WO2014046193A1

WO2014046193A1 - Organocopper complex, organocopper complex solution, copper oxide thin film, method for producing copper oxide thin film, and compound

Info

Publication number: WO2014046193A1
Application number: PCT/JP2013/075325
Authority: WO
Inventors: 真宏高田; 由夫稲垣; 亮浜崎; 野村　公篤; 田中　淳; 鈴木　真之
Original assignee: 富士フイルム株式会社
Priority date: 2012-09-20
Filing date: 2013-09-19
Publication date: 2014-03-27
Also published as: KR20150043489A; JP2014076987A; TW201412753A; JP5988941B2; KR101748050B1

Abstract

Provided are: an organocopper complex having a structure represented by general formula (1); a copper oxide thin film comprising the organocopper complex; a method for producing the copper oxide thin film; and a compound constituting the organocopper complex. R¹¹, R¹², R²¹ and R²² each represent an alkyl group, a non-aromatic hydrocarbon group having an unsaturated bond, an aryl group, or a heteroaryl group. R¹¹ and R²¹ may form rings that are linked to each other, and R¹² and R²² may form rings that are linked to each other. R³¹ and R³² each represent a hydrogen atom, an alkyl group, and alkoxy group, a non-aromatic hydrocarbon group having an unsaturated bond, an aryl group, a heteroaryl group, or a hydroxy group. When all of R¹¹, R¹², R²¹ and R²² represent a methyl group, R³¹ and R³² each represent an alkyl group, an aryl group, an alkoxy group, or a hydroxy group.

Description

Organic copper complex, organic copper complex solution, copper oxide thin film, method for producing copper oxide thin film, and compound

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.

Various oxide thin films are used for thin film semiconductor devices. For example, a 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.

Moreover, these thin film semiconductor devices are applied to various uses. For example, applications using the Cu ₂ O thin film, 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.
In particular, 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.

By the way, as 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.
For example, Thin Solid Films, 442 (2003) 48 discloses forming a copper oxide thin film using a sol-gel method. In addition, as 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. , A step of applying by any one of spray coating methods, a step of applying a solution to the substrate surface and then evaporating the solvent to dry the solution composition to a predetermined thickness, and a group 18 noble gas Oxidation having the performance of a p-type semiconductor by a manufacturing method including a step of heat treatment at 300 ° C. to 700 ° C. for 1 minute to 3 hours in an inert gas atmosphere alone or in combination of two or more selected from the group and nitrogen It is disclosed that a copper (I) film is formed (see, for example, JP-A-2011-119454).
Also, examples of copper complexes are disclosed in Monatschefte fur Chemie, 98, (1967), 564.

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.

In particular, in recent years, since a lighter and more flexible thin film semiconductor device is required, it is required to use a flexible substrate, specifically, for example, a resin substrate. ing. However, in the heat treatment at 300 ° C. or higher, it is necessary to consider the heat resistance of the base material, so that the selectivity of the base material and peripheral members is lowered.

In the method disclosed in Japanese Patent Application Laid-Open No. 2011-119454, when a copper (I) oxide film is formed, copper (I) oxide or the like is generated by thermally decomposing a copper compound. A copper compound that can be decomposed in a temperature range below 300 ° C. at which a copper thin film can be formed on a resin substrate has not been known. In addition, the thermal decomposition characteristics of the copper complex disclosed in Monatschefte fur Chemie, 98, (1967), 564 were also unknown.

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.

In order to achieve the above object, the following invention is provided.
<1> An organic copper complex having a structure represented by the following general formula 1.

In General Formula 1, 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. Represents a non-aromatic hydrocarbon group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. R ¹¹ and R ²¹ may be connected to each other to form a ring, and 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. Represents a non-aromatic hydrocarbon group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 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 groups represented by R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , and R ³² may be substituted with a monovalent substituent. However, when R ¹¹ , R ¹² , R ²¹ , and R ²² all represent a methyl group, 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.

<2> 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, and 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, and 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.

<3> The organic copper complex according to <1> or <2>, wherein R ¹¹ and R ¹² in the general formula 1 are the same, and R ²¹ and R ²² are the same.

<4> The organocopper complex according to any one of <1> to <3>, wherein R ³¹ and R ³² in the general formula 1 are the same.

<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.

<6> In any one of <3> to <5>, wherein 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.

<7> Any one of <4> to <6>, wherein 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.

<9> An organic copper complex solution containing the organic copper complex according to any one of <1> to <8> and a solvent.

<10> The organic copper complex solution according to <9>, including at least two types of the organic copper complex.

<11> The organic copper complex solution according to <9> or <10>, wherein the concentration of the organic copper complex is 0.01 mol / L to 0.3 mol / L.

<12> The organic copper complex solution according to any one of <9> to <11>, wherein the solvent is an aprotic polar solvent.

<13> A copper oxide thin film obtained by drying and heat-treating the coating film of the organocopper complex solution according to any one of <9> to <12>.

<14> The copper oxide thin film according to <13>, which contains at least monovalent copper.

<15> An organic copper complex solution coating film forming step of coating the organic copper complex solution according to any one of <9> to <12> on a substrate to form an organic copper complex solution coating film; ,
A drying step of drying the organic copper complex solution coating film to obtain an organic copper complex film;
A heat treatment step of heating the organic copper complex film at 230 ° C. or higher and lower than 300 ° C. to form a copper oxide thin film;
It is a manufacturing method of the copper oxide thin film containing this.

<16> 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.

In general formula 2, 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. However, when R ¹³ and R ²³ represent a methyl group, 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. .

According to the present invention, 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.
Further, according to the present invention, there is provided 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

It is a schematic cross section of a pn junction solar cell showing an example of a configuration of a pn junction solar cell according to an embodiment. It is the structure of the copper complex 1-1 obtained by Example 1-1. It is the structure of the copper complex 2-1 obtained in Example 1-5. It is the structure of the copper complex 5-1 obtained in Example 1-7. It is the structure of the copper complex 107-1 obtained in Example 1-9. It is the structure of the copper complex 108-1 obtained in Example 1-11. It is the structure of the copper complex 109-1 obtained in Example 1-13. It is the structure of the copper complex 110-1 obtained in Example 1-15. It is the structure of copper complex 29-1 obtained in Example 1-21. 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.

Hereinafter, the organic copper complex and the organic copper complex solution of the present invention will be described in detail.

<Organic copper complex>
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”).
In forming a copper oxide thin film, by using a specific copper complex as a raw material, a copper oxide can be obtained even when the specific copper complex is heat-treated at a low temperature (for example, less than 300 ° C.). . As described later, 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.

In General Formula 1, 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. Represents a non-aromatic hydrocarbon group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. R ¹¹ and R ²¹ may be connected to each other to form a ring, and 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. Represents a non-aromatic hydrocarbon group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 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 groups represented by R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , and R ³² may be substituted with a monovalent substituent. However, when R ¹¹ , R ¹² , R ²¹ , and R ²² all represent a methyl group, 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.

In general formula ^1, 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.

In the general formula 1, 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 | combination of a specific copper complex is easy, the production cost of a specific copper complex can be reduced.
In the general formula 1, 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.

On the other hand, in the general formula 1, when R ¹¹ and R ¹² are different from each other and R ²¹ and R ²² are different from each other, when the specific copper complex is prepared in an organic copper complex solution described later, the specific copper complex is dissolved in the solvent. Can increase the sex. Moreover, since it becomes difficult to crystallize a specific copper complex, the film density of the copper oxide thin film obtained by drying and heating the coating film of an organic copper complex solution tends to become uniform.

In General Formula 1, when 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. For example, a methyl group, an ethyl group, a propyl group, an n-hexyl group, n -Nonyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, 1,3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetramethyl Examples include a butyl group, a cyclohexyl group, and a benzyl group.
When 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.

In General Formula 1, when 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. For example, 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.
When 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.

In the general formula 1, when 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. Among these, 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. When 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.

In General Formula 1, when 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, Furthermore, you may have a substituent. Examples of 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. Among these, 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.
When 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.
In the present invention, 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.

Among the above, 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. When 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.

In General Formula 1, when 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. Group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, 1,3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group , A benzyl group, a cyclohexyl group, and the like.
When R ³¹ or R ³² represents an alkyl group, R ³¹ and 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.

In General Formula 1, when 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.
When R ³¹ or R ³² represents an alkoxy 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.

In the general formula 1, when 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.
When R ³¹ or R ³² represents a non-aromatic hydrocarbon group having an unsaturated bond, 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.

In General Formula 1, when 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. . 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. Among these, 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. When 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.

In the general formula 1, when 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. Examples of 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. Among the above, the heteroaryl group represented as R ³¹ or R ³² is preferably a thiophene ring, a furan ring, or an oxazole group.
When 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.

When R ¹¹ , R ¹² , R ²¹ , and R ²² in General Formula 1 all represent a methyl group, R ³¹ and R ³² are each independently an alkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. An aryl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group. That is, when R ¹¹ , R ¹² , R ²¹ , and R ²² all represent a methyl group, R ³¹ and R ³² are not each represented by a hydrogen atom.

Among the above, 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. When 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. Compared with the case, the temperature required for the specific copper complex to be completely decomposed can be lowered. This is because 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. When 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.
By R ³¹ and / or R ³² is an alkyl group, it is possible to lower the thermal decomposition temperature of the particular copper complexes. In addition, by 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.

H in the C—H bond of each of the above groups represented by R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , and R ³² in General Formula 1 may be substituted with a monovalent substituent. .
Examples of the substituent 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 atom (fluorine atom, chlorine atom, iodine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group) 1-methylbutoxy group, cyclohexyloxy group, etc.), aryloxy group (phenyloxy group, 4-methylphenyloxy group, -Methylphenyloxy group, 2-methylphenyloxy group, 4-chlorophenyloxy group, 2-chlorophenyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, 2-ethylhexyloxycarbonyl group, Phenyloxyethyloxycarbonyl group, 2,4-di-t-amylphenyloxyethylcarbonyl group, etc.), acyloxy group (acetyloxy group, propanoyloxy group, hexanoyloxy group, 2-ethylhexanoyloxy group, benzoyl) Oxy group, 4-methoxybenzoyloxy group, 2-chlorobenzoyloxy group, etc.), acylamino group (acetylamino group, propanoylamino group, hexanoylamino group, 2-ethylhexanoylamino group, benzoylamino) Group, 4-methoxybenzoylamino group, N-methylacetylamino group, N-methylbenzoylamino group, 2-oxopyrrolidino group, etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group) N, N-diethylcarbamoyl group, N, N-dibutylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), cyano group, carboxy group, sulfo group, heterocyclic group (2-thienyl group, 4-pyridyl group) Group, 2-furyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, and benzotriazol-1-yl group). These substituents may be further substituted with another substituent.
As the substituent, an alkyl group or an aryl group is preferable, and a methyl group, an ethyl group, or a phenyl group is more preferable. In addition, 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. For example, when 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. . Further, 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.

As an example of the specific copper complex, 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.

In Tables 1-2 and 4-7, Ph represents a phenyl group. In the exemplified compounds 20 to 39 shown in Table 2, R ¹¹ and R ²¹ are connected to each other to form a ring, and 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 , and “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.

Other forms of organocopper complex The organocopper complex of the present invention is the specific copper complex described above. In forming the copper oxide thin film, a monomer derived from the following general formula 1 is used as a repeating unit. And / 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.

In Reference Compound 1 and Reference Compound 2, it is multimerized via R ¹¹ , R ¹² , R ²¹ , and R ²² of General Formula 1, but it may be multiplied via R ³¹ or R ³² . In Reference Compound 1 and Reference Compound 2, 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.

Next, the compound (ligand) which forms a specific copper complex by coordinating to a copper ion will be described.
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.

In general formula 2, 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. A 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. However, when R ¹³ and R ²³ represent a methyl group, 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. .

In 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. And the definition of R ³³ is the same as the definitions of R ³¹ and R ^{32 in} formula 1.

When R ¹³ and R ²³ in General Formula 2 each represent a methyl group, 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. For example, when 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. Further, 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, and 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.

Next, a method for synthesizing the specific copper complex will be described.
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.

The kind of cupric salt is not particularly limited.
Examples of 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.
Among these, 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.
When using alcohol as a solvent, it is preferable to use it on the comparatively low-temperature conditions which do not exceed 50 degreeC from a viewpoint of suppressing decomposition | disassembly of the compound represented by General formula 2.
In addition, in order to remove oil-soluble impurities generated by mixing the 1,3-dicarbonyl compound represented by the general formula 2 and the cupric salt, the solvent is water-immiscible such as toluene or xylene. An organic solvent may coexist.

Further, in order to capture the acid generated by the reaction of the compound represented by the general formula 2 and the cupric salt, 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.

In the general formula 1, in each combination of 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 | dissolves in a solvent and forms a copper oxide thin film.

<Organic copper complex solution>
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. Hereinafter, the organocopper complex solution of the present invention is also referred to as a specific solution.
By dissolving the specific copper complex in a solvent to form a solution, a copper oxide thin film can be easily formed at a low temperature from a coating film formed by coating the solution on a substrate or the like. Moreover, the copper oxide thin film without a bias | inclination in copper concentration can be obtained by melt | dissolving a specific copper complex in a solvent to make a solution.
In addition to the specific copper complex and the solvent, 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.

Specific copper complex 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.

Solvent 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.
Examples of 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.
Examples of organic solvents 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.

Among the above, 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.
Examples of 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.
Among these 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.

In addition, 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.
When 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. When 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.
For example, N, N-dimethylacetamide, which is an amide solvent, 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.
In addition, a solvent may use only 1 type and may mix and use 2 or more types.

Metal Compound 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.

<Copper oxide thin film>
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. For example, when a copper oxide thin film is used as a p-type semiconductor layer of a pn junction solar cell, the thickness of the copper oxide thin film may be in the range of 0.01 μm to 20 μm.
You may adjust the thickness of a copper oxide thin film by drying the coating film of a specific solution, and also apply | coating a specific solution, and overlaying a specific solution.
The copper oxide thin film of this invention can be manufactured with the following manufacturing method, for example.

<Method for producing copper oxide thin film>
The manufacturing method of the copper oxide thin film of this invention apply | coats the organic copper complex solution containing the organic copper complex which has the structure represented by the general formula 1 and the solvent on the base material, and the organic copper complex solution. An organic copper complex solution coating film forming step of forming a coating film, a drying step of drying the organic copper complex solution coating film to obtain an organic copper complex film, and heating the organic copper complex film at 230 ° C. or more and less than 300 ° C. And 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. An energy beam irradiation step of irradiating an atomic beam, X-rays, γ-rays, visible light, etc.).
Hereinafter, 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. Examples of the substrate include inorganic materials such as glass, silicon, and metal, resins, and composite materials of inorganic materials and resins.

Examples of 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.

Among the above, the base material is preferably a flexible material. By forming a copper oxide thin film using a flexible substrate, it is possible to produce a copper oxide thin film that can be bent or a copper oxide thin film that is difficult to break even if dropped.
Among these, from the viewpoint of light weight and flexibility, the base material is preferably a resin or a composite base material obtained using a resin and a material other than resin. As 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 μm to 1000 μm, and more preferably 50 μm to 500 μm. When the thickness of the base material is 50 μm or more, the flatness of the base material itself is improved, and when the thickness of the base material is 1000 μm 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 μm or less because the flexibility is further improved.

The method for applying the specific solution on the substrate is not particularly limited. For example, 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.
In particular, 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.
When forming a thinner organic copper complex solution coating film, for example, the concentration of the specific copper complex in the specific solution may be lowered. Moreover, when apply | coating a specific solution with a spin coat method, a thin organic copper complex solution coating film can be obtained by making the base-material rotation speed at the time of apply | coating a specific solution on a base material high.
When forming a thicker organic copper complex solution coating film, for example, the concentration of the specific copper complex in the specific solution may be increased. Moreover, when apply | 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 | coating a specific solution on a base material low.

Drying step In the drying step, 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.
In addition, since the organic copper complex 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 | membrane obtained after a drying process is also called precursor film | membrane.

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. For example, 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.
When using a heat resistant resin substrate as the substrate, the heating temperature of the coating film is preferably lower than the glass transition temperature of the resin.
In addition, 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. When the temperature of the heat treatment is 230 ° C. or higher, the thermal decomposition of the specific copper complex proceeds sufficiently, and a dense copper oxide thin film can be obtained. Moreover, 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. In addition, 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.

The heat treatment step is preferably performed in 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.
In particular, from the viewpoint of obtaining a monovalent copper oxide thin film, 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.
For example, when 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%].
When the 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.

In addition, you may repeat each process mentioned above repeatedly.
For example, repeating an organic copper complex solution coating film forming process for coating a specific solution on a substrate and a drying process for drying the coating film (coating the specific solution again on the dried coating film and drying). Thus, the thickness of the organic copper complex film can be adjusted.

Other Steps 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.

Energy ray irradiation step In the energy ray irradiation step, 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, γ 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.

By passing through each process demonstrated above, a copper oxide thin film is manufactured on a base material.
In particular, since 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.

In addition, when the copper oxide thin film is formed in a reducing atmosphere, the content of copper atoms with respect to all atoms constituting the copper oxide thin film is preferably 70 atomic% or more. When the copper atom content is 70 atom% 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.

<Thin film semiconductor device>
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. 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. In addition, by using a flexible base material, 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. Furthermore, since it is lightweight, the burden on a building at the time of installing on the roof of a building is reduced.

In addition, 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.
Moreover, when a thin film semiconductor device is equipped with a base material, 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. Examples of 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. In particular, 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.

<Solar cell>
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. For example, it is good also as a pn junction type solar cell using the thin film semiconductor device which has a pn junction provided with the p-type semiconductor layer containing the copper oxide thin film of this invention, and an n-type semiconductor layer.
As a more specific embodiment of the 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.

An example of a pn junction solar cell will be described with reference to FIG.
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.
When the p-type semiconductor layer 14 and the n-type semiconductor layer 16 are laminated adjacent to each other, a pn junction solar cell can be obtained.

If it is transparent as the transparent substrate 10, 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. Examples of the transparent substrate include a glass substrate and a resin substrate. In the present invention, since a copper oxide thin film can be formed at a low temperature (230 ° C. or more and less than 300 ° C.) by using a specific solution containing a specific copper complex, a resin substrate having low heat resistance is used as a transparent substrate. Can be used.
Examples of 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.

As described above, 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. Specific examples of 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.
As the metal electrode 18, for example, Pt, Al, Cu, Ti, Ni, or the like can be used.

Examples will be described below, but the present invention is not limited to these examples.

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. While vigorously stirring the obtained mixed solution, 200 mL of toluene was added to the mixed solution, and then 400 mL of water was further added and vigorously stirred. After standing for 1 hour, the mixture was filtered with suction, and the filtrate was washed with 200 mL of water to obtain copper complex 1-1 (Exemplary Compound 1) as 13 g of light blue crystals.

To 5.5 g of the obtained crystals, 48 mL of N, N-dimethylacetamide was added and dissolved by heating. After the obtained liquid was filtered, the filtrate was cooled to room temperature, 20 mL of toluene was added with vigorous stirring, and then 200 mL of water was added, and then left for 30 minutes. The resulting crystals were collected by suction filtration, and the crystals were washed with 30 mL of toluene little by little. The crystals were air-dried and then dried under reduced pressure to obtain 4.55 g of light blue crystals. This crystal was dissolved in tetrahydrofuran, and toluene was added to the resulting solution, and water was added to such an extent that no precipitation occurred immediately. When the obtained liquid was left overnight at room temperature, a columnar single crystal having a length of about 0.3 mm was obtained. The obtained columnar single crystal was subjected to X-ray crystal structure analysis. Details will be described later.

Example 1-2
Synthesis example B of exemplary compound 1 (specific copper complex)
First, sodium meldrum acid salt Houghton and D.H. J. et al. The compound was synthesized according to the synthesis method of Compound 1 described in Lapham, Synthesis, 1982, page 451.
Next, 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. Insoluble matter was removed by filtration, and a solution prepared by dissolving 3.23 g (24 mmol) of anhydrous copper chloride in 20 mL of N, N-dimethylacetamide was added dropwise to the filtrate over 5 minutes while stirring the filtrate. While vigorously stirring the resulting mixture, 150 mL of water was added in three portions, and the resulting crystals were collected by filtration, washed twice with 50 mL of water, and air dried to obtain 7.25 g of light blue crystals. 7.25 g of this crystal was dissolved in 50 mL of N, N-dimethylacetamide and filtered. Thereafter, while the filtrate was vigorously stirred, 25 mL of water was added, and 175 mL of water was further added and stirred. The obtained mixture was immersed in an ice-water bath and cooled to 15 ° C., and the resulting crystals were collected by filtration. The obtained crystals were washed with 50 mL of water and then dried under reduced pressure to obtain 4.75 g of copper complex 1-2 (Exemplary Compound 1) as light blue crystals.

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. Thereafter, the resulting solution was reacted at room temperature for 1 hour, and then the reaction solution was acidified with 1N-HCl, washed with water, dried over MgSO ₄ , and then the solvent was distilled off to obtain a reddish brown oily substance. Got. The oily substance was repeatedly purified twice by silica gel chromatography (Hexane: AcOEt = 10: 1 to 5: 1) to obtain 7.44 g of Compound A.
When the obtained compound A was analyzed by ¹ H-NMR (CDCl ₃ ), the following results were obtained and it was confirmed that the compound A had the following structure represented by the general formula 2. δ 1.74 (s, 6H), 2.68 (s, 3H), 15.13 (s, 1H).

To 1.86 g (10 mmol) of the obtained compound A, 10 mL of N, N-dimethylacetamide was added and dissolved to obtain a compound A solution. Thereafter, a solution obtained by dissolving 650 mg (5 mmol) of anhydrous copper chloride in 5 mL of N, N-dimethylacetamide was added to the compound A solution, and then 1.4 mL (10 mmol) of triethylamine was added, followed by stirring at room temperature for 30 minutes. 90 mL of water was added to the resulting mixture with vigorous stirring, and then allowed to stand for 30 minutes. The resulting crystals were collected by filtration, washed with water, and dried to give 1.9 g of a light blue powder of copper complex 1- 3 (Exemplary Compound 1) was obtained.

Example 1-4
Synthesis example D of exemplary compound 1 (specific copper complex)
In 80 mL of water, 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. Thereafter, 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.

10 mL of N, N-dimethylacetamide was added to and dissolved in 2.00 g (10 mmol) of the obtained compound B to obtain a compound B solution. Thereafter, a solution obtained by dissolving 650 mg (5 mmol) of anhydrous copper chloride in 5 mL of N, N-dimethylacetamide was added to the compound B solution, and then 1.4 mL (10 mmol) of triethylamine was added, followed by stirring at room temperature for 30 minutes. 90 mL of water was added to the resulting mixture while stirring vigorously, and the mixture was allowed to stand for 30 minutes. The resulting crystals were collected by filtration, washed with water and dried to give 2 g of a light blue powder of copper complex 2-1 ( Exemplified compound 2) was obtained.

To the obtained crystals, 48 mL of N, N-dimethylacetamide was added and dissolved by heating. After the obtained liquid was filtered, the filtrate was cooled to room temperature, 20 mL of toluene was added with vigorous stirring, and then 200 mL of water was added, and then left for 30 minutes. The resulting crystals were collected by suction filtration, and the crystals were washed with 30 mL of toluene little by little. The crystals were air-dried and then dried under reduced pressure to obtain light blue crystals. This complex was dissolved in tetrahydrofuran, toluene was added to the resulting solution, and water was added so that no precipitation occurred immediately. When the obtained liquid was left overnight at room temperature, a columnar single crystal having a length of about 0.3 mm was obtained. The obtained columnar single crystal was subjected to X-ray crystal structure analysis. Details will be described later.

Example 1-6
Synthesis Example F of Illustrative Compound 2 (Specific Copper Complex)
In 80 mL of water, 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. Thereafter, 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.

To 2.6 g (10 mmol) of the obtained compound C, 10 mL of N, N-dimethylacetamide was added and dissolved to obtain a compound C solution. Thereafter, a solution obtained by dissolving 650 mg (5 mmol) of anhydrous copper chloride in 5 mL of N, N-dimethylacetamide was added to the compound C solution, and then 1.4 mL (10 mmol) of triethylamine was added, followed by stirring at room temperature for 30 minutes. 90 mL of water was added to the resulting mixture while stirring vigorously, and the mixture was allowed to stand for 30 minutes. The resulting crystals were collected by filtration and washed with water. Next, it was dispersed in 50 mL of xylene, washed, filtered and dried to obtain copper complex 5-1 (Exemplary Compound 5) as 2 g of a light blue powder.

Example 1-8
Synthesis example H of exemplary compound 5 (specific copper complex)
In 80 mL of water, 2.62 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. Thereafter, 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.

In 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)
In 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. Got.

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.

In 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)
In 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. Got.

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.

In 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)
In 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. Got.

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.

In 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)
In 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.

In 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.

For the mass spectrum measurement, Applied Biosystems Voyager System 6306 was used, α-cyano-4-hydroxycinnamic acid was used for the matrix, and chloroform was used for the solvent. Hereinafter, the same conditions were used for the compounds whose mass spectra were measured.

Example 1-18
Synthesis example T of exemplary compound 111 (specific copper complex)
In 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 ) δ1.9 (s, 3H), 2.4 (s, 3H), 7.4-7.5 (m, 2H), 7.5-7.6 (M, 3H)

In 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 ) δ1.8 (s, 3H), 2.4 (s, 3H), 6.9-7.2 (m, 4H)

In 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)

In 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)

In 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 ) δ1.8 (s, 6H), 6.8-7.3 (m, 4H)

In 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.

In 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.

<X-ray structural analysis>
Among the specific copper complexes synthesized as described above, copper complex 1-1, copper complex 2-1, copper complex 5-1, copper complex 107-1, copper complex 108-1, copper complex 109-1, X-ray crystal structure analysis was performed on copper complex 110-1 and copper complex 29-1. For the analysis, a desktop single crystal X-ray structure analyzer XtaLAB mini manufactured by Rigaku Corporation was used, and the measurement was performed at 23 ° C. Various parameters obtained as a result of the analysis are shown below. Note that 1 mm is 0.1 nm.

Copper complex 1-1
Molecular formula: C ₁₆ H ₁₈ CuO ₁₀
Molecular weight: 433.86
Crystalline system: trigonal
Space group: R-3
Unit cell parameters: a = 25.176 (4) Å, c = 8.955 (2) Å, V = 4916 (2) Å ³
Calculated density: 1.32 g / cm ³
R value: 0.07
Rw value: 0.13
GOF: 1.21

Here, 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, and GOF represents the correlation coefficient ( Goodness of fitness). R value, Rw value and GOF of the following copper complex 2-1, copper complex 5-1, copper complex 107-1, copper complexes 108-1, 109-1, copper complex 110-1, and copper complex 29-1. The definition of is the same for each. In addition, 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 2-1
Molecular formula: C ₁₈ H ₂₂ CuO ₁₀
Molecular weight: 461.91
Crystalline system: trigonal
Space group: R-3
Unit cell parameters: a = 25.053 (8) Å, c = 9.171 (3) Å, V = 4985 (3) Å ³
Calculated density: 1.39 g / cm ³
R value: 0.06
Rw value: 0.12
GOF: 1.24

Copper complex 5-1
Molecular formula: C ₂₈ H ₂₆ CuO ₁₀
Molecular weight: 586.05
Crystalline system: triclinic
Space group: P-1
Unit cell parameters: a = 9.360 (2) Å, b = 14.777 (3) Å, c = 20.751 (4) Å, V = 2631 (1) Å ³
Calculated density: 1.48 g / cm ³
R value: 0.04
Rw value: 0.10
GOF: 1.06

Copper complex 107-1
Molecular formula: C ₂₀ H ₂₂ CuO ₁₀
Molecular weight: 485.92
Crystalline system: Triclinic space group: P-1
Unit cell parameters: a = 9.299 (6) Å, b = 10.743 (7) Å, c = 10.937 (7) Å, a = 72.377 (6) °, b = 76.686 ( 6) °, c = 79.268 (6) °, V = 1005 (1) Å ³
Calculated density: 1.61 g / cm ³
R value: 0.05
Rw value: 0.14
GOF: 1.11

Copper complex 108-1
Molecular formula: C ₁₈ H ₂₂ O ₁₂ Cu
Molecular weight: 493.9
Crystalline system: Monoclinic space group: P21 / c
Unit cell parameters: a = 10.718 (5) Å, b = 8.662 (4) Å, c = 11.479 (5) Å, b = 109.187 (4) °, V = 1006.6Å ³
Calculated density: 1.63 g / cm ³
R value: 0.03
Rw value: 0.08
GOF: 1.01

Copper complex 109-1
Molecular formula: C ₁₆ H ₁₆ BR ₂ CuO ₁₀
Molecular weight: 591.65
Crystalline system: Monoclinic space group: C2 / c
Unit cell parameters: a = 15.96 (1) Å, b = 7.449 (6) Å, c = 17.88 (1) Å, a = 90 °, b = 95.184 (7) °, c = 90 °, V = 2118 (3) Å ³
Calculated density: 2.012 g / cm ³
R value: 0.17
Rw value: 0.52
GOF: 2.29

Copper complex 110-1
Molecular formula: C ₃₂ H ₃₆ CuO ₁₃
Molecular weight: 692.16
Crystalline system: Monoclinic space group: C2 / c
Unit cell parameters: a = 23.007 (9) Å, b = 15.779 (9) Å, c = 17.007 (8) Å, beta = 92.111 (6) °, V = 6195 (5) ^{３ 3}
Calculated density: 1.48 g / cm ³
R value: 0.06
Rw value: 0.11
GOF: 0.99

Copper complex 29-1
Molecular formula: C ₂₂ H ₂₆ CuO ₁₀
Molecular weight: 513.98
Crystalline system: Monoclinic space group: P21 / c
Unit cell parameters: a = 10.630 (3) Å, b = 12.571 (3) Å, c = 9.197 (2) Å, beta = 114.173 (2) °, V = 1121.3 ( 5) Å ³
Calculated density: 1.523 g / cm ³
R value: 0.04
Rw value: 0.08
GOF: 1.07

In addition, 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.

<Pyrolysis analysis>
Next, the mass change (TG; Thermogravimetry), differential heat (DTA; Differential Thermal Analysis), and mass of volatile components (MS; Mass) generated by heating the obtained copper complex 1-1. Differential thermogravimetry-mass spectrometry (TG-DTA-MS) was performed to measure (spectrometry).
The measurement conditions were a temperature increase from room temperature to 300 ° C. at 2.0 ° C./min in an atmosphere of Ar (80% by volume) and O ₂ (20% by volume). FIG. 10 shows the results of TG-DTA, and FIG. 11 shows the results of MS analysis.
In FIG. 10, the curve (A) is a TG curve of the copper complex 1-1, and 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, and 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.

The mass reduction of the copper complex 1-1 occurs in two stages of 150 ° C. to 180 ° C. and 180 ° C. to 230 ° C., and in the first stage of mass reduction, m / z = 43 (CH ₃ CO), m / z = 58 (CH ₃ COCH ₃ ) peak, CO ₂ (m / z = 44) peak, and H ₂ O (m / z = 18) peak were confirmed. 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. In addition, m / z means mass to charge ratio.

Further, powder X-ray diffraction measurement was performed on the powder obtained by heating the copper complex 1-1 in air at 230 ° C. for 1 hour. For the measurement, RINT-Ultima III manufactured by Rigaku Corporation was used. The obtained diffraction pattern is shown in FIG. All obtained peaks were consistent with Cu ₂ O (JCPDS # 05-0667). That is, it was confirmed that the copper complex 1-1 obtained in Example 1-1 was thermally decomposed at a low temperature of 230 ° C. to form Cu ₂ O.

The thermogravimetric analysis (TG) 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, and 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.
For all of the copper complexes 107-1 to 133-1, the thermal decomposition was completed at less than 300 ° C. On the other hand, 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.

Similarly, copper complex solutions summarized in Table 14 below were prepared.

Example 3
Preparation of Cu ₂ O thin film Example 3-1: The substrate surface was a silicon substrate. Using the copper complex solution (copper complex solution 1) prepared in Example 2-1, 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.

Heat treatment process 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. Further, 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%). Was given.
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. For the measurement, RINT-Ultima III manufactured by Rigaku Corporation was used, and evaluation was performed by 2θ measurement with an incident angle fixed at 0.35 °.
In FIG. 14, the annealing atmosphere is fixed at O ₂ / (Ar + O ₂ ) = 0.2 (oxygen concentration in the furnace during heat treatment is 20% by volume), 200 ° C., 230 ° C., 250 ° C., 280 ° C., 300 ° C. Or an XRD (X-ray Diffraction) pattern of a thin film that has been heat-treated at each annealing temperature of 350 ° C. 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).

In FIG. 15, the annealing temperature is fixed at 250 ° C., and O ₂ / (Ar + O ₂ ) = 0 (oxygen concentration 0 vol%), 0.005 (oxygen concentration 0.5 vol%), 0.015 (oxygen concentration 1. 5 (vol%), 0.05 (oxygen concentration 5 vol%), 0.1 (oxygen concentration 10 vol%), 0.2 (oxygen concentration 20 vol%), 0.5 (oxygen concentration 50 vol%), 0 6 shows an XRD pattern of a thin film that has been heat-treated in each annealing atmosphere of 0.6 (oxygen concentration 60% by volume), 0.8 (oxygen concentration 80% by volume), or 1.0 (oxygen concentration 100% by volume).

Regarding O ₂ / (Ar + O ₂ ) = 0.005 to 0.05 (curve (B) to curve (D)), only the peak of Cu ₂ O could be confirmed.
In the range of O ₂ / (Ar + O ₂ ) of 0.1 to 0.5 (curve (E) to curve (G)), only the peak of Cu ₂ O was confirmed. On the other hand, no clear peak could be confirmed from the samples of O ₂ / (Ar + O ₂ ) = 0.8 or more (curve (I) to curve (J)). In addition, when O ₂ / (Ar + O ₂ ) = 0 (curve (A)), a peak of Cu (JCPDS # 04-0836) was confirmed.

In addition, 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).

In the XRD pattern (curve (H)) of O ₂ / (Ar + O ₂ ) = 0.6, a clear peak was not confirmed, so the range in which Cu ₂ O was obtained was 0.005 (oxygen concentration 0.5 vol%) It was found that ≦ O ₂ / (Ar + O ₂ ) ≦ 0.5 (oxygen concentration 50% by volume).

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.

Heat treatment process 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.

When the thin film X-ray diffraction measurement was similarly performed on the Cu ₂ O thin film 6, the peak of Cu ₂ O was mainly confirmed.

Similarly, a precursor thin film was prepared, and a Cu ₂ O thin film was prepared under the same conditions as the precursor thin film 6. The results are summarized in Table 15. In addition, when thin film X-ray diffraction measurement was performed, A in which the peak of Cu ₂ O was mainly confirmed was represented by A, and B was mainly unidentified. Also in the Cu ₂ O thin films 7 to 15, when thin film X-ray diffraction measurement was performed, it was confirmed that the main peak was derived from Cu ₂ O.

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 | membrane 2 (Organic copper complex film | membrane with a base material) with a film thickness of about 40 nm was obtained.
The obtained precursor thin film 2 was subjected to a heat treatment at an annealing temperature of 250 ° C. and an annealing atmosphere of O ₂ / (Ar + O ₂ ) = 0.15 for 3 minutes. Similar to the result of -1, only the peak of Cu ₂ O was confirmed.

Since 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.

The disclosures of Japanese Patent Application Nos. 2012-207255 and 2013-192216 are incorporated herein by reference in their entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.

Claims

An organocopper complex having a structure represented by the following general formula 1.

In General Formula 1, 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. Represents a non-aromatic hydrocarbon group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. R 11 and R 21 may be connected to each other to form a ring, and 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. Represents a non-aromatic hydrocarbon group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 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 groups represented by R 11 , R 12 , R 21 , R 22 , R 31 , and R 32 may be substituted with a monovalent substituent. However, when R 11 , R 12 , R 21 , and R 22 all represent a methyl group, 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 the 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, and 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, and R 31 and R 32 are each independently a hydrogen atom, carbon 2. The organocopper complex according to claim 1, which 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 organic copper complex according to claim 1 or 2, wherein R 11 and R 12 in the general formula 1 are the same, and R 21 and R 22 are the same.
The organocopper complex according to any one of claims 1 to 3, wherein R 31 and R 32 in the general formula 1 are the same.
The organocopper complex according to claim 1, 2 or 4, wherein R 11 and R 12 in the general formula 1 are different from each other, and R 21 and R 22 are different from each other.
6. The organic according to any one of claims 3 to 5, wherein 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. Copper complex.
The 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. The organocopper complex described.
The organic copper complex according to any one of claims 1 to 7, which is used for forming a copper oxide thin film.
An organic copper complex solution comprising the organic copper complex according to any one of claims 1 to 8 and a solvent.
The organocopper complex solution according to claim 9, comprising at least two of the organocopper complexes.
The organic copper complex solution according to claim 9 or 10, wherein the concentration of the organic copper complex is 0.01 mol / L to 0.3 mol / L.
The organic copper complex solution according to any one of claims 9 to 11, wherein the solvent is an aprotic polar solvent.
A copper oxide thin film obtained by drying and heat-treating the coating film of the organocopper complex solution according to any one of claims 9 to 12.
The copper oxide thin film according to claim 13, comprising at least monovalent copper.
An organic copper complex solution coating film forming step of coating the organic copper complex solution according to any one of claims 9 to 12 on a substrate to form an organic copper complex solution coating film;
Drying the organic copper complex solution coating film to obtain an organic copper complex film;
The organic copper complex film is heated at 230 ° C. or higher and lower than 300 ° C. to form a copper oxide thin film,
The manufacturing method of the copper oxide thin film containing this.
16. The method for producing a copper oxide thin film according to claim 15, wherein in the heat treatment step, the organic copper complex film is heated in an atmosphere having an oxygen concentration of 0.5 volume% to 50 volume%.
The compound which is represented by the following general formula 2 and forms an organocopper complex according to any one of claims 1 to 8 by coordination with a copper ion.

In general formula 2, 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. However, when R 13 and R 23 represent a methyl group, 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. .