WO2014046193A1 - 有機銅錯体、有機銅錯体溶液、銅酸化物薄膜、銅酸化物薄膜の製造方法、および、化合物 - Google Patents

有機銅錯体、有機銅錯体溶液、銅酸化物薄膜、銅酸化物薄膜の製造方法、および、化合物 Download PDF

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WO2014046193A1
WO2014046193A1 PCT/JP2013/075325 JP2013075325W WO2014046193A1 WO 2014046193 A1 WO2014046193 A1 WO 2014046193A1 JP 2013075325 W JP2013075325 W JP 2013075325W WO 2014046193 A1 WO2014046193 A1 WO 2014046193A1
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group
carbon atoms
copper complex
thin film
copper
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French (fr)
Japanese (ja)
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真宏 高田
由夫 稲垣
亮 浜崎
野村　公篤
田中　淳
鈴木　真之
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/08—Copper compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H01L21/02579—P-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02623—Liquid deposition
    • H01L21/02628—Liquid deposition using solutions

Definitions

  • the present invention relates to an organic copper complex, an organic copper complex solution, a copper oxide thin film, a method for producing a copper oxide thin film, and a compound.
  • cuprous oxide (Cu 2 O) thin film which is one of copper oxide thin films, is a direct-transition semiconductor that exhibits p-type conductivity, and is therefore used as a p-type semiconductor.
  • a Cu 2 O thin film is a p-type semiconductor, n-type semiconductor such as ZnO or IGZO thin film such as a solar cell pn junction (e.g., JP 2006-9083 And a light-emitting diode (for example, see JP-A-2001-210864), a field effect transistor (for example, see JP-A-2008-10861), and a thermoelectric conversion bonded to a copper electrode.
  • An element for example, see Japanese Patent Application Laid-Open No. 2000-230867) is known.
  • a Cu 2 O thin film is expected as a photoelectric conversion material for solar cells because it has a band gap of about 2.1 eV and absorbs light in the visible light region to generate carriers. Further, Cu 2 O has low toxicity and has little influence on the environment.
  • a method for forming a copper oxide thin film there are a sputtering method and a vacuum film forming method such as MBE (Molecular Beam Epitaxy) method, and a wet method such as a solution coating method and a sol-gel method. It is done.
  • MBE Molecular Beam Epitaxy
  • a wet method such as a solution coating method and a sol-gel method.
  • Thin Solid Films, 442 (2003) 48 discloses forming a copper oxide thin film using a sol-gel method.
  • a thin film forming method by solution coating for example, a solution in which a copper aminopolycarboxylic acid complex and / or a copper polycarboxylic acid complex is dissolved is applied to a substrate surface by spin coating, dipping, bar coating, or flow coating.
  • Thin film formation by the vacuum film forming method generally requires a large vacuum apparatus, and thus the manufacturing cost of the thin film formation increases. Therefore, it has been required to form a thin film by a wet method as shown in Thin Solid Films, 442 (2003) 48 and Japanese Patent Application Laid-Open No. 2011-119454. If it is a wet method, since it can form into a large area with a simple apparatus, it can form at low cost. However, formation of a copper oxide thin film by a wet method has so far required annealing treatment (heating treatment) at a high temperature. As described above, for example, in the method disclosed in JP2011-119454A, a high temperature of 300 ° C. or higher is necessary. Such annealing treatment at a high temperature is disadvantageous in terms of energy cost, and there are problems such as low selectivity of the base material and peripheral members.
  • the present invention relates to an organic copper complex capable of forming a copper oxide thin film by annealing at a low temperature, a compound serving as a ligand thereof, and an organic capable of forming a copper oxide thin film by annealing at a low temperature. It aims at providing the organic copper complex solution containing a copper complex, and it aims at solving this subject. It is another object of the present invention to provide a copper oxide thin film produced by a method for producing a copper oxide thin film rich in substrate selectivity and a method for producing a copper oxide thin film rich in substrate selectivity. The purpose is to solve the problem.
  • R 11 , R 12 , R 21 , and R 22 may be the same or different from each other, and are each independently an alkyl group having 1 to 20 carbon atoms or a carbon number 2 having an unsaturated bond.
  • R 11 and R 21 may be connected to each other to form a ring
  • R 12 and R 22 may be connected to each other to form a ring.
  • R 31 and R 32 may be the same or different from each other, and each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a carbon number 2 having an unsaturated bond.
  • H in the C—H bond of each of the groups represented by R 11 , R 12 , R 21 , R 22 , R 31 , and R 32 may be substituted with a monovalent substituent.
  • R 31 and R 32 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group.
  • R 11 , R 12 , R 21 , and R 22 in General Formula 1 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • R 11 And R 21 may be connected to each other to form a ring
  • R 12 and R 22 may be connected to each other to form a ring
  • R 31 and R 32 are each independently a hydrogen atom.
  • the organocopper complex according to ⁇ 1> which represents an atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydroxy group.
  • ⁇ 5> The organocopper complex according to ⁇ 1>, ⁇ 2>, or ⁇ 4>, in which R 11 and R 12 in General Formula 1 are different from each other, and R 21 and R 22 are different from each other.
  • R 11 , R 12 , R 21 , and R 22 in the general formula 1 are each independently an alkyl group having 1 to 4 carbon atoms. It is an organocopper complex of description.
  • R 31 and R 32 in the general formula 1 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. It is an organocopper complex as described in one.
  • ⁇ 8> The organocopper complex according to any one of ⁇ 1> to ⁇ 7>, which is used for forming a copper oxide thin film.
  • the organic copper complex solution according to ⁇ 9> including at least two types of the organic copper complex.
  • the heat treatment step is the method for producing a copper oxide thin film according to ⁇ 15>, wherein the organic copper complex film is heated in an atmosphere having an oxygen concentration of 0.5 volume% to 50 volume%.
  • ⁇ 17> A compound which is represented by the following general formula 2 and forms an organocopper complex according to any one of ⁇ 1> to ⁇ 8> by coordination with a copper ion.
  • R 13 and R 23 may be the same as or different from each other, and each independently represents an alkyl group having 1 to 20 carbon atoms and a non-aromatic carbon atom having 2 to 20 carbon atoms having an unsaturated bond.
  • a hydrogen group, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms is represented.
  • R 13 and R 23 may be connected to each other to form a ring.
  • R 33 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a non-aromatic hydrocarbon group having 2 to 20 carbon atoms having an unsaturated bond, or an aryl having 6 to 20 carbon atoms. Group, a heteroaryl group having 3 to 20 carbon atoms, or a hydroxy group. Note that H in the C—H bond of each of the above groups represented by R 13 , R 23 , and R 33 may be substituted with a monovalent substituent.
  • R 33 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group.
  • an organic copper complex capable of forming a copper oxide thin film by annealing at a low temperature a compound serving as a ligand of the organic copper complex, and a copper oxide thin film by annealing at a low temperature
  • An organocopper complex solution containing an organocopper complex capable of forming an is provided.
  • Example 1 is a TG (Thermogravimetry) -DTA (Differential Thermal Analysis) curve of the copper complex 1-1 obtained in Example 1-1.
  • 2 is an MS (Mass Spectrometry) curve of the copper complex 1-1 obtained in Example 1-1.
  • 2 is a powder X-ray diffraction curve of a powder obtained by heating the copper complex 1-1.
  • 2 is a TG (Thermogravimetry) curve of the copper complex 2-1 obtained in Example 1-5 and the copper complex 5-1 obtained in Example 1-7. It is an XRD (X-ray Diffraction) pattern of the Cu 2 O thin film obtained in Example 3-1. It is an XRD (X-ray Diffraction) pattern of the Cu 2 O thin film obtained in Example 3-1.
  • the organocopper complex of the present invention is an organocopper complex having a structure represented by the following general formula 1 (hereinafter also referred to as “specific copper complex”).
  • specific copper complex a structure represented by the following general formula 1
  • a specific copper complex solution is prepared using a specific copper complex and a solvent, and this is coated on a substrate and heated to easily form a copper oxide thin film on the substrate. Can do.
  • R 11 , R 12 , R 21 , and R 22 may be the same or different from each other, and are each independently an alkyl group having 1 to 20 carbon atoms or a carbon number 2 having an unsaturated bond.
  • R 11 and R 21 may be connected to each other to form a ring
  • R 12 and R 22 may be connected to each other to form a ring.
  • R 31 and R 32 may be the same or different from each other, and each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a carbon number 2 having an unsaturated bond.
  • H in the C—H bond of each of the groups represented by R 11 , R 12 , R 21 , R 22 , R 31 , and R 32 may be substituted with a monovalent substituent.
  • R 31 and R 32 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Represents a group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group.
  • R 11, R 12, R 21, and R 22 are each independently an alkyl group having 1 to 20 carbon atoms, or, or an aryl group having 6 to 20 carbon atoms, and R 11 More preferably, R 21 is connected to each other to form a ring, and R 12 and R 22 are connected to each other to form a ring, and R 31 and R 32 are each independently a hydrogen atom. More preferably, it represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydroxy group.
  • the specific copper complex when R 11 and R 12 are the same, and R 21 and R 22 are the same, the specific copper complex has a symmetrical structure, a single product is easily obtained, and purification is easy. It becomes easy. Moreover, since the synthesis
  • R 31 and R 32 when R 31 and R 32 are the same, the decomposition temperature of the specific copper complex tends to be uniform, and the specific copper complex is prepared in an organic copper complex solution described later. Even when dried and heated, a copper oxide thin film having a uniform film density is easily obtained.
  • R 11 , R 12 , R 21 , or R 22 represents an alkyl group
  • the alkyl group has 1 to 20 carbon atoms and may further have a substituent.
  • the alkyl group represented by R 11 , R 12 , R 21 , or R 22 may be linear, branched, or cyclic.
  • Examples include a butyl group, a cyclohexyl group, and a benzyl group.
  • R 11 , R 12 , R 21 , or R 22 represents an alkyl group
  • R 11 , R 12 , R 21 , and R 22 may be the same as or different from each other.
  • the alkyl group represented by R 11 , R 12 , R 21 , or R 22 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Moreover, it is preferable that it is linear or branched, and it is more preferable that it is linear.
  • the ring formed by linking R 11 and R 21 and the ring formed by linking R 12 and R 22 each preferably have 3 to 10 carbon atoms, and preferably 4 to 8 carbon atoms. More preferred is 5-7.
  • R 11 , R 12 , R 21 , or R 22 represents a non-aromatic hydrocarbon group having an unsaturated bond
  • the non-aromatic hydrocarbon group having the unsaturated bond has a carbon number of 2 to 20, and may further have a substituent.
  • the non-aromatic hydrocarbon group having an unsaturated bond represented as R 11 , R 12 , R 21 , or R 22 may be linear, branched, or cyclic.
  • a vinyl group, an allyl group Examples include crotyl group, propargyl group, 5-hexenyl group, 4-methyl-1-pentenyl group, methallyl group, 1-cyclohexenyl group, and 1-cyclopentenyl group.
  • R 11 , R 12 , R 21 , or R 22 represents a non-aromatic hydrocarbon group having an unsaturated bond
  • R 11 , R 12 , R 21 , and R 22 may be the same as each other, May be different.
  • the number of carbon atoms of the non-aromatic hydrocarbon group having an unsaturated bond represented by R 11 , R 12 , R 21 , or R 22 is preferably 2 to 10, and more preferably 2 to 6. 2 to 4 are more preferable. Moreover, it is preferable that it is linear or branched, and it is more preferable that it is linear.
  • R 11 , R 12 , R 21 , or R 22 represents an aryl group
  • the aryl group is a monocyclic or condensed ring aryl group having 6 to 20 carbon atoms, and a substituent. You may have.
  • Examples of aryl groups include phenyl, naphthyl, anthryl, phenanthryl, biphenylyl, m-tolyl, p-tolyl, m-anisyl, p-anisyl, m-chlorophenyl, p-chlorophenyl. Group, xylyl group and the like.
  • the aryl group represented by R 11 , R 12 , R 21 , or R 22 is preferably a phenyl group, an m-tolyl group, a p-tolyl group, an m-anisyl group, or a p-anisyl group.
  • R 11 , R 12 , R 21 , or R 22 represents an aryl group
  • R 11 , R 12 , R 21 , and R 22 may be the same as or different from each other.
  • the number of carbon atoms of the aryl group represented by R 11 , R 12 , R 21 , or R 22 is preferably 6-10.
  • the aryl group is preferably unsubstituted.
  • R 11 , R 12 , R 21 , or R 22 represents a heteroaryl group
  • the heteroaryl group is a monocyclic or condensed ring heteroaryl group having 3 to 20 carbon atoms
  • heteroaryl groups include thiophene rings, furan rings, pyrrole rings, imidazole rings, oxazole rings, thiazole rings, and benzo condensed rings (for example, benzothiophene) and dibenzodi condensed rings (for example, dibenzothiophene, carbazole).
  • 3-methylthiophene ring and 3,4-diethylthiophene ring.
  • the heteroaryl group represented as R 11 , R 12 , R 21 , or R 22 is preferably a thiophene ring, a furan ring, or an oxazole group.
  • R 11 , R 12 , R 21 , or R 22 represents a heteroaryl group, R 11 , R 12 , R 21 , and R 22 may be the same as or different from each other.
  • the heteroaryl group represented by R 11 , R 12 , R 21 , or R 22 preferably has 3 to 10 carbon atoms.
  • the heteroaryl group is preferably unsubstituted.
  • the “aryl group” represents a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic compound having at least one selected from a benzene ring system and a non-benzene ring system aromatic ring
  • the “heteroaryl group” represents a group in which at least one carbon atom on the aromatic ring in the aryl group is replaced with a heteroatom.
  • R 11 , R 12 , R 21 , and R 22 in the general formula 1 are preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • R 11 , R 12 , R 21 , and R 22 are an alkyl group having 1 to 4 carbon atoms, the molecular weight of the specific copper complex becomes small and is easily decomposed by heating. Furthermore, even when the specific copper complex is prepared in an organic copper complex solution described later, and the coating film of the organic copper complex solution is dried and heated, the specific copper complex is easily decomposed and the organic component hardly remains in the film. Become.
  • R 31 or R 32 represents an alkyl group
  • the alkyl group has 1 to 20 carbon atoms and may further have a substituent.
  • the alkyl group represented by R 31 or R 32 may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, a t-butyl group, an n-hexyl group, and an n-nonyl group.
  • R 31 or R 32 may be the same as or different from each other.
  • the alkyl group represented by R 31 or R 32 preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms.
  • R 31 or R 32 represents an alkoxy group
  • the alkoxy group has 1 to 20 carbon atoms and may further have a substituent.
  • the alkoxy group represented by R 31 or R 32 may be linear, branched or cyclic, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a 1-methylbutoxy group, And a cyclohexyloxy group.
  • R 31 and R 32 may be the same as or different from each other.
  • the number of carbon atoms of the alkoxy group represented by R 31 or R 32 is preferably 1 to 12, more preferably 1 to 8, and still more preferably 1 to 6. Further, the alkoxy group represented by R 31 or R 32 is preferably a straight-chain or branched.
  • R 31 or R 32 represents a non-aromatic hydrocarbon group having an unsaturated bond
  • the non-aromatic hydrocarbon group having an unsaturated bond has 2 to 20 carbon atoms, , May have a substituent.
  • the non-aromatic hydrocarbon group having an unsaturated bond represented as R 31 or R 32 may be linear, branched or cyclic, and examples thereof include a vinyl group, allyl group, crotyl group, propargyl group, 5 -Hexenyl group, 4-methyl-1-pentenyl group, methallyl group, 1-cyclohexenyl 1-cyclopentenyl group and the like.
  • R 31 and R 32 may be the same as or different from each other.
  • the number of carbon atoms of the non-aromatic hydrocarbon group having an unsaturated bond represented by R 31 or R 32 is preferably 2 to 10, more preferably 2 to 6, and further preferably 2 to 4. . Further, the non-aromatic hydrocarbon group having an unsaturated bond represented as R 31 or R 32 is preferably linear or branched, and more preferably linear.
  • R 31 or R 32 represents an aryl group
  • the aryl group is a monocyclic or condensed ring aryl group having 6 to 20 carbon atoms, and may further have a substituent.
  • aryl groups include phenyl, naphthyl, anthryl, phenanthryl, biphenylyl, m-tolyl, p-tolyl, m-anisyl, p-anisyl, m-chlorophenyl, p-chlorophenyl. Group, xylyl group and the like.
  • the aryl group represented by R 31 or R 32 is preferably a phenyl group, an m-tolyl group, a p-tolyl group, an m-anisyl group, or a p-anisyl group.
  • R 31 or R 32 represents an aryl group
  • R 31 and R 32 may be the same as or different from each other.
  • the number of carbon atoms of the aryl group represented by R 31 or R 32 is preferably 6-10.
  • the aryl group is preferably unsubstituted.
  • R 31 or R 32 represents a heteroaryl group
  • the heteroaryl group is a monocyclic or condensed heteroaryl group having 3 to 20 carbon atoms, and further has a substituent. May be.
  • heteroaryl groups include thiophene rings, furan rings, pyrrole rings, imidazole rings, oxazole rings, thiazole rings, and benzo condensed rings (for example, benzothiophene) and dibenzodi condensed rings (for example, dibenzothiophene, carbazole). , 3-methylthiophene ring and 3,4-diethylthiophene ring.
  • the heteroaryl group represented as R 31 or R 32 is preferably a thiophene ring, a furan ring, or an oxazole group.
  • R 31 or R 32 represents a heteroaryl group
  • R 31 and R 32 may be the same as or different from each other.
  • the heteroaryl group represented by R 31 or R 32 preferably has 3 to 10 carbon atoms.
  • the heteroaryl group is preferably unsubstituted.
  • R 31 and R 32 are each independently an alkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms.
  • R 31 and R 32 in General Formula 1 are each independently preferably an alkyl group, an alkoxy group, a non-aromatic hydrocarbon group having an unsaturated bond, an aryl group, or a heteroaryl group.
  • R 31 and R 32 are any of an alkyl group, a non-aromatic hydrocarbon group having an unsaturated bond, an aryl group, a heteroaryl group, or an alkoxy group, both R 31 and R 32 represent a hydrogen atom.
  • the temperature required for the specific copper complex to be completely decomposed can be lowered.
  • an alkyl group, a non-aromatic hydrocarbon group having an unsaturated bond, an aryl group, a heteroaryl group, or an alkoxy group is sterically larger than a hydrogen atom, so that intermediate products of thermal decomposition are bonded to each other. This is thought to be difficult.
  • a copper complex is heated, intermediate products generated by thermal decomposition of the copper complex may be bonded to each other, and a high molecular weight compound that is difficult to be thermally decomposed may be generated. If such a high molecular weight compound is produced, heating may be required to decompose the high molecular weight compound.
  • the specific copper complex having a sterically large group is considered to have a great effect of preventing the formation of a high molecular weight compound during thermal decomposition.
  • R 31 and R 32 in the general formula 1 are more preferably an alkyl group or an alkoxy group.
  • R 31 and / or R 32 is an alkyl group, it is possible to lower the thermal decomposition temperature of the particular copper complexes.
  • R 31 and / or R 32 is an alkoxy group, because certain copper complexes will contain oxygen in the molecular structure, tends copper oxide is obtained.
  • R 11 , R 12 , R 21 , R 22 , R 31 , and R 32 in General Formula 1 may be substituted with a monovalent substituent.
  • substituents that R 11 , R 12 , R 21 , R 22 , R 31 , or R 32 in General Formula 1 may further have are not particularly limited, and are a hydroxyl group, an alkyl group (methyl group, ethyl group, Hexyl group, t-butyl group, cyclohexyl group, etc.), aryl group (phenyl group, m-tolyl group, p-tolyl group, m-anisyl group, p-anisyl group etc.), acyl group (acetyl group, propanoyl group, Hexanoyl group, octanoyl group, 2-ethylhexanoyl group, benzoyl group, etc.), halogen
  • substituents may be further substituted with another substituent.
  • an alkyl group or an aryl group is preferable, and a methyl group, an ethyl group, or a phenyl group is more preferable.
  • the substituent when the substituent is an alkyl group, the substituent preferably has 1 to 20 carbon atoms.
  • the specific copper complex of the present invention is not particularly limited as long as the chemical structure is represented by the general formula 1, and can take various structures.
  • R 11 , R 12 , R 21 , R 22 , R 31 , and R 32 are all the same group (for example, an alkyl group), each carbon number may be the same or different.
  • R 11 may be a combination of different groups such as an alkyl group having a large number of carbon atoms, R 12 is an aryl group, and R 21 is an alkoxy group.
  • Exemplified Compound 1 to Exemplified Compound 135 are shown in Tables 1 to 8 below, but the specific copper complex of the present invention is not limited to these.
  • Ph represents a phenyl group.
  • R 11 and R 21 are connected to each other to form a ring
  • R 12 and R 22 are connected to each other to form a ring.
  • R 11 -R 21 represents a divalent linking group represented by R 11 -R 21
  • R 12 -R 22 represents a divalent linking group represented by R 12 -R 22. Indicates a group. Therefore, for example, when “R 11 -R 21 ” is (CH 2 ) 4 , the ring formed by connecting R 11 and R 21 to each other is a 5-membered ring.
  • the specific copper complex of the present invention represented by the general formula 1 forms a compound having a higher molecular weight when R 11 , R 12 , R 21 , R 22 , R 31 , or R 32 serves as a linkage. Also good. For example, you may connect with the other specific copper complex adjacent through a water molecule etc. Hydrogen bonds by water molecules or the like are weakly bonded and sufficiently desorbed below the decomposition temperature of the specific copper complex, so that the characteristics of the present invention are not easily impaired.
  • organocopper complex of the present invention is the specific copper complex described above.
  • a monomer derived from the following general formula 1 is used as a repeating unit.
  • / or a polymer partially having a skeleton represented by the general formula 1 may be used.
  • Specific examples include compounds such as Reference Compound 1 and Reference Compound 2 in which R 11 , R 12 and the like in General Formula 1 are linked.
  • Reference compound 1 has a structure such as a trimer of a specific copper complex in which R 11 to R 31 are all methyl groups. That is, in the reference compound 1, R 11 of the specific copper complex is connected to R 12 of another specific copper complex by a linking group, and R 21 of the specific copper complex is connected to R 22 of another specific copper complex. It has a connected structure.
  • Reference compound 2 is represented as an oligomer or polymer having a trimer having a slightly different form from that of reference compound 1 as a repeating unit. In Reference Compound 2, n is the number of repeating units and represents an integer of 1 or more.
  • the linking group is a single bond, but is not limited to a single bond, and is a divalent or higher hydrocarbon group, amide group, ester group, carbonyl group, oxygen atom, nitrogen atom, or the like. There may be.
  • the specific copper complex represented by the general formula 1 of the present invention is formed using a 1,3-dicarbonyl compound represented by the following general formula 2 as a ligand.
  • R 13 and R 23 may be the same as or different from each other, and each independently represents an alkyl group having 1 to 20 carbon atoms and a non-aromatic carbon atom having 2 to 20 carbon atoms having an unsaturated bond.
  • a hydrogen group, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms is represented.
  • R 13 and R 23 may be connected to each other to form a ring.
  • R 33 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a non-aromatic hydrocarbon group having 2 to 20 carbon atoms having an unsaturated bond, or an aryl having 6 to 20 carbon atoms.
  • R 33 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group.
  • R 13 , R 23 , and R 33 in General Formula 2 the definition of R 13 is the same as the definitions of R 11 and R 12 in General Formula 1, and the definition of R 23 is R 21 and R 22 in General Formula 1.
  • R 33 is the same as the definitions of R 31 and R 32 in formula 1.
  • R 33 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or Represents a hydroxy group. That is, when R 13 and R 23 both represent a methyl group, R 33 represents a hydrogen atom, a non-aromatic hydrocarbon group having 2 to 20 carbon atoms having an unsaturated bond, and a heteroaryl group having 3 to 20 carbon atoms. Does not represent.
  • the compound used as a ligand in the specific copper complex of the present invention is not particularly limited as long as the chemical structure is represented by the general formula 2, and can take various structures.
  • R 13 , R 23 , or R 33 are all the same group (for example, an alkyl group)
  • the carbon number of each group may be the same or different.
  • R 13 may be a combination of different groups such as an alkyl group having a large number of carbon atoms
  • R 23 is an aryl group
  • R 33 is an alkoxy group.
  • Illustrative compounds L-1 to L-56 are shown in the following Tables 9 to 12 as examples of the compound represented by the general formula 2, but the above compounds in the present invention are not limited thereto.
  • the synthesis of the specific copper complex represented by the general formula 1 of the present invention is performed by mixing the 1,3-dicarbonyl compound represented by the general formula 2 and a cupric salt.
  • cupric salt is not particularly limited.
  • cupric salts include copper and hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromous acid, bromic acid, perbromic acid, hypoiodous acid, hypochlorous acid, Iodic acid, iodic acid, periodic acid, boric acid, carbonic acid, orthocarbonic acid, carboxylic acid, silicic acid, nitric acid, nitric acid, phosphorous acid, phosphoric acid, arsenic acid, sulfurous acid, sulfuric acid, sulfonic acid, sulfinic acid, chromium Acids, or salts with oxo acids such as permanganic acid (ie cupric oxoacids); and cupric halide salts such as cupric chloride, cupric bromide, and cupric iodide Etc.
  • oxo acids such as permanganic acid (ie cupric oxoacids)
  • cupric chloride cupric bromide, cupric iodide, cupric nitrate, cupric sulfate, cupric acetate, and cupric benzoate are readily available, solvents It is preferable in terms of solubility in water and difficulty in forming by-products.
  • the 1,3-dicarbonyl compound represented by the general formula 2 and the cupric salt are preferably dissolved in a solvent to form a solution and then mixed.
  • the solvent is not particularly limited as long as it dissolves the 1,3-dicarbonyl compound and the cupric salt, and any solvent such as water, alcohol, or a water-miscible aprotic organic solvent is used. be able to. From the viewpoint of suppressing the decomposition of the compound represented by the general formula 2, water or a water-miscible aprotic organic solvent is particularly preferable.
  • the solvent is water-immiscible such as toluene or xylene.
  • An organic solvent may coexist.
  • a base is allowed to coexist in the mixed reaction system, or before mixing with the cupric salt. It is preferable to prepare a salt of the compound represented by Formula 2 in advance.
  • Examples of bases that coexist in the mixed reaction system include alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxides (magnesium hydroxide, calcium hydroxide, water) Barium oxide, etc.), basic oxides (magnesium oxide, calcium oxide, etc.), and organic bases with poor nucleophilicity (triethylamine, 1,8-diazabiccyclo [5.4.0] undec-7-ene, etc.) Can be mentioned.
  • the mixed form of the 1,3-dicarbonyl compound represented by the general formula 2 and the cupric salt may be a mixing method in which water is added after the reaction in a water-miscible organic solvent, or the general formula 2
  • a mixing method in which an aqueous solution of a cupric salt is added to a solution in which a ligand represented by formula (1) is dissolved in a water-miscible organic solvent is preferable because a copper complex that is hardly soluble in water can be precipitated.
  • the mixing reaction temperature is not particularly limited, but is preferably 0 ° C. to 50 ° C., more preferably 10 ° C. to 40 ° C.
  • R 11 and R 12 , R 21 and R 22 , and R 31 and R 32 when synthesizing a specific copper complex in which at least one set is a combination of different groups, in this way, synthesis may be performed. That is, R 11 and R 12 , R 21 and R 22 are prepared by mixing two compounds different in at least one of R 11 , R 21 and R 31 in the general formula 2 and reacting with a cupric salt. In addition, a specific copper complex in which at least one of R 31 and R 32 is a combination of different groups is obtained.
  • the specific copper complex of the present invention may be used as it is, or may be used after being dispersed or dissolved in a solvent, or may be used by mixing with other solid substances. Especially, it is preferable to use a specific copper complex for the use which melt
  • the organic copper complex solution of the present invention contains the organic copper complex (specific copper complex) represented by the general formula 1 described above and a solvent.
  • the organocopper complex solution of the present invention is also referred to as a specific solution.
  • the specific solution is a metal compound such as an organic copper complex other than the specific copper complex, a surfactant, and / or an oxidizing agent, as long as the effects of the present invention are not impaired.
  • the additive may be included.
  • the details of the specific copper complex are as described above.
  • the specific solution may contain only one type of the specific copper complex, or may contain two or more types. When the specific solution contains two or more types of specific copper complexes, the crystallinity of the coating film formed using the specific solution can be lowered.
  • the concentration of the specific copper complex in the specific solution is not particularly limited, but the film thickness is increased when the specific solution is applied to a substrate or the like to form a coating film, and the specific copper complex is precipitated in the specific solution. From the viewpoints of suppressing and improving the flatness of the coating film, 0.01 mol / L to 0.3 mol / L is preferable.
  • the specific solution contains at least one solvent.
  • the solvent is not particularly limited as long as it can dissolve the specific copper complex, and may be an inorganic solvent or an organic solvent.
  • inorganic solvents include acids such as acetic acid, hydrochloric acid, and phosphoric acid; aqueous solutions of inorganic salts such as aqueous sodium hydroxide, aqueous potassium hydroxide, and aqueous sodium chloride; and water.
  • organic solvents examples include amide solvents (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), alcohol solvents (tert-butyl alcohol, isopropanol, ethanol, methanol, 2,2,3,3-tetrafluoro -1-propanol, 2-diethylaminoethanol, etc.), ketone solvents (acetone, N-methylpyrrolidone, sulfolane, N, N-dimethylimidazolidinone, etc.), ether solvents (eg tetrahydrofuran), nitrile solvents (eg acetonitrile), and Other examples include hetero atom-containing solvents other than those described above.
  • amide solvents N, N-dimethylformamide, N, N-dimethylacetamide, etc.
  • alcohol solvents tert-butyl alcohol, isopropanol, ethanol, methanol, 2,2,3,3-tetrafluoro -1-prop
  • the solvent of the specific solution is preferably an organic solvent and more preferably an aprotic polar solvent from the viewpoint of increasing the solubility of the specific copper complex.
  • the aprotic polar solvent include N, N-dimethylformamide, N, N-dimethylacetamide, pyridine, tetrahydrofuran, N-methylpyrrolidone, sulfolane, acetonitrile, and N, N— Examples thereof include dimethyl imidazolidinone.
  • N, N-dimethylformamide, N, N-dimethylacetamide, pyridine, and tetrahydrofuran are preferably used as the solvent for the specific solution from the viewpoint of further increasing the solubility of the specific copper complex.
  • aprotic polar solvents N, N-dimethylformamide, N, N-dimethylacetamide, pyridine, and tetrahydrofuran are preferably used as the solvent for the specific solution from the viewpoint of further increasing the solubility of the specific copper complex. Can do.
  • the boiling point of the solvent is preferably 80 ° C. to 200 ° C. from the viewpoint of reducing the load during the drying process when the specific solution is applied to form the copper oxide thin film.
  • the boiling point of the solvent is 80 ° C. or higher, the drying speed of the coating film obtained from the specific solution does not become too fast, and the smoothness in the film can be improved.
  • the boiling point of the solvent is 200 ° C. or less, the solvent is likely to volatilize from the coating film and is easily removed from the coating film.
  • N, N-dimethylacetamide which is an amide solvent
  • N, N-dimethylacetamide can dissolve a specific copper complex at 0.2 mol / L at room temperature and 0.3 mol / L under heating conditions below the boiling point, and has a boiling point. Since it is 165 degreeC, it can use suitably as a solvent of a specific solution.
  • a solvent may use only 1 type and may mix and use 2 or more types.
  • the specific solution may contain a metal compound other than the specific copper complex (also referred to as “other metal compound”) as long as the effects of the present invention are not impaired.
  • Other metal compounds are not particularly limited, and examples include strontium compounds.
  • a copper oxide thin film containing SrCu 2 O 2 can be formed by, for example, dissolving a strontium compound in a solvent and obtaining a specific solution together with the specific copper complex.
  • the copper oxide thin film of this invention is formed by drying and heat-processing the coating film of the organocopper complex solution (specific solution) of this invention. That is, the copper oxide thin film of the present invention is obtained by subjecting a coating solution of a specific solution formed by, for example, applying a specific solution on a base material and drying the substrate to a heat treatment (annealing treatment). It is a thin film formed on top.
  • the copper oxide thin film of the present invention may be a monovalent copper oxide thin film or a divalent copper oxide thin film.
  • the copper oxide thin film of the present invention may be a thin film made of a composite copper oxide containing a monovalent copper oxide and a divalent copper oxide. From the viewpoint of causing the copper oxide thin film of the present invention to function as a semiconductor, the copper oxide thin film preferably contains at least monovalent copper. From the viewpoint of forming a copper oxide thin film that is a p-type semiconductor layer on a substrate at a low temperature, the copper oxide thin film of the present invention is preferably a thin film made of monovalent copper oxide. Examples of the monovalent copper oxide include Cu 2 O and SrCu 2 O 2 .
  • the copper oxide thin film preferably has a monovalent copper content of 70 atomic% or more in the total copper contained in the copper oxide thin film.
  • the mobility at the time of using a copper oxide thin film as a semiconductor can be improved because content of monovalent copper in all copper is 70 atomic% or more.
  • the content of monovalent copper in the total copper contained in the copper oxide thin film is more preferably 90 atomic% or more, and further preferably 95 atomic% or more.
  • the thickness of the copper oxide thin film is not particularly limited, and a thickness suitable for the intended use of the copper oxide thin film can be selected.
  • a thickness suitable for the intended use of the copper oxide thin film can be selected.
  • the thickness of the copper oxide thin film may be in the range of 0.01 ⁇ m to 20 ⁇ m. You may adjust the thickness of a copper oxide thin film by drying the coating film of a specific solution, and also apply
  • the copper oxide thin film of this invention can be manufactured with the following manufacturing method, for example.
  • the manufacturing method of the copper oxide thin film of this invention apply
  • a heat treatment step of forming a copper oxide thin film When the manufacturing method of a copper oxide thin film is the said structure, a copper oxide thin film can be manufactured at low temperature and the selectability of a base material can be made high.
  • the method for producing a copper oxide thin film of the present invention may further include other steps in addition to the above steps as long as the effects of the present invention are not impaired.
  • Examples of other processes include cooling processes for cooling the copper oxide thin film obtained by the heat treatment process, and energy rays (electron beams, infrared rays, ultraviolet rays, vacuum ultraviolet rays, etc.) on the organic copper complex film obtained after the drying step.
  • the copper oxide thin film of the present invention will be described while explaining in detail each step included in the method for producing a copper oxide thin film of the present invention.
  • Organic copper complex solution coating film forming step In the organic copper complex solution coating film forming step, an organic copper complex solution (specific solution) containing a specific copper complex and a solvent is applied onto a substrate, and the organic copper complex solution coating film is formed. It is formed.
  • the specific solution may be applied to the surface of the substrate, or may be applied to another layer provided on the substrate. Examples of other layers provided on the substrate include an adhesive layer for improving the adhesion between the substrate and the organic copper complex solution coating film, and a transparent conductive layer.
  • Substrate The type of the substrate is not particularly limited, and can be used in a form suitable for the intended use.
  • the substrate include inorganic materials such as glass, silicon, and metal, resins, and composite materials of inorganic materials and resins.
  • resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide Fluorine resin such as polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin , Synthetic resins such as aromatic ethers, maleimide-olefins, cellulose, and episulfide compounds And the like.
  • An example of a composite material of an inorganic material and a resin is a composite plastic material of a resin and an inorganic material. That is, composite plastic material of resin and silicon oxide particles, composite plastic material of resin and metal nanoparticles, composite plastic material of resin and inorganic oxide nanoparticles, composite plastic material of resin and inorganic nitride nanoparticles, Composite plastic material of resin and carbon fiber, composite plastic material of resin and carbon nanotube, composite plastic material of resin and glass flake, composite plastic material of resin and glass fiber, composite plastic material of resin and glass beads, Composite plastic material of resin and clay mineral, composite plastic material of resin and particles having mica-derived crystal structure, laminated plastic material having at least one bonding interface between resin and thin glass, and inorganic layer and organic By laminating layers alternately, at least 1 Composite material or the like having a barrier property having more bonding interface.
  • the base material is preferably a flexible material.
  • the base material is preferably a resin or a composite base material obtained using a resin and a material other than resin.
  • a composite base material the laminated base material which bonded the resin plate to the metal plate is mentioned, for example.
  • the thickness of the substrate is not particularly limited, but is preferably 50 ⁇ m to 1000 ⁇ m, and more preferably 50 ⁇ m to 500 ⁇ m.
  • the thickness of the base material is 50 ⁇ m or more, the flatness of the base material itself is improved, and when the thickness of the base material is 1000 ⁇ m or less, the flexibility of the base material itself is improved and the thin film semiconductor device described later is flexible. It becomes easier to use as a semiconductor device. Further, the thickness is more preferably 500 ⁇ m or less because the flexibility is further improved.
  • the method for applying the specific solution on the substrate is not particularly limited.
  • the spin coating method, the dip method, the ink jet method, the dispenser method, the screen printing method, the relief printing method, the intaglio printing method, the spray coating method, etc. can be used.
  • the inkjet method, the dispenser method, the screen printing method, the relief printing method, and the intaglio printing method can form a coating film at an arbitrary position on the substrate, and a patterning step after the film formation is unnecessary. Therefore, the process cost can be reduced. Further, since the pattern can be formed without removing the coating film, the environmental load can be reduced.
  • the thickness of the organic copper complex solution coating film can be arbitrarily changed depending on the concentration of the specific copper complex in the specific solution and the application conditions of the specific solution.
  • concentration of the specific copper complex in the specific solution may be lowered.
  • a thin organic copper complex solution coating film can be obtained by making the base-material rotation speed at the time of apply
  • a thicker organic copper complex solution coating film for example, the concentration of the specific copper complex in the specific solution may be increased.
  • coating a specific solution with a spin coat method a thick organic copper complex solution coating film can be obtained by making the base-material rotation speed at the time of apply
  • the organic copper complex solution coating film is dried to obtain an organic copper complex film. That is, the drying step is a step of volatilizing the solvent contained in the organic copper complex solution coating film.
  • membrane obtained after a drying process is a precursor from which a copper oxide thin film is obtained by heating, the organic copper complex film
  • the method for volatilizing the solvent contained in the organic copper complex solution coating film and the drying conditions are not particularly limited as long as it is a technique or a condition capable of removing the solvent contained in the specific solution from the coating film.
  • the coating film is heated, the coating film is placed under a reduced pressure environment, or the coating film is heated while placed under a reduced pressure environment.
  • the heating temperature of the coating film is preferably lower than the glass transition temperature of the resin.
  • the residual amount of the solvent in the organic copper complex film after the drying step is not particularly limited, but from the viewpoint of increasing the film density after the heat treatment step, the total mass of the organic copper complex film obtained after the drying step is The total mass of the solvent is preferably 50% by mass or less.
  • Heat treatment step In the heat treatment step, the organic copper complex film is heated at 230 ° C. or higher and lower than 300 ° C. (annealing treatment) to form a copper oxide thin film.
  • the heat treatment (annealing) of the organic copper complex film is performed by heating the organic copper complex film at 230 ° C. or higher and lower than 300 ° C.
  • the thermal decomposition of the specific copper complex proceeds sufficiently, and a dense copper oxide thin film can be obtained.
  • the selectivity of the peripheral member of copper oxide thin films, such as a base material used when obtaining the copper oxide thin film by heating the organic copper complex film is improved by the temperature of the heat treatment being less than 300 ° C.
  • the heat treatment time varies depending on the type of base material used and / or the thickness of the organic copper complex film, but may be, for example, 1 minute to 3 hours.
  • the method for the heat treatment is not particularly limited, and examples thereof include heating with an electric furnace, infrared lamp heating, and heating with a hot plate.
  • the heat treatment can be completed in a short time by using a rapid heat treatment apparatus (RTA apparatus; Rapid Thermal Annealing apparatus) using lamp heating.
  • RTA apparatus Rapid Thermal Annealing apparatus
  • the heat treatment step is preferably performed in an atmosphere containing oxygen.
  • an atmosphere containing oxygen By heat-treating the organic copper complex film in an atmosphere containing oxygen, a copper oxide thin film can be easily obtained.
  • the oxygen concentration in the atmosphere containing oxygen is more preferably 0.5 volume% to 50 volume%.
  • the “oxygen concentration in an atmosphere containing oxygen” is the oxygen concentration in the heating container (furnace) of the heating device when the heat treatment is performed by the heating device.
  • the inside of the heating container including the base material on which the organic copper complex film is formed is filled with a mixed gas of oxygen (O 2 ) and inert gas argon (Ar), “atmosphere containing oxygen” Is calculated as 100 ⁇ O 2 / (Ar + O 2 ) [volume%].
  • oxygen concentration in the atmosphere containing oxygen is high, Cu 2 O is easily obtained.
  • the oxygen concentration is more preferably 0.5% to 10% by volume.
  • a copper oxide containing monovalent copper such as Cu 2 O on the base material by heat-treating the organocopper complex film in a more preferable oxygen concentration range (0.5 volume% to 50 volume%).
  • a thin film can be obtained.
  • the manufacturing method of the copper oxide thin film of the present invention includes, in addition to the organic copper complex solution coating film forming step, the drying step, and the heat treatment step, in addition to the cooling step and / or the energy ray irradiation step. You may have the process of.
  • Cooling step In the cooling step, the copper oxide thin film obtained by the heat treatment step is cooled. By cooling the copper oxide thin film, throughput can be increased and productivity can be improved.
  • the method for cooling the copper oxide thin film is not particularly limited. For example, the method of air-cooling a copper oxide thin film, the method of making the base material with which the copper oxide thin film was formed contact the metal plate of room temperature (for example, 25 degreeC), etc. are mentioned.
  • the organic copper complex film obtained after the drying step is irradiated with energy rays (electron rays, infrared rays, ultraviolet rays, vacuum ultraviolet rays, atomic rays, X rays, ⁇ rays, visible rays, etc.).
  • energy rays electron rays, infrared rays, ultraviolet rays, vacuum ultraviolet rays, atomic rays, X rays, ⁇ rays, visible rays, etc.
  • a dense film having a high film density can be obtained by irradiating the organic copper complex film with energy rays.
  • a copper oxide thin film is manufactured on a base material.
  • a copper oxide thin film containing monovalent copper for example, a Cu 2 O thin film functions as a p-type semiconductor
  • a Cu 2 O thin film formed on a substrate is suitable for various thin film semiconductor devices. Can be used.
  • the content of copper atoms with respect to all atoms constituting the copper oxide thin film is preferably 70 atomic% or more.
  • the mobility when the copper oxide thin film is used as a conductor can be improved.
  • the content of copper atoms with respect to all atoms contained in the copper oxide thin film is more preferably 90 atomic% or more, and further preferably 95 atomic% or more.
  • the thin film semiconductor of this invention can be set as a semiconductor device by having a base material and the p-type semiconductor layer which is located on a base material and consists of a copper oxide thin film. That is, the thin film semiconductor device of the present invention includes a base material and a copper oxide thin film manufactured by the method of manufacturing the copper oxide thin film of the present invention or the copper oxide thin film of the present invention.
  • the thin film semiconductor of the present invention may further include a flexible base material, and the p-type semiconductor layer may be positioned on the base material.
  • a p-type semiconductor layer By having a p-type semiconductor layer on a base material having flexibility, a thin film semiconductor device that is bent and hardly broken even when dropped can be obtained.
  • the thin film semiconductor device can be reduced in weight and can be carried in a form in which the thin film semiconductor device is wound. Therefore, it can be suitably used as a power source for mobile devices, for example.
  • it since it is lightweight, the burden on a building at the time of installing on the roof of a building is reduced.
  • the example of the base material which a thin film semiconductor device can be equipped with is the same as the example of the base material used with the manufacturing method of the copper oxide thin film of this invention, and its preferable aspect is also the same.
  • a p-type semiconductor layer should just be located on a base material, and may have another layer between a p-type semiconductor layer and a base material.
  • the other layers include various functional layers such as an adhesive layer that enhances the adhesion between the p-type semiconductor layer and the substrate.
  • a thin film semiconductor device using a copper oxide thin film can be applied to various applications, for example, a solar cell, a light emitting diode, a field effect transistor, a thermoelectric conversion element, and the like.
  • a thin film semiconductor device using a Cu 2 O thin film has a band gap of about 2.1 eV, absorbs light in the visible light region, and generates carriers. Therefore, the thin film semiconductor device is preferably used as a photoelectric conversion material for a solar cell. Can do.
  • the thin film semiconductor device provided with the copper oxide thin film of this invention or the copper oxide thin film manufactured by the manufacturing method of the copper oxide thin film of this invention can be used suitably as a solar cell.
  • a pn junction solar cell for example, a p-type semiconductor layer and an n-type semiconductor layer are provided adjacent to each other on a transparent conductive film formed on a transparent substrate.
  • a form in which a metal electrode is formed on the n-type semiconductor layer is conceivable.
  • FIG. 1 shows a schematic cross-sectional view of a pn junction solar cell 100 according to an embodiment of the present invention.
  • the pn junction solar cell 100 includes a transparent substrate 10, a transparent conductive film 12 provided on the transparent substrate 10, a p-type semiconductor layer 14 including the copper oxide thin film of the present invention on the transparent conductive film 12, and p An n-type semiconductor layer 16 provided on the n-type semiconductor layer 14 and a metal electrode 18 provided on the n-type semiconductor layer 16 are included.
  • a pn junction solar cell can be obtained.
  • the same material as the material mentioned as an example of the base material used with the manufacturing method of the copper oxide thin film of this invention can be used.
  • the transparent substrate include a glass substrate and a resin substrate.
  • a resin substrate having low heat resistance is used as a transparent substrate.
  • the resin substrate having low heat resistance include polysulfone, polyethersulfone, polyarylate, polyamide, polyimide, polyamideimide, and polyetherimide.
  • Examples of the transparent conductive film 12 include a film made of In 2 O 3 : Sn (ITO), SnO 2 : Sb, SnO 2 : F, ZnO: Al, ZnO: F, CdSnO 4 , or the like.
  • ITO In 2 O 3
  • SnO 2 Sb
  • SnO 2 F
  • ZnO Al
  • ZnO F
  • CdSnO 4 CdSnO 4
  • the copper oxide thin film (for example, Cu 2 O thin film) of the present invention is used as the p-type semiconductor layer 14.
  • the n-type semiconductor layer 16 is preferably a metal oxide.
  • the metal oxide include metal oxides including at least one of Ti, Zn, Sn, and In, and more specifically, TiO 2 , ZnO, SnO 2 , IGZO, and the like. Is mentioned.
  • the n-type semiconductor layer is preferably formed by a wet method (also referred to as a liquid phase method) in the same manner as the p-type semiconductor layer from the viewpoint of manufacturing cost.
  • the metal electrode 18 for example, Pt, Al, Cu, Ti, Ni, or the like can be used.
  • Example 1 Synthesis of Specific Copper Complex Exemplified Compound 1 was synthesized based on Synthetic Examples A to D (The synthesized Exemplified Compound 1 is referred to as Copper Complex 1-1 to Copper Complex 1-4, respectively).
  • Exemplified Compound 2 was synthesized based on Synthetic Example E and Synthetic Example F, respectively (the synthesized Exemplified Compound 2 is referred to as Copper Complex 2-1 and Copper Complex 2-2, respectively).
  • Exemplified Compound 5 was synthesized based on Synthetic Example G and Synthetic Example H, respectively (the synthesized Exemplified Compound 5 is referred to as Copper Complex 5-1 and Copper Complex 5-2, respectively).
  • Exemplified compound 107 was synthesized based on Synthetic Example K and Synthetic Example L, respectively (the synthesized exemplified compound 107 is referred to as copper complex 107-1 and copper complex 107-2, respectively).
  • Exemplary compound 108 was synthesized based on Synthesis Example M and Synthesis Example N, respectively (the synthesized exemplary compound 108 is referred to as copper complex 108-1 and copper complex 108-2, respectively).
  • Exemplified compound 109 was synthesized based on Synthetic Example O and Synthetic Example P, respectively (the synthesized exemplified compound 109 is referred to as a copper complex 109-1 and a copper complex 109-2, respectively).
  • the exemplary compound 110 was synthesized based on Synthesis Example Q and Synthesis Example R, respectively (the synthesized exemplary compound 110 is referred to as a copper complex 110-1 and a copper complex 110-2, respectively).
  • the exemplified compound 111 was synthesized based on Synthesis Example S and Synthesis Example T, respectively (the synthesized exemplified compound 111 is referred to as a copper complex 111-1 and a copper complex 111-2, respectively).
  • the exemplified compound 58 was synthesized based on Synthesis Example U (the synthesized exemplified compound 58 is referred to as a copper complex 58-1).
  • the exemplified compound 126 was synthesized based on Synthesis Example V (the synthesized exemplified compound 126 is referred to as a copper complex 126-1).
  • Exemplary compound 29 was synthesized based on Synthesis Example W (synthesized exemplary compound 29 is referred to as copper complex 29-1).
  • the exemplified compound 131 was synthesized based on Synthesis Example X (the synthesized exemplified compound 131 is referred to as a copper complex 131-1).
  • the exemplary compound 132 was synthesized based on Synthesis Example Y (the synthesized exemplary compound 132 is referred to as a copper complex 132-1).
  • the exemplary compound 133 was synthesized based on Synthesis Example Z (the synthesized exemplary compound 133 is referred to as a copper complex 133-1).
  • Example 1-1 Synthesis example A of exemplary compound 1 (specific copper complex) After adding 9.5 g of 1,8-diazabiccyclo [5.4.0] undec-7-ene to 50 mL of N, N-dimethylacetamide, 9 g of meldrum acid was intermittently added over 5 minutes while cooling with water. To obtain a mixed solution. During this time, the liquid temperature of the mixed liquid was 18 ° C. to 28 ° C. Further, 7 mL of acetic anhydride was added dropwise to the mixture over 5 minutes, and then left overnight at room temperature. Cupric chloride (4.2 g) was dissolved in 25 mL of N, N-dimethylacetamide, added to the mixture, and allowed to stand at room temperature for 1 hour.
  • Example 1-2 Synthesis example B of exemplary compound 1 (specific copper complex)
  • 8 g (48 mmol) of the obtained Meldrum's sodium salt was dispersed in 40 mL of N, N-dimethylacetamide and stirred, while stirring for 10 minutes in a solution of 5.2 mL of acetic anhydride in 10 mL of N, N-dimethylacetamide. The resulting mixture was allowed to stand overnight at room temperature.
  • Example 1-3 Synthesis example C of exemplary compound 1 (specific copper complex) Meldrum's acid (7.2 g, 0.05 M) is dissolved in dichloromethane (60 mL), the internal temperature is set to ⁇ 5 ° C., pyridine (7.9 g, 0.1 M) is gradually added, and the mixture is stirred for about 10 minutes and mixed. A liquid was obtained. Then, a solution of acetyl chloride (4.3 g, 0.055 M) in dichloromethane (20 mL) was added dropwise to the obtained mixture over 20 minutes.
  • pyridine 7.9 g, 0.1 M
  • Example 1-4 Synthesis example D of exemplary compound 1 (specific copper complex)
  • 1.86 g (10 mmol) of Compound A was added, 10 mL of 1 mol / L sodium hydroxide solution was further added, and the mixture was stirred for about 10 minutes to dissolve Compound A to obtain Compound A Solution 2.
  • a solution obtained by dissolving 1.24 g (5 mmol) of copper sulfate pentahydrate in 20 mL of water was added to the compound A solution 2 and stirred at room temperature for 30 minutes.
  • the resulting crystals were collected by filtration, washed with water, and dried to obtain 1.6 g of a light blue powder of copper complex 1-4 (Exemplary Compound 1).
  • Example 1-5 Synthesis Example E of Exemplified Compound 2 (Specific Copper Complex) E First, Y. Oikawa, K .; Sugano, O .; Yonemitsu, J. et al. Org. Chem. , Vol. 43, 2087 (1978), Compound B having the following structure represented by General Formula 2 was obtained according to the synthesis method of Compound 3a.
  • Example 1-6 Synthesis Example F of Illustrative Compound 2 (Specific Copper Complex)
  • 2.00 g (10 mmol) of Compound B was added, and further 10 mL of 1 mol / L sodium hydroxide solution was added and stirred for about 10 minutes to dissolve Compound B to obtain Compound B Solution 2.
  • a solution obtained by dissolving 1.24 g (5 mmol) of copper sulfate pentahydrate in 20 mL of water was added to the compound B solution 2 and stirred at room temperature for 30 minutes.
  • the resulting crystals were collected by filtration, washed with water, and dried to obtain copper complex 2-2 (Exemplary Compound 2) as 2.0 g of a light blue powder.
  • Example 1-7 Synthesis example G of exemplary compound 5 (specific copper complex) First, Y. Oikawa, K .; Sugano, O .; Yonemitsu, J. et al. Org. Chem. , Vol. 43, 2087 (1978), compound C having the following structure represented by general formula 2 was synthesized according to the synthesis method of compound 3i.
  • Example 1-8 Synthesis example H of exemplary compound 5 (specific copper complex)
  • 8.62 g (10 mmol) of Compound C was added, and 10 mL of a 1 mol / L sodium hydroxide solution was further added, and the mixture was stirred for about 10 minutes to dissolve Compound C to obtain Compound C Solution 2.
  • a solution obtained by dissolving 1.24 g (5 mmol) of copper sulfate pentahydrate in 20 mL of water was added to the compound C solution 2 and stirred at room temperature for 30 minutes.
  • the resulting crystals were collected by filtration, washed with water, and dried to obtain copper complex 5-2 (Exemplary Compound 5) as 1.9 g of a light blue powder.
  • Example 1-9 Synthesis example K of exemplary compound 107 (specific copper complex) First, in Example 1-5, a similar reaction was carried out using cyclopropanecarboxylic acid chloride in place of propionyl chloride used in the synthesis of Compound B to synthesize Compound E having the following structure.
  • Example 1-5 the same reaction was carried out using 2.1 g (10 mmol) of Compound E instead of Compound B of Synthesis Example E, and copper complex 107-1 (Exemplary Compound 107) was obtained as 2.1 g of light blue powder. Got. The copper complex 107-1 was also recrystallized in the same manner as in Example 1-5 to produce a single crystal, and X-ray crystal structure analysis was performed.
  • Example 1-10 Synthesis example L of exemplary compound 107 (specific copper complex)
  • Example 1-6 the same reaction was performed using 1.7 g (10 mmol) of Compound E instead of Compound B of Synthesis Example F, and copper complex 107-2 (Exemplary Compound 107) was prepared as 1.9 g of light blue powder.
  • 1.7 g (10 mmol) of Compound E instead of Compound B of Synthesis Example F
  • copper complex 107-2 Example 1-10
  • Example 1-10 Synthesis example L of exemplary compound 107 (specific copper complex)
  • Example 1-6 the same reaction was performed using 1.7 g (10 mmol) of Compound E instead of Compound B of Synthesis Example F, and copper complex 107-2 (Exemplary Compound 107) was prepared as 1.9 g of light blue powder.
  • Example 1-11 Synthesis example M of exemplary compound 108 (specific copper complex) First, Canadian Journal of Chemistry, 1992, vol. 70, p. Compound F having the following structure was synthesized according to the synthesis method described in 1427 to 1445.
  • Example 1-5 the same reaction was carried out using 2.2 g (10 mmol) of Compound F instead of Compound B of Synthesis Example E, and copper complex 108-1 (Exemplary Compound 108) was obtained as 1.6 g of light blue powder. Got. The copper complex 108-1 was also recrystallized in the same manner as in Example 1-5 to produce a single crystal, and an X-ray crystal structure analysis was performed.
  • Example 1-12 Synthesis example N of exemplary compound 108 (specific copper complex)
  • Example 1-6 the same reaction was carried out using 1.7 g (10 mmol) of Compound F instead of Compound B of Synthesis Example F, and copper complex 108-2 (Exemplary Compound 108) was obtained as 1.4 g of a light blue powder.
  • Example 1-13 Synthesis Example O of Exemplified Compound 109 (Specific Copper Complex) O First, in Example 1-5, the same reaction was carried out using bromoacetic chloride instead of propionyl chloride used in the synthesis of Compound B, thereby synthesizing Compound G having the following structure.
  • Example 1-5 the same reaction was performed using 2.7 g (10 mmol) of Compound G instead of Compound B of Synthesis Example E, and copper complex 109-1 (Exemplary Compound 109) was obtained as 2.2 g of light blue powder. Got. The copper complex 109-1 was recrystallized in the same manner as in Example 1-5 to produce a single crystal, and an X-ray crystal structure analysis was performed.
  • Example 1-14 Synthesis example P of exemplary compound 109 (specific copper complex)
  • Example 1-6 the same reaction was performed using 2.7 g (10 mmol) of Compound G instead of Compound B of Synthesis Example F, and copper complex 109-2 (Exemplary Compound 109) was obtained as 2.4 g of light blue powder.
  • Example 1-14 Synthesis example P of exemplary compound 109 (specific copper complex)
  • the same reaction was performed using 2.7 g (10 mmol) of Compound G instead of Compound B of Synthesis Example F, and copper complex 109-2 (Exemplary Compound 109) was obtained as 2.4 g of light blue powder.
  • Example 1-15 Synthesis Example Q of Exemplified Compound 110 (Specific Copper Complex) First, Canadian Journal of Chemistry, 1992, vol. 70, p.
  • Compound H having the following structure was synthesized according to the synthesis method described in 1427 to 1445.
  • Example 1-5 the same reaction was performed using 3.1 g (10 mmol) of Compound H instead of Compound B of Synthesis Example E, and copper complex 110-1 (Exemplary Compound 110) was prepared as 2.7 g of a light blue powder. Got. The copper complex 110-1 was recrystallized in the same manner as in Example 1-5 to produce a single crystal, and an X-ray crystal structure analysis was performed.
  • Example 1-16 Synthesis example R of exemplary compound 110 (specific copper complex)
  • Example 1-6 the same reaction was carried out using 3.1 g (10 mmol) of Compound H instead of Compound B of Synthesis Example F, and copper complex 110-2 (Exemplary Compound 110) was prepared as 2.2 g of light blue powder. Got.
  • Example 1-17 Synthesis example S of exemplary compound 111 (specific copper complex) First, in Example 1-5, the same reaction was carried out using methoxyacetic acid chloride instead of propionyl chloride used in the synthesis of Compound B to synthesize Compound I having the following structure.
  • Example 1-5 a similar reaction was performed using 2.2 g (10 mmol) of Compound I instead of Compound B of Synthesis Example E, and copper complex 111-1 (Exemplary Compound 111) was obtained as 2.0 g of a light blue powder. Got. The structure was confirmed from the mass spectrum of the obtained copper complex.
  • Example 1-18 Synthesis example T of exemplary compound 111 (specific copper complex)
  • Example 1-6 the same reaction was carried out using 2.2 g (10 mmol) of Compound I in place of Compound B of Synthesis Example F, and copper complex 111-2 (Exemplary Compound 111) was prepared as 1.7 g of light blue powder. Got.
  • Example 1-19 Synthesis Example U of Exemplary Compound 58 (Specific Copper Complex) First, 14 g (100 mmol) of Meldrum's acid and 13 g (100 mmol) of acetophenone were heated and refluxed in toluene (200 mL) for 30 minutes, followed by silica gel column purification using n-hexane, ethyl acetate and chloroform as developing solvents. 4.2 g of intermediate J ′ was obtained. Thereafter, the same reaction was carried out using 4 g (20 mmol) of the intermediate J ′ in place of Meldrum's acid used in the synthesis of Compound B in Example 1-5, and 4.4 g of Compound L-19 having the following structure: Was synthesized. I H-NMR (400 MHz, DMSO-d 6 ) ⁇ 1.9 (s, 3H), 2.4 (s, 3H), 7.4-7.5 (m, 2H), 7.5-7.6 (M, 3H)
  • Example 1-5 the same reaction was performed using 2.2 g (10 mmol) of Compound L-19 instead of Compound B of Synthesis Example E, and copper complex 58-1 (Exemplary Compound) was obtained as 0.8 g of light blue powder. 58). The structure was confirmed from the mass spectrum of the obtained copper complex.
  • Example 1-20 Synthesis example V of exemplary compound 126 (specific copper complex) The reaction was carried out using 2-acetylthiophene instead of acetophenone of Example 1-19 to obtain 4.2 g of intermediate K ′. Thereafter, a similar reaction was carried out using 4.2 g (20 mmol) of the intermediate K ′ in place of Meldrum's acid used in the synthesis of Compound B in Example 1-5, and 3.6 g of Compound L having the following structure: -29 was synthesized.
  • I H-NMR 400 MHz, DMSO-d 6 ) ⁇ 1.8 (s, 3H), 2.4 (s, 3H), 6.9-7.2 (m, 4H)
  • Example 1-5 the same reaction was carried out using 2.5 g (10 mmol) of compound L-29 instead of compound B of Synthesis Example E, and copper complex 126-1 (exemplary compound) was prepared as 0.6 g of a light blue powder. 126) was obtained. The structure was confirmed from the mass spectrum of the obtained copper complex.
  • Example 1-21 Synthesis example W of Exemplified compound 29 (specific copper complex) The reaction was carried out using cyclohexanone instead of acetophenone of Example 1-19 to obtain 9.2 g of intermediate L ′. Thereafter, the same reaction was carried out using 3.7 g (20 mmol) of the intermediate L ′ in place of Meldrum's acid used in the synthesis of Compound B in Example 1-5, and 4.1 g of Compound L having the following structure: -39 was synthesized.
  • I H-NMR 400 MHz, CDCl 3 ) 1.5-1.8 (m, 6H), 1.9-2.4 (m, 7H)
  • Example 1-5 the same reaction was carried out using 2.3 g (10 mmol) of compound L-39 instead of compound B of Synthesis Example E, and copper complex 29-1 (exemplary compound) was obtained as 2.1 g of a light blue powder. 29) was obtained.
  • the copper complex 29-1 was also recrystallized in the same manner as in Example 1-5 to produce a single crystal, and an X-ray crystal structure analysis was performed.
  • Example 1-22 Synthesis Example X of Exemplified Compound 131 (Specific Copper Complex) The reaction was carried out using 7-octen-2-one instead of acetophenone of Example 1-19 to obtain 2.2 g of intermediate L ′. Thereafter, in the synthesis of Compound B in Example 1-5, the same reaction was carried out using 3.7 g (20 mmol) of the intermediate M ′ instead of Meldrum's acid used, and 2.4 g of the compound having the following structure L-48 was synthesized.
  • I H-NMR 400 MHz, CDCl 3 ) 1.2-1.3 (m, 11H), 2.7 (s, 3H), 4.9 to 6.1 (m, 3H)
  • Example 1-5 the same reaction was carried out using 2.4 g (10 mmol) of compound L-48 instead of compound B of synthesis example E, and copper complex 131-1 (exemplary compound) was prepared as 0.6 g of a light blue powder. 131). The structure was confirmed from the mass spectrum of the obtained copper complex.
  • Example 1-23 Synthesis example Y of exemplary compound 132 (specific copper complex) First, in Example 1-5, the same reaction was carried out using 2-furancarboxylic acid chloride in place of propionyl chloride used in the synthesis of Compound B to synthesize Compound L-7 having the following structure.
  • I H-NMR 400 MHz, DMSO-d 6 ) ⁇ 1.8 (s, 6H), 6.8-7.3 (m, 4H)
  • Example 1-5 the same reaction was carried out using 2.4 g (10 mmol) of compound L-7 instead of compound B of Synthesis Example E, and copper complex 132-1 (exemplary compound) was prepared as 0.7 g of light blue powder. 132). The structure was confirmed from the mass spectrum of the obtained copper complex.
  • Example 1-24 Synthesis example Z of exemplary compound 133 (specific copper complex) First, in Example 1-5, the same reaction was carried out using 6-heptenecarboxylic acid chloride in place of propionyl chloride used in the synthesis of Compound B to synthesize Compound O having the following structure.
  • Example 1-5 the same reaction was carried out using 2.5 g (10 mmol) of Compound O instead of Compound B of Synthesis Example E, and copper complex 133-1 (Exemplary Compound 133) was obtained as 0.8 g of a light blue powder. Got. The structure was confirmed from the mass spectrum of the obtained copper complex.
  • R-3 represents the symbol of the space group
  • the R value represents the “relative residue” of the least square method
  • the Rw value represents the “weighted relative residue” of the least square method
  • GOF represents the correlation coefficient ( Goodness of fitness).
  • the definition of is the same for each.
  • P-1, P21 / c, and C2 / c in the copper complex 5-1, the copper complex 107-1, the copper complexes 108-1, 109-1, the copper complex 110-1, and the copper complex 29-1 are , Represents space group symbol.
  • copper complex 1-1, copper complex 2-1, copper complex 5-1, copper complex 107-1, copper complex 108-1, copper complex 109-1, copper complex 110- obtained by X-ray structural analysis
  • the structural formulas for 1 and copper complex 29-1 are shown in FIGS. 2 to 9, respectively. Based on the above results, copper complex 1-1, copper complex 2-1, copper complex 5-1, copper complex 107-1, copper complex 108-1, copper complex 109-1, copper complex 110-1, and copper complex Regarding 29-1, it was confirmed that all were obtained as a complex represented by the general formula 1 described above.
  • the curve (A) is a TG curve of the copper complex 1-1
  • the curve (B) is a DTA curve of the copper complex 1-1
  • the broken line (C) represents the decrease from the copper complex 1-1 when CO 2 and acetone are desorbed from the copper complex 1-1; -47.1% by mass
  • the broken line (D) is all The amount of decrease from the copper complex 1-1 when the copper complex is changed to Cu 2 O; represents ⁇ 83.7% by mass.
  • Meldrum acid is known to decompose into acetone, CO 2 and ketene during thermal decomposition, and it is considered that the thermal decomposition of meltrum acid occurs in the first stage.
  • m / z means mass to charge ratio.
  • thermogravimetric analysis was similarly performed on the copper complex 2-1 and the copper complex 5-1.
  • the results are shown in FIG.
  • Curve (A) is a TG curve of copper complex 2-1
  • curve (B) is a TG curve of copper complex 5-1. Similar to the copper complex 1-1, mass reduction was observed in two stages, and it was confirmed that the mass reduction converged at less than 300 ° C.
  • Completion of thermal decomposition is judged from the fact that the mass reduction is greater than the calculated value that causes the Cu complex to decompose and Cu 2 O, the mass reduction has converged, and that no sublimation has occurred from DTA data. did.
  • Table 13 summarizes the TG results for other copper complexes.
  • a sample whose thermal decomposition is completed at less than 300 ° C. is indicated by A, and a sample having a temperature of 300 ° C. or higher is indicated by B.
  • the thermal decomposition was completed at less than 300 ° C.
  • the thermal decomposition temperature was 500 ° C. or higher in the method performed in the above-mentioned Japanese Patent Application Laid-Open No. 2011-119454 (specifically, the compounds described in paragraphs 0046 to 0056 of Japanese Patent Application Laid-Open No. 2011-119454).
  • Example 2 Preparation Example of Copper Complex Solution
  • Example 2-1 A copper complex solution 1 as a specific solution was prepared using the copper complex 1-1. 1.95 g of copper complex 1-1 was weighed, added to 30 mL of N, N-dimethylacetamide at room temperature (25 ° C., the same applies hereinafter) with stirring, and stirred for 30 minutes to give a dark blue color of 0.15 mol / L. A transparent solution (copper complex solution 1) was obtained.
  • Example 2-2 0.65 g of the copper complex 1-1 was weighed and added to 30 mL of 2,2,3,3-tetrafluoro-1-propanol heated at 90 ° C. with stirring, and stirred for 30 minutes. A dark blue transparent solution of L (copper complex solution 2) was obtained.
  • Example 2-3 0.33 g of the copper complex 1-1 was weighed, added to 30 mL of normal 2-diethylaminoethanol with stirring, and stirred for 30 minutes to obtain a 0.025 mol / L transparent solution (copper complex solution 3). .
  • Example 2-4 0.65 g of the copper complex 1-1 was weighed, added to 30 mL of normal temperature pyridine while stirring, and stirred for 30 minutes to obtain a 0.05 mol / L transparent solution (copper complex solution 4).
  • Example 2-5 0.65 g of the copper complex 1-1 was weighed, added to 30 mL of normal temperature tetrahydrofuran with stirring, and stirred for 30 minutes to obtain a 0.05 mol / L transparent solution (copper complex solution 5).
  • Example 2-6 A copper complex solution 6 as a specific solution was prepared using the copper complex 1-1 and the copper complex 2-1. 1.3 g of copper complex 1-1 and 1.4 g of copper complex 2-1 were weighed and added to 30 mL of N, N-dimethylacetamide at room temperature with stirring, and stirred for 30 minutes, so that the copper complex concentration was 0. A 2 mol / L dark blue transparent solution (copper complex solution 6) was obtained.
  • Example 3 Preparation of Cu 2 O thin film
  • the substrate surface was a silicon substrate.
  • a Cu 2 O thin film was prepared by the following procedure. .
  • Organic copper complex solution coating film forming step and drying step The copper complex solution 1 is spin-coated on a 25 mm square silicon substrate at a rotational speed of 3000 rpm for 60 seconds and then dried on a hot plate heated to 200 ° C. for 5 minutes. By repeating the process five times, a precursor film 1 (organic copper complex film) having a film thickness of about 40 nm was obtained.
  • the obtained precursor thin film 1 was heated in the following annealing temperature and the following annealing atmosphere.
  • the annealing was performed at each annealing temperature of 200 ° C., 230 ° C., 250 ° C., 280 ° C., 300 ° C., or 350 ° C.
  • the annealing atmosphere is O 2 / (Ar + O 2 ) flow rate ratio (volume basis), 0 (that is, oxygen concentration in the furnace at the time of heat treatment 0 volume%), 0.1 (oxygen concentration 10 volume%)
  • Heat treatment is performed by changing to 0.2 (oxygen concentration 20 vol%), 0.5 (oxygen concentration 50 vol%), 0.8 (oxygen concentration 80 vol%), or 1.0 (oxygen concentration 100 vol%).
  • Heat treatment is performed by changing to 0.2 (oxygen concentration 20 vol%), 0.5 (oxygen concentration 50 vol%), 0.8 (oxygen concentration 80 vol%), or 1.0 (oxygen concentration 100 vol%).
  • the heat treatment was performed using a high-speed heat treatment apparatus (AW-410 manufactured by Allwin21).
  • the temperature was raised to a desired temperature at 50 ° C./sec, held for 3 minutes, and then cooled in the furnace.
  • the total gas flow rate during the heat treatment was 2 L / min.
  • Thin film X-ray diffraction measurement was performed on each of the obtained Cu 2 O thin films.
  • RINT-Ultima III manufactured by Rigaku Corporation was used, and evaluation was performed by 2 ⁇ measurement with an incident angle fixed at 0.35 °.
  • At 200 ° C. indicated by curve F no peak could be confirmed.
  • the peaks of Cu 2 O JDPDS # 05-0667) were mainly confirmed at 230 ° C., 250 ° C., and 280 ° C. indicated by curves E to C.
  • the peak indicated by (c) in FIG. 14 represents the presence of Cu 2 O (111), and the peak indicated by (d) represents the presence of Cu 2 O (200). Further, at 300 ° C. indicated by the curve B and 350 ° C. indicated by the curve A, a peak of CuO (JCPDS # 48-1548) was confirmed in addition to the peak of Cu 2 O.
  • the peak indicated by (a) in FIG. 14 represents the presence of CuO (11-1), and the peak indicated by (b) represents the presence of CuO (111).
  • the peak shown by (a) in FIG. 15 represents the presence of Cu (111), and the peak shown by (b) represents the presence of Cu (200). Further, the peak indicated by (c) in FIG. 15 represents the presence of Cu 2 O (111), the peak indicated by (d) represents the presence of Cu 2 O (200), and is indicated by (e). The peak represents the presence of Cu 2 O (220).
  • Example 3-2 A Cu 2 O thin film was produced using the copper complex solution (copper complex solution 6) produced in Example 2-6.
  • Organic copper complex solution coating film forming step and drying step The copper complex solution 6 is spin-coated on a 25 mm square silicon substrate at a rotational speed of 3000 rpm for 60 seconds, and then dried on a hot plate heated to 200 ° C. for 5 minutes. By repeating the process 5 times, a precursor thin film 6 (organic copper complex film) having a film thickness of about 40 nm was obtained.
  • the precursor thin film 6 is heat-treated under the conditions of an annealing temperature of 250 ° C. and an annealing atmosphere of O 2 / (Ar + O 2 ) flow rate ratio (volume basis) of 0.2 (oxygen concentration 20% by volume). To obtain a Cu 2 O thin film 6.
  • Example 3-3 Base material surface is resin substrate Using the copper complex solution 1-1 prepared in Example 2-1, a Cu 2 O thin film was prepared by the following procedure. First, a laminated base material having a polyimide resin substrate that was detachably attached to a 25 mm square silicon substrate via an acrylic adhesive was prepared as a base material. Next, the process of spin-coating the copper complex solution 1-1 on the polyimide resin substrate surface of the laminated base material at a rotational speed of 3000 rpm for 60 seconds and then drying it on a hot plate heated to 200 ° C. for 5 minutes 5 times By repeating, the precursor film
  • a laminated base material having a polyimide resin substrate that was detachably attached to a 25 mm square silicon substrate via an acrylic adhesive was prepared as a base material.
  • the Cu 2 O thin film obtained as described above functions as a p-type semiconductor, it can be applied to a thin film semiconductor device. Moreover, by manufacturing a thin film semiconductor device with a configuration adjacent to a member to be an n-type semiconductor, a thin film semiconductor device having a pn junction can be obtained, and it is also suitable for application to a pn junction solar cell. Further, as can be seen from Example 3-2, a Cu 2 O thin film, which is a copper oxide thin film, can be produced even when annealing is performed at a heating temperature of 250 ° C. It can also be used as a base material, and it can be seen that a flexible thin film semiconductor device can be manufactured.

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57130987A (en) * 1980-12-24 1982-08-13 Isf Spa Ketohydroxyiminocephalosporins
JP2001518457A (ja) * 1997-09-29 2001-10-16 ザ、プロクター、エンド、ギャンブル、カンパニー １，３‐ジオキサン‐４，６‐ジオン類からβ‐ケトエステル芳香プロアコードを製造するための方法
WO2002096915A1 (en) * 2001-05-25 2002-12-05 Samsung Fine Chemicals Co., Ltd. Process for producing optically pure δ - hydroxy-β -ketoester derivatives
JP2005173198A (ja) * 2003-12-11 2005-06-30 Konica Minolta Medical & Graphic Inc 熱現像写真感光材料及びその画像形成方法
JP2006515597A (ja) * 2003-01-09 2006-06-01 アステラス製薬株式会社 ピロロピリダジン誘導体
JP2011119454A (ja) * 2009-12-03 2011-06-16 Tftech:Kk ｐ型半導体の性能を持つ酸化銅（Ｉ）膜の製造方法および該膜作成用の溶液の製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451746B1 (en) * 2000-11-03 2002-09-17 Chemlink Laboratories, Llc Carrier for liquid ingredients to be used in effervescent products

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57130987A (en) * 1980-12-24 1982-08-13 Isf Spa Ketohydroxyiminocephalosporins
JP2001518457A (ja) * 1997-09-29 2001-10-16 ザ、プロクター、エンド、ギャンブル、カンパニー １，３‐ジオキサン‐４，６‐ジオン類からβ‐ケトエステル芳香プロアコードを製造するための方法
WO2002096915A1 (en) * 2001-05-25 2002-12-05 Samsung Fine Chemicals Co., Ltd. Process for producing optically pure δ - hydroxy-β -ketoester derivatives
JP2006515597A (ja) * 2003-01-09 2006-06-01 アステラス製薬株式会社 ピロロピリダジン誘導体
JP2005173198A (ja) * 2003-12-11 2005-06-30 Konica Minolta Medical & Graphic Inc 熱現像写真感光材料及びその画像形成方法
JP2011119454A (ja) * 2009-12-03 2011-06-16 Tftech:Kk ｐ型半導体の性能を持つ酸化銅（Ｉ）膜の製造方法および該膜作成用の溶液の製造方法

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
BIHLMAYER, G. A. ET AL.: "Cyclic acylals. XVII. Hydroxy- and aminomethylene derivatives of Meldrum's acid", MONATSHEFTE FUER CHEMIE, vol. 98, no. 3, 1967, pages 564 - 78 *
GEORGIADES, SAVVAS N. ET AL.: "Synthetic libraries of tyrosine-derived bacterial metabolites", BIOORGANIC & MEDICINAL CHEMISTRY LETTERS, vol. 18, no. 10, 2008, pages 3117 - 3121 *
KNOTH, TANJA ET AL.: "The Ras Pathway Modulator Melophlin A Targets Dynamins", ANGEWANDTE CHEMIE, INTERNATIONAL EDITION, vol. 48, no. 39, 2009, pages 7240 - 7245 *
LERMER, LEONARD ET AL.: "The synthesis of P-keto lactones via cyclization of P-keto ester dianions or the cyclization of Meldrum's acid derivatives", CANADIAN JOURNAL OF CHEMISTRY, vol. 70, no. 5, 1992, pages 1427 - 45 *
LI, AN-HU E ET AL.: "Synthesis, CoMFA Analysis, and Receptor Docking of 3,5-Diacyl-2,4- Dialkylpyridine Derivatives as Selective A3 Adenosine Receptor Antagonists", JOURNAL OF MEDICINAL CHEMISTRY, vol. 42, no. 4, 1999, pages 706 - 721 *
PEMBERTON, NILS ET AL.: "Synthesis of Multi Ring-Fused 2-Pyridones via an Acyl-Ketene Imine Cyclocondensation", ORGANIC LETTERS, vol. 8, no. 5, 2006, pages 935 - 938 *
YAMAMOTO, YUTAKA ET AL.: "1,3-Oxazines and related compounds. V. N-Acylacetylation of carboxamides with the diketene- halotrimethylsilane system or acyl Meldrum's acids", CHEMICAL & PHARMACEUTICAL BULLETIN, vol. 30, no. 10, 1982, pages 3505 - 12 *

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