JP2014160805A - Electronic device, solar cell, solar cell module, and composition for forming semiconductor layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electronic device, having excellent performance, using a substituted tetrabenzoporphyrin compound as a semiconductor material.SOLUTION: The electronic device includes a semiconductor layer containing a compound represented by a general formula (1) below.

Description

  The present invention relates to an electronic device, a solar cell, and a solar cell module using a tetrabenzoporphyrin compound in which one meso position is substituted with a specific organic group, and one meso position is replaced with a specific organic group. The present invention relates to a semiconductor layer forming composition containing a tetrabenzoporphyrin compound.

  Electronic devices using organic compounds as semiconductor materials are attracting attention as electronic devices of the next generation of electronic devices using silicon. As such an organic electronic device, an organic transistor, an organic solar cell, an organic electroluminescence element, and the like are known.

  Among them, Patent Document 1 and Non-Patent Document 1 describe examples in which a tetrabenzoporphyrin compound in which the meso position is not substituted is used as a semiconductor material when manufacturing a field effect transistor element and a photoelectric conversion element. An electronic device using a tetrabenzoporphyrin compound has advantages such as high solvent resistance. However, in order to improve the performance of organic electronic devices so as to achieve higher mobility in field effect transistor elements or to improve photoelectric conversion efficiency by increasing current values in organic solar cells, semiconductor materials Further improvement of the semiconductor properties of the tetrabenzoporphyrin compound used as a material is demanded. In this regard, the semiconductor characteristics of the tetrabenzoporphyrin compounds described in Patent Document 1 and Non-Patent Document 1 were not sufficient.

  Patent Document 2 proposes to use a tetrabenzoporphyrin compound in which two meso positions are substituted with an organic group as a semiconductor material.

  On the other hand, Patent Document 3 and Non-Patent Document 2 disclose a method for producing a tetrabenzoporphyrin compound in which one meso position is substituted with an organic group. Specifically, Patent Document 3 describes a method for coupling a pyrrole derivative using a specific aldehyde compound, and Non-Patent Document 2 describes a method for allowing an organolithium reagent to act on tetrabenzoporphyrin or a precursor thereof. Although there is room for improvement, each is disclosed.

Appl. Phys. Lett., 2004, 84, No. 12, 2085-2087. Heterocycles, 2005, 65, No. 4, 879-886.

JP 2008-135622 A JP 2011-061095 A Japanese Patent Laying-Open No. 2005-068042

  According to the study by the present inventors, in the tetrabenzoporphyrin compound described in Patent Document 2 in which two meso positions are substituted with an organic group, the energy of the compound is introduced by introducing the substituent into the meso position. The effect of adjusting the level and the effect of shifting the light absorption band were observed. However, there is a problem that the crystallinity of the compound is lowered, and further improvement has been demanded in order to realize higher mobility.

  On the other hand, the properties of tetrabenzoporphyrin compounds described in Patent Document 3 and Non-Patent Document 2 in which one meso position is substituted with an organic group have not been well known. For example, Patent Document 3 only suggests that a porphyrin compound in which the meso position is substituted with an alkyl group may be used as a material for a monomolecular film or a surfactant. Is not disclosed.

  An object of the present invention is to provide an electronic device having excellent characteristics using a substituted tetrabenzoporphyrin compound as a semiconductor material.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have introduced a specific substituent at one meso position of a tetrabenzoporphyrin compound, and an electronic device using the obtained compound as a semiconductor material As a result, the present invention was achieved.

（上式において、Ｘは２価の連結基又は直接結合を表し、Ａｌｋｙｌは炭素数２以上２０以下のアルキル基を表し、Ｍは２個の水素原子、２価の金属原子、又は金属原子を含む２価の原子団を表し、Ｒ^１１〜Ｒ^１４、Ｒ^２１〜Ｒ^２４、Ｒ^３１〜Ｒ^３４、及びＲ^４１〜Ｒ^４４は、それぞれ独立に水素原子又は１価の置換基を表す。）
また、前記一般式（１）におけるＸがアリーレン基であることが好ましい。
また、前記アリーレン基がフェニレン基であることが好ましい。
また、前記一般式（１）におけるＡｌｋｙｌが炭素数２以上１２以下のアルキル基であることが好ましい。
また、前記半導体層が、下記一般式（２）で表される化合物を含有する層を形成する工程と、前記一般式（２）で表される化合物を前記一般式（１）で表される化合物へと変換する工程と、を含む方法により形成されることが好ましい。

（上式において、Ｘは２価の連結基又は直接結合を表し、Ａｌｋｙｌは炭素数２以上２０以下のアルキル基を表し、Ｍは２個の水素原子、２価の金属原子、又は金属原子を含む２価の原子団を表し、Ｑ^１は−ＣＲ^１５Ｒ^１６−ＣＲ^１７Ｒ^１８−で表される２価の基を表し、Ｑ^２は−ＣＲ^２５Ｒ^２６−ＣＲ^２７Ｒ^２８−で表される２価の基を表し、Ｑ^３は−ＣＲ^３５Ｒ^３６−ＣＲ^３７Ｒ^３８−で表される２価の基を表し、Ｑ^４は−ＣＲ^４５Ｒ^４６−ＣＲ^４７Ｒ^４８−で表される２価の基を表し、Ｒ^１１〜Ｒ^１８、Ｒ^２１〜Ｒ^２８、Ｒ^３１〜Ｒ^３８、及びＲ^４１〜Ｒ^４８は、それぞれ独立に水素原子又は１価の置換基を表す。）
また、前記電子デバイスが、電界効果トランジスタ素子であることが好ましい。
また、前記電子デバイスが、光電変換素子であることが好ましい。
また、本発明に係る太陽電池は、前記光電変換素子を備える。
また、本発明に係る太陽電池モジュールは、前記太陽電池を備える。
また、本発明に係る半導体層形成用組成物は、上記一般式（２）で表される化合物と溶媒とを含有することを特徴とする。 That is, the electronic device according to the present invention includes a semiconductor layer containing a compound represented by the following general formula (1).

(In the above formula, X represents a divalent linking group or a direct bond, Alkyl represents an alkyl group having 2 to 20 carbon atoms, M represents two hydrogen atoms, a divalent metal atom, or a metal atom. And a divalent atomic group including R ^{11 to} R ¹⁴ , R ^{21 to} R ²⁴ , R ^{31 to} R ³⁴ , and R ^{41 to} R ⁴⁴ each independently represents a hydrogen atom or a monovalent substituent.)
Moreover, it is preferable that X in the said General formula (1) is an arylene group.
The arylene group is preferably a phenylene group.
Moreover, it is preferable that Alkyl in the said General formula (1) is a C2-C12 alkyl group.
Further, the semiconductor layer includes a step of forming a layer containing a compound represented by the following general formula (2), and the compound represented by the general formula (2) is represented by the general formula (1). It is preferable to form by the method including the process of converting into a compound.

(In the above formula, X represents a divalent linking group or a direct bond, Alkyl represents an alkyl group having 2 to 20 carbon atoms, M represents two hydrogen atoms, a divalent metal atom, or a metal atom. Q ¹ represents a divalent group represented by —CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ —, and Q ² represents —CR ²⁵ R ²⁶ —CR ²⁷ R ²⁸ —. is the divalent radical, ^{Q 3} is ^{-CR 35 R 36 -CR 37 R 38} - represents a divalent group represented by, ^{Q 4} is ^{-CR 45 R 46 -CR 47 R 48} - Table R ^{11 to} R ¹⁸ , R ^{21 to} R ²⁸ , R ^{31 to} R ³⁸ , and R ^{41 to} R ⁴⁸ each independently represent a hydrogen atom or a monovalent substituent.
The electronic device is preferably a field effect transistor element.
Moreover, it is preferable that the said electronic device is a photoelectric conversion element.
Moreover, the solar cell which concerns on this invention is equipped with the said photoelectric conversion element.
The solar cell module according to the present invention includes the solar cell.
Moreover, the composition for semiconductor layer formation concerning this invention contains the compound and solvent which are represented by the said General formula (2), It is characterized by the above-mentioned.

  An electronic device having excellent characteristics using a substituted tetrabenzoporphyrin compound as a semiconductor material can be provided.

It is sectional drawing which represents typically the structure of the photoelectric conversion element as one Embodiment of this invention. It is sectional drawing which represents typically the structure of the solar cell as one Embodiment of this invention. It is sectional drawing which represents typically the structure of the solar cell module as one Embodiment of this invention. It is sectional drawing which represents typically the structure of the field effect transistor element as one Embodiment of this invention. It is a thin film X-ray diffraction (XRD) (out of plane method) spectrum of the semiconductor film of each tetrabenzoporphyrin compound (Examples 1-1 to 1-6). The thin film X-ray diffraction (XRD) (out of plane method) spectrum of FIG. 5 is expanded in the range of 2 ° to 10 ° in the horizontal axis (2θ) direction. It is a thin film X-ray diffraction (XRD) (out of plane method) spectrum of the semiconductor film of each tetrabenzoporphyrin compound (Comparative Examples 1-1 to 1-7). It is a thin film X-ray diffraction (XRD) (out of plane method) spectrum of the semiconductor film of each tetrabenzoporphyrin compound (Example 1-7 and Comparative Examples 1-8 and 1-9). Thin film X-ray diffraction (XRD) of each tetrabenzoporphyrin compound (Examples 1-1, 1-3 to 1-5, and Comparative Examples 1-1, 1-2, 1-7) (in plane method) ) Spectrum. It is a thin film X-ray diffraction (XRD) (in plane method) spectrum of the semiconductor film of each tetrabenzoporphyrin compound (Example 1-7 and Comparative Examples 1-8 and 1-9). It is a thin film X-ray diffraction (XRD) (in plane method) spectrum of the semiconductor film of a tetrabenzoporphyrin compound (Example 1-7).

  Hereinafter, embodiments of the present invention will be described in detail. The description of the configuration described below is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to these contents as long as it does not exceed the gist thereof.

<1.1 Monosubstituted Tetrabenzoporphyrin Compound According to the Present Invention>
Hereinafter, the compound represented by the general formula (1) that can be used as a semiconductor material of the electronic device according to the present invention will be described. The compound represented by the general formula (1) is a tetrabenzoporphyrin compound in which one meso position is substituted with a specific organic group (hereinafter referred to as a mono-substituted tetrabenzoporphyrin compound according to the present invention).

(About X)
In the formula (1), X represents a divalent linking group or a direct bond. The linking group is not particularly limited, but is preferably an atom selected from Group 16 elements or a divalent organic group.

  In this specification, the group 16 element refers to a group 16 element shown in the periodic table of the IUPAC 2005 recommended version (Recommendations of IUPAC 2005). Specific examples of atoms selected from Group 16 elements include oxygen atoms, sulfur atoms, and selenium atoms. Among these, an oxygen atom or a sulfur atom is preferable in that the compound easily takes a crystal structure due to hydrogen bonding.

  The divalent organic group is not particularly limited and may be linear or branched. Further, it may be a chain or may have a ring. Furthermore, the divalent organic group may have a saturated bond, a double bond, and a triple bond.

  Specific examples of the divalent organic group include an arylene group, an aryleneoxy group, an alkenylene group, and an alkyleneoxy group.

  Examples of the arylene group include a divalent aromatic hydrocarbon group and a divalent aromatic heterocyclic group. The arylene group may be substituted with an alkyl group or an alkoxy group, and the alkyl group or alkoxy group that substitutes the arylene group preferably has 1 or more and 2 or less carbon atoms.

  Specific examples of such a divalent aromatic hydrocarbon group include a phenylene group, a biphenylene group, a methylphenylene group, an ethylphenylene group, a methoxyphenylene group, an ethoxyphenylene group, an azulylene group, and a naphthylene group (preferably 2,7 -Naphthylene group), anthrylene group (preferably 2,7-anthrylene group), fluorenylene group, naphthacenylene group, phenanthrylene group, etc., and may be substituted with an alkyl group or an alkoxy group having 6 to 14 carbon atoms. An aromatic hydrocarbon group is mentioned.

  Specific examples of such a divalent aromatic heterocyclic group include a thienylene group, a bithienylene group, a cyclopentadithiophenylene group, a pyridylene group, an oxazolene group, a thiazolene group, a benzothiadiazolene group, a benzothienylene group, Examples thereof include a dibenzothienylene group, a furylene group, a pyrazylene group, a pyrimidylene group, a pyrazoylene group, an imidazolylene group, and a phenylcarbazoylene group.

  The aryleneoxy group is a divalent organic group in which an oxygen atom is bonded to the above-described arylene group, and more specifically, a divalent organic group represented by -Ar-O- (wherein Ar is Represents an arylene group). From the viewpoint of improving the semiconductor properties of the compound due to conjugation, it is more preferable that Ar is bonded to the porphyrin ring and the oxygen atom (O) is bonded to Alkyl.

Examples of the alkenylene group include a vinylene group (—CH═CH—) and a propenylene group (—CH ₂ —CH═CH—).

Examples of the alkyleneoxy group include a methyleneoxy group (—CH ₂ O—) or an ethyleneoxy group (—CH ₂ CH ₂ O—).

Moreover, these substituents may be substituted by a monovalent substituent described later as an example of R ^{11 to} R ⁴⁴ .

  Among the above, X is preferably a direct bond, an oxygen atom, a sulfur atom, an arylene group, or an aryleneoxy group. Of these, a direct bond, an arylene group, or an aryleneoxy group is more preferable, and an arylene group or an aryleneoxy group is more preferable in order to improve the film formability of the film.

  Among the arylene groups, a phenylene group is more preferable, and a 1,4-phenylene group or a 1,3-phenylene group is particularly preferable. Among the aryleneoxy groups, a divalent organic group in which an oxygen atom is bonded to a phenylene group, preferably a 1,4-phenylene group or a 1,3-phenylene group is preferable. The reason why these groups are preferable is that the phenylene group is a small 6-membered ring arylene group, and since the parent tetrabenzoporphyrin compound is a π-fused compound, good film formability and electrical characteristics This is because it is expected to be obtained.

(About Alkyl)
In the formula (1), Alkyl represents an alkyl group having 2 to 20 carbon atoms. It is preferable that the number of carbon atoms of Alkyl is 20 or less because the heat resistance of the semiconductor layer containing the compound can be improved. Moreover, it is preferable that the number of carbon atoms of Alkyl is 2 or more because good semiconductor characteristics tend to be obtained. For this reason, Alkyl having 2 to 20 carbon atoms is extremely important for obtaining a good semiconductor layer.

  Further, the number of carbon atoms of Alkyl is more preferably 2 or more and 16 or less, and particularly preferably 2 or more and 12 or less. This is because, when the number of carbon atoms is within this range, a heat-resistant and well-packed crystal structure is expected to be formed, and thus high semiconductor characteristics are expected.

  The shape of the alkyl group is not particularly limited, and may be a linear, branched or cyclic alkyl group. However, in order to improve semiconductor characteristics, it is particularly preferable that it is linear.

  The alkyl group may have a monovalent substituent described later. Among them, the alkyl group preferably has a halogen atom as a substituent, and particularly preferably has a fluorine atom as a substituent, in that it is less likely to cause steric hindrance and the HOMO level of the compound may be lowered. .

(About M)
In Formula (1), M represents a divalent atomic group containing two hydrogen atoms, a divalent metal atom, or a metal atom. In the formula (1), the broken line connecting M and the nitrogen atom (N) indicates that the nitrogen atom may be coordinated to M, but the bond between the nitrogen atom and M may not exist. For example, when M is a divalent metal atom, the nitrogen atom is usually coordinated to M. That is, in this case, the broken line indicates a coordination bond. On the other hand, when M is two hydrogen atoms, M is not bonded to a hydrogen atom. That is, in this case, the broken line indicates the absence of coupling.

  Specific examples of the divalent metal atom include copper, zinc, magnesium, palladium (II), nickel (II), cobalt (II), lead (II), iron (II), silver (II), platinum (II ) And the like. Especially, copper or zinc is preferable at the point from which a favorable semiconductor characteristic is easy to be obtained.

A divalent atomic group containing a metal atom is an atomic group that is divalent as a whole by combining a metal atom having a valence greater than divalent, such as trivalent or tetravalent, and an atom or atomic group. means. Specific examples of the divalent atomic group containing a metal atom include TiO, VO, SiO, AlZ, GaZ, InZ, TiZ ₂ , Sn (IV) Z ₂ , SiZ ₂ , Fe (III) Z, and the like ( Z represents a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, a hydroxyl group, or a ligand).

上式において、Ｍ^１は２価より大きい価数を持つ金属原子を、Ｒ^ａはアルキル基を、Ｒ^ｂは水素原子又はアルキル基を、それぞれ表す。 Examples of the divalent atomic group to which the ligand is bonded include those shown below, but are not particularly limited.

In the above formula, M ¹ represents a metal atom having a valence greater than divalent, R ^a represents an alkyl group, and R ^b represents a hydrogen atom or an alkyl group.

(About R ^{11 to} R ⁴⁴ )
In formula (1), R ^{11 to} R ¹⁴ , R ^{21 to} R ²⁴ , R ^{31 to} R ³⁴ , and R ^{41 to} R ⁴⁴ each independently represent a hydrogen atom or a monovalent substituent.

  Examples of the monovalent substituent include a halogen atom or a monovalent organic group.

  Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Among these, a fluorine atom that is sterically small and is considered to lower the HOMO energy level of the compound by electron withdrawing property is preferable.

  The monovalent organic group is not particularly limited and may be a linear organic group or a branched organic group. Further, the monovalent organic group may be a chain or may have a ring. Furthermore, the monovalent organic group may have a saturated bond, a double bond, and a triple bond.

  The monovalent organic group includes amino group, hydroxyl group, nitro group, cyano group, carboxyl group, acyl group, oxycarbonyl group, silyl group, boryl group, aromatic hydrocarbon group, aromatic heterocyclic group, aryloxy group, It is preferably selected from the group consisting of an alkyl group, a perfluoroalkyl group, an alkenyl group, an alkynyl group, and an alkoxy group.

  The amino group preferably has 2 to 20 carbon atoms, and examples thereof include an alkylamino group and an arylamino group. Specific examples include aromatic substituted amino groups such as a diphenylamino group or a ditolylamino group.

  The acyl group preferably has 2 to 16 carbon atoms, and specific examples include formyl group, acetyl group, benzoyl group and the like.

  As the oxycarbonyl group, those having 2 to 10 carbon atoms are preferable, and specific examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.

  As the silyl group, those having 2 to 20 carbon atoms are preferable, and specific examples include a trimethylsilyl group and a triphenylsilyl group.

  As the boryl group, those having 2 to 20 carbon atoms are preferable, and specific examples thereof include aromatic substituted boryl groups such as a dimesitylboryl group.

  As the aromatic hydrocarbon group, those having 6 to 20 carbon atoms are preferable. The aromatic hydrocarbon group is not limited to a monocyclic group, and may be a condensed polycyclic hydrocarbon group or a ring-linked hydrocarbon group. Specific examples include monocyclic groups such as phenyl groups, condensed polycyclic hydrocarbon groups such as phenanthryl groups, naphthyl groups, anthryl groups, fluorenyl groups, pyrenyl groups, perylenyl groups; or biphenyl groups, terphenyl groups, etc. Examples thereof include a ring-linked hydrocarbon group. The aromatic hydrocarbon group is preferably a phenyl group, a naphthyl group, a pyrenyl group, or a perylenyl group.

  As the aromatic heterocyclic group, those having 4 to 30 carbon atoms are preferred, and specific examples include pyridyl group, thienyl group, furyl group, oxazolyl group, thiazolyl group, oxadiazolyl group, benzothienyl group, dibenzofuryl group, Examples thereof include a dibenzothienyl group, a pyrazyl group, a pyrimidyl group, a pyrazolyl group, an imidazolyl group, and a phenylcarbazolyl group. Preferable examples of the aromatic heterocyclic group include pyridyl group, thienyl group, imidazolyl group, benzothienyl group, dibenzofuryl group, dibenzothienyl group, and phenanthryl group.

  In the present specification, an aromatic hydrocarbon group and an aromatic heterocyclic group are collectively referred to as an aryl group.

  As the aryloxy group, those having 6 to 16 carbon atoms are preferable, and specific examples thereof include a phenyloxy group.

  As the alkyl group, those having 1 to 20 carbon atoms are preferable. The alkyl group may be straight chain or branched. Further, it may be a chain or may have a ring. Specific examples of the alkyl group include a methyl group, an ethyl group, an i-propyl group, a t-butyl group, and a cyclohexyl group.

  A perfluoroalkyl group is an alkyl group having 2 or more, preferably 3 or more fluorine atoms. As the perfluoroalkyl group, those having 1 to 20 carbon atoms are preferable, and it is more preferable that all hydrogen atoms are substituted with fluorine atoms. Specific examples of the perfluoroalkyl group include a trifluoromethyl group.

  The alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, and specific examples thereof include a vinyl group. As will be described later, the alkenyl group may be substituted with a further substituent, and among them, the alkenyl group is preferably substituted with a phenyl group. Specific examples in this case include a styryl group or a diphenylvinyl group.

  As the alkynyl group, those having 2 to 20 carbon atoms are preferable, and specific examples include a methylethynyl group, a phenylethynyl group, or a trimethylsilylethynyl group.

  As the alkoxy group, those having 2 to 20 carbon atoms are preferable. The alkoxy group may be a straight chain or may have a branch. Further, it may be a chain or may have a ring. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group and the like.

  Moreover, these monovalent substituents may be substituted with one or more additional substituents. Examples of the further one or more substituents include the same monovalent substituents as described above.

Also, R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ²¹ and R ²² , R ²³ and R ²⁴ , R ³¹ and R ³² , R ³³ and R ³⁴ , R ⁴¹ and R ⁴² , or R ⁴³ and R ⁴⁴ May be bonded to each other to form a ring.

Among them, R ^{11 to} R ¹⁴ , R ^{21 to} R ²⁴ , R ^{31 to} R ³⁴ , and R ^{41 to} R ⁴⁴ are hydrogen atoms in that the monosubstituted tetrabenzoporphyrin compound according to the present invention easily takes a crystal structure. Preferably there is.

Non-limiting examples of monosubstituted tetrabenzoporphyrin compounds according to the present invention are listed below.

<1.2 Features of Monosubstituted Tetrabenzoporphyrin Compounds According to the Present Invention>
Most tetrabenzoporphyrin compounds are known to be p-type semiconductors. Further, in Japanese Patent Application Laid-Open No. 2011-061095, the effect of adjusting the energy level and the effect of shifting the light absorption band can be obtained by substituting two meso positions of the tetrabenzoporphyrin compound with an organic group. It has been reported. However, the field effect transistor device using the disubstituted tetrabenzoporphyrin compound thus obtained has a problem of low performance (hole mobility).

  On the other hand, it has been found that a semiconductor layer using a monosubstituted tetrabenzoporphyrin compound has a significant difference in semiconductor characteristics depending on a substituent introduced at a meso position. In particular, when a monosubstituted tetrabenzoporphyrin compound substituted with a specific substituent (—X-Alkyl) having an alkyl group having 2 to 20 carbon atoms was used, an unsubstituted tetrabenzoporphyrin compound was used. Higher semiconductor properties were observed than in the case. High semiconductor characteristics can improve the performance of electronic devices, such as high mobility when field effect transistor elements are manufactured, and high photoelectric conversion efficiency that increases current values when organic solar cells are manufactured. It is preferable to connect.

  This difference is due to the steric hindrance due to the substituent at the meso position, while the disubstituted tetrabenzoporphyrin compound has a lower crystallinity and it is difficult to obtain a good film, whereas when the monosubstituted tetrabenzoporphyrin compound is used, One reason is that a good film is likely to be obtained due to smaller steric hindrance.

  Further, even when a substituent having no alkyl group having 2 to 20 carbon atoms and having only an alkyl group having 1 carbon atom (methyl group) was introduced into the meso position, high semiconductor characteristics were not observed. .

  This is due to the influence of the alkyl group (methyl group) having 1 carbon atom and the influence of the alkyl group having 2 or more carbon atoms, which are known in the tetrathiafulvalene (TTF) compound known as a donor molecule of the organic conductor. Can be explained for the same reason. That is, a TTF compound modified with a methyl group has a crystal structure that is almost the same as an unmodified (zero carbon number) TTF compound. However, a compound modified with an alkyl group having 2 or more carbon atoms has a completely different crystal structure from an unmodified (zero carbon number) TTF compound due to the steric hindrance due to the alkyl group. As a result, some organic conductors containing a TTF compound having a methyl group exhibit superconductivity, while some organic conductors containing a TTF compound having an alkyl group having 2 or more carbon atoms are superconductive. There is nothing to show conduction ("Chemicals of organic conductors-semiconductors, metals, superconductors", Gunji Saito, Maruzen (2003)).

  As in the case of the TTF compound, the monosubstituted tetrabenzoporphyrin compound according to the present invention was substituted with a methyl group by introducing a specific organic group having an alkyl group having 2 to 20 carbon atoms into the meso position. It is considered that a crystal structure different from that of the monosubstituted tetrabenzoporphyrin compound can be obtained.

  The crystal structure can be analyzed by a thin film X-ray diffraction (XRD) method in addition to the single crystal X-ray structure analysis method. In the film of the monosubstituted tetrabenzoporphyrin compound substituted with a specific organic group having an alkyl group having 2 to 20 carbon atoms according to the present invention, out using RINT2000 (50 kV, 250 mA (CuKα)) manufactured by Rigaku Corporation. In the measurement by the of plane method, it has a strong peak between 2θ = 2-4 °. Moreover, it has four or more peaks with periodicity in 2 (theta) = 8-25 degrees by the measurement by an in plane method.

  Although the detailed crystal structure is unknown, a strong peak between 2θ = 2-4 ° (out of plane method) and four or more peaks having a periodicity between 2θ = 8-25 ° (in plane method) In the high semiconductor characteristics of the monosubstituted tetrabenzoporphyrin compound substituted with a specific organic group having an alkyl group having 2 to 20 carbon atoms according to the present invention, the crystal structure is observed. It is thought that it is connected.

  JP-A-2005-068042 describes that a porphyrin compound in which the meso position is substituted with a long-chain alkyl group is expected to be amphiphilic. However, according to the above results, in the monosubstituted tetrabenzoporphyrin compound according to the present invention, high semiconductor characteristics are exhibited because the alkyl group having 2 to 20 carbon atoms greatly affects the crystal structure of the compound. It is thought that it was done.

<1.3 Precursor of monosubstituted tetrabenzoporphyrin compound according to the present invention>
The monosubstituted tetrabenzoporphyrin compound according to the present invention can be obtained by a conversion reaction from the precursor. Hereinafter, the precursor of the monosubstituted tetrabenzoporphyrin compound according to the present invention will be described. This precursor is a compound that can be converted into the monosubstituted tetrabenzoporphyrin compound according to the present invention by performing a conversion reaction such as a heat conversion reaction. The structure of the precursor is not particularly limited as long as the monosubstituted tetrabenzoporphyrin compound according to the present invention can be obtained, but preferably has a bicyclo ring structure in terms of solubility, and is represented by the following formula (2). More preferably, it is a monosubstituted tetrabicycloporphyrin compound (hereinafter referred to as a monosubstituted tetrabicycloporphyrin compound according to the present invention).

In the formula (2), Alkyl, M, R ^{11 to} R ¹⁴ , R ^{21 to} R ²⁴ , R ^{31 to} R ³⁴ , and R ^{41 to} R ⁴⁴ are the same as those in the formula (1).

In the formula (2), Q ^{1 to} Q ⁴ are leaving groups. By detaching Q ^{1 to} Q ⁴ , the monosubstituted tetrabicycloporphyrin compound is converted into a monosubstituted tetrabenzoporphyrin compound.

More specifically, Q ¹ represents a divalent group represented by —CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ —, and Q ² represents 2 represented by —CR ²⁵ R ²⁶ —CR ²⁷ R ²⁸ —. Q ³ represents a divalent group represented by —CR ³⁵ R ³⁶ —CR ³⁷ R ³⁸ —, and Q ⁴ represents 2 represented by —CR ⁴⁵ R ⁴⁶ —CR ⁴⁷ R ⁴⁸ —. Represents a valent group.

R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , and R ⁴⁸ are Each independently represents a hydrogen atom or a monovalent substituent. Monovalent substituents may be the same as those listed for R ¹¹ .

^The molecular weight of Q 1 to Q ⁴ is preferably 28 to 200. When the molecular weight is within this range, when the monosubstituted tetrabicycloporphyrin compound is converted into the monosubstituted tetrabenzoporphyrin compound, the desorbed Q ^{1 to} Q ⁴ are easily removed out of the system. From this point of view, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , and R ⁴⁸ is more preferably each independently a methyl group or a hydrogen atom, and particularly preferably a hydrogen atom.

  Since the monosubstituted tetrabicycloporphyrin compound has a bulky bicyclo skeleton, the crystallinity is relatively low and the solubility is high. On the other hand, a monosubstituted tetrabicycloporphyrin compound can be converted into a monosubstituted tetrabenzoporphyrin compound having high planarity and higher crystallinity. For this reason, a solution containing a mono-substituted tetrabicycloporphyrin compound, which is a soluble precursor, is formed by coating, for example, and then converted into a mono-substituted tetrabenzoporphyrin compound by heating to convert the crystal into a mono-substituted tetrabenzoporphyrin compound. A layer containing a tetrabenzoporphyrin compound having good properties can be obtained.

<1.4 Production Method of Monosubstituted Tetrabicycloporphyrin Compound>
Below, some of the manufacturing methods of the monosubstituted tetrabicycloporphyrin compound concerning this invention are demonstrated. However, the production method of the monosubstituted tetrabicycloporphyrin compound according to the present invention is not limited to the following method.

<1.4.1 Production Method Using Monosubstituted Tetrabicyclo Compound Substituted with Bromo Group>
First, a compound represented by the following general formula (4) is produced. The compound represented by the general formula (4) can be produced by bromination reaction of the compound represented by the general formula (3). For example, the compound represented by the general formula (4) can be produced by reacting the compound represented by the general formula (3) with a bromination reagent. As an example of a bromination reagent, N-bromosuccinimide (NBS) is mentioned, for example. The compound represented by the general formula (3) can be produced by coupling a pyrrole derivative, for example, as described in JP-A No. 2003-304014. In Formula (3) and Formula (4), M, R ^{11 to} R ¹⁴ , R ^{21 to} R ²⁴ , R ^{31 to} R ^34, R ^{41 to} R ⁴⁴ , and Q ^{1 to} Q ⁴ are respectively represented by Formula (2). ).

  Next, the monosubstituted tetrabicycloporphyrin compound (2) according to the present invention is produced by cross-coupling the compound represented by the general formula (4) and the compound represented by Alkyl-XY. be able to. Here, Alkyl and X are the same as those in the formula (1). Y is a functional group capable of proceeding with a cross-coupling reaction, such as a halogen atom or a boronic acid group. Examples of the cross-coupling reaction catalyst include a palladium catalyst. More specifically, reaction conditions for Suzuki-Miyaura cross-coupling reaction or reaction conditions for Buchwald-Hartwig reaction may be used.

<1.4.2 Production Method Using Aldehyde Compound>
Similar to the production method described in JP-A-2005-068042, a pyrrole derivative is used in the presence of an aldehyde compound having a substituent Alkyl-X- or an alcohol compound that can be converted into an aldehyde compound by oxidation in the system. By coupling, the monosubstituted tetrabicycloporphyrin compound according to the present invention can also be produced.

<1.4.3 Production Method Using Nucleophile>
Similar to the production method described in Heterocycles, 2005, 65, No. 4, 879-886., A compound represented by the above general formula (3) and a nucleophilic reagent having a substituent Alkyl-X— ( For example, the monosubstituted tetrabicycloporphyrin compound according to the present invention can be produced by reacting with an organic lithium reagent or the like.

  Among the above production methods, a production method using a monosubstituted tetrabicycloporphyrin compound (4) substituted with a bromo group is preferable because separation and purification from by-products are simple. This is because the compound represented by the general formula (4) can be relatively separated and produced, so that the desired monosubstituted tetrabicycloporphyrin compound (2) can be selectively obtained with high yield. .

<1.5 Method for producing monosubstituted tetrabenzoporphyrin compound>
As described above, the monosubstituted tetrabenzoporphyrin compound according to the present invention is obtained by a conversion reaction of the monosubstituted tetrabicycloporphyrin compound according to the present invention which is a precursor. Specifically, by heating the monosubstituted tetrabicycloporphyrin compound (2), the reverse Diels-Alder reaction proceeds to obtain the monosubstituted tetrabenzoporphyrin compound (1).

  The heating temperature is not particularly limited as long as the conversion reaction proceeds, but is usually 100 ° C or higher, preferably 130 ° C or higher, more preferably 150 ° C or higher. On the other hand, it is usually 400 ° C. or lower, preferably 300 ° C. or lower, more preferably 250 ° C. or lower. When the temperature is low, it is preferable to perform the reaction for a longer time. It is desirable to perform the reaction at 150 ° C. for 3 hours or longer, at 180 ° C. for 10 minutes or longer, and at 200 ° C. for 5 minutes or longer. By performing the reaction for a longer time at a higher temperature, the conversion yield can be increased. On the other hand, when the conversion reaction is performed after the monosubstituted tetrabicycloporphyrin compound (2) is applied to the substrate, the influence of heating on the substrate can be reduced by performing the reaction at a lower temperature for a shorter time. .

  In addition, when performing the conversion reaction, in addition to heating by heat transfer using a heater, light of a wavelength absorbed by a carbon dioxide laser, an infrared lamp, or the monosubstituted tetrabicycloporphyrin compound (2) may be irradiated. . At this time, it is also possible to heat the monosubstituted tetrabicycloporphyrin compound (2) by providing a layer that absorbs light in the vicinity of the monosubstituted tetrabicycloporphyrin compound (2) and absorbing the light in this layer. .

  The reaction atmosphere in the heating reaction is not particularly defined, but an inert gas such as nitrogen or argon, or a vacuum is preferable in terms of preventing oxidation by oxygen atoms in the atmosphere.

<1.6 Method for Producing Metal Complex of Monosubstituted Tetrabenzoporphyrin Compound>
In the monosubstituted tetrabenzoporphyrin compound (1) or monosubstituted tetrabicycloporphyrin compound (2) in which M is a divalent metal atom or a divalent atomic group containing a metal atom, M is two hydrogen atoms. The monosubstituted tetrabenzoporphyrin compound (1) or the monosubstituted tetrabicycloporphyrin compound (2) can be produced by a known complex formation reaction.

  Below, the manufacturing method of the monosubstituted tetrabenzoporphyrin compound (1) in case M is zinc (Zn) is demonstrated as a representative example. A monosubstituted tetrabicycloporphyrin compound represented by the following general formula (5) produced by the above-described method in an appropriate solvent such as a mixed solvent of chloroform and methanol, and an acetate such as zinc acetate dihydrate Can be reacted to produce a zinc complex of a monosubstituted tetrabicycloporphyrin compound represented by the following general formula (6).

  And the zinc complex of a monosubstituted tetrabenzoporphyrin compound can be manufactured by performing the heat conversion reaction of the zinc complex (6) of the obtained monosubstituted tetrabicycloporphyrin compound as mentioned above.

When M is other than zinc, there is no particular limitation. For example, M is a divalent metal atom such as copper, lead, magnesium, palladium, nickel, cobalt, lead, silver, platinum, or TiO, VO, Even in the case of a divalent atomic group containing a metal atom such as SiO, SnCl ₂ , AlCl, InCl, or FeCl, a metal complex of a monosubstituted tetrabenzoporphyrin compound can be produced in the same manner.

<2. Composition for forming semiconductor layer>
When forming the semiconductor layer containing the monosubstituted tetrabenzoporphyrin compound according to the present invention, the semiconductor layer can be formed by directly applying a composition containing the monosubstituted tetrabenzoporphyrin compound. On the other hand, the semiconductor layer containing the monosubstituted tetrabenzoporphyrin compound according to the present invention can be formed by using the composition containing the monosubstituted tetrabicycloporphyrin compound according to the present invention. Specifically, the composition containing the monosubstituted tetrabicycloporphyrin compound according to the present invention is applied, and the monosubstituted tetrabicycloporphyrin compound according to the present invention is converted into the monosubstituted tetrabenzoporphyrin compound according to the present invention by a thermal conversion reaction. Thus, a semiconductor layer containing the monosubstituted tetrabenzoporphyrin compound according to the present invention can be formed.

  In addition, among the above, it is preferable to form the semiconductor layer using the composition containing the monosubstituted tetrabicycloporphyrin compound according to the present invention. Since the tetrabenzoporphyrin compound has relatively high planarity, it often has high crystallinity and low solubility. On the other hand, a tetrabicycloporphyrin compound has a sterically bulky bicyclo structure, and thus often has low crystallinity and good solubility. Therefore, application of a composition having a tetrabicycloporphyrin compound is often easy, and a film having low crystallinity or an amorphous film is often obtained by application. For this reason, by using the composition containing the monosubstituted tetrabicycloporphyrin compound according to the present invention, it is easier to use the composition according to the present invention than when using the composition containing the monosubstituted tetrabenzoporphyrin compound according to the present invention. It is expected that a semiconductor layer containing a monosubstituted tetrabenzoporphyrin compound can be formed.

  Hereinafter, a composition for forming a semiconductor layer for forming a semiconductor layer containing a monosubstituted tetrabenzoporphyrin compound according to the present invention (hereinafter referred to as a composition for forming a semiconductor layer according to the present invention) will be described. The composition for forming a semiconductor layer according to the present invention contains the monosubstituted tetrabenzoporphyrin compound according to the present invention or the monosubstituted tetrabicycloporphyrin compound according to the present invention and a solvent. As described above, the composition for forming a semiconductor layer according to the present invention preferably contains the monosubstituted tetrabicycloporphyrin compound according to the present invention and a solvent. The monosubstituted tetrabenzoporphyrin compound according to the present invention or the monosubstituted tetrabicycloporphyrin compound according to the present invention contained in the composition for forming a semiconductor layer according to the present invention can be produced according to the above method.

  As the solvent contained in the composition for forming a semiconductor layer according to the present invention, as long as it can uniformly dissolve or disperse the monosubstituted tetrabenzoporphyrin compound according to the present invention or the monosubstituted tetrabicycloporphyrin compound according to the present invention, There is no particular limitation. Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane, decane, etc .; aromatic hydrocarbons such as toluene, xylene, chlorobenzene, orthodichlorobenzene; lower grades such as methanol, ethanol, propanol, etc. Alcohols; ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; esters such as ethyl acetate, butyl acetate and methyl lactate; halogen hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane and trichloroethylene; diethyl ether; Examples include ethers such as tetrahydrofuran and 1,4-dioxane; and amides such as dimethylformamide and dimethylacetamide.

  Among them, preferably, aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane, decane; aromatic hydrocarbons such as toluene, xylene, chlorobenzene, orthodichlorobenzene; preferably methanol, ethanol, propanol, etc. Is a lower alcohol having 6 or less carbon atoms; ketones such as acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, and methyl lactate; halogens such as chloroform, methylene chloride, dichloroethane, trichloroethane, and trichloroethylene Hydrocarbons; or ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane.

  Particularly preferably, aromatic hydrocarbons such as toluene, xylene, chlorobenzene and orthodichlorobenzene; ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; halogen hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane and trichloroethylene Or ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane.

  As a solvent, 1 type may be used independently and 2 or more types may be used together by arbitrary combinations and a ratio.

  The composition for forming a semiconductor layer according to the present invention may contain two or more kinds of at least one of the monosubstituted tetrabenzoporphyrin compound according to the present invention and the monosubstituted tetrabicycloporphyrin compound according to the present invention. For example, the composition for forming a semiconductor layer according to the present invention may contain a monosubstituted tetrabenzoporphyrin compound according to the present invention or an isomer mixture of the monosubstituted tetrabicycloporphyrin compound according to the present invention. The composition for forming a semiconductor layer according to the present invention contains the monosubstituted tetrabenzoporphyrin compound according to the present invention or the isomer mixture of the monosubstituted tetrabicycloporphyrin compound according to the present invention. It is preferable because the property can be increased. Although the detailed mechanism is not clear, it is considered that the intermolecular interaction between isomers is usually weaker than the intermolecular interaction between the same molecules, which is one of the reasons why the storage stability is improved. That is, when a plurality of isomers coexist in the solution, it is difficult to arrange the molecules regularly, so that it is assumed that precipitation of solid components due to crystallization or the like hardly occurs. For this reason, the mono-substituted tetrabenzoporphyrin compound according to the present invention or the mono-substituted tetrabicycloporphyrin compound according to the present invention contained in the composition for forming a semiconductor layer according to the present invention may have more isomers. It is preferable to have a structure.

  The amount of the monosubstituted tetrabenzoporphyrin compound according to the present invention or the monosubstituted tetrabicycloporphyrin compound according to the present invention contained in the composition for forming a semiconductor layer according to the present invention is not particularly limited, but is usually 0.01% by mass. As mentioned above, Preferably it is 0.1 mass% or more, and is 10 mass% or less normally, Preferably it is 1 mass% or less. When the content is in this range, film formation becomes easier and the storage stability of the composition tends to be improved.

  The composition for forming a semiconductor layer according to the present invention may further contain a substance other than the monosubstituted tetrabenzoporphyrin compound according to the present invention, the monosubstituted tetrabicycloporphyrin compound according to the present invention, and the solvent. For example, the composition for forming a semiconductor layer according to the present invention may contain an n-type semiconductor material in addition to the monosubstituted tetrabenzoporphyrin compound according to the present invention or the monosubstituted tetrabicycloporphyrin compound according to the present invention. The n-type semiconductor material is not particularly limited and may be, for example, a fullerene compound.

  The composition for forming a semiconductor layer according to the present invention may have good storage stability in a solution state. When the composition is allowed to stand at 25 ° C. after preparation, it is usually after 1 day, preferably after 2 days, more preferably after 7 days, and particularly preferably after 20 days. This means that no solid precipitates. In particular, the monosubstituted tetrabicycloporphyrin compound according to the present invention is considered to have a weaker intermolecular interaction than the monosubstituted tetrabenzoporphyrin compound according to the present invention. Therefore, the composition for forming a semiconductor layer containing the monosubstituted tetrabicycloporphyrin compound according to the present invention is considered to have higher storage stability than the composition containing the monosubstituted tetrabenzoporphyrin compound according to the present invention.

  Formation of the semiconductor layer of an electronic device using the composition for forming a semiconductor layer according to the present invention can be performed, for example, as follows. That is, a semiconductor layer can be formed by a method including a step of coating and forming the semiconductor layer forming composition according to the present invention on a substrate. When the composition for forming a semiconductor layer containing the monosubstituted tetrabicycloporphyrin compound according to the present invention is used, a layer of the composition for forming a semiconductor layer is formed by applying the composition for forming a semiconductor layer on a substrate. Then, a semiconductor layer containing the monosubstituted tetrabenzoporphyrin compound according to the present invention can be formed by performing a heat conversion reaction.

<3. Electronic device>
Next, an electronic device using the monosubstituted tetrabenzoporphyrin compound according to the present invention (hereinafter referred to as an electronic device according to the present invention) will be described. The electronic device according to the present invention includes the monosubstituted tetrabenzoporphyrin compound according to the present invention as a semiconductor material, and more specifically includes a semiconductor layer containing the monosubstituted tetrabenzoporphyrin compound according to the present invention.

  In this specification, an electronic device is a device that has two or more electrodes, the current flowing between the electrodes and the generated voltage are controlled by electricity, light, magnetism, or a chemical substance, or the applied voltage or current. This is a device that generates light, electric field, and magnetic field. For example, there are an element that controls current and voltage by applying voltage and current, an element that controls voltage and current by applying a magnetic field, and an element that controls voltage and current by applying a chemical substance. Examples of this control include rectification, switching, amplification, and oscillation.

  Examples of the electronic device include a resistor, a rectifier (diode), a switching element (transistor, thyristor), an amplifying element (transistor), a memory element, a chemical sensor, etc., or a device in which these elements are combined and integrated. Further, a photoelectric conversion element or a solar cell that generates an electromotive force by light, or an optical element such as a photodiode or a phototransistor that generates a photocurrent can be used.

  More specific examples of electronic devices are described in S.A. M.M. Examples include those described in Sze, Physics of Semiconductor Devices, 2nd Edition (Wiley Interscience 1981).

  The monosubstituted tetrabenzoporphyrin compound according to the present invention can be used as an organic semiconductor material in these electronic devices. That is, the layer containing the monosubstituted tetrabenzoporphyrin compound according to the present invention can be used as a semiconductor layer of an electronic device.

  Especially, it is preferable that the semiconductor layer containing the monosubstituted tetrabenzoporphyrin compound which concerns on this invention is used in a field effect transistor element, a photoelectric conversion element, a solar cell, or an electroluminescent element.

  The semiconductor layer containing the monosubstituted tetrabenzoporphyrin compound according to the present invention provided in the electronic device may further contain an organic semiconductor material other than the monosubstituted tetrabenzoporphyrin compound according to the present invention.

  However, the monosubstituted tetrabenzoporphyrin compound according to the present invention may be used in applications other than organic semiconductors in electronic devices. For example, a monosubstituted tetrabenzoporphyrin compound film according to the present invention can be formed at a desired position of an electronic device, and this film can be used as a wiring or as an insulating layer in a capacitor or FET. In this case, the conductivity of the mono-substituted tetrabenzoporphyrin compound film according to the present invention can be controlled by controlling the molecular structure or doping.

In this specification, “semiconductor” is defined by the magnitude of carrier mobility in a solid state. As is well known, the carrier mobility indicates how fast (or many) charges (holes or electrons) move. Specifically, the “semiconductor” in this specification has a carrier mobility at room temperature of 1.0 × 10 ⁻⁷ cm ² / V · s or more, preferably 1.0 × 10 ⁻⁶ cm ² / V · s or more, more preferably Is 1.0 × 10 ⁻⁵ cm ² / V · s or more. The carrier mobility can be measured by, for example, IV characteristic measurement of a field effect transistor element or time-of-flight method.

The semiconductor layer containing the monosubstituted tetrabenzoporphyrin compound according to the present invention has a carrier mobility at room temperature of 1.0 × 10 ⁻⁷ cm ² / V · s or more, preferably 1.0 × 10 ⁻⁶ cm ² / V · s or more. More preferably, it is 1.0 × 10 ⁻⁵ cm ² / V · s or more.

  An electronic device including a semiconductor layer containing a monosubstituted tetrabenzoporphyrin compound according to the present invention is produced by a method including a step of applying the semiconductor layer forming composition according to the present invention on a substrate as described above, for example. can do. Specifically, first, a layer containing a monosubstituted tetrabicycloporphyrin compound according to the present invention is formed by applying a composition for forming a semiconductor layer containing the monosubstituted tetrabicycloporphyrin compound according to the present invention on a substrate. Form. Next, the monosubstituted tetrabicycloporphyrin compound according to the present invention is converted into the monosubstituted tetrabenzoporphyrin compound according to the present invention. In this manner, a semiconductor layer containing the monosubstituted tetrabenzoporphyrin compound according to the present invention can be formed. Here, the substrate on which the composition for forming a semiconductor layer is applied may have other layers or other structures such as electrodes.

  Hereinafter, as a typical example of an electronic device, a field effect transistor (FET) element, a photoelectric conversion element, a solar cell, and a solar cell module using the monosubstituted tetrabenzoporphyrin compound according to the present invention will be described.

<4. Field Effect Transistor (FET) Device>
The field effect transistor (FET) element (hereinafter referred to as the FET element according to the present invention) using the monosubstituted tetrabenzoporphyrin compound according to the present invention will be described in detail below. The FET device according to the present invention contains the monosubstituted tetrabenzoporphyrin compound according to the present invention as a semiconductor material.

  FIG. 4 is a diagram schematically showing an example of the structure of the FET element according to the present invention. In FIG. 4, 51 is a semiconductor layer, 52 is an insulator layer, 53 and 54 are source and drain electrodes, 55 is a gate electrode, and 56 is a substrate. 4A to 4D each show an example of the structure of an FET element according to the present invention. Hereinafter, these examples of the FET according to the present invention will be described.

For example, platinum, gold, aluminum, chromium, nickel, copper, titanium, magnesium, calcium, barium, sodium, and other metals as well as In ₂ are used for the source and drain electrodes 53 and 54 and the gate electrode 55. Conductive oxides such as O ₃ , SnO ₂ , ITO; conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene; Bronsted acids such as hydrochloric acid, sulfuric acid, sulfonic acid, PF ₆ , AsF ₆ , FeCl _3, etc. A dopant such as a Lewis acid, a halogen atom such as iodine, or a metal atom such as sodium or potassium added to the conductive polymer as described above; or a conductive material in which carbon black or metal particles are dispersed. A conductive material such as a conductive composite material is used.

  Examples of the material used for the insulator layer 52 include polymers such as polymethyl methacrylate, polystyrene, polyvinylphenol, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, epoxy resin, and phenol resin. These copolymers; oxides such as silicon dioxide, aluminum oxide and titanium oxide; nitrides such as silicon nitride; ferroelectric oxides such as strontium titanate and barium titanate; or these oxides and nitrides Or a polymer in which particles of a ferroelectric oxide or the like are dispersed.

  In general, the larger the capacitance of the insulating film, the more advantageous is that the gate voltage can be driven at a lower voltage. This can be realized by using an insulating material having a large dielectric constant or by reducing the thickness of the insulator layer. Insulator layers are materials such as coating methods (spin coating and blade coating), vapor deposition methods, sputtering methods, printing methods such as screen printing and inkjet, and a method of forming an oxide film on a metal so as to form alumite on aluminum. It can be manufactured by a method according to characteristics.

  The FET element according to the present invention usually has a base material 56, and the above-described structures 51 to 56 are produced on the base material 56. The material of the substrate is not particularly limited as long as the effects of the present invention are not significantly impaired. Preferable examples of the base material include inorganic materials such as quartz, glass, sapphire, and titania, and flexible base materials. A flexible base material is a base material whose curvature radius is usually 0.1 mm or more and 10000 mm or less. In the case of producing a flexible electronic device, the radius of curvature is preferably 0.3 mm or more, more preferably 1 mm or more, in order to achieve both flexibility and characteristics as a support. It is preferably 3000 mm or less, and more preferably 1000 mm or less. The radius of curvature can be obtained with a confocal microscope (for example, a shape measurement laser microscope VK-X200 manufactured by Keyence Co., Ltd.) obtained by bending a base material that has been bent to a point where no damage such as distortion or cracking appears. Specific examples of the flexible substrate include, but are not limited to, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyimide, nylon, polystyrene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, fluororesin film, vinyl chloride. Polyolefins such as polyethylene; organic materials such as cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene, and epoxy resin; paper materials such as paper or synthetic paper; stainless steel, titanium, aluminum, etc. Examples thereof include composite materials such as those obtained by coating or laminating the surface of a metal to impart insulating properties.

  Furthermore, the characteristics of the FET element can be improved by processing the substrate. The reason is presumed that by adjusting the hydrophilicity / hydrophobicity of the substrate, the film quality of the semiconductor layer to be formed can be improved, and in particular, the characteristics of the interface portion between the substrate and the semiconductor layer can be improved. The Such substrate treatment includes hydrophobization treatment using hexamethyldisilazane, cyclohexene, octadecyltrichlorosilane, etc .; acid treatment using acids such as hydrochloric acid, sulfuric acid, acetic acid; sodium hydroxide, potassium hydroxide, Alkaline treatment using calcium hydroxide, ammonia, etc .; ozone treatment; fluorination treatment; plasma treatment using oxygen, argon, etc .; Langmuir Blodget film formation treatment; or other insulator or semiconductor thin film formation treatment , Etc.

  The semiconductor layer 51 is a layer containing the monosubstituted tetrabenzoporphyrin compound according to the present invention. The semiconductor layer 51 is formed in a film shape directly on the base material or via another layer. But the semiconductor layer 51 may contain other compounds (other organic semiconductors, etc.) in addition to the monosubstituted tetrabenzoporphyrin compound according to the present invention. The semiconductor layer 51 may have a stacked structure including a plurality of layers that include different materials or have different components.

  The film thickness of the semiconductor layer 51 is not limited. For example, in the case of a horizontal field effect transistor element, the element characteristics do not depend on the film thickness of the semiconductor layer 51 as long as the film thickness is equal to or greater than a predetermined film thickness. However, since the leakage current often increases when the film thickness becomes too thick, the film thickness of the semiconductor layer is usually 1 nm or more, preferably 10 nm or more. From the viewpoint of cost, it is usually 10 μm or less, preferably 500 nm or less.

  Moreover, the semiconductor layer 51 does not need to be a uniform film formed on the substrate. For example, the semiconductor layer 51 may be configured as a deposit attached to the substrate 56 or other elements on the substrate 56. Such a semiconductor layer 51 can be formed by attaching the composition for forming a semiconductor layer according to the present invention as droplets to the substrate 56 or other elements on the substrate 56. In this case, the thickness of the deposit is preferably within the above range.

  The FET device according to the present invention can be manufactured according to a conventional method. For example, the FET element according to the present invention can be manufactured by sequentially forming the gate electrode 55, the insulator layer 52, the semiconductor layer 51, the source and drain electrodes 53 and 54 on the base material 56. As described above, the semiconductor layer 51 can be formed by coating the film forming composition according to the present invention and performing a conversion reaction as necessary.

<5. Photoelectric conversion element>
Hereinafter, a photoelectric conversion element using the monosubstituted tetrabenzoporphyrin compound according to the present invention (hereinafter referred to as a photoelectric conversion element according to the present invention) will be described in detail. The photoelectric conversion element according to the present invention has at least one pair of electrodes and an active layer disposed between the electrodes. The active layer contains the monosubstituted tetrabenzoporphyrin compound according to the present invention.

  Hereinafter, a photoelectric conversion element according to an embodiment of the present invention will be described with reference to FIG. As shown in FIG. 1, a photoelectric conversion element 107 according to this embodiment includes a base 106, an anode 101, a hole extraction layer 102, and an active layer 103 (a layer containing a p-type semiconductor material and an n-type semiconductor material). , An electron extraction layer 104 and a cathode 105 are sequentially formed. The photoelectric conversion element according to this embodiment is not limited to the configuration shown in FIG. For example, the substrate 106, the cathode 105, the electron extraction layer 104, the active layer 103, the hole extraction layer 102, and the anode 101 may be sequentially formed. The hole extraction layer 102 and the electron extraction layer 104 are not essential for the photoelectric conversion element, and the photoelectric conversion element may not include at least one of the hole extraction layer 102 and the electron extraction layer 104. Hereinafter, each structure which comprises the photoelectric conversion element 107 is demonstrated in detail.

<5.1 Active layer>
The active layer 103 refers to a layer in which photoelectric conversion is performed, and usually contains a p-type semiconductor compound and an n-type semiconductor compound. The p-type semiconductor compound is a compound that works as a p-type semiconductor material, and the n-type semiconductor compound is a compound that works as an n-type semiconductor material. When the photoelectric conversion element 107 receives light, the light is absorbed by the active layer 103, electricity is generated at the interface between the p-type semiconductor compound and the n-type semiconductor compound, and the generated electricity is extracted from the anode 101 and the cathode 105.

  As the material of the active layer 103, either an inorganic compound or an organic compound may be used, but it is preferable that the active layer 103 can be formed by a simple coating process. In this respect, the active layer 103 is preferably an organic active layer made of an organic compound. In the following description, it is assumed that the active layer 103 is an organic active layer. The active layer 103 in the present invention contains a monosubstituted tetrabenzoporphyrin compound according to the present invention which is an organic compound as a p-type semiconductor material.

  As the layer structure of the active layer 103, a thin film stacked type in which a p-type semiconductor compound layer (p layer) and an n-type semiconductor compound layer (n layer) are stacked, a p-type semiconductor compound and an n-type semiconductor compound are mixed. Examples include a bulk heterojunction type having a layer (i layer). In addition, a layer in which a p-type semiconductor compound and an n-type semiconductor compound are mixed, and at least one of a p-type semiconductor compound layer and an n-type semiconductor compound layer may be stacked. As such a structure, a structure in which a p layer, an i layer, and an n layer are laminated (pin lamination type), a structure in which a p layer and an i layer are laminated, and an i layer and an n layer are laminated. Structure is mentioned.

  The thickness of the active layer 103 is not particularly limited, but is preferably 10 nm or more and 1000 nm or less, and more preferably 50 nm or more and 200 nm or less. Since the uniformity of the layer is maintained when the thickness of the active layer is 10 nm or more, it is difficult to cause a short circuit. In addition, when the thickness of the active layer is 1000 nm or less, the internal resistance can be reduced, and further, the distance between the electrodes is reduced, so that the charge diffusion can be improved.

  The thickness of each of the p-type semiconductor compound layer, the i-layer, and the n-type semiconductor compound layer is not particularly limited, but is usually 3 nm or more, preferably 10 nm or more, and usually 200 nm or less, The thickness is preferably 100 nm or less. By setting the thickness of each layer in the above range, a film having high uniformity and transmittance and low series resistance can be obtained.

  The p-type semiconductor compound constituting the p-type semiconductor compound layer and the i layer, and the n-type semiconductor compound constituting the n-type semiconductor compound layer and the i layer will be described below.

<5.1.1 p-type semiconductor compound>
As the p-type semiconductor compound, at least the monosubstituted tetrabenzoporphyrin compound according to the present invention is used. That is, at least one of the p-type semiconductor compound layer and the i layer contains the monosubstituted tetrabenzoporphyrin compound according to the present invention. However, at least one of the p-type semiconductor compound layer and the i-layer may contain a p-type semiconductor compound other than the monosubstituted tetrabenzoporphyrin compound according to the present invention.

<5.1.2 n-type semiconductor compound>
The n-type semiconductor compound is not particularly limited. For example, a fullerene compound, a quinolinol derivative metal complex represented by 8-hydroxyquinoline aluminum, a condensed ring tetracarboxylic acid diimide such as naphthalenetetracarboxylic acid diimide, and perylenetetracarboxylic acid diimide. Terpyridine metal complex, tropolone metal complex, flavonol metal complex, perinone derivative, benzimidazole derivative, benzoxazole derivative, benzthiazole derivative, oxadiazole derivative, thiadiazole derivative, triazole derivative, aldazine derivative, bisstyryl derivative, pyrazine derivative, phenanthroline Derivatives, quinoxaline derivatives, benzoquinoline derivatives, bipyridine derivatives, anthracene, pyrene, naphthacene, pentacene, etc. Aromatic total fluoride, single-walled carbon nanotubes, polyquinoline, polypyridine, polyaniline, poly (benzo-bis-imidazo benzo phenanthroline), boron polymers include polyphenylene vinylene or the like which is cyano substituted. As the n-type semiconductor compound, one type of compound may be used, or two or more types of compounds may be used.

Among the above n-type semiconductor compounds, in particular, the use of fullerene compounds is preferable from the viewpoint of performance, and C ₆₀ fullerene compounds or C ₇₀ fullerene compounds are more preferable. Among them, a C ₆₀ fullerene compound or a C ₇₀ fullerene compound having two or more organic groups having 1 to 50 carbon atoms which may be different from each other is particularly preferable. Moreover, the organic groups may be connected to form a ring.

Specific examples of the C ₆₀ fullerene derivative having two or more organic groups having 1 to 50 carbon atoms which may be different from each other include fullerene having a silylalkyl group in which an aromatic group is bonded to a silicon atom as an organic group. Is mentioned. Further, specific examples in the case where two or more organic groups are linked to form a ring include fullerene in which the formed ring is indene, fullerene in which the formed ring is quinodimethane, PC ₆₁ BM , PC ₇₁ BM and the like formed fullerene in which the formed ring is a 3-membered ring. Specific examples of preferred fullerene compounds include the following.

<5.1.3 Formation Method of Active Layer>
Next, a method for forming each layer of the active layer will be described. Although there is no particular limitation on the method of forming each layer of the active layer, a coating solution containing a semiconductor compound is applied using a wet coating method such as a spin coating method, an inkjet method, a doctor blade method, or a drop casting method. It is preferable to form each layer.

  The solvent of the coating solution is not particularly limited as long as it can uniformly dissolve the semiconductor compound. For example, aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane, decane; toluene, xylene, Aromatic hydrocarbons such as chlorobenzene and orthodichlorobenzene; lower alcohols such as methanol, ethanol and propanol; ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; esters such as ethyl acetate, butyl acetate and methyl lactate Halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane, trichloroethylene; ethers such as ethyl ether, tetrahydrofuran, 1,4-dioxane; or dimethylformamide, dimethylacetamide It can be selected from the amides.

  In particular, the p-type semiconductor compound layer containing the monosubstituted tetrabenzoporphyrin compound according to the present invention is formed by a method including the step of coating and forming the semiconductor layer forming composition according to the present invention as described above. Can do. However, the method for forming the p-type semiconductor compound layer is not limited to this method.

  Further, the i layer containing the monosubstituted tetrabenzoporphyrin compound according to the present invention is formed by a method including a step of coating and forming the semiconductor layer forming composition according to the present invention, which further contains an n-type semiconductor compound. can do. However, the method for forming the i layer is not limited to this method.

<5.2 Substrate>
The photoelectric conversion element 107 has a base material 106 that usually serves as a support. That is, the anode 101, the cathode 105, and the active layer 103 are formed on the base material. But the photoelectric conversion element which concerns on this invention does not need to have the base material 106. FIG.

  The material of the substrate 106 is not particularly limited as long as the effects of the present invention are not significantly impaired. Preferable examples of the material of the substrate 106 include inorganic materials such as quartz, glass, sapphire, and titania, and flexible substrates. Specific examples of the flexible substrate include, but are not limited to, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyimide, nylon, polystyrene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, fluororesin film, vinyl chloride. Polyolefins such as polyethylene; organic materials such as cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene, epoxy resin; paper materials such as paper or synthetic paper; stainless steel, titanium, aluminum, etc. Examples thereof include composite materials such as those obtained by coating or laminating the surface of a metal to impart insulating properties.

  Examples of the glass include soda glass, blue plate glass, and non-alkali glass. Among these, alkali-free glass is preferable in that there are few eluted ions from the glass.

  There is no restriction | limiting in the shape of the base material 106, For example, things, such as plate shape, a film form, or a sheet form, can be used. Moreover, although there is no restriction | limiting in the film thickness of the base material 106, Usually, it is 5 micrometers or more, Preferably it is 20 micrometers or more, On the other hand, it is 20 mm or less normally, Preferably it is 10 mm or less. The film thickness of the substrate 106 is preferably 5 μm or more because the possibility that the strength of the photoelectric conversion element is insufficient is reduced. It is preferable that the thickness of the substrate 106 is 20 mm or less because the cost is suppressed and the weight does not increase. When the material of the substrate 106 is glass, the film thickness is usually 0.01 mm or more, preferably 0.1 mm or more, and is usually 10 mm or less, preferably 5 mm or less. It is preferable that the glass substrate 106 has a film thickness of 0.01 mm or more because mechanical strength increases and it is difficult to break. Moreover, it is preferable that the film thickness of the glass substrate 106 is 5 mm or less because the weight does not increase.

<5.3 Electron extraction layer>
The electron extraction layer 104 has a role that enables electrons generated in the active layer 103 to be smoothly extracted from the cathode 105. As described above, the electron extraction layer 104 is not an essential component for the photoelectric conversion element. When the photoelectric conversion element 107 includes the electron extraction layer 104, the electron extraction layer 104 is disposed between the cathode 105 and the active layer 103 as illustrated in FIG. 1.

  The material that can be used for the electron extraction layer 104 is not particularly limited as long as it can improve the efficiency of extracting electrons from the active layer 103 to the cathode 105, and may be an inorganic compound or an organic compound. Also good.

  Examples of the inorganic compound material include alkali metal salts such as lithium, sodium, potassium and cesium; alkaline earth metals such as magnesium, calcium and barium or salts thereof; or zinc oxide, titanium oxide, aluminum oxide and indium oxide. Examples include metal oxides having n-type semiconductor characteristics.

  Preferred alkali metal salts are alkali metal fluoride salts such as lithium fluoride, sodium fluoride, potassium fluoride, and cesium fluoride. The alkaline earth metal or salt thereof is preferably calcium or barium. The metal oxide having n-type semiconductor characteristics is preferably zinc oxide, titanium oxide, or indium oxide, and particularly preferably zinc oxide.

  Examples of the organic compound material include bathocuproin (BCP), bathophenanthrene (Bphen), (8-hydroxyquinolinato) aluminum (Alq3), boron compound, oxadiazole compound, benzimidazole compound, naphthalenetetracarboxylic anhydride (NTCDA). ), Perylenetetracarboxylic anhydride (PTCDA), or a phosphine compound having a double bond between a phosphorus group atom and a Group 16 element of the periodic table such as a phosphine oxide compound or a phosphine sulfide compound.

  Among these, a phosphine oxide compound or a phosphine sulfide compound is preferable. More preferred is a phosphine oxide compound substituted with an aryl group or a phosphine sulfide compound substituted with an aryl group, and particularly preferred are two or more triarylphosphine oxide compounds, triarylphosphine sulfide compounds and diarylphosphine oxide units. Aromatic hydrocarbon compound having two or more diarylphosphine sulfide units, triarylphosphine oxide compound substituted with fluorine atom or perfluoroalkyl group, or aromatic having two or more diarylphosphine oxide units Group hydrocarbon compound.

  Moreover, you may dope alkali metal or alkaline-earth metal further with respect to the material of these organic compounds.

  Although there is no special restriction | limiting in the film thickness of the electron extraction layer 104, Usually, 0.01 nm or more, Preferably it is 0.1 nm or more. On the other hand, it is usually 200 nm or less, preferably 100 nm or less. By setting the film thickness of the electron extraction layer 104 in this range, electrons can be easily extracted and the photoelectric conversion efficiency is improved.

  There is no limitation on the method for forming the electron extraction layer 104. For example, when a material having sublimation property is used, the electron extraction layer 104 can be formed by a vacuum evaporation method or the like. Further, when a material soluble in a solvent is used, it can be formed by a wet coating method such as a spin coating method or an ink jet method.

<5.4 Hole Extraction Layer>
The hole extraction layer 102 has a role that allows holes generated in the active layer 103 to be smoothly extracted by the anode 101. Note that the hole extraction layer 102 is not an essential component for the photoelectric conversion element 107 as is the case with the electron extraction layer 104. When the photoelectric conversion element 107 includes the hole extraction layer 102, the hole extraction layer 102 is disposed between the anode 101 and the active layer 103 as illustrated in FIG. 1.

  The material of the hole extraction layer 102 is not particularly limited as long as it can improve the efficiency of extracting holes from the active layer 103 to the anode 101. Examples of suitable materials include: conductive polymers in which polythiophene, polypyrrole, polyacetylene, triphenylenediamine, polyaniline, etc. are doped with sulfonic acid, iodine, etc .; polythiophene derivatives having sulfonyl groups as substituents; arylamines, etc. Examples thereof include conductive organic compounds; Nafion; or metal oxides such as copper oxide, nickel oxide, manganese oxide, molybdenum oxide, vanadium oxide, and tungsten oxide.

  Among them, preferred is a conductive polymer doped with sulfonic acid, and more preferred is poly (3,4-ethylenedioxythiophene) poly (styrenesulfonic acid) (PEDOT: polythiophene derivative doped with polystyrene sulfonic acid). PSS).

  As a material for the hole extraction layer 102, a thin film of metal such as gold, indium, silver, or palladium can be used. Thin films such as metals may be used alone or in combination with the above organic materials.

  Although there is no special restriction | limiting in the film thickness of the positive hole taking-out layer 102, Usually, it is 0.5 nm or more. On the other hand, it is usually 400 nm or less, preferably 200 nm or less. By setting the film thickness of the hole extraction layer 104 within this range, holes can be easily extracted and the photoelectric conversion efficiency can be improved.

  The formation method of the hole extraction layer 102 is not limited. For example, when a material having sublimation property is used, the hole extraction layer 102 can be formed by a vacuum evaporation method or the like. Further, when a material soluble in a solvent is used, it can be formed by a wet coating method such as a spin coating method or an ink jet method.

Especially, when using PEDOT: PSS as a material of the hole taking-out layer 102, it is preferable to form the hole taking-out layer 104 by the method of apply | coating a dispersion liquid. PEDOT: The dispersion of PSS, and CLEVIOS ^TM series of Heraeus, Inc., include Agfa Corp. of ORGACON ^TM series and the like.

  When the hole extraction layer 104 is formed by a coating method, a surfactant may be further contained in the coating solution. By using the surfactant, generation of dents due to adhesion of minute bubbles or foreign matters and uneven coating in the drying process is suppressed. As the surfactant, a known surfactant (cationic surfactant, anionic surfactant, or nonionic surfactant) can be used. Among these, it is preferable to use a silicon-based surfactant, an acetylenic diol-based surfactant, or a fluorine-based surfactant. As surfactant, only 1 type may be used and 2 or more types may be used together by arbitrary combinations and a ratio.

<5.5 Anode>
The anode 101 has a function of collecting holes generated by light absorption. One of the anode 101 and the cathode 105 described later needs to have a light-transmitting property, and both electrodes may have a light-transmitting property. Having translucency means that the solar ray transmittance is 40% or more. It is preferable that the sunlight transmittance of at least one of the anode 101 and the cathode 105 is 70% or more because sufficient light reaches the active layer 103. The solar ray transmittance can be measured with a normal spectrophotometer (for example, U-4100 manufactured by Hitachi High-Tech).

  Although there is no particular limitation on the material of the anode 101, it is preferable to use a conductive material having a work function larger than that of the cathode 105 because holes generated in the active layer 103 can be taken out smoothly. However, when the hole extraction layer 102 is provided, a material having a small work function can be used.

  Examples of the material of the anode 101 include conductive metal oxides such as nickel oxide, tin oxide, indium oxide, indium tin oxide (ITO), indium-zinc oxide (IZO), titanium oxide, indium oxide, and zinc oxide. Or a metal such as chromium or cobalt or an alloy thereof. These materials are preferred because they have a large work function.

  A conductive polymer material represented by PEDOT: PSS, polypyrrole doped with iodine or the like, polyaniline, or the like can itself be used as the material of the anode 101. However, a conductive polymer material may be laminated on a material that does not have a large work function, such as aluminum or magnesium, and may be used as the anode 101.

  When the anode 101 is a transparent electrode, it is preferable to use a light-transmitting conductive metal oxide such as ITO, zinc oxide or tin oxide as the material of the anode 101, and ITO is particularly preferable.

  Further, the anode 101 may have a single layer structure or a laminated structure. In addition, by performing surface treatment on the anode 101, electrical characteristics, wetting characteristics, and the like can be improved.

  The film thickness of the anode 101 is not particularly limited, but is usually 10 nm or more, preferably 20 nm or more, and more preferably 50 nm or more. On the other hand, it is usually 10 μm or less, preferably 1 μm or less, more preferably 500 nm or less. When the film thickness of the anode 101 is 10 nm or more, the sheet resistance is suppressed, and when the film thickness of the anode 101 is 10 μm or less, light can be efficiently converted into electricity without reducing the light transmittance. it can.

  Although the sheet resistance of the anode 101 is not particularly limited, it is usually 1Ω / □ or more, while it is 1000Ω / □ or less, preferably 500Ω / □ or less, more preferably 100Ω / □ or less. By setting the sheet resistance within this range, light can be efficiently converted into electricity. The sheet resistance can be determined using a normal resistivity meter (for example, Loresta GP manufactured by Mitsubishi Chemical Analytech Co., Ltd.).

  Examples of a method for forming the anode 101 include a dry film forming method such as an evaporation method or a sputtering method, or a wet film forming method in which an ink containing nanoparticles or a precursor is applied to form a film.

<5.6 Cathode>
The cathode 105 has a function of collecting electrons generated in the active layer 103 by light absorption. Although there is no particular limitation on the material of the cathode 105, electrons generated in the active layer 103 can be taken out smoothly by using a material having a work function smaller than that of the anode 101. Similarly to the anode 101, the cathode 105 can be made of a material having a work function that is not small by using the electron extraction layer 104 formed of a conductive material such as titania.

  Examples of the material of the cathode 105 include platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, lithium, sodium, potassium, cesium, calcium, magnesium, or an alloy thereof; lithium fluoride, fluorine Inorganic salts such as cesium oxide; or metal oxides such as nickel oxide, aluminum oxide, lithium oxide, and cesium oxide.

  In the case where the cathode 105 is a transparent electrode, it is preferable to use ITO, zinc oxide or tin oxide conductive metal oxide as the material, and ITO is particularly preferable.

  Further, the cathode 105 may have a single layer structure or a laminated structure. In addition, by performing surface treatment on the cathode 105, electrical characteristics, wetting characteristics, and the like can be improved.

  The film thickness of the cathode 105 is not particularly limited, but is usually 10 nm or more, preferably 20 nm or more, more preferably 50 nm or more. On the other hand, it is usually 10 μm or less, preferably 1 μm or less, more preferably 500 nm or less. When the film thickness of the cathode 105 is 10 nm or more, sheet resistance is suppressed, and when the film thickness of the cathode 105 is 10 μm or less, light can be efficiently converted into electricity without reducing light transmittance. it can.

  The sheet resistance of the cathode 105 is not particularly limited, but is usually 1000Ω / □ or less, preferably 500Ω / □ or less, and more preferably 100Ω / □ or less. Although there is no restriction on the lower limit, it is usually 1Ω / □ or more. By setting the sheet resistance of the cathode 105 within the above range, light can be efficiently converted into electricity.

  As a formation method of the cathode 105, there are a vacuum film formation method such as an evaporation method or a sputtering method, or a wet application method in which an ink containing nanoparticles or a precursor is applied to form a film.

<5.8 Method for Manufacturing Photoelectric Conversion Element>
The photoelectric conversion element according to this embodiment can be manufactured by sequentially forming each constituent element using the above constituent materials and forming method.

  After laminating anode 101 and cathode 105, the photoelectric conversion element is heated in a temperature range of usually 50 ° C. or higher, preferably 80 ° C. or higher, usually 300 ° C. or lower, preferably 280 ° C. or lower, more preferably 250 ° C. or lower. It is preferable to do this (hereinafter, this process is referred to as annealing process).

  By performing the annealing process at a temperature of 50 ° C. or higher, the adhesion between the layers of the photoelectric conversion element, for example, the adhesion of at least one of the electron extraction layer 104 and the cathode 105 and the electron extraction layer 104 and the active layer 103 is improved. Is preferable. By improving the adhesion between the layers, the thermal stability and durability of the photoelectric conversion element can be improved.

  It is preferable to perform the annealing process at a temperature of 300 ° C. or lower because the possibility that the organic compound in the active layer 103 is thermally decomposed is reduced.

  In the annealing treatment, stepwise heating may be performed within the above temperature range. The heating time is usually 1 minute or longer, preferably 3 minutes or longer from the viewpoint of sufficiently obtaining the effect of the annealing treatment. On the other hand, from the viewpoint of preventing thermal deterioration of the organic compound in the active layer 103, it is usually 3 hours or less, preferably 1 hour or less. The annealing process is preferably terminated when the open-circuit voltage, the short-circuit current, and the fill factor, which are parameters indicating the solar cell performance, reach a constant value.

  The annealing treatment is preferably performed under normal pressure and in an inert gas atmosphere from the viewpoint of ease of operation and prevention of deterioration of the photoelectric conversion element. As a heating method, the photoelectric conversion element may be placed on a heat source such as a hot plate, or the photoelectric conversion element may be placed in a heating atmosphere such as an oven. The heating may be performed batchwise or continuously.

<5.8 Photoelectric conversion characteristics>
The photoelectric conversion characteristics of the photoelectric conversion element 107 can be obtained as follows. That is, the photoelectric conversion element 107 is irradiated with light having an AM 1.5G condition with a solar simulator at an irradiation intensity of 100 mW / cm ² to measure current-voltage characteristics. From the obtained current-voltage curve, photoelectric conversion characteristics such as photoelectric conversion efficiency (PCE), short circuit current density (Jsc), open circuit voltage (Voc), fill factor (FF), series resistance, and shunt resistance can be obtained.

  Although there is no special restriction | limiting, the photoelectric conversion efficiency of the photoelectric conversion element which concerns on this invention is 0.5% or more normally, Preferably it is 1% or more, More preferably, it is 3% or more. On the other hand, there is no particular limitation on the upper limit, and the higher the better.

Moreover, as a method for measuring the durability of the photoelectric conversion element, a method for obtaining a maintenance ratio of the photoelectric conversion efficiency before and after exposing the photoelectric conversion element to the atmosphere can be mentioned.
(Maintenance rate) = (Photoelectric conversion efficiency after N hours of atmospheric exposure) / (Photoelectric conversion efficiency immediately before atmospheric exposure)

  In order to put a photoelectric conversion element into practical use, it is important to have high photoelectric conversion efficiency and high durability in addition to simple and inexpensive manufacture. From this viewpoint, the maintenance rate of photoelectric conversion efficiency before and after exposure to the atmosphere for one week is preferably 60% or more, more preferably 80% or more, and the higher the better.

<6 Solar Cell According to the Present Invention>
The photoelectric conversion element 107 according to the present invention is preferably used as a solar cell, particularly a solar cell element of a thin film solar cell.

  FIG. 2 is a cross-sectional view schematically showing the configuration of a thin film solar cell as one embodiment of the present invention. As shown in FIG. 2, the thin film solar cell 14 of this embodiment includes a weather-resistant protective film 1, an ultraviolet cut film 2, a gas barrier film 3, a getter material film 4, a sealing material 5, and a solar cell element. 6, a sealing material 7, a getter material film 8, a gas barrier film 9, and a back sheet 10 are provided in this order. And light is irradiated from the side (downward in the figure) where the weather-resistant protective film 1 is formed, and the solar cell element 6 generates power. In addition, when using a highly waterproof sheet such as a sheet in which a fluororesin film is bonded to both surfaces of an aluminum foil as the back sheet 10 described later, at least one of the getter material film 8 and the gas barrier film 9 may not be used depending on the application. Also good.

<6.1 Weatherproof Protective Film>
The weather-resistant protective film 1 is a film that protects the solar cell element 6 from weather changes. By covering the solar cell element 6 with the weather-resistant protective film 1, the solar cell element 6 and the like are protected from weather changes and the power generation capacity is kept high. Since the weather-resistant protective film 1 is located on the outermost layer of the thin-film solar cell 14, it is used as a surface covering material for the thin-film solar cell 14 such as weather resistance, heat resistance, transparency, water repellency, contamination resistance, and mechanical strength. It is preferable to have a suitable performance and to maintain it for a long period of time in outdoor exposure.

  Moreover, it is preferable that the weather-resistant protective film 1 transmits visible light from the viewpoint of not preventing the solar cell element 6 from absorbing light. For example, the transmittance of visible light (wavelength 360 to 830 nm) is preferably 80% or more, and the upper limit is not limited. Furthermore, since the thin-film solar cell 14 is often heated by receiving light, it is preferable that the weather-resistant protective film 1 also has heat resistance. From this viewpoint, the melting point of the constituent material of the weather-resistant protective film 1 is usually 100 ° C. or higher and 350 ° C. or lower.

  The material which comprises the weather-resistant protective film 1 is arbitrary as long as it can protect the solar cell element 6 from a weather change. Examples of such materials are polyethylene resin, polypropylene resin, cyclic polyolefin resin, AS (acrylonitrile-styrene) resin, ABS (acrylonitrile-butadiene-styrene) resin, polyvinyl chloride resin, fluorine resin, polyethylene terephthalate, polyethylene naphthalate. Examples thereof include polyester resins such as phthalate, phenol resins, polyacrylic resins, polyamide resins such as various nylons, polyimide resins, polyamide-imide resins, polyurethane resins, cellulose resins, silicon resins, and polycarbonate resins.

  In addition, the weather-resistant protective film 1 may be formed with 1 type of material, and may be formed with 2 or more types of materials. Moreover, although the weather-resistant protective film 1 may be formed with the single layer film, the laminated | multilayer film provided with the film of two or more layers may be sufficient as it.

  The thickness of the weather-resistant protective film 1 is not particularly defined, but is usually 10 μm or more and 200 μm or less.

  Moreover, you may perform surface treatment, such as a corona treatment and a plasma treatment, for the weather-resistant protective film 1 in order to improve adhesiveness with another film.

  The weatherproof protective film 1 is preferably provided on the outer side as much as possible in the thin-film solar cell 14. This is because more of the constituent members of the thin-film solar cell 14 can be protected.

<6.2 UV cut film>
The ultraviolet cut film 2 is a film that prevents the transmission of ultraviolet rays. The ultraviolet cut film 2 is provided in the light receiving portion of the thin-film solar cell 14, and the ultraviolet cut film 2 covers the light receiving surface 6a of the solar cell element 6, so that the solar cell element 6 and, if necessary, the gas barrier films 3 and 9 are exposed to ultraviolet rays. The power generation capacity can be maintained at a high level.

  The degree of the ability to suppress the transmission of ultraviolet rays required for the ultraviolet cut film 2 is preferably such that the transmittance of ultraviolet rays (for example, wavelength of 300 nm) is 50% or less, and there is no limit on the lower limit. Moreover, it is preferable that the ultraviolet cut film 2 transmits visible light from the viewpoint of not preventing the solar cell element 6 from absorbing light. For example, the transmittance of visible light (wavelength 360 to 830 nm) is preferably 80% or more, and the upper limit is not limited.

  Furthermore, since the thin film solar cell 14 is often heated by receiving light, the ultraviolet cut film 2 preferably has heat resistance. From this viewpoint, the melting point of the constituent material of the ultraviolet cut film 2 is usually 100 ° C. or higher and 350 ° C. or lower.

  Moreover, it is preferable that the ultraviolet cut film 2 is high in flexibility, has good adhesion to an adjacent film, and can cut water vapor and oxygen.

  The material which comprises the ultraviolet cut film 2 is arbitrary if the intensity | strength of an ultraviolet-ray can be weakened. Examples of the material include films formed by blending an ultraviolet absorber with an epoxy, acrylic, urethane, or ester resin. Further, a film in which a layer of an ultraviolet absorbent dispersed or dissolved in a resin (hereinafter referred to as “ultraviolet absorbing layer” as appropriate) is formed on a base film may be used.

  Examples of the ultraviolet absorber that can be used include salicylic acid-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ones. In addition, a ultraviolet absorber may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio. As described above, a film in which an ultraviolet absorbing layer is formed on a base film can also be used as the ultraviolet absorbing film. Such a film can be produced, for example, by applying a coating solution containing an ultraviolet absorber on a substrate film and drying it.

  Although the material of a base film is not specifically limited, For example, polyester is mentioned at the point from which the balance of heat resistance and a softness | flexibility is obtained.

  When an example of a specific product of the ultraviolet cut film 2 is given, cut ace (manufactured by MKV Plastic Co., Ltd.) and the like can be mentioned. In addition, the ultraviolet cut film 2 may be formed with 1 type of material, and may be formed with 2 or more types of materials.

  Further, the ultraviolet cut film 2 may be formed of a single layer film, but may be a laminated film including two or more layers. The thickness of the ultraviolet cut film 2 is not particularly limited, but is usually 5 μm or more and 200 μm or less.

  Although the ultraviolet cut film 2 should just be provided in the position which covers at least one part of the light-receiving surface 6a of the solar cell element 6, Preferably it is provided in the position which covers all the light-receiving surfaces 6a of the solar cell element 6. FIG. However, the ultraviolet cut film 2 may be provided at a position other than the position covering the light receiving surface 6 a of the solar cell element 6.

<6.3 Gas barrier film>
The gas barrier film 3 is a film that prevents permeation of water and oxygen. By covering the solar cell element 6 with the gas barrier film 3, the solar cell element 6 can be protected from water and oxygen, and the power generation capacity can be kept high.

Although the degree of moisture-proof capability required for the gas barrier film 3 varies depending on the type of the solar cell element 6 and the like, the water vapor transmission rate per unit area (1 m ² ) per day is usually 1 × 10 ^−1. It is preferable that it is below g / m < ² > / day, and there is no restriction | limiting in a minimum.

Although the degree of oxygen permeability required for the gas barrier film 3 varies depending on the type of the solar cell element 6 and the like, the oxygen permeability per unit area (1 m ² ) per day is usually 1 × 10 ^−. It is preferably ¹ cc / m ² / day / atm or less, and the lower limit is not limited.

  Moreover, it is preferable that the gas barrier film 3 transmits visible light from the viewpoint of not preventing the solar cell element 6 from absorbing light. For example, the transmittance of visible light (wavelength 360 to 830 nm) is usually 60% or more, and there is no upper limit.

  Furthermore, since the thin film solar cell 14 is often heated by receiving light, it is preferable that the gas barrier film 3 also has heat resistance. From this viewpoint, the melting point of the constituent material of the gas barrier film 3 is usually 100 ° C. or higher and 350 ° C. or lower.

  The specific configuration of the gas barrier film 3 is arbitrary as long as the solar cell element 6 can be protected from water. However, since the manufacturing cost increases as the amount of water vapor or oxygen that can permeate the gas barrier film 3 increases, it is preferable to use an appropriate film considering these points comprehensively.

Among them, suitable gas barrier film 3, for example, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) base film on the silicon oxide film and the (SiO _x) was vacuum vapor deposition of the like.

  In addition, the gas barrier film 3 may be formed with 1 type of material, and may be formed with 2 or more types of materials. The gas barrier film 3 may be formed of a single layer film, but may be a laminated film including two or more layers.

  The thickness of the gas barrier film 3 is not particularly defined, but is usually 5 μm or more and 200 μm or less.

  As long as the gas barrier film 3 covers the solar cell element 6 and can be protected from moisture and oxygen, the formation position is not limited. However, the front surface of the solar cell element 6 (surface on the light receiving surface side, lower surface in FIG. 2) and It is preferable to cover the back surface (the surface opposite to the light receiving surface; the upper surface in FIG. 2). This is because the front and back surfaces of the thin film solar cell 14 are often formed in a larger area than the other surfaces. In this embodiment, the gas barrier film 3 covers the front surface of the solar cell element 6, and a gas barrier film 9 described later covers the back surface of the solar cell element 6. In addition, when using a highly waterproof sheet such as a sheet in which a fluororesin film is bonded to both surfaces of an aluminum foil as the back sheet 10 described later, at least one of the getter material film 8 and the gas barrier film 9 may not be used depending on the application. Also good.

<6.4 Getter Material Film>
The getter material film 4 is a film that absorbs at least one of moisture and oxygen. By covering the solar cell element 6 with the getter material film 4, the solar cell element 6 and the like are protected from at least one of moisture and oxygen, and the power generation capacity is kept high. Here, unlike the gas barrier film 3 as described above, the getter material film 4 does not prevent moisture permeation but absorbs moisture. By using a film that absorbs moisture, the getter material film 4 captures moisture that slightly enters the space formed by the gas barrier films 3 and 9 when the solar cell element 6 is covered with the gas barrier film 3 or the like. The influence of moisture on the solar cell element 6 can be eliminated.

The degree of moisture absorption capacity of the getter material film 4 is usually 0.1 mg / cm ² or more, and although there is no upper limit, it is usually 10 mg / cm ² or less. Further, when the solar cell element 6 is covered with the gas barrier films 3 and 9 or the like by the getter material film 4 absorbing oxygen, the oxygen that slightly enters the space formed by the gas barrier films 3 and 9 is obtained as the getter material. The film 4 can capture and eliminate the influence of oxygen on the solar cell element 6.

  Furthermore, it is preferable that the getter material film 4 transmits visible light from the viewpoint of not preventing the solar cell element 6 from absorbing light. For example, the transmittance of visible light (wavelength 360 to 830 nm) is usually 60% or more, and there is no upper limit.

  Furthermore, since the thin film solar cell 14 is often heated by receiving light, the getter material film 4 preferably has heat resistance. From this viewpoint, the melting point of the constituent material of the getter material film 4 is usually 100 ° C. or higher and 350 ° C. or lower.

  The material constituting the getter material film 4 is arbitrary as long as it can absorb at least one of moisture and oxygen. Examples of the materials include alkali metal, alkaline earth metal or alkaline earth metal oxides; alkali metal or alkaline earth metal hydroxides; silica gel; zeolitic compounds; magnesium sulfate. And sulfates such as sodium sulfate and nickel sulfate; or organometallic compounds such as aluminum metal complexes and aluminum oxide octylates. Specifically, examples of the alkaline earth metal include calcium, strontium, and barium. Examples of the alkaline earth metal oxide include calcium oxide, strontium oxide, and barium oxide. Other examples include zirconium-aluminum-barium oxide and aluminum metal complexes. Specific product names include, for example, OleDry (Futaba Electronics).

  Examples of the substance that absorbs oxygen include activated carbon, silica gel, activated alumina, molecular sieve, magnesium oxide, and iron oxide. In addition, iron, manganese, zinc, or inorganic salts such as sulfates, chlorides, and nitrates of these metals are also included.

  In addition, the getter material film 4 may be formed of one type of material or may be formed of two or more types of materials. The getter material film 4 may be formed of a single layer film, but may be a laminated film including two or more layers.

  The thickness of the getter material film 4 is not particularly specified, but is usually 5 μm or more and 200 μm or less.

  The formation position of the getter material film 4 is not limited as long as it is in the space formed by the gas barrier films 3 and 9, but the front surface of the solar cell element 6 (the surface on the light receiving surface side, the lower surface in FIG. 2). And it is preferable to cover the back surface (surface opposite to the light receiving surface; upper surface in FIG. 2). This is because, in the thin film solar cell 14, the front and back surfaces are often formed in a larger area than the other surfaces, and therefore moisture and oxygen tend to enter through these surfaces. From this viewpoint, the getter material film 4 is preferably provided between the gas barrier film 3 and the solar cell element 6.

  In this embodiment, the getter material film 4 covers the front surface of the solar cell element 6, a getter material film 8 described later covers the back surface of the solar cell element 6, and the getter material films 4 and 8 are respectively the solar cell element 6 and the gas barrier film 3. , 9 are located between them. In addition, when using a highly waterproof sheet such as a sheet in which a fluororesin film is bonded to both surfaces of an aluminum foil as the back sheet 10 described later, at least one of the getter material film 8 and the gas barrier film 9 may not be used depending on the application. Also good.

<6.5 Sealant>
The sealing material 5 is a film that reinforces the solar cell element 6. Since the solar cell element 6 is thin, the strength is usually weak, and thus the strength of the thin film solar cell tends to be weak. However, the strength can be maintained high by the sealing material 5.

  Moreover, it is preferable that the sealing material 5 has high strength from the viewpoint of maintaining the strength of the thin-film solar cell 14. The specific strength is related to the strength of the weatherproof protective film 1 other than the sealing material 5 and the strength of the back sheet 10 and is generally difficult to define, but the thin film solar cell 14 as a whole has good bending workability. However, it is desirable to have a strength that does not cause peeling of the bent portion.

  Moreover, it is preferable that the sealing material 5 permeate | transmits visible light from a viewpoint which does not prevent the light absorption of the solar cell element 6. FIG. For example, the transmittance of visible light (wavelength 360 to 830 nm) is usually 60% or more, and there is no upper limit.

  The thickness of the sealing material 5 is not particularly specified, but is usually 2 μm or more and 700 μm or less.

  The T-type peel adhesion strength of the sealing material 5 to the substrate is usually 1 N / inch or more and usually 2000 N / inch or less. It is preferable that the T-type peel adhesive strength is 1 N / inch or more in terms of ensuring the long-term durability of the module. It is preferable that the T-type peel adhesive strength is 2000 N / inch or less in that the base material, the barrier film, and the adhesive can be separated and discarded when the solar cell is discarded. The T-type peel adhesion strength is measured by a method according to JIS K6854-3 (1999).

  The constituent material of the sealing material 5 is not particularly limited as long as it has the above characteristics, but sealing of organic / inorganic solar cells, sealing of organic / inorganic LED elements, sealing of electronic circuit boards, etc. In general, a sealing material generally used can be used.

  Specifically, a thermosetting resin composition or a thermoplastic resin composition and an active energy ray curable resin composition can be mentioned. The active energy ray-curable resin composition is, for example, a resin that is cured by ultraviolet rays, visible light, electron beams, or the like. More specifically, an ethylene-vinyl acetate copolymer (EVA) resin composition, a hydrocarbon resin composition, an epoxy resin composition, a polyester resin composition, an acrylic resin composition, and a urethane resin composition. Or a silicon-based resin composition, etc., depending on the main chain, branched chain, terminal chemical modification of each polymer, adjustment of molecular weight, additives, etc., thermosetting, thermoplastic and active energy ray curable, etc. The characteristics are expressed.

  Moreover, since the thin film solar cell 14 is often heated by receiving light, it is preferable that the sealing material 5 also has heat resistance. From this viewpoint, the melting point of the constituent material of the sealing material 5 is usually 100 ° C. or higher and 350 ° C. or lower.

The density of the constituent material for sealing material in the sealing material 5 is preferably 0.80 g / cm ³ or more, and there is no upper limit. The measurement and evaluation of density can be performed by a method based on JIS K7112 (1999).

  Although there is no restriction | limiting in the position which provides the sealing material 5, Usually, it provides so that the solar cell element 6 may be inserted | pinched. This is for reliably protecting the solar cell element 6. In this embodiment, the sealing material 5 and the sealing material 7 are provided on the front surface and the back surface of the solar cell element 6, respectively.

<6.6 Solar Cell Element>
The solar cell element 6 is the same as the photoelectric conversion element 107 described above. That is, the thin-film solar cell 14 can be manufactured using the photoelectric conversion element 107.

  Although only one solar cell element 6 may be provided for each thin film solar cell 14, usually two or more solar cell elements 6 are provided. The specific number of solar cell elements 6 may be set arbitrarily. When a plurality of solar cell elements 6 are provided, the solar cell elements 6 are often arranged in an array.

  When a plurality of solar cell elements 6 are provided, the solar cell elements 6 are usually electrically connected to each other, and electricity generated from the connected group of solar cell elements 6 is taken out from a terminal (not shown). At this time, the solar cell elements are usually connected in series in order to increase the voltage.

  Thus, when connecting the solar cell elements 6, it is preferable that the distance between the solar cell elements 6 is small, and the clearance between the solar cell element 6 and the solar cell element 6 is preferably narrow. This is because the light receiving area of the solar cell element 6 is widened to increase the amount of received light, and the amount of power generated by the thin film solar cell 14 is increased.

<6.7 Sealant>
The sealing material 7 is a film similar to the sealing material 5 described above, and the same material as the sealing material 7 can be used in the same manner except that the arrangement position is different. Moreover, since the constituent member on the back side of the solar cell element 6 does not necessarily need to transmit visible light, a member that does not transmit visible light can be used.

<6.8 Getter Material Film>
The getter material film 8 is the same film as the getter material film 4 described above, and the same material as the getter material film 4 can be used as necessary, except for the arrangement position. Moreover, since the constituent member on the back side of the solar cell element 6 does not necessarily need to transmit visible light, a member that does not transmit visible light can be used.

<6.9 Gas barrier film>
The gas barrier film 9 is the same film as the gas barrier film 3 described above, and the same material as the gas barrier film 9 can be used as necessary except that the arrangement position is different. Moreover, since the constituent member on the back side of the solar cell element 6 does not necessarily need to transmit visible light, a member that does not transmit visible light can be used.

<6.10 Backsheet>
The back sheet 10 is the same film as the weather-resistant protective film 1 described above, and the same material as the weather-resistant protective film 1 can be used in the same manner except that the arrangement position is different. In addition, if the back sheet 10 is difficult to permeate water and oxygen, the back sheet 10 can also function as a gas barrier layer. Moreover, since the constituent member on the back side of the solar cell element 6 does not necessarily need to transmit visible light, a member that does not transmit visible light can be used.

<6.11 Dimensions>
The thin film solar cell 14 of the present embodiment is usually a thin film member. Thus, by forming the thin film solar cell 14 as a film-like member, the thin film solar cell 14 can be easily installed in a building material, an automobile, an interior, or the like. The thin-film solar cell 14 is light and difficult to break. Therefore, a highly safe solar cell can be obtained, and can be applied to curved surfaces, so that it can be used for more applications. Since it is thin and light, it is preferable in terms of distribution such as transportation and storage. Furthermore, since it is in the form of a film, a roll-to-roll type production is possible and a significant cost cut is possible.

  Although there is no restriction | limiting in the specific dimension of the thin film solar cell 14, The thickness is usually 300 micrometers or more and 3000 micrometers or less.

<6.12 Manufacturing Method>
Although there is no restriction | limiting in the manufacturing method of the thin film solar cell 14 of this embodiment, For example, as a solar cell manufacturing method of the form of FIG. 2, after producing the laminated body shown by FIG. Is mentioned. Since the solar cell element of this embodiment is excellent in heat resistance, it is preferable in that deterioration due to the laminate sealing step is reduced.

  The laminate production shown in FIG. 2 can be performed using a known technique. The method of the laminate sealing step is not particularly limited as long as the effects of the present invention are not impaired, but for example, wet lamination, dry lamination, hot melt lamination, extrusion lamination, coextrusion molding lamination, extrusion coating, photocuring adhesive Laminate, thermal laminate, etc. are mentioned. Among them, a laminating method using a photo-curing adhesive having a proven record in organic EL device sealing, a hot melt laminate or a thermal laminate having a proven record in solar cells is preferable, and a hot melt laminate or a thermal laminate is a sheet-like sealing material. It is more preferable at the point which can be used.

  The heating temperature in the laminate sealing step is usually 130 ° C or higher, preferably 140 ° C or higher, and is usually 180 ° C or lower, preferably 170 ° C or lower. The heating time in the laminate sealing step is usually 10 minutes or longer, preferably 20 minutes or longer, and is usually 100 minutes or shorter, preferably 90 minutes or shorter. The pressure in the laminate sealing step is usually 0.001 MPa or more, preferably 0.01 MPa or more, and usually 0.2 MPa or less, preferably 0.1 MPa or less. By setting the pressure within this range, sealing can be performed reliably, and the reduction of the film thickness due to the protrusion of the sealing materials 5 and 7 from the end portion and overpressurization can be suppressed, thereby ensuring dimensional stability. In addition, what connected two or more solar cell elements 6 in series or in parallel can be manufactured similarly to the above.

<6.13 Applications>
There is no restriction | limiting in the use of the solar cell which concerns on this invention, especially the thin film solar cell 14 mentioned above, It can use for arbitrary uses. Examples of the field to which the thin-film solar cell according to the present invention is applied include building material solar cells, automobile solar cells, interior solar cells, railway solar cells, marine solar cells, airplane solar cells, and spacecrafts. Solar cells, solar cells for home appliances, solar cells for mobile phones, solar cells for toys, and the like.

  The solar cell according to the present invention, particularly the thin film solar cell, may be used as it is, or may be used as a solar cell module by installing one or more solar cells on a substrate. For example, as schematically shown in FIG. 3, a solar cell module 13 including a thin film solar cell 14 on the substrate 12 may be prepared and used at a place of use. That is, the solar cell module 13 can be manufactured using the thin film solar cell 14. As a specific example, when a building material plate is used as the base material 12, a solar cell panel can be produced as the solar cell module 13 by providing the thin film solar cell 14 on the surface of the plate material.

  The substrate 12 is a support member that supports the thin film solar cell 14. Examples of the material for forming the substrate 12 include inorganic materials such as quartz, glass, sapphire, and titania, and flexible substrates. Specific examples of the flexible substrate include, but are not limited to, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyimide, nylon, polystyrene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, fluororesin film, vinyl chloride. Polyolefins such as polyethylene; organic materials (resin base materials) such as cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene, epoxy resin; paper materials such as paper or synthetic paper; stainless steel, A composite material such as a metal foil made of titanium, aluminum or the like, whose surface is coated or laminated in order to impart insulation, can be used.

  In addition, 1 type may be used for the material of a base material, and 2 or more types may be used together by arbitrary combinations and a ratio. Moreover, carbon fiber may be included in these organic materials or paper materials to reinforce the mechanical strength. When the example of the base material 12 is given, Alpolic (registered trademark; manufactured by Mitsubishi Plastics) and the like may be mentioned.

  Although there is no restriction | limiting in the shape of the base material 12, Usually, a board | plate material is used. Moreover, what is necessary is just to set the material of the base material 12, a dimension, etc. arbitrarily according to the use environment. This solar cell panel can be installed on the outer wall of a building.

  Hereinafter, embodiments of the present invention will be described by way of examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

<Synthesis example>
Each tetrabicycloporphyrin compound (hereinafter referred to as BCODP) was synthesized according to the following Synthesis Examples 1-17. ¹ H-NMR and ¹³ C-NMR were measured using a Varian NMR System-500. The absorption spectrum was measured using JASCO V-630 iRM. MALDI-TOF mass spectrometry was performed using a BRUKER DATONICS autoflex II spectrometer.

Synthesis of (Synthesis Example 1) _{BCODP-Br-H 2} and _{BCODP-Br 2} -H 2

BCODP-H ₂ (200 mg, 0.32 mmol) synthesized according to the method described in JP-A No. 2003-304014 and N-bromosuccinimide (40 mg, 0.22 mmol) were added to a 200 mL brown eggplant-shaped flask, and chloroform was added. Dissolved. After refluxing at 70 ° C. for 24 hours under an argon atmosphere, the solvent was removed, the residue was dissolved again in chloroform (10 mL), and washed with water (3 times) and saturated brine (1 time). After dehydration with sodium sulfate, the solvent was removed. The product was separated by silica gel column chromatography (solvent: chloroform / hexane = 7/3) and reprecipitated with methanol (3 mL), respectively, to obtain BCODP-Br-H ₂ (76 mg, 0.11 mmol, 54% yield), and _{BCODP-Br 2 -H 2 (12} mg, was obtained 0.016 mmol, yield 5%).

^{5-bromo-2 1,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7 1,} 7 4, 12 ^1, 12 4, 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-Br-H ₂ ):
Brown powder Melting point> 200 ℃ (decomposition)
¹ H-NMR (CDCl ₃ ): δ = 10.31 (s, 2H, 10-, 20-), 10.22 (s, 1H, 15-), 7.15 (m, 8H), 6.59 (m, 2H), 5.74 ( m, 6H), 2.21 (m, 8H), 7.91 (m, 8H), -4.11 (brs, 2H, NH)
MS (MALDI-TOF): m / z: 701 (M ⁺ )
UV / Vis (CHCl ₃ ): λ _max (lgε) = 400 (5.12), 503 (4.16), 535 (3.58), 573 (3.70), 625 nm (2.97)

5,15-Dibromo ^{- 21,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7} 1, ^{7 4,} 12 1, ¹² 4, 17 ^1, 17 ⁴ - tetra ethanolate tetrabenzoporphyrazine porphine _{(BCODP-Br 2 -H 2)} :
Brown powder Melting point> 200 ℃ (decomposition)
¹ H-NMR (CDCl ₃ ): δ = 10.23 (s, 2H), 7.25 (m, 8H), 6.50 (m, 4H), 5.70 (m, 4H), 2.17 (m, 8H), 2.01 (m, 4H), 1.91 (m, 4H), -3.25 (brs, 2H, NH)
MS (MALDI-TOF): m / z: 780 (M ⁺ )

Synthesis Example 2 Synthesis of BCODP-Br-Zn

BCODP-Br-H ₂ (78 mg, 0.11 mmol) synthesized in Synthesis Example 1 was added to a 50 mL eggplant-shaped flask and dissolved in chloroform (10 mL). Zinc acetate dihydrate (200 mg, 0.91 mmol) dissolved in methanol (2 mL) was further added, and the mixture was stirred at room temperature for 30 minutes. After removing the solvent, the residue was dissolved in chloroform (10 mL) and washed with water (3 times) and saturated brine (1 time). The obtained reaction mixture was dried over anhydrous sodium sulfate, separated by silica gel column chromatography (solvent: chloroform), and reprecipitated using methanol (5 mL), whereby BCODP-Br-Zn (80 mg, yield). 95%) was obtained as a magenta powder.

^{5-bromo-2 1,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7 1,} 7 4, 12 ^1, 12 4, 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporfinato zinc (BCODP-Br-Zn):
¹ H-NMR (CDCl ₃ ): δ = 10.33 (m, 3H), 7.14 (m, 8H), 6.69 (m, 2H), 5.79 (m, 2H), 5.75 (m, 4H), 1.9-2.2 ( m, 16H)
MS (MALDI-TOF): m / z: 764 (M ⁺ )

(Synthesis Example 3) _BCODP-Br 2 -Zn Synthesis of

In 50mL eggplant-shaped _{flask, BCODP-Br 2 -H 2 (} 30 mg, 0.038 mmol) synthesized in Synthesis Example 1 was added and dissolved in chloroform (10 mL). Zinc acetate dihydrate (100 mg, 0.46 mmol) dissolved in methanol (2 mL) was further added, and the mixture was stirred at room temperature for 30 minutes. After removing the solvent, the residue was dissolved in chloroform (10 mL) and washed with water (3 times) and saturated brine (1 time). The reaction mixture was dried over anhydrous sodium sulfate, separated by silica gel column chromatography (solvent: chloroform), and reprecipitated with methanol (5 mL), so that BCODP-Br ₂ -Zn (31 mg, yield) 96%) was obtained as a magenta powder.

5,15-Dibromo ^{- 21,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7} 1, ^{7 4,} 12 1, ¹² 4, 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporfinato zinc (BCODP-Br ₂ -Zn):
¹ H-NMR (CDCl ₃ ): δ = 10.21 (m, 2H), 7.11 (m, 8H), 6.62 (m, 4H), 5.72 (m, 4H), 1.9-2.2 (m, 16H)
MS (MALDI-TOF): m / z: 842 (M ⁺ )

Synthesis Example 4 Synthesis of BCODP-4-pentylphenyl-H ₂

In a 100 mL eggplant-shaped flask, BCODP-Br-Zn (10 mg, 0.013 mmol) synthesized in Synthesis Example 2, 4-pentylphenylboronic acid (4.5 mg, 0.024 mmol), potassium carbonate (3 mg, 0.032 mmol), and Add a spatula full of tetrakis (triphenylphosphine) palladium (0) (about 5 mg) and dissolve in a mixed solvent of tetrahydrofuran and water (tetrahydrofuran / water = 7/3) (40 mL). Reflux at 1 ° C. for 1 day. After removing the solvent, it was dissolved in chloroform, washed with water and saturated brine, dehydrated with sodium sulfate, and then the solvent was removed. Subsequently, an acetic acid solution was prepared, and a few drops of dilute hydrochloric acid were added thereto, followed by stirring for 30 minutes to perform metal removal. The obtained product was separated by silica gel column chromatography (solvent: chloroform), and reprecipitated with methanol (1 mL), whereby BCODP-4-pentylphenyl-H ₂ (9 mg, yield 90%). )

5-4- pentylphenyl ^{- 21,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7} 1, 7 ^4, 12 1, 12 ⁴ , 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-4-pentylphenyl-H ₂ ):
Brown powder Melting point> 200 ℃ (decomposition)
¹ H-NMR (CDCl ₃ ): δ = 10.37 (s, 2H, 10-, 20-), 10.26 (s, 1H, 15-), 8.12 (m, 2H), 7.61 (m, 2H), 7.14 ( m, 4H), 7.00 (m, 2H), 6.70 (m, 2H), 5.76 (s, 2H), 5.73 (s, 2H), 5.70 (s, 2H), 3.75 (m, 2H), 3.09 (m , 2H), 2.22 (m, 4H), 2.06 (m, 2H), 2.00 (m, 2H), 1.70 (m, 2H), 1.59 (m, 6H), 1.05 (m, 3H), -4.35 (brs , 2H, NH)
MS (MALDI-TOF): m / z: 769 (M ⁺ )
UV / Vis (CHCl ₃ ): λ _max (lgε) = 405 (5.35), 500.5 (4.30), 534 (3.97), 567.5 (3.96), 619 (3.40)

Synthesis Example 5 Synthesis of BCODP-4-pentylphenyl-Zn

BCODP-4-pentylphenyl-H ₂ (50 mg, 0.065 mmol) synthesized in Synthesis Example 4 was added to a 50 mL eggplant-shaped flask and dissolved in chloroform (10 mL). Zinc acetate dihydrate (200 mg, 0.91 mmol) dissolved in methanol (2 mL) was further added, and the mixture was stirred at room temperature for 30 minutes. After removing the solvent, the residue was dissolved in chloroform (10 mL) and washed with water (3 times) and saturated brine (1 time). The reaction mixture was dried over anhydrous sodium sulfate, separated by silica gel column chromatography (solvent: chloroform), and reprecipitated with methanol (5 mL), whereby BCODP-4-pentylphenyl-Zn (53 mg, 0.064 mmol, yield 98%) was obtained as a magenta powder.

5-4- pentylphenyl ^{- 21,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7} 1, 7 ^4, 12 1, 12 ⁴ , 17 ¹ , 17 ⁴ -Tetraethanotetrabenzoporfinato zinc (BCODP-4-pentylphenyl-Zn):
¹ H-NMR (CDCl ₃ ): δ = 10.40 (m, 2H), 10.36 (m, 1H), 8.13 (m, 2H), 7.62 (m, 2H), 7.16 (m, 4H), 7.01 (m, 2H), 6.70 (m, 2H), 5.78 (s, 4H), 5.72 (m, 2H), 3.70 (m, 2H), 3.10 (m, 2H), 1.6-2.2 (m, 20H), 1.05 (m , 3H)
MS (MALDI-TOF): m / z: 830 (M ⁺ )

Synthesis Example 6 Synthesis of BCODP-4-ethylphenyl-H ₂

In a 100 mL eggplant-shaped flask, BCODP-Br-Zn (100 mg, 0.13 mmol), 4-ethylphenylboronic acid (30 mg, 0.20 mmol), potassium carbonate (41 mg, 0.39 mmol) synthesized in Synthesis Example 2 and Add a spatula full of tetrakis (triphenylphosphine) palladium (0) (about 5 mg) and dissolve in a mixed solvent of tetrahydrofuran and water (tetrahydrofuran / water = 7/3) (80 mL). Reflux at 1 ° C. for 1 day. After removing the solvent, the residue was dissolved in chloroform (10 mL), washed with water (3 times) and saturated brine (1 time), dehydrated with sodium sulfate, and then the solvent was removed. Subsequently, an acetic acid solution (10 mL) was prepared, and a few drops of dilute hydrochloric acid was added thereto, followed by stirring for 30 minutes to perform demetalization. The obtained product was separated by silica gel column chromatography (solvent: chloroform) and reprecipitated with methanol (2 mL), whereby BCODP-4-ethylphenyl-H ₂ (70 mg, 0.096 mmol, yield). 74%).

5-4- ^{ethyl-phenyl-2 1,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7} 1, 7 ^4, 12 1, 12 ⁴ , 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-4-ethylphenyl-H ₂ )
Brown powder Melting point> 200 ℃ (decomposition)
¹ H-NMR (CDCl ₃ ): δ = 10.37 (s, 2H, 10-, 20-), 10.26 (s, 1H, 15-), 8.14 (m, 2H), 7.63 (m, 2H), 7.14 ( m, 4H), 7.01 (m, 2H), 6.72 (m, 2H), 5.76 (s, 2H), 5.71 (m, 4H), 3.74 (m, 2H), 3.13 (m, 2H), 2.22 (m , 4H), 2.06 (m, 2H), 1.97 (m, 2H), 1.82 (m, 2H), 1.71 (m, 2H), 1.60 (m, 2H), 1.05 (m, 3H), -4.35 (brs , 2H, NH)
MS (MALDI-TOF): m / z: 725 (M ⁺ )
UV / Vis (CHCl ₃ ): λ _max (lgε) = 398.5 (5.20), 499.5 (4.22), 531 (3.71), 567 (3.85), 618 (3.04)

Synthesis Example 7 Synthesis of BCODP-4-butylphenyl-H ₂

In a 100 mL eggplant-shaped flask, BCODP-Br-Zn (10 mg, 0.013 mmol), 4-butylphenylboronic acid (4.5 mg, 0.024 mmol), potassium carbonate (3 mg, 0.032 mmol) synthesized in Synthesis Example 2 and Add a spatula full of tetrakis (triphenylphosphine) palladium (0) (about 5 mg) and dissolve in a mixed solvent of tetrahydrofuran and water (tetrahydrofuran / water = 7/3) (40 mL). Reflux at 1 ° C. for 1 day. After removing the solvent, it was dissolved in chloroform, washed with water and saturated brine, dehydrated with sodium sulfate, and then the solvent was removed. Subsequently, an acetic acid solution was prepared, and a few drops of dilute hydrochloric acid were added thereto, followed by stirring for 30 minutes to perform metal removal. The obtained product was separated by silica gel column chromatography (solvent: chloroform) and reprecipitated with methanol (1 mL), so that BCODP-4-butylphenyl-H ₂ (7 mg, yield 70%). )

5-4- butyl ^{phenyl-2 1,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7} 1, 7 ^4, 12 1, 12 ⁴ , 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-4-butylphenyl-H ₂ )
Brown powder Melting point> 200 ℃ (decomposition)
¹ H-NMR (CDCl ₃ ): δ = 10.36 (s, 2H, 10-, 20-), 10.26 (s, 1H, 15-), 8.12 (m, 2H), 7.61 (m, 2H), 7.14 ( m, 4H), 7.00 (m, 2H), 6.70 (m, 2H), 5.76 (s, 2H), 5.73 (s, 2H), 5.70 (s, 2H), 3.75 (m, 2H), 3.09 (m , 2H), 2.22 (m, 4H), 2.06 (m, 2H), 2.00 (m, 2H), 1.70 (m, 2H), 1.59 (m, 6H), 1.14 (m, 3H), -4.35 (brs , 2H, NH)
MS (MALDI-TOF): m / z: 754 (M ⁺ )
UV / Vis (CHCl ₃ ): λ _max (lgε) = 402 (5.14), 499.5 (4.13), 531.5 (3.75), 566.5 (3.84), 617.5 (3.20)

Synthesis Example 8 Synthesis of BCODP-4-octylphenyl-H ₂

In a 100 mL eggplant-shaped flask, BCODP-Br-Zn (100 mg, 0.13 mmol), 4-octylphenylboronic acid (46 mg, 0.195 mmol), potassium carbonate (41 mg, 0.39 mmol), and spatula synthesized in Synthesis Example 2 A cup of tetrakis (triphenylphosphine) palladium (0) (about 5 mg) was added and dissolved in a mixed solvent of tetrahydrofuran and water (tetrahydrofuran / water = 7/3) (80 mL). At reflux for 1 day. After removing the solvent, the residue was dissolved in chloroform (10 mL), washed with water (3 times) and saturated brine (1 time), dehydrated with sodium sulfate, and then the solvent was removed. Subsequently, the solution was made into an acetic acid solution (10 mL), and a few drops of dilute hydrochloric acid were added, followed by stirring for 30 minutes for demetalization. The obtained product was separated by silica gel column chromatography (solvent: chloroform) and reprecipitated with methanol (2 mL), so that BCODP-4-octylphenyl-H ₂ (75 mg, 0.092 mmol, yield) Rate 71%).

5-4- octylphenyl ^{- 21,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7} 1, 7 ^4, 12 1, 12 ⁴ , 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-4-octylphenyl-H ₂ ):
Brown powder Melting point> 200 ℃ (decomposition)
¹ H-NMR (CDCl ₃ ): δ = 10.36 (s, 2H, 10-, 20-), 10.26 (s, 1H, 15-), 8.14 (m, 2H), 7.62 (m, 2H), 7.14 ( m, 4H), 7.00 (m, 2H), 6.70 (m, 2H), 5.76 (s, 2H), 5.73 (m, 4H), 3.74 (m, 2H), 3.09 (m, 2H), 2.23-1.81 (m, 16H), 1.70-1.31 (m, 9H), 0.95-0.91 (m, 6H), -4.35 (brs, 2H, NH)
MS (MALDI-TOF): m / z: 810 (M ⁺ )
UV / Vis (CHCl ₃ ): λ _max (lgε) = 399 (5.23), 499.5 (4.23), 531 (3.71), 567 (3.86), 618 (2.98)

Synthesis Example 9 Synthesis of BCODP-4-butoxyphenyl-H ₂

In a 100 mL eggplant-shaped flask, BCODP-Br-Zn (100 mg, 0.13 mmol) synthesized in Synthesis Example 2, 4-butoxyphenylboronic acid pinacol ester (53 mg, 0.20 mmol), potassium carbonate (36 mg, 0.26 mmol) , And a spatula full of tetrakis (triphenylphosphine) palladium (0) (about 5 mg), dissolved in a mixed solvent of tetrahydrofuran and water (tetrahydrofuran / water = 7/3) (40 mL), and under argon atmosphere , And refluxed at 75 ° C. for 1 day. After removing the solvent, it was dissolved in chloroform, washed with water (3 times) and saturated brine (1 time), dehydrated with sodium sulfate, and then the solvent was removed. Subsequently, an acetic acid solution was prepared, and a few drops of dilute hydrochloric acid were added thereto, followed by stirring for 30 minutes to perform metal removal. The obtained product was separated by silica gel column chromatography (solvent: chloroform) and reprecipitated with methanol (2 mL), whereby BCODP-4-butoxyphenyl-H ₂ (44 mg, 0.06 mmol, yield). 44%).

5-4- ^{butoxy-phenyl-2 1,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7} 1, 7 ^4, 12 1, 12 ⁴ , 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-4-butoxyphenyl-H ₂ ):
Brown powder Melting point> 200 ℃ (decomposition)
¹ H-NMR (CDCl ₃ ): δ = 10.37 (s, 2H, 10-, 20-), 10.26 (s, 1H, 15-), 8.12 (m, 2H), 7.37 (m, 2H), 7.14 ( m, 4H), 7.01 (m, 2H), 6.75 (m, 2H), 5.75 (s, 4H), 5.71 (s, 2H), 4.38 (m, 2H), 3.85 (m, 2H), 2.22 (m , 4H), 2.06 (m, 2H), 2.00 (m, 2H), 1.70 (m, 2H), 1.59 (m, 3H), 1.05 (m, 3H), -4.35 (brs, 2H, NH)
MS (MALDI-TOF): m / z: 771 (M ⁺ )
UV / Vis (CHCl ₃ ): λ _max (lgε) = 400 (5.19), 499.5 (4.20), 532 (3.75), 567 (3.88), 617.5 (3.12)

Synthesis Example 10 Synthesis of BCODP-ethyl-H ₂

In a 100 mL brown eggplant-shaped flask, BCODP-Br-Zn (20 mg, 0.026 mmol), potassium carbonate (10 mg, 0.078 mmol), ethyl boronic acid (2.9 mg, 0.039 mmol) synthesized in Synthesis Example 2 and a spatula Dichloro [1,1-bis (diphenylphosphino) ferrocene] palladium / dichloromethane adduct (PdCl ₂ (dppf) · CH ₂ Cl ₂ , about 5 mg) was added, and a mixed solvent of tetrahydrofuran and water (tetrahydrofuran / water = 10/1) (5.5 mL) and refluxed at 75 ° C. for 1 day under an argon atmosphere. After removing the solvent, it was dissolved in chloroform, washed with water (3 times) and saturated brine (1 time), dehydrated with sodium sulfate, and then the solvent was removed. Subsequently, an acetic acid solution was prepared, and a few drops of dilute hydrochloric acid were added thereto, followed by stirring for 30 minutes to perform metal removal. The obtained product was separated by silica gel column chromatography (solvent: chloroform) and reprecipitated using methanol (5 mL) to obtain BCODP-ethyl-H ₂ (1 mg, yield 6%). It was.

^{5-ethyl-2 1,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7 1,} 7 4, 12 ^1, 12 4, 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-ethyl-H ₂ ):
¹ H-NMR (CDCl ₃ ): δ = 10.30 (s, 2H), 10.15 (s, 1H), 7.14 (m, 8H), 5.83-5.75-5.69 (m, 8H), 5.46-5.35 (d, 2H ), 2.43 (s, 3H), 2.21 (m, 8H), 1.93 (m, 8H), -4.00 (brs, 2H, NH, -4.13)
MS (MALDI-TOF): m / z: 651 (M ⁺ )

Synthesis Example 11 Synthesis of BCODP-n-hexyl-H ₂

Using a syringe, add 1-hexene (0.16 mL, 1.3 mmol) and 9-borabicyclo [3.3.1] nonane (9-BBN, 0.50 M tetrahydrofuran solution, 2.0 mL, 0.98 mmol) to a 50 mL eggplant-shaped flask. In addition, it was dissolved in tetrahydrofuran (5 mL) and stirred at room temperature for 9 hours to prepare an n-hexyl-9-BBN / tetrahydrofuran solution. Next, in a 100 mL eggplant type flask, BCODP-Br-Zn (50 mg, 0.065 mmol) synthesized in Synthesis Example 2 and a spatula full of dichloro [1,1-bis (diphenylphosphino) ferrocene] palladium / dichloromethane adduct (PdCl ₂ (dppf) · CH ₂ Cl ₂ , about 5 mg) and potassium carbonate (27 mg, 0.20 mmol) were added, and a mixed solvent of tetrahydrofuran and water (tetrahydrofuran / water = 10/1) (23 mL) Dissolved in. Under an argon atmosphere, the prepared n-hexyl-9-BBN / tetrahydrofuran solution (7 mL) was further added with a syringe, and the mixture was refluxed at 75 ° C. for 1 day. After cooling to room temperature, a 30% aqueous hydrogen peroxide solution (0.32 mL) and a 3M aqueous sodium hydroxide solution (0.32 mL) were added and stirred for 1 hour. The product was extracted with hexane (50 mL), washed with water (3 times) and saturated brine (1 time), dried over anhydrous sodium sulfate, and the solvent was removed. Subsequently, an acetic acid solution was prepared, and a few drops of dilute hydrochloric acid were added thereto, followed by stirring for 30 minutes to perform metal removal. The obtained product was separated by silica gel column chromatography (solvent: ethyl acetate / hexane = 1/9), and reprecipitated with acetone and water (acetone / water = 1/5) (5 mL). -n- hexyl -H ₂ was obtained (13 mg, 0.019 mmol, 29 % yield).

5-n-hexyl ^{- 21,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7} 1, ^{7 4,} 12 1, ¹² 4, 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-n-hexyl-H ₂ ):
¹ H-NMR (CDCl ₃ ): δ = 10.30 (s, 2H), 10.14 (s, 1H,) 7.13 (m, 8H), 5.81-5.69 (m, 8H), 5.38-5.29 (m, 2H), 2.84-2.74 (d, 2H), 2.19 (m, 8H), 1.93 (m, 4H), 1.68 (m, 2H), 1.25 (s, 6H), 1.05 (t, 3H), 0.88 (m, 2H) , -4.00 (brs, 2H, NH, -4.20)
¹³ C-NMR (CDCl ₃ ): δ = 150.8 (s), 149.4 (s), 148.1 (s), 146.5 (s), 140.6 (brs, 140.0), 137.7 (brs, 137.5), 136.9 (t, 136.5 ), 120.8 (brs), 120.7 (t, 120.6), 97.08 (d, -97.05), 96.4 (s), 95.7 (s), 40.4 (s), 38.8 (t, 38.7), 36.4 (d, 36.3) , 36.0 (s), 34.3 (s), 32.3 (d), 31.9 (s), 30.2 (s), 29.7 (t, 29.6), 29.3 (s), 28.1 (brs, 28.0), 27.8 (s), 27.5 (d, 27.4), 27.1 (s), 22.7 (s), 18.8 (s), 14.2 (s), 14.1 (s)
MS (MALDI-TOF): m / z: 707 (M ⁺ )
UV / Vis (CHCl ₃ ): λmax (lgε) = 403 (5.04), 502 (4.07), 535 (3.45), 571 (3.63), 637 (2.06)

Synthesis Example 12 Synthesis of BCODP-phenyl-H ₂

In a 100 mL eggplant-shaped flask, BCODP-Br-Zn (76 mg, 0.10 mmol), potassium carbonate (28 mg, 0.2 mmol), phenylboronic acid (18 mg, 0.15 mmol) synthesized in Synthesis Example 2 and a spatula Tetrakis (triphenylphosphine) palladium (0) (about 5 mg) was dissolved in a mixed solvent of tetrahydrofuran and water (tetrahydrofuran / water = 7/3) (40 mL), and it was kept at 75 ° C. for 1 day under an argon atmosphere. Refluxed. After removing the solvent, it was dissolved in chloroform, washed with water (3 times) and saturated brine (1 time), dehydrated with sodium sulfate, and then the solvent was removed. Subsequently, an acetic acid solution was prepared, and a few drops of dilute hydrochloric acid were added thereto, followed by stirring for 30 minutes to perform metal removal. Separation by silica gel column chromatography (solvent: chloroform) and reprecipitation using methanol (2 mL) gave BCODP-phenyl-H ₂ (66 mg, yield 95%).

^{5-phenyl-2 1,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7 1,} 7 4, 12 ^1, 12 4, 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-phenyl-H ₂ ):
Chestnut powder Melting point> 200 ℃ (decomposition)
¹ H NMR (CDCl ₃ ): δ = 10.37 (s, 2H, 10-, 20-), 10.27 (s, 1H, 15-), 8.25 (m, 2H), 7.93 (m, 1H), 7.82 (m , 2H), 7.25 (m, 4H), 7.02 (m, 2H), 6.73 (m, 2H), 5.73 (m, 6H), 3.70 (m, 2H), 2.08 (m, 8H), 1.86 (m, 8H), -4.28 (brs, 2H, NH)
MS (MALDI-TOF): m / z: 699 (M ⁺ )
UV / Vis (CHCl ₃ ): λ _max (lgε) = 397 (5.19), 499 (4.19), 530 (3.66), 567 (3.74), 618 (2.91)

(Synthesis Example 13) Synthesis of BCODP-diphenyl-H ₂

In a 100 mL eggplant-shaped flask, BCODP-Br ₂ -Zn (20 mg, 0.024 mmol), potassium carbonate (7.9 mg, 0.057 mmol), phenylboronic acid (6.4 mg, 0.052 mmol) synthesized in Synthesis Example 3 and a spatula Of tetrakis (triphenylphosphine) palladium (0) (about 5 mg) was dissolved in a mixed solvent of tetrahydrofuran and water (tetrahydrofuran / water = 7/3) (40 mL), and at 75 ° C. under argon atmosphere. Refluxed for 1 day. After removing the solvent, it was dissolved in chloroform, washed with water (3 times) and saturated brine (1 time), dehydrated with sodium sulfate, and then the solvent was removed. Subsequently, an acetic acid solution was prepared, and a few drops of dilute hydrochloric acid were added thereto, followed by stirring for 30 minutes to perform metal removal. The obtained product was separated by silica gel column chromatography (solvent: chloroform) and reprecipitated with methanol (2 mL) to obtain BCODP-diphenyl-H ₂ (14 mg, yield 78%). It was.

5,15 diphenyl ^{- 21,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7} 1, ^{7 4,} 12 1, ¹² 4, 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-diphenyl-H ₂ ):
Chestnut powder Melting point> 200 ℃ (decomposition)
¹ H NMR (CDCl ₃ ): δ = 10.33 (s, 2H, 10-, 20-), 8.13 (m, 4H), 7.61 (m, 4H), 7.01 (m, 4H), 6.71 (m, 4H) , 5.70 (m, 4H), 3.80 (m, 4H), -3.83 (brs, 2H, NH)
MS (MALDI-TOF): m / z: 714 (M ⁺ )
UV / Vis (CHCl ₃ ): λ _max (lgε) = 408 (5.25), 504 (4.19), 536.5 (3.61), 571.5 (3.89), 617.5 (3.53)

Synthesis Example 14 Synthesis of BCODP-methyl-H ₂

In a 100 mL eggplant-shaped flask, BCODP-Br-Zn (71 mg, 0.092 mmol), potassium carbonate (38 mg, 0.28 mmol), methylboronic acid (17 mg, 0.28 mmol) synthesized in Synthesis Example 2 and a spatula full of dichloromethane [1,1-bis (diphenylphosphino) ferrocene] palladium / dichloromethane adduct (PdCl ₂ (dppf) · CH ₂ Cl ₂ , about 5 mg) was added, and a mixed solvent of tetrahydrofuran and water (tetrahydrofuran / water = 7 / 3) (20 mL) and refluxed at 75 ° C. for 1 day under an argon atmosphere. After removing the solvent, it was dissolved in chloroform, washed with water (3 times) and saturated brine (1 time), dehydrated with sodium sulfate, and then the solvent was removed. Subsequently, an acetic acid solution was prepared, and a few drops of dilute hydrochloric acid were added thereto, followed by stirring for 30 minutes to perform metal removal. The obtained product was separated by silica gel column chromatography (solvent: chloroform) and reprecipitated using methanol (2 mL) to obtain BCODP-methyl-H ₂ (41 mg, yield 69%). It was.

^{5-methyl-2 1,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7 1,} 7 4, 12 ^1, 12 4, 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-methyl-H ₂ ):
¹ H-NMR (CDCl ₃ ): δ = 10.27 (s, 2H), 10.14 (s, 1H), 7.13 (m, 8H), 5.95 (m, 2H), 5.74 (m, 6H), 5.01 (s, 3H), 2.19 (m, 8H), 1.95 (m, 8H), -3.95 (brs, 2H, NH, -4.07)
¹³ C-NMR (CDCl ₃ ): δ = 150.4 (s), 149.4 (s), 148.2 (s), 146.9 (s), 140.9 (brs, 140.5), 140.2 (brs, 140.0), 137.9 (brs, 137.6 ), 136.9 (t, 136.5), 114.8 (t, 114.7), 96.6 (s), 95.8 (s), 40.2 (s), 36.37 (d, 36.29), 36.0 (s), 27.9 (s), 27.46 ( s), 27.15 (d, 27.12)
MS (MALDI-TOF): m / z: 637 (M ⁺ )
UV / Vis (CHCl ₃ ): λ _max (lgε) = 400 (4.97), 502 (3.99), 535 (3.44), 571 (3.54), 637 (2.06)

Synthesis Example 15 Synthesis of BCODP-3-methoxyphenyl-H ₂

In a 100 mL eggplant-shaped flask, BCODP-Br-Zn (10 mg, 0.013 mmol), potassium carbonate (3 mg, 0.032 mmol), 3-methoxyphenylboronic acid (4.5 mg, 0.024 mmol) synthesized in Synthesis Example 2 and Put a spatula full of tetrakis (triphenylphosphine) palladium (0) (about 5 mg) and dissolve in a mixed solvent of tetrahydrofuran and water (tetrahydrofuran / water = 7/3) (40 mL). Reflux at 1 ° C. for 1 day. After removing the solvent, the residue was dissolved in chloroform (10 mL), washed with water (3 times) and saturated brine (1 time), dehydrated with sodium sulfate, and then the solvent was removed. Subsequently, an acetic acid solution was prepared, and a few drops of dilute hydrochloric acid were added thereto, followed by stirring for 30 minutes to perform metal removal. The obtained product was separated by silica gel column chromatography (solvent: chloroform), and reprecipitated using methanol (2 mL), so that BCODP-3-methoxyphenyl-H ₂ (7 mg, yield 77%). )

5-3- methoxyphenyl ^{- 21,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7} 1, 7 ^4, 12 1, 12 ⁴ , 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-3-methoxyphenyl-H ₂ ):
Brown powder Melting point> 200 ℃ (decomposition)
¹ H-NMR (CDCl ₃ ): δ = 10.37 (s, 2H, 10-, 20-), 10.27 (s, 1H, 15-), 7.97-7.66 (m, 3H), 7.51 (m, 1H), 7.14 (m, 4H), 7.02 (m, 1H), 6.74 (m, 2H), 5.72 (m, 6H), 3.98 (m, 3H), 3.81 (m, 2H), 2.21 (m, 4H), 2.07 (m, 2H), 1.95 (m, 4H), 1.85 (m, 2H), 1.76 (m, 2H), 1.60 (m, 2H), -4.30 (brs, 2H, NH)
MS (MALDI-TOF): m / z: 728 (M ⁺ )
UV / Vis (CHCl ₃ ): λ _max (lgε) = 399 (5.22), 499 (4.24), 531 (3.64), 568 (3.87), 620 (2.80)

Synthesis Example 16 Synthesis of BCODP-4-methoxyphenyl-H ₂

In a 100 mL eggplant-shaped flask, BCODP-Br-Zn (60 mg, 0.079 mmol), potassium carbonate (22 mg, 0.16 mmol), 4-methoxyphenylboronic acid (21 mg, 0.12 mmol) synthesized in Synthesis Example 2, and Put a spatula full of tetrakis (triphenylphosphine) palladium (0) (about 5 mg) and dissolve in a mixed solvent of tetrahydrofuran and water (tetrahydrofuran / water = 7/3) (40 mL). Reflux at 1 ° C. for 1 day. After removing the solvent, the residue was dissolved in chloroform (10 mL), washed with water (3 times) and saturated brine (1 time), dehydrated with sodium sulfate, and then the solvent was removed. Subsequently, an acetic acid solution was prepared, and a few drops of dilute hydrochloric acid were added thereto, followed by stirring for 30 minutes to perform metal removal. The obtained product was separated by silica gel column chromatography (solvent: chloroform), and reprecipitated with methanol (2 mL), whereby BCODP-4-methoxyphenyl-H ₂ (52 mg, yield 90%). )

5-4- methoxyphenyl ^{- 21,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7} 1, 7 ^4, 12 1, 12 ⁴ , 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-4-methoxyphenyl-H ₂ )
Brown powder Melting point> 200 ℃ (decomposition)
¹ H-NMR (CDCl ₃ ): δ = 10.37 (s, 2H, 10-, 20-), 10.26 (s, 1H, 15-), 8.13 (m, 2H), 7.34 (m, 2H), 7.14 ( m, 4H), 7.01 (m, 2H), 6.72 (m, 2H), 5.76 (m, 4H), 5.72 (m, 2H), 4.19 (m, 3H), 3.81 (s, 2H), 2.22-1.41 (m, 16H), -4.34 (brs, 2H, NH)
MS (MALDI-TOF): m / z: 728 (M ⁺ )
UV / Vis (CHCl ₃ ): λ _max (lgε) = 399 (5.23), 501 (4.30), 531 (3.82), 568 (3.88), 620 (3.19)

Synthesis Example 17 Synthesis of BCODP-4-tolyl-H ₂

In a 100 mL eggplant-shaped flask, BCODP-Br-Zn (100 mg, 0.13 mmol), potassium carbonate (41 mg, 0.39 mmol), 4-tolylboronic acid (27 mg, 0.20 mmol) synthesized in Synthesis Example 2 and a spatula Of tetrakis (triphenylphosphine) palladium (0) (about 5 mg) was dissolved in a mixed solvent of tetrahydrofuran and water (tetrahydrofuran / water = 7/3) (80 mL), and the mixture was heated at 75 ° C. under argon atmosphere. Refluxed for 1 day. After removing the solvent, the residue was dissolved in chloroform (10 mL), washed with water (3 times) and saturated brine (1 time), dehydrated with sodium sulfate, and then the solvent was removed. Subsequently, an acetic acid solution was prepared, and a few drops of dilute hydrochloric acid were added thereto, followed by stirring for 30 minutes to perform metal removal. The obtained product was separated by silica gel column chromatography (solvent: chloroform) and reprecipitated with methanol (2 mL), so that BCODP-4-tolyl-H ₂ (76 mg, yield 82%) Got.

5-4- tolyl ^{- 21,} 2 ^{4, 7 1,} 7 ^4, 12 1, 12 ^4, 17 1, 17 ⁴ - ^{tetrahydro-2 1,} 2 ^{4, 7} 1, ^{7 4,} 12 1, ¹² 4, 17 ¹ , 17 ⁴ -tetraethanotetrabenzoporphine (BCODP-4-tolyl-H ₂ ):
Brown powder Melting point> 200 ℃ (decomposition)
¹ H-NMR (CDCl ₃ ): δ = 10.37 (s, 2H, 10-, 20-), 10.26 (s, 1H, 15-), 8.11 (m, 2H), 7.63 (m, 2H), 7.14 ( m, 4H), 7.01 (m, 2H), 6.70 (m, 2H), 5.76 (s, 2H), 5.73 (s, 2H), 3.77 (m, 2H), 2.83 (m, 2H), 2.22 (m , 4H), 2.06 (m, 2H), 1.97 (m, 2H), 1.82 (m, 2H), 1.71 (m, 2H), 1.60 (m, 2H), 1.05 (m, 3H), -4.35 (brs , 2H, NH)
MS (MALDI-TOF): m / z: 712 (M ⁺ )
UV / Vis (CHCl ₃ ): λ _max (lgε) = 398.5 (5.23), 499.5 (4.24), 531.5 (3.76), 566.5 (2.90), 618 (3.09)

Synthesis Example 18 Synthesis of tetrabenzoporphyrin compound

  Each of the monosubstituted tetrabicycloporphyrin compounds (BCODP) obtained in Synthesis Example 4 to Synthesis Example 17 is almost quantitative by heating at 180 ° C. for 60 minutes, 200 ° C. for 30 minutes, or 210 ° C. for 20 minutes. To the corresponding monosubstituted tetrabenzoporphyrin compound (hereinafter referred to as BP). Each of the obtained monosubstituted tetrabenzoporphyrin compounds is represented by the following formula.

<Example 1: Preparation of semiconductor film and measurement of thin film X-ray diffraction (XRD)>
(1. Measurement by out of plane method)
(Examples 1-1 to 1-6)
Each tetrabicycloporphyrin compound obtained in Synthesis Examples 4 to 9 (Example 1-1: BCODP-4-pentylphenyl-H ₂ , Example 1-2: BCODP-4-pentylphenyl-Zn, Example 1- 3: BCODP-4- ethylphenyl -H _2, example 1-4: BCODP-4- butylphenyl -H _2, example 1-5: BCODP-4- octylphenyl -H _2, example 1-6: A chloroform solution (10 mg / mL) of BCODP-4-butoxyphenyl-H ₂ ) was prepared. Each film was spin-coated on a glass (Pyrex (registered trademark)) substrate using a spin coater MS-A100 (manufactured by Mikasa) to produce a good film. Then, the tetrabicycloporphyrin compound was converted into the tetrabenzoporphyrin compound by performing a heat treatment at 210 ° C. for 20 minutes using a hot plate HP-2SA (manufactured by ASONE). Thus, each tetrabenzoporphyrin compound (Example 1-1: BP-4-pentylphenyl-H ₂ , Example 1-2: BP-4-pentylphenyl-Zn, Example 1-3: BP-4-ethyl Phenyl-H ₂ , Example 1-4: BP-4-butylphenyl-H ₂ , Example 1-5: BP-4-octylphenyl-H ₂ , Example 1-6: BP-4-butoxyphenyl- A semiconductor film of H ₂ ) was produced.

  The obtained film was subjected to thin film X-ray diffraction (XRD) measurement (out of plane method) under the following conditions. The results are shown in FIG. FIG. 6 shows an enlarged view of the thin film X-ray diffraction (XRD) (out of plane method) spectrum of FIG. 5 in the range of 2 ° to 10 ° in the horizontal axis (2θ) direction. As a control, FIGS. 5 and 6 also show thin film X-ray diffraction (XRD) (out of plane method) spectra for a glass substrate on which a semiconductor film was not formed.

(Comparative Examples 1-1 to 1-7)
As comparative examples, BCODP-H ₂ synthesized according to the method described in JP-A No. 2003-304014 and the tetrabicycloporphyrin compounds obtained in Synthesis Examples 12-17 (Comparative Example 1-1: BCODP-H ₂ , Comparative Example) 1-2: BCODP-phenyl-H ₂ , Comparative Example 1-3: BCODP-diphenyl-H ₂ , Comparative Example 1-4: BCODP-methyl-H ₂ , Comparative Example 1-5: BCODP-3-methoxyphenyl- H ₂ , Comparative Example 1-6: BCODP-4-methoxyphenyl-H ₂ , Comparative Example 1-7: BCODP-4-tolyl-H ₂ ) Similarly tetrabenzoporphyrin compound (Comparative example 1-1: _{BP-H 2,} Comparative example 1-2: BP- phenyl -H _2, Comparative example 1-3: BP- diphenyl -H _2, Comparative example 1 4: BP- methyl -H _2, Comparative Example 1-5: BP-3- methoxyphenyl -H _2, Comparative Example 1-6: BP-4-methoxyphenyl -H _2, Comparative Example 1-7: BP-4 -Tolyl-H ₂ ) was prepared, and thin film X-ray diffraction (XRD) (out of plane method) measurement was performed. The results are shown in FIG.

(Example 1-7)
A chloroform solution (10 mg / mL) of the tetrabicycloporphyrin compound (BCODP-n-hexyl-H ₂ ) obtained in Synthesis Example 11 was prepared. Using a spin coater MS-A100 (manufactured by Mikasa), spin-coating the solution on a glass substrate (FLAT ITO film made by Geomat Corp.) on which an indium tin oxide (ITO) transparent conductive film (155 nm thickness) is deposited. Produced a good film. Then, the tetrabicycloporphyrin compound was converted into the tetrabenzoporphyrin compound by performing a heat treatment at 180 ° C. for 60 minutes using a hot plate HP-2SA (manufactured by ASONE). Thus, a semiconductor film of a tetrabenzoporphyrin compound (BP-n-hexyl-H ₂ ) was produced.

  The obtained film was subjected to thin film X-ray diffraction (XRD) measurement (out of plane method) under the following conditions. The results are shown in FIG. As a control, a thin film X-ray diffraction (XRD) (out of plane method) spectrum of a glass substrate on which ITO is deposited without producing a semiconductor film is also shown in FIG.

(Comparative Examples 1-8 to 1-9)
As comparative examples, BCODP-H ₂ synthesized according to the method described in JP-A-2003-304014 and the tetrabicycloporphyrin compound obtained in Synthesis Example 14 (Comparative Example 1-8: BCODP-H ₂ , Comparative Example 1- 9: BCODP-methyl-H ₂ ) and each of the tetrabenzoporphyrin compounds (Comparative Example 1-8: BP-H ₂ , Comparative Example 1-9: BP-methyl-H) as in Example 1-7. The semiconductor film of ₂ ) was obtained on a glass substrate on which ITO was deposited. Thin film X-ray diffraction (XRD) measurement (out of plane method) was performed on the obtained film. The results are shown in FIG.

  5 to 8, the positions of the baselines of the respective spectra are shifted in order to facilitate the discrimination of the respective spectra.

(Measurement condition)
Measuring device RINT2000 manufactured by Rigaku Corporation
Optical system Oblique incident X-ray diffraction optical system Measurement conditions out of plane method X-ray output 50 kV, 250 mA (CuKα)
Scanning axis 2θ
Incident angle (θ) 0.2 °
Scanning range (2θ) 2-50 °
Scanning speed 3 ° / min

Here, the d value was obtained from Bragg's law (2 dsin θ = λ).
d: Crystal plane spacing θ: X-ray incident angle (θ)
λ: X-ray wavelength (1.541 mm)

  As shown in Examples 1-1 to 1-7, in a film of a monosubstituted tetrabenzoporphyrin compound substituted with a specific organic group having an alkyl group having 2 to 20 carbon atoms, an out of plane method is used. A strong peak was observed between 2θ = 2 ° and 4 °. Table 1 shows the 2θ value and d value of the peak observed between 2θ = 2 ° and 4 ° for Example 1-1 and Examples 1-3 to 1-5. As shown in Table 1, as the carbon number of the alkyl group increased, a tendency for the d value to increase was observed.

(2. Measurement by in-plane method)
Semiconductor films (Example 1- 1) obtained on glass (Pyrex (registered trademark)) substrates in Examples 1-1, 1-3 to 1-5, and Comparative Examples 1-1, 1-2, and 1-7. 1: BP-4-pentylphenyl -H _2, example 1-3: BP-4-ethylphenyl -H _2, example 1-4: BP-4-butylphenyl -H _2, example 1-5: BP-4-octylphenyl -H _2, Comparative example 1-1: _{BP-H 2,} Comparative example 1-2: BP- phenyl -H _2, Comparative example 1-7: BP-4-tolyl -H ₂₎ for The thin film X-ray diffraction (XRD) measurement (in-plane method) was performed under the following conditions. The results are shown in FIG.

Moreover, the semiconductor film (Example 1-7: BP-n-hexyl-H ₂ , Comparative Example) obtained on the glass substrate on which ITO was deposited in Example 1-7 and Comparative Examples 1-8 and 1-9. 1-8: BP-H ₂ and Comparative Example 1-9: BP-methyl-H ₂ ), thin film X-ray diffraction (XRD) measurement (in plane method) was performed under the following conditions. The results are shown in FIG. As a control, a thin film X-ray diffraction (XRD) (in-plane method) spectrum of a glass substrate on which ITO is deposited without producing a semiconductor film is also shown in FIG. FIG. 11 shows only the measurement result of the semiconductor film of Example 1-7 (BP-n-hexyl-H ₂ ) with the intensity on the vertical axis enlarged.

  In FIGS. 9 and 10, the base line position of each spectrum is shifted in order to facilitate discrimination of each spectrum.

(Measurement condition)
Measuring device RINT2000 manufactured by Rigaku Corporation
Optical system Oblique incident X-ray diffraction optical system Measurement conditions in plane method X-ray output 50 kV, 250 mA (CuKα)
Scanning axis Φ / 2θ χ
Incident angle (θ) 0.2 °
Fixed angle (2θ) 0.2 °
Scanning range (2θ χ) 2-50 °
Step width 0.05 °
Measurement time 3.0sec

  Films of monosubstituted tetrabenzoporphyrin compounds substituted with specific organic groups having an alkyl group having 2 to 20 carbon atoms as shown in Examples 1-1, 1-3 to 1-5, and 1-7 In, 4 or more peaks with periodicity were observed between 2θ = 8 ° and 25 ° by the in-plane method.

  A monosubstituted tetrabenzoporphyrin compound substituted with a specific organic group having an alkyl group having 2 or more carbon atoms exhibits a similar peak group, whereas it has an alkyl group (methyl group) having 1 carbon atom. Monosubstituted tetrabenzoporphyrin compounds substituted with specific organic groups showed different peak groups. As described above, the monosubstituted tetrabenzoporphyrin compound substituted with a specific organic group having an alkyl group having 2 or more carbon atoms and the specific organic group having an alkyl group (methyl group) having 1 carbon atom are substituted. It can be seen that the monosubstituted tetrabenzoporphyrin compound has a completely different crystal structure.

<Example 2: Production and evaluation of field effect transistor (FET) element>
(Examples 2-1 to 2-7)
On an n-type silicon (Si) substrate (Sb-doped, resistivity 0.02 Ω · cm or less, manufactured by SUMCO) on which an oxide film having a thickness of 300 nm is formed, the length (L) is 100 μm and the width (W) is photolithography. Gold electrodes having a gap of 500 μm were formed as a source electrode and a drain electrode. Further, a part of the oxide film at a position different from this electrode was scraped off and used as a gate electrode.

Next, each tetrabicycloporphyrin compound obtained in Synthesis Examples 4 to 9 and 11 (Example 2-1: BCODP-4-pentylphenyl-H ₂ , Example 2-2: BCODP-4-pentylphenyl-Zn example 2-3: BCODP-4- ethylphenyl -H _2, example 2-4: BCODP-4- butylphenyl -H _2, example 2-5: BCODP-4- octylphenyl -H _2, carried Example 2-6: A chloroform solution (10 mg / mL) of BCODP-4-butoxyphenyl-H ₂ and Example 2-7: BCODP-n-hexyl-H ₂ ) was prepared. A spin coater MS-A100 (Mikasa Co., Ltd.) was used to spin coat each solution onto the above-described substrate, thereby forming a good film. Then, the tetrabicycloporphyrin compound was converted into the tetrabenzoporphyrin compound by performing a heat treatment at 210 ° C. for 20 minutes using a hot plate HP-2SA (manufactured by ASONE). Thus, each tetrabenzoporphyrin compound (Example 2-1: BP-4-pentylphenyl-H ₂ , Example 2-2: BP-4-pentylphenyl-Zn, Example 2-3: BP-4-ethyl phenyl -H _2, example 2-4: BP-4-butylphenyl -H _2, example 2-5: BP-4-octylphenyl -H _2, example 2-6: BP-4-butoxyphenyl - H ₂ , Example 2-7: BP-n-hexyl-H ₂ ) semiconductor film was formed on a substrate on which an electrode was formed. In this way, an FET element was produced.

  The FET characteristics of the fabricated FET elements were evaluated using a semiconductor parameter analyzer 4155C (manufactured by Agilent Technologies). The results are shown in Table 2.

Specifically, when a voltage Vd (-60 to 0 V) is applied between the source electrode and the drain electrode and a voltage Vg (-60 to 30 V) is applied between the source electrode and the gate electrode, the semiconductor The current Id flowing through the membrane was measured. When the threshold voltage is Vt, the capacitance per unit area of the insulating film is Ci, the distance between the source electrode and the drain electrode is L, the width is W, and the hole mobility of the semiconductor film is μ, these relationships are Id = [mu] Ci when the can Vd <the Vg-Vt be expressed as (W / L) [(Vg -Vt) Vd- (Vd 2/2)]
When Vd> Vg−Vt Id = (1/2) μCi (W / L) (Vg−Vt) ²

The hole mobility μ can be obtained from either of the above two formulas according to the current-voltage characteristics. In this example, according to the equation (saturation current portion) when Vd> Vg−Vt, the hole mobility μ was calculated from the slope when Id ^1/2 and Vd were plotted.

(Comparative Examples 2-1 to 2-7)
As a comparative example, tetra bicycloporphyrin compound obtained in _{BCODP-H 2} and Synthesis Example 12 to 17 (Comparative Example 2-1: _{BCODP-H 2,} Comparative Example 2-2: BCODP- phenyl -H _2, Comparative Example 2 -3: BCODP- diphenyl -H _2, Comparative example 2-4: BCODP- methyl -H _2, Comparative example 2-5: BCODP-3- methoxyphenyl -H _2, Comparative example 2-6: BCODP-4- methoxy Using each of phenyl-H ₂ and Comparative Example 2-7: BCODP-4-tolyl-H ₂ ), the tetrabenzoporphyrin compound (Comparative Example 2- 1: BP-H ₂ , Comparative Example 2-2: BP-phenyl-H ₂ , Comparative Example 2-3: BP-diphenyl-H ₂ , Comparative Example 2-4: BP-methyl-H ₂ , Comparative Example 2- 5: BP-3- Tokishifeniru -H _2, Comparative Example 2-6: BP-4-methoxyphenyl -H _2, Comparative Example 2-7: to prepare an FET device having a BP-4-tolyl -H ₂₎ semiconductor film. In addition, the FET characteristics of the created FET elements were evaluated in the same manner as in Examples 2-1 to 2-7. The results are shown in Table 2.

  As shown in Examples 2-1 to 2-7, an FET element including a semiconductor layer containing a monosubstituted tetrabenzoporphyrin compound substituted with a specific organic group having an alkyl group having 2 to 20 carbon atoms is , Showed a large hole mobility μ. Thus, the monosubstituted tetrabenzoporphyrin compound substituted with a specific organic group having an alkyl group having 2 to 20 carbon atoms, that is, the monosubstituted tetrabenzoporphyrin compound according to the present invention exhibits good semiconductor properties. .

  More specifically, the FET devices according to Examples 2-1 to 2-7 have a hole mobility μ higher than that of an FET device (Comparative Example 2-1) including a semiconductor layer containing an unsubstituted tetrabenzoporphyrin compound. Indicated.

  Further, the FET elements according to Examples 2-1 to 2-7 are FET elements including a semiconductor layer containing a mono-substituted or di-substituted tetrabenzoporphyrin compound substituted with an organic group that does not include an alkyl group (Comparative Example). The hole mobility μ was larger than 2-2, 2-3).

  Furthermore, the FET elements according to Examples 2-1 to 2-7 are monosubstituted tetrabenzoporphyrin compounds substituted with an organic group containing a methyl group but having no alkyl group having 2 to 20 carbon atoms. The hole mobility μ was larger than that of the FET element (Comparative Examples 2-4 to 2-7) including the semiconductor layer to be contained.

  As described in Example 1, monosubstituted tetrabenzoporphyrin compounds (Examples 2-1 to 2-7) substituted with a specific organic group having an alkyl group having 2 to 20 carbon atoms are as follows: Although details are unknown, it has a characteristic crystal structure. A monocrystalline tetrabenzoporphyrin compound in which this characteristic crystal structure is substituted with a specific organic group having an alkyl group having 2 to 20 carbon atoms, that is, a high semiconductor property of the monosubstituted tetrabenzoporphyrin compound according to the present invention It is thought that it is connected to.

<Example 3: Production and evaluation of photoelectric conversion element>
A glass substrate on which a transparent conductive film (155 nm thickness) of indium tin oxide (ITO) is patterned and deposited (FLAT ITO film manufactured by Geomatic Corp.) is subjected to ultrasonic cleaning with ultrapure water to which a surfactant is added, water cleaning with ultrapure water, After cleaning in the order of ultrasonic cleaning with ultra pure water, it was dried with nitrogen blow, and finally ultraviolet ozone cleaning was performed.

Poly (3,4-ethylenedioxythiophene) poly (styrenesulfonic acid) (PEDOT: PSS) aqueous dispersion (manufactured by Heraeus Co., Ltd., trade name “CLEVIOS ^™ PVP AI4083) as a hole extraction layer on the washed substrate. ) Was spin-coated using a spin coater ACT-300DII (manufactured by Active). Thereafter, using a hot plate HP-2SA (manufactured by ASONE), the substrate was heated in the atmosphere at 120 ° C. for 10 minutes, and further heated in nitrogen at 180 ° C. for 3 minutes. The film thickness of the hole extraction layer thus obtained was about 30 nm.

Next, BCODP-H ₂ synthesized according to the method described in JP-A-2003-304014 as in Synthesis Example 1 is mixed with chloroform (manufactured by Wako Pure Chemical Industries, Ltd.) and monochlorobenzene (manufactured by Kanto Chemical Co., Inc.). A solution dissolved at 0.5 mass% in a solvent (chloroform / monochlorobenzene = 1/2, mass ratio) was prepared and filtered under a nitrogen atmosphere.

On the hole extraction layer, the obtained filtrate was spin-coated at 1500 rpm using a spin coater MS-A100 (manufactured by Mikasa) in a nitrogen atmosphere, and heated at 180 ° C. for 20 minutes using a hot plate. As described above, BCODP-H ₂ is converted into BP-H ₂ which is a p-type semiconductor material by heating. In this manner, a p-type semiconductor compound layer (film thickness of about 25 nm) containing BP-H ₂ was formed on the hole extraction layer.

Subsequently, BCODP-4-pentylphenyl-H ₂ synthesized in 0.8% by mass of Synthesis Example 4 in a mixed solvent of chloroform and monochlorobenzene (chloroform / monochlorobenzene = 1/1, mass ratio), 0 A liquid in which 6% by mass of 1- (3-methoxycarbonyl) propyl-1-phenyl [6,6] -C61 (PC ₆₁ BM, manufactured by Frontier Carbon Co.), which is a fullerene derivative, was dissolved was prepared, and a nitrogen atmosphere Filtered under.

The obtained filtrate was spin-coated on a p-type semiconductor compound layer at 1500 rpm in a nitrogen atmosphere, and heated on a hot plate at 180 ° C. for 20 minutes. As described above, BCODP-4- pentylphenyl -H ₂ by heating are converted into BP-4-pentylphenyl -H _2. Thus, on the p-type semiconductor compound layer, a mixture layer (thickness: about 100 nm) containing BP-4-pentylphenyl-H ₂ which is a p-type semiconductor compound and fullerene derivative PC ₆₁ BM which is an n-type semiconductor compound. Formed.

Subsequently, the phosphine oxide compound POPy ₂ synthesized according to the method described in JP 2011-119648 A was placed in a metal boat arranged in a vacuum evaporation apparatus. Then, by heating the Popy _2, by depositing until thickness 6nm on the mixed layer, thereby forming an electron extraction layer.

  Further, an aluminum electrode (thickness: 80 nm) was provided on the electron extraction layer by vacuum deposition, and then heated at 180 ° C. for 5 minutes on a hot plate to produce a 5 mm square photoelectric conversion element.

About the photoelectric conversion element produced as mentioned above, the current-voltage characteristic was measured. Measurement of the current-voltage characteristics of the photoelectric conversion element was performed as follows. That is, a 4 mm square metal mask is attached to the photoelectric conversion element, a solar simulator with an air mass (AM) of 1.5 G and an irradiance of 100 mW / cm ² is used as an irradiation light source, and a source meter (type 2400 manufactured by Keithley) is used. Current-voltage characteristics were measured.

The produced photoelectric conversion element had an open circuit voltage of 0.48 V, a short-circuit current density of 3.5 mA / cm ² , a fill factor of 0.39, and a photoelectric conversion efficiency of 0.65%.

  As described above, the monosubstituted tetrabenzoporphyrin compound substituted with a specific organic group having an alkyl group having 2 to 20 carbon atoms, that is, the monosubstituted tetrabenzoporphyrin compound according to the present invention is an active component of a photoelectric conversion element. It can be used as a layer material.

DESCRIPTION OF SYMBOLS 101 Anode 102 Hole taking-out layer 103 Active layer 104 Electron taking-out layer 105 Cathode 106 Base material 107 Photoelectric conversion element 1 Weatherproofing protective film 2 Ultraviolet cut film 3, 9 Gas barrier film 4, 8 Getter material film 5, 7 Sealing material 6 Solar cell element 10 Back sheet 12 Base material 13 Solar cell unit 14 Thin film solar cell 51 Semiconductor layer 52 Insulator layers 53 and 54 Source electrode and drain electrode 55 Gate electrode 56 Base material

Claims (10)

An electronic device comprising a semiconductor layer containing a compound represented by the following general formula (1).

(In the above formula, X represents a divalent linking group or a direct bond,
Alkyl represents an alkyl group having 2 to 20 carbon atoms,
M represents two hydrogen atoms, a divalent metal atom, or a divalent atomic group containing a metal atom,
R ^{11 to} R ¹⁴ , R ^{21 to} R ²⁴ , R ^{31 to} R ³⁴ , and R ^{41 to} R ⁴⁴ each independently represent a hydrogen atom or a monovalent substituent. )   The electronic device according to claim 1, wherein X in the general formula (1) is an arylene group.   The electronic device according to claim 2, wherein the arylene group is a phenylene group.   The electronic device according to any one of claims 1 to 3, wherein Alkyl in the general formula (1) is an alkyl group having 2 to 12 carbon atoms. The semiconductor layer is
Forming a layer containing a compound represented by the following general formula (2);
Converting the compound represented by the general formula (2) into the compound represented by the general formula (1);
The electronic device according to claim 1, wherein the electronic device is formed by a method including:

(In the above formula, X represents a divalent linking group or a direct bond,
Alkyl represents an alkyl group having 2 to 20 carbon atoms,
M represents two hydrogen atoms, a divalent metal atom, or a divalent atomic group containing a metal atom,
Q ¹ represents a divalent group represented by —CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ —,
Q ² represents a divalent group represented by —CR ²⁵ R ²⁶ —CR ²⁷ R ²⁸ —,
Q ³ represents a divalent group represented by —CR ³⁵ R ³⁶ —CR ³⁷ R ³⁸ —,
Q ⁴ represents a divalent group represented by —CR ⁴⁵ R ⁴⁶ —CR ⁴⁷ R ⁴⁸ —,
R ^{11 to} R ¹⁸ , R ^{21 to} R ²⁸ , R ^{31 to} R ³⁸ , and R ^{41 to} R ⁴⁸ each independently represent a hydrogen atom or a monovalent substituent. )   6. The electronic device according to claim 1, wherein the electronic device is a field effect transistor element.   The electronic device according to claim 1, wherein the electronic device is a photoelectric conversion element.   A solar cell comprising the photoelectric conversion element according to claim 7.   A solar cell module comprising the solar cell according to claim 8. A composition for forming a semiconductor layer, comprising a compound represented by the following general formula (2) and a solvent.

(In the above formula, X represents a divalent linking group or a direct bond,
Alkyl represents an alkyl group having 2 to 20 carbon atoms,
M represents two hydrogen atoms, a divalent metal atom, or a divalent atomic group containing a metal atom,
Q ¹ represents a divalent group represented by —CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ —,
Q ² represents a divalent group represented by —CR ²⁵ R ²⁶ —CR ²⁷ R ²⁸ —,
Q ³ represents a divalent group represented by —CR ³⁵ R ³⁶ —CR ³⁷ R ³⁸ —,
Q ⁴ represents a divalent group represented by —CR ⁴⁵ R ⁴⁶ —CR ⁴⁷ R ⁴⁸ —,
R ^{11 to} R ¹⁸ , R ^{21 to} R ²⁸ , R ^{31 to} R ³⁸ , and R ^{41 to} R ⁴⁸ each independently represent a hydrogen atom or a monovalent substituent. )

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