JP5363164B2 - Benzofluoranthene compound and organic thin film solar cell using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electronics material, in particular, a compound favorably used as the material of an organic thin-film solar cell. <P>SOLUTION: A benzo fluoranthane compound represented by formula (A). In the formula, R<SB>1</SB>-R<SB>12</SB>are each hydrogen, halogen, substituted or not substituted C<SB>1</SB>-C<SB>40</SB>alkyl group, substituted or not substituted C<SB>2</SB>-C<SB>40</SB>alkenyl group, substituted or not substituted C<SB>2</SB>-C<SB>40</SB>alkynyl group, C<SB>6</SB>-C<SB>40</SB>substituted or not substituted aryl group, substituted or not substituted C<SB>3</SB>-C<SB>40</SB>hetero-aryl group, substituted or not substituted C<SB>1</SB>-C<SB>40</SB>alkoxy group, or substituted or not substituted C<SB>6</SB>-C<SB>40</SB>aryloxy group, adjacent ones of R<SB>1</SB>-R<SB>12</SB>may be mutually bonded to form a ring and the ring may have a substituent. At least one of R<SB>1</SB>-R<SB>12</SB>is a predetermined amino group. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a novel benzofluoranthene compound and an organic thin-film solar cell using the same.

An organic thin film solar cell is a device that shows an electrical output with respect to an optical input, as represented by a photodiode or an imaging device that converts an optical signal into an electrical signal, or a solar cell that converts optical energy into electrical energy, It is a device that exhibits a response opposite to that of an electroluminescence (EL) element that exhibits an optical output with respect to an electrical input. In particular, solar cells have attracted a great deal of attention as a clean energy source in recent years against the background of fossil fuel depletion and global warming, and research and development have been actively conducted.
Conventionally, silicon solar cells represented by single crystal Si, polycrystal Si, amorphous Si, etc. have been put into practical use. However, as the cost and raw material Si shortage problems surface, The demand for next generation solar cells is increasing. Against this background, organic solar cells are attracting much attention as next-generation solar cells next to silicon-based solar cells because they are inexpensive, have low toxicity, and do not have a fear of shortage of raw materials.

An organic solar cell basically has an n layer that transports electrons and a p layer that transports holes, and is roughly classified into two types depending on the material constituting each layer.
A layer in which a sensitizing dye such as ruthenium dye is adsorbed on the surface of an inorganic semiconductor such as titania as the n layer and an electrolyte solution is used as the p layer is called a dye-sensitized solar cell (so-called Gretzell cell). Although it has been energetically studied since 1991 due to its high conversion efficiency, since it uses a solution, it has drawbacks such as liquid leakage when used for a long time.
In order to overcome such drawbacks, recently, studies have been made to find an all-solid-state dye-sensitized solar cell by solidifying an electrolyte solution. However, the technology for impregnating organic matter into the pores of porous titania has a high degree of difficulty, and a cell capable of expressing high conversion efficiency with high reproducibility has not been completed.
On the other hand, organic thin-film solar cells consisting of organic thin films in both the n-layer and p-layer are all solid, so they have no drawbacks such as liquid leakage, are easy to manufacture, and do not use ruthenium, which is a rare metal. Attracted attention and researched energetically.

  Organic thin-film solar cells have been researched with single-layer films using merocyanine dyes, etc., but it has been found that conversion efficiency can be improved by using p-layer / n-layer multilayer films. Multilayer films are becoming mainstream. The materials used at this time were copper phthalocyanine (CuPc) for the p layer and peryleneimides (PTCBI) for the n layer.

Subsequently, it has been found that the conversion efficiency is improved by inserting an i layer (a mixed layer of p material and n material) between the p layer and the n layer to increase the number of layers. However, the materials used at this time were still phthalocyanines and peryleneimides. Further Thereafter, further conversion efficiency stack cell configuration in the p / i / n layers be stacked several layers have been found to improve the material system at that time was phthalocyanines and C _60.

On the other hand, in an organic thin film solar cell using a polymer, a conductive polymer is used as a p material, a C ₆₀ derivative is used as an n material, and they are mixed and heat-treated to induce micro-layer separation to form a heterointerface. Research on so-called bulk heterostructures has been mainly conducted to increase the conversion efficiency and improve the conversion efficiency. Here material system that has been used is mostly soluble polythiophene derivative called P3HT as p material was soluble C ₆₀ derivatives referred to as PCBM as an n material.

As described above, in the organic thin film solar cell, the conversion efficiency has been improved by optimizing the cell configuration and morphology, but the material system used in the organic thin film solar cell has not made much progress since the early days, and phthalocyanines, peryleneimides still remain. Class C ₆₀ has been used. Therefore, development of a new material system to replace them has been eagerly desired.

  In general, the operation process of an organic solar cell consists of (1) light absorption and exciton generation, (2) exciton diffusion, (3) charge separation, (4) carrier movement, and (5) electromotive force generation. Yes. Since organic substances generally do not have many absorption characteristics that match the sunlight spectrum, high conversion efficiency cannot often be achieved. In this regard, for example, the development of organic EL elements has been energetically performed in recent years, and among them, amine compounds that are excellent hole transport materials and hole injection materials have been found. Since such amine compounds have excellent hole transport properties, they have the potential to be used as p materials for organic thin film solar cells. However, since it does not show light absorption in the visible light region, it has the disadvantage that the absorption characteristics with respect to the sunlight spectrum are insufficient and the photoelectric conversion efficiency is not sufficient.

By the way, it is generally known that in order for an organic compound to have absorption in the visible light region, the π-electron conjugated system may be enlarged to increase the absorption maximum wavelength. However, if the conjugated system is expanded too much and the molecular weight becomes too large, the difficulty of purification becomes difficult due to a decrease in solubility in a solvent, or the sublimation temperature becomes high due to an increase in sublimation temperature. Thus, polyacenes are known as examples of compounds in which the absorption wavelength is efficiently increased while suppressing the molecular weight to some extent.
For example, Patent Documents 1 and 2 disclose techniques for applying polyacenes to solar cell materials. However, in general, polyacenes are unstable with respect to light and oxygen when the number of condensed rings is increased in order to expand the visible absorption region, so that purification and handling become difficult, and high purity is difficult. Had drawbacks.

JP 2007-335760 A JP 2008-34764 A

  An object of the present invention is to provide a compound useful as an organic electronic material. In particular, it is to provide a compound that exhibits highly efficient photoelectric conversion characteristics when used in an organic thin film solar cell.

（式中、Ｒ_１〜Ｒ_１２はそれぞれ、水素、ハロゲン、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルキル基、Ｃ_２〜Ｃ_４０の置換もしくは無置換のアルケニル基、Ｃ_２〜Ｃ_４０の置換もしくは無置換のアルキニル基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリール基、Ｃ_３〜Ｃ_４０の置換もしくは無置換のヘテロアリール基、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルコキシ基、又はＣ_６〜Ｃ_４０の置換もしくは無置換のアリールオキシ基であり、Ｒ_１〜Ｒ_１２のうち隣り合うものは互いに結合して環を形成してもよく、この環は置換基を有していてもよい。
Ｒ_１〜Ｒ_１２のうち少なくともひとつは、下記式（Ｓ）で表されるアミノ基である。）

（式中、Ｒ_ａ及びＲ_ｂはそれぞれ、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリール基又はＣ_１〜Ｃ_４０の置換もしくは無置換のアルキル基である。）
２．下記式（Ｂ）で表される１に記載のベンゾフルオランテン化合物。

（式中、Ｒ_１〜Ｒ_１４はそれぞれ、水素、ハロゲン、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルキル基、Ｃ_２〜Ｃ_４０の置換もしくは無置換のアルケニル基、Ｃ_２〜Ｃ_４０の置換もしくは無置換のアルキニル基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリール基、Ｃ_３〜Ｃ_４０の置換もしくは無置換のヘテロアリール基、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルコキシ基、又はＣ_６〜Ｃ_４０の置換もしくは無置換のアリールオキシ基である。
Ｒ_１〜Ｒ_１４のうち少なくともひとつは、前記式（Ｓ）で表されるアミノ基である。）
３．下記式（Ｃ）で表される１に記載のベンゾフルオランテン化合物。

（式中、Ｒ_１〜Ｒ_１４はそれぞれ、水素、ハロゲン、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルキル基、Ｃ_２〜Ｃ_４０の置換もしくは無置換のアルケニル基、Ｃ_２〜Ｃ_４０の置換もしくは無置換のアルキニル基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリール基、Ｃ_３〜Ｃ_４０の置換もしくは無置換のヘテロアリール基、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルコキシ基、又はＣ_６〜Ｃ_４０の置換もしくは無置換のアリールオキシ基である。
Ｒ_１〜Ｒ_１４のうち少なくともひとつは、前記式（Ｓ）で表されるアミノ基である。）
４．前記Ｒ_２又はＲ_３が、Ｃ_６〜Ｃ_４０の置換もしくは無置換のジアリールアミノ基である１〜３のいずれかに記載のベンゾフルオランテン化合物。
５．前記Ｒ_１３が、Ｃ_６〜Ｃ_４０の置換もしくは無置換のジアリールアミノ基である３に記載のベンゾフルオランテン化合物。
６．上記１〜５のいずれかに記載のベンゾフルオランテン化合物からなる有機薄膜太陽電池材料。
７．上記６に記載の材料を含む有機薄膜太陽電池。
８．一対の電極の間に、少なくともｐ層を有し、前記ｐ層が６に記載の材料を含有する７に記載の有機薄膜太陽電池。 According to the present invention, the following benzofluoranthene compounds and the like are provided.
1. A benzofluoranthene compound represented by the following formula (A).

Wherein R _{1 to} R ₁₂ are each hydrogen, halogen, C _{1 to} C ₄₀ substituted or unsubstituted alkyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkenyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkynyl _group, a substituted or unsubstituted aryl group having _C 6 ~C _40, C 3 ~C substituted or unsubstituted heteroaryl group _40, a substituted or unsubstituted alkoxy group C 1 _{-C 40} Or a substituted or unsubstituted aryloxy group having ₆ to ₄₀ carbon atoms, and adjacent ones of R _{1 to} R ₁₂ may be bonded to each other to form a ring, and this ring has a substituent. It may be.
At least one of R _{1 to} R ₁₂ is an amino group represented by the following formula (S). )

(In the formula, each of R _a and R _b is a C _{6 to} C ₄₀ substituted or unsubstituted aryl group or a C _{1 to} C ₄₀ substituted or unsubstituted alkyl group.)
2. The benzofluoranthene compound according to 1, which is represented by the following formula (B).

Wherein R _{1 to} R ₁₄ are each hydrogen, halogen, C _{1 to} C ₄₀ substituted or unsubstituted alkyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkenyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkynyl _group, a substituted or unsubstituted aryl group having _C 6 ~C _40, C 3 ~C substituted or unsubstituted heteroaryl group _40, a substituted or unsubstituted alkoxy group C 1 _{-C 40} Or a C ₆ -C ₄₀ substituted or unsubstituted aryloxy group.
At least one of R _{1 to} R ₁₄ is an amino group represented by the formula (S). )
3. The benzofluoranthene compound according to 1, which is represented by the following formula (C).

Wherein R _{1 to} R ₁₄ are each hydrogen, halogen, C _{1 to} C ₄₀ substituted or unsubstituted alkyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkenyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkynyl _group, a substituted or unsubstituted aryl group having _C 6 ~C _40, C 3 ~C substituted or unsubstituted heteroaryl group _40, a substituted or unsubstituted alkoxy group C 1 _{-C 40} Or a C ₆ -C ₄₀ substituted or unsubstituted aryloxy group.
At least one of R _{1 to} R ₁₄ is an amino group represented by the formula (S). )
4). The benzofluoranthene compound according to any one of 1 to 3, wherein R ₂ or R ₃ is a C ₆ -C ₄₀ substituted or unsubstituted diarylamino group.
5. 4. The benzofluoranthene compound according to 3, wherein R ₁₃ is a C ₆ -C ₄₀ substituted or unsubstituted diarylamino group.
6). Organic thin-film solar cell material which consists of a benzofluoranthene compound in any one of said 1-5.
7). 7. An organic thin film solar cell comprising the material according to 6 above.
8). 8. The organic thin-film solar cell according to 7, which has at least a p-layer between a pair of electrodes, and the p-layer contains the material according to 6.

  The benzofluoranthene compound of the present invention can be used for organic electronic materials. In particular, an organic thin film solar cell exhibiting highly efficient energy conversion characteristics when used as an organic thin film solar cell material can be obtained.

The compound of the present invention is a benzofluoranthene compound represented by the following formula (A).

In formula (A), R _{1 to} R ₁₂ are each hydrogen, halogen, C ₁ -C ₄₀ substituted or unsubstituted alkyl group, C ₂ -C ₄₀ substituted or unsubstituted alkenyl group, C ₂ -C _{40 40} substituted or unsubstituted alkynyl groups, C _{6 to} C ₄₀ substituted or unsubstituted aryl groups, C _{3 to} C ₄₀ substituted or unsubstituted heteroaryl groups, C _{1 to} C ₄₀ substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group _C 6 _{-C 40.}
Adjacent ones of R _{1 to} R ₁₂ may be bonded to each other to form a ring such as a benzene ring. This ring may have a substituent. Examples of the substituent include the same groups as R _{1 to} R ₁₂ described above and an amino group represented by the formula (S) described later.

式（Ｓ）において、Ｒ_ａ及びＲ_ｂはそれぞれ、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリール基又はＣ_１〜Ｃ_４０の置換もしくは無置換のアルキル基である。 In the compound of the present invention, at least one of R _{1 to} R _{12 in} the formula (A) is an amino group represented by the following formula (S).

In the formula (S), R _a and R _b are each a C _{6 to} C ₄₀ substituted or unsubstituted aryl group or a C _{1 to} C ₄₀ substituted or unsubstituted alkyl group.

  Of the benzofluoranthene compounds represented by the formula (A), compounds represented by the following formula (B) or (C) (dibenzofluoranthene compounds) are preferred.

In the formula, each of R _{1 to} R ₁₄ is the same group as R _{1 to} R _{12 in} the above formula (A). At least one of R _{1 to} R ₁₄ is an amino group represented by the above formula (S).

Regarding R _{1 to} R _{14 in} formulas (A) to (C), the substituted or unsubstituted alkyl group of C _{1 to} C ₄₀ may be linear, branched or cyclic. Specific examples include methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, 3, 7 -Dimethyloctyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, norbornyl, trifluoromethyl, trichloromethyl, benzyl, α, α-dimethylbenzyl, 2-phenylethyl, 1-phenylethyl, etc. . Of these, methyl, ethyl, propyl, isopropyl, tert-butyl, cyclohexyl and the like are preferable from the viewpoint of availability of raw materials.

A substituted or unsubstituted alkenyl group having C ₂ -C ₄₀ straight chain, may be either branched or cyclic, as their specific examples include vinyl, propenyl, butenyl, oleyl, eicosapentaenoic enyl, Docosahexaenyl, styryl, 2,2-diphenylvinyl, 1,2,2-triphenylvinyl, 2-phenyl-2-propenyl and the like can be mentioned. Of these, vinyl, styryl, 2,2-diphenylvinyl and the like are preferable from the viewpoint of availability of raw materials.

Substituted or unsubstituted alkynyl group C ₂ -C ₄₀ straight chain, it may be either branched or cyclic, as their specific examples include ethenyl, propynyl, 2-phenylethenyl and the like . Of these, ethenyl, 2-phenylethenyl, and the like are preferable from the viewpoint of availability of raw materials.

Specific examples of the C ₆ -C ₄₀ substituted or unsubstituted aryl group include phenyl, 2-tolyl, 4-tolyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, 4-cyanophenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, terphenylyl, 3,5-diphenylphenyl, 3,4-diphenylphenyl, pentaphenylphenyl, 4- (2,2-diphenylvinyl) phenyl, 4- (1,2,2-tri Phenylvinyl) phenyl, fluorenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 2-anthryl, 9-phenanthryl, 1-pyrenyl, chrycenyl, naphthacenyl, coronyl and the like. Of these, phenyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl and the like are preferable from the viewpoint of availability of raw materials.

For substituted or unsubstituted heteroaryl group C ₃ -C _40, coupling position when the nitrogen-containing heterocyclic ring azole may be coupled with nitrogen, not only a carbon. Specific examples thereof include furan, thiophene, pyrrole, imidazole, benzimidazole, pyrazole, benzpyrazole, triazole, oxadiazole, pyridine, pyrazine, triazine, quinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, carbazole and the like. Can be mentioned. Of these, furan, thiophene, pyridine, carbazole and the like are preferable from the viewpoint of availability of raw materials.

The substituted or unsubstituted alkoxy group of C _{1 to} C ₄₀ may be linear, branched or cyclic, and specific examples thereof include methoxy, ethoxy, 1-propyloxy, 2-propyloxy 1-butyloxy, 2-butyloxy, sec-butyloxy, tert-butyloxy, pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, 2-ethylhexyloxy, 3,7-dimethyloctyloxy, cyclopropyloxy, cyclopentyloxy Cyclohexyloxy, 1-adamantyloxy, 2-adamantyloxy, norbornyloxy, trifluoromethoxy, benzyloxy, α, α-dimethylbenzyloxy, 2-phenylethoxy, 1-phenylethoxy and the like. Of these, methoxy, ethoxy, ter-butyloxy and the like are preferable from the viewpoint of availability of raw materials.

The C _{6 to} C ₄₀ substituted or unsubstituted aryloxy group may be linear, branched or cyclic, and specific examples thereof include a substituent in which the aryl group is bonded via oxygen. Is mentioned. Of these, phenoxy, naphthoxy, phenanthryloxy and the like are preferable from the viewpoint of availability of raw materials.

Examples of R _a and R _b of the amino group represented by the above formula (S) include C _{6 to} C ₄₀ substituted or unsubstituted aryl groups or C _{1 to} C ₄₀ substituted or unsubstituted alkyl groups. And the same groups as R _{1 to} R ₁₄ in the above formulas (A) to (C).
Specific examples of the amino group represented by the formula (S) include methylphenylamino, diphenylamino, di-p-tolylamino, dim-tolylamino, phenylm-tolylamino, phenyl-1-naphthylamino, and phenyl-2-naphthyl. Amino, phenyl (sec-butylphenyl) amino, phenyl t-butylamino, bis (4-methoxyphenyl) amino, dimethylamino, methylethylamino, diethylamino, bis (2-hydroxyethyl) amino, bis (2-methoxyethyl) ) Amino, piperidino, morpholino and the like.
Of these, diphenylamino, ditolylamino, bis (4-methoxyphenyl) amino, dimethylamino, diethylamino, piperidino and the like are preferable from the viewpoint of availability of raw materials.

Examples of the compound of the present invention include the following compounds.

There are various routes for synthesizing the compounds of the present invention. Among them, the synthetic route for cyclizing the phenanthrene derivative is that the raw materials are easily available, the reaction conditions are mild, and the target product is given in a high yield. To preferred. An example of a synthesis route is shown.

In the formula, R _{1 to} R ₁₄ are groups similar to the above formulas (A) to (C), respectively. X is a halogen such as iodine, bromine or chlorine, or a trifluoromethanesulfonyloxy (trifuryloxy) group, a nonafluorobutanesulfonyloxy (nonafuryloxy) group, a toluenesulfonyloxy (tosyloxy) group, a methanesulfonyloxy (mesyloxy) group Represents a pseudohalogen group such as Of these, halogens such as chlorine and bromine are preferred in view of availability of raw materials.

As a catalyst used for the ring closure reaction, combinations of various metals and ligands can be used. As for the metal species, nickel and palladium are preferable in terms of giving a high yield. For example, nickel chloride, dichlorobis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel, bis (cyclooctadiene) nickel, nickeltetra Examples thereof include carbonyl, bis (acetylacetonato) nickel, nickelocene, tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate and palladium chloride.
As for the ligand, triphenylphosphine, tri-o-tolylphosphine, 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl (BINAP), 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene (XantPhos), 1,2-bis (diphenylphosphino) benzene, 1,1'-bis (diphenylphosphino) ferrocene (DPPF), tri-t-butylphosphine, 2- (dicyclohexylphosphine Fino) biphenyl (JohnPhos), 2- (dicyclohexylphosphino) -2 ′-(N, N-dimethylamino) biphenyl (DavePhos), 2- (2-dicyclohexylphosphino) -2 ′, 6′-dimethoxybiphenyl ( S-Phos), 2- (2-dicyclohexylphosphino) -2 ′, 4 ′ 6'-triisopropylbiphenyl (X-Phos) phosphines such as is preferred.

  In the reaction, it is preferable to add a base. Examples of the base that can be used in this reaction include carbonates such as potassium carbonate and cesium carbonate, alkoxides such as sodium t-butoxide, diazabicycloundecene, diaza Examples include organic bases such as bicyclononene, triethylamine, diisopropylethylamine (Hueig's base), pyridine, 4-dimethylaminopyridine (DMAP), and organics such as diazabicycloundecene in terms of giving high yields. Bases are preferred.

It is also possible to add a phase transfer catalyst in order to increase the reactivity of the base. Examples of the phase transfer catalyst include tetrabutylammonium hydrogen sulfate and benzyltriethylammonium chloride.
When such a preferable synthesis route is selected, the substitution position of the amino group in the present invention is such that raw materials are readily available, synthesis can be performed with a small number of synthesis steps, and high yield is obtained under mild reaction conditions. In the reaction formulas I to III, R ₁ or R ₃ in the above formulas (A) to (C) is preferable, and in the reaction formula III, R ₁₃ is preferable.

The benzofluoranthene compound of the present invention can be used for organic electronic materials. In particular, it is suitable as an organic thin film solar cell material.
When using the compound of this invention for the member of an organic thin-film solar cell, the member may be formed from the compound of this invention alone, and may be formed from the mixture of the compound of this invention, and another component. .
The organic thin film solar cell using the organic thin film solar cell material of the present invention exhibits highly efficient conversion characteristics.

The cell structure of the organic thin film solar cell of the present invention is not particularly limited as long as it is a structure containing the compound of the present invention between a pair of electrodes. Specifically, a structure having the following configuration on a stable insulating substrate can be given.
(1) Lower electrode / organic compound layer / upper electrode (2) Lower electrode / p layer / n layer / upper electrode (3) Lower electrode / p layer / i layer (or mixed layer of p and n materials) / n Layer / upper electrode (4) Lower electrode / mixed layer of p material and n material / upper electrode and a structure in which the p layer and the n layer in the configurations (2) and (3) are replaced.

Moreover, you may provide a buffer layer between an electrode and an organic layer as needed. For example, as a specific example, when a buffer layer is provided in the configuration (1), a structure having the following configuration can be given.
(5) Lower electrode / buffer layer / p layer / n layer / upper electrode (6) Lower electrode / p layer / n layer / buffer layer / upper electrode (7) Lower electrode / buffer layer / p layer / n layer / buffer Layer / Top electrode

  The organic thin film solar cell material of the present invention can be used for, for example, an organic compound layer, p layer, n layer, i layer, a mixed layer of p material and n material, and a buffer layer. In particular, it is preferably used as a material for the p layer.

  In the organic thin-film solar cell of the present invention, any material constituting the battery may contain the material of the present invention. Moreover, the member containing the material of this invention may contain the other component collectively. About the member and mixed material which do not contain the material of this invention, the well-known member and material used with an organic thin film solar cell can be used. Hereinafter, each component will be briefly described.

1. Lower electrode, upper electrode The material of the lower electrode and the upper electrode is not particularly limited, and a known conductive material can be used. For example, a metal such as tin-doped indium oxide (ITO), gold (Au), osmium (Os), palladium (Pd) can be used as the electrode connected to the p layer, and silver as the electrode connected to the n layer. Metals such as (Ag), aluminum (Al), indium (In), calcium (Ca), platinum (Pt), lithium (Li), and binary metal systems such as Mg: Ag, Mg: In, and Al: Li In addition, an exemplary electrode material connected to the p layer can be used.

  In order to obtain highly efficient photoelectric conversion characteristics, for example, when the organic thin film solar cell is a solar cell, it is desirable that at least one surface of the solar cell is sufficiently transparent in the solar spectrum. The transparent electrode is formed using a known conductive material so as to ensure predetermined translucency by a method such as vapor deposition or sputtering. The light transmittance of the electrode on the light receiving surface is preferably 10% or more. In a preferred configuration of the pair of electrode configurations, one of the electrode portions includes a metal having a high work function, and the other includes a metal having a low work function.

2. Organic compound layer One of a p layer, a mixed layer of p material and n material, or an n layer. When the material of the present invention is used for the organic compound layer, specifically, the lower electrode / the single layer of the material of the present invention / the upper electrode, the lower electrode / the material of the present invention, and the n layer material or p layer described later. Examples include a mixed layer / top electrode material.

3. p layer, n layer, i layer When the material of the present invention is used for the p layer, the n layer is not particularly limited, but a compound having a function as an electron acceptor is preferable. For example, if the organic _compound, C _60, fullerene derivatives such as _{C 70,} carbon nanotube, perylene derivatives, polycyclic quinone, quinacridone, the polymeric CN- poly (phenylene - vinylene), MEH-CN-PPV, - CN group or CF ₃ group-containing polymers, their -CF ₃ substituted polymers, poly (fluorene) derivatives and the like can be mentioned. A material having high electron mobility is preferred. Further, a material having a small electron affinity is preferable. Thus, a sufficient open-circuit voltage can be realized by combining materials having a small electron affinity as the n layer.

Moreover, if it is an inorganic compound, the inorganic semiconductor compound of an n-type characteristic can be mentioned. Specifically, doping semiconductors and compound semiconductors such as n-Si, GaAs, CdS, PbS, CdSe, InP, Nb ₂ O ₅ , WO ₃ , Fe ₂ O ₃ , titanium dioxide (TiO ₂ ), monoxide Examples include titanium oxide such as titanium (TiO) and dititanium trioxide (Ti ₂ O ₃ ), and conductive oxides such as zinc oxide (ZnO) and tin oxide (SnO ₂ ). You may use combining more than a seed. Preference is given to using titanium oxide, particularly preferably titanium dioxide.

  When the material of the present invention is used for the n layer, the p layer is not particularly limited, but a compound having a function as a hole acceptor is preferable. For example, in the case of an organic compound, N, N′-bis (3-tolyl) -N, N′-diphenylbenzidine (mTPD), N, N′-dinaphthyl-N, N′-diphenylbenzidine (NPD), 4, Amine compounds represented by 4 ′, 4 ″ -tris (phenyl-3-tolylamino) triphenylamine (MTDATA), etc., phthalocyanine (Pc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), titanyl phthalocyanine (TiOPc) ), Phthalocyanines such as octaethylporphyrin (OEP), platinum octaethylporphyrin (PtOEP), zinc tetraphenylporphyrin (ZnTPP) and the like, and polymer compounds such as polyhexylthiophene (P3HT), Methoxyethylhexyloxyphe Vinylene (MEHPPV) main chain type conjugated polymers such as side chain type polymers such as represented by polyvinyl carbazole, and the like.

  When the material of the present invention is used for the i layer, the i layer may be formed by mixing with the p layer compound or the n layer compound, but the material of the present invention can also be used alone as the i layer. In this case, any of the above exemplary compounds can be used for the p layer or the n layer.

4). Buffer layer In general, organic thin film solar cells often have a thin total film thickness, and therefore, the upper electrode and the lower electrode are short-circuited, and the yield of cell fabrication often decreases. In such a case, it is preferable to prevent this by laminating a buffer layer.

As a preferable compound for the buffer layer, a compound having sufficiently high carrier mobility is preferable so that the short-circuit current does not decrease even when the film thickness is increased. For example, if it is a low molecular compound, the aromatic cyclic acid anhydride represented by NTCDA shown below etc. will be mentioned, and if it is a high molecular compound, poly (3,4-ethylenedioxy) thiophene: polystyrene sulfonate (PEDOT: PSS), polyaniline: camphorsulfonic acid (PANI: CSA), and other known conductive polymers.

  In addition, the buffer layer may have a role of preventing excitons from diffusing to the electrodes and deactivating. Inserting a buffer layer as an exciton blocking layer in this way is effective for increasing efficiency. The exciton blocking layer can be inserted on either the anode side or the cathode side, or both can be inserted simultaneously. In this case, as a preferable material for the exciton blocking layer, for example, a well-known material for a hole barrier layer or a material for an electron barrier layer in organic EL applications can be used. A preferable material for the hole blocking layer is a compound having a sufficiently large ionization potential, and a preferable material for the electron blocking layer is a compound having a sufficiently small electron affinity. Specifically, bathocuproin (BCP), bathophenanthroline (BPhen), and the like, which are well-known materials for organic EL applications, can be used as the cathode-side hole barrier layer material.

さらに、バッファー層には、上記ｎ層材料として例示した無機半導体化合物を用いてもよい。また、ｐ型無機半導体化合物としてはＣｄＴｅ、ｐ−Ｓｉ、ＳｉＣ、ＧａＡｓ、ＷＯ_３等を用いることができる。

Furthermore, you may use the inorganic semiconductor compound illustrated as said n layer material for a buffer layer. As the p-type inorganic semiconductor compound, CdTe, p-Si, SiC, GaAs, WO ₃ or the like can be used.

5. Substrate The substrate preferably has mechanical and thermal strength and transparency. For example, there are a glass substrate and a transparent resin film. Transparent resin films include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone. , Polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide, polyimide, polypropylene, etc. It is.

  The formation of each layer of the organic thin film solar cell of the present invention is performed by a dry film formation method such as vacuum deposition, sputtering, plasma, ion plating, or wet film formation such as spin coating, dip coating, casting, roll coating, flow coating, and ink jet. The law can be applied.

  The thickness of each layer is not particularly limited, but is set to an appropriate thickness. Since it is generally known that the exciton diffusion length of an organic thin film is short, if the film thickness is too thick, the exciton is deactivated before reaching the heterointerface, resulting in low photoelectric conversion efficiency. If the film thickness is too thin, pinholes and the like are generated, so that sufficient diode characteristics cannot be obtained, resulting in a decrease in conversion efficiency. The normal film thickness is suitably in the range of 1 nm to 10 μm, but more preferably in the range of 5 nm to 0.2 μm.

  In the case of the dry film forming method, a known resistance heating method is preferable, and for forming the mixed layer, for example, a film forming method by simultaneous vapor deposition from a plurality of evaporation sources is preferable. More preferably, the substrate temperature is controlled during film formation.

  In the case of a wet film forming method, a material for forming each layer is dissolved or dispersed in an appropriate solvent to prepare a light-emitting organic solution to form a thin film, and any solvent can be used. For example, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole, methanol, Alcohol solvents such as ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, hexane, octane, decane, tetralin, Examples include ester solvents such as ethyl acetate, butyl acetate, and amyl acetate. Of these, hydrocarbon solvents or ether solvents are preferable. These solvents may be used alone or in combination. In addition, the solvent which can be used is not limited to these.

In the present invention, in any organic thin film layer of the organic thin film solar cell, an appropriate resin or additive may be used for improving the film formability and preventing pinholes in the film. Usable resins include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose and other insulating resins and copolymers thereof, poly-N-vinyl. Examples thereof include photoconductive resins such as carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole.
Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.

[Benzofluoranthene compound]
Example 1
Compound A was synthesized by the following reaction.

(1) Synthesis of Intermediate A1 Under a nitrogen atmosphere, 9-bromophenanthrene (7.0 g, 27 mmol), 2,5-dichlorophenylboronic acid (6.2 g, 32 mmol, 1.2 eq.), Tetrakis (triphenylphosphine) Palladium (0) (0.62 g, 0.54 mmol, 2% Pd) was dissolved in 1,2-dimethoxyethane (100 ml), 2M aqueous sodium carbonate solution (10.3 g, 97 mmol, 3 eq./50 ml) was added, Refluxed for 11 hours. The reaction mixture was diluted with toluene (100 ml), the organic layer was separated, washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate and evaporated to give a pale yellow oil. This was purified by column chromatography (silica gel / hexane + 5% dichloromethane followed by hexane + 10% dichloromethane) to give a white solid (7.2 g, 83%).

The results of nuclear magnetic resonance measurement ( ¹ H-NMR) of this solid are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.39 (1H, dd, J = 9 Hz, 2 Hz), 7.44 (1H, d, J = 2 Hz), 7.47-7.55 ( 3H, m), 7.60-7.71 (4H, m), 7.88 (1H, d, J = 8 Hz), 8.72 (1H, d, J = 8 Hz), 8.76 (1H, d, J = 8Hz)

(2) Synthesis of Intermediate A2 Under a nitrogen atmosphere, diphenylamine (4.1 g, 24 mmol, 1.1 eq.), Intermediate A1 (7.2 g, 22 mmol), tris (dibenzylideneacetone) dipalladium (0) (0 20 g, 0.22 nol, 2% Pd), sodium t-butoxide (3.0 g, 31 mmol, 1.4 eq.) Was suspended in anhydrous toluene (50 ml), and a tri-t-butylphosphine / toluene solution (66 wt%, 0.11 ml, 0.36 mmol, 0.8 eq. To Pd) was added, and the mixture was stirred at 100 ° C. for 10 hours. The reaction mixture was filtered off through a silica gel pad and washed with toluene (200 ml). The brown oil obtained by concentrating the filtrate was purified by column chromatography (silica gel / hexane + 17% dichloromethane, hexane + 33% dichloromethane) to obtain a yellow amorphous solid (6.4 g, 64%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.00 (2H, t, J = 7 Hz), 7.10-7.16 (5H, m), 7.22-7.27 (5H, m), 7.39 (1H, d, J = 8 Hz), 7.55-7.67 (6H, m), 7.87 (1H, d, J = 8 Hz), 8.69 (1H, d, J = 8 Hz), 8.73 (1H, d, J = 8 Hz)

(3) Synthesis of Compound A Under a nitrogen atmosphere, intermediate A2 (6.4 g, 14 mmol), tris (dibenzylideneacetone) dipalladium (0) (0.32 g, 0.35 mmol, 5% Pd), 1,8 -Diazabicyclo [5.4.0] -7-undecene (3.0 g, 20 mmol, 1.4 eq.) Was dissolved in anhydrous DMF (35 ml), and a tri-t-butylphosphine / toluene solution (66 wt%, 0.21 ml, 0.69 mmol, 1 eq. To Pd) was added, and the mixture was stirred at 140 ° C. for 10 hours. The reaction mixture was diluted with toluene (200 ml), washed with water (100 ml) and saturated brine (50 ml), dried over anhydrous sodium sulfate and evaporated to give a brown oil. This was purified by column chromatography (silica gel / hexane + 17% dichloromethane, hexane + 33% dichloromethane) to give a yellow solid (4.8 g, 82%). This was recrystallized from toluene (20 ml) + ethanol (30 ml) to obtain yellow plate crystals (4.7 g).

The results of measuring the purity of this solid by electrolytic detachment mass spectrometry (FDMS) and liquid chromatography (HPLC) are shown below.
FDMS: Calculated value C ₃₂ H ₂₁ N = 419, measured value m / z = 419 (M ⁺ , 100)
HPLC: 99.6% (detection wavelength 254 nm: area%)

The obtained solid (4.1 g) was purified by sublimation at 280 ° C. and 2.5 × 10 ⁻⁴ Pa to obtain a yellow amorphous solid (3.6 g).
HPLC: 99.8% (detection wavelength 254 nm: area%)
The physical properties are as follows.
Melting point (mp): 157 ° C. (DSC)
Absorption maximum wavelength (CH ₂ Cl ₂ ): 425 nm

Example 2
Compound B was synthesized by the following reaction.

(1) Synthesis of Intermediate B1 9-Bromophenanthrene (5.0 g, 19 mmol), 2,4-dichlorophenylboronic acid (4.5 g, 24 mmol, 1.2 eq.), Tetrakis (triphenylphosphine) under nitrogen atmosphere Palladium (0) (0.45 g, 0.39 mmol, 2% Pd) was dissolved in 1,2-dimethoxyethane (70 ml), 2M aqueous sodium carbonate solution (7.6 g, 72 mmol, 3 eq./36 ml) was added, Refluxed for 11 hours. The reaction mixture was diluted with toluene (200 ml), the organic layer was separated, washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate and evaporated to give a brown oil. This was purified by column chromatography (silica gel / hexane + 5% dichloromethane followed by hexane + 10% dichloromethane) to give a white solid (5.2 g, 85%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.34 (1H, d, J = 8 Hz), 7.37 (1H, d, J = 9 Hz, 2 Hz), 7.48 (1H, t, J = 7 Hz), 7.52 (1H, d, J = 8 Hz), 7.58 (1H, d, J = 2 Hz), 7.59-7.70 (4H, m), 7.87 (1H, d, J = 8 Hz), 8.72 (1H, d, J = 8 Hz), 8.75 (1H, d, J = 8 Hz)

(2) Synthesis of intermediate B2 Under a nitrogen atmosphere, diphenylamine (3.0 g, 18 mmol, 1.1 eq.), Intermediate B1 (5.2 g, 16 mmol), tris (dibenzylideneacetone) dipalladium (0) (0 .15 g, 0.16 nol, 2% Pd), sodium t-butoxide (2.2 g, 23 mmol, 1.4 eq.) Was suspended in anhydrous toluene (35 ml), and a tri-t-butylphosphine / toluene solution (66 wt%, 0.08 ml, 0.26 mmol, 0.8 eq. To Pd) was added, and the mixture was stirred at 100 ° C. for 10 hours. The reaction mixture was filtered off through a silica gel pad and washed with toluene (200 ml). The brown oil obtained by concentrating the filtrate was purified by column chromatography (silica gel / hexane + 17% dichloromethane) to obtain a yellow amorphous solid (4.5 g, 62%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.06 (1H, dd, J = 8 Hz, 2 Hz), 7.10 (2H, t, J = 7 Hz), 7.21-7.27 ( 6H, m), 7.33 (4H, t, J = 8 Hz), 7.56-7.68 (6H, m), 7.89 (1H, d, J = 7 Hz), 8.72 (1H, d, J = 8 Hz), 8.76 (1H, d, J = 8 Hz)

(3) Synthesis of Compound B In a nitrogen atmosphere, intermediate B2 (4.5 g, 9.9 mmol), tris (dibenzylideneacetone) dipalladium (0) (0.23 g, 0.25 mmol, 5% Pd), 1 , 8-diazabicyclo [5.4.0] -7-undecene (2.1 g, 14 mmol, 1.4 eq.) Was dissolved in anhydrous DMF (25 ml) and a tri-t-butylphosphine / toluene solution (66 wt%, .0. 15 ml, 0.49 mmol, 1 eq. To Pd) was added, and the mixture was stirred at 140 ° C. for 10 hours. The reaction mixture was diluted with toluene (200 ml), washed with water (100 ml) and saturated brine (50 ml), dried over anhydrous sodium sulfate and evaporated to give a brown oil. This was purified by column chromatography (silica gel / hexane + 10% dichloromethane, hexane + 17% dichloromethane) to give a yellow solid (1.1 g, 27%). This was recrystallized from toluene (20 ml) + ethanol (20 ml) to obtain yellow plate crystals (0.74 g).

FDMS: Calculated value C ₃₂ H ₂₁ N = 419, measured value m / z = 419 (M ⁺ , 100)
HPLC: 99.9% (detection wavelength 254 nm: area%)

The obtained solid (0.73 g) was purified by sublimation at 260 ° C./1.2×10 ⁻⁴ Pa to obtain a yellow solid (0.68 g).
HPLC: 99.4% (detection wavelength 254 nm: area%)
mp: 211 ° C. (DSC)
Absorption maximum wavelength (CH ₂ Cl ₂ ): 415 nm

Example 3
Compound C was synthesized by the following reaction.

(1) Synthesis of Intermediate C1 Under a nitrogen atmosphere, 7-bromobenz [a] anthracene (5.2 g, 17 mmol), 2,4-dichlorophenylboronic acid (3.7 g, 19 mmol, 1.2 eq.), Tetrakis (tri Phenylphosphine) palladium (0) (0.37 g, 0.32 mmol, 2% Pd) was suspended in 1,2-dimethoxyethane (60 ml), and 2M aqueous sodium carbonate solution (6.0 g, 57 mmol, 3 eq./30 ml) Was added and refluxed for 11 hours. The reaction mixture was diluted with toluene (200 ml), the organic layer was separated, washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / hexane + 17% dichloromethane followed by hexane + 33% dichloromethane) to give a pale yellow solid (5.9 g, 93%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.28 (1H, d, J = 9 Hz), 7.32 (1H, d, J = 8 Hz), 7.45-7.48 (3H, m), 7.53-7.58 (2H, m), 7.61 (1H, t, J = 7 Hz), 7.68-7.72 (2H, m), 7.81 (1H, d, J = 8 Hz), 8.17 (1 H, d, J = 8 Hz), 8.88 (1 H, d, J = 8 Hz), 9.29 (1 H, s)

(2) Synthesis of Intermediate C2 Under a nitrogen atmosphere, diphenylamine (3.2 g, 19 mmol, 1.2 eq.), Intermediate C1 (5.9 g, 16 mmol), tris (dibenzylideneacetone) dipalladium (0) (0 .15 g, 0.16 nol, 2% Pd), sodium t-butoxide (2.2 g, 23 mmol, 1.4 eq.) Was suspended in anhydrous toluene (45 ml), and a tri-t-butylphosphine / toluene solution (66 wt%, 0.08 ml, 0.26 mmol, 0.8 eq. To Pd) was added, and the mixture was stirred at 100 ° C. for 10 hours. The reaction mixture was filtered off through a silica gel pad and washed with toluene (200 ml). The red oil obtained by concentrating the filtrate was purified by column chromatography (silica gel / hexane + 17% dichloromethane, followed by hexane + 33% dichloromethane) to give a red amorphous solid (8.0 g, 98%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.07-7.49 (13H, m), 7.56-7.67 (6H, m), 7.82 (1H, d, J = 7 Hz), 8.17 (1 H, d, J = 8 Hz), 8.88 (1 H, d, J = 8 Hz), 9.27 (1 H, s)

(3) Synthesis of Compound C Under nitrogen atmosphere, intermediate C2 (8.0 g, 9.9 mmol), tris (dibenzylideneacetone) dipalladium (0) (0.58 g, 0.64 mmol, 8% Pd), 1 , 8-diazabicyclo [5.4.0] -7-undecene (3.6 g, 24 mmol, 1.5 eq.) Was dissolved in anhydrous DMF (35 ml) and a tri-t-butylphosphine / toluene solution (66 wt%, .0. 58 ml, 1.9 mmol, 1.5 eq. To Pd) was added, and the mixture was stirred at 140 ° C. for 10 hours. The reaction mixture was diluted with toluene (200 ml), washed with water (100 ml) and saturated brine (50 ml), dried over anhydrous sodium sulfate and evaporated to give an orange solid. This was purified by column chromatography (silica gel / hexane + 33% dichloromethane, hexane + 66% dichloromethane) to obtain an orange solid (6.0 g, yield 80%). This was found to be a mixture of compound C (60%) and isomer C (40%) from ¹ H-NMR results. This was recrystallized twice from toluene (100 ml) to obtain Compound C as an orange solid (2.4 g, yield 32%).

FDMS: calculated value C ₃₆ H ₂₃ N = 469, measured value m / z = 469 (M ⁺ , 100)
HPLC: 99.6% (detection wavelength 254 nm: area%)

The obtained solid (1.66 g) was purified by sublimation at 300 ° C. and 5.9 × 10 ⁻⁴ Pa to obtain an orange solid (1.58 g).
HPLC: 99.4% (detection wavelength 254 nm: area%)
Mp: 264 ° C (DSC)
Absorption maximum wavelength (CH ₂ Cl ₂ ): 480 nm.

Example 4
Compound D was synthesized by the following reaction.

(1) Synthesis of Intermediate D1 Under a nitrogen atmosphere, 7-bromobenz [a] anthracene (5.2 g, 17 mmol), 2,5-dichlorophenylboronic acid (3.7 g, 19 mmol, 1.2 eq.), Tetrakis (tri Phenylphosphine) palladium (0) (0.37 g, 0.32 mmol, 2% Pd) was suspended in 1,2-dimethoxyethane (60 ml), and 2M aqueous sodium carbonate solution (6.0 g, 57 mmol, 3 eq./30 ml) Was added and refluxed for 11 hours. The reaction mixture was diluted with toluene (200 ml), the organic layer was separated, washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / hexane + 10% dichloromethane followed by hexane + 17% dichloromethane) to give a yellow solid (4.0 g, 63%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.28 (1H, d, J = 9 Hz), 7.41 (1H, d, J = 3 Hz), 7.46-7.49 (3H, m), 7.54-7.63 (4H, m), 7.69 (1H, dt, J = 7 Hz, 2 Hz), 7.81 (1H, dd, J = 7 Hz, 2 Hz), 8.17 ( 1H, d, J = 8 Hz), 8.87 (1H, d, J = 8 Hz), 9.29 (1H, s)

(2) Synthesis of intermediate D2 Under a nitrogen atmosphere, diphenylamine (2.2 g, 13 mmol, 1.2 eq.), Intermediate D1 (4.0 g 16 mmol), tris (dibenzylideneacetone) dipalladium (0) (0.10 g) , 0.11 mmol, 2% Pd), sodium t-butoxide (1.5 g, 16 mmol, 1.4 eq.) In anhydrous toluene (30 ml), and tri-butylphosphine / toluene solution (66 wt%, 0. (05 ml, 0.16 mmol, 0.8 eq. To Pd) was added, and the mixture was stirred at 100 ° C. for 10 hours. The reaction mixture was filtered off through a silica gel pad and washed with toluene (200 ml). The orange oil obtained by concentrating the filtrate was purified by column chromatography (silica gel / hexane + 17% dichloromethane) to give a yellow solid (4.9 g, 88%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 6.98 (2H, t, J = 7 Hz), 7.13 (1H, d, J = 3 Hz), 7.16-7.26 (9H, m), 7.43-7.67 (8H, m), 7.82 (1H, d, J = 8 Hz), 8.14 (1H, d, J = 8 Hz), 8.85 (1H, d, J = 8Hz), 9.23 (1H, s)

(3) Synthesis of Compound D Under nitrogen atmosphere, intermediate C2 (4.9 g, 9.7 mmol), tris (dibenzylideneacetone) dipalladium (0) (0.36 g, 0.39 mmol, 8% Pd), 1 , 8-diazabicyclo [5.4.0] -7-undecene (2.2 g, 14 mmol, 1.5 eq.) Was dissolved in anhydrous DMF (20 ml) and a tri-t-butylphosphine / toluene solution (66 wt%, .0. 36 ml, 1.2 mmol, 1.5 eq. To Pd) was added, and the mixture was stirred at 140 ° C. for 10 hours. The reaction mixture was diluted with toluene (200 ml), washed with water (100 ml) and saturated brine (50 ml), dried over anhydrous sodium sulfate and evaporated to give a dark yellow solid. This was purified by column chromatography (silica gel / hexane + 33% dichloromethane, hexane + 66% dichloromethane) to obtain an orange solid (3.1 g, yield 68%). This was found to be a mixture of compound D (90%) and isomer D (10%) from ¹ H-NMR results. This was recrystallized from toluene (60 ml) to obtain Compound D as an orange solid (2.2 g, yield 46%).

FDMS: calculated value C ₃₆ H ₂₃ N = 469, measured value m / z = 469 (M ⁺ , 100)
HPLC: 98.6% (detection wavelength 254 nm: area%)

The obtained solid (2.13 g) was purified by sublimation at 320 ° C. and 6.2 × 10 ⁻⁴ Pa to obtain an orange solid (2.00 g).
HPLC: 98.5% (detection wavelength 254 nm: area%)
Mp: 258 ° C (DSC)
Absorption maximum wavelength (CH ₂ Cl ₂ ): 480 nm.

Example 5
Compound E was synthesized by the following reaction.

(1) Synthesis of Intermediate E1 1,2-Benzanthraquinone (6.4 g, 25 mmol) was dissolved in acetic acid (100 ml), bromine (15 g, 94 mmol, 3.8 eq.) Was added, and the mixture was stirred at 110 ° C. for 6 hours. . The reaction mixture was diluted with water (100 ml), and the solid was filtered off and washed with water and methanol to give a yellow solid (7.6 g, 90% crude). This was recrystallized from toluene (100 ml) to obtain yellow needle crystals (5.7 g, yield 68%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.59 (1H, dd, J = 9 Hz, 7 Hz), 7.77-7.85 (2H, m), 7.97 (1H, dd, J = 7 Hz, 1 Hz), 8.27 (1H, dd, J = 7 Hz, 2 Hz), 8.31 (1H, dd, J = 8 Hz, 2 Hz), 8.49 (1H, d, J = 9 Hz), 8.71 (1H, dd, J = 9 Hz, 1 Hz), 9.72 (1H, d, J = 9 Hz)

(2) Synthesis of Intermediate E2 Intermediate E1 (5.7 g, 17 mmol) was suspended in acetic acid (400 ml), and 57% hydroiodic acid (50 ml, 0.38 mol, 22 eq.) And phosphinic acid (25 ml) were suspended. In addition, the mixture was refluxed for 33 hours. The reaction mixture was diluted with water (200 ml), and the solid was filtered off and washed with water and methanol to obtain a pale yellow solid (4.5 g, yield 86%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.48-7.64 (3H, m), 7.77-7.89 (2H, m), 8.04-8.13 (3H, m), 8.38 (1H, s), 8.79 (1H, d, J = 8 Hz), 9.13 (1H, s)

(3) Synthesis of Intermediate E3 Under a nitrogen atmosphere, intermediate E2 (3.5 g, 11 mmol), 2,4-dichlorophenylboronic acid (2.6 g, 14 mmol, 1.2 eq.), Tetrakis (triphenylphosphine) palladium (0) (0.25 g, 0.22 mmol, 2% Pd) was suspended in 1,2-dimethoxyethane (90 ml), 2M aqueous sodium carbonate solution (4.5 g, 42 mmol, 3 eq./25 ml) was added, Refluxed for 11 hours. The reaction mixture was diluted with toluene (100 ml), the organic layer was separated, washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and evaporated to give a dark brown oil. This was purified by column chromatography (silica gel / hexane + 17% dichloromethane) to obtain a white solid (2.2 g, yield 55%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.26 (1H, d, J = 9 Hz), 7.34 (1H, d, J = 8 Hz), 7.39 (1H, dd, J = 8 Hz, 2 Hz), 7.46 (1 H, d, J = 7 Hz), 7.53-7.58 (2 H, m), 7.59 (1 H, d, J = 2 Hz), 7.71-7. 74 (2H, m), 8.02-8.04 (1H, m), 8.13-8.15 (1H, m), 8.34 (1H, s), 8.92 (1H, d, J = 8Hz), 9.22 (1H, s)

(4) Synthesis of Intermediate E4 Under a nitrogen atmosphere, diphenylamine (1.2 g, 7.1 mmol, 1.2 eq.), Intermediate E3 (2.3 g, 6.0 mmol), tris (dibenzylideneacetone) dipalladium ( 0) (0.08 g, 0.09 mmol, 3% Pd), sodium t-butoxide (0.8 g, 8.3 mmol, 1.4 eq.) Was suspended in anhydrous toluene (20 ml) and tri-t-butylphosphine / Toluene solution (66 wt%, 0.04 ml, 0.13 mmol, 0.8 eq. To Pd) was added and stirred at 100 ° C. for 10 hours. The reaction mixture was filtered off through a silica gel pad and washed with toluene (200 ml). The yellow oil obtained by concentrating the filtrate was purified by column chromatography (silica gel / hexane + 17% dichloromethane) to obtain a yellow solid (1.6 g, yield 53%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.05-7.08 (2H, m), 7.19-7.24 (4H, m), 7.28-7.36 (4H, m), 7.45 (1H, d, J = 9 Hz), 7.53-7.58 (4H, m), 7.71-7.79 (4H, m), 8.03-8.05 ( 1H, m), 8.11-8.15 (1H, m), 8.36 (1H, s), 8.90 (1H, d, J = 8 Hz), 9.22 (1H, s)

(5) Synthesis of Compound E Intermediate E4 (1.6 g, 3.2 mmol), tris (dibenzylideneacetone) dipalladium (0) (0.14 g, 0.15 mmol, 10% Pd) under a nitrogen atmosphere, 1 , 8-diazabicyclo [5.4.0] -7-undecene (0.7 g, 4.6 mmol, 1.5 eq.) In anhydrous DMF (15 ml) was dissolved in tri-t-butylphosphine / toluene solution (66 wt%, 0.14 ml, 0.46 mmol, 1.5 eq. To Pd) was added, and the mixture was stirred at 140 ° C. for 10 hours. The reaction mixture was diluted with toluene (200 ml), washed with water (100 ml) and saturated brine (50 ml), dried over anhydrous sodium sulfate and evaporated to give a tan oil. This was purified by column chromatography (silica gel / hexane + 33% dichloromethane) to obtain a yellow solid (1.4 g, yield 90%). This was recrystallized from toluene (20 ml) + ethanol (30 ml) to obtain yellow needle crystals (1.0 g).

FDMS: calculated value C ₃₆ H ₂₃ N = 469, measured value m / z = 469 (M ⁺ , 100)
HPLC: 99.8% (detection wavelength 254 nm: area%)

The obtained solid (1.0 g) was purified by sublimation at 300 ° C./6.2×10 ⁻⁴ Pa to obtain a yellow solid (0.86 g).
HPLC: 99.7% (detection wavelength 254 nm: area%)
Mp: 226 ° C (DSC)
Absorption maximum wavelength (CH ₂ Cl ₂ ): 455 nm

Example 6
Compound F was synthesized by the following reaction.

(1) Synthesis of intermediate F1 Under a nitrogen atmosphere, intermediate E2 (3.5 g, 11 mmol), 2,5-dichlorophenylboronic acid (2.6 g, 14 mmol, 1.2 eq.), Tetrakis (triphenylphosphine) palladium (0) (0.25 g, 0.22 mmol, 2% Pd) was suspended in 1,2-dimethoxyethane (90 ml), 2M aqueous sodium carbonate solution (4.5 g, 42 mmol, 3 eq./25 ml) was added, Refluxed for 11 hours. The reaction mixture was diluted with toluene (100 ml), the organic layer was separated, washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and evaporated to give a dark brown oil. This was purified by column chromatography (silica gel / hexane + 17% dichloromethane) to obtain a pale yellow solid (2.5 g, yield 61%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.27 (1H, d, J = 9 Hz), 7.39 (1H, dd, J = 9 Hz, 2 Hz), 7.42 (1H, d, J = 2Hz), 7.47 (1H, d, J = 8Hz), 7.49 (1H, d, J = 9Hz), 7.54-7.57 (2H, m), 7.71 (1H, d, J = 8 Hz), 7.73 (1H, d, J = 9 Hz), 8.02-8.04 (1H, m), 8.12-8.15 (1H, m), 8.34 ( 1H, s), 8.92 (1H, d, J = 8 Hz), 9.21 (1H, s)

(2) Synthesis of intermediate F2 Under a nitrogen atmosphere, diphenylamine (1.4 g, 8.3 mmol, 1.2 eq.), Intermediate F1 (2.5 g, 6.7 mmol), tris (dibenzylideneacetone) dipalladium ( 0) (0.09 g, 0.10 mmol, 3% Pd), sodium t-butoxide (0.9 g, 9.4 mmol, 1.4 eq.) Was suspended in anhydrous toluene (20 ml) and tri-t-butylphosphine / A toluene solution (66 wt%, 0.05 ml, 0.16 mmol, 0.8 eq. To Pd) was added, and the mixture was stirred at 100 ° C. for 11 hours. The reaction mixture was filtered off through a silica gel pad and washed with toluene (200 ml). The yellow oil obtained by concentrating the filtrate was purified by column chromatography (silica gel / hexane + 17% dichloromethane) to give a yellow solid (2.9 g, yield 86%).
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.01-7.75 (17H, m), 8.02-8.24 (3H, m), 8.34 (1H, s), 8 .48-8.57 (1H, m), 8.86 (1H, d, J = 8 Hz), 9.19 (1H, s)

(3) Synthesis of Compound F Under a nitrogen atmosphere, intermediate F2 (2.9 g, 5.7 mmol), tris (dibenzylideneacetone) dipalladium (0) (026 g, 0.28 mmol, 10% Pd), 1,8 -Diazabicyclo [5.4.0] -7-undecene (1.3 g, 8.6 mmol, 1.5 eq.) Was dissolved in anhydrous DMF (25 ml) and tri-butylphosphine / toluene solution (66 wt%, 0.0. 26 ml, 0.85 mmol, 1.5 eq. To Pd) was added, and the mixture was stirred at 140 ° C. for 10 hours. The reaction mixture was diluted with toluene (200 ml), washed with water (100 ml) and saturated brine (50 ml), dried over anhydrous sodium sulfate and evaporated to give a tan oil. This was purified by column chromatography (silica gel / hexane + 33% dichloromethane) to obtain a yellow solid (1.8 g, yield 67%). This was recrystallized from toluene (20 ml) + ethanol (30 ml) to obtain yellow plate crystals (0.88 g).

FDMS: calculated value C ₃₆ H ₂₃ N = 469, measured value m / z = 469 (M ⁺ , 100)
HPLC: 99.6% (detection wavelength 254 nm: area%)

The obtained solid (0.87 g) was purified by sublimation at 280 ° C./8.3×10 ⁻⁴ Pa to obtain a yellow solid (0.79 g).
HPLC: 99.4% (detection wavelength 254 nm: area%)
Mp: 249 ° C (DSC)
Absorption maximum wavelength (CH ₂ Cl ₂ ): 419 nm

Example 7
Compound G was synthesized by the following reaction.

(1) Synthesis of Intermediate G1 Under a nitrogen atmosphere, intermediate E2 (4.9 g, 16 mmol), 2-bromophenylboronic acid (3.5 g, 17 mmol, 1.1 eq.), Tetrakis (triphenylphosphine) palladium ( 0) (0.37 g, 0.32 mmol, 2% Pd) was suspended in 1,2-dimethoxyethane (120 ml), 2M aqueous sodium carbonate solution (5.5 g, 52 mmol, 3 eq./26 ml) was added, and 11 Reflux for hours. The reaction mixture was diluted with toluene (200 ml), the organic layer was separated, washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate and evaporated to give a brown oil. This was purified by column chromatography (silica gel / hexane + 17% dichloromethane) to obtain a white solid (2.0 g, 33%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.28 (1H, d, J = 9 Hz), 7.31-7.35 (1H, m), 7.41-7.57 (5H, m), 7.71 (1H, d, J = 9 Hz), 7.72 (1H, d, J = 8 Hz), 7.76 (1H, d, J = 7 Hz), 8.02-8.04 ( 1H, m), 8.13-78.15 (1H, m), 8.34 (1H, s), 8.92 (1H, d, J = 8 Hz), 9.23 (1H, s)

(2) Synthesis of intermediate G2 Under nitrogen atmosphere, intermediate G1 (2.0 g, 5.2 mmol), dichlorobis (triphenylphosphine) palladium (II) (0.37 g, 0.53 mmol, 10% Pd), 1 , 8-diazabicyclo [5.4.0] -7-undecene (1.1 g, 7.2 mmol, 1.4 eq.) Was dissolved in anhydrous DMF (20 ml) and stirred at 140 ° C. for 10 hours. The reaction mixture was diluted with toluene (200 ml), and palladium black was filtered off. The filtrate was washed with water (100 ml) and saturated brine (50 ml), dried over anhydrous sodium sulfate, and evaporated to give a pale green solid. This was purified by column chromatography (silica gel / hexane + 33% dichloromethane, followed by hexane + dichloromethane, and finally dichloromethane only) to give a pale yellow solid (1.3 g, 83%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.42-7.46 (2H, m), 7.57-7.61 (2H, m), 7.78 (1H, t, J = 7Hz), 7.93 (1H, dd, J = 7Hz, 2Hz), 7.97 (1H, d, J = 7Hz), 8.03 (1H, dd, J = 7Hz, 2Hz), 8.07- 8.09 (1H, m), 8.12-8.15 (1H, m), 8.29 (1H, s), 8.56 (1H, s), 8.56 (1H, d, J = 8Hz), 9.11 (1H, s)

(3) Synthesis of Intermediate G3 Under a nitrogen atmosphere, Intermediate G2 (1.3 g, 4.3 mmol) was suspended in anhydrous DMF (50 ml), to which N-bromosuccinimide (0.84 g, 4.7 mmol, 1 .1 eq.) In anhydrous DMF (5 ml) was added and stirred at 50 ° C. for 10 hours. The reaction mixture was diluted with water (100 ml) and the solid was filtered off and washed with water (50 ml) and methanol (20 ml) to give a pale orange solid (1.5 g, 92%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.41-7.47 (2H, m), 7.61 (1H, t, J = 7 Hz), 7.68 (1H, t, J = 7 Hz), 7.77 (1 H, t, J = 8 Hz), 7.89 (1 H, d, J = 6 Hz), 7.94 (1 H, d, J = 7 Hz), 8.09 (1 H, d, J = 8 Hz), 8.50 (1 H, d, J = 8 Hz), 8.58 (1 H, d, J = 8 Hz), 8.90 (1 H, s), 9.08 (1 H, s)

(4) Synthesis of Compound G Under a nitrogen atmosphere, diphenylamine (0.8 g, 4.7 mmol, 1.2 eq.), Intermediate G3 (1.5 g, 3.9 mmol), tris (dibenzylideneacetone) dipalladium (0 ) (0.05 g, 0.055 mmol, 3% Pd), sodium t-butoxide (0.5 g, 5.2 mmol, 1.3 eq.) Was suspended in anhydrous toluene (50 ml), and tri-t-butylphosphine / toluene A solution (66 wt%, 0.03 ml, 0.098 mmol, 0.9 eq. To Pd) was added, and the mixture was stirred at 100 ° C. for 11 hours. The reaction mixture was diluted with methanol (100 ml) and the solid was filtered off to give a dark green solid (1.46 g, 86% crude). This was purified by column chromatography (silica gel / hexane + 50% dichloromethane followed by hexane + 67% dichloromethane) to give a yellow solid (1.4 g, 77%). This was recrystallized from toluene (100 ml) to obtain yellow plate crystals (1.1 g).

FDMS: calculated value C ₃₆ H ₂₃ N = 469, measured value m / z = 469 (M ⁺ , 100)
HPLC: 99.4% (detection wavelength 254 nm: area%)

The obtained solid (1.12 g) was purified by sublimation at 300 ° C. and 6.1 × 10 ⁻⁴ Pa to obtain a yellow solid (1.09 g).
HPLC: 99.4% (detection wavelength 254 nm: area%)
Absorption maximum wavelength (CH ₂ Cl ₂ ): 441 nm

  It has been clarified that the compound of the present invention is easier to purify and handle than conventional polyacene compounds and can be synthesized with a high purity of 98% or more.

[Production of organic thin-film solar cells]
Example 8-14
A glass substrate with an ITO transparent electrode having a thickness of 25 mm × 75 mm × 0.7 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. The glass substrate with the transparent electrode line after the cleaning is mounted on the substrate holder of the vacuum deposition apparatus, and first, the transparent electrode is covered on the surface on which the transparent electrode line as the lower electrode is formed. Any one of the compounds A to G shown in Table 1 was formed into a p layer by resistance heating vapor deposition at a thickness of 30 nm at 1 Å / s. Subsequently, C60 having a thickness of 60 nm was formed on the p layer by resistance heating vapor deposition at 1 Å / s. Furthermore, 10 nm bathocuproine (BCP) was deposited at 1 cm / s as a buffer layer. Finally, metal Al was deposited as a counter electrode to a thickness of 80 nm to form an organic solar cell. The area was 0.5 cm ² . The thus obtained organic solar cell was measured for IV characteristics under AM1.5 conditions (light intensity 100 mW / cm ² ). As a result, open circuit voltage (Voc), short circuit current density (Jsc), fill factor (FF), and conversion efficiency (η) are shown in Table 1.

Example 15
An organic solar cell was produced and evaluated in the same manner as in Example 8 except that C60 in Example 8 was changed to C70. The results are shown in Table 1.

Example 16
A glass substrate with an ITO transparent electrode having a thickness of 25 mm × 75 mm × 0.7 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. A glass substrate with a transparent electrode line after cleaning is mounted on a substrate holder of a vacuum deposition apparatus, and a film thickness of 5 nm is first formed so as to cover the transparent electrode on the surface on which a transparent electrode line as a lower electrode is formed. The compound D was formed into a p layer by resistance heating vapor deposition at 1 Å / s. Subsequently, a 15 nm i layer (mixing ratio p: n = 1: 1) was formed on this compound D film by co-evaporation of Compound D at 0.2 Å / s and C60 at 0.2 こ の / s. On top of this, C60 having a film thickness of 45 nm was deposited by resistance heating vapor deposition at 1 Å / s to form an n layer, and 10 nm of bathocuproine (BCP) as a buffer layer was deposited by resistance heating vapor deposition at 1 Å / s. Finally, metal Al was continuously deposited as a counter electrode to a thickness of 80 nm to form an organic solar cell. The area was 0.5 cm ² .
The evaluation results of this organic solar cell are shown in Table 1.

Comparative Example 1
An organic solar cell was prepared and evaluated in the same manner as in Example 8 except that Compound A was changed to mTPD. The results are shown in Table 1.

ここで、Ｖｏｃは開放端電圧、Ｊｓｃは短絡電流密度、ＦＦは曲線因子、Ｐｉｎは入射光エネルギーである。従って同じＰｉｎに対して、Ｖｏｃ、Ｊｓｃ及びＦＦがいずれも大きな化合物ほど優れた変換効率を示す。 Generally, the photoelectric conversion efficiency (η) of a solar cell is expressed by the following equation.

Here, Voc is an open circuit voltage, Jsc is a short circuit current density, FF is a fill factor, and Pin is incident light energy. Therefore, for the same Pin, a compound having a larger Voc, Jsc, and FF shows better conversion efficiency.

  As can be seen from Table 1, the compound of the present invention has improved conversion efficiency as compared with the conventional amine compound (Comparative Example compound), and it has become clear that excellent solar cell characteristics are exhibited.

The compounds of the present invention can be used for organic electronic materials such as organic electroluminescent materials, organic semiconductor materials, organic field effect transistor materials, organic solar cell materials and the like. In particular, it is suitable as an organic thin film solar cell material.
The organic thin film solar cell of the present invention can be used for watches, mobile phones, mobile personal computers and the like.

Claims (7)

An organic thin film solar cell material comprising a benzofluoranthene compound represented by the following formula (A).

Wherein R _{1 to} R ₁₂ are each hydrogen, halogen, C _{1 to} C ₄₀ substituted or unsubstituted alkyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkenyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkynyl _group, a substituted or unsubstituted aryl group having _C 6 ~C _40, C 3 ~C substituted or unsubstituted heteroaryl group _40, a substituted or unsubstituted alkoxy group C 1 _{-C 40} Or a substituted or unsubstituted aryloxy group having ₆ to ₄₀ carbon atoms, and adjacent ones of R _{1 to} R ₁₂ may be bonded to each other to form a ring, and this ring has a substituent. Provided that R ₇ and R ₈ are not bonded to each other to form a ring.
At least one of R _{1 to} R ₁₂ is an amino group represented by the following formula (S). )

(In the formula, each of R _a and R _b is a C _{6 to} C ₄₀ substituted or unsubstituted aryl group or a C _{1 to} C ₄₀ substituted or unsubstituted alkyl group.) The organic thin-film solar cell material according to claim 1, wherein the benzofluoranthene compound is represented by the following formula (B).

Wherein R _{1 to} R ₁₄ are each hydrogen, halogen, C _{1 to} C ₄₀ substituted or unsubstituted alkyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkenyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkynyl _group, a substituted or unsubstituted aryl group having _C 6 ~C _40, C 3 ~C substituted or unsubstituted heteroaryl group _40, a substituted or unsubstituted alkoxy group C 1 _{-C 40} Or a C ₆ -C ₄₀ substituted or unsubstituted aryloxy group.
At least one of R _{1 to} R ₁₄ is an amino group represented by the formula (S). ) The organic thin-film solar cell material according to claim 1, wherein the benzofluoranthene compound is represented by the following formula (C).

Wherein R _{1 to} R ₁₄ are each hydrogen, halogen, C _{1 to} C ₄₀ substituted or unsubstituted alkyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkenyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkynyl _group, a substituted or unsubstituted aryl group having _C 6 ~C _40, C 3 ~C substituted or unsubstituted heteroaryl group _40, a substituted or unsubstituted alkoxy group C 1 _{-C 40} Or a C ₆ -C ₄₀ substituted or unsubstituted aryloxy group.
At least one of R _{1 to} R ₁₄ is an amino group represented by the formula (S). ) The organic thin film solar cell material according to claim 1, wherein R ₂ or R ₃ is a C ₆ -C ₄₀ substituted or unsubstituted diarylamino group. The organic thin-film solar cell material according to claim 3, wherein R ₁₃ is a C ₆ -C ₄₀ substituted or unsubstituted diarylamino group. The organic thin-film solar cell containing the material in any one of Claims 1-5 . Having at least a p-layer between a pair of electrodes;
The organic thin-film solar cell of Claim 6 in which the said p layer contains the material in any one of Claims 1-5 .