KR20150043489A - Organocopper complex, organocopper complex solution, copper oxide thin film, method for producing copper oxide thin film, and compound - Google Patents

Abstract

An organic copper complex having a structure represented by the following general formula (1), a copper oxide thin film by an organic copper complex, a method of producing the copper oxide thin film, and a compound constituting an organic copper complex. R ¹¹ , R ¹² , R ²¹ , and R ²² each independently represent an alkyl group, a non-aromatic hydrocarbon group having an unsaturated bond, an aryl group, or a heteroaryl group. 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 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a non-aromatic hydrocarbon group having an unsaturated bond, an aryl group, a heteroaryl group or a hydroxyl group. When R ¹¹ , R ¹² , R ²¹ and R ²² all represent a methyl group, R ³¹ and R ³² represent an alkyl group, an aryl group, an alkoxy group or a hydroxyl group.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic copper complex, an organic copper complex solution, a copper oxide thin film, a method for producing the copper oxide thin film,

The present invention relates to an organic copper complex, an organic copper complex solution, a copper oxide thin film, a method for producing the copper oxide thin film, and a compound.

Various thin oxide films are used for the thin film semiconductor device. For example, copper oxide (Cu ₂ O) thin film, which is one of the copper oxide thin films, is used as a p-type semiconductor in that it is a direct transition semiconductor showing p-type conductivity.

In addition, these thin film semiconductor devices have been applied to various applications. For example, Cu ₂ O for use with thin film, p-type semiconductor thin film of Cu ₂ O and n-type semiconductor thin film of ZnO or the like, for IGZO pn junction solar cells (for example, Japanese Unexamined Patent Application Publication No. 2006-9083 Japanese Unexamined Patent Application Publication No. 2008-10861), a light emitting diode (see, for example, Japanese Patent Application Laid-Open No. 2001-210864), a field effect transistor (see, A thermoelectric conversion element (see, for example, Japanese Patent Application Laid-Open No. 2000-230867) bonded to the copper electrode is known.

Particularly, the Cu ₂ O thin film is expected to be a photoelectric conversion material of a solar cell because it has a band gap of about 2.1 eV and absorbs light in a visible light region to generate a carrier. In addition, Cu ₂ O has low toxicity and small environmental impact.

Examples of techniques for forming the oxide thin film include a vacuum film forming method such as a sputtering method and MBE (molecular beam epitaxy) method, and a wet method such as a solution coating method and a sol-gel method.

For example, in Thin Solid Films, 442 (2003) 48, it is disclosed that a copper oxide thin film is formed using a sol-gel method. As a method for forming a thin film by solution application, for example, a method in which a solution in which a diaminopolycarboxylic acid complex and / or a polycarboxylic acid complex is dissolved is spin-coated, dip-coated, bar- A step of applying a solution by any of a flow coating method and a spray coating method, a step of applying a solution to the surface of a substrate, followed by evaporating the solvent to dry the solution composition to a predetermined thickness, (I) film having the performance of a p-type semiconductor is formed by a manufacturing method including a step of performing heat treatment at 300 to 700 ° C for 1 minute to 3 hours in an inert gas atmosphere selected from the group consisting of a combination of two or more materials selected from the group consisting of (See, for example, Japanese Laid-Open Patent Publication No. 2011-119454).

Also, Monatschefte fur Chemie, 98, (1967), 564 discloses an example of a copper complex.

In general, since a large-sized vacuum apparatus is required for forming a thin film by the vacuum film forming method, the manufacturing cost of the thin film forming is increased. For this reason, it has been required to form a thin film by a wet process as shown in Thin Solid Films, 442 (2003) 48 or Japanese Patent Application Laid-Open No. 11-14545. In the wet method, since a film can be formed in a large area with a simple device, film formation can be performed at low cost.

However, in order to form the copper oxide thin film in the wet process, annealing (heat treatment) at a high temperature has heretofore been required. As described above, for example, in the method disclosed in Japanese Patent Application Laid-Open No. 2011-119454, it is necessary to have a high temperature of 300 占 폚 or higher. Such annealing at a high temperature is disadvantageous in terms of energy cost, and there is a problem that the selectivity of the substrate and surrounding members is lowered.

Particularly, in recent years, there is a demand for a thin film semiconductor device which is lighter and more flexible, so that it is required to use a flexible substrate, specifically, a resin substrate, for example. However, in the heat treatment at 300 占 폚 or more, since the heat resistance of the base material needs to be taken into account, 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 copper (I) film is formed, copper (I) is generated by decomposing the copper (I) film by heat. However, since the copper The compound capable of decomposing in a temperature range of less than 300 DEG C which is capable of being formed is not known. Also, the pyrolysis characteristics of the complexes disclosed in Monatschefte fur Chemie, 98, (1967), 564 were unclear.

The present invention relates to an organic copper complex solution capable of forming a copper oxide thin film by annealing at a low temperature and a compound as a ligand thereof and an organic copper complex solution containing an organic copper complex capable of forming a copper oxide thin film by annealing at a low temperature And an object of the present invention is to solve such a problem.

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 selectivity of a substrate and a method for producing a copper oxide thin film having a high selectivity for a substrate, do.

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).

[Chemical Formula 1]

In the general formula (1), R ¹¹ , R ¹² , R ²¹ and R ²² may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms, a non-aromatic hydrocarbon group having 2 to 20 carbon atoms having an unsaturated bond , 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 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, a non-aromatic hydrocarbon group having 2 to 20 carbon atoms having an unsaturated bond, An aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a hydroxyl group. H in the CH 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. When R ¹¹ , R ¹² , R ²¹ and R ²² all represent a methyl group, R ³¹ and R ³² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms An alkoxy group, or a hydroxyl group.

<2> 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 are connected to each other may form a ring, and, R ¹² and R ²² are optionally and connected to each other to form a ring, R ³¹ and R ³² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, having 1 to 20 alkoxy group, An aryl group having 6 to 20 carbon atoms, or a hydroxyl group.

<3> is an organic copper complexes described in the formula 1 R ¹¹ and R ¹² are the same, and in R ²¹ and R ²² have the same <1> or <2>.

<4> R ³¹ and R ³² in the general formula 1 are the same organic copper complexes as those described in any one of <1> to <3>.

<5> The organic copper complex according to <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 copper complex according to 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.

&Lt; 7 &gt; The organic dyme complex according to any one of &lt; 4 &gt; to &lt; 6 &gt;, 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.

<8> The organic copper complex according to any one of <1> to <7> which is used for forming a copper oxide thin film.

<9> A solution of an organic copper complex according to any one of <1> to <8> and a solvent.

<10> The organic copper complex solution according to <9>, which contains at least two organic copper complexes.

<11> The organic dyestuff solution according to <9> or <10>, wherein the concentration of the organic dyes 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 heating a coating film of the organic copper complex solution according to any one of <9> to <12>.

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

<15> An organic copper complex solution film-forming process for forming an organic copper complex solution coating film by applying the organic copper complex solution according to any one of <9> to <12>

A drying step of drying the organic copper complex solution coating film to obtain an organic copper complex film,

The organic copper complex film is heated at a temperature of 230 ° C or more and less than 300 ° C to form a copper oxide thin film,

The method comprising the steps of:

<16> The heat treatment step is a 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% by volume to 50% by volume.

<17> A compound represented by the following general formula (2) and constituting the organic copper complex according to any one of <1> to <8> by coordination with a copper ion.

(2)

In the general formula 2, R ¹³ and R ²³ may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms, a non-aromatic hydrocarbon group having 2 to 20 carbon atoms having an unsaturated bond, an aryl group having 6 to 20 carbon atoms Or a heteroaryl group having 3 to 20 carbon atoms. 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, an aryl group having 6 to 20 carbon atoms, Or a hydroxyl group. H in the CH bond of each of the groups represented by R ¹³ , R ²³ , and R ³³ may be substituted with a monovalent substituent. Provided that 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 hydroxyl group.

According to the present invention, an organic copper complex capable of forming a copper oxide thin film by annealing at a low temperature and a compound serving as a ligand of the organic copper complex and an organic copper complex capable of forming a copper oxide thin film by annealing at a low temperature &Lt; / RTI &gt; 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 selectivity of a substrate, and a method for producing a copper oxide thin film having a high selectivity for a substrate.

1 is a schematic cross-sectional view of a pn junction type solar cell showing an example of the configuration of a pn junction type solar cell according to the embodiment.
2 shows the structure of the copper complex 1-1 obtained in Example 1-1.
3 shows the structure of the copper complex 2-1 obtained in Example 1-5.
4 shows the structure of the copper complex 5-1 obtained in Example 1-7.
5 shows the structure of the copper complex 107-1 obtained in Example 1-9.
6 shows the structure of the copper complex 108-1 obtained in Example 1-11.
7 shows the structure of the copper complex 109-1 obtained in Example 1-13.
8 shows the structure of the copper complex 110-1 obtained in Example 1-15.
9 shows the structure of the copper complex 29-1 obtained in Example 1-21.
10 is a TG (Thermogravimetry) -DTA (differential thermal analysis) curve of the copper complex 1-1 obtained in Example 1-1.
11 is an MS (Mass Spectrometry) curve of the copper complex 1-1 obtained in Example 1-1.
12 is a powder X-ray diffraction curve of the powder obtained by heating the copper complex 1-1.
13 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.
14 is an X-ray diffraction (XRD) pattern of the Cu ₂ O thin film obtained in Example 3-1.
15 is an X-ray diffraction (XRD) pattern of the Cu ₂ O thin film obtained in Example 3-1.

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

<Organic copper complexes>

The organic copper complex of the present invention is an organic copper complex having a structure represented by the following general formula (hereinafter also referred to as &quot; specific copper complex &quot;).

In the formation of the copper oxide thin film, the copper oxide can be obtained even when the specific copper complex is subjected to heat treatment at a low temperature (for example, less than 300 ° C) by using a specific copper complex as a raw material. As described later, a copper complex thin film can be easily formed on a substrate by preparing a specific copper complex solution using a specific copper complex and a solvent, applying the solution to a substrate, and heating it.

(3)

In the general formula (1), R ¹¹ , R ¹² , R ²¹ and R ²² may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms, a non-aromatic hydrocarbon group having 2 to 20 carbon atoms having an unsaturated bond , 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 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, a non-aromatic hydrocarbon group having 2 to 20 carbon atoms having an unsaturated bond, An aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a hydroxyl group. H in the CH 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. When R ¹¹ , R ¹² , R ²¹ and R ²² all represent a methyl group, R ³¹ and R ³² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms An alkoxy group, or a hydroxyl group.

In the general formula 1, R ¹¹ , R ¹² , R ²¹ and R ²² each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, or R ¹¹ and R ²¹ are connected to each other it is to form a ring, and R ¹² and R ²² are connected to each other is more preferable that to form a ring, and further, R ³¹ and R ³² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms An alkoxy group, an aryl group having 6 to 20 carbon atoms, or a hydroxyl 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 takes a symmetrical structure, so that a single product tends to be easily obtained, and purification is facilitated. In addition, since the synthesis of a specific copper complex is easy, the production cost of a specific copper complex can be lowered.

When R ³¹ and R ³² are the same in the general formula 1, the decomposition temperature of the specific copper complex is likely to be uniform, and the specific copper complex is prepared as an organic copper complex solution to be described later, Even when heated, a copper oxide thin film having a uniform film density tends to be obtained.

On the other hand, when R ¹¹ and R ¹² are different from each other and R ²¹ and R ²² are different from each other in the general formula 1, when a specific copper complex is prepared in an organic copper complex solution to be described later, The solubility can be increased. Further, since the specific copper complex does not crystallize well, the film density of the copper oxide thin film obtained by drying and heating the coating film of the organic copper complex solution tends to become uniform.

In the 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, and examples thereof include a methyl group, an ethyl group, a propyl group, Ethylhexyl group, 1, 3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetra A methylbutyl 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 or different.

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 more preferably 1 to 4 carbon atoms. Further, it is preferably a linear or branched type, more preferably a linear type.

The ring formed by connecting R ¹¹ and R ²¹ and the ring formed by connecting R ¹² and R ²² are each preferably 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, still more preferably 5 to 7 carbon atoms Do.

In the 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 2 to 20 carbon atoms, You can have it. The non-aromatic hydrocarbon group having an unsaturated bond represented by R ¹¹ , R ¹² , R ²¹ or R ²² may be linear, branched or cyclic, and examples thereof include a vinyl group, an allyl group, , A propargyl group, a 5-hexenyl group, a 4-methyl-1-pentenyl group, a metallyl group, a 1-cyclohexenyl group and a 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 or different.

The non-aromatic hydrocarbon group having an unsaturated bond represented by R ¹¹ , R ¹² , R ²¹ or R ²² preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. Further, it is preferably a linear or branched type, more preferably a linear type.

In the general formula (1), when R ¹¹ , R ¹² , R ²¹ , or R ²² represents an aryl group, the aryl group may be a monocyclic or condensed ring aryl group having 6 to 20 carbon atoms and may further have a substituent. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylyl group, an m-tolyl group, a p-tolyl group, A chlorophenyl group, and a xylyl group. Among them, the aryl group represented by R ¹¹ , R ¹² , R ²¹ or R ²² is preferably a phenyl group, m-tolyl group, p-tolyl group, m-anisyl group and 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 or different.

The aryl group represented by R ¹¹ , R ¹² , R ²¹ , or R ²² preferably has 6 to 10 carbon atoms. The aryl group is preferably an indeterminate group.

When R ¹¹ , R ¹² , R ²¹ , or R ²² in the general formula (1) represents a heteroaryl group, the heteroaryl group is a monocyclic or condensed ring heteroaryl group having 3 to 20 carbon atoms and further has a substituent . Examples of the heteroaryl group include a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, and benzooxycarbonyl rings (for example, benzothiophene) For example, dibenzothiophene, carbazole), 3-methylthiophene ring, and 3,4-diethylthiophene ring. Among them, the heteroaryl group represented by R ¹¹ , R ¹² , R ²¹ , or R ²² is preferably a thiophene ring, a furan ring, and 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 or different.

The heteroaryl group represented by R ¹¹ , R ¹² , R ²¹ , or R ²² preferably has 3 to 10 carbon atoms. Further, the heteroaryl group is preferably an indeterminate group.

In the present invention, the "aryl group" refers to a group obtained by removing one hydrogen atom on the aromatic ring from an aromatic compound having at least one aromatic ring selected from benzene ring systems and non-benzene ring systems, and " Means a group in which at least one of the carbon atoms on the aromatic ring in the aryl group is substituted with a hetero atom.

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 alkyl groups having 1 to 4 carbon atoms, the molecular weight of the specific copper complex becomes small and is easily decomposed by heating. In addition, when a specific copper complex is prepared with an organic copper complex solution to be described later, and the coating film of the organic copper complex solution is dried and heated, the specific copper complex is liable to be decomposed and the organic component does not remain well in the film.

In the 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, ethyl group, propyl group, t-butyl group, n-hexyl 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 A benzyl group, and a cyclohexyl group.

When R ³¹ or R ³² represents an alkyl group, R ³¹ and R ³² may be the same or different.

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 even more preferably 1 to 6 carbon atoms.

In the general formula (1), when R ³¹ or R ³² represents an alkoxy group, the alkoxy group may have 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 cyclohexyloxy group, and the like.

When R ³¹ or R ³² represents an alkoxy group, R ³¹ and R ³² may be the same or different.

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 even more preferably 1 to 6. The alkoxy group represented by R ³¹ or R ³² is preferably a linear or branched type.

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 the unsaturated bond has 2 to 20 carbon atoms and may further have a substituent. The non-aromatic hydrocarbon group having an unsaturated bond represented by R ³¹ or R ³² may be linear, branched or cyclic. Examples thereof include a vinyl group, an allyl group, a crotyl group, a propargyl group, a 5- A hexenyl group, a 4-methyl-1-pentenyl group, a metallyl group, a 1-cyclohexyl group and a 1-cyclopentenyl group.

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 or different.

The non-aromatic hydrocarbon group having an unsaturated bond represented by R ³¹ or R ³² preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The non-aromatic hydrocarbon group having an unsaturated bond represented by R ³¹ or R ³² is preferably a linear or branched type, more preferably a linear type.

In the general formula (1), when R ³¹ or R ³² represents an aryl group, the aryl group may be a monocyclic or condensed ring aryl group having 6 to 20 carbon atoms and may further have a substituent. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylyl group, an m-tolyl group, a p-tolyl group, A chlorophenyl group, and a xylyl group. Among them, the aryl group represented by R ³¹ or R ³² is preferably a phenyl group, m-tolyl group, p-tolyl group, m-anisyl group, and p-anisyl group. When R ³¹ or R ³² represents an aryl group, R ³¹ and R ³² may be the same or different.

The aryl group represented by R ³¹ or R ³² preferably has 6 to 10 carbon atoms. The aryl group is preferably an indeterminate group.

In the general formula (1), when R ³¹ or R ³² represents a heteroaryl group, the heteroaryl group is a monocyclic or condensed ring heteroaryl group having 3 to 20 carbon atoms and may further have a substituent. Examples of the heteroaryl group include a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, and benzooxycarbonyl rings (for example, benzothiophene) For example, dibenzothiophene, carbazole), 3-methylthiophene ring and 3,4-diethylthiophene ring. Among them, the heteroaryl group represented by R ³¹ or R ³² is preferably a thiophene ring, a furan ring, and an oxazole group.

When R ³¹ or R ³² represents a heteroaryl group, R ³¹ and R ³² may be the same or different.

The heteroaryl group represented by R ³¹ or R ³² preferably has 3 to 10 carbon atoms. Further, the heteroaryl group is preferably an indeterminate group.

When all of R ¹¹ , R ¹² , R ²¹ and R ²² in the general formula (1) represents a methyl group, R ³¹ and R ³² each independently represent 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 hydroxyl 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 all hydrogen atoms.

R ³¹ and R ³² in the general formula (1) are preferably, independently of each other, an alkyl group, an alkoxy group, a non-aromatic hydrocarbon group having an unsaturated bond, an aryl group or a heteroaryl group. R ³¹ and R ³² have any of the non-aromatic hydrocarbon group, an aryl group, a heteroaryl group, or an alkoxy group having an alkyl group, an unsaturated bond as long as it, R ³¹ and R ³² are both compared with a case represents a hydrogen atom, a certain copper complexes The temperature required for complete decomposition can be lowered. This is thought to be because the intermediate products of pyrolysis are difficult to bond because the alkyl group, the non-aromatic hydrocarbon group having an unsaturated bond, the aryl group, the heteroaryl group, or the alkoxy group is three-dimensionally larger than the hydrogen atom. When the copper complex is heated, the intermediate products generated by pyrolysis of the copper complex may bond to each other, resulting in a high molecular weight compound that does not pyrolyze well. When such a high molecular weight compound is produced, additional heating may be required to decompose a high molecular weight compound. It is believed that the specific copper complex has a sterically large group, so that the effect of inhibiting the production of a high molecular weight compound at the time of thermal decomposition is high.

R ³¹ and R ³² in the general formula (1) are more preferably an alkyl group or an alkoxy group.

When R ³¹ and / or R ³² is an alkyl group, the thermal decomposition temperature of the specific copper complex can be lowered. Further, when R ³¹ and / or R ³² is an alkoxy group, the copper oxide is easily obtained because the specific copper complex contains oxygen in the molecular structure.

H in the CH bond represented by R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , and R ³² in the general formula 1 may be substituted with a monovalent substituent.

Examples of the substituent which R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ or R ³² in the general formula 1 may further have are not particularly limited and include a hydroxyl group, an alkyl group (such as a methyl group, , an acyl group (e.g., an acetyl group, a propanoyl group, a hexanoyl group, an iso-propyl group, an iso-propyl group, A halogen atom (fluorine atom, chlorine atom, iodine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, Cyclohexyloxy group, etc.), an aryloxy group (such as a phenyloxy group, a 4-methylphenyloxy group, a 3-methylphenyloxy group, a 2-methylphenyloxy group, a 4-chlorophenyloxy group, Oxo group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, 2-ethylhexyloxycarbonyl group, phenyl Aminophenyloxyethylcarbonyl group and the like), an acyloxy group (an acetyloxy group, a propanoyloxy group, a hexanoyloxy group, a 2-ethylhexanoyloxy group, a benzoyloxy group, a 4-di- (Methoxybenzoyloxy group, 2-chlorobenzoyloxy group and the like), an acylamino group (acetylamino group, propanoylamino group, hexanoylamino group, 2-ethylhexanoylamino group, benzoylamino group, 4-methoxybenzoylamino group, N- A carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-diethyl (2-thienyl group, 4-pyridyl group, 2-thienyl group, 2-thienylthio group and the like), a cyano group, a carboxyl group, a sulfo group, a heterocyclic group Furyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1- Group, and benzotriazol-1-yl group and the like, and so on). These substituents may be further substituted with other substituents.

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. 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 its chemical structure is represented by general formula (1), and various structures can be employed. 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), the carbon numbers may be the same or different. Also, R ¹¹ may be a combination of different groups such as an alkyl group having a larger number of carbon atoms, R ¹² an aryl group, and R ^{21 an} alkoxy group.

Illustrative Compounds 1 to 135 as examples of specific copper complexes are shown in Tables 1 to 8 below, but the specific copper complexes of the present invention are not limited thereto.

In Tables 1 to 2 and Tables 4 to 7, Ph represents a phenyl group. In the Exemplary Compounds 20 to 39 shown in Table 2, R ¹¹ and R ²¹ are connected to each other to form a ring, R ¹² and R ²² are connected to each other to form a ring, and "R ¹¹ - R ²¹ ", the R -R ¹¹ represents a divalent linking group represented by ^21," R ¹² -R ²² ", the represents a divalent connecting group represented by R ¹² -R ^22. Thus, for example, when "R ¹¹ -R ²¹ " is (CH ₂ ) ₄ , the ring formed by connecting R ¹¹ and R ²¹ is a five-membered ring.

In the specific divalent compound of the present invention represented by the general formula (1), R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ or R ³² may be linked to form a compound having a higher molecular weight. For example, it may be connected to other specific copper complexes adjacent to each other via water molecules or the like. Hydrogen bonds due to water molecules or the like are weakly bonded and sufficiently desorb at a temperature lower than the decomposition temperature of a specific copper complex, so that the characteristics of the present invention are not impaired.

Other forms of organic copper complexes

The organic copper complexes of the present invention are the specific copper complexes described above. However, for the formation of the copper oxide thin films, a multimer having a repeating unit derived from the following general formula 1 and / or a skeleton represented by general formula A polymer having a part thereof may be used.

Concretely, compounds such as Reference Compound 1 and Reference Compound 2 to which R ¹¹ and R ¹² in general formula 1 are connected can be mentioned.

[Chemical Formula 4]

[Chemical Formula 5]

Reference compound 1 has the same structure as the trimer of a specific copper complex in which R ¹¹ to R ³¹ are all methyl groups. In short, reference compound 1 has a structure in which R ¹¹ of a specific copper complex is linked to R ¹² of another specific copper complex, and R ²¹ of a specific copper complex is linked to R ²² of another specific copper complex by a linking group. Reference compound 2 is shown as an oligomer or polymer having a repeating unit of a trimer which is slightly different from the reference compound 1. In Reference Compound 2, n represents the number of repeating units and represents an integer of 1 or more.

In reference compound 1 and reference compound 2, R ¹¹ , R ¹² , R ²¹ , and R ²² in general formula 1 are increased in quantity, but may be increased in amount through R ³¹ or R ³² . In Reference Compound 1 and Reference Compound 2, the linking group is a single bond but not limited to a single bond, and may be a divalent or higher-valent hydrocarbon group, amide group, ester group, carbonyl group, oxygen atom or nitrogen atom.

Next, a compound (ligand) that forms a specific copper complex by coordination with 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.

[Chemical Formula 6]

In the general formula 2, R ¹³ and R ²³ may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms, a non-aromatic hydrocarbon group having 2 to 20 carbon atoms having an unsaturated bond, an aryl group having 6 to 20 carbon atoms Or a heteroaryl group having 3 to 20 carbon atoms. 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, an aryl group having 6 to 20 carbon atoms, Or a hydroxyl group. H in the CH bond of each of the groups represented by R ¹³ , R ²³ , and R ³³ may be substituted with a monovalent substituent. Provided that 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 hydroxyl group.

In R ¹³ , R ²³ , and R ³³ in Formula 2, the definition of R ¹³ is the same as that of R ¹¹ and R ¹² in Formula 1, and the definition of R ²³ is the same as that of R ²¹ and as defined in R ^22, and the definition of R ³³ is as defined for R ³¹ and R ³² in the general formula (1).

When all of R ¹³ and R ²³ in the general formula 2 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 hydroxyl group . That is, when R ¹³ and R ²³ all represent a methyl group, R ³³ does not represent a hydrogen atom, a non-aromatic hydrocarbon group having an unsaturated bond, a carbon number of 2 to 20, or a heteroaryl group having a carbon number of 3 to 20.

The compound used as the ligand in the specific copper complex of the present invention is not particularly limited as long as its chemical structure is represented by the general formula 2, and various structures can be employed. For example, when R ¹³ , R ²³ , or R ³³ are all the same group (for example, an alkyl group), the carbon numbers of the respective groups may be the same or different. Also, R ¹³ may be a combination of different groups such as an alkyl group having a large number of carbon atoms, R ^{23 an} aryl group, and R ^{33 an} alkoxy group.

Exemplary compounds L-1 to L-56 are shown in the following Tables 9 to 12 as an example of the compound represented by the general formula 2, but the compounds in the present invention are not limited thereto.

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

The synthesis of the specific copper complex represented by the general formula (1) of the present invention is carried out by mixing the 1,3-dicarbonyl compound represented by the general formula (2) with a second basic salt.

The type of the second copper salt is not particularly limited.

Examples of the second copper salt include copper salts such as copper, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromic acid, abrobic acid, bromic acid, perbromic acid, hypoiodic acid, It is possible to use salts of oxoacids such as boric acid, carbonic acid, orthotonic acid, carboxylic acid, silicic acid, nitric acid, phosphoric acid, phosphoric acid, sulfuric acid, sulfuric acid, sulfonic acid, sulfinic acid, chromic acid or permanganic acid ); And halogenated dibasic salts such as cupric chloride, cupric bromide, and cupric iodide.

Among the above, it is preferable that the amount of cobalt chloride, cupric bromide, cupric iodide, cupric nitrate, cupric sulfate, cupric acetate, This is preferable in that the product is not generated well.

The 1,3-dicarbonyl compound and the second equivalent salt represented by the general formula (2) are preferably dissolved in a solvent to prepare a solution and then mixed. The solvent is not particularly limited as long as it dissolves the 1,3-dicarbonyl compound and the second equivalent salt, and any solvent such as water, alcohol, or water-miscible aprotic organic solvent may be used. From the viewpoint of inhibiting the decomposition of the compound represented by the general formula (2), among them, water or a water-miscible aprotic organic solvent is preferable.

When an alcohol is used as the solvent, it is preferably used under relatively low temperature conditions not exceeding 50 캜 from the viewpoint of suppressing the decomposition of the compound represented by the general formula (2).

In addition, in order to remove impurities of the usability generated by mixing the 1,3-dicarbonyl compound and the second copper salt represented by the general formula 2 with a solvent, a water-incompatible organic solvent such as toluene or xylene coexists .

In order to capture an acid generated by the reaction between the compound represented by the general formula (2) and the second copper salt, a compound represented by the general formula (2) is previously mixed in the mixing reaction system with a base or before mixing with the second copper salt. As a salt.

Examples of the base coexisting in the mixing reaction system include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide and barium hydroxide, basic oxides such as magnesium oxide and calcium oxide, And organic bases lacking nucleophilicity (triethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene, etc.).

Examples of the mixing form of the 1,3-dicarbonyl compound and the second copper salt represented by the general formula 2 include a mixing method in which water is added after the reaction in a water miscible organic solvent or a method of mixing a ligand represented by the general formula 2 The mixing method of adding the aqueous solution of the second copper salt to the solution dissolved in the water-miscible organic solvent is preferable because the copper complex which is not soluble in water can be precipitated. The mixing reaction temperature is not particularly limited, but is preferably 0 ° C to 50 ° C, and more preferably 10 ° C to 40 ° C.

In the case of synthesizing a specific copper complex which is a combination of at least one group in each combination of R ¹¹ and R ¹² , R ²¹ and R ²² and R ³¹ and R ^{32 in} the general formula 1, .

In other words, R ¹¹ and R ¹² , R ²¹ and R ²² , and R ²¹ and R ^{22 may be} obtained 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 second basic salt. , And at least one pair of R ³¹ and R ³² is a combination of different groups.

The specific copper complex of the present invention may be used as it is, dispersed in a solvent, dissolved or used in combination with another solid material.

Among them, it is preferable to use the specific copper complex as a solvent for dissolving in a solvent to form a copper oxide thin film.

<Organic copper complex solution>

The organic copper complex solution of the present invention includes the organic copper complex (specific copper complex) represented by the general formula 1 described above and a solvent. Hereinafter, the organic copper complex solution of the present invention is also referred to as a specific solution.

By dissolving a specific copper complex in a solvent to form a solution, the copper oxide thin film can be easily formed at a low temperature from a coating film formed by coating a solution on a substrate or the like. Further, by dissolving a specific copper complex in a solvent to prepare a solution, a copper oxide thin film having no localized concentration can be obtained.

The specific solution may contain, in addition to the specific copper compound and the solvent, a metal compound such as an organic copper complex other than the specific copper complex, a surfactant and / or an additive such as an oxidizing agent to the extent that the effect of the present invention is not impaired .

Specific copper complex

Details of the specific copper complexes have already been described.

The specific solution may contain only one species of specific copper complex, or may contain two or more species.

When a specific solution contains two or more kinds of specific copper complexes, the crystallinity of a coating film formed using a specific solution can be lowered.

The concentration of the specific copper complex in the specific solution is not particularly limited. However, it is preferable that the specific solution is applied to a substrate or the like to increase the film thickness when the coating film is formed, thereby suppressing the precipitation of the specific copper complex in the specific solution, It is preferable that the concentration is from 0.01 mol / l to 0.3 mol / l.

menstruum

A particular solution comprises at least one of the solvents.

The solvent is not particularly limited as long as it is a solvent capable of dissolving a specific copper complex, and may be an inorganic solvent or an organic solvent.

Examples of the inorganic solvent include acids such as acetic acid, hydrochloric acid, and phosphoric acid; An aqueous solution of an inorganic salt such as an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, and an aqueous solution of sodium chloride; And water.

Examples of the organic solvent include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, alcohol solvents (tert-butyl alcohol, isopropanol, ethanol, methanol, 2,2,3,3- Diethylaminoethanol), ketone solvents (acetone, N-methylpyrrolidone, sulfolane, N, N-dimethylimidazolidinone and the like), ether solvents (such as tetrahydrofuran, ), A nitrile solvent (acetonitrile and the like), and other hetero atom-containing solvents other than the above.

Among the above, the solvent of the specific solution is preferably an organic solvent, 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-dimethylimidazolidinone.

Among these aprotic polar solvents, N, N-dimethylformamide, N, N-dimethylacetamide, pyridine, and tetrahydrofuran are preferably used as the solvent of the specific solution in view of increasing the solubility of the specific copper complex Can be used.

From the viewpoint of reducing the load at the time of drying at the time of forming the copper oxide thin film by applying a specific solution, the boiling point of the solvent is preferably 80 to 200 캜.

When the boiling point of the solvent is 80 DEG C or higher, the drying rate of the coating film obtained from the specific solution is not excessively fast, and the smoothness of the film can be improved. When the boiling point of the solvent is 200 占 폚 or lower, the solvent is easily volatilized from the coating film, and the coating film is easily removed.

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 at a boiling point or lower, Therefore, it can be preferably used as a solvent for a specific solution.

The solvent may be used alone, or two or more solvents may be mixed and used.

Metal compound

The specific solution may contain a metal compound (also referred to as &quot; another metal compound &quot;) other than the specific copper complex insofar as the effect of the present invention is not impaired.

Other metal compounds are not particularly limited, and examples thereof include strontium compounds.

A copper oxide thin film containing SrCu ₂ O ₂ can be formed by dissolving, for example, a strontium compound in a solvent with a specific copper complex to obtain a specific solution.

&Lt; Copper oxide thin film &

The copper oxide thin film of the present invention is formed by drying and heat-treating a coating film of the organic copper complex solution (specific solution) of the present invention.

In short, the copper oxide thin film of the present invention is a thin film formed on a substrate by heating (annealing) a coating solution of a specific solution formed by applying a specific solution onto, for example, a substrate and drying.

The copper oxide thin film of the present invention may be a monovalent copper oxide thin film or a divalent copper oxide thin film. Further, the copper oxide thin film of the present invention may be a thin film made of a composite copper oxide containing monovalent copper oxide and divalent copper oxide.

From the viewpoint that the copper oxide thin film of the present invention functions as a semiconductor, the copper oxide thin film preferably contains at least a monovalent copper.

In view of forming a copper oxide thin film as 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 monovalent copper oxides include Cu ₂ O and SrCu ₂ O ₂ .

It is preferable that the copper oxide thin film has a monovalent copper content of 70 atomic% or more in the total copper contained in the copper oxide thin film. When the copper content of the total copper is 70 atomic% or more, the mobility when the copper oxide thin film is used as a semiconductor can be improved.

The content of monovalent copper in the total copper contained in the copper oxide thin film is more preferably 90 atomic% or more, and still more 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, in the case where the 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 탆 to 20 탆.

The thickness of the copper oxide thin film may be adjusted by repeating the topping of the specific solution by drying the coating film of the specific solution and applying a specific solution or the like.

The copper oxide thin film of the present invention can be produced, for example, by the following production method.

&Lt; Production method of copper oxide thin film &gt;

The method for producing a copper oxide thin film of the present invention is a method for coating a substrate with a solution of an organic copper complex containing an organic copper complex and a solvent having the structure represented by the general formula 1 as described above to form a coating film of an organic copper complex solution A drying step of drying the organic copper complex solution coating film to obtain an organic copper complex film; a step of heating the organic copper complex film at a temperature of not less than 230 占 폚 and less than 300 占 폚 to form a copper oxide thin film; .

When the method for producing the copper oxide thin film is configured as described above, the copper oxide thin film can be produced at a low temperature, and the selectivity of the substrate can be increased.

The method for producing the copper oxide thin film of the present invention may further include other steps in addition to the respective steps as far as the effect of the present invention is not impaired. Examples of other processes include energy ray (electron beam, infrared ray, ultraviolet ray, vacuum ultraviolet ray, atomic beam, X-ray, gamma-ray Ray, a visible ray, etc.), and the like.

Hereinafter, the copper oxide thin film of the present invention will be described in detail with reference to the respective steps included in the method for producing the copper oxide thin film of the present invention.

Organic copper complex solution coating film forming process

In the step of forming the organic copper complex solution coating film, an organic copper complex solution (specific solution) containing a specific copper complex and a solvent is applied on the substrate to form a coating film of the organic copper complex solution.

The specific solution may be applied to the surface of the substrate, or may be applied on another layer formed on the substrate.

Examples of other layers formed on the substrate include an adhesive layer for improving adhesion between the substrate and the organic co-complex solution coating film, and a transparent conductive layer.

materials

The type of the substrate is not particularly limited and may be used in a form suitable for the intended use. Examples of the substrate include inorganic materials such as glass, silicon, and metals, resins, composites of inorganic materials and resins, and the like.

Examples of the resin include polyolefins such as polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyallylate, allyl diglycol carbonate, polyamide, polyimide , Fluorine resins such as polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin and polychlorotrifluoroethylene, liquid crystal polymers, acrylic resins, epoxy resins, silicone resins, A synthetic resin such as an ionomer resin, a cyanate resin, a crosslinked fumaric acid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, and an episulfide compound.

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, a composite resin material of resin and silicon oxide particle, a composite plastic material of resin and metal nanoparticle, a composite plastic material of resin and inorganic oxide nanoparticle, a composite plastic material of resin and inorganic nitride nanoparticle, a composite of resin and carbon fiber Plastic materials, composite plastic materials of resin and carbon nanotubes, composite plastic materials of resin and glass flake, composite plastic materials of resin and glass fiber, composite plastic materials of resin and glass beads, composite plastic material of resin and clay mineral, resin And a composite plastic material of particles having a mica-derived crystal structure, a laminated plastic material having at least one bonding interface between the resin and the thin glass, and a barrier layer having at least one bonding interface And a composite material having performance.

Among them, the base material is preferably a flexible material. The copper oxide thin film is formed by using a flexible substrate to manufacture a copper oxide thin film to be bent or a copper oxide thin film which is not cracked well even when it is dropped.

Among them, a composite material obtained by using a resin or a resin and a material other than a resin is preferable as a substrate, in terms of being lightweight and having flexibility. As the composite substrate, for example, a laminated substrate obtained by laminating a resin plate to a metal plate can be given.

The thickness of the base material is not particularly limited, but is preferably 50 탆 to 1000 탆, more preferably 50 탆 to 500 탆. When the thickness of the substrate is 50 mu m or more, the flatness of the substrate itself is improved. When the thickness of the substrate is 1000 mu m or less, the flexibility of the substrate itself is improved and it is easier to use the thin film semiconductor device to be described later as a flexible semiconductor device It becomes. Further, when it is 500 탆 or less, it is more preferable because flexibility is further improved.

The method of applying a specific solution onto a substrate is not particularly limited and may be selected from the group consisting of a spin coating method, a dip method, an ink jet method, a dispenser method, a screen printing method, a relief printing method, a concave printing method, Can be used.

Particularly, the inkjet method, the dispenser method, the screen printing method, the relief printing method, and the concave printing method can reduce the process cost in that a coating film can be formed at any position on the substrate and a patterning step after the film formation is unnecessary . Further, since the pattern can be formed without removing the coating film, the environmental load can also 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 or the application condition of the specific solution.

In the case of forming a thinner organic copper complex solution coating film, for example, the concentration of a specific copper complex in a specific solution may be lowered. When a specific solution is applied by a spin coating method, a thin coating film of a solution of an organic copper complex solution can be obtained by increasing the number of revolutions of the substrate when the specific solution is applied onto the substrate.

In the case of forming a coating film of a thicker organic copper complex solution, for example, the concentration of a specific copper complex in a specific solution may be increased. When the specific solution is applied by the spin coating method, a thick organic copper complex solution coating film can be obtained by lowering the substrate rotation speed when the specific solution is applied on the substrate.

Drying process

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.

Further, since the organic copper complex film obtained after the drying step is a precursor which can obtain a thin copper oxide film by heating, the organic copper complex film obtained after the drying step is also referred to as a precursor film.

The method for volatilizing the solvent contained in the organic copper complex solution coating film and the drying conditions are not particularly limited as long as it is a method or condition capable of removing the solvent contained in the specific solution from the coating film. For example, the coating film may be heated, the coating film may be placed under a reduced pressure environment, or the coating film may be heated while being kept under a reduced pressure environment.

When a weak resin substrate is used as the substrate, the heating temperature of the coating film is preferably lower than the glass transition temperature of the resin.

The amount of the solvent remaining in the organic copper complex film after the drying step is not particularly limited. However, from the viewpoint of increasing the film density after the heat treatment step, the total mass of the solvent is 50 By mass or less.

Heat treatment process

In the heat treatment step, the organic copper complex film is heated (annealing) at a temperature of 230 ° C or more and less than 300 ° C to form a copper oxide thin film.

The heating treatment (annealing treatment) of the organic copper complex film is carried out by heating the organic copper complex film at 230 캜 or more and less than 300 캜. When the temperature of the heat treatment is 230 占 폚 or higher, pyrolysis of the specific copper complex proceeds sufficiently, and a dense copper oxide thin film can be obtained. Further, when the temperature of the heat treatment is less than 300 占 폚, the selectivity of the peripheral members of the copper oxide thin film such as the substrate used for obtaining the copper oxide thin film by heating the organic copper complex film is improved.

The heat treatment time varies depending on the type of substrate to be used and / or the film thickness of the organic copper complex film, and may be, for example, from 1 minute to 3 hours.

The method of the heat treatment is not particularly limited, and examples thereof include heating with an electric furnace, heating with an infrared lamp, and heating with a hot plate. In addition, by using a rapid thermal annealing apparatus (RTA apparatus) or the like using lamp heating, the heat treatment can be completed in a short time.

Further, the heat treatment step is preferably carried out in an atmosphere containing oxygen. By subjecting the organic copper complex film to a heat treatment in an atmosphere containing oxygen, a copper oxide thin film is apt to be 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 &quot; oxygen concentration in the atmosphere containing oxygen &quot; is the oxygen concentration in the heating vessel (furnace) of the heating apparatus when the heating treatment is performed by the heating apparatus.

For example, when the heating vessel including the substrate having the organic copper complex film formed therein is filled with the mixed gas of oxygen (O ₂ ) and argon (Ar) which is an inert gas, the "oxygen concentration in the atmosphere containing oxygen" O ₂ / (Ar + O ₂ ) [% by volume].

If the oxygen concentration in the atmosphere containing oxygen is high, Cu ₂ O tends to be easily obtained. The oxygen concentration is more preferably 0.5 volume% to 10 volume%.

A copper oxide thin film containing a monovalent copper such as Cu ₂ O can be obtained on the substrate by heating the organic copper complex film at the more preferable range of the oxygen concentration (0.5 volume% to 50 volume%).

Further, each of the steps described above may be repeatedly performed.

For example, the organic copper complex solution coating film forming process of applying a specific solution onto a substrate and the drying process of drying the coating film are repeated (by applying a specific solution onto the dried coating film again and drying) The thickness of the organic copper complex film can be adjusted.

Other processes

The method for producing a copper oxide thin film of the present invention may further include other steps such as a cooling step and / or an energy ray irradiation step in addition to the organic copper complex solution film formation step, the drying step, and the heat treatment step .

Cooling process

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 is increased and productivity can be improved.

The method of cooling the copper oxide thin film is not particularly limited. For example, a method of air-cooling the copper oxide thin film and a method of bringing the substrate formed with the copper oxide thin film into contact with a metal plate at room temperature (for example, 25 DEG C).

Energy ray irradiation process

In the energy ray irradiation step, an energy ray (electron beam, infrared ray, ultraviolet ray, vacuum ultraviolet ray, atomic ray, X ray, γ ray, visible ray, etc.) is irradiated to the organic copper complex film obtained after the drying step.

By irradiating the energy ray to the organic copper complex film, a dense film having a high film density can be obtained.

By passing through each of the above-described steps, a copper oxide thin film is produced on a substrate.

In particular, since the copper oxide thin film including 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 can be preferably used for various thin film semiconductor devices.

When the copper oxide thin film is formed in a reducing atmosphere, it is preferable that the content of copper atoms to the total atoms constituting the copper oxide thin film is 70 atomic% or more. Since the content of copper atoms is 70 atomic% or more, the mobility when the copper oxide thin film is used as a conductor can be improved.

The content of copper atoms relative to the total atoms contained in the copper oxide thin film is more preferably 90 atomic% or more, and still more preferably 95 atomic% or more.

<Thin Film Semiconductor Device>

The thin film semiconductor of the present invention can be a semiconductor device by having a base material and a p-type semiconductor layer formed on the base material and made of a copper oxide thin film.

That is, the thin film semiconductor device of the present invention comprises a substrate, a copper oxide thin film of the present invention, or a copper oxide thin film produced by the method for producing the copper oxide thin film of the present invention.

The thin film semiconductor of the present invention may further comprise a flexible substrate, and the p-type semiconductor layer may be located on the substrate. By providing the p-type semiconductor layer on the flexible substrate, the thin film semiconductor device can be bent and can not be broken even if it is dropped. Further, by using the flexible substrate, the thin film semiconductor device becomes light in weight and can be transported in the form of winding the thin film semiconductor device, so that it can be suitably used as a power source for mobile devices, for example. Furthermore, because of its light weight, the burden on the building when installed on the roof of the building is alleviated.

Examples of the substrate that the thin film semiconductor device can be provided are the same as those of the substrate used in the method for producing the copper oxide thin film of the present invention, and preferred embodiments are also the same.

When the thin film semiconductor device is provided with a substrate, the p-type semiconductor layer may be located on the substrate, and another layer may be provided between the p-type semiconductor layer and the substrate. Other layers include various functional layers such as an adhesive layer for enhancing the adhesion between the p-type semiconductor layer and the base material.

The thin film semiconductor device using the copper oxide thin film can be applied to various applications, for example, a solar cell, a light emitting diode, a field effect transistor, and a thermoelectric conversion element. In particular, a thin film semiconductor device using a Cu ₂ O thin film can be preferably used as a photoelectric conversion material of a solar cell in that it has a band gap of about 2.1 eV, absorbs light in a visible light region, and generates a carrier.

<Solar Cell>

The thin film semiconductor device comprising the copper oxide thin film of the present invention or the copper oxide thin film produced by the method for producing the copper oxide thin film of the present invention can be preferably used as a solar cell. For example, a pn junction solar cell may be formed using a thin film semiconductor device having a p-type semiconductor layer and a p-type semiconductor layer including the copper oxide thin film of the present invention.

In a more specific embodiment of the pn junction type solar cell, for example, a p-type semiconductor layer and an n-type semiconductor layer are formed adjacent to each other on a transparent conductive film formed on a transparent substrate, and a p- And a metal electrode is formed on the layer.

An example of a pn junction solar cell will be described with reference to Fig.

1 is a schematic 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 formed on the transparent substrate 10, and a p-type cladding layer 12 formed on the transparent conductive film 12, An n-type semiconductor layer 16 formed on the p-type semiconductor layer 14 and a metal electrode 18 formed on the n-type semiconductor layer 16. The n-

the p-type semiconductor layer 14 and the n-type semiconductor layer 16 are laminated adjacent to each other, thereby making a pn junction type solar cell.

As the transparent substrate 10, if it is transparent, the same material as the example of the substrate used in the method for producing the copper oxide thin film of the present invention can be used. Examples of the transparent substrate include a glass substrate and a resin substrate. In the present invention, a resin substrate having low heat resistance can be used as a transparent substrate because a copper oxide thin film can be formed at a low temperature (230 DEG C or more and less than 300 DEG C) by using a specific solution containing a specific copper complex.

Examples of the resin substrate having low heat resistance include polysulfone, polyether sulfone, polyallylate, polyamide, polyimide, polyamideimide, and polyetherimide.

Examples of the transparent conductive film 12 include films made of In ₂ O ₃ : Sn (ITO), SnO ₂ : Sb, SnO ₂ : F, ZnO: Al, ZnO: F, CdSnO ₄ ,

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.

As the n-type semiconductor layer 16, a metal oxide is preferable. Specific examples of the metal oxide include oxides of metals including at least one of Ti, Zn, Sn, and In. More specifically, TiO ₂ , ZnO, SnO ₂ , and IGZO, . 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 production cost.

As the metal electrode 18, for example, Pt, Al, Cu, Ti, Ni, or the like can be used.

Example

EXAMPLES Hereinafter, examples will be described, but the present invention is not limited at all by these examples.

Example 1

Synthesis of specific copper complexes

Exemplified Compound 1 was synthesized on the basis of Synthesis Examples A to D, respectively (Exemplified Compound 1 synthesized was referred to as Synthesis Compound 1-1 to Synthesis Compound 1-4, respectively).

Exemplified Compound 2 was synthesized on the basis of Synthesis Example E and Synthesis Example F, respectively (Synthesis Example Compound 2 was referred to as Synthesis Compound 2-1 and Synthesis Compound 2-2, respectively).

Exemplified Compound 5 was synthesized on the basis of Synthesis Example G and Synthesis Example H, respectively (the synthesized Exemplified Compound 5 is referred to as a copper complex 5-1 and a copper complex 5-2, respectively).

Exemplary Compound 107 was synthesized on the basis of Synthesis Examples K and L, respectively (Exemplified Compound 107 synthesized was referred to as divalent complex 107-1 and divalent complex 107-2, respectively).

Exemplary Compound 108 was synthesized on the basis of Synthesis Example M and Synthesis Example N, respectively (the synthesized Example Compound 108 is referred to as a divalent complex 108-1 and a divalent complex 108-2, respectively).

Example Compound 109 was synthesized on the basis of Synthesis Example O and Synthesis Example P, respectively (the synthesized Example Compound 109 is referred to as a divalent complex 109-1 and a divalent complex 109-2, respectively).

Exemplary Compound 110 was synthesized on the basis of Synthesis Example Q and Synthesis Example R, respectively (the synthesized Compound 110 was referred to as a divalent complex 110-1 and a divalent complex 110-2, respectively).

Exemplary Compound 111 was synthesized on the basis of Synthesis Example S and Synthesis Example T, respectively (the synthesized Example Compound 111 was referred to as a divalent complex 111-1 and a divalent complex 111-2, respectively).

Exemplary Compound 58 was synthesized on the basis of Synthesis Example U (Exemplified Compound 58 synthesized was referred to as divalent complex 58-1).

Exemplified Compound 126 was synthesized on the basis of Synthesis Example V (Exemplified Compound 126 synthesized is referred to as divalent complex 126-1).

Exemplified Compound 29 was synthesized on the basis of Synthesis Example W (Exemplified Compound 29 synthesized is referred to as divalent complex 29-1).

Example Compound 131 was synthesized on the basis of Synthesis Example X (the exemplified compound 131 synthesized was referred to as a copper complex 131-1).

Exemplary Compound 132 was synthesized based on Synthesis Example Y (Exemplified Compound 132 synthesized is referred to as Synthesis Compound 132-1).

Exemplary Compound 133 was synthesized based on Synthesis Example Z, respectively (Exemplified Compound 133 synthesized is referred to as divalent complex 133-1).

Example 1-1

Synthesis Example A of Exemplary Compound 1 (Specific Doping Compound) A

9.5 g of 1,8-diazabicyclo [5.4.0] undec-7-ene was added to 50 ml of N, N-dimethylacetamide, and 9 g of Meldrum acid was added intermittently for 5 minutes while water- , To obtain a mixed solution. During this time, the liquid temperature of the mixed liquid was 18 ° C to 28 ° C.

To the mixed solution was further added dropwise 7 ml of acetic anhydride over 5 minutes, and then left at room temperature for one night. 4.2 g of cupric chloride was dissolved in 25 ml of N, N-dimethylacetamide, added to the above mixture, and left 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, followed by vigorous stirring. After allowing to stand for 1 hour, the mixture was subjected to suction filtration, and the filtrate was washed with 200 ml of water to obtain a copper complex 1-1 (Exemplified Compound 1) as 13 g of water-colored crystals.

To 5.5 g of the obtained crystals, 48 ml of N, N-dimethylacetamide was added and the mixture was dissolved by heating. The resulting liquid was filtered, and the filtrate was cooled to room temperature. While vigorously stirring, 20 ml of toluene was added, and then 200 ml of water was added, followed by allowing to stand for 30 minutes. The resulting crystals were collected by suction filtration and 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 a colorless crystal. This crystal was dissolved in tetrahydrofuran, toluene was added to the obtained solution, and water was added so that precipitation did not occur immediately. The resulting liquid was allowed to stand at room temperature overnight. As a result, 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.

Examples 1-2

Synthesis Example B of Exemplified Compound 1 (Specific Doping Compound)

First, sodium meldrumate was synthesized according to the synthesis method of Compound 1 described in P. Houghton and D. J. Lapham, Synthsis, 1982, page 451.

Subsequently, 8 g (48 mmol) of the resulting sodium manganate salt was dispersed in 40 ml of N, N-dimethylacetamide, and while stirring, 5.2 ml of acetic anhydride was dissolved in 10 ml of N, N-dimethylacetamide Over 10 minutes, and the obtained mixed solution was allowed to stand at room temperature for one night. Insoluble materials were removed by filtration, and a solution obtained by dissolving 3.23 g (24 mmol) of anhydrous sodium chloride in 20 ml of N, N-dimethylacetamide while stirring the filtrate was added dropwise to the filtrate over 5 minutes. While vigorously stirring the obtained mixed solution, 150 ml of water was added in three portions. The obtained crystals were collected by filtration, washed twice with 50 ml of water, and air-dried to obtain 7.25 g of a scouring crystal. 7.25 g of this crystal was dissolved in 50 ml of N, N-dimethylacetamide and filtered. Then, while stirring the filtrate vigorously, 25 ml of water was added, and further 175 ml of water was added and stirred. The resulting mixture was immersed in an ice-water bath and cooled to 15 DEG C, and then crystals were collected by filtration. The resulting crystals were washed with 50 ml of water and then dried under reduced pressure to obtain 4.75 g of a complex (1-2) (Exemplified Compound 1) as crystals.

Example 1-3

Synthesis Example C of Exemplary Compound 1 (Specific Doping Compound) C

Melamine acid (7.2 g, 0.05 M) was dissolved in dichloromethane (60 ml), and the temperature inside was changed to -5 ° C. Pyridine (7.9 g, 0.1 M) was slowly added and stirred for about 10 minutes to obtain a mixed solution . Then, to the obtained mixed solution, a solution of acetyl chloride (4.3 g, 0.055 M) in dichloromethane (20 ml) was added dropwise over 20 minutes. Thereafter, the resulting solution was reacted at room temperature for 1 hour. The reaction solution was made acidic with 1 N HCl, washed with water, dried over MgSO ₄ , and the solvent was distilled off to obtain a reddish brown oil. The oil was purified twice by silica gel chromatography (Hexane: AcOEt = 10: 1 to 5: 1) to obtain 7.44 g of Compound A.

The obtained Compound A was analyzed by ¹ H-NMR (CDCl ₃ ), and the following results were obtained, confirming that the compound had the following structure represented by the general formula (2). [delta] 1.74 (s, 6H), 2.68 (s, 3H), 15.13 (s, 1H).

(7)

10 ml of N, N-dimethylacetamide was added to 1.86 g (10 mmol) of Compound A obtained and dissolved to obtain a Compound A solution. Then, a solution of 650 mg (5 mmol) of anhydrous copper chloride in 5 ml of N, N-dimethylacetamide was added to the solution of Compound A, followed by 1.4 ml (10 mmol) of triethylamine, Lt; / RTI &gt; for 30 minutes. 90 ml of water was added with vigorous stirring, and the mixture was allowed to stand for 30 minutes. The resulting crystals were collected by filtration, washed with water, and dried to obtain 1.9 g of the dyestuff 1-3 1).

Examples 1-4

Synthesis Example D of Exemplary Compound 1 (Specific Dye Complex)

1.86 g (10 mmol) of Compound A was added to 80 ml of water, 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 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 Compound A solution 2 and stirred at room temperature for 30 minutes. The resulting crystal was filtered, washed with water, and dried to obtain 1.6 g of a dyestuff compound 1-4 (Exemplified Compound 1) as a scouring powder.

Examples 1-5

Synthesis Example of Exemplary Compound 2 (Specific Doping Compound) E

First, Y. Oikawa, K. Sugano, O. Yonemitsu, J. Org. Chem., Vol. 43, 2087 (1978), compound B of the following structure represented by general formula 2 was obtained.

[Chemical Formula 8]

N, N-dimethylacetamide (10 mL) was added to and dissolved in 2.00 g (10 mmol) of the obtained compound B to obtain a compound B solution. Then, a solution of 650 mg (5 mmol) of anhydrous copper chloride in 5 ml of N, N-dimethylacetamide was added to the solution of the compound B, followed by the addition of 1.4 ml (10 mmol) of triethylamine, Lt; / RTI &gt; for 30 minutes. 90 ml of water was added with vigorous stirring, and the mixture was allowed to stand for 30 minutes. The resulting crystals were collected by filtration, washed with water, and dried to obtain 2 g of a copper complex 2-1 2).

To the obtained crystals, 48 ml of N, N-dimethylacetamide was added and dissolved by heating. The resulting liquid was filtered, and the filtrate was cooled to room temperature. While vigorously stirring, 20 ml of toluene was added, and then 200 ml of water was added, followed by allowing to stand for 30 minutes. The resulting crystals were collected by suction filtration and washed with 30 ml of toluene little by little. The crystals were air-dried, and then dried under reduced pressure to obtain search crystals. The complex was dissolved in tetrahydrofuran, toluene was added to the obtained solution, and water was added so that precipitation did not occur immediately. The resultant liquid was allowed to stand at room temperature overnight. As a result, 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.

Examples 1-6

Synthesis Example F of Exemplary Compound 2 (Specific Doping Compound) F

2.00 g (10 mmol) of Compound B was added to 80 ml of water, 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 B to obtain Compound B Solution 2 . Then, a solution of 1.24 g (5 mmol) of copper sulfate pentahydrate in 20 ml of water was added to the solution of Compound B 2, and the mixture was stirred at room temperature for 30 minutes. The resulting crystals were collected by filtration, washed with water, and dried to obtain a copper complex 2-2 (Exemplary Compound 2) as 2.0 g of a silver powder.

Examples 1-7

Synthesis Example of Exemplified Compound 5 (Specific Doping Compound) G

First, Y. Oikawa, K. Sugano, O. Yonemitsu, J. Org. Chem., Vol. 43, 2087 (1978), Compound C having the following structure represented by Formula 2 was synthesized.

[Chemical Formula 9]

N, N-dimethylacetamide (10 ml) was added to and dissolved in 2.6 g (10 mmol) of the obtained compound C to obtain a solution of Compound C. Thereafter, a solution of 650 mg (5 mmol) of anhydrous copper chloride in 5 ml of N, N-dimethylacetamide was added to the solution of Compound C, followed by 1.4 ml (10 mmol) of triethylamine, Lt; / RTI &gt; for 30 minutes. 90 ml of water was added while vigorously stirring the resulting mixture, and the mixture was allowed to stand for 30 minutes. The resulting crystals were collected by filtration and washed with water. Subsequently, the resultant was dispersed in 50 ml of xylene, washed, collected by filtration, and dried to obtain a copper complex 5-1 (Exemplified Compound 5) as 2 g of a silver powder.

To the obtained crystals, 48 ml of N, N-dimethylacetamide was added and dissolved by heating. The resulting liquid was filtered, and the filtrate was cooled to room temperature. While vigorously stirring, 20 ml of toluene was added, and then 200 ml of water was added, followed by allowing to stand for 30 minutes. The resulting crystals were collected by suction filtration and washed with 30 ml of toluene little by little. The crystals were air-dried, and then dried under reduced pressure to obtain search crystals. The complex was dissolved in tetrahydrofuran, toluene was added to the obtained solution, and water was added so that precipitation did not occur immediately. The resultant liquid was allowed to stand at room temperature overnight. As a result, 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.

Examples 1-8

Synthesis Example of Exemplary Compound 5 (Specific Doping Compound) H

To the 80 ml of water was added 2.62 g (10 mmol) of the compound C, 10 ml of a 1 mol / l sodium hydroxide solution was further added, and the mixture was stirred for about 10 minutes to dissolve the compound C, . Thereafter, a solution obtained by dissolving 1.24 g (5 mmol) of copper sulfate pentahydrate in 20 ml of water was added to the solution of Compound C 2, and the mixture was stirred at room temperature for 30 minutes. The resulting crystals were filtered, washed with water, and dried to obtain 1.25 g of a copper complex 5-2 (Exemplified Compound 5) as a scouring powder.

Examples 1-9

Synthesis Example K of Exemplary Compound 107 (specific dope complex)

First, in Example 1-5, the same reaction was carried out using cyclopropanecarboxylic acid chloride instead of the propionyl chloride used in the synthesis of Compound B to synthesize Compound E having the following structure.

[Chemical formula 10]

In Example 1-5, the same reaction was carried out using 2.1 g (10 mmol) of the compound E instead of the compound B of the synthesis example E to obtain a dope 107-1 (Exemplified Compound 107) as a governing powder (2.1 g) &Lt; / RTI &gt;

The copper complex 107-1 was subjected to recrystallization in the same manner as in Example 1-5 to prepare a single crystal, and an X-ray crystal structure analysis was carried out.

Example 1-10

Synthesis Example of Exemplary Compound 107 (Specific Doping Compound) L

The same reaction as in Example 1-6 was conducted using 1.7 g (10 mmol) of the compound E instead of the compound B of the Example F to obtain 1.9 g of the dope 107-2 (Exemplified Compound 107) as a goalk powder, .

Example 1-11

Synthesis Example M of Exemplified Compound 108 (specific dope complex)

First, Compound F having the following structure was synthesized according to the synthesis method described in Canadian Journal of Chemistry, 1992, vol. 70, p. 1427-1445.

(11)

The same reaction as in Example 1-5 was conducted using 2.2 g (10 mmol) of the compound F instead of the compound B of the synthesis example E to obtain the copper complex 108-1 (Exemplified Compound 108) as 1.6 g of a goethite powder, &Lt; / RTI &gt;

The copper complex 108-1 was subjected to recrystallization in the same manner as in Example 1-5 to prepare a single crystal, and an X-ray crystal structure analysis was carried out.

Examples 1-12

Synthesis Example of Exemplary Compound 108 (Specific Dye Complex) N

In the same manner as in Example 1-6, the same reaction was carried out using 1.7 g (10 mmol) of Compound F instead of the compound B of Synthesis Example F to obtain 1.4 g of a dope 108-2 (Exemplified Compound 108) .

Examples 1-13

Synthesis Example of Exemplary Compound 109 (Specific Doping Compound) O

First, in Example 1-5, the same reaction was carried out using bromoacetic acid chloride instead of the propionyl chloride used in the synthesis of Compound B to synthesize Compound G of the following structure.

[Chemical Formula 12]

In Example 1-5, the same reaction was carried out using 2.7 g (10 mmol) of the compound G instead of the compound B in the synthesis example E to obtain 2.2 g of the dyestuff 109-1 (Exemplified Compound 109) &Lt; / RTI &gt;

The copper complex 109-1 was subjected to recrystallization in the same manner as in Example 1-5 to prepare a single crystal, and an X-ray crystal structure analysis was carried out.

Examples 1-14

Synthesis Example of Exemplary Compound 109 (Specific Doping Compound) P

In Example 1-6, the same reaction was carried out using 2.7 g (10 mmol) of Compound G instead of the compound B in Synthesis Example F to obtain 2.4 g of the dyestuff 109-2 (Exemplified Compound 109) as a scouring powder, .

Examples 1-15

Synthesis Example of Exemplary Compound 110 (Specific Doping Compound) Q

First, Compound H having the following structure was synthesized according to the synthesis method described in Canadian Journal of Chemistry, 1992, vol.70, p.1427 to 1445.

[Chemical Formula 13]

The same reaction as in Example 1-5 was conducted using 3.1 g (10 mmol) of the compound H instead of the compound B of the synthesis example E to obtain the dope 110-1 (Exemplified Compound 110) as 2.7 g of a goethite powder, &Lt; / RTI &gt;

The copper complex 110-1 was subjected to recrystallization in the same manner as in Example 1-5 to prepare a single crystal, and an X-ray crystal structure analysis was carried out.

Examples 1-16

Synthesis Example of Exemplary Compound 110 (Specific Dye Complex) R

The same reaction as in Example 1-6 was conducted using 3.1 g (10 mmol) of Compound H instead of the compound B of Synthesis Example F to obtain 2.2 g of the dope 110-2 (Exemplified Compound 110) as a governing powder, .

Examples 1-17

Synthesis Example of Exemplary Compound 111 (Specific Doping Compound) S

First, in Example 1-5, the same reaction was carried out using methoxyacetic acid chloride instead of the propionyl chloride used in the synthesis of Compound B to synthesize Compound I having the following structure.

[Chemical Formula 14]

The same reaction as in Example 1-5 was conducted using 2.2 g (10 mmol) of the compound I instead of the compound B of the synthesis example E to obtain a copper complex 111-1 (Exemplified Compound 111) as a 2.0 g of a silver powder, &Lt; / RTI &gt; The structure was confirmed from the mass spectrum of the obtained copper complex.

For mass spectrometry, α-cyano-4-hydroxy cinnamic acid was used for the matrix and chloroform was used for the solvent using Applied Biosystems Voyager Syetem 6306. Hereinafter, the same conditions as those for the mass spectrometer were used.

Example 1-18

Synthesis Example of Exemplary Compound 111 (Specific Doping Compound) T

The same reaction was carried out as in Example 1-6, except that 2.2 g (10 mmol) of Compound I was used instead of the compound B of Synthesis Example F to obtain the copper complex 111-2 (Exemplified Compound 111) as 1.7 g of a silver powder, .

Example 1-19

Synthesis Example of Exemplary Compound 58 (Specific Doping Compound) U

14 g (100 mmol) of meldrum acid and 13 g (100 mmol) of acetophenone were heated under reflux for 30 minutes in toluene (200 ml), and then n-hexane, ethyl acetate and chloroform were used as developing solvents Silica gel column purification was carried out to obtain 4.2 g of Intermediate J '. Thereafter, the same reaction was carried out using 4 g (20 mmol) of Intermediate J 'in place of Meldrum acid used in the synthesis of Compound B in Example 1-5 to obtain 4.4 g of the compound L- 19 were synthesized.

[Chemical Formula 15]

In Example 1-5, the same reaction was carried out using 2.2 g (10 mmol) of the compound L-19 instead of the compound B of the synthesis example E to obtain 0.8 g of the dyestuff 58-1 (Exemplified Compound 58). The structure was confirmed from the mass spectrum of the obtained copper complex.

Examples 1-20

Synthesis Example V of Exemplary Compound 126 (Specific Doping Compound) V

Reaction was carried out using 2-acetylthiophene instead of acetophenone of Example 1-19 to obtain 4.2 g of Intermediate K '. Thereafter, the same reaction was carried out using 4.2 g (20 mmol) of Intermediate K 'instead of Melamine acid used in the synthesis of Compound B in Example 1-5 to obtain 3.6 g of Compound L- 29 was synthesized.

[Chemical Formula 16]

In Example 1-5, the same reaction was carried out using 2.5 g (10 mmol) of the compound L-29 instead of the compound B of the synthesis example E to obtain 0.6 g of the dope complex 126-1 (the exemplified compound 126). The structure was confirmed from the mass spectrum of the obtained copper complex.

Examples 1-21

Synthesis Example of Exemplary Compound 29 (Specific Doping Compound) W

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 Intermediate L 'instead of Melamine acid used in the synthesis of Compound B in Example 1-5 to obtain 4.1 g of Compound L- 39 was synthesized.

[Chemical Formula 17]

In Example 1-5, the same reaction was carried out using 2.3 g (10 mmol) of the compound L-39 instead of the compound B of the synthesis example E to obtain 2.1 g of the dyestuff 29-1 (Exemplified Compound 29).

The copper complex 29-1 was subjected to recrystallization in the same manner as in Example 1-5 to prepare a single crystal, and an X-ray crystal structure analysis was carried out.

Examples 1-22

Synthesis Example of Exemplary Compound 131 (Specific Doping Compound) X

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, the same reaction was carried out using 3.7 g (20 mmol) of Intermediate M 'instead of the molar acid used in the synthesis of Compound B in Example 1-5 to obtain 2.4 g of the compound L -48.

[Chemical Formula 18]

In Example 1-5, the same reaction was carried out using 2.4 g (10 mmol) of the compound L-48 instead of the compound B of the synthesis example E to obtain 0.6 g of the dyestuff 131-1 131). The structure was confirmed from the mass spectrum of the obtained copper complex.

Examples 1-23

Synthesis Example of Exemplary Compound 132 (Specific Dye Complex) Y

First, in Example 1-5, the same reaction was carried out using 2-furancarboxylic acid chloride instead of the propionyl chloride used in the synthesis of Compound B to synthesize Compound L-7 having the following structure.

[Chemical Formula 19]

In Example 1-5, the same reaction was carried out using 2.4 g (10 mmol) of the compound L-7 instead of the compound B of the synthesis example E to obtain 0.7 g of a copper complex 132-1 (Exemplified Compound 132). The structure was confirmed from the mass spectrum of the obtained copper complex.

Examples 1-24

Synthesis Example Z of Exemplary Compound 133 (Specific Dye Complex) Z

First, in Example 1-5, the same reaction was carried out using 6-heptenecarboxylic acid chloride instead of the propionyl chloride used in the synthesis of Compound B to synthesize Compound O of the following structure.

[Chemical Formula 20]

The same reaction was carried out as in Example 1-5 with the exception that 2.5 g (10 mmol) of Compound O was used instead of the compound B of Synthesis Example E to obtain a copper complex 133-1 (Exemplified Compound 133) as 0.8 g of a silver powder, &Lt; / RTI &gt; The structure was confirmed from the mass spectrum of the obtained copper complex.

<X-ray structure analysis>

Among the specific copper complexes synthesized as described above, the copper complex 1-1, the copper complex 2-1, the copper complex 5-1, the copper complex 107-1, the copper complex 108-1, the copper complex 109-1, the copper complex 110 -1, and the copper complex 29-1 were subjected to X-ray crystal structure analysis. The analysis was performed using a desktop single crystal X-ray structural analyzer XtaLAB mini manufactured by Rigaku Corporation under the conditions of 23 占 폚. The various parameters obtained as a result of the analysis are shown below. Further, 1 ANGSTROM is 0.1 nm.

Copper complex 1-1

Molecular formula: C ₁₆ H ₁₈ CuO ₁₀

Molecular weight: 433.86

Political: 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 / cm3

R value: 0.07

Rw value: 0.13

GOF: 1.21

Here, R-3 represents the symbol of space group, R value represents &quot; relative residue &quot; of the least squares method, Rw represents the &quot; weight relative residue &quot; of fitness. R value and Rw value of the following copper complex 2-1, copper complex 5-1, copper complex 107-1, copper complexes 108-1 and 109-1, copper complex 110-1, and copper complex 29-1 and GOF Are also the same definition. P-1, P21 / c, and C2 / C in the copper complex 5-1, the copper complex 107-1, the copper complexes 108-1 and 109-1, the copper complex 110-1, c represents the symbol of space group.

Copper complex 2-1

Molecular formula: C ₁₈ H ₂₂ CuO ₁₀

Molecular weight: 461.91

Political: 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 / cm3

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

Politics: 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 / cm3

R value: 0.04

Rw value: 0.10

GOF: 1.06

The complex 107-1

Molecular formula: C ₂₀ H ₂₂ CuO ₁₀

Molecular weight: 485.92

Politics: Three companies

Space group: P-1

A = 72.377 (6), b = 76.686 (6), c = 79.268 (6), and a unit cell parameter: a = 9.299 (6) °, V = 1005 (1) Å ³

Calculated density: 1.61 g / cm3

R value: 0.05

Rw value: 0.14

GOF: 1.11

Complex 108-1

Molecular formula: C ₁₈ H ₂₂ O ₁₂ Cu

Molecular weight: 493.9

Politics:

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 = 1006.6 Å 3

Calculated density: 1.63 g / cm3

R value: 0.03

Rw value: 0.08

GOF: 1.01

Complex 109-1

Molecular formula: C ₁₆ H ₁₆ BR ₂ CuO ₁₀

Molecular weight: 591.65

Politics:

Space group: C2 / c

A = 90, b = 95.184 (7), c = 90, V = 2118 (1) 3) Å ³

Calculated density: 2.012 g / cm3

R value: 0.17

Rw value: 0.52

GOF: 2.29

The complex complex 110-1

Molecular formula: C ₃₂ H ₃₆ CuO ₁₃

Molecular weight: 692.16

Politics:

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) Å 3

Calculated density: 1.48 g / cm3

R value: 0.06

Rw value: 0.11

GOF: 0.99

Complex 29-1

Molecular formula: C ₂₂ H ₂₆ CuO ₁₀

Molecular weight: 513.98

Politics:

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 &lt; 3 &gt;

R value: 0.04

Rw value: 0.08

GOF: 1.07

Further, the copper complex 1-1, the copper complex 2-1, the copper complex 5-1, the copper complex 107-1, the copper complex 108-1, the copper complex 109-1, the copper complex 110-1, And the copper complex 29-1 are shown in Figs. 2 to 9, respectively.

From the above results, it was found that the copper complex 1-1, the copper complex 2-1, the copper complex 5-1, the copper complex 107-1, the copper complex 108-1, the copper complex 109-1, the copper complex 110-1, -1, it was confirmed that they were all obtained as the complex represented by the general formula 1 already described.

<Pyrolysis Analysis>

Next, a mass change (TG), a differential thermal analysis (DTA), and a mass spectrometry (MS) of a volatile component of the copper complex 1-1 generated by heating the obtained copper complex 1-1 are measured For the measurement, differential thermal weight-mass analysis (TG-DTA-MS) was performed.

The measurement conditions are, and the mixture was heated under Ar (80% by volume), O ₂ (20 volume%) of the atmosphere, from room temperature to 2.0 ℃ / min up to 300 ℃. FIG. 10 shows TG-DTA results, and FIG. 11 shows MS analysis results.

10, the curve A is the TG curve of the copper complex 1-1, and the curve B is the DTA curve of the copper complex 1-1. The broken line (C) shows the amount of reduction from the copper complex 1-1 when CO ₂ and acetone are desorbed from the copper complex 1-1; -47.1 mass%, the broken line (D) represents the reduction amount from the copper complex 1-1 when it is assumed that all copper complexes are Cu ₂ O; -83.7 mass%.

The reduction of the mass of the copper complex 1-1 takes place in two steps of 150 ° C to 180 ° C and 180 ° C to 230 ° C, and m / z = 43 (CH ₃ CO), which is caused by acetone, , a peak of m / z = 58 (CH ₃ COCH ₃ ), a peak of CO ₂ (m / z = 44) and a peak of H ₂ O (m / z = 18) Meldrum acid is known to decompose into acetone, CO ₂ and ketene during pyrolysis, and it is thought that pyrolysis of Meldrum acid occurred in the first stage. Also, m / z means the mass transfer ratio.

Further, Powder X-ray diffraction measurement of the powder obtained by heating the copper complex 1-1 at room temperature and 230 占 폚 for 1 hour was carried out. RINT-Ultima III manufactured by Rigaku Corporation was used for the measurement. The obtained diffraction pattern is shown in Fig. All of the obtained peaks were consistent with Cu ₂ O (JCPDS # 05-0667). That is, the embodiment 1-1 copper complex obtained in Example 1-1, it was confirmed that the thermal decomposition to form a Cu ₂ O at a low temperature of 230 ℃.

The copper complex 2-1 and the copper complex 5-1 were subjected to the same thermogravimetric analysis (TG). The results are shown in Fig. The curve A is the TG curve of the copper complex 2-1 and the curve B is the TG curve of the copper complex 5-1. It was confirmed that the mass reduction in two steps was observed in the same manner as in the case of the copper complex 1-1.

Completion of pyrolysis was judged from the fact that the reduction of the mass occurred more than the calculated value at which the copper complex was decomposed to generate Cu ₂ O, the mass reduction proceeded, and the sublimation did not occur from the DTA data.

The results of TG of other copper complexes are summarized in Table 13. A indicates that pyrolysis has been completed at temperatures below 300 ° C, and B indicates temperatures above 300 ° C.

For the copper complexes 107-1 to 133-1, pyrolysis was completed at temperatures lower than 300 占 폚. On the other hand, in the method described in the above-mentioned Japanese Patent Laid-Open Publication No. 2011-119454 (specifically, the compound described in paragraphs 0046 to 0056 of Japanese Laid-Open Patent Publication No. 2011-119454), the thermal decomposition temperature was 500 ° C or more.

Example 2

Preparation 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 the copper complex 1-1 was weighed and added to 30 ml of N, N-dimethylacetamide at room temperature (25 DEG C, the same applies hereinafter) with stirring, and stirred for 30 minutes to obtain a 0.15 mol / 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 to 90 占 폚 with stirring, and the mixture was stirred for 30 minutes to obtain a 0.05 mol / Thereby obtaining a blue transparent solution (copper complex solution 2).

Example 2-3

0.33 g of the copper complex 1-1 was weighed and added to 30 ml of 2-diethylaminoethanol at room temperature with stirring, followed by stirring for 30 minutes to obtain 0.025 mol / l of a transparent solution (Coomplex Solution 3).

Examples 2-4

0.65 g of the copper complex 1-1 was weighed out and added to 30 ml of pyridine at room temperature with stirring, and the mixture was stirred for 30 minutes to obtain a 0.05 mol / l transparent solution (Coomplex Solution 4).

Example 2-5

0.65 g of the copper complex 1-1 was weighed and added to 30 ml of tetrahydrofuran at room temperature with stirring, followed by stirring for 30 minutes to obtain a 0.05 mol / l transparent solution (Coomplex Solution 5).

Examples 2-6

Using the copper complex 1-1 and the copper complex 2-1, a copper complex solution 6 as a specific solution was prepared. 1.3 g of the copper complex 1-1 and 1.4 g of the copper complex 2-1 were weighed and added to 30 ml of N, N-dimethylacetamide at room temperature with stirring, and the mixture was stirred for 30 minutes to obtain a solution having a copper complex concentration of 0.2 mol / l To obtain a deep blue transparent solution (copper complex solution 6).

In the same manner, the copper complex solution summarized in Table 14 was prepared.

Example 3

Fabrication of Cu ₂ O thin films

Example 3-1:

A Cu ₂ O thin film was prepared by using the copper complex solution (copper complex solution 1) prepared in Example 2-1 in the following procedure.

Organic copper complex solution coating film forming process and drying process

The copper complex solution 1 was spin-coated on a silicon substrate having a length of 25 mm at a rotation speed of 3000 rpm for 60 seconds and then dried on a hot plate heated at 200 캜 for 5 minutes to obtain a film thickness A precursor film 1 (organic copper complex film) of about 40 nm was obtained.

Heat treatment process

The obtained precursor thin film 1 was heated at the following annealing temperature and under the following annealing atmosphere.

The annealing was performed at annealing temperatures of 200 ° C, 230 ° C, 250 ° C, 280 ° C, 300 ° C, or 350 ° C. The addition, the annealing atmosphere, O ₂ / (Ar + O ₂₎ flow rate ratio (volume basis) to 0 (that is, an oxygen concentration of 0% by volume in the furnace during the heat treatment), 0.1 (oxygen concentration: 10% by volume), 0.2 ( (Oxygen concentration of 20 vol%), 0.5 (oxygen concentration of 50 vol%), 0.8 (oxygen concentration of 80 vol%), or 1.0 (oxygen concentration of 100 vol%).

The heating treatment was carried out using a high-speed heat treatment apparatus (AW-410 manufactured by Allwin 21), heated to a desired temperature at 50 ° C / sec, held for 3 minutes, and then cooled in a furnace. The total gas flow rate during the heat treatment was 2 L / min.

Each Cu ₂ O thin film thus obtained was subjected to thin-film X-ray diffraction measurement. For the measurement, evaluation was carried out using 2-theta measurement in which the incident angle was fixed at 0.35 占 using RINT-Ultima III manufactured by Rigaku Corporation.

14, the annealing atmosphere was fixed at O ₂ / (Ar + O ₂ ) = 0.2 (oxygen concentration in the furnace at the time of heat treatment: 20 vol%) and annealed at 200 ° C., 230 ° C., 250 ° C., 280 ° C., Or an X-ray diffraction (X-ray diffraction) pattern of a thin film subjected to a heat treatment at an annealing temperature of 350 ° C. Peak could not be confirmed at 200 ° C indicated by the curve F. Peaks of Cu ₂ O (JDPDS # 05-0667) were mainly confirmed at 230 ° C, 250 ° C, and 280 ° C as indicated by curves E to C, respectively.

The peak indicated by (c) in FIG. 14 indicates the presence of Cu ₂ O (111), and the peak indicated by (d) indicates the presence of Cu ₂ O (200).

Further, at 300 ° C indicated by the curve B and at 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 shown in (a) of FIG. 14 indicates the presence of CuO (11-1), and the peak shown in (b) indicates the presence of CuO (111).

Secure the annealing temperature to 15 to _{250 ℃, O 2 / (Ar} + O 2) = 0 ( oxygen concentration of 0% by volume), 0.005 (0.5% by volume of oxygen concentration), 0.015 (1.5% by volume of oxygen concentration), 0.05 (Oxygen concentration of 5 vol%), 0.1 (oxygen concentration of 10 vol%), 0.2 (oxygen concentration of 20 vol%), 0.5 %), Or 1.0 (oxygen concentration: 100% by volume).

Only the peak of Cu ₂ O was confirmed for O ₂ / (Ar + O ₂ ) = 0.005 to 0.05 (curve (B) to curve (D)).

Only a peak of Cu ₂ O was confirmed in the range of O ₂ / (Ar + O ₂ ) of 0.1 to 0.5 (curve (E) to curve (G)). On the other hand, a clear peak could not be confirmed from the sample of O ₂ / (Ar + O ₂ ) = 0.8 or more (curve (I) to curve (J)). Further, at O ₂ / (Ar + O ₂ ) = 0 (curve A), a peak of Cu (JCPDS # 04-0836) was confirmed.

In addition, the peak shown in (a) of Fig. 15 indicates the presence of Cu (111), and the peak shown in (b) indicates the presence of Cu (200). Also, the peak shown in Figure 15 in (c) peak shown by the peak indicated by represents the presence of _{Cu 2 O (111), (} d) denotes the presence of _{Cu 2 O (200), (} e) the Cu ₂ O (220).

_{O 2 / (Ar + O 2} ) = The XRD pattern (curve (H)) of 0.6 because a clear peak was not confirmed, the range is Cu ₂ O is obtained from 0.005 (oxygen concentration 0.5 vol%) ≤ O ₂ / ( Ar + O ₂ )? 0.5 (oxygen concentration: 50% by volume).

Example 3-2

A Cu ₂ O thin film was prepared using the copper complex solution (copper complex solution 6) prepared in Example 2-6.

Organic copper complex solution coating film forming process and drying process

The copper complex solution 6 was spin-coated on a silicon substrate having a length of 25 mm at a rotation speed of 3000 rpm for 60 seconds and then dried on a hot plate heated at 200 캜 for 5 minutes to obtain a film thickness A precursor thin film 6 (organic copper complex film) of about 40 nm was obtained.

Heat treatment process

Under the conditions of the precursor thin film 6, the annealing temperature 250 ℃, annealing atmosphere _{O 2 / (Ar + O 2} ) flow rate ratio (volume basis) to 0.2 (oxygen concentration of 20% by volume), and subjected to a heat treatment Cu ₂ O Thin film 6 was obtained.

The Cu ₂ O thin film 6 was subjected to the same thin film X-ray diffraction measurement, and as a result, a peak of Cu ₂ O was mainly confirmed.

Subsequently, a precursor thin film was prepared and a Cu ₂ O thin film was produced under the same conditions as the precursor thin film 6. Table 15 summarizes the results. Further, when the thin film X-ray diffraction measurement was carried out, the peak of Cu ₂ O was mainly identified as A, and the case where B was mainly confirmed was confirmed. Also in the Cu ₂ O thin films 7 to 15, when the thin film X-ray diffraction measurement was carried out, it was confirmed that the main peak was derived from Cu ₂ O.

Example 3-3:

A Cu ₂ O thin film was prepared by using the copper complex solution 1-1 prepared in Example 2-1 in the following procedure.

First, as a substrate, a laminated substrate having a polyimide resin substrate peelably adhered to a silicon substrate of 25 mm in length with an acrylic pressure-sensitive adhesive interposed therebetween was prepared.

Next, the copper complex solution 1-1 was spin-coated on the surface of the polyimide resin substrate of the laminated substrate at a rotation speed of 3000 rpm for 60 seconds and then dried for 5 minutes on a hot plate heated to 200 DEG C, By repeating this process, a precursor film 2 (organic copper complex film on which a substrate was formed) having a film thickness of about 40 nm was obtained.

The obtained precursor thin film 2 was subjected to a heat treatment for 3 minutes at an annealing temperature of 250 캜 and an annealing atmosphere of O ₂ / (Ar + O ₂ ) = 0.15. As a result, in the thin film X- 1, only a peak of Cu ₂ O was confirmed.

Since the Cu ₂ O thin film thus obtained functions as a p-type semiconductor, it can be applied to a thin film semiconductor device. In addition, by forming the thin film semiconductor device in a configuration adjacent to the member to be an n-type semiconductor, a thin film semiconductor device having a pn junction can be obtained, and is also suitable for application to a pn junction solar cell.

Further, as can be seen from Example 3-2, since a Cu ₂ O thin film which is a copper oxide thin film can be produced even by annealing at a heating temperature of 250 ° C, a flexible resin substrate weak in heat can also be used as a substrate And it is also possible to manufacture a flexible thin film semiconductor device.

The disclosures of Japanese Patent Application Nos. 2012-207255 and 2013-192216 are hereby incorporated by reference in their entirety.

All publications, patent applications, and technical specifications described in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, and technical specification were specifically and individually recorded as being incorporated by reference. Accepted.

Claims (17)

An organic copper complex having a structure represented by the following general formula (1).
[Chemical Formula 1]

In the general formula (1), R ¹¹ , R ¹² , R ²¹ and R ²² may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms, a non-aromatic hydrocarbon group having 2 to 20 carbon atoms having an unsaturated bond , 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 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, a non-aromatic hydrocarbon group having 2 to 20 carbon atoms having an unsaturated bond, An aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a hydroxyl group. H in the CH 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. When R ¹¹ , R ¹² , R ²¹ and R ²² all represent a methyl group, R ³¹ and R ³² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms An alkoxy group, or a hydroxyl group. The method according to claim 1,
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 are connected to each other to form a ring and may be, R ¹² and R ²² is may form a ring are connected to each other, R ³¹ and R ³² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, having 6 to An aryl group having 1 to 20 carbon atoms, or an organic copper complex showing a hydroxyl group. 3. The method 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. 4. The method according to any one of claims 1 to 3,
Wherein R ³¹ and R ³² in the general formula 1 are the same organic dyes. The method according to any one of claims 1, 2, and 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 method 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. 7. The method according to any one of claims 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. 8. The method according to any one of claims 1 to 7,
Organic copper complexes used in the formation of copper oxide thin films. 9. A solution of an organic copper complex according to any one of claims 1 to 8 and a solvent. 10. The method of claim 9,
An organic copper complex solution comprising at least two organic copper complexes. 11. The method according to claim 9 or 10,
Wherein the concentration of said organic copper complex is 0.01 mol / l to 0.3 mol / l. 12. The method 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 heating a coating film of the organic copper complex solution according to any one of claims 9 to 12. 14. The method of claim 13,
Wherein the copper oxide thin film comprises at least copper. An organic copper complex solution coating film forming process for forming an organic copper complex solution coating film by applying the organic copper complex solution according to any one of claims 9 to 12 on a substrate,
A drying step of drying the organic copper complex solution coating film to obtain an organic copper complex film,
The organic copper complex film is heated at a temperature of 230 ° C or more and less than 300 ° C to form a copper oxide thin film,
Wherein the copper oxide thin film has a thickness of 10 nm or less. 16. The method of claim 15,
Wherein the heating treatment step heats the organic copper complex film in an atmosphere having an oxygen concentration of 0.5% by volume to 50% by volume. The compound represented by the following general formula (2) and constituting the organic copper complex according to any one of claims 1 to 8 by coordinating to a copper ion.
(2)

In the general formula 2, R ¹³ and R ²³ may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms, a non-aromatic hydrocarbon group having 2 to 20 carbon atoms having an unsaturated bond, an aryl group having 6 to 20 carbon atoms Or a heteroaryl group having 3 to 20 carbon atoms. 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, an aryl group having 6 to 20 carbon atoms, Or a hydroxyl group. The H in the CH bond of each of the groups represented by R ¹³ , R ²³ and R ³³ may be substituted with a monovalent substituent. Provided that 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 hydroxyl group.

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