Material for chemical vapor deposition, film production method and film

Abstract

Novel materials for chemical vapor deposition, film production methods, and films are provided. A material for chemical vapor deposition represented by formula (1) is provided. (In the formula, E represents an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom. R1, R2, and R3 are each independently a hydrogen atom or a linear, branched, or cyclic C1-7 organic group, and at least one of R1, R2, and R3 contains a fluorine atom. The case where R1, R2, and R3 are all hydrogen atoms is not included. > # imgabs0 #

Description

Technical Field

[0001] The present disclosure relates to chemical vapor deposition materials, film production methods, and films. Background Art

[0002] In batteries, durability and high ionic conductivity are required. For example, in lithium-ion batteries, it is necessary to maintain electrode durability and have high ionic conductivity. Regarding durability, it is known to provide a film covering the positive electrode and the negative electrode in a lithium-ion battery. Lithium phosphorus oxynitride (LiPON), lithium niobate (LiNbO3), lithium titanate (Li2TiO3), etc. are examples of compounds contained in the film.

[0003] Patent Document 1 discloses chemical vapor deposition materials for producing lithium phosphorus oxygen nitrogen layers.

[0004] Prior art documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Unexamined Patent 2017-48445 Summary of the invention

[0007] Problem that the invention aims to solve

[0008] An object of the present disclosure is to provide novel chemical vapor deposition materials, film production methods, and films.

[0009] Means of solving the problem

[0010] The inventors of the present invention have found that the above-mentioned problems can be solved by a chemical vapor deposition material represented by the following formula (1).

[0011] [1] A chemical vapor deposition material represented by the following formula (1).

[0012] [Chemical symbol 1]

[0013]

[0014] (Here, E is an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom.

[0015] R 1 , R 2 and R 3 Each is independently a hydrogen atom or a C1-7 straight chain, branched chain or cyclic organic group,

[0016] And R 1 , R 2 and R 3 At least one of them contains a fluorine atom.

[0017] Moreover, R 1 , R 2and R 3 Not all are hydrogen atoms.)

[0018] [2] The chemical vapor deposition material as described in [1], wherein

[0019] R 1 , R 2 and R 3 Each is independently a hydrogen atom or a C1-5 fluorinated alkyl group, a C2-5 alkenyl group, a C2-5 fluorinated alkenyl group or a C1-5 fluorinated alkoxyalkyl group.

[0020] [3] The chemical vapor deposition material as described in [1] or [2], wherein

[0021] R 1 , R 2 and R 3 At least one of them is -CF3, -CF2CF3, -CF2CF2CF3, -(CH2CH=CH2) or -(CH2OCH2CF3).

[0022] [4] The chemical vapor deposition material as described in any one of [1] to [3], wherein

[0023] R 1 It is -CF3.

[0024] [5] The chemical vapor deposition material as described in any one of [1] to [4], wherein

[0025] R 2 and R 3 At least one of them is a hydrogen atom.

[0026] [6] The chemical vapor deposition material as described in any one of [1] to [5], wherein

[0027] E is an oxygen atom.

[0028] [7] A film production method comprising a forming step of vapor-depositing the chemical vapor deposition material described in any one of [1] to [6] onto a substrate to form a film.

[0029] [8] The film production method according to [7], wherein

[0030] The forming step is carried out in the presence of at least one co-reactant selected from the group consisting of: O2, O3, H2O, H2O2, NO, NO2, N2O, PH3 and TMPO.

[0031] [9] The film production method according to [7] or [8], wherein

[0032] The temperature of the reactor in the forming step is ≥150°C to ≤350°C.

[0033]

[10] The film production method according to any one of [7] to [9], wherein

[0034] The film contains Li x O y F z The compound represented

[0035] in

[0036] 2.6≤x≤4.3,

[0037] 1.8≤y≤2.3 and

[0038] 4.3≤z≤6.6.

[0039]

[11] The film production method according to any one of [7] to

[10] , wherein

[0040] The reflectance of the film is ≥1.1 to ≤1.5.

[0041]

[12] a membrane,

[0042] It contains Li x O y F z The compound represented

[0043] in

[0044] 2.6≤x≤4.3,

[0045] 1.8≤y≤2.3 and

[0046] 4.3≤z≤6.6.

[0047]

[13] The film according to

[12] , wherein

[0048] The reflectance of the film is ≥1.1 to ≤1.5.

[0049] Advantages of the present invention

[0050] The present disclosure allows for the provision of novel chemical vapor deposition materials, film production methods, and films.

[0051] Embodiments of the present invention

[0052] The following describes embodiments of the present disclosure, but the present disclosure is not particularly limited to these embodiments and can be implemented by appropriate modifications. Moreover, any of the various configurations described below can be implemented in combination.

[0053] Definition of terms

[0054] Standard abbreviations for elements from the periodic table are used in this specification. Therefore, the elements are represented by these abbreviations. For example, Li represents lithium, O represents oxygen, S represents sulfur, Se represents selenium, Te represents tellurium, H represents hydrogen, C represents carbon, and F represents fluorine. The same applies to other elements.

[0055] In this specification, CVD (Chemical Vapor Deposition) means a chemical vapor deposition method or a chemical vapor deposition method, and ALD (Atomic Layer Deposition) means an atomic layer deposition method. It should be noted that ALD is a type of CVD.

[0056] In the present specification, an "organic group" is a group containing at least one carbon atom.

[0057] In this specification, a "fluorinated alkyl group" is an alkyl group (functional group) in which one or more of its hydrogen atoms are replaced by fluorine. n H 2n+1 (where n≥1) represents. "Fluorinated alkyl" is synonymous with fluoroalkyl.

[0058] In the present specification, a "fluorinated alkenyl group" is an alkenyl group (functional group) in which one or more of its hydrogen atoms are replaced by fluorine. n H 2n-1 (where n≥2) indicates.

[0059] In the present specification, a "fluorinated alkoxyalkyl group" is an alkoxyalkyl group (functional group) in which one or more of its hydrogen atoms are replaced by fluorine. n H 2n+1 O (wherein n is an integer ≥ 1), and the alkoxyalkyl group is represented by the general formula C n H 2n+1 OC m H 2m (wherein n and m are each independently an integer ≥ 1).

[0060] In this specification, "TMPO" means trimethyl phosphate.

[0061] When used in this specification, the abbreviation "Me" represents a methyl group, the abbreviation "Et" represents an ethyl group; the abbreviation "Pr" represents a propyl group; the abbreviation " n Pr" means "normal" or straight-chain propyl; the abbreviation " i Pr" means isopropyl; the abbreviation "Bu" means butyl; the abbreviation " n"Bu" means "normal" or straight-chain butyl; the abbreviation " t "Bu" means tert-butyl, also known as 1,1-dimethylethyl; the abbreviation " s Bu" means sec-butyl, also known as 1-methylpropyl; and the abbreviation " i Bu" means isobutyl, also known as 2-methylpropyl.

[0062] Chemical Vapor Deposition Materials

[0063] The chemical vapor deposition material related to the embodiment of the present invention is represented by the following formula (1).

[0064] [Chemical Symbol 2]

[0065]

[0066] (Here, E is an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom.

[0067] R 1 , R 2 and R 3 Each is independently a hydrogen atom or a C1-7 straight chain, branched chain or cyclic organic group,

[0068] And R 1 , R 2 and R 3 At least one of them contains a fluorine atom.

[0069] Moreover, R 1 , R 2 and R 3 Not all are hydrogen atoms.)

[0070] This type of chemical vapor deposition material allows novel chemical vapor deposition materials to be provided.

[0071] Metal

[0072] The chemical vapor deposition material has Li (lithium) as its metal element.

[0073] Atom E

[0074] The atom E belongs to Group 16 of the periodic table. For example, it is an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom. The atom E is preferably an oxygen atom.

[0075] Substituent R 1 , R 2 and R 3

[0076] R 1 , R 2 and R 3 are each independently a hydrogen atom or a C1-7 linear, branched or cyclic organic group.1 , R 2 and R 3 At least one of them contains a fluorine atom.

[0077] Moreover, R 1 , R 2 and R 3 Not all are hydrogen atoms.

[0078] Examples of the C1-7 straight chain organic group are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, vinyl, propenyl and the like.

[0079] Examples of C1-7 branched organic groups are tert-butyl, sec-butyl and isobutyl.

[0080] Examples of the C1-7 cyclic organic group are cyclic alkyl, alkenyl and alkynyl groups.

[0081] The above-mentioned C1-7 organic group may have a divalent heteroatom-containing group between carbon-carbon bonds, and some or all of the hydrogen atoms of the above-mentioned organic group may be substituted with a monovalent heteroatom-containing group.

[0082] Examples of the hetero atom in the divalent or monovalent hetero atom-containing group are oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, halogen atom, etc. Examples of the halogen atom are fluorine atom, chlorine atom, bromine atom and iodine atom.

[0083] Examples of the divalent heteroatom-containing group are -CO-, -CS-, -NH-, -O-, -S-, -SO2-, and divalent groups containing combinations of these.

[0084] Examples of the monovalent heteroatom-containing group are a hydroxyl group, a carboxyl group, a sulfanyl group, a cyano group, a nitro group, a halogen atom and the like.

[0085] Preferably, R 1 , R 2 and R 3 Each is independently a hydrogen atom or a C1-5 fluorinated alkyl group, a C2-5 alkenyl group, a C2-5 fluorinated alkenyl group or a C2-5 fluorinated alkoxyalkyl group.

[0086] More preferably, R 1 , R 2 and R 3 At least one of them is -CF3, -CF2CF3, -CF2CF2CF3, -(CH2CH=CH2) or -(CH2OCH2CF3).

[0087] Even more preferably, R 1 It is -CF3.

[0088] Particularly preferably, R 2 and R 3At least one of them is a hydrogen atom.

[0089] Specific Examples of Chemical Vapor Deposition Materials

[0090] The following are examples of chemical vapor deposition materials.

[0091] Li-OCH2CF3, Li-OCH2CF2CF3, Li-OC(CH2CH=CH2)(CF3)2, Li-OC(CF3)3, Li-OCH(CF3)2, Li-O(CH2)2OCH2CF3, Li-OC(CH3)(CF3)2, Li-OCH(CH2OCH2CF3)2

[0092] [Chemical Symbol 3]

[0093]

[0094] Below are some more examples of chemical vapor deposition materials.

[0095] LiOC(Et)2(CF3), LiOC(Pr)2(CF3), LiOC( n Bu)2(CF3), LiOC( i Bu)2(CF3), LiOC( t Bu)2(CF3), LiOC( s Bu)2(CF3), LiOC(MeEt)(CF3), LiOC(MePr)(CF3), LiOC(Me n Bu)(CF3), LiOC(Me i Bu)(CF3), LiOC(Me t Bu)(CF3), LiOC(Me s Bu)(CF3), LiOCH2(CF2CF3), LiOCH(CF2CF3)2, LiOC(CH3)2(CF2CF3), LiOC(MeEt)(CF2CF3)LiOC(MePr)(CF2CF3), LiOC(Me i Bu)(CF2CF3), LiOC(MenBu)(CF2CF3), LiOC(MetBu)(CF2CF3), LiOC(Me s Bu)(CF2CF3), LiOC(CH3)(CF2CF3)2, LiOC(CF2CF3)3, LiOC(Et)(CF3)2, LiOC( n Pr)(CF3)2、LiOC( i Pr)(CF3)2、LiOC( nBu)(CF3)2、LiOC( t Bu)(CF3)2、LiOC( s Bu)(CF3)2、LiOC( i Bu)(CF3)2、LiO(CH2)2OCH2CF3、LiO(CH2)2OCH(CF3)2、LiO(CH2)2OC(CF3)3、LiO(CH2)2OC(CH3)(CF 3)2、LiO(CH2)2OC(CH3)2(CF3)、LiO(CH2)2OC(Et)2(CF3)、LiO(CH2)2OC(Pr)2(CF3)、LiO(CH2)2OC( n Bu)2(CF3)、LiO(CH2)2OC( i Bu)2(CF3)、LiO(CH2)2OC( t Bu)2(CF3)、LiO(CH2)2OC( s Bu)2(CF3)、LiO(CH2)2OC(MeEt)(CF3)、LiO(CH2)2OC(MePr)(CF3)、LiO(CH2)2OC(Me n Bu)(CF3)、LiO(CH2)2OC(MeiBu)(CF3)、LiO(CH2)2OC(MetBu)(CF3)、LiO(CH2)2OC(Me s Bu)(CF3)、LiO(CH2)2OCH2(CF2CF3)、LiO(CH2)2OCH(CF2CF3)2、LiO(CH2)2OC(CH3)2(CF2CF3)、LiO(CH2)2OC(MeEt)(CF2CF3)、LiO(CH2)2OC(MePr)(CF2CF3)、LiO(CH2)2OC(MeEt)(CF2CF3) i Bu)(CF2CF3)、

[0096] LiO(CH2)2OC(Me n Bu)(CF2CF3)、LiO(CH2)2OC(Me t Bu)(CF2CF3)、LiO(CH2)2OC(Me s Bu)(CF2CF3)、LiO(CH2)2OC(CH3)(CF2CF3)2、LiO(CH2)2OC(CF2CF3)3、LiO(CH2)2OC(CH2CH=CH2)(CF3)2、LiO(CH2)2OC(Et)(CF3)2、LiO(CH2)2OC( n Pr)(CF3)2、LiO(CH2)2OC(i Pr)(CF3)2、LiO(CH2)2OC( n Bu)(CF3)2、LiO(CH2)2OC( t Bu)(CF3)2、LiO(CH2)2OC( s Bu)(CF3)2、LiO(CH2)2OC( i Bu)(CF3)2、LiOCH(Me)CH2OCH2CF3、LiOCH(Me)CH2OCH(CF3)2、LiOCH(Me)CH2OC(CF3)3、LiOCH(Me)CH2OC(CH3)(CF3)2、LiOCH(Me)CH2OC(CH3)2(CF3)、LiOCH(Me)CH2OC(Et)2(CF3)、LiOCH(Me)CH2OC(Pr)2(CF3)、LiOCH(Me)CH2OC( n Bu)2(CF3)、LiOCH(Me)CH2OC( i Bu)2(CF3)、LiOCH(Me)CH2OC( t Bu)2(CF3)、LiOCH(Me)CH2OC( s Bu)2(CF3)、LiOCH(Me)CH2OC(MeEt)(CF3)、LiOCH(Me)CH2OC(MePr)(CF3)、LiOCH(Me)CH2OC(Me n Bu)(CF3)、LiOCH(Me)CH2OC(Me i Bu)(CF3)、LiOCH(Me)CH2OC(Me t Bu)(CF3)、LiOCH(Me)CH2OC(Me s Bu)(CF3)、LiOCH(Me)CH2OCH2(CF2CF3)、LiOCH(Me)CH2OCH(CF2CF3)2、LiOCH(Me)CH2OC(CH3)2(CF2CF3)、LiOCH(Me)CH2OC(MeEt)(CF2CF3)、LiOCH(Me)CH2OC(MePr)(CF2CF3)、LiOCH(Me)CH2OC(Me i Bu)(CF2CF3)、LiOCH(Me)CH2OC(MenBu)(CF2CF3)、LiOCH(Me)CH2OC(Me t Bu)(CF2CF3)、LiOCH(Me)CH2OC(Me sBu)(CF2CF3)、LiOCH(Me)CH2OC(CH3)(CF2CF3)2、LiOCH(Me)CH2OC(CF2CF3)3、LiOCH(Me)CH2OC(CH2CH=CH2)(CF3)2、

[0097] LiOCH(Me)CH2OC(Et)(CF3)2、LiOCH(Me)CH2OC( n Pr)(CF3)2、LiOCH(Me)CH2OC( i Pr)(CF3)2、LiOCH(Me)CH2OC( n Bu)(CF3)2、LiOCH(Me)CH2OC( t Bu)(CF3)2、LiOCH(Me)CH2OC( s Bu)(CF3)2、LiOCH(Me)CH2OC( i Bu)(CF3)2、LiOCH2CH(Me)OCH2CF3、LiOCH2CH(Me)OCH(CF3)2、LiOCH2CH(Me)OC(CF3)3、LiOCH2CH(Me)OC(CH3)(CF 3)2、LiOCH2CH(Me)OC(CH3)2(CF3)、LiOCH2CH(Me)OC(Et)2(CF3)、LiOCH2CH(Me)OC(Pr)2(CF3)、LiOCH2CH(Me)OC( n Bu)2(CF3)、LiOCH2CH(Me)OC( i Bu)2(CF3)、LiOCH2CH(Me)OC( t Bu)2(CF3)、LiOCH2CH(Me)OC( s Bu)2(CF3)、LiOCH2CH(Me)OC(MeEt)(CF3)、LiOCH2CH(Me)OC(MePr)(CF3)、LiOCH2CH(Me)OC(Me n Bu)(CF3)、LiOCH2CH(Me)OC(Me i Bu)(CF3)、LiOCH2CH(Me)OC(MetBu)(CF3)、LiOCH2CH(Me)OC(Me sBu)(CF3)、LiOCH2CH(Me)OCH2(CF2CF3)、LiOCH2CH(Me)OCH(CF2CF3)2、LiOCH2CH(Me)OC(CH3)2(CF2CF3)、LiOCH2CH(Me)OC(MeEt)(CF2CF3)、LiOCH2CH(Me)OC(MePr)(CF2CF3)、LiOCH2CH(Me)OC(Me i Bu)(CF2CF3)、LiOCH2CH(Me)OC(Me n Bu)(CF2CF3)、LiOCH2CH(Me)OC(Me t Bu)(CF2CF3)、LiOCH2CH(Me)OC(Me s Bu)(CF2CF3)、LiOCH2CH(Me)OOC(CH3)(CF2CF3)2、LiOCH2CH(Me)OC(CF2CF3)3、LiOCH2CH(Me)OC(CH2CH=CH2)(CF3)2、LiOCH2CH(Me)OC(Et)(CF3)2、LiOCH2CH(Me)OC( n Pr)(CF3)2、LiOCH2CH(Me)OC( i Pr)(CF3)2、LiOCH2CH(Me)OC( n Bu)(CF3)2、LiOCH2CH(Me)OC( t Bu)(CF3)2、

[0098] LiOCH2CH(Me)OC( s Bu)(CF3)2、LiOCH2CH(Me)OC( i Bu)(CF3)2、LiO(CH2)3OCH2CF3、LiO(CH2)3OCH(CF3)2、LiO(CH2)3OC(CF3)3、LiO(CH2)3OC(CH3)(CF3)2、LiO(CH2)3OC(CH3)2(CF3)、LiO(CH2)3OC(Et)2(CF3)、LiO(CH2)3OC(Pr)2(CF3)、LiO(CH2)3OC( n Bu)2(CF3)、LiO(CH2)3OC( i Bu)2(CF3)、LiO(CH2)3OC( t Bu)2(CF3)、LiO(CH2)3OC( sBu)2(CF3)、LiO(CH2)3OC(MeEt)(CF3)、LiO(CH2)3OC(MePr)(CF3)、LiO(CH2)3OC(Me n Bu)(CF3)、LiO(CH2)3OC(Me i Bu)(CF3)、LiO(CH2)3OC(Me t Bu)(CF3)、LiO(CH2)3OC(Me s Bu)(CF3)、LiO(CH2)3OCH2(CF2CF3)、LiO(CH2)3OCH(CF2CF3)2、LiO(CH2)3OC(CH3)2(CF2CF3)、LiO(CH2)3OC(MeEt)(CF2CF3)、LiO(CH2)3OC(MePr)(CF2CF3)、LiO(CH2)3OC(MePr)(CF2CF3) i Bu)(CF2CF3)、LiO(CH2)3OC(Me n Bu)(CF2CF3)、LiO(CH2)3OC(Me t Bu)(CF2CF3)、LiO(CH2)3OC(Me s Bu)(CF2CF3)、LiO(CH2)3OC(CH3)(CF2CF3)2、LiO(CH2)3OC(CF2CF3)3、LiO(CH2)3OC(CH2CH=CH2)(CF3)2、LiO(CH2)3OC(Et)(CF3)2、LiO(CH2)3OC( n Pr)(CF3)2、LiO(CH2)3OC( i Pr)(CF3)2、LiO(CH2)3OC( n Bu)(CF3)2、LiO(CH2)3OC( t Bu)(CF3)2、LiO(CH2)3OC( s Bu)(CF3)2、LiO(CH2)3OC( i Bu)(CF3)2、LiO(CH2)2CH(Me)OCH2CF3、LiO(CH2)2CH(Me)OCH(CF3)2、LiO(CH2)2CH(Me)OC(CF3)3、LiO(CH2)2CH(Me)OC(CH3)(CF 3)2、LiO(CH2)2CH(Me)OC(CH3)2(CF3)、LiO(CH2)2CH(Me)OC(Et)2(CF3)、LiO(CH2)2CH(Me)OC(Pr)2(CF3)、LiO(CH2)2CH(Me)OC( nBu)2(CF3)、LiO(CH2)2CH(Me)OC( i Bu)2(CF3)、

[0099] LiO(CH2)2CH(Me)OC( t Bu)2(CF3)、LiO(CH2)2CH(Me)OC( s Bu)2(CF3)、LiO(CH2)2CH(Me)OC(MeEt)(CF3)、LiO(CH2)2CH(Me)OC(MePr)(CF3)、LiO(CH2)2CH(Me)OC(Me n Bu)(CF3)、LiO(CH2)2CH(Me)OC(Me i Bu)(CF3)、LiO(CH2)2CH(Me)OC(Me t Bu)(CF3)、LiO(CH2)2CH(Me)OC(Me s Bu)(CF3)、LiO(CH2)2CH(Me)OCH2(CF2CF3)、LiO(CH2)2CH(Me)OCH(CF2CF3)2、LiO(CH2)2CH(Me)OC(CH3)2(CF2CF3)、LiO(CH2)2CH(Me)OC(MeEt)(CF2CF3)、LiO(CH2)2CH(Me)OC(MePr)(CF2CF3)、LiO(CH2)2CH(Me)OC(Me i Bu)(CF2CF3)、LiO(CH2)2CH(Me)OC(Me n Bu)(CF2CF3)、LiO(CH2)2CH(Me)OC(Me t Bu)(CF2CF3)、LiO(CH2)2CH(Me)OC(Me s Bu)(CF2CF3)、LiO(CH2)2CH(Me)OC(CH3)(CF2CF3)2、LiO(CH2)2CH(Me)OC(CF2CF3)3、LiO(CH2)2CH(Me)OC(CH2CH=CH2)(CF3)2、LiO(CH2)2CH(Me)OC(Et)(CF3)2、LiO(CH2)2CH(Me)OC( n Pr)(CF3)2、LiO(CH2)2CH(Me)OC(iPr)(CF3)2、LiO(CH2)2CH(Me)OC( n Bu)(CF3)2、LiO(CH2)2CH(Me)OC( tBu)(CF3)2、LiO(CH2)2CH(Me)OC( s Bu)(CF3)2、LiO(CH2)2CH(Me)OC( i Bu)(CF3)2、LiOCH(Me)(CH2)2OCH2CF3、LiOCH(Me)(CH2)2OCH(CF3)2、LiOCH(Me)(CH2)2OC(CF3)3、LiOCH(Me)(CH2)2OC(CH3)(CF3)2、LiOCH(Me)(CH2)2OC(CH3)2(CF3)、LiOCH(Me)(CH2)2OC(Et)2(CF3)、LiOCH(Me)(CH2)2OC(Pr)2(CF3)、LiOCH(Me)(CH2)2OC( n Bu)2(CF3)、LiOCH(Me)(CH2)2OC( i Bu)2(CF3)、LiOCH(Me)(CH2)2OC( t Bu)2(CF3)、LiOCH(Me)(CH2)2OC( s Bu)2(CF3)、LiOCH(Me)(CH2)2OC(MeEt)(CF3)、LiOCH(Me)(CH2)2OC(MePr)(CF3)、LiOCH(Me)(CH2)2OC(Me n Bu)(CF3)、LiOCH(Me)(CH2)2OC(Me i Bu)(CF3)、

[0100] LiOCH(Me)(CH2)2OC(Me t Bu)(CF3)、LiOCH(Me)(CH2)2OC(Me s Bu)(CF3)、LiOCH(Me)(CH2)2OCH2(CF2CF3)、LiOCH(Me)(CH2)2OCH(CF2CF3)2、LiOCH(Me)(CH2)2OC(CH3)2(CF2CF3)、LiOCH(Me)(CH2)2OC(MeEt)(CF2CF3)、LiOCH(Me)(CH2)2OC(MePr)(CF2CF3)、LiOCH(Me)(CH2)2OC(Me i Bu)(CF2CF3)、LiOCH(Me)(CH2)2OC(MenBu)(CF2CF3)、LiOCH(Me)(CH2)2OC(Me t Bu)(CF2CF3)、LiOCH(Me)(CH2)2OC(Me sBu)(CF2CF3)、LiOCH(Me)(CH2)2OC(CH3)(CF2CF3)2、LiOCH(Me)(CH2)2OC(CF2CF3)3、LiOCH(Me)(CH2)2OC(CH2CH=CH2)(CF3)2、LiOCH(Me)(CH2)2OC(Et)(CF3)2、LiOCH(Me)(CH2)2OC( n Pr)(CF3)2、LiOCH(Me)(CH2)2OC( i Pr)(CF3)2、LiOCH(Me)(CH2)2OC( n Bu)(CF3)2、LiOCH(Me)(CH2)2OC( t Bu)(CF3)2、LiOCH(Me)(CH2)2OC( s Bu)(CF3)2、LiOCH(Me)(CH2)2OC( i Bu)(CF3)2, LiOC(Me)2(CH2)2OCH2CF3, LiOC(Me)2(CH2)2OCH(CF3)2, LiOC(Me)2(CH2)2OC(CF3)3, LiOC(Me)2(CH2)2OC(CH3)(CF3)2, LiOC(Me)2(CH2)2OC(CH3)2(CF3), LiOC(Me)2(CH2)2OC(Et)2(CF3), LiOC(Me)2(CH2)2OC(Pr)2(CF3), LiOC(Me)2(CH2)2OC(nBu)2(CF3), LiOC(Me)2(CH2)2OC( i Bu)2(CF3), LiOC(Me)2(CH2)2OC( t Bu)2(CF3), LiOC(Me)2(CH2)2OC( s Bu)2(CF3),

[0101] LiOC(Me)2(CH2)2OC(MeEt)(CF3), LiOC(Me)2(CH2)2OC(MePr)(CF3), LiOC(Me)2(CH2)2OC(Me n Bu)(CF3), LiOC(Me)2(CH2)2OC(MeiBu)(CF3), LiOC(Me)2(CH2)2OC(Me t Bu)(CF3), LiOC(Me)2(CH2)2OC(Me sBu)(CF3), LiOC(Me)2(CH2)2OCH2(CF2CF3), LiOC(Me)2(CH2)2OCH(CF2CF3)2, LiOC(Me)2(CH2)2OC(CH3)2(CF2CF3), LiOC(Me)2(CH2)2OC(MeEt)(CF2CF3), LiOC(Me)2(CH2)2OC(MePr)(CF2CF3), LiOC(Me)2(CH2)2OC(Me i Bu)(CF2CF3), LiOC(Me)2(CH2)2OC(Me n Bu)(CF2CF3), LiOC(Me)2(CH2)2OC(Me t Bu)(CF2CF3), LiOC(Me)2(CH2)2OC(Me s Bu)(CF2CF3), LiOC(Me)2(CH2)2OC(CH3)(CF2CF3)2, LiOC(Me)2(CH2)2OC(CF2CF3)3, LiOC(Me)2(CH2)2OC(CH2CH=CH2)(CF3)2, LiOC(Me)2(CH2)2OC(Et)(CF3)2, LiOC(Me)2(CH2)2OC( n Pr)(CF3)2、LiOC(Me)2(CH2)2OC( i Pr)(CF3)2LiOC(Me)2(CH2)2OC( n Bu)(CF3)2、LiOC(Me)2(CH2)2OC( t Bu)(CF3)2、LiOC(Me)2(CH2)2OC( s Bu)(CF3)2、LiOC(Me)2(CH2)2OC( i Bu)(CF3)2, LiOC(Me)2(CH2)2OCH2CF3, LiOC(Me)2(CH2)2OCH(CF3)2, LiOC(Me)2(CH2)2OC(CF3)3, LiOC(Me)2(CH2)2OC(CH3)(CF3)2, LiOC(Me)2(CH2)2OC(CH3)2(CF3), LiOC(Me)2(CH2)2OC(CH2CH=CH2)(CF3)2, LiOC(Me)2(CH2)2OC(Et)(CF3)2, LiOC(Me)2(CH2)2OC( n Pr)(CF3)2、LiOC(Me)2(CH2)2OC( i Pr)(CF3)2、LiOC(Me)2(CH2)2OC(n Bu)(CF3)2、LiOC(Me)2(CH2)2OC( t Bu)(CF3)2、LiOC(Me)2(CH2)2OC(sBu)(CF3)2、LiOC(Me)2(CH2)2OC( i Bu)(CF3)2, LiOC(CH2)2(Me)2OCH2CF3, LiOC(CH2)2(Me)2OCH(CF3)2, LiOC(CH2)2(Me)2OC(CF3)3, LiOC(CH2)2(Me)2OC(CH3)(CF3)2, LiOC(CH2)2(Me)2OC(CH3)2(CF3), LiOC(CH2)2(Me)2OC(Et)2(CF3), LiOC(CH2)2(Me)2OC(Pr)2(CF3), LiOC(CH2)2(Me)2OC( n Bu)2(CF3), LiOC(CH2)2(Me)2OC( i Bu)2(CF3), LiOC(CH2)2(Me)2OC( t Bu)2(CF3), LiOC(CH2)2(Me)2OC( s Bu)2(CF3), LiOC(CH2)2(Me)2OC(MeEt)(CF3), LiOC(CH2)2(Me)2OC(MePr)(CF3), LiOC(CH2)2(Me)2OC(Me n Bu)(CF3), LiOC(CH2)2(Me)2OC(Me i Bu)(CF3),

[0102] LiOC(CH2)2(Me)2OC(Me t Bu)(CF3), LiOC(CH2)2(Me)2OC(Me s Bu)(CF3), LiOC(CH2)2(Me)2OCH2(CF2CF3), LiOC(CH2)2(Me)2OCH(CF2CF3)2, LiOC(CH2)2(Me)2OC(CH3)2(CF2CF3), LiOC(CH2)2(Me)2OC(MeEt)(CF2CF3), LiOC(CH2)2(Me)2OC(MePr)(CF2CF3), LiOC(CH2)2(Me)2OC(Me i Bu)(CF2CF3), LiOC(CH2)2(Me)2OC(Me nBu)(CF2CF3)、LiOC(CH2)2(Me)2OC(MetBu)(CF2CF3)、LiOC(CH2)2(Me)2OC(Me s Bu)(CF2CF3), LiOC(CH2)2(Me)2OC(CH3)(CF2CF3)2LiOC(CH2)2(Me)2OC(CF2CF3)3, LiOC(CH2)2(Me)2OC(CH2CH=CH2)(CF3)2, LiOC(CH2)2(Me)2OC(Et)(CF3)2, LiOC(CH2)2(Me)2OC( n Pr)(CF3)2、LiOC(CH2)2(Me)2OC( i Pr)(CF3)2、LiOC(CH2)2(Me)2OC( n Bu)(CF3)2、LiOC(CH2)2(Me)2OC( t Bu)(CF3)2、LiOC(CH2)2(Me)2OC( s Bu)(CF3)2、LiOC(CH2)2(Me)2OC( i Bu)(CF3)2、

[0103] LiOCH[(CH2)2OCH2CF3]2、LiOCH[(CH2)2OCH(CF3)2]2、LiOCH[(CH2)2OC(CF3)3]2、LiOCH[(CH2)2OC(CH3)(CF3)2]2、 LiOCH[(CH2)2OC(CH3)2(CF3)]2、LiOCH[(CH2)2OC(Et)2(CF3)]2、LiOCH[(CH2)2OC(Pr)2(CF3)]2、LiOCH[(CH2)2OC( n Bu)2(CF3)]2、LiOCH[(CH2)2OC( i Bu)2(CF3)]2、LiOCH[(CH2)2OC( t Bu)2(CF3)]2、LiOCH[(CH2)2OC( s Bu)2(CF3)]2、LiOCH[(CH2)2OC(MeEt)(CF3)]2、LiOCH[(CH2)2OC(MePr)(CF3)]2、LiOCH[(CH2)2OC(Me n Bu)(CF3)]2、LiOCH[(CH2)2OC(Me i Bu)(CF3)]2、LiOCH[(CH2)2OC(Me tBu)(CF3)]2, LiOCH[(CH2)2OC(Me s Bu)(CF3)]2, LiOCH[(CH2)2OCH2(CF2CF3)]2, LiOCH[(CH2)2OCH(CF2CF3)2]2, LiOCH[(CH2)2OC(CH3)2(C F2CF3)]2LiOCH[(CH2)2OC(MeEt)(CF2CF3)]2, LiOCH[(CH2)2OC(MePr)(CF2CF3)]2, LiOCH[(CH2)2OC(Me i Bu)(CF2CF3)]2, LiOCH[(CH2)2OC(Me n Bu)(CF2CF3)]2, LiOCH[(CH2)2OC(Me t Bu)(CF2CF3)]2, LiOCH[(CH2)2OC(Me s Bu)(CF2CF3)]2, LiOCH[(CH2)2OC(CH3)(CF2CF3)2]2, LiOCH[(CH2)2OC(CF2CF3)3]2, LiOCH[(CH2)2OC(CH2CH=CH2)(CF3)2]2, LiOCH[(CH2)2OC(Et)(CF3)2]2, LiOCH[(CH2)2OC( n Pr)(CF3)2]2, LiOCH[(CH2)2OC( i Pr)(CF3)2]2, LiOCH[(CH2)2OC( n Bu)(CF3)2]2, LiOCH[(CH2)2OC( t Bu)(CF3)2]2, LiOCH[(CH2)2OC( s Bu)(CF3)2]2, LiOCH[(CH2)2OC( i Bu)(CF3)2]2, LiOC(Et)2(CF2H), LiOC(Et)2(CFH2), LiOC(Et)2(CF3), LiOCH(CF2H)2, LiSCH(CF3)2, LiSeCH(CF3)2, LiTeCH(CF3)2

[0104] Method for producing chemical vapor deposition materials

[0105] Chemical vapor deposition materials can generally be produced according to the following scheme (A).

[0106] [Chemical Symbol 4]

[0107]

[0108] (R' is a hydrocarbon group. 1 , R 2 and R 3 As defined above for formula (1).

[0109] The following procedure is a specific example of a production method. A round-bottomed flask with a dropping funnel attached is prepared. The round-bottomed flask is attached to a distillation unit. An organic solvent in which a specified amount of a Li source (e.g., n-butyl lithium) is dissolved is introduced into the dropping funnel. An organic solvent in which a specified amount of a carbon source (e.g., HOCH(CF3)2) is dissolved is then introduced into the round-bottomed flask. Next, while the dropping funnel is cooled to approximately -30°C to -10°C, the organic solvent in the dropping funnel is stirred and introduced dropwise into the round-bottomed flask. This provides a precipitate. The organic solvent is removed from the resulting precipitate (e.g., by creating a vacuum in a round-bottomed flask) to obtain a solid. The resulting solid is then subjected to further decompression (e.g., <0.01 kPa), and the round-bottomed flask is heated to approximately 100°C to 180°C. This produces the target chemical vapor deposition material. The various chemical vapor deposition materials of the above-described embodiments are obtained by appropriately changing the specified carbon source.

[0110] Membrane production method

[0111] The film production method of the embodiment of the present invention includes: an introducing step, in which the above-mentioned chemical vapor deposition material is introduced into a reactor accommodating a substrate; and a forming step, in which at least some of the chemical vapor deposition material is deposited onto the substrate.

[0112] Introduction steps

[0113] In this step, the chemical vapor deposition materials described above are introduced into a reactor containing a substrate. The type of substrate onto which the film is to be deposited is selected to suit the end use. Examples of substrates are Si substrates and electrodes for batteries.

[0114] The reactor can be any closed container or chamber of a device capable of performing vapor deposition inside it. Specific examples include, but are not limited to, parallel plate reactors, cold wall reactors, hot wall reactors, single wafer reactors, multi-wafer reactors, and other types of deposition systems.

[0115] Next, a gas containing the vaporized chemical vapor deposition material is introduced into the reactor. A pure (single) compound or a blended (multiple) compound in a liquid state can be supplied to the vaporizer and vaporized before being introduced into the reactor. Alternatively, the chemical vapor deposition material can be vaporized by passing a carrier gas through a container containing the chemical vapor deposition material, or by bubbling a carrier gas through the chemical vapor deposition material. Next, a gas containing a carrier gas and a vaporized compound is introduced into the reactor. If necessary, the container can be heated to a temperature at which the chemical vapor deposition material has a sufficient vapor pressure. There is no restriction on the carrier gas; Ar, He, N2 and mixtures of these can be used. Alternatively, instead of adopting a method involving bubbling a carrier gas (called a bubbling method), the compound can be vaporized by direct liquid injection (DLI).

[0116] In the introducing step, a co-reactant may also be introduced into the reactor. The co-reactant is preferably selected from the group consisting of O2, O3, H2O, H2O2, NO, N2O, NO2, trimethyl phosphate (also known as TMPO), its oxygen radicals, and mixtures thereof. Other co-reactants may also be used, such as alcohols, ammonia, polyamines, hydrazine, dimethylethylphosphoramide, and sulfates.

[0117] For example, the container is maintained at a temperature in the range of 0° C. to about 150° C. Those skilled in the art will appreciate that the amount of compound vaporized can be controlled by adjusting the temperature of the container by known methods.

[0118] The reactor is maintained at a pressure in the range of about 0.5 mTorr to about 20 Torr.

[0119] Formation steps

[0120] In the forming step, the above-mentioned chemical vapor deposition material is vapor-deposited onto a substrate to form a film.

[0121] In this step, in an example of atomic layer deposition type process, the chemical vapor deposition material in the gas phase is introduced into the reactor, in which the material is contacted with a suitable substrate. Then the excessive chemical vapor deposition material can be removed from the reactor by purging and / or exhausting the reactor. The co-reactant is introduced into the reactor and reacted with the chemical vapor deposition material absorbed in a self-terminating manner. Excessive co-reactants are removed from the reactor by purging and / or exhausting the reactor. When the desired film is a metal oxide film, the 2-stage process can provide the desired film thickness, or the 2-stage process can be repeated until a film with a desired thickness is obtained.

[0122] Alternatively, when the desired film is a metal oxide film, after the above-mentioned 2-stage process, the chemical vapor deposition material vapor can continue to be introduced into the reactor. This chemical vapor deposition material is selected based on the characteristics of the metal oxide to be deposited. After it is introduced into the reactor, the compound is contacted with the substrate. Excess compounds are removed from the reactor by purging and / or exhausting the reactor. The co-reactant can be introduced into the reactor again to react with the chemical vapor deposition material; the co-reactant can be the same or different from the co-reactant in the above-mentioned 2-stage process. Preferably, a co-reactant different from the co-reactant in the above-mentioned 2-stage process is introduced into the reactor. Excess co-reactants are removed from the reactor by purging and / or exhausting the reactor. If the desired film thickness is achieved, this process can be terminated. However, if a thicker film is desired, the entire 4-stage process can be repeated. The number of repeated cycles of the 4-stage process is preferably 50-1000 cycles, more preferably 100-800 cycles, and even more preferably 200-600 cycles. A film having a desired composition and thickness can be deposited by alternately supplying chemical vapor deposition materials and co-reactants. The 6-stage process can also be repeated using multiple types (e.g., 2 types) of co-reactants, respectively. The number of repeated cycles of the 6-stage process is, for example, 100 to 600 cycles.

[0123] This step can be carried out in the presence of at least one co-reactant selected from the group consisting of: O2, O3, H2O, H2O2, NO, NO2, N2O, PH3 and TMPO. Specifically, the addition of the co-reactant to the reactor allows the formation of a film on the substrate. In this step, the temperature of the reactor is preferably ≥130°C to ≤350°C, more preferably ≥130°C to ≤300°C, even more preferably ≥130°C to ≤250°C, and particularly preferably ≥130°C to ≤200°C. By using a relatively low reactor temperature, a film can be formed on a heat-sensitive substrate. For example, a film can be formed on a lithium-ion battery electrode.

[0124] In another embodiment, the temperature of the reactor in this step is preferably ≥130° C. to ≤350° C., more preferably ≥150° C. to ≤350° C., even more preferably ≥170° C. to ≤350° C., and particularly preferably ≥200° C. to ≤350° C. By using a relatively high reactor temperature, a film can be formed at a high growth rate.

[0125] In this embodiment, the film growth rate per cycle is preferably to More preferred to And even more preferably to The faster the film growth rate, the more efficiently the film can be formed.

[0126] Compounds contained in the membrane

[0127] The film produced by the above film production method contains metal oxyfluoride. Here, the metal oxyfluoride contains Li, oxygen and fluorine.

[0128] The membrane produced by the above membrane production method contains Li x O y F z Here, the compound is such that 2.6≤x≤4.3, 1.8≤y≤2.3, and 4.3≤z≤6.6. The composition of the compound can be calculated from the analysis results obtained using a commercially available element analyzer and the stoichiometric calculation using those analysis results. It should be noted that the compound contained in the film may be substantially Li x O y F z (≥99% Li by mass x O y F z ) or may contain impurities (e.g., LiOF and / or LiCF).

[0129] The film produced by the above-mentioned film production method has a reflectance of ≥1.1 to ≤1.5. The reflectance can be measured using a commercially available spectroscopic ellipsometer (ie, ellipsometer).

[0130] membrane

[0131] The film in the embodiment of the present invention contains Li x O y F z A compound represented by wherein 2.6≤x≤4.3, 1.8≤y≤2.3 and 4.3≤z≤6.6. The composition of the compound can be calculated from the analysis results obtained using a commercially available element analyzer and the stoichiometric calculation using those analysis results. Here, the compound Li contained in the film x O y F z Preferably, it constitutes ≥50% by mass, more preferably ≥60% by mass, even more preferably ≥70% by mass and particularly preferably ≥90% by mass.

[0132] The film of the present invention has a reflectance of ≥1.1 to ≤1.5. The reflectance can be measured using a commercially available spectroscopic ellipsometer. Because the film has a relatively low reflectance, it will have a variety of uses.

[0133] The film thickness is preferably ≧0.1 nm to ≦100 nm, more preferably ≧1 nm to ≦50 nm.

[0134] use

[0135] The chemical vapor deposition materials and films of the embodiments of the present invention can be used to produce lithium oxide, lithium oxyfluoride or alkali-containing mixed metal oxyfluoride films for various applications, such as coating lithium metal, and coating cathodes and anodes in lithium batteries. The lithium oxyfluoride film has improved resistance to oxidants; this improved resistance can give the solid electrolyte intermediate improved resistance to gradual degradation that reduces the battery charging efficiency.

[0136] Examples

[0137] The following examples are provided to illustrate the purposes of the disclosure of this specification, and it should be fully understood that any specific embodiment or embodiment group of the present invention may not necessarily provide all the advantages of the method described in this specification. Although specific embodiments and examples are disclosed below, it will be understood by those skilled in the art that the present invention includes obvious modifications and exceeds the specific disclosed inventive embodiments and / or purposes. Therefore, it should be understood that the scope of the present invention disclosed is not limited to the specific embodiments described below.

[0138] Synthesis of Chemical Vapor Deposition Materials

[0139] Prepare a 500mL round-bottom flask with an attached 100mL dropping funnel. Attach a distillation unit to this round-bottom flask. Attach a 250mL round-bottom flask to the distillation unit. Then 58ml of n-hexane (n-hexane manufactured by Kanto Chemical Co., Inc.) in which 2.6M n-butyl lithium (manufactured by Kanto Chemical Co., Inc.) is dissolved is introduced into the dropping funnel. Then 200mL of n-hexane (manufactured by Tokyo Chemical Industry Co., Ltd.) in which 150mmol HOCH(CF3)2 is dissolved is introduced into the 500mL round-bottom flask. Next, while the dropping funnel is cooled to -20°C, stir the n-hexane in the dropping funnel and introduce it dropwise into the 500mL round-bottom flask. This provides a precipitate. The n-hexane is removed from the resulting precipitate to obtain a solid. The resulting solid was then subjected to further decompression to vacuum (<0.01 kPa) and the 500 mL round bottom flask was heated to approximately 150° C. This produced the target chemical vapor deposition material.

[0140] 1H NMR (C6D6, 400 MHz) results are as follows. From these results, it was confirmed that the target chemical vapor deposition material was Li-O-CH(CF3)2. NMR measurements were performed using a Bruker Ascend 400 MHz NMR unit.

[0141] 1H NMR(C6D6,400MHz): δ3.988(1H,d,O-CH(CF3)2); 13C NMR(C6D6 / D6-DMSO101MHz): 68.827(m,O-CH(CF3)2), 123.1(q,1JCF=288.6Hz,O-CH(CF3)2); 19F NMR(C6D6,376MHz):-78.415(s,Li-O-CH(CF3)2); 1Li NMR(C6D6,156MHz):0.211(s,Li-O-CH(CF3)2).

[0142] Film formation

[0143] Sample 1

[0144] The Li-O-CH(CF3)2 synthesized in the above-mentioned "Synthesis of Chemical Vapor Deposition Materials" was introduced into a container (purchased from Japan Advanced Chemicals Co., Ltd). The interior of the container was then set to 78°C. At this time, the pressure was 10 Torr. The container was connected to allow the gas in the container to be supplied to the reactor.

[0145] Next, a Si substrate (produced by Mitsubishi Materials Corporation, product name: P-type silicon wafer) washed with a 1 vol% HF solution was introduced into the reactor. The temperature and pressure inside the reactor were set to 200°C and 1 Torr, the atmosphere around the substrate was changed as described below, and the cycle was repeated 400 times. This resulted in the formation of a film.

[0146] Change of atmosphere

[0147] (1) 4 sccm Li-O-CH(CF3)2 (2.5 s)

[0148] (2) 300 sccm nitrogen (30 s)

[0149] (3) 20 sccm H2O gas (1s)

[0150] (4) 300 sccm nitrogen (30 s)

[0151] This series (1) to (4) constitutes one cycle.

[0152] Sample 2

[0153] The film was formed by the same method as Sample 1, except that in the "atmosphere change", step (1) was 5 s.

[0154] Sample 3

[0155] The film was formed by the same method as Sample 1, except that in the "atmosphere change", step (1) was 10 s.

[0156] Sample 4

[0157] The film was formed by the same method as Sample 1, except that in the "atmosphere change", step (1) was 15 s.

[0158] Sample 5

[0159] A film was formed by the same method as Sample 1, except that the temperature inside the reactor was 175°C.

[0160] Sample 6

[0161] A film was formed by the same method as Sample 1 except for the following.

[0162] Set the temperature inside the reactor to 175°C

[0163] In "Atmosphere Change", (1) is 5s

[0164] Sample 7

[0165] A film was formed by the same method as Sample 1 except for the following.

[0166] Set the temperature inside the reactor to 175°C

[0167] In "Atmosphere Change", (1) is 10 seconds

[0168] Sample 8

[0169] A film was formed by the same method as Sample 1 except for the following.

[0170] Set the temperature inside the reactor to 175°C

[0171] In "Atmosphere Change", (1) is 15 seconds

[0172] Sample 9

[0173] A film was formed by the same method as Sample 1 except for the following.

[0174] Set the temperature inside the reactor to 150°C

[0175] In "Atmosphere Change", (1) is 15 seconds

[0176] ·The number of cycles is 600

[0177] Sample 10

[0178] The Li-O-CH(CF3)2 synthesized in the above-mentioned "Synthesis of Chemical Vapor Deposition Materials" is introduced into a first container (purchased from Japan Advanced Chemicals Co., Ltd.). The interior of the first container is then set to 78°C. At this time, the pressure is 20 Torr. TMPO (manufactured by Aldrich) is added to a second container (purchased from Japan Advanced Chemicals Co., Ltd.). The interior of the second container is then set to 80°C. At this time, the pressure is 20 Torr. The first container and the second container are connected to allow gas to be supplied to the reactor.

[0179] Next, a Si substrate (manufactured by Mitsubishi Materials Corporation, product name: P-type silicon wafer) washed with a 1 vol% HF solution was introduced into the reactor. The temperature and pressure inside the reactor were set to 200°C and 1 Torr, the atmosphere around the substrate was changed as described below, and the cycle was repeated 400 times. This resulted in the formation of a film.

[0180] Change of atmosphere

[0181] (1) 1 sccm Li-O-CH(CF3)2(5s)

[0182] (2) 300 sccm nitrogen (5s)

[0183] (3) 30 sccm TMPO (5 s)

[0184] (4) 300 sccm nitrogen (5s)

[0185] (5) 50sccm ozone gas (5s)

[0186] (6) 300 sccm nitrogen (5s)

[0187] This series (1) to (6) constitutes one cycle.

[0188] Sample 11

[0189] The film was formed by the same method as Sample 10, except that in the "atmosphere change", step (1) was 20 s.

[0190] Sample 12

[0191] A film was formed by the same method as Sample 10, except that the temperature inside the reactor was 250°C.

[0192] Sample 13

[0193] A film was formed by the same method as Sample 10 except for the following.

[0194] Set the temperature inside the reactor to 250°C

[0195] In "Atmosphere Change", step (1) is 10 seconds

[0196] Sample 14

[0197] A film was formed by the same method as Sample 10 except for the following.

[0198] Set the temperature inside the reactor to 250°C

[0199] In "Atmosphere Change", step (1) is 15 seconds

[0200] Sample 15

[0201] A film was formed by the same method as Sample 10 except for the following.

[0202] Set the temperature inside the reactor to 250°C

[0203] In "Atmosphere Change", step (1) is 20 seconds

[0204] Sample 16

[0205] A film was formed by the same method as Sample 10 except for the following.

[0206] Set the temperature inside the reactor to 250°C

[0207] In "Atmosphere Change", step (1) is 25 seconds

[0208] Sample 17

[0209] A film was formed by the same method as Sample 10, except that the temperature inside the reactor was 275°C.

[0210] Sample 18

[0211] A film was formed by the same method as Sample 10 except for the following.

[0212] Set the temperature inside the reactor to 275°C

[0213] In "Atmosphere Change", step (1) is 10 seconds

[0214] Sample 19

[0215] A film was formed by the same method as Sample 10 except for the following.

[0216] Set the temperature inside the reactor to 275°C

[0217] In "Atmosphere Change", step (1) is 15 seconds

[0218] Sample 20

[0219] A film was formed by the same method as Sample 10 except for the following.

[0220] Set the temperature inside the reactor to 275°C

[0221] In "Atmosphere Change", step (1) is 20 seconds

[0222] Sample 21

[0223] A film was formed by the same method as Sample 10 except for the following.

[0224] Set the temperature inside the reactor to 275°C

[0225] In "Atmosphere Change", step (1) is 25 seconds

[0226] Sample 22

[0227] A film was formed by the same method as Sample 10, except that the temperature inside the reactor was 300°C.

[0228] Sample 23

[0229] A film was formed by the same method as Sample 10 except for the following.

[0230] Set the temperature inside the reactor to 300°C

[0231] In "Atmosphere Change", step (1) is 10 seconds

[0232] Sample 24

[0233] A film was formed by the same method as Sample 10 except for the following.

[0234] Set the temperature inside the reactor to 300°C

[0235] In "Atmosphere Change", step (1) is 15 seconds

[0236] Sample 25

[0237] A film was formed by the same method as Sample 10 except for the following.

[0238] Set the temperature inside the reactor to 300°C

[0239] In "Atmosphere Change", step (1) is 20 seconds

[0240] Sample 26

[0241] The Li-O-CH(CF3)2 synthesized in the above-mentioned "Synthesis of Chemical Vapor Deposition Materials" was introduced into a container (purchased from Japan Advanced Chemicals Co., Ltd.). The interior of the container was then set to 78°C. At this time, the pressure was 20 Torr. The container was connected to allow gas to be supplied to the reactor.

[0242] Next, a Si substrate (manufactured by Mitsubishi Materials Corporation, product name: P-type silicon wafer) washed with a 1 vol% HF solution was introduced into the reactor. The temperature and pressure inside the reactor were set to 200°C and 1 Torr, the atmosphere around the substrate was changed as described below, and the cycle was repeated 400 times. This resulted in the formation of a film.

[0243] Change of atmosphere

[0244] (1) 1 sccm Li-O-CH(CF3)2(5s)

[0245] (2) 300 sccm nitrogen (5s)

[0246] (3) 50sccm ozone gas (5s)

[0247] (4) 300 sccm nitrogen (5s)

[0248] This series (1) to (4) constitutes one cycle.

[0249] Sample 27

[0250] The film was formed by the same method as Sample 26, except that in the "atmosphere change", step (1) was 20 s.

[0251] Sample 28

[0252] A film was formed by the same method as Sample 26, except that the temperature inside the reactor was 250°C.

[0253] Sample 29

[0254] A film was formed by the same method as Sample 26 except for the following.

[0255] Set the temperature inside the reactor to 250°C

[0256] In "Atmosphere Change", (1) is 20 seconds

[0257] Sample 30

[0258] A film was formed by the same method as Sample 26, except that the temperature inside the reactor was 275°C.

[0259] Sample 31

[0260] A film was formed by the same method as Sample 26 except for the following.

[0261] Set the temperature inside the reactor to 275°C

[0262] In "Atmosphere Change", step (1) is 20 seconds

[0263] Sample 32

[0264] A film was formed by the same method as Sample 26, except that the temperature inside the reactor was 300°C.

[0265] Sample 33

[0266] A film was formed by the same method as Sample 26 except for the following.

[0267] Set the temperature inside the reactor to 300°C

[0268] In "Atmosphere Change", step (1) is 20 seconds

[0269] Membrane analysis

[0270] The films of samples 1 to 33 were analyzed using an ellipsometer (manufactured by Semilab, product name: SE-2000). The analysis results of each sample (film growth rate ( (Angstrom) / cycle) and reflectance) are compiled in Tables 1 to 3. In the tables, "-" indicates that the component is not used. Also, in these tables, Li-HFIP represents Li-O-CH(CF3)2.

[0271] [Table 1]

[0272]

[0273] [Table 2]

[0274]

[0275] [Table 3]

[0276]

Claims

1. A chemical vapor deposition material represented by the following formula (1): [Chemical symbol 1] (Here, E is an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom; R 1 , R 2 and R 3 Each is independently a hydrogen atom or a C1-7 straight chain, branched chain or cyclic organic group, And R 1 , R 2 and R 3 At least one of them contains a fluorine atom; Moreover, R 1 , R 2 and R 3 not all hydrogen atoms).

2. The chemical vapor deposition material according to claim 1, wherein: R 1 , R 2 and R 3 Each is independently a hydrogen atom or a C1-5 fluorinated alkyl group, a C2-5 alkenyl group, a C2-5 fluorinated alkenyl group or a C2-5 fluorinated alkoxyalkyl group.

3. The chemical vapor deposition material according to claim 2, wherein: R 1 , R 2 and R 3 At least one of them is -CF3, -CF2CF3, -CF2CF2CF3, -(CH2CH=CH2) or -(CH2OCH2CF3).

4. The chemical vapor deposition material according to claim 3, wherein: R1 is -CF3.

5. The chemical vapor deposition material according to claim 4, wherein: R 2 and R 3 At least one of them is a hydrogen atom.

6. The chemical vapor deposition material according to claim 1, wherein: E is an oxygen atom.

7. A film production method comprising a forming step of vapor-depositing the chemical vapor deposition material according to any one of claims 1 to 6 onto a substrate to form a film.

8. The film production method according to claim 7, wherein: The forming step is carried out in the presence of at least one co-reactant selected from the group consisting of: O2, O3, H2O, H2O2, NO, NO2, N2O, PH3 and TMPO.

9. The film production method according to claim 8, wherein: The temperature of the reactor in the forming step is ≥130°C to ≤350°C.

10. The film production method according to claim 7, wherein: The film contains Li x O y F z The compound represented in 2.6≤x≤4.3， 1.8≤y≤2.3, and 4.3≤z≤6.6。 11. The film production method according to claim 10, wherein The reflectance of the film is ≥1.1 to ≤1.

5.

12. A membrane comprising Li x O y F z The compounds represented by 2.6≤x≤4.3， 1.8≤y≤2.3, and 4.3≤z≤6.6。 13. The film of claim 12, wherein The reflectance of the film is ≥1.1 to ≤1.5.

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