JP2013237822A - Annelation aromatic derivative composition, photoelectric transducer, solar cell, organic photocatalyst, and method of manufacturing layer containing the annelation aromatic derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an annelation aromatic derivative composition in which an annelation aromatic derivative that is insoluble in a solvent, and has been assumed to be difficult to handle can be dissolved in a solvent.SOLUTION: An annelation aromatic derivative composition includes: a polar organic solvent; an annelation aromatic derivative (for instance, perylene derivative) that is at least insoluble with the polar organic solvent in normal temperature and normal pressure; and a salt (for instance, the salt that contents one that can become a fluoride ion source and consists of a quaternary ammonium) that makes the annelation aromatic derivative mixed in the polar organic solvent dissolve in the polar organic solvent. In addition, the maximum zone of an integration value of an absorbance of the annelation aromatic derivative is in either of a visible light zone or a near infrared zone.

Description

  The present invention relates to a condensed aromatic derivative composition and a method for producing the same. Moreover, it is related with the photoelectric conversion element containing the layer or particle | grains formed using the said condensed-ring-aromatic-derivative composition, a solar cell, and an organic photocatalyst.

  Solar cells are attracting widespread attention from society as an environmentally harmonious technology that realizes a sustainable society. The mainstream of solar cells, which are currently in widespread use, uses silicon semiconductors, but interest is increasing in solar cells using organic materials that are advantageous in terms of cost. As a solar cell using an organic material, there are a dye-sensitized type using an electrolyte and a thin film type. Among these, the thin-film type is particularly expected, including the possibility of application development to new applications, because there is no fear of leakage of the electrolyte, and it is lightweight and excellent in flexibility.

  One of the compounds that greatly contributed to the high efficiency of organic thin film solar cells is a fullerene derivative having a spherical carbon network structure and specific electronic properties. As the fullerene derivative, PCBM (phenyl C61-butyric acid methyl ester) is known. In recent years, a photoelectric conversion element using a fullerene derivative (Patent Document 1) exhibiting higher conversion efficiency than PCBM has been proposed. In addition, fullerene derivatives having a silylmethyl group as a substituent have been proposed as a fullerene derivative that improves the poor solubility of the fullerene derivative in Patent Document 1 in a solvent (Patent Documents 2 and 3). Furthermore, a photoelectric conversion element (non-patent document 1) having a p-i-n layer type photoelectric conversion layer is also disclosed.

  Moreover, the example which uses a carbon nanotube for a photoelectric conversion element material is also disclosed (patent document 4). In this document, as a method for solubilizing single-walled carbon nanotubes, both ends of single-walled carbon nanotubes are open ends and solubilized by introducing a long-chain alkyl group having 4 or more carbon atoms into the open ends. Yes. Patent Document 5 discloses a method for solubilizing carbon nanotubes in an ionic liquid.

  In addition to solar cells, there is a photocatalyst as an environmentally friendly technology. Photocatalysts using titanium oxide have already reached the level of practical use, and are applied to the decomposition, deodorization, deodorization, antibacterial, sterilization, removal of harmful substances, and prevention of fogging of glass and mirrors. Since titanium oxide is an ultraviolet light responsive type, it exhibits excellent effects in outdoor applications. The group of the present inventors has recently proposed an organic photocatalyst that can be used in the visible light band (Patent Documents 6 to 9, Non-Patent Document 2).

International Publication No. 2008/059771 JP 2011-98906 A JP 2011-258980 A JP2011-040435A JP 2004-255481 A International Publication No. 2006/115271 International Publication No. 2005/063393 JP 2009-28669 A JP 2011-147849 A

E. Nakamura et al, J Am. Chem. Soc., 131, 16048-16050, 2009 K. Nagai et al, ACS Appl. Mater. Interfaces, 3 (6), 1902-1909, 2011

  In order to realize high-efficiency photoelectric conversion in a solar cell, it is desirable to use a material having absorption characteristics that can effectively utilize inexhaustible sunlight (natural light) and indoor illumination light. However, the above-described fullerene derivatives have a problem that the ultraviolet light has an absorption maximum and absorption in the visible light band is small.

  In order to provide absorption in the visible light band, it is generally effective to lengthen the absorption maximum wavelength by expanding the π-electron conjugated system. However, when the conjugated system is expanded to increase the molecular weight, there arises a problem that the solubility in a solvent is lowered and purification becomes difficult, and the wet coating method cannot be applied. In order to solve this problem, it is conceivable to expand the conjugated system to increase the molecular weight, and further introduce a functional group that enhances the solubility and dissolve it in the solvent. However, there is a problem that the process is increased and the cost is increased. In addition, it is difficult to synthesize a functional group into an insoluble compound. In addition, the functional group for solubilization has a problem that it does not absorb light or conduct electricity, and the theoretical photoelectric function cannot be sufficiently exhibited. Although described in the problem in the visible light band, a similar problem may occur in applications where it is desired to provide an absorption characteristic in the near-infrared light band having a longer wavelength than the visible light band. Moreover, it is not limited to a solar cell, The same subject may arise about the whole photoelectric conversion element and an organic photocatalyst.

  The present invention has been made in view of the above background, and the object of the present invention is to provide a condensed aromatic derivative that dissolves in a solvent a condensed aromatic derivative that has been difficult to handle due to insolubility in the solvent. PROBLEM TO BE SOLVED: To provide a composition and a method for producing a condensed ring aromatic derivative-containing layer, and to provide a photoelectric conversion element, a solar cell, and an organic photocatalyst including a layer or particles formed using the condensed ring aromatic derivative composition It is.

  The condensed aromatic derivative composition according to the present invention includes the condensed organic compound mixed with the polar organic solvent, the polar organic solvent and the polar organic solvent that is insoluble at least at room temperature and normal pressure. And a salt in which the cyclic aromatic derivative is dissolved in the polar organic solvent, and the maximum band of the integrated value of the absorbance of the condensed aromatic derivative is in either the visible light band or the near-infrared light band. There is something.

  The photoelectric conversion element according to the present invention includes a layer obtained from the condensed aromatic derivative composition of the above aspect.

  The solar cell concerning this invention contains the photoelectric conversion element of the said aspect.

  The organic photocatalyst concerning this invention contains the layer or particle | grains obtained from the condensed aromatic derivative composition of the said aspect.

  The method for producing a condensed ring aromatic derivative-containing layer according to the first aspect of the present invention is a method of applying the condensed ring aromatic derivative composition according to the above aspect and drying to obtain a coating film.

  In the method for producing a condensed aromatic derivative-containing layer of the second aspect according to the present invention, the condensed aromatic derivative composition of the above aspect is added to a poor solvent to form nanoparticles of the condensed aromatic derivative. Then, a dispersion liquid of the obtained nanoparticles is prepared, applied, and dried to obtain a coating film.

  According to the present invention, there are provided a condensed aromatic derivative composition in which a condensed aromatic derivative that has been difficult to handle due to insolubility in a solvent is dissolved in a solvent, and a method for producing a condensed aromatic derivative-containing layer. It has an excellent effect of being able to. Moreover, it has the outstanding effect that the photoelectric conversion element containing the layer or particle | grains formed from the condensed aromatic derivative composition, a solar cell, and an organic photocatalyst can be provided.

1 is a schematic cross-sectional view of an organic photocatalyst according to Embodiment 1. FIG. FIG. 3 is a schematic cross-sectional view of an organic photocatalyst according to Embodiment 2. FIG. 4 is a schematic cross-sectional view of an organic photocatalyst according to Embodiment 3. FIG. 6 is a schematic cross-sectional view showing an example of a photoelectric conversion layer according to Embodiment A. FIG. 6 is a schematic cross-sectional view illustrating an example of a photoelectric conversion layer according to Embodiment B. 10 is a schematic cross-sectional view showing an example of a photoelectric conversion layer according to Embodiment C. FIG. The photograph of the condensed aromatic derivative composition which concerns on an Example. The photograph after re-precipitating the condensed aromatic derivative which concerns on an Example, and leaving still. XRD pattern of PTCBI obtained by sublimation method and reprecipitation method. The absorption spectrum of the diluted solution of the condensed-ring aromatic derivative composition of Examples 1-5. The absorption spectrum of the diluted solution of the condensed aromatic derivative composition of Example 6. The absorption spectrum of PTCBI obtained by the sublimation method.

  Hereinafter, an example of an embodiment to which the present invention is applied will be described. It goes without saying that other embodiments may also belong to the category of the present invention as long as they match the gist of the present invention.

[Fused Ring Aromatic Derivative Composition] The fused ring aromatic derivative composition according to the present invention is insoluble in a polar organic solvent at least at room temperature and pressure, and a polar organic solvent is added thereto by adding a salt thereto. It contains a condensed ring aromatic derivative that becomes soluble in water. The condensed aromatic derivative composition may contain other components other than those described above without departing from the spirit of the present invention.

  Here, “insoluble” includes those in which the solvent is soluble in a trace amount, and at least 0.01% by mass or more is insoluble in 100 parts by mass of the solvent at normal temperature and normal pressure. In other words, a material that does not dissolve at all but dissolves less than 0.01% by mass is “non-soluble”, and a material that dissolves 0.01% by mass or more has “soluble”. Although the solid content concentration (mass% which the total amount of a non-volatile component occupies in the composition whole quantity containing a volatile component) of a condensed-ring aromatic derivative composition is not specifically limited, For example, 0.1 mass%-2 mass% It is.

  In the fused aromatic derivative of the present invention, the maximum band of the integrated value of absorbance is in either the visible light band or the near infrared light band. In the present specification, “visible light band” refers to a band of 400 nm or more and 800 nm or less, and “near infrared light band” refers to a band of 800 nm to 2000 nm. Further, “ultraviolet light band” refers to a band of 200 nm to 400 nm.

  The condensed ring aromatic derivative of the present invention is not particularly limited as long as it satisfies the above conditions, but is preferably a condensed ring of five or more rings. Preferred examples of the fused aromatic derivative include benzopyrene-benzo [a] pyrene, benzo [e] pyrene, benzo [a] fluoranthene, benzo [b] fluoranthene, benzo [j] fluoranthene, benzo [k] fluoranthene, and dibenz. [A, h] anthracene, dibenz [a, j] anthracene, pentacene, perylene, picene, tetraphenylene, anthanthrene, 1,12-benzoperylene, circulene, corannulene, coronene, dicolonylene, diindenoperylene, helicene, Examples include heptacene, hexacene, ketrene, ovalen, zetrene, graphene, carbon nanotubes, and derivatives thereof. Of these, perylene and derivatives thereof, coronene and derivatives thereof, graphene and derivatives thereof, and carbon nanotubes and derivatives thereof are particularly preferable. One type or a plurality of types of condensed ring aromatic derivatives may be used.

The perylene derivative refers to a compound having a basic skeleton of perylene. The perylene derivative suitable for the present invention is not particularly limited as long as it does not depart from the gist of the present invention. Preferred examples include peryleneimides represented by the chemical formulas (1) and (2) and compounds of the chemical formula (3). Is mentioned.
In the formula, R ¹ and R ² each independently represents an alkyl group or an aryl group.

The salt used in the condensed aromatic derivative composition of the present invention is not particularly limited as long as it shows a strong interaction with the condensed aromatic derivative and can be solubilized in a polar organic solvent. It is not limited. Preferable examples include a salt serving as a fluorine ion source. Preferable examples of the salt serving as the fluorine ion source include quaternary ammonium salts and quaternary phosphonium salts. Although a quaternary ammonium salt is not specifically limited, Chemical formula (4) can be mentioned as a preferable example. Further, the quaternary phosphonium salt is not particularly limited, but a preferable example is the chemical formula (5). In addition, the kind of salt may use a single kind or multiple kinds.
(Wherein R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a linear or branched alkyl group having 1 to 22 carbon atoms, an alkylene group, or an aromatic group, which may have a functional group. .)
(In the formula, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a linear or branched alkyl group having 1 to 22 carbon atoms which may have a functional group, or a phenyl group. )

  Among the chemical formulas (4), particularly preferred are benzyltrimethylammonium fluoride, benzyltrimethylammonium hydrodiene = difluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium. Examples include fluoride and benzyltrimethylammonium fluoride. Of the chemical formula (5), tetraphenylphosphonium fluoride, tetrabutylphosphonium fluoride, butyltriphenylphosphonium fluoride, trioctylethylphosphonium fluoride, benzyltriphenylphosphonium fluoride, ethyltriphenylphosphonium fluoride are particularly preferable. Do.

  A more preferable example of the salt serving as the fluorine ion source is a quaternary ammonium salt, and a quaternary alkyl ammonium salt is particularly preferable. Among these, particularly preferred examples include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, and tetraoctylammonium fluoride.

  Although it does not specifically limit as a polar organic solvent in the range which does not deviate from the meaning of this invention, An aprotic polar organic solvent and the polar organic solvent according to it are mentioned as a preferable example. Specific examples include N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc), tetrahydrofuran (THF), diethyl sulfoxide, N-methyl. Examples include formamide, formamide, 2-pyrrolidirone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, acetamide, N-methylpropanamide, hexamethylphosphoric triamide, and the like. The polar organic solvent may be one type or a plurality of types of mixed systems. Moreover, the nonpolar organic solvent may be added in the range which does not deviate from the meaning of this invention.

  The condensed aromatic derivative composition of the present invention may contain an electron donor compound dissolved in a polar organic solvent. Although it does not restrict | limit especially as an electron donor compound in the range which does not deviate from the meaning of this invention, A macrocyclic ligand compound or its metal complex can be mentioned as a suitable example. The “macrocyclic ligand compound” is a compound containing an atom having an unpaired electron that can be a metal ligand on the ring, and the “metal complex” is a coordination atom on the macrocyclic compound. Is a compound coordinated to a metal atom. The atom having an unpaired electron is, for example, a nitrogen atom or an oxygen atom, and preferred examples include a nitrogen atom. Examples of the metal atom include each metal element of Groups 1 to 15 of the periodic table. A preferred metal atom is a metal element of Groups 4 to 14 of the periodic table. As the metal complex, one in which a metal atom and a macrocyclic ligand compound are 1: 1 (molar ratio) to form a planar four-coordinate complex is used.

  Specific examples of the macrocyclic ligand compound or the metal complex thereof include phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, and the like.

A phthalocyanine derivative means a compound having a basic phthalocyanine skeleton. Specific examples include phthalocyanine derivatives represented by the following formula (6A) or (6B).
In the formula, M ¹ represents a metal atom selected from the group consisting of groups 4 to 14 of the periodic table or an atomic group containing the metal atom, and a dotted line represents a coordinate bond.

Preferable examples of the “metal atom of Group 4 to 14 of the periodic table” represented by M ¹ include Group 4 (particularly Ti), Group 5 (particularly V), Group 6 (particularly Mo), Group 7 ( In particular, Mn), Group 8 (Fe, Ru, Os), Group 9 (Co, Rh, Ir), Group 10 (Ni, Pd, Pt), Group 11 (particularly Cu), Group 12 (particularly Zn) , Group 13 (particularly Al) and Group 14 (particularly Pb). The “atomic group containing the metal atom” means a metal (for example, Ti—O) coordinated with another ligand (for example, oxygen or cyano group). The same applies to the following.

Preferred examples of the phthalocyanine derivative include phthalocyanine represented by the above formula (6A), and M ¹ in the above formula (6B) is Co, Pt, Os, Mn, Ir, Fe, Rh, Cu, Zn, Ni, Pd or Examples include Ru phthalocyanine derivatives and chloroaluminum phthalocyanine. Among these, metal-free phthalocyanine, zinc phthalocyanine or copper phthalocyanine is particularly preferable from the viewpoint of activity in organic oxidative decomposition, and cobalt phthalocyanine is preferable from the viewpoint of the amount of oxygen generated in the decomposition of water. These compounds are either commercially available or can be easily produced by those skilled in the art.

A naphthalocyanine derivative means a compound having a basic skeleton of naphthalocyanine. Specific examples include naphthalocyanine derivatives represented by the following formula (7A) or (7B).
In the formula, M ² represents a metal atom selected from the group consisting of groups 4 to 14 of the periodic table or an atomic group containing the metal atom, and a dotted line represents a coordinate bond.

Preferable examples of the “metal atoms of groups 4 to 14 of the periodic table represented by M ² ” include group 4 (particularly Ti), group 5 (particularly V), group 6 (particularly Mo), group 7 ( In particular, Mn), Group 8 (Fe, Ru, Os), Group 9 (Co, Rh, Ir), Group 10 (Ni, Pd, Pt), Group 11 (particularly Cu), Group 12 (particularly Zn) , Group 13 (particularly Al) and Group 14 (particularly Pb).

Preferable examples of naphthalocyanine derivatives include naphthalocyanine represented by the above formula (7A), and M ² in the above formula (7B) is Co, Pt, Os, Mn, Ir, Fe, Rh, Cu, Zn, Ni, Pd. Alternatively, a naphthalocyanine derivative that is Ru can be given. Among these, metal-free naphthalocyanine, zinc naphthalocyanine or copper naphthalocyanine is preferable from the viewpoint of activity in organic oxidative decomposition, and cobalt naphthalocyanine is preferable from the viewpoint of the amount of oxygen generated in the decomposition of water. These compounds are either commercially available or can be easily produced by those skilled in the art.

A porphyrin derivative means a compound having a basic skeleton of porphyrin. Specific examples include porphyrin derivatives represented by the following formula (8A) or (8B).
In the formula, R ¹¹ is independently a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and M ³ is a metal atom selected from the group consisting of groups 4 to 14 of the periodic table or an atomic group containing the metal atom The dotted line indicates a coordination bond.

Here, examples of the alkyl group represented by R ¹¹ include a linear or branched alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and the like. The aryl group represented by the above R ^11, include an aryl group having a monocyclic or bicyclic, specifically phenyl, naphthyl. Examples of the heteroaryl group represented by R ¹¹ include pyridyl and pyrazinyl.

Of the metal atoms in groups 4 to 14 of the periodic table represented by M ³ , group 4 (particularly Ti), group 5 (particularly V), group 6 (particularly Mo), group 7 (particularly Mn ), Group 8 (Fe, Ru, Os), Group 9 (Co, Rh, Ir), Group 10 (Ni, Pd, Pt), Group 11 (particularly Cu), Group 12 (particularly Zn), Group 13 (Especially Al) and group 14 (especially Pb).

Preferred examples of the porphyrin derivative include porphyrins represented by the above formula (8A), M ³ in the above formula (8B) being Co, Pt, Os, Mn, Ir, Fe, Rh, Cu, Zn, Ni, Pd or Examples thereof include porphyrin derivatives in which Ru and R ¹¹ are phenyl or a hydrogen atom. Among these, metal-free porphyrin, zinc porphyrin, or copper porphyrin is particularly preferable from the viewpoint of activity in organic oxidative decomposition, and cobalt porphyrin is preferable from the viewpoint of the amount of oxygen generated in the decomposition of water. These compounds are either commercially available or can be easily produced by those skilled in the art.

  Other preferred examples of the electron donor compound include a conductive polymer. Specific examples of the conductive polymer include polythiophene derivatives, polyphenylene vinylene derivatives, polyfluorene copolymers, and the like.

Specific examples of the polythiophene derivative include a polythiophene derivative represented by the following formula (9).
In the formula, n represents an integer of 50 to 500, and R ¹² each independently represents a linear alkyl group having 1 to 8 carbon atoms such as hexyl, octyl, or methyl group.

  The condensed aromatic derivative composition of the present invention may contain other additives and polymers without departing from the spirit of the present invention. For example, paraffin and silica particles may be suitably added. Further, the condensed ring aromatic derivative composition may contain an n-type organic semiconductor compound such as fullerenes (such as C60) other than the condensed ring aromatic derivative. Further, the solvent in the condensed aromatic derivative composition is mainly composed of a polar organic solvent, but may contain a solvent classified other than the polar organic solvent without departing from the gist of the present invention. In addition, the fused aromatic derivative of the present invention does not need to introduce a functional group for dissolution, and has a merit that a complicated synthesis step is not necessary. It does not exclude the introduction. For example, a functional group can be introduced to shift the absorption wavelength band.

  According to the condensed aromatic derivative composition of the present invention, there is an excellent effect that a condensed aromatic derivative that has been insoluble in a solvent and difficult to handle can be dissolved in a solvent. In addition, since the maximum band of the integrated value of absorbance of the fused aromatic derivative is in either the visible light band or the near infrared light band, fullerene etc. in which the maximum band of the integrated value of absorbance is in the ultraviolet light band Can provide n-type organic semiconductors of different wavelength bands.

[Method for Producing Fused Aromatic Derivative-Containing Layer] Hereinafter, an example of a method for producing a condensed aromatic derivative-containing layer of the present invention will be described. In addition, as long as it agree | coincides with the meaning of this invention, another manufacturing method can also belong to the category of this invention. The condensed aromatic derivative-containing layer of the present invention can be obtained by a wet method. The film thickness of the condensed aromatic derivative-containing layer is not particularly limited, and may be set to an optimal film thickness as appropriate according to the application.

(Production Method 1) A condensed ring aromatic derivative-containing layer can be obtained by coating the condensed ring aromatic derivative composition of the present invention on a substrate and drying it. In the condensed aromatic derivative composition, the solvent is adjusted as necessary so that the solid content concentration is appropriate. The coating method is not particularly limited, but is a die coating method, a spin coating method, a dip coating method, a roll coating method, a bead coating method, a spray coating method, a bar coating method, a gravure coating method, an ink jet method, a screen printing method. And an offset printing method. The substrate is not particularly limited but is preferably selected in consideration of affinity.

  The coating film obtained by coating is dried to remove the solvent. The drying method is not particularly limited, and heating, air drying, reduced pressure, vacuum, or the like can be used. Before drying or after drying, a step of removing the salt can be added as necessary. The method for removing the salt is not particularly limited, and a known method can be appropriately used. For example, salt can be easily removed by washing with water.

  According to the present invention, it is possible to provide a composition in which a condensed aromatic derivative that has been insoluble in a solvent and difficult to handle is dissolved, and thus a coating film can be easily formed by a wet method. In addition, the coating film which mixed the electron donor compound and the electron-accepting compound can also be obtained by using what added the electron donor compound in the condensed-ring aromatic derivative composition.

  Further, since the condensed aromatic derivative-containing layer can be formed by a wet method, a condensed aromatic derivative-containing layer having a desired pattern shape can be easily obtained using a lift-off method, a screen printing method, or the like. There are also benefits.

(Manufacturing method 2) Next, an example of the method different from the said manufacturing method 1 is demonstrated. The condensed aromatic derivative-containing layer according to production method 2 is obtained by coating a dispersion of a condensed aromatic derivative with a wet method. The dispersion of the condensed aromatic derivative is, for example, dropping the condensed aromatic derivative composition into a poor solvent to form condensed aromatic derivative nanoparticles, and then the condensed aromatic derivative nanoparticles are dispersed. It is obtained by preparing a dispersion.

  Although the preparation method of the dispersion liquid of a condensed-ring aromatic derivative is not specifically limited, As a preferable example, the following method can be illustrated. That is, the condensed aromatic derivative composition and the poor solvent are mixed. The solvent Svγ is selected so that it is compatible with the solvent in the composition and becomes a poor solvent for the condensed aromatic derivative. The ratio of the solvent and the poor solvent Svγ in the composition is not particularly limited. For example, the solvent in the composition: the poor solvent Svγ = 1: 4 to 1: 1000. Although not particularly limited, usually, the solvent in the composition is dropped into a large amount of the poor solvent Svγ.

  The poor solvent Svγ is not particularly limited as long as the above conditions are satisfied, but water may be mentioned as a preferred example. As the water, purified water such as ultrapure water, distilled water, and deionized water can be suitably applied, but tap water or the like may be used. Other preferred examples of the poor solvent Svγ include ethanol, methanol, acetone, hexane and the like. At this time, the particles are dispersed in the solvent by stirring or the like. The particle size and shape can be adjusted by changing the surface potential (zeta (ζ) potential) of the condensed aromatic derivative nanoparticles. When the poor solvent is aqueous, the surface potential of the condensed aromatic derivative nanoparticles can be adjusted by adjusting the pH. The pH can be adjusted by dropping an acidic aqueous solution or an alkaline aqueous solution. Although the coating method, the drying method after a coating film, etc. are not specifically limited, The method of the manufacturing method 1 can be illustrated.

  According to production method 2, by using a condensed aromatic derivative composition in which a condensed aromatic derivative that has been difficult to handle due to insolubility in a solvent is dissolved in a solvent, a dispersion of the condensed aromatic derivative is obtained. Easy to prepare. Therefore, there is a merit that a condensed aromatic derivative-containing layer can be easily obtained. In addition, since the particle size of the fused aromatic derivative can be easily adjusted, it is particularly useful when it is desired to adjust to the nanoparticle size.

(Manufacturing method 3) The condensed aromatic derivative containing layer which concerns on the manufacturing method 3 is a coating film which consists of a pn junction type nanoparticle. The pn junction type particle includes a condensed aromatic derivative nanoparticle in which a condensed aromatic derivative that is a plurality of p-type organic semiconductor compounds forms a domain, and an electron donor compound that is a plurality of n-type organic semiconductor compounds. This is a particle in which electron-donating nanoparticles forming a domain are associated. In other words, the pn junction type particle is composed of a condensed aromatic derivative nanoparticle in which a condensed aromatic derivative is a main component or agglomerated alone, and an electron donating property in which an electron donor compound is a main component or agglomerated alone. Nanoparticles form a pn junction surface and are associated with each other. In the pn junction type particle, a pn junction surface is formed at the interface between the condensed aromatic derivative nanoparticle and the electron donating nanoparticle.

  Although the manufacturing method of a pn junction type nanoparticle is not specifically limited, The following method can be mentioned. That is, in the condensed ring aromatic derivative composition of the present invention, after preparing a composition containing an electron donor compound that dissolves in the solvent in the composition, the poor solvent Svγ is added. The ratio of the poor solvent Svγ to the solvent in the composition and the poor solvent are not particularly limited, but preferred examples include those similar to Production Method 2.

  By the above method, a pn junction type particle in which a condensed aromatic derivative and an electron donor compound are associated can be easily obtained. Thereafter, an association promotion treatment of the condensed aromatic derivative nanoparticles and the electron donating nanoparticles is further performed. At this time, the particles are dispersed in the solvent by stirring or the like. For example, the association can be promoted by changing the surface potential (zeta (ζ) potential) of the fused-ring aromatic derivative nanoparticles and the electron-donating nanoparticles. When the poor solvent is aqueous, the surface potential of the condensed aromatic derivative nanoparticles and the electron donating nanoparticles can be adjusted by adjusting the pH. The pH can be adjusted by dropping an acidic aqueous solution or an alkaline aqueous solution. By changing the surface potential, the association between the condensed aromatic derivative nanoparticles and the electron donating nanoparticles is promoted, and a pn junction type particle having a large particle size can be obtained. Examples of other methods for promoting association include a method of adding a surfactant, a method of centrifuging, and a method of standing for a time.

  Fused aromatic derivative-containing layer containing pn-junction type particles by preparing the dispersion liquid of the obtained pn-junction type particles as it is or after purification again, coating and drying Can be obtained.

  According to production method 3, by using a condensed aromatic derivative composition in which a condensed aromatic derivative that has been difficult to handle due to insolubility in a solvent is dissolved in a solvent, p- containing a condensed aromatic derivative is used. A dispersion of n-junction particles can be easily prepared. Therefore, there is a merit that a condensed aromatic derivative-containing layer can be easily obtained. In addition, the particle size of the pn junction type particles containing the condensed aromatic derivative can be easily prepared. This is particularly useful when it is desired to adjust the nanoparticle size.

[Photocatalyst] Next, the organic photocatalyst of the present invention will be described with reference to FIGS. 1A to 1C.
(Embodiment 1) The organic photocatalyst 101 of Embodiment 1 has a p-type contact between an electron donor (p-type organic semiconductor) layer 1 and an electron acceptor (n-type organic semiconductor) layer 2 as shown in FIG. 1A. It has an -n junction interface. In the organic photocatalyst of the present invention, electron carriers and hole carriers are generated at the interface where the electron donor compound and the electron accepting compound are in contact with each other by light irradiation, and unidirectional photoinduced electron transfer occurs. Carriers generated by this light irradiation are used for decomposition of an object to be treated (for example, an inorganic substance containing organic matter, nitrogen, sulfur, or phosphorus). The electron acceptor layer 2 is composed of the condensed aromatic derivative-containing layer of the present invention.

  The lamination method of the electron donor layer 1 and the electron acceptor layer 2 is not particularly limited, but from the viewpoint of simplifying the production process, both the electron donor layer 1 and the electron acceptor layer 2 are formed by a wet method. The method is preferred. The electron acceptor layer 2 can be formed by the coating method of the condensed aromatic derivative-containing layer described above. The electron donor layer 1 can be obtained by preparing a composition in which an electron donor compound is dissolved in a solvent, coating the substrate, and drying. Alternatively, a composition in which an electron donor compound is dispersed in a solvent may be applied and dried. Examples of the coating method include those exemplified in the description of the above-described condensed aromatic derivative-containing layer. Further, instead of the wet method, the electron donor layer 1 may be formed by a vacuum deposition method, a sputtering method, an electrochemical coating (electrodeposition), a method of kneading into a substrate, or the like. The material of the substrate may be any material that does not depart from the spirit of the present invention, and examples thereof include ceramics, metals, alloys, wood, concrete, paper, and fibers. In addition, the shape of the substrate may be any depending on the application.

  The electron donor compound is not particularly limited as long as it has a good pn junction relationship with the condensed aromatic derivative contained in the condensed aromatic derivative composition of the present invention. The electron donor compound may be a single compound or a mixture of two or more. Preferable examples include those exemplified as compounds that may be added to the condensed aromatic derivative composition of the present invention.

  Although the thickness of the electron donor layer 1 and the electron acceptor layer 2 is not specifically limited, For example, it is about 5-500 nm, Preferably it is about 20-200 nm, More preferably, it is about 30-90 nm. The thickness of the electron acceptor layer 2 is not particularly limited, but is, for example, about 10 to 800 nm, preferably about 50 to 600 nm, and more preferably about 100 to 400 nm.

  The organic photocatalyst of the present invention exhibits resolution by contacting with a decomposition target such as an organic substance contained in a gas phase or an aqueous phase or an inorganic substance containing nitrogen, sulfur or phosphorus under light irradiation. Substances to be decomposed include odor-causing substances, dust, microorganisms, viruses, sick house syndrome causative substances (formaldehyde, etc.), odor components (cigarette odor, pet odor, etc.), harmful substances (dioxin, PCB, etc.), agricultural chemicals, ethylene gas , Nitrogen compounds (such as ammonia and NOx), sulfur compounds (such as mercaptans and sulfides), and phosphorus compounds (such as organic phosphorus).

  The organic photocatalyst of the present invention uses a condensed aromatic derivative in which the maximum band of the integrated value of absorbance is either the visible light band or the near-infrared light band, and therefore at wavelengths corresponding to these bands. It can be suitably applied. In particular, natural light (wavelength of 300 to 800 nm), particularly visible light (wavelength of about 400 nm or more, particularly about 400 to 750 nm) can be used by using a condensed aromatic derivative having good absorption in the visible light band.

  Since the organic photocatalyst of the present invention is stable against water, it is possible to efficiently carry out treatment of water containing the decomposition target. For example, the powder obtained by pulverizing the organic photocatalyst can be dispersed in the water to be treated and irradiated with light to treat the water. After the treatment, the powder is filtered to obtain treated water, and the powder can be collected. The water phase (treated water) includes, for example, industrial circulating water, industrial wastewater, industrial wastewater, clean water, sewage, soil and groundwater, ponds, pools, domestic wastewater, residual agricultural chemicals, baths, water storage Examples include tanks, lakes, and dams. These aqueous phases are not particularly limited in pH, hardness and the like, and can be treated efficiently. In particular, the pH is preferably about 7 to 11. Alternatively, a visible light responsive photocatalyst may be mixed into the paint to form a paint composition having photocatalytic activity.

  The organic photocatalyst of Embodiment 1 has the merit that the production process is simple because the condensed aromatic derivative-containing layer can be easily formed by a wet method by using the above-described condensed aromatic derivative composition. In particular, it can be used both indoors and outdoors by using a condensed aromatic derivative having a maximum absorbance integrated band in the visible light band. In particular, it is excellent in that the photocatalyst can be efficiently exhibited by effectively using indoor illumination light or the like. Further, by using a condensed aromatic derivative having a maximum absorbance integrated band in the near-infrared light band, the photocatalytic ability can be controlled by turning on / off light irradiation in a near-infrared band.

Embodiment 2 FIG. 1B shows a schematic cross-sectional view of an organic photocatalyst of Embodiment 2. In the organic photocatalyst 102, an electron donor layer 1 and an electron acceptor layer 2 are laminated on the adsorbent 3 in this order. The type of the adsorbent 3 is not particularly limited, but a high adsorbent material such as activated carbon, activated alumina, molecular sieve, silica gel, clay, or a polymer material capable of forming a thin film such as ion exchange resin, chitosan, polypropylene, or organic gel. Etc. Among these, an ion exchange resin is particularly suitable for adsorption of amines and carboxylic acids as the object to be treated. When the object to be treated is an amine, a cation exchange resin is preferable. Specifically, a perfluorosulfonic acid or a salt thereof / PTFE (polytetrafluoroethylene) copolymer (for example, Nafion (registered trademark)), , Perfluorocarboxylic acid or a salt thereof / PTFE copolymer (for example, Flemion (registered trademark)), and the like. When the object to be treated is a carboxylic acid, an anion exchange resin is preferable.

  The form of the adsorbent 3 is not particularly limited, and may be an arbitrary shape as a substrate, or may be a layer or a powder. Further, the adsorbent 3 itself may be used as a base material. When the adsorbent 3 is used, a form in which the adsorbent is in contact with all or a part of the surface of the electron donor layer 1 of the electron donor layer 1 and the electron acceptor layer 2 which are pn junctions is preferable. The purification includes, for example, a method of filtering the dispersion using a filter and further purifying the obtained pn junction type particles as necessary.

  Examples of the visible light responsive organic photocatalyst 102 include, for example, a Nafion membrane as the adsorbent 3, that is, a perfluorosulfonic acid or a salt thereof / PTFE (polytetrafluoroethylene) copolymer (about 1 to 150 μm), Examples of the electron donor layer 1 include phthalocyanine (about 30 to 90 nm) and an electron acceptor layer 2 in which perylene (about 100 to 400 nm) is laminated in this order. In order to increase the activity of the photocatalyst, silver, copper or the like may be added as necessary in addition to the electron donor compound and the electron accepting compound.

  The film thickness of the adsorbent layer 3 can be set as appropriate. The thickness of the adsorbent is, for example, about 1 to 200 μm, preferably about 10 to 100 μm. The photocatalyst 102 can also be used as a photocatalyst with a three-layer film, but if necessary, a pressure-sensitive adhesive layer may be provided on the three-layer film and adhered to a substrate, or pulverized and cut into a powder form. . Alternatively, the adsorbent 3, the electron donor layer 1, and the electron acceptor layer 2 may be laminated directly on the substrate.

  According to the organic photocatalyst of Embodiment 2, the same effect as that of Embodiment 1 can be obtained. Moreover, since the adsorbent is used, there is an excellent effect that the photocatalytic ability can be exhibited more efficiently.

Embodiment 3 FIG. 1C illustrates an example of an organic photocatalyst different from the above embodiment. The organic photocatalyst 103 is composed of pn junction type particles. Although the manufacturing method of pn junction type particle | grains is not specifically limited, The method of patent document 7 can be utilized suitably. Specifically, after preparing a dispersion of pn junction-type particles as in production method 3 described above, pn junction-type particles are obtained by removing the dispersion solvent. The pn junction type particle is one in which an electron-donating nanoparticle 10 and two electron-accepting nanoparticles 20 which are two p-type organic semiconductor nanoparticles form an aggregate. As the electron-accepting nanoparticles 20, condensed aromatic derivative nanoparticles are used.

  The number of particles that the electron-donating nanoparticles 10 and the electron-accepting nanoparticles 20 associate with each other is not particularly limited, and is arbitrary. That is, the pn junction type particle of the present invention comprises an aggregate of M (positive integer) electron-donating nanoparticles 10 and N (positive integer) electron-accepting nanoparticles 20. Depending on the purpose of use, the electron donating nanoparticles 10 are excessive (M> N) pn junction type particles, or the electron accepting nanoparticles 20 are excessive (M <N) pn junction type particles. be able to. The shape of the electron-donating nanoparticle 10 and the electron-accepting nanoparticle 20 forming the domain is not particularly limited, and may be crystalline or amorphous.

  When the pn junction type particles are used as a photocatalyst, a monodispersed system composed of an aggregate having substantially the same number of particles may be used, or a polydispersed aggregate may be used. In addition to a photocatalyst composed of one type of pn junction type particles, a photocatalyst blended with a plurality of types of pn junction type particles may be used.

  The electron donating nanoparticle 10 is a particle in which an electron donating compound that is a p-type organic semiconductor compound is aggregated, or a particle in which an electron donating compound is aggregated as a main component. The electron-accepting nanoparticles 20 are particles in which a condensed ring aromatic derivative that is an n-type organic semiconductor compound is aggregated, or particles in which a condensed ring aromatic derivative is aggregated as a main component. As other components, for example, metal fine particles can be contained.

  The number of molecules that the electron donating compound and the condensed aromatic derivative aggregate is not particularly limited, but the average particle size to be obtained is set to be nano-order (1 nm or more and less than 1000 nm). It is known that the exciton diffusion length is usually around 10 nm. By making the average particle diameter nano-sized, it becomes possible to increase the efficiency of exciton transfer to the pn junction surface, and the catalyst efficiency can be increased. In addition, by making the average particle diameter nano-sized, it is possible to expect an increase in catalyst efficiency due to an increase in surface area.

  From the viewpoint of simplifying the production process, the average particle diameter of the electron donating nanoparticles 10 and the electron accepting nanoparticles 20 is preferably 10 nm or more. Further, from the viewpoint of increasing the catalyst efficiency, the average particle diameter of the electron donating nanoparticles 10 and the electron accepting nanoparticles 20 is preferably 100 nm or less.

  The pn junction type particles may be used in combination with an adsorbent. The utilization method by the combination of an adsorbent and pn junction type particles is not particularly limited and can be used. The adsorbent is preferably in contact with the pn junction type particles, but may be disposed at a close position. Laminating a thin film made of pn junction type particles on a thin film adsorbent, blending powder adsorbent and pn junction type particles, or forming a film from the blended particles can do. Although an adsorbent is not specifically limited, What was mentioned above can be illustrated. The average particle size of the pn junction type particles is not particularly limited. Nano size may be sufficient and micro size etc. may be sufficient.

  In the pn junction-type particles, excitons are generated in each of the electron-accepting nanoparticles and the electron-donating nanoparticles formed of condensed aromatic derivative nanoparticles by light irradiation. The excitons move to the pn junction surface and become electron carriers and hole carriers. That is, charge separation occurs near the pn junction surface. Then, unidirectional photo-induced electron transfer occurs, and an object to be treated (for example, an inorganic substance containing organic matter, nitrogen, sulfur, or phosphorus) is decomposed by an oxidation / reduction reaction by a carrier.

  Since the pn junction-type particle | grains of Embodiment 3 are particle shapes, the shaping | molding process according to a need can be performed easily. For this reason, it can be used for a wide range of applications. For example, pn junction type particles may be used as a photocatalyst in the form of particles, or may be used as a film by applying a resuspended material in water to a substrate or the like, or as a paste material. You can also. Further, the pn junction type particles may be kneaded with a resin such as a paint. Further, as described above, a film in which an adsorbent and pn junction type particles are blended may be formed.

It is also possible to use as an electrode by forming pn junction-type particles in a film shape and coating the surface of the electrode substrate. Examples of the electrode substrate include a conductive transparent glass substrate, a metal substrate, and a carbon-based substrate. Specific examples include a conductive transparent glass substrate coated with indium-tin oxide (ITO) or the like; a metal substrate such as platinum; a carbon-based substrate such as graphite, diamond, or glassy carbon. The resistance value of the electrode substrate is, for example, 5 to 100 Ω / cm ² , preferably 8 to 20 Ω / cm ² . Various shapes can be adopted for the electrode substrate, but a plate-like or substrate-like shape having a large electrode surface that increases the efficiency of electrolysis or light irradiation is preferred.

  A film containing pn junction type particles is laminated on the surface of the electrode substrate. The thickness of the film is, for example, about 10 to 100 nm. A material carrying a transition metal catalyst (for example, Ni, Pd, Pt, Ir catalyst, preferably Pt or Ir catalyst) may be laminated on the upper layer of the pn junction type particles.

  An electrode employing such a configuration functions as an anode electrode (anode) and oxidizes and decomposes organic substances. In the anode electrode, electrons excited by light (particularly visible light) flow in the direction of the electrode substrate, and holes generated by photoexcitation flow in the direction of the electrolyte. At the interface with the electrolytic solution, organic substances are oxidatively decomposed by holes. That is, it acts as an efficient photoanode electrode in the aqueous phase.

  According to the photocatalyst of Embodiment 3, the same effect as the organic photocatalyst of Embodiment 1 can be obtained. Moreover, the photocatalyst of Embodiment 3 has the outstanding merit that it can be made into a particle shape, without performing a grinding | pulverization process.

[Photoelectric Conversion Element] Next, an example of the photoelectric conversion element of the present invention will be described with reference to FIGS. 2A to 2C.

(Embodiment A) The photoelectric conversion element 201 includes a photoelectric conversion layer 25A, a first electrode 21, and a second electrode 22, as shown in FIG. 2A. The photoelectric conversion layer 25 </ b> A is sandwiched between the first electrode 21 and the second electrode 22 and is a pn heterojunction type in which two layers of the electron donor layer 1 and the electron acceptor layer 2 are laminated.

  The first electrode 21 and the second electrode 22 are thin film electrodes. The material of the first electrode 21 and the second electrode 22 is not particularly limited, and is a material that can receive light for inducing photoelectric conversion in the photoelectric conversion layer 25 in at least one of the first electrode 21 and the second electrode 22. There is a need to. When the visible light band is used for photoelectric conversion, at least one of the first electrode 21 and the second electrode 22 is transparent such as indium tin oxide (ITO), indium oxide / zinc oxide (IZO), and zinc oxide (ZnO). A conductive thin film is preferred. Examples of electrode materials other than these include metals such as Al and Au, and alloy materials that combine Al, Au, Co, Ni, Pt, Ag, Li, In, Ca, Mg, LiF, and the like.

  The first electrode 21 can be formed by a known method such as a sputtering method on an insulating substrate such as a plastic substrate such as glass, quartz, or polycarbonate. The second electrode 22 can be formed on the photoelectric conversion layer 25 by a known method such as a sputtering method.

  Although the film thickness of the electron donor layer 1 and the electron acceptor layer 2 is not specifically limited, For example, it is about 5 nm-1000 nm. More preferably, it is 10 nm or more, More preferably, it is 20 nm or more. Moreover, it is more preferable that it is 100 nm or less, and it is further more preferable that it is 50 nm or less. The method for forming the photoelectric conversion layer 25A is not particularly limited, but from the viewpoint of simplifying the production process, a method of forming both the electron donor layer 1 and the electron acceptor layer 2 by a wet method is preferable. A preferred method for forming the electron donor layer 1 and the electron acceptor layer 2 is as described above.

  A hole extraction layer and a buffer layer may be provided between the photoelectric conversion layer 25 </ b> A and the first electrode 21. Similarly, an electron extraction layer or a buffer layer may be provided between the photoelectric conversion layer 25 </ b> A and the second electrode 22. For these layers, known materials can be used without limitation.

  According to the photoelectric conversion element according to Embodiment A, it is possible to provide a condensed aromatic derivative composition in which a condensed aromatic derivative that has been difficult to handle due to insolubility in a solvent can be provided. A coating film can be formed. As a result, a photoelectric conversion element containing a condensed aromatic derivative can be easily produced.

  According to the photoelectric conversion element of Embodiment A, it can be applied to all uses that require photoelectric conversion ability. Moreover, since it is a thin film, it can be easily molded and can be applied in various ways. By using a condensed aromatic derivative having a maximum integrated band of absorbance in the visible light band, it can be used both indoors and outdoors. In particular, the photoelectric conversion ability can be efficiently exhibited by effectively using indoor illumination light or the like. Therefore, it is suitable for the rechargeable battery use by room light. Further, it can be widely applied to applications using n-type organic semiconductors such as optical switching devices, sensors, and organic ELs. In addition, by using a condensed aromatic derivative having a maximum absorbance integrated band in the near-infrared light band, it can be applied to applications in which photoelectric conversion ability is controlled by on / off of near-infrared broadband light irradiation.

(Embodiment B) The photoelectric conversion element 202 includes a photoelectric conversion layer 25 </ b> B, a first electrode 21, and a second electrode 22 as illustrated in FIG. 2B. The photoelectric conversion layer 25B is a layer in which an electron donor and an electron acceptor are mixed, and is a bulk heterojunction type.

  The photoelectric conversion layer 25B is prepared by preparing a composition containing an electron donor compound that is dissolved in the polar solvent in the condensed ring aromatic derivative composition of the present invention and coating the composition on the first electrode 21. (See Manufacturing Method 1). The method for preparing the composition is not particularly limited. For example, a composition comprising a condensed aromatic derivative composition and a solution in which an electron donor compound is dissolved is separately prepared, and these are mixed and stirred. An electron donor compound can be added directly to the aromatic derivative composition.

  As another method for forming the photoelectric conversion layer 25B, by preparing a dispersion of pn-junction nano-particles as in the production method 3 of the condensed ring aromatic derivative composition, and applying and drying the dispersion You may form the layer which consists of a pn junction type nanoparticle.

  According to the photoelectric conversion element according to Embodiment B, the same effects as those of Embodiment A can be obtained.

(Embodiment C) As shown in FIG. 2C, the photoelectric conversion element 203 includes a photoelectric conversion layer 25 </ b> C, a first electrode 21, and a second electrode 22. The photoelectric conversion layer 25C is an interpenetrating junction type composed of a pin layer.

  Although the formation method of 25 C of photoelectric converting layers is not specifically limited, For example, it can obtain by the following method. That is, a solution containing an electron donor compound is applied to form the electron donor layer 1, and then a condensed aromatic derivative composition in which the electron donor compound is mixed is applied. Next, a condensed aromatic derivative composition not mixed with an electron donor compound is applied. Thereafter, for example, by heating to about 150 to 200 ° C., a pin structure can be formed.

  According to the photoelectric conversion element according to Embodiment C, the same effects as those of Embodiment A can be obtained. Moreover, according to the photoelectric conversion element which concerns on Embodiment C, since a pn junction surface can be ensured large, there exists a merit that photoelectric conversion can be performed more efficiently.

  Note that the above-described photoelectric conversion element is an example, and it goes without saying that various modifications are possible. For example, as a solar cell, a photoelectric conversion layer pattern is formed in a matrix on a transparent substrate with a transparent electrode, an upper electrode layer is formed thereon, an insulating layer having an electrode outlet is formed on the upper electrode, A structure in which current collecting wiring is provided over the insulating layer may be employed. A plurality of types of photoelectric conversion layers having different absorption bands may be arranged.

<Example>
Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

Example 1 First, perylenetetraacetic acid bisimidazole (perylenetetracarboxybenzimidazole) (PTCBI) was purified by a sublimation method. Next, 3.855 g of tetrabutylammonium fluoride (TBAF) was added to 72.471 g of dimethylacetamide (DMAc), followed by stirring for 5 minutes to prepare a 5.32 mass% DMAc / TBAF solution. 0.100 g of PTCBI was dissolved in 77.65 g of the obtained DMAc / TBAF solution and stirred overnight to obtain a 0.129% by mass PTCBI / DMAc / TBAF solution. The resulting solution is shown in FIG. 3A. From the figure, it was confirmed that PTCBI was dissolved as a solution.

  Subsequently, 60 mL of the obtained 0.129 mass% PTCBI / DMAc / TBAF solution was added dropwise at a rate of 1.75 mL / min to water (600 mL) that was vigorously stirred at a rotation speed of 70 rpm, and 30 minutes after the addition. By continuing stirring, fine particles of PTCBI were obtained. Thereafter, 5 mL of 1M NaClaq was added to the obtained suspension (300 mL), salted out, and allowed to stand overnight. A photograph of the sample after standing is shown in FIG. 3B. The sample after standing was filtered (hydrophilic PTFE membrane, pore size: 0.2 μm) to collect particles and washed with water.

The obtained particles after reprecipitation were placed on 0.7 × 0.7 cm ² on a glass substrate, and a powder X-ray diffraction (XRD) pattern was measured. The result is shown in FIG. As a reference, the results of XRD measurement of PTCBI after purification by the sublimation method are also shown. From the figure, it was confirmed that the PTCBI obtained by the reprecipitation method was broad because it had a small particle shape, but was the same as the PTCBI purified by the sublimation method.

  (Example 2) A condensed aromatic derivative composition was prepared in the same manner as in Example 1 except that the solvent was changed from DMAc to DMF.

  (Example 3) A condensed aromatic derivative composition was prepared in the same manner as in Example 1 except that the solvent was changed from DMAc to NMP.

  (Example 4) A condensed aromatic derivative composition was prepared in the same manner as in Example 1 except that the solvent was changed from DMAc to DMSO.

  Example 5 A condensed aromatic derivative composition was prepared in the same manner as in Example 1 except that the solvent was changed from DMAc to THF.

  Example 6 A condensed ring aromatic derivative composition was prepared in the same manner as in Example 1 except that PTCBI was changed to a carbon nanotube as a condensed ring aromatic derivative.

  In each of Examples 1 to 5, it was confirmed that PTCBI was dissolved in each polar solvent. In Example 6, it was confirmed that the carbon nanotubes were dissolved in the polar solvent. Next, in Examples 1 to 5, a 60-fold diluted solution of a saturated solution was prepared, and the absorption spectrum is shown in FIG. Moreover, in Example 6, the 60-fold dilution solution of a saturated solution was prepared, and the result of having measured the absorption spectrum is shown in FIG. From these figures, it can be seen that good absorption characteristics are shown in the visible light band.

  As a comparative example, FIG. 7 shows the absorbance measurement results of a deposited film obtained by depositing PTCBI on a glass substrate by a sublimation method. The absorbance indicates the value at a coating film of 10 nm. 5 and 7, it can be seen that the PTCBI of Examples 1 to 5 shows an absorption spectrum in the visible light band similar to the deposited film.

DESCRIPTION OF SYMBOLS 1 Electron donor layer 2 Electron acceptor layer 3 Adsorbent 10 Electron donating nanoparticle 20 Electron accepting nanoparticle 21 1st electrode 22 2nd electrode 25 Photoelectric conversion layer 101-103 Organic photocatalyst 201-203 Photoelectric conversion element

Claims (16)

A polar organic solvent,
A fused aromatic derivative that is insoluble in the polar organic solvent at least at room temperature and pressure, and
A salt that dissolves the fused aromatic derivative mixed in the polar organic solvent in the polar organic solvent, and
A condensed aromatic derivative composition wherein the maximum band of the integrated value of absorbance of the condensed aromatic derivative is either a visible light band or a near infrared light band.   The condensed ring aromatic derivative composition according to claim 1, wherein the condensed ring aromatic derivative has 5 or more rings.   The condensed ring aromatic derivative composition according to claim 1 or 2, wherein the condensed ring aromatic derivative is a perylene derivative.   The condensed aromatic derivative composition according to any one of claims 1 to 3, wherein at least a part of the salt can serve as a fluorine ion source.   The condensed ring aromatic derivative composition according to any one of claims 1 to 4, wherein at least a part of the salt is a quaternary ammonium salt including a fluorine ion source.   The condensed aromatic according to any one of claims 1 to 5, wherein the polar organic solvent is any one of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide, and tetrahydrofuran. Group derivative composition.   Furthermore, the condensed aromatic derivative composition of any one of Claims 1-6 containing an electron donor compound.   8. The condensed ring aromatic derivative composition according to claim 7, wherein the electron donor compound is a polymer compound.   9. The condensed aromatic derivative composition according to claim 7 or 8, wherein the electron donor compound is a heterocyclic polymer compound.   The condensed electron derivative composition according to claim 7, wherein the electron donor compound is any one of a porphyrin compound, a phthalocyanine compound, and a polythiophene. A photoelectric conversion element including a photoelectric conversion layer,
The photoelectric conversion element containing the layer obtained from the condensed aromatic derivative composition of any one of Claims 1-10 in at least one part of the said photoelectric converting layer.   The photoelectric conversion element according to claim 11, wherein the photoelectric conversion layer is sandwiched between a pair of electrodes.   The solar cell containing the photoelectric conversion element of Claim 11 or 12.   The organic photocatalyst containing the layer or particle | grains obtained from the condensed ring aromatic derivative composition of any one of Claims 1-10.   The manufacturing method of the condensed aromatic derivative containing layer which apply | coats the condensed aromatic derivative composition of any one of Claims 1-10, and obtains a coating film by drying. The fused ring aromatic derivative composition according to any one of claims 1 to 10 is added to a poor solvent to form nanoparticles of the fused ring aromatic derivative,
A method for producing a condensed aromatic derivative-containing layer, in which a dispersion of the obtained nanoparticles is prepared, applied, and dried to obtain a coating film.