the section "(2) Introduction of first raw material gas" of "B1. Metal layer formation process".

[0214] (3) Other gases In this step, the reactive gas 202 may contain other gases. Examples of these other gases include organic amine compounds such as monoalkylamines, dialkylamines, and trialkylamines; nitriding gases obtained by vaporizing hydrazine, etc.; sulfurizing gases such as sulfur, hydrogen sulfide, dimethyl sulfide, diethyl sulfide, and diisopropyl sulfide; and inert gases such as argon and nitrogen. Two or more of these other gases may be used in mixture form. In the manufacturing method of this disclosure, from the viewpoint of facilitating the formation of an organic-inorganic hybrid film, the content of the other gases in the reactive gas is preferably 50% by volume or less, more preferably 10% by volume or less, and even more preferably 5% by volume or less.

[0215] From the viewpoint of facilitating the formation of organic-inorganic hybrid films, this step is preferably performed after the metal layer formation step or the organic layer formation step.

[0216] B4. Other steps The manufacturing method disclosed herein may include other steps such as an exhaust step, a plasma treatment step, an annealing step, a reflow step, etc.

[0217] (1) Exhaust Process 1 This process, performed after the metal layer formation process, involves exhausting (203) the unreacted first raw material gas that did not participate in the formation of the metal layer or by-product gases generated during the formation of the metal layer from the film deposition chamber 100. Ideally, the unreacted first raw material gas and by-product gases should be completely exhausted from the film deposition chamber 100 in this process, but complete exhaust is not always necessary. Examples of exhaust methods include purging the system of the film deposition chamber 100 with an inert gas (purge gas 204) such as helium, nitrogen, or argon; exhausting the system by reducing the pressure while controlling the degree of pressure reduction with a vacuum pump 107 and an automatic pressure controller 108; and methods combining these. The exhausted first raw material gas is liquefied in a cooling trap 109. When reducing the pressure within the system, the degree of reduction is preferably in the range of 0.01 Pa to 300 Pa, more preferably in the range of 0.05 Pa to 200 Pa, and particularly preferably in the range of 0.1 Pa to 150 Pa. This is because the exhaust of the first raw material gas is sufficient, and the formation of the organic-inorganic hybrid membrane is facilitated.

[0218] (2) Exhaust process 2 This process is performed after the organic layer formation process to exhaust (203) the unreacted second raw material gas that did not participate in the formation of the organic layer, or by-product gases generated during the formation of the organic layer, from inside the film formation chamber 100. In this process, it is ideal that the unreacted second raw material gas and by-product gases are completely exhausted from inside the film formation chamber 100, but it is not necessarily required to exhaust them completely. The exhaust method and degree of reduced pressure can be carried out under the same conditions as in exhaust process 1.

[0219] (3) Exhaust Process 3 This process is performed after the reactive gas introduction process to exhaust (203) unreacted reactive gas that did not participate in the reaction with the metal layer or organic layer, or by-product gases generated by the reaction between the metal layer or organic layer and the reactive gas, from inside the film deposition chamber 100. In this process, it is ideal that the unreacted reactive gas and by-product gases are completely exhausted from inside the film deposition chamber 100, but it is not necessarily required to exhaust them completely. The exhaust method and degree of reduced pressure can be carried out under the same conditions as in Exhaust Process 1.

[0220] (4) Plasma Treatment Step The manufacturing method of the present disclosure may include a plasma treatment step in which a voltage is applied to a first raw material gas, a second raw material gas, or a reactive gas to induce plasma formation in order to promote the formation of the metal layer or the organic layer. Plasma-formed reactive gas can also be used in this step. As a method for inducing plasma formation of a reactive gas, for example, a method of applying a direct current (DC) current, an alternating current (RF) current, microwaves, etc., to the reactive gas. Specifically, as shown in Figures 3 and 4, an RF matching system 106 connected to a high-frequency (RF) power supply 105 can be installed in the film deposition chamber 100, and plasma formation can be performed within the film deposition chamber 100.

[0221] In this process, as shown in Figures 3 and 4, an RF matching system 106 connected to a high-frequency (RF) power supply 105 is installed in the deposition chamber 100, allowing the first or second raw material gas to be plasma-generated within the deposition chamber 100. In this process, if the power applied when the voltage is too high, it will cause significant damage to the substrate S supporting the metal layer and organic layer. Therefore, the power applied when the voltage is to be applied is preferably in the range of 10W to 1,500W, more preferably in the range of 30W to 1,000W, and preferably in the range of 50W to 600W.

[0222] (5) Annealing Process This process may be an annealing process for the organic-inorganic hybrid film in order to improve the electrical properties of the organic-inorganic hybrid film. In this process, the organic-inorganic hybrid film may be annealed in an inert atmosphere. In this process, there is no temperature limit as long as the temperature does not damage the organic-inorganic hybrid film, however, for example, it is preferably in the range of 100°C to 270°C, more preferably in the range of 150°C to 260°C, and even more preferably in the range of 200°C to 250°C.

[0223] (6) Reflow Process This process may be a process in which the organic-inorganic hybrid film is heated after the organic-inorganic hybrid film has been formed in order to fill in any steps in the hybrid film. There is no temperature limit in the reflow process as long as the temperature does not damage the organic-inorganic hybrid film, but for example, it is preferably in the range of 200°C to 600°C, more preferably in the range of 230°C to 550°C, and particularly preferably in the range of 250°C to 500°C.

[0224] B5. Film Formation Cycle In the manufacturing method disclosed herein, from the viewpoint of facilitating the formation of an organic-inorganic hybrid film, it is preferable that the metal layer formation step and exhaust step 1, the organic layer formation step and exhaust step 2, and the reactive gas introduction step and exhaust step 3 are performed as a set. The order of the metal layer formation step, organic layer formation step, and reactive gas introduction step is not limited. For example, the organic layer formation step or the reactive gas introduction step may be performed after the metal layer formation step and exhaust step 1, or the metal layer formation step and exhaust step 1 may be repeated. The metal layer formation step or the reactive gas introduction step may be performed after the organic layer formation step and exhaust step 2, or the organic layer formation step and exhaust step 2 may be repeated. The metal layer formation step, organic layer formation step, and reactive gas introduction step can be freely performed until an organic-inorganic hybrid film of the required thickness is obtained.

[0225] B6. Organic-Inorganic Hybrid Film The above organic-inorganic hybrid film can have a metal layer and an organic layer, each independently having a thickness of about 0.1 Å to about 1,000 Å, preferably 1 Å to 800 Å, more preferably 10 Å to 600 Å, and particularly preferably 50 Å to 500 Å. Applications of the above organic-inorganic hybrid film include use in photoresists, gas storage materials, catalysts, conductive materials, and magnetic materials in semiconductor manufacturing.

[0226] C. Embodiments of Organic-Inorganic Hybrid Films As embodiments of organic-inorganic hybrid films, for example, it is possible to form fine patterns on the organic-inorganic hybrid film by lithography. Examples of pattern formation methods for forming the fine patterns include a manufacturing method comprising: (1) an organic film hybrid film formation step for forming an organic-inorganic hybrid film; (2) an exposure step for exposing the organic-inorganic hybrid film; and (3) a processing step such as developing the exposed organic-inorganic hybrid film.

[0227] C1. Organic-Inorganic Hybrid Film Formation Process The process for forming the organic-inorganic hybrid film is described in detail in section B. Film Formation Process, so the explanation here is omitted. When performing the exposure process described later, the film thickness of the organic-inorganic hybrid film is preferably 50 nm or less. This is because a film thickness of 50 nm or less allows for uniform exposure.

[0228] C2. In the exposure process pattern formation method, the exposure process can be carried out by a well-known method. There are no restrictions on the wavelength of the light source used in the exposure process, but for example, infrared light, visible light, ultraviolet light, far ultraviolet or extreme ultraviolet (EUV) is preferred, and in particular, an exposure process using light with a wavelength of 10 nm or more and 300 nm or less is preferred. Specifically, examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, EUV (13 nm), and electron beams.

[0229] When exposing the above organic-inorganic hybrid film by electron beam lithography, the suitable electron beam energy can be in the range of approximately 5 V to approximately 200 kV, preferably 7.5 V to 150 kV. The beam dose at 130 kV is 0.1 μC / cm². 2 1 mC / cm or more 2 Preferably, 1 μC / cm 2 More than 5000μC / cm 2 The following may be done. The above exposure process may be performed multiple times.

[0230] C3. Processing steps: After the exposure step described above, the process typically includes a developing step, in which the image is developed using a developer solution, and a rinsing step, in which a rinse solution is used.

[0231] (1) Development process The development process is a process of developing the exposed organic-inorganic hybrid film with a developer. The development method can be a well-known development method, for example, a method of immersing the organic-inorganic hybrid film in a tank filled with developer for a certain period of time, a method of building up the developer on the surface of the organic-inorganic hybrid film by surface tension and holding it there for a certain period of time, or a method of spraying the developer onto the surface of the organic-inorganic hybrid film. The development time is preferably 10 seconds or more and 300 seconds or less, and more preferably 20 seconds or more and 120 seconds or less. The developer can be a known developer, for example, the developer described in Japanese Patent Application Publication No. 2024-029021. The development process may be performed multiple times.

[0232] (2) Rinsing process The rinsing process is a process in which the film is washed with a rinsing solution after the developing process described above. The washing process can be carried out by a well-known washing method, for example, a method in which the organic-inorganic hybrid film is rotated and the rinse solution is continuously discharged, a method in which the organic-inorganic hybrid film is immersed in a tank filled with rinsing solution for a certain period of time, or a method in which the rinsing solution is sprayed onto the surface of the organic-inorganic hybrid film. The rinsing time is preferably 10 seconds or more and 300 seconds or less, and more preferably 20 seconds or more and 120 seconds or less. A known rinsing solution can be used as the rinsing solution. The rinsing process may be carried out multiple times.

[0233] (3) Other processing steps After the exposure step described above, it is preferable to perform a bake treatment after exposure in order to provide a large contrast in the properties of the material between the area irradiated with an electron beam and the area that was not irradiated. It is also preferable to perform a bake treatment after the rinsing step described above in order to dry the rinsing liquid. The heating temperature is preferably 80°C to 400°C, more preferably 100°C to 350°C, and even more preferably 120°C to 330°C, for both the bake treatment after the exposure step and the bake treatment after the rinsing step. The heating time is preferably 10 seconds to 1,000 seconds, more preferably 30 seconds to 300 seconds, and even more preferably 40 seconds to 120 seconds, for both the bake treatment after the exposure step and the bake treatment after the rinsing step. Heating may be performed using ancillary equipment of the exposure apparatus or developing apparatus, or it may be performed using a heating device such as a hot plate.

[0234] The present disclosure will be further described below with reference to examples. However, the present disclosure is not limited by the following examples. In the compounds used in the examples, "tAm" represents a tert-amyl group, "Me" represents a methyl group, "tBu" represents a tert-butyl group, "aamd" represents an amidinate group, "Et" represents an ethyl group, "sBu" represents a sec-butyl group, "acac" represents an acetylacetonate group, "nBu" represents an n-butyl group, "Cp" represents a cyclopentadienyl group, and "iPr" represents an isopropyl group.

[0235] [Example 1] Production of Bismuth Organic-Inorganic Hybrid Film 1 Compound No. 1-21 represented by general formula (1) was used as the first thin film formation raw material, and compound No. 2-3 represented by general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0236] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-3 Bis(trimethylsilyl) oxalate Substrate: Silicon wafer

[0237] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 85°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-3) obtained was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0238] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing bismuth atoms, and its carbon content was 14.3 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 7.3 nm, and the film thickness obtained per cycle was approximately 0.007 nm.

[0239] [Example 2] Production of Bismuth Organic-Inorganic Hybrid Film 2 The first and second thin film formation raw materials were the same as those in Example 1, but the film formation conditions were changed as described below to produce an organic-inorganic hybrid film on a silicon wafer substrate.

[0240] (Conditions) Reaction temperature (substrate temperature): 100°C First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-3 Bis(trimethylsilyl) oxalate Reactive gas: Water vapor Substrate: Silicon wafer

[0241] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-3) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 85°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0242] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing bismuth atoms, and its carbon content was 23.5 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 27.0 nm, and the film thickness obtained per cycle was approximately 0.054 nm.

[0243] [Example 3] Production of Bismuth Organic-Inorganic Hybrid Film 3 A bismuth organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions, using compound No. 1-21 represented by general formula (1) as the first thin film formation raw material, and compound No. 2-3 represented by general formula (2-1) and compound No. 2-12 represented by general formula (2-2) as the second thin film formation raw materials.

[0244] (Conditions) Reaction temperature (substrate temperature): 100°C First thin film forming raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film forming raw material A: Compound No. 2-3 Bis(trimethylsilyl) oxalate Second thin film forming raw material B: Compound No. 2-12 Bis(trimethylsilyl)phenyl phosphate

[0245] (Process) The following series of processes (1) to (6) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material A for thin film formation was vaporized under the conditions of raw material container temperature: 85°C and raw material container internal pressure: 26.7 Pa (0.2 torr). The second raw material gas A (vapor of compound No. 2-3) was introduced into the film formation chamber, and the metal layer and the second raw material gas A were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas A and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (5) The second raw material B for thin film formation was vaporized under the conditions of raw material container temperature: 85°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas B (vapor of compound No. 2-12) obtained was introduced into the film formation chamber, and the metal layer or organic layer was reacted with the second raw material gas B for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas B and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0246] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing bismuth atoms, and its carbon content was 23.5 atom%. Furthermore, when the film thickness of the organic-inorganic hybrid film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 27.0 nm, and the film thickness obtained per cycle was approximately 0.054 nm.

[0247] [Example 4] Manufacturing of Bismuth Organic-Inorganic Hybrid Film 4 The first and second thin film formation raw materials were the same as those in Example 3, but the film formation conditions were changed as described below to manufacture an organic-inorganic hybrid film on a silicon wafer substrate.

[0248] (Conditions) Reaction temperature (substrate temperature): 100°C First thin film forming raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film forming raw material A: Compound No. 2-3 Bis(trimethylsilyl) oxalate Second thin film forming raw material B: Compound No. 2-12 Bis(trimethylsilyl)phenyl phosphate

[0249] (Process) The following series of processes (1) to (6) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material B for thin film formation was vaporized under the conditions of raw material container temperature: 85°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas B (vapor of compound No. 2-12) obtained was introduced into the film formation chamber, and the metal layer and the second raw material gas B were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas B and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (5) The second raw material gas A (vapor of compound No. 2-3), obtained by vaporizing the second thin film forming raw material A under the conditions of raw material container temperature: 85°C and raw material container internal pressure: 26.7 Pa (0.2 torr), was introduced into the film formation chamber, and the metal layer or organic layer was reacted with the second raw material gas A for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas A and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0250] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing bismuth atoms, and its carbon content was 23.5 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 27.0 nm, and the film thickness obtained per cycle was approximately 0.054 nm.

[0251] [Example 5] Manufacturing of Bismuth Organic-Inorganic Hybrid Film 5 The first and second thin film formation raw materials were the same as those in Example 3, but the film formation conditions were changed as described below to manufacture an organic-inorganic hybrid film on a silicon wafer substrate.

[0252] (Conditions) Reaction temperature (substrate temperature): 100°C First thin film forming raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film forming raw material A: Compound No. 2-3 Bis(trimethylsilyl) oxalate Second thin film forming raw material B: Compound No. 2-12 Bis(trimethylsilyl)phenyl phosphate Reactive gas: Water vapor

[0253] (Process) The following series of processes (1) to (12) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas A (vapor of compound No. 2-3), obtained by vaporizing the second thin film forming raw material A under the conditions of raw material container temperature: 85°C and raw material container pressure: 26.7 Pa (0.2 torr), was introduced into the film formation chamber, and the metal layer and the second raw material gas A were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas A and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were discharged from the system by argon purging for 15 seconds (exhaust step 3). (9) The second raw material gas B (vapor of compound No. 2-12), obtained by vaporizing the second thin film forming raw material B under the conditions of raw material container temperature: 85°C and raw material container pressure: 26.7 Pa (0.2 torr), was introduced into the film formation chamber, and the metal layer or organic layer was reacted with the second raw material gas B for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (10) Unreacted second raw material gas B and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).(11) A reactive gas was introduced into the film deposition chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (12) Unreacted reactive gas and by-product gases were discharged from the system by argon purging for 15 seconds (exhaust step 3).

[0254] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing bismuth atoms, and its carbon content was 23.5 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 27.0 nm, and the film thickness obtained per cycle was approximately 0.054 nm.

[0255] [Example 6] Manufacturing of Bismuth Organic-Inorganic Hybrid Film 6 The first and second thin film formation raw materials were the same as those in Example 3, but the film formation conditions were changed as described below to manufacture an organic-inorganic hybrid film on a silicon wafer substrate.

[0256] (Conditions) Reaction temperature (substrate temperature): 100°C First thin film forming raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film forming raw material A: Compound No. 2-3 Bis(trimethylsilyl) oxalate Second thin film forming raw material B: Compound No. 2-12 Bis(trimethylsilyl)phenyl phosphate

[0257] (Process) The following series of processes (1) to (12) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas B (vapor of compound No. 2-12), obtained by vaporizing the second thin film formation raw material B under the conditions of raw material container temperature: 85°C and raw material container pressure: 26.7 Pa (0.2 torr), was introduced into the film formation chamber, and the metal layer and the second raw material gas B were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas B and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were discharged from the system by argon purging for 15 seconds (exhaust step 3). (9) The second raw material gas A (vapor of compound No. 2-3), obtained by vaporizing the second thin film forming raw material A under the conditions of raw material container temperature: 85°C and raw material container pressure: 26.7 Pa (0.2 torr), was introduced into the film formation chamber, and the metal layer or organic layer was reacted with the second raw material gas A for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (10) Unreacted second raw material gas A and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).(11) A reactive gas was introduced into the film deposition chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (12) Unreacted reactive gas and by-product gases were discharged from the system by argon purging for 15 seconds (exhaust step 3).

[0258] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing bismuth atoms, and its carbon content was 23.5 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 27.0 nm, and the film thickness obtained per cycle was approximately 0.054 nm.

[0259] [Example 7] Manufacturing of Bismuth Organic-Inorganic Hybrid Film 7 Compound No. 1-1 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-8 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was manufactured on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0260] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-1 Bi(CH2SiMe3)3 Second thin film formation raw material: Compound No. 2-8 Bis(trimethylsilyl) methylmalonate Substrate: Silicon wafer

[0261] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-1) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 70°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-1 from the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-8) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0262] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing bismuth atoms, and its carbon content was 20.1 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 5.8 nm, and the film thickness obtained per cycle was approximately 0.006 nm.

[0263] [Example 8] Production of Bismuth Organic-Inorganic Hybrid Film 8 Compound No. 1-3 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-3 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0264] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-3 Bi[N(Me)SiMe3]3 Second thin film formation raw material: Compound No. 2-3 Bis(trimethylsilyl) oxalate Substrate: Silicon wafer

[0265] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-3) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 80°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-3 from the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-3) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0266] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing bismuth atoms, and its carbon content was 15.5 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 10.9 nm, and the film thickness obtained per cycle was approximately 0.011 nm.

[0267] [Example 9] Production of Antimony Organic-Inorganic Hybrid Film 1 Compound No. 1-34 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-2 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0268] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-34 Sb(CH2SiMe3)3 Second thin film formation raw material: Compound No. 2-2 1,2-bis(trimethylsilylthio)ethane substrate: Silicon wafer

[0269] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-34) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 65°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-34 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 70°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-2) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0270] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing antimony, and its carbon content was 18.9 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 8.2 nm, and the film thickness obtained per cycle was approximately 0.008 nm.

[0271] [Example 10] Production of tin organic-inorganic hybrid film 1 Compound No. 1-284 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-4 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0272] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-284 Sn(NMe2)4 Second thin film formation raw material: Compound No. 2-4 Dimethyl oxalate substrate: Silicon wafer

[0273] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-284) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-284 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-4) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0274] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing tin, and its carbon content was 15.2 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 6.5 nm, and the film thickness obtained per cycle was approximately 0.007 nm.

[0275] [Example 11] Production of tin organic-inorganic hybrid film 2 Compound No. 1-322 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-11 represented by the above general formula (2-1) was used as the second thin film formation raw material, and an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0276] (Manufacturing conditions) Manufacturing method: ALD method Reaction temperature (substrate temperature): 100°C First thin film formation raw material: Compound No. 1-322 Sn(NMe2)(tBu-aamd) Second thin film formation raw material: Compound No. 2-11 Bis(trimethylsilyl) terephthalate Substrate: Silicon wafer

[0277] The following series of steps (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-322) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 65°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-322 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation step). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust step 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 95°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-11) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0278] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing tin, and its carbon content was 27.8 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 21.9 nm, and the film thickness obtained per cycle was approximately 0.022 nm.

[0279] [Example 12] Production of a cobalt organic-inorganic hybrid film Compound No. 1-117 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-7 represented by the above general formula (2-1) was used as the second thin film formation raw material, and an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0280] (Manufacturing conditions) Manufacturing method: ALD method Reaction temperature (substrate temperature): 150°C First thin film formation raw material: Compound No. 1-117 Co[OCH(tBu)CH2N(Et)Me]2 Second thin film formation raw material: Compound No. 2-7 Bis(trimethylsilyl) malonate

[0281] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-117) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 105°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-117 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-7) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0282] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing cobalt, and its carbon content was 19.3 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 9.7 nm, and the film thickness obtained per cycle was approximately 0.010 nm.

[0283] [Example 13] Production of nickel organic-inorganic hybrid film Compound No. 1-169 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-5 represented by the above general formula (2-1) was used as the second thin film formation raw material, and an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0284] (Conditions) Reaction temperature (substrate temperature): 100°C First thin film formation raw material: Compound No. 1-169 Ni[OCH(Et)CH2N(Et)Me]2 Second thin film formation raw material: Compound No. 2-5 Diethyl oxalate substrate: Silicon wafer

[0285] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-169) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 85°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-169 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-5) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0286] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing nickel, and its carbon content was 12.9 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 7.1 nm, and the film thickness obtained per cycle was approximately 0.007 nm.

[0287] [Example 14] Production of copper organic-inorganic hybrid film 1 Compound No. 1-221 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-5 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0288] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (4)) First thin film formation raw material: Compound No. 1-221 Cu[OCH(Me)CH2N(Et)Me]2 Second thin film formation raw material: Compound No. 2-5 Diethyl oxalate substrate: Silicon wafer

[0289] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-221) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 75°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-221 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-5) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0290] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing copper atoms, and its carbon content was 14.1 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 17.5 nm, and the film thickness obtained per cycle was approximately 0.018 nm.

[0291] [Example 15] Production of Zinc Organic-Inorganic Hybrid Film 1. Compound No. 1-254 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-9 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0292] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-254 Zn(Et)(sBu-acac-dikethymine) Second thin film formation raw material: Compound No. 2-9 1,4-bis(trimethylsilyloxy)benzene substrate: silicon wafer

[0293] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-254) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 95°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-254 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 60°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-9) obtained was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0294] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing zinc atoms, and its carbon content was 29.5 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 11.3 nm, and the film thickness obtained per cycle was approximately 0.011 nm.

[0295] [Example 16] Production of Zirconium Organic-Inorganic Hybrid Film 1. Compound No. 1-367 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-2 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0296] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-367 Zr(NET2)4 Second thin film formation raw material: Compound No. 2-2 1,2-bis(trimethylsilylthio)ethane substrate: silicon wafer

[0297] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-367) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 100°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-367 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 70°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-2) obtained was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0298] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing zirconium atoms, and its carbon content was 22.4 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 8.7 nm, and the film thickness obtained per cycle was approximately 0.009 nm.

[0299] [Example 17] Production of Titanium Organic-Inorganic Hybrid Film 1. Using compound No. 1-345 represented by the above general formula (1) as the first thin film formation raw material, and compound No. 2-1 represented by the above general formula (2-1) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0300] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-345 Ti(NMe2)4 Second thin film formation raw material: Compound No. 2-1 1,2-bis(trimethylsilyloxy)ethane substrate: silicon wafer

[0301] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-345) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-345 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-1) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0302] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing titanium atoms, and its carbon content was 19.8 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 13.1 nm, and the film thickness obtained per cycle was approximately 0.013 nm.

[0303] [Example 18] Production of Titanium Organic-Inorganic Hybrid Film 2 Compound No. 1-346 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-7 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0304] (Conditions) Reaction temperature (substrate temperature): 150°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-346 Ti(nBuCp)Cl3 Second thin film formation raw material: Compound No. 2-7 Bis(trimethylsilyl) malonate Substrate: Silicon wafer

[0305] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-346) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 130°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-346 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-7) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0306] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing titanium atoms, and its carbon content was 20.5 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 6.9 nm, and the film thickness obtained per cycle was approximately 0.007 nm.

[0307] [Example 19] Production of Hafnium Organic-Inorganic Hybrid Film 1. Compound No. 1-389 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-4 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0308] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-389 Hf[N(Et)Me]4 Second thin film formation raw material: Compound No. 2-4 Dimethyl oxalate substrate: Silicon wafer

[0309] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-389) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 70°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-389 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-4) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0310] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing hafnium atoms, and its carbon content was 13.9 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 15.2 nm, and the film thickness obtained per cycle was approximately 0.015 nm.

[0311] [Example 20] Production of Hafnium Organic-Inorganic Hybrid Film 2 Compound No. 1-391 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-9 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0312] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (4)) First thin film formation raw material: Compound No. 1-391 Hf(Cp)(OtBu)3 Second thin film formation raw material: Compound No. 2-9 1,4-bis(trimethylsilyloxy)benzene substrate: Silicon wafer

[0313] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-391) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 60°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-391 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 60°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-9) obtained was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0314] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing hafnium atoms, and its carbon content was 31.2 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 10.4 nm, and the film thickness obtained per cycle was approximately 0.010 nm.

[0315] [Example 21] Production of Aluminum Organic-Inorganic Hybrid Film 1. Compound No. 1-446 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-11 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0316] (Conditions) Reaction temperature (substrate temperature): 100°C First thin film formation raw material: Compound No. 1-446 Al(Me)2(iPr-aamd) Second thin film formation raw material: Compound No. 2-11 Bis(trimethylsilyl) terephthalate Substrate: Silicon wafer

[0317] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-446) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-446 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 95°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-11) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0318] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing aluminum atoms, and its carbon content was 28.7 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 18.3 nm, and the film thickness obtained per cycle was approximately 0.018 nm.

[0319] [Example 22] Production of Aluminum Organic-Inorganic Hybrid Film 2 Compound No. 1-428 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-5 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0320] (Conditions) Reaction temperature (substrate temperature): 100°C First thin film formation raw material: Compound No. 1-428 Al[N(Et)Me]2[N(Me)CH2CH2NMe2] Second thin film formation raw material: Compound No. 2-5 Diethyl oxalate substrate: Silicon wafer

[0321] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-428) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 70°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-428 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-5) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0322] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing aluminum atoms, and its carbon content was 15.1 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 7.8 nm, and the film thickness obtained per cycle was approximately 0.008 nm.

[0323] [Example 23] Production of Gallium Organic-Inorganic Hybrid Film 1. Compound No. 1-475, represented by the above general formula (1), was used as the first thin film formation raw material, and compound No. 2-8, represented by the above general formula (2-1), was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0324] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-475 [Ga(NMe2)3]2 Second thin film formation raw material: Compound No. 2-8 Bis(trimethylsilyl) methylmalonate Substrate: Silicon wafer

[0325] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-475) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 100°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-475 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-8) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0326] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing gallium atoms, and its carbon content was 23.4 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 20.1 nm, and the film thickness obtained per cycle was approximately 0.020 nm.

[0327] [Example 24] Production of Indium Organic-Inorganic Hybrid Film 1. Compound No. 1-527 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-3 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0328] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-527 In(Me)2(tBu-diketone) Second thin film formation raw material: Compound No. 2-3 Bis(trimethylsilyl) oxalate Substrate: Silicon wafer

[0329] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-527) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-527 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-3) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0330] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing indium atoms, and its carbon content was 13.6 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 12.4 nm, and the film thickness obtained per cycle was approximately 0.012 nm.

[0331] [Example 25] Production of Indium Organic-Inorganic Hybrid Film 2 Compound No. 1-539 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-1 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0332] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (4)) First thin film formation raw material: Compound No. 1-539 In(Me)2(sBu-acac-dikethymine) Second thin film formation raw material: Compound No. 2-1 1,2-bis(trimethylsilyloxy)ethane substrate: Silicon wafer

[0333] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-539) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-539 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-1) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0334] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing indium atoms, and its carbon content was 21.7 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 6.2 nm, and the film thickness obtained per cycle was approximately 0.006 nm.

[0335] [Example 26] Production of Indium Organic-Inorganic Hybrid Film 3. Compound No. 1-524 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-2 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0336] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (4)) First thin film formation raw material: Compound No. 1-524 In(Me)2(CH2CH2CH2NET2) Second thin film formation raw material: Compound No. 2-2 1,2-bis(trimethylsilylthio)ethane substrate: Silicon wafer

[0337] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-524) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 55°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-524 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 70°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-2) obtained was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0338] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing indium atoms, and its carbon content was 19.2 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 16.8 nm, and the film thickness obtained per cycle was approximately 0.017 nm.

[0339] [Example 27] Production of Molybdenum Organic-Inorganic Hybrid Film 1. Compound No. 1-572 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-4 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0340] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (4)) First thin film formation raw material: Compound No. 1-572 Mo(=NtBu)2(NMe2)2 Second thin film formation raw material: Compound No. 2-4 Dimethyl oxalate substrate: Silicon wafer

[0341] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-572) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 55°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-572 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 40°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-4) obtained from this vaporization was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0342] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing molybdenum atoms, and its carbon content was 16.3 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 11.7 nm, and the film thickness obtained per cycle was approximately 0.012 nm.

[0343] [Example 28] Production of Molybdenum Organic-Inorganic Hybrid Film 2 Compound No. 1-554 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-9 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0344] (Conditions) Reaction temperature (substrate temperature): 150°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-554 Mo(iPrCp)2H2 Second thin film formation raw material: Compound No. 2-9 1,4-bis(trimethylsilyloxy)benzene substrate: silicon wafer

[0345] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-554) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 115°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-554 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 60°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-9) obtained was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0346] The composition of the obtained organic-inorganic hybrid film was analyzed by X-ray diffraction, and the carbon content in the organic-inorganic hybrid film was measured by X-ray photoelectron spectroscopy. The organic-inorganic hybrid film was a thin film containing molybdenum atoms, and its carbon content was 32.1 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 8.5 nm, and the film thickness obtained per cycle was approximately 0.009 nm.

[0347] [Example 29] Manufacturing of Bismuth Organic-Inorganic Hybrid Film 9 Compound No. 1-21 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-52 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was manufactured on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0348] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-52 2-iodomalonate bis(trimethylsilyl) Substrate: Silicon wafer

[0349] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-52) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0350] The obtained organic-inorganic hybrid film was subjected to compositional analysis by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and peaks of 619 eV and 630 eV originating from iodine were identified. The thin film contained bismuth atoms and iodine atoms, and the carbon content was 13.5 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 28.8 nm, and the film thickness obtained per cycle was approximately 0.058 nm.

[0351] [Example 30] Production of tin organic-inorganic hybrid film 3 Compound No. 1-280 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-49 represented by the above general formula (2-3) was used as the second thin film formation raw material, and an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0352] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (8)) First thin film formation raw material: Compound No. 1-280 Sn(OtBu)4 Second thin film formation raw material: Compound No. 2-49 2-fluoromalonate bis(trimethylsilyl) Reactive gas: Water vapor Substrate: Silicon wafer

[0353] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-280) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-280 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-49) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0354] The obtained organic-inorganic hybrid film was subjected to compositional analysis by X-ray photoelectron spectroscopy. Peaks of 487 eV and 495 eV originating from Sn-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 685 eV originating from fluorine were identified. The thin film contained tin and fluorine atoms, and the carbon content was 15.3 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 25.6 nm, and the film thickness obtained per cycle was approximately 0.051 nm.

[0355] [Example 31] Production of Aluminum Organic-Inorganic Hybrid Film 3 Compound No. 1-424 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-53 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0356] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-424 Al(OiPr)3 Second thin film formation raw material: Compound No. 2-53 2-dimethyl fluoromalonate Reactive gas: Water vapor Substrate: Silicon wafer

[0357] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-424) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-424 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-53) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0358] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks were identified: a 74 eV peak originating from Al-O bonds, a 289 eV peak originating from ester bonds, a 531 eV peak originating from CO bonds, and a 685 eV peak originating from fluorine. This indicated that the thin film contained aluminum and fluorine atoms, with a carbon content of 12.7 atoms. Furthermore, when the film thickness was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 23.2 nm, and the film thickness obtained per cycle was approximately 0.046 nm.

[0359] [Example 32] Production of Bismuth Organic-Inorganic Hybrid Film 10 Using compound No. 1-21 represented by the above general formula (1) as the first thin film formation raw material, and using compound No. 2-56 represented by the above general formula (2-3) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0360] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-56 2-iodomalonate dimethyl Reactive gas: Water vapor Substrate: Silicon wafer

[0361] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-56) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0362] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and peaks of 619 eV and 630 eV originating from iodine were identified. This indicated that the thin film contained bismuth and iodine atoms, and the carbon content was 13.6 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 29.1 nm, and the film thickness obtained per cycle was approximately 0.058 nm.

[0363] [Example 33] Production of Indium Organic-Inorganic Hybrid Film 4. Compound No. 1-518 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-55 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0364] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-518 In(OiPr)3 Second thin film formation raw material: Compound No. 2-55 2-Dimethyl bromomalonate Reactive gas: Water vapor Substrate: Silicon wafer

[0365] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-518) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-518 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-55) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0366] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 444 eV and 452 eV originating from In-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 70 eV originating from bromine were identified. The thin film contained indium and bromine atoms, and the carbon content was 11.8 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 25.5 nm, and the film thickness obtained per cycle was approximately 0.051 nm.

[0367] [Example 34] Production of Zinc Organic-Inorganic Hybrid Film 2 Compound No. 1-254 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-54 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0368] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-254 Zn(Et)(sBu-acac-dikethymine) Second thin film formation raw material: Compound No. 2-54 2-chloromalonate dimethyl Reactive gas: Water vapor Substrate: Silicon wafer

[0369] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-254) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-254 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-54) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0370] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 1022 eV and 1045 eV originating from Zn-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 199 eV originating from chlorine were identified. This indicated that the thin film contained zinc atoms and chlorine atoms, and the carbon content was 13.0 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 26.3 nm, and the film thickness obtained per cycle was approximately 0.053 nm.

[0371] [Example 35] Production of Zirconium Organic-Inorganic Hybrid Film 2 Compound No. 1-367 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-67 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0372] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-367 Zr(NET2)4 Second thin film formation raw material: Compound No. 2-67 Bis(trimethylsilyl)2,3-dibromosuccinate Reactive gas: Water vapor Substrate: Silicon wafer

[0373] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-367) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-367 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-67) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0374] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 181 eV and 184 eV originating from Zr-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 70 eV originating from bromine were identified. This indicated that the thin film contained zirconium and bromine atoms, and the carbon content was 9.9 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 19.3 nm, and the film thickness obtained per cycle was approximately 0.039 nm.

[0375] [Example 36] Production of Titanium Organic-Inorganic Hybrid Film 3 Compound No. 1-345 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-64 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0376] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-345 Ti(NMe2)4 Second thin film formation raw material: Compound No. 2-64 Dimethyl 2,2-diiodomalonic acid ester Reactive gas: Water vapor Substrate: Silicon wafer

[0377] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-345) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-345 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-64) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0378] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 458 eV and 464 eV originating from Ti-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and peaks of 619 eV and 630 eV originating from iodine were identified. The thin film contained titanium atoms and iodine atoms, and the carbon content was 10.1 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 23.3 nm, and the film thickness obtained per cycle was approximately 0.047 nm.

[0379] [Example 37] Production of Hafnium Organic-Inorganic Hybrid Film 3 Compound No. 1-389 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-71 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0380] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-389 Hf[N(Et)Me]4 Second thin film formation raw material: Compound No. 2-71 Dimethyl 2,3-dibromosuccinate Reactive gas: Water vapor Substrate: Silicon wafer

[0381] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-389) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-389 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-71) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0382] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 14 eV and 16 eV originating from Hf-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 70 eV originating from bromine were identified. This indicated that the thin film contained hafnium and bromine atoms, and the carbon content was 11.7 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 20.4 nm, and the film thickness obtained per cycle was approximately 0.041 nm.

[0383] [Example 38] Production of Aluminum Organic-Inorganic Hybrid Film 4. Compound No. 1-428 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-80 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0384] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (8)) First thin film formation raw material: Compound No. 1-428 Al[N(Et)Me]2[N(Me)CH2CH2NMe2] Second thin film formation raw material: Compound No. 2-80 Dimethyl 3-iodocyclopropane-1,2-dicarboxylic acid ester Reactive gas: Water vapor Substrate: Silicon wafer

[0385] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-428) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-428 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-80) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0386] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks were identified at 74 eV originating from Al-O bonds, 289 eV originating from ester bonds, 531 eV originating from CO bonds, and 619 eV and 630 eV originating from iodine. This indicated that the thin film contained aluminum and iodine atoms, and the carbon content was 13.9 atom%. Furthermore, when the film thickness was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 17.7 nm, and the film thickness obtained per cycle was approximately 0.035 nm.

[0387] [Example 39] Production of Bismuth Organic-Inorganic Hybrid Film 11 Using compound No. 1-21 represented by the above general formula (1) as the first thin film formation raw material, and using compound No. 2-81 represented by the above general formula (2-3) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0388] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-81 Bis(trimethylsilyl)2,2'-thiodiacetic acid Reactive gas: Water vapor Substrate: Silicon wafer

[0389] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-81) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0390] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 228 eV originating from sulfur were identified. This indicated that the thin film contained bismuth atoms and sulfur atoms, and the carbon content was 12.4 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 22.2 nm, and the film thickness obtained per cycle was approximately 0.044 nm.

[0391] [Example 40] Production of tin organic-inorganic hybrid film 4 Compound No. 1-280 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-82 represented by the above general formula (2-3) was used as the second thin film formation raw material, and an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0392] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (8)) First thin film formation raw material: Compound No. 1-280 Sn(OtBu)4 Second thin film formation raw material: Compound No. 2-82 Dimethyl 2,2'-thiodiacetic acid Reactive gas: Water vapor Substrate: Silicon wafer

[0393] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-280) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-280 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-82) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0394] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 487 eV and 495 eV originating from Sn-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 228 eV originating from sulfur were identified. The thin film contained tin and sulfur atoms, and the carbon content was 17.9 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 25.6 nm, and the film thickness obtained per cycle was approximately 0.051 nm.

[0395] [Example 41] Production of Indium Organic-Inorganic Hybrid Film 5. Compound No. 1-539 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-83 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0396] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (8)) First thin film formation raw material: Compound No. 1-539 In(Me)2(sBu-acac-dikethymine) Second thin film formation raw material: Compound No. 2-83 Bis(trimethylsilyl)2,2'-disulfanediyldiacetic acid Reactive gas: Water vapor Substrate: Silicon wafer

[0397] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-539) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-539 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-83) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0398] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 444 eV and 452 eV originating from In-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 227 eV originating from sulfur were identified, indicating that the thin film contained indium atoms and sulfur atoms, with a carbon content of 14.1 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 18.9 nm, and the film thickness obtained per cycle was approximately 0.038 nm.

[0399] [Example 42] Production of Molybdenum Organic-Inorganic Hybrid Film 3 Compound No. 1-572 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-84 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0400] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (8)) First thin film formation raw material: Compound No. 1-572 Mo(=NtBu)2(NMe2)2 Second thin film formation raw material: Compound No. 2-84 Dimethyl 2,2'-disulfanediyldiacetic acid Reactive gas: Water vapor Substrate: Silicon wafer

[0401] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-572) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-572 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-84) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0402] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 228 eV and 232 eV originating from Mo-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 227 eV originating from sulfur were identified. This indicated that the thin film contained molybdenum and sulfur atoms, and the carbon content was 21.5 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 21.5 nm, and the film thickness obtained per cycle was approximately 0.043 nm.

[0403] [Example 43] Production of tin organic-inorganic hybrid film 5 Compound No. 1-322 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-15 represented by the above general formula (2-1) was used as the second thin film formation raw material, and an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0404] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (8)) First thin film formation raw material: Compound No. 1-322 Sn(NMe2)(tBu-aamd) Second thin film formation raw material: Compound No. 2-15 Bis(trimethylsilyl)thiophene-2,5-dicarboxylic acid ester Reactive gas: Water vapor Substrate: Silicon wafer

[0405] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-322) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-322 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-15) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0406] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 487 eV and 495 eV originating from Sn-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 228 eV originating from sulfur were identified. The thin film contained tin and sulfur atoms, and the carbon content was 23.5 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 13.8 nm, and the film thickness obtained per cycle was approximately 0.028 nm.

[0407] [Example 44] Production of tin organic-inorganic hybrid film 6 Compound No. 1-284 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-94 represented by the above general formula (2-3) was used as the second thin film formation raw material, and an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0408] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (4)) First thin film formation raw material: Compound No. 1-284 Sn(NMe2)4 Second thin film formation raw material: Compound No. 2-94 (E)-2,3-dibrobuter-2-ene-1,4-diol Reactive gas: Water vapor Substrate: Silicon wafer

[0409] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-284) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-284 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-94) obtained was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0410] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks at 487 eV and 495 eV originating from Sn-O bonds, peaks at 286 eV and 531 eV originating from C-O bonds, and a peak at 70 eV originating from bromine were identified. This indicated that the thin film contained tin and bromine atoms, and the carbon content was 12.2 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 22.4 nm, and the film thickness obtained per cycle was approximately 0.045 nm.

[0411] [Example 45] Production of Antimony Organic-Inorganic Hybrid Film 2 Compound No. 1-34 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-89 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0412] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-34 Sb(CH2SiMe3)3 Second thin film formation raw material: Compound No. 2-89 CH2(OH)CH(OH)CH2Cl Reactive gas: Water vapor Substrate: Silicon wafer

[0413] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-34) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-34 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-89) obtained was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0414] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks at 528 eV and 537 eV originating from Sb-O bonds, peaks at 286 eV and 531 eV originating from C-O bonds, and a peak at 199 eV originating from chlorine were identified. This indicated that the thin film contained antimony and chlorine atoms, and the carbon content was 9.5 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 27.8 nm, and the film thickness obtained per cycle was approximately 0.056 nm.

[0415] [Example 46] Production of Bismuth Organic-Inorganic Hybrid Film 12 Using compound No. 1-1 represented by the above general formula (1) as the first thin film formation raw material, and using compound No. 2-96 represented by the above general formula (2-3) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0416] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-1 Bi(CH2SiMe3)3 Second thin film formation raw material: Compound No. 2-96 S(CH2CH2OH)2 Substrate: Silicon wafer

[0417] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-1) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-1 from the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-96) obtained was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0418] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, peaks of 286 eV and 531 eV originating from C-O bonds, and a peak of 228 eV originating from sulfur were identified, indicating that the thin film contained bismuth and sulfur atoms, with a carbon content of 14.5 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 25.0 nm, and the film thickness obtained per cycle was approximately 0.050 nm.

[0419] [Example 47] Production of copper organic-inorganic hybrid film 2 Compound No. 1-221 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-87 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0420] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (8)) First thin film formation raw material: Compound No. 1-221 Cu[OCH(Me)CH2N(Et)Me]2 Second thin film formation raw material: Compound No. 2-87 1,4-Dithiane-2,5-diol Reactive gas: Water vapor Substrate: Silicon wafer

[0421] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-221) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-221 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-87) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0422] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, peaks of 286 eV and 531 eV originating from C-O bonds, and a peak of 228 eV originating from sulfur were identified. The thin film contained copper and sulfur atoms, and the carbon content was 15.1 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 19.9 nm, and the film thickness obtained per cycle was approximately 0.040 nm.

[0423] [Example 48] Production of Aluminum Organic-Inorganic Hybrid Film 5 Compound No. 1-446 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-97 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0424] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-446 Al(Me)2(iPr-aamd) Second thin film formation raw material: Compound No. 2-97 2,2'-disulfanediylbis(ethane-1-ol) Substrate: Silicon wafer

[0425] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-446) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-446 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-97) obtained was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0426] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. A peak at 74 eV originating from Al-O bonds, peaks at 286 eV and 531 eV originating from C-O bonds, and a peak at 228 eV originating from sulfur were identified, indicating that the thin film contained aluminum and sulfur atoms, with a carbon content of 13.0 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 30.6 nm, and the film thickness obtained per cycle was approximately 0.061 nm.

[0427] [Example 49] Production of Gallium Organic-Inorganic Hybrid Film 2 Compound No. 1-475 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-98 represented by the above general formula (2-3) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0428] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (4)) First thin film formation raw material: Compound No. 1-475 [Ga(NMe2)3]2 Second thin film formation raw material: Compound No. 2-98 2,2'-(ethane-1,2-diylbis(sulfandiyl))bis(ethane-1-ol) Substrate: Silicon wafer

[0429] (Process) The following series of processes (1) to (4) constituted one cycle, and this was repeated 1000 times. (1) The first raw material gas (vapor of compound No. 1-475) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-475 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that was not deposited was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) The second raw material for thin film formation was vaporized under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr). The second raw material gas (vapor of compound No. 2-98) obtained was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (4) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2).

[0430] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 1117 eV and 1144 eV originating from Ga-O bonds, peaks of 286 eV and 531 eV originating from C-O bonds, and a peak of 228 eV originating from sulfur were identified, indicating that the thin film contained gallium and sulfur atoms, with a carbon content of 17.0 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 17.6 nm, and the film thickness obtained per cycle was approximately 0.035 nm.

[0431] [Example 50] Production of Bismuth Organic-Inorganic Hybrid Film 13 Using compound No. 1-21 represented by the above general formula (1) as the first thin film formation raw material, and compound No. 2-85 represented by the above general formula (2-3) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0432] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-85 Dimethyl-λ3-silyl 2-[(((2-oxo-2-((trimethylsilyl)oxy)ethyl)thio)carbonothio)thio]acetic acid ester Reactive gas: Water vapor Substrate: Silicon wafer

[0433] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-85) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0434] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 228 eV originating from sulfur were identified. This indicated that the thin film contained bismuth atoms and sulfur atoms, and the carbon content was 11.2 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 21.2 nm, and the film thickness obtained per cycle was approximately 0.042 nm.

[0435] [Example 51] Production of Bismuth Organic-Inorganic Hybrid Film 14 Using compound No. 1-21 represented by the above general formula (1) as the first thin film formation raw material, and compound No. 2-86 represented by the above general formula (2-3) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0436] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-86 Dimethylcarbonotrithioate Reactive gas: Water vapor Substrate: Silicon wafer

[0437] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-86) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0438] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-S bonds, a peak of 285 eV originating from C-S bonds, and a peak of 228 eV originating from sulfur were identified, indicating that the thin film contained bismuth atoms and sulfur atoms, with a carbon content of 4.6 atoms. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 20.8 nm, and the film thickness obtained per cycle was approximately 0.042 nm.

[0439] [Example 52] Production of Bismuth Organic-Inorganic Hybrid Film 15 Using compound No. 1-21 represented by the above general formula (1) as the first thin film formation raw material, and compound No. 2-42 represented by the above general formula (2-1) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0440] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-42 Dimethyl acetylenedicarboxylate Reactive gas: Water vapor Substrate: Silicon wafer

[0441] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-42) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0442] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, a peak of 289 eV originating from ester bonds, and a peak of 531 eV originating from CO bonds were identified, indicating that the thin film contained bismuth atoms, and the carbon content was 10.5 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 20.2 nm, and the film thickness obtained per cycle was approximately 0.040 nm.

[0443] [Example 53] Production of Bismuth Organic-Inorganic Hybrid Film 16 Using compound No. 1-21 represented by the above general formula (1) as the first thin film formation raw material, and compound No. 2-32 represented by the above general formula (2-1) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0444] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-32 1,3,5-triazine-2,4,6-trimethyl tricarboxylic acid Reactive gas: Water vapor Substrate: Silicon wafer

[0445] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-32) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0446] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 400 eV originating from CN bonds were identified. The thin film contained bismuth atoms and nitrogen atoms, and the carbon content was 13.3 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 15.9 nm, and the film thickness obtained per cycle was approximately 0.032 nm. The carbon content was 13.3 atom%.

[0447] [Example 54] Production of Bismuth Organic-Inorganic Hybrid Film 17 Using compound No. 1-21 represented by the above general formula (1) as the first thin film formation raw material, and compound No. 2-24 represented by the above general formula (2-1) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0448] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-24 Pyrazine-2,5-dicarboxylate dimethyl Reactive gas: Water vapor Substrate: Silicon wafer

[0449] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-24) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0450] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 400 eV originating from CN bonds were identified. The thin film contained bismuth atoms and nitrogen atoms, and the carbon content was 20.1 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 18.8 nm, and the film thickness obtained per cycle was approximately 0.038 nm.

[0451] [Example 55] Production of Bismuth Organic-Inorganic Hybrid Film 18 Using compound No. 1-21 represented by the above general formula (1) as the first thin film formation raw material, and compound No. 2-110 represented by the above general formula (2-3) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0452] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-110 2-iodoisophthalate dimethyl Reactive gas: Water vapor Substrate: Silicon wafer

[0453] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-110) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0454] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and peaks of 619 eV and 630 eV originating from iodine were identified. This indicated that the thin film contained bismuth and iodine atoms, and the carbon content was 13.5 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 18.6 nm, and the film thickness obtained per cycle was approximately 0.037 nm.

[0455] [Example 56] Production of Bismuth Organic-Inorganic Hybrid Film 19 Using compound No. 1-21 represented by the above general formula (1) as the first thin film formation raw material, and compound No. 2-106 represented by the above general formula (2-3) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0456] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-106 3,4-diiodo-1H-pyrrole-2,5-dicarboxylic acid dimethyl ester Reactive gas: Water vapor Substrate: Silicon wafer

[0457] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-106) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0458] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, a peak of 400 eV originating from CN bonds, and peaks of 619 eV and 630 eV originating from iodine were identified. The thin film contained bismuth atoms and iodine atoms, and the carbon content was 21.1 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 14.3 nm, and the film thickness obtained per cycle was approximately 0.029 nm.

[0459] [Example 57] Production of Bismuth Organic-Inorganic Hybrid Film 20 Using compound No. 1-21 represented by the above general formula (1) as the first thin film formation raw material, and compound No. 2-102 represented by the above general formula (2-3) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0460] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-102 3-iodo-1H-pyrrole-2,5-dicarboxylate dimethyl Reactive gas: Water vapor Substrate: Silicon wafer

[0461] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-102) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0462] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, a peak of 400 eV originating from CN bonds, and peaks of 619 eV and 630 eV originating from iodine were identified. The thin film contained bismuth atoms and iodine atoms, and the carbon content was 19.9 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 10.8 nm, and the film thickness obtained per cycle was approximately 0.020 nm.

[0463] [Example 58] Production of Bismuth Organic-Inorganic Hybrid Film 21 Using compound No. 1-21 represented by the above general formula (1) as the first thin film formation raw material, and compound No. 2-20 represented by the above general formula (2-1) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0464] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-20 1H-pyrrole-2,5-dicarboxylic acid Reactive gas: Water vapor Substrate: Silicon wafer

[0465] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-20) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0466] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 400 eV originating from CN bonds were identified. The thin film contained bismuth atoms and nitrogen atoms, and the carbon content was 16.1 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 15.6 nm, and the film thickness obtained per cycle was approximately 0.031 nm.

[0467] [Example 59] Production of Bismuth Organic-Inorganic Hybrid Film 22 Compound No. 1-21 represented by the above general formula (1) was used as the first thin film formation raw material, and compound No. 2-28 represented by the above general formula (2-1) was used as the second thin film formation raw material. An organic-inorganic hybrid film was produced on a silicon wafer substrate under the following conditions using the ALD apparatus shown in Figure 1.

[0468] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-28 Piperazine-2,5-dicarboxylate dimethyl Reactive gas: Water vapor Substrate: Silicon wafer

[0469] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-28) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0470] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and a peak of 400 eV originating from CN bonds were identified. The thin film contained bismuth atoms and nitrogen atoms, and the carbon content was 18.3 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 10.9 nm, and the film thickness obtained per cycle was approximately 0.020 nm.

[0471] [Example 60] Production of Bismuth Organic-Inorganic Hybrid Film 23 Using compound No. 1-21 represented by the above general formula (1) as the first thin film formation raw material, and compound No. 2-60 represented by the above general formula (2-3) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0472] (Conditions) Reaction temperature (substrate temperature): 100°C (Steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-60 Dimethyl 2-iodo-2-methylmalonate Reactive gas: Water vapor Substrate: Silicon wafer

[0473] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas (vapor of compound No. 1-21) obtained by vaporizing the first thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and compound No. 1-21 in the first raw material gas was deposited on the surface of the substrate silicon wafer for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form a metal layer (metal layer formation process). (2) The first raw material gas that did not deposit was exhausted from the system by argon purging for 15 seconds (exhaust process 1). (3) A reactive gas was introduced into the film formation chamber, and the metal layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction process). (4) Unreacted reactive gas and by-product gases were removed from the system by argon purging for 15 seconds (exhaust step 3). (5) The second raw material gas (vapor of compound No. 2-60) obtained by vaporizing the second thin film formation raw material under the conditions of raw material container temperature: 90°C and raw material container pressure: 26.7 Pa (0.2 torr) was introduced into the film formation chamber, and the metal layer and the second raw material gas were reacted for 10 seconds at a system pressure of 26.7 Pa (0.2 torr) to form an organic layer (organic layer formation step). (6) Unreacted second raw material gas and by-product gases were exhausted from the system by argon purging for 15 seconds (exhaust step 2). (7) The reactive gas was introduced into the film formation chamber, and the organic layer and the reactive gas were reacted for 0.1 seconds at a system pressure of 26.7 Pa (0.2 torr) (reactive gas introduction step). (8) Unreacted reactive gases and by-product gases were removed from the system by argon purging for 15 seconds (exhaust process 3).

[0474] The obtained organic-inorganic hybrid film was analyzed by X-ray photoelectron spectroscopy. Peaks of 159 eV and 164 eV originating from Bi-O bonds, a peak of 289 eV originating from ester bonds, a peak of 531 eV originating from CO bonds, and peaks of 619 eV and 630 eV originating from iodine were identified. This indicated that the thin film contained bismuth and iodine atoms, and the carbon content was 12.7 atom%. Furthermore, when the film thickness of the thin film was measured using a scanning electron microscope, the organic-inorganic hybrid film formed on the substrate was a smooth film with a thickness of 23.8 nm, and the film thickness obtained per cycle was approximately 0.048 nm.

[0475] [Example 61] Production of Bismuth Organic-Inorganic Hybrid Film 24 Using compound No. 1-21 represented by the above general formula (1) as the first thin film formation raw material, and compound No. 2-46 represented by the above general formula (2-1) as the second thin film formation raw material, an organic-inorganic hybrid film was produced on a silicon wafer substrate using the ALD apparatus shown in Figure 1 under the following conditions.

[0476] (Conditions) Reaction temperature (substrate temperature): 100°C (steps (1) to (8)) First thin film formation raw material: Compound No. 1-21 Bi(OtAm)3 Second thin film formation raw material: Compound No. 2-46 Dimethyl carbonate Reactive gas: Water vapor Substrate: Silicon wafer

[0477] (Process) The following series of processes (1) to (8) constituted one cycle, and this was repeated 500 times. (1) The first raw material gas...

Claims

1. A method for producing an organic-inorganic hybrid film that forms an organic-inorganic hybrid film satisfying both of the following conditions (A) and (B) by using a first raw material for thin film formation and a second raw material for thin film formation, wherein condition (A) is that the first raw material for thin film formation contains a compound represented by the following general formula (1) as a metal material, (In general formula (1), M represents a metal atom, L represents a ligand that bonds to the metal atom represented by M, the ligand may be of two or more types, t is the number of metal atoms represented by M and represents a number of 1 or more and 5 or less, u represents the number of each ligand that bonds to the metal atom represented by M, and at least one of the ligands represented by L is selected from a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms (*-OR 1 ), a monoalkylamino group (*-NHR 1 ), a dialkylamino group (*-NR 1 R 2 ), an alkyleneamino group (*-(CR 4 R 5 ) m -NR 6 R 7 ), an alkyl(alkyleneamino)amino group (*-NR 1 ((CR 4 R 5 ) m -NR 6 R 7 )), a trialkylsilyl group (*-SiR 1 R 2 R 3 ), an alkylenetrialkylsilyl group (*-(CH2) m -SiR 1 R 2 R 3 ), an alkyl(trimethylsilyl)amino group (*-NR 1 -SiMe3), a bis(trialkylsilyl)amino group (*-N(SiR 1 R 2 R 3 )2), an alkylimido group (*=NR 1 ), acetonitrile group (*-NC-CH3), carbonyl group (*=C=O), nitroso group (*-N=O), aryl group with 6 to 20 carbon atoms, cyclopentadiene compound, diketnate structure (*-O-C(R 4 ) = C(R 5 )-C(=O)-R 6 ), ketoimaginate structure (*-N(R 4 )-C(R 5 ) = C(R 6 )-C(=O)-R 7 ), dikethiminate structure (*-N(R 4 )-C(R 5 ) = C(R 6 ) - C (= NR 7 )-R 8 ), amidinate structure (*-N(R 4 )-C(R 5 ) = NR 6 ) and amino alcohol structure (*-O-(CR 4 R 5 ) m -NR 6 R 7 A group selected from the group consisting of ) and R 1 , R 2 and R 3 Each of these independently represents an alkyl group having 1 to 10 carbon atoms, and R 4 , R 5 , R 6 , R 7 and R 8 Each of the following independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, m represents an integer between 1 and 10, and if m is 2 or more, there are multiple R 4 , R 5 (These may be the same or different, and * represents the bonding position with the metal atom represented by M.) Condition (B) is that the second thin film forming raw material contains, as an organic material, a compound represented by the following general formula (2-1), a compound represented by the following general formula (2-2), a compound represented by the following general formula (2-3), 4-isocyanatophenol, isocyanatoethyl acetate, or phenylethylene glycol. (In general formula (2-1), A represents a direct bond, a divalent aliphatic group having 1 to 20 carbon atoms, a divalent aromatic group having 6 to 20 carbon atoms, or a divalent heterocyclic group having 2 to 20 carbon atoms, X 1 This represents a hydrocarbon group or trialkylsilyl group having 1 to 10 carbon atoms, Y 1 -O-, -S-, -OCO-, -COO- and -N(X 2 ) - represents a divalent group selected from the group, Y 1 X in 2 (This represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a trialkylsilyl group.) (In general formula (2-2), X 2 and X 3 Each of these independently represents a hydrogen atom, a monovalent hydrocarbon group with 1 to 4 elementary atoms, or a trialkylsilyl group, Z 1 This represents a monovalent aliphatic group having 1 to 20 carbon atoms, a monovalent aromatic group having 6 to 20 carbon atoms, or a monovalent heterocyclic group having 2 to 20 carbon atoms. 2 (This represents a direct bond or -O-.) (In general formula (2-3), A 2 This represents a divalent aliphatic group with 1 to 20 carbon atoms, a divalent aromatic group with 6 to 20 carbon atoms, or a heterocyclic group or carbonyl group with 2 to 20 carbon atoms. 3 -O-, -OCO-, -COO- and -N(X 5 ) - represents a divalent group selected from the group, X 4 and X 5 Each of these independently represents a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 4 carbon atoms, or a trialkylsilyl group, and n represents 0 or 1. However, as described above, A 2 A divalent aliphatic group with 1 to 20 carbon atoms, represented by A, represents a group in which at least one methylene group is substituted with a thioether, thioester, dithioester, or trithioester, or at least one hydrogen atom is substituted with a halogen atom, or at least one heteroatom is contained. 2 A divalent aromatic group having 6 to 20 carbon atoms, represented by , has at least one methylene group substituted with a thioether, thioester, dithioester, or trithioester, or at least one hydrogen atom is a halogen atom or -(Y 3 ) n -X 4 Represents a group that is substituted with or contains at least one heteroatom, and A 2 A heterocyclic group having 2 to 20 carbon atoms, represented by , represents a group in which at least one methylene group is substituted with a thioether, thioester, dithioester, or trithioester, or in which at least one hydrogen atom is substituted with a halogen atom. ) Method for producing an organic-inorganic hybrid film.

2. A method for producing an organic-inorganic hybrid film according to claim 1, comprising: a metal layer formation step of introducing a first raw material gas obtained by vaporizing the first raw material for forming a thin film into a film formation chamber in which a substrate has been previously installed, and depositing a metal material contained in the first raw material gas onto the surface of the substrate to form a metal layer; and an organic layer formation step of introducing a second raw material gas obtained by vaporizing the second raw material for forming a thin film into a film formation chamber, and depositing an organic material contained in the second raw material gas onto the surface of the substrate on which the metal layer has been formed to form an organic layer.

3. A method for producing an organic-inorganic hybrid film according to claim 1, comprising: an organic layer formation step of introducing a second raw material gas obtained by vaporizing the second thin film forming raw material into a film formation chamber in which a substrate has been previously installed, and depositing an organic material contained in the second raw material gas onto the surface of the substrate to form an organic layer; and a metal layer formation step of introducing a first raw material gas obtained by vaporizing the first thin film forming raw material into a film formation chamber, and depositing a metal material contained in the first raw material gas onto the surface of the substrate on which the organic layer has been formed to form a metal layer.

4. A method for producing an organic-inorganic hybrid film according to claim 2 or 3, further comprising alternately repeating a metal layer formation step of reacting the organic layer with the first raw material gas to form a metal layer, and an organic layer formation step of reacting the metal layer with the second raw material gas to form an organic layer.

5. A method for producing an organic-inorganic hybrid film according to claim 2 or 3, wherein the organic layer formation step involves forming an organic layer using a second thin-film forming raw material containing a compound represented by general formula (2-1), a compound represented by general formula (2-2), a compound represented by general formula (2-3), 4-isocyanatophenol, isocyanatoethyl acetate, or phenylethylene glycol, and then further forming an organic layer using a second thin-film forming raw material containing a compound different from the compound used to form the organic layer, selected from the compound represented by general formula (2-1), a compound represented by general formula (2-2), a compound represented by general formula (2-3), 4-isocyanatophenol, isocyanatoethyl acetate, or phenylethylene glycol.

6. The method for producing an organic-inorganic hybrid film according to claim 1, wherein the metal material is a compound comprising, in the general formula (1), a group selected from the group consisting of: the metal atom represented by M is a bismuth atom or an antimony atom, and the ligand represented by L is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms (*-OR 1 ), a monoalkylamino group (*-NHR 1 ), a dialkylamino group (*-NR 1 R 2 ), an alkylenetrialkylsilyl group (*-(CH2)n-SiR 1 R 2 R 3 ), an alkyl(trimethylsilyl)amino group (*-NR 1 -SiMe3), a bis(trialkylsilyl)amino group (*-N(SiR 1 R 2 R 3 )2), an alkylsilylamino group (*-NR 1 -SiMe 3 ), an aryl group having 6 to 20 carbon atoms, a cyclopentadiene compound, a diketonate structure (*-O-C(R 4 )=C(R 5 )-C(=O)-R 6 ), a ketoiminate structure (*-N(R 4 )-C(R 5 )=C(R 6 )-C(=O)-R 7 ), a diketiminate structure (*-N(R 4 )-C(R 5 )=C(R 6 )-C(=NR 7 )-R 8 ) and an amidinate structure (*-N(R 4 )-C(R 5 )=NR 6 ).

7. The metal material is such that, in the general formula (1), the metal atom represented by M is a cobalt atom, a nickel atom, a copper atom, or a zinc atom, and the ligand represented by L is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms (*-OR 1 ), monoalkylamino group (*-NHR 1 ), dialkylamino group (*-NR 1 R 2 ), alkylene amino group (*-(CR 4 R 5 ) m -NR 6 R 7 ), bis(trialkylsilylamino) group (*-N(SiR 1 R 2 R 3 )2), aryl group having 6 to 20 carbon atoms, cyclopentadiene compound, diketnate structure (*-O-C(R 4 ) = C(R 5 )-C(=O)-R 6 ), ketoimaginate structure (*-N(R 4 )-C(R 5 ) = C(R 6 )-C(=O)-R 7 ), dikethiminate structure (*-N(R 4 )-C(R 5 ) = C(R 6 ) - C (= NR 7 )-R 8 ), amidinate structure (*-N(R 4 )-C(R 5 ) = NR 6 ) and amino alcohol structure (*-O-(CR 4 R 5 ) m -NR 6 R 7 A method for producing an organic-inorganic hybrid film according to claim 1, comprising a compound containing a group selected from the group consisting of ).

8. The metal material is such that, in the general formula (1), the metal atom represented by M is a tin atom, and the ligand represented by L is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms (*-OR 1 ), monoalkylamino group (*-NHR 1 ), dialkylamino group (*-NR 1 R 2 ), bis(trialkylsilylamino) group (*-N(SiR 1 R 2 R 3 )2), aryl group having 6 to 20 carbon atoms, cyclopentadiene compound, diketnate structure (*-O-C(R 4 ) = C(R 5 )-C(=O)-R 6 ), ketoimaginate structure (*-N(R 4 )-C(R 5 ) = C(R 6 )-C(=O)-R 7 ), dikethiminate structure (*-N(R 4 )-C(R 5 ) = C(R 6 ) - C (= NR 7 )-R 8 ) and amidinate structure (*-N(R 4 )-C(R 5 ) = NR 6 A method for producing an organic-inorganic hybrid film according to claim 1, comprising a compound containing a group selected from the group consisting of ).

9. The metal material is such that, in the general formula (1), the metal atom represented by M is a titanium atom, a zirconium atom, or a hafnium atom, and the ligand represented by L is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms (*-OR 1 ), monoalkylamino group (*-NHR 1 ), dialkylamino group (*-NR 1 R 2 ), alkylenthryalkylsilyl group (*-(CH2)n-SiR 1 R 2 R 3 ), bis(trialkylsilyl)amino group (*-N(SiR 1 R 2 R 3 )2) A method for producing an organic-inorganic hybrid film according to claim 1, wherein the compound comprises a group selected from the group consisting of an aryl group having 6 or more and 20 or fewer carbon atoms and a cyclopentadiene compound.

10. The metal material is such that, in the general formula (1), the metal atom represented by M is an aluminum atom, a gallium atom, or an indium atom, and the ligand represented by L is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms (*-OR 1 ), monoalkylamino group (*-NHR 1 ), dialkylamino group (*-NR 1 R 2 ), alkylene amino group (*-(CR 4 R 5 ) m -NR 6 R 7 ), alkyl (alkylene amino) amino group (*-NR 1 ((CR 4 R 5 ) m -NR 6 R 7 )), bis(trialkylsilylamino) group (*-N(SiR 1 R 2 R 3 )2), aryl group having 6 to 20 carbon atoms, cyclopentadiene compound, diketnate structure (*-O-C(R 4 ) = C(R 5 )-C(=O)-R 6 ), ketoimaginate structure (*-N(R 4 )-C(R 5 ) = C(R 6 )-C(=O)-R 7 ), dikethiminate structure (*-N(R 4 )-C(R 5 ) = C(R 6 ) - C (= NR 7 )-R 8 ) and amidinate structure (*-N(R 4 )-C(R 5 ) = NR 6 A method for producing an organic-inorganic hybrid film according to claim 1, comprising a compound containing a group selected from the group consisting of ).

11. The metal material is such that, in the general formula (1), the metal atom represented by M is a molybdenum atom, and the ligand represented by L is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a monoalkylamino group (*-NHR 1 ), dialkylamino group (*-NR 1 R 2 ), alkylene amino group (*-(CR 4 R 5 ) m -NR 6 R 7 ), bis(trialkylsilylamino) group (*-N(SiR 1 R 2 R 3 ) 2) Alkylimide group (* = NR 1 ), acetonitrile group (*-NC-CH3), carbonyl group (*=C=O), nitroso group (*-N=O), aryl group with 6 to 20 carbon atoms, cyclopentadiene compound, diketnate structure (*-O-C(R 4 ) = C(R 5 )-C(=O)-R 6 ), ketoimaginate structure (*-N(R 4 )-C(R 5 ) = C(R 6 )-C(=O)-R 7 ), dikethiminate structure (*-N(R 4 )-C(R 5 ) = C(R 6 ) - C (= NR 7 )-R 8 ) and amidinate structure (*-N(R 4 )-C(R 5 ) = NR 6 A method for producing an organic-inorganic hybrid film according to claim 1, comprising a compound containing a group selected from the group consisting of ).

12. A method for producing an organic-inorganic hybrid film according to claim 2 or 3, comprising a reactive gas introduction step of introducing a reactive gas containing at least one selected from water vapor, oxygen, ozone, hydrogen, halogen, hydrogen halide, and monovalent or divalent alcohol having 1 to 10 carbon atoms into the film formation chamber, and bringing the reactive gas into contact with the metal layer or the organic layer.

13. A method for producing an organic-inorganic hybrid film according to claim 2 or claim 3, further comprising an exposure step of exposing the organic-inorganic hybrid film using light with a wavelength of 10 nm to 300 nm.

14. An organic-inorganic hybrid film manufactured using the method for manufacturing an organic-inorganic hybrid film described in any one of claims 1 to 3.

15. The organic-inorganic hybrid film according to claim 14, wherein the thickness of the organic-inorganic hybrid film is 50 nm or less.

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