JP2009060053A - Photoelectric conversion element - Google Patents

Abstract

Provided are a photoelectric conversion element using an organic semiconductor compound having high photoelectric conversion efficiency, and a solar cell and an organic electroluminescence element comprising the photoelectric conversion element.
A photoelectric conversion element including at least one single crystal of an organic semiconductor compound having an aspect ratio of 2 or more.
[Selection figure] None

Description

  The present invention relates to a photoelectric conversion element including an organic semiconductor compound, and relates to a solar cell including the photoelectric conversion element. More specifically, the present invention relates to a bulk heterojunction solar cell using an organic semiconductor compound. The present invention also relates to an organic electroluminescence device comprising the photoelectric conversion device that emits light by converting electric energy into light.

  Future energy problems are an important issue worldwide, but energy sources to meet energy demand include thermal power, nuclear power, hydropower, wind power, and solar power. Of these, thermal power uses fossil fuels as an energy source, but this fuel is not inexhaustible and cannot be fully relied upon. In recent years, nuclear power has become a problem in particular with regard to the disposal and safety of radioactive waste, so it cannot be fully relied upon. Therefore, in addition to these two types of energy, there are thermal power, wind power, and solar energy. Among these, solar energy is safe and inexhaustible as long as the sun exists. It is expected to be one of the supplements, and active research and practical use are being carried out.

Conventionally, a silicon semiconductor has been the mainstream as a semiconductor material constituting a solar cell. However, since many silicon semiconductors in practical use are single crystals, it is difficult to increase the area. Moreover, since it is a single crystal, there is a problem that it is expensive and the manufacturing cost is higher than that of thermal power. For this reason, cost reduction and area increase are important, and various studies have been made in recent years.
As one of them, a bulk heterojunction solar cell using an organic semiconductor compound has been proposed. (For example, see Patent Document 1). This is to form a solar cell by forming a pn junction from a p-type and an n-type organic semiconductor.
In this solar cell, the organic semiconductor compound is usually used in an amorphous state. Therefore, from the viewpoint of promptly separating the charge separation state generated by light absorption into electrons and holes, the mobility of electrons or holes in the amorphous state cannot be said to be sufficiently high, but the point of photoelectric conversion efficiency. The improvement is expected from.
In general, it is known that an organic semiconductor compound has higher electron or hole mobility in a crystal than in an amorphous state. Therefore, even in a solar cell using an organic semiconductor compound, a method using an organic semiconductor compound in a crystalline state has been proposed so far (for example, see Patent Document 2), but the crystal of the organic semiconductor compound used is The shape was not controlled and sufficient performance was not achieved.

On the other hand, organic electroluminescent elements (hereinafter also referred to as “organic EL elements”) are actively researched and developed because they can emit light with high luminance when driven at a low voltage. An organic electroluminescent element has an organic compound layer between a pair of electrodes, and electrons injected from the cathode and holes injected from the anode are recombined in the organic compound layer to emit the energy of the generated excitons. It is used for. Although many studies have been made in recent years, no element has been developed that achieves both high efficiency and high durability.
In addition, an invention relating to an organic EL element that uses a material that combines only a stable six-membered aromatic ring with a view to a highly durable material is disclosed (see, for example, Patent Document 3). However, sufficient performance was still not obtained.
Usually, an organic semiconductor compound used for an organic EL element is used in an amorphous state, and thus there has been a problem that movement of electrons or holes is slow. In general, in an organic semiconductor compound, a single crystal has a faster movement of electrons or holes than an amorphous state, and it tends to be preferable as an organic EL element. It has been difficult to obtain and has not yet exhibited sufficient characteristics as an organic EL element.

JP-A-9-246580 JP 2002-76391 A JP 2002-356449 A

  An object of this invention is to provide the photoelectric conversion element using the organic-semiconductor compound with high photoelectric conversion efficiency. Moreover, an object of this invention is to provide the solar cell and organic electroluminescent element which consist of this photoelectric conversion element.

  As a result of intensive studies, the present inventors have found an unexpected effect that a solar cell containing at least one organic semiconductor compound single crystal having an aspect ratio of 2 or more gives high photoelectric conversion efficiency. Further, the present inventors have found an unexpected effect that an organic electroluminescence device containing a single crystal of an organic semiconductor compound having a specific shape gives high luminous efficiency. The present invention has been made based on such findings.

The problems of the present invention have been solved by the following means.
[1] A photoelectric conversion element comprising at least one single crystal of an organic semiconductor compound having an aspect ratio of 2 or more.
[2] The photoelectric conversion element as described in the item [1], wherein the single crystal of the organic semiconductor compound has a flat plate shape and is oriented in a horizontal direction with respect to the substrate.
[3] A solar cell comprising the photoelectric conversion element according to the item [1] or [2].
[4] The solar cell according to item [3], wherein the organic semiconductor compound is a phthalocyanine compound.
[5] The solar cell according to item [3] or [4], which is a bulk heterojunction solar cell containing a p-type organic semiconductor compound and an n-type organic semiconductor compound as the organic semiconductor compound.
[6] The solar cell according to [5], wherein the p-type organic semiconductor is a single crystal of a phthalocyanine compound, and the n-type organic semiconductor is a fullerene compound.
[7] An organic EL device comprising the photoelectric conversion device according to the item [1] or [2].
[8] The photoelectric conversion element according to the item [7], wherein the single crystal thickness of the organic semiconductor compound is in the range of 0.1 nm to 1 μm.
[9] The organic EL device according to [7] or [8], wherein the organic semiconductor compound is a compound having a condensed aromatic hydrocarbon ring.
[10] The organic EL device according to any one of [7] to [9], wherein the organic EL device is a dye-dispersed light-emitting device, and the single crystal of the organic semiconductor compound is a light-emitting material.
[11] The organic EL device according to any one of [7] to [10], wherein poly (N-vinylcarbazole) is used as a binder.

  The photoelectric conversion element of the present invention has high photoelectric conversion efficiency. The solar cell of the present invention has high photoelectric conversion efficiency, and the organic EL device of the present invention has high external quantum efficiency.

Hereinafter, the present invention will be described in detail.
The photoelectric conversion element of the present invention includes at least one single crystal of an organic semiconductor compound having an aspect ratio of 2 or more. Here, the aspect ratio refers to the longest distance / thickness when a single crystal is projected from directly above the substrate. The aspect ratio of the single crystal of the organic semiconductor compound used in the photoelectric conversion element of the present invention is more preferably 3 or more.
The single crystal of the organic semiconductor compound is preferably flat and is oriented in the horizontal direction with respect to the substrate. Here, “flat plate” refers to a plane (A) with respect to a plane (A) having the largest area among planes including the long axis of the single crystal and a plane (B) including a normal of the single crystal to the plane. ) And the ratio of the area of the plane (B) (A) / (B) is 2.0 or more. Further, “orienting in the horizontal direction with respect to the substrate” means that the major axis of the single crystal exists in an arrangement of 0 to 30 ° on average with respect to the substrate.
The photoelectric conversion element of the present invention is defined as an element that converts light energy and electric energy, and can be applied to any application as long as an exchange process of light energy and electric energy is included. The photoelectric conversion element of the present invention can be used for an image sensor such as a CCD and an optical sensor in addition to a solar cell and an organic EL element.

Hereinafter, the solar cell comprising the photoelectric conversion element of the present invention will be described.
Examples of the support used in the solar cell of the present invention include glass, transparent ceramics, metal, and plastic film. Glass and transparent ceramics lack flexibility compared to metal and plastic films. For a low-cost and flexible photoelectric conversion element or photoelectrochemical cell, it is preferable to use a transparent polymer film provided with the conductive layer. Transparent polymer films include tetraacetylcellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndioctaic polyester (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAr). ), Polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, brominated phenoxy and the like. When a transparent conductive support is used, light is preferably incident from the support side. In this case, the coating amount of the conductive metal oxide is preferably 0.01 to 100 g per 1 m ² of a glass or plastic support.

  The solar cell of the present invention forms a pn junction from an n-type organic semiconductor and a p-type organic semiconductor, and contains at least one single crystal of an organic semiconductor compound having an aspect ratio of 2 or more. A bulk heterojunction solar cell containing a p-type organic semiconductor compound and an n-type organic semiconductor compound is preferable.

  The n-type organic semiconductor compound used in the present invention is an acceptor organic semiconductor compound, which is mainly represented by an electron-transporting organic compound and refers to an organic compound having a property of easily accepting electrons. Examples of the n-type organic semiconductor used in the solar cell of the present invention include fullerene or fullerene compounds, carbon nanotubes, carbon nanotube derivatives, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene. Derivatives, fluoranthene derivatives), 5- to 7-membered heterocyclic compounds containing nitrogen atom, oxygen atom, sulfur atom (eg, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine , Acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzotriazole, Zooxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, oxadiazole, imidazopyridine, pyralidine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine, etc.), polyarylene compounds , Fluorene compounds, cyclopentadiene compounds, silyl compounds, and metal complexes having a nitrogen-containing heterocyclic compound as a ligand. Preferred are fullerenes and fullerene compounds.

The fullerene, fullerene C _60, fullerene C _70, fullerene C _76, fullerene C _78, fullerene C _80, fullerene C _82, fullerene C _84, fullerene C _90, fullerene C _96, fullerene C _240, fullerene C _540, mixed Fullerene and fullerene nanotube are represented, and the fullerene compound represents a compound having a substituent added thereto.

  In the present invention, when a specific moiety is referred to as a “group”, the moiety may be unsubstituted or substituted with one or more (up to the maximum possible) substituents. Means good. For example, “alkyl group” means a substituted or unsubstituted alkyl group. In addition, the substituent that can be used in the compound in the present invention may be any substituent.

When such a substituent is W, the substituent represented by W is not particularly limited, and examples thereof include halogen atoms, alkyl groups (cycloalkyl groups, bicycloalkyl groups, tricycloalkyl groups). ), Alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups (also referred to as heterocyclic groups), cyano groups, hydroxyl groups, nitro groups, carboxyl groups, Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonyl Amino group, alkoxycarbonylamino group, Oxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl Group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group Hydrazino group, ureido group, boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—OSO ₃ H), or other known substituents. Can be mentioned.

  More specifically, W represents a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a C 5-30 bicycloalkane, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl) and tricyclo structures with more ring structures It is intended to. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituent described below represents an alkyl group having such a concept, but further includes an alkenyl group and an alkynyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (Substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2 2] is intended to encompass oct-2-en-4-yl). ], An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably a substituted or unsubstituted aryl having 6 to 30 carbon atoms) Groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocycles A monovalent group obtained by removing one hydrogen atom from a compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, Cation such as 2-pyrimidinyl, 2-benzothiazolyl, 1-methyl-2-pyridinio, 1-methyl-2-quinolinio A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t- Butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy groups (preferably silyloxy groups having 3 to 20 carbon atoms such as trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy groups ( Preferably, the substituted or unsubstituted hete having 2 to 30 carbon atoms is used. Ring oxy group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, 6 to 6 carbon atoms) 30 substituted or unsubstituted arylcarbonyloxy groups such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy groups (preferably substituted with 1 to 30 carbon atoms) Or an unsubstituted carbamoyloxy group such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoy Ruoxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxy A carbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino A group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, Nilino, N-methyl-anilino, diphenylamino), ammonio groups (preferably ammonio groups, substituted or unsubstituted alkyls having 1 to 30 carbon atoms, aryl, heterocyclic groups substituted ammonio groups such as trimethylammonio, triethyl Ammonio, diphenylmethylammonio), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms) , For example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted with 1 to 30 carbon atoms or Unsubstituted Minocarbonylamino group, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxy having 2 to 30 carbon atoms) Carbonylamino group, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms) Substituted or unsubstituted aryloxycarbonylamino groups such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonyl Ruamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octyl Aminosulfonyl), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms, such as methylsulfonyl) Amino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio having 1 to 30 carbon atoms) Group, for example Thio, ethylthio, n-hexadecylthio), arylthio groups (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thio groups (preferably A substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted group having 0 to 30 carbon atoms) Sulfamoyl groups such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- ( N′-phenylcarbamoyl) sulfamoyl), sulfo group Alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p- Methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, Phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, carbon number 4 ~ Heterocyclic carbonyl groups bonded to carbonyl groups by 30 substituted or unsubstituted carbon atoms, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p- t-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadeci Oxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, for example, Phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably 2-30 carbon atoms) Substituted or unsubstituted phosphino groups such as dimethylphosphino Diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyl An oxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably carbon A substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a phospho group, and a silyl group (preferably a substituted or unsubstituted group having 3 to 30 carbon atoms) Substituted silyl groups such as trimethylsilyl, t-butyldimethyl Tilsilyl, phenyldimethylsilyl), a hydrazino group (preferably a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms, such as trimethylhydrazino), or a ureido group (preferably a substituted or unsubstituted group having 0 to 30 carbon atoms). Represents a ureido group, such as N, N-dimethylureido.

  In addition, two Ws can be combined to form a ring (aromatic or non-aromatic, hydrocarbon ring or heterocyclic ring. These can be further combined to form a polycyclic fused ring. For example, a benzene ring or a naphthalene ring. , Anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, India Lysine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, benzimidazole ring, imidazopyridine ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenazole ring A nanthridine ring, Kurijin ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring or a phenazine ring, and the like.) Can also be formed.

Among the above substituents W, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such substituents include —CONHSO ₂ — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), or —SO ₂ NHSO ₂ — group (sulfonylsulfamoyl group). Group).
More specifically, an alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), an arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), an alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl), or an arylsulfonyl An aminocarbonyl group (for example, p-methylphenylsulfonylaminocarbonyl) is mentioned.

  The fullerene compound preferably used in the present invention is a compound represented by the following general formula (1).

In the general formula (1), R ₁ represents a substituent. As the substituent, the aforementioned W can be used. Preferred examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group. Preferred examples and preferred specific examples thereof include those represented by W. The alkyl group is more preferably an alkyl group having 1 to 12 carbon atoms, and the aryl group and the heterocyclic group are preferably a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, Biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring , Benzimidazole ring, imidazopyridine ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring Thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring or phenazine ring, more preferably benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyridine ring, imidazole ring, oxazole ring, or thiazole A ring, particularly preferably a benzene ring, a naphthalene ring, or a pyridine ring. These may further have a substituent, and the substituents may be bonded as much as possible to form a ring. When n is 2 or more, the plurality of R ₁ may be the same or different. Moreover, several R < ₁ > may combine as much as possible and may form a ring.

  n represents an integer of 1 to 60, preferably an integer of 1 to 10.

  Specific examples of the fullerene compound preferably used in the present invention are listed below, but the present invention is not limited thereto.

  Fullerenes and fullerene compounds used in the present invention are described in the Chemical Society of Japan, Quarterly Chemical Review No. 43 (1999), JP-A-10-167994, JP-A-11-255508, JP-A-11-255509, JP-A-2002-241323, JP-A-2003-19681, and the like. It can also be used. Fullerenes and fullerene compounds used in the present invention are disclosed in, for example, the Chemical Society of Japan, Quarterly Chemical Review No. 43 (1999), JP-A-10-167994, JP-A-11-255508, JP-A-11-255509, JP-A-2002-241323, JP-A-2003-19681, etc. It can be produced according to the method described.

  The p-type organic semiconductor compound used in the present invention is a donor organic semiconductor compound, which is mainly represented by a hole-transporting organic compound and refers to an organic compound having a property of easily donating electrons. More specifically, an organic compound having a smaller ionization potential when two organic materials are used in contact with each other. Therefore, any organic compound can be used as the donor organic compound as long as it is an electron-donating organic compound. For example, triarylamine compounds, benzidine compounds, pyrazoline compounds, styrylamine compounds, hydrazone compounds, triphenylmethane compounds, carbazole compounds, polysilane compounds, thiophene compounds, phthalocyanine compounds, cyanine compounds, merocyanine compounds, oxonol compounds, polyamine compounds, indoles Compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), nitrogen-containing heterocyclic compounds The metal complex etc. which it has as can be used. Not limited to this, as described above, any organic compound having an ionization potential smaller than that of the organic compound used as the n-type (acceptor property) compound may be used as the donor organic semiconductor. As the p-type organic semiconductor, a phthalocyanine compound is particularly preferable.

The solar cell of the present invention contains a single crystal of an organic semiconductor compound having an aspect ratio (the longest distance / thickness when a single crystal is projected from directly above the substrate) of 2.0 or more.
The method for producing a single crystal is not particularly limited, but a recrystallization method from a supersaturated solution, a crystallization method from a gas phase such as vapor deposition onto a solid substrate, and the like are preferably used. The aspect ratio is 2 or more, more preferably 3 or more. About the thickness of a single crystal, it is the range of 0.1 nm-10 cm, Preferably, it is the range of 1 nm-1 mm. More preferably, it is the range of 10 nm-100 micrometers.
Examples of the single crystal of the organic semiconductor compound having an aspect ratio of 2 or more include single crystals of hydrocarbon compounds, phthalocyanine compounds, perylene compounds, and the like.

  It is preferable to use electrodes having different work functions. As an electrode, metal (for example, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon, or conductive metal oxide (indium-tin composite oxide, tin oxide doped with fluorine, etc.) Can be mentioned. The thickness of the electrode layer is preferably about 0.02 to 10 μm.

  The lower the surface resistance of the support with electrodes, the better. The range of the surface resistance is preferably 100Ω / □ or less, more preferably 40Ω / □ or less. The lower limit is not particularly limited, but is usually about 0.1Ω / □.

  Examples of the method of coating the organic semiconductor layer on the conductive support include a method of applying a dispersion or colloidal solution of the organic semiconductor compound on the conductive support. In consideration of mass production of solar cells, liquid properties, and flexibility of the support, a wet film application method is relatively advantageous. As a wet film application method, a coating method and a printing method are typical.

  As a method for producing a dispersion containing a single crystal of an organic semiconductor compound, there are a method of dispersing while pulverizing a single crystal using a mill, a method of depositing an organic semiconductor compound as a single crystal in a solvent and using it as it is. Can be mentioned. Examples of the dispersion medium include water or various organic solvents (for example, methanol, ethanol, isopropyl alcohol, dichloromethane, acetone, acetonitrile, ethyl acetate, etc.). During dispersion, a polymer, surfactant, acid, chelating agent, or the like may be used as a dispersion aid as necessary.

  The application method is disclosed in Japanese Patent Publication No. 58-4589 as a roller method, a dip method as an application system, an air knife method, a blade method, etc. as a metering system, and the application and metering can be performed in the same part. The wire bar method, the slide hopper method, the extrusion method, the curtain method and the like described in U.S. Pat. Nos. 2,681,294, 2761419, 2761791 and the like are preferable. As a general-purpose machine, a spin method or a spray method is also preferably used.

  Conventionally, as the wet printing method, intaglio, rubber plate, screen printing and the like are preferred, including the three major printing methods of letterpress, offset and gravure.

  A preferable film application method is selected from the above methods depending on the liquid viscosity and wet thickness.

  The liquid viscosity greatly depends on the type and dispersibility of the organic semiconductor compound, the type of solvent used, and additives such as surfactants and binders. For high-viscosity liquids (for example, 0.01 to 500 Poise), the extrusion method or casting method is preferable. For low-viscosity liquids (for example, 0.1 Poise or less), the slide hopper method, wire bar method, or spin method is preferable, and a uniform film is formed It is possible.

  Even in the case of applying a low-viscosity liquid by the extrusion method, the application is possible if the application amount is a certain amount.

  Further, screen printing is often used for coating a high-viscosity paste of an organic semiconductor compound single crystal, and this method can also be used.

  As described above, a wet film applying method may be appropriately selected in accordance with parameters such as the liquid viscosity of the coating liquid, the coating amount, the support, and the coating speed.

  In the solar cell manufacturing process of the present invention, an electric field, a magnetic field, light, or polarized light may be applied from the outside in order to control the arrangement of the organic semiconductor compound single crystal.

Next, the organic EL element (organic electroluminescent element) of the present invention will be described.
The light emitting device of the present invention is not particularly limited in terms of system, driving method, usage pattern, and the like.

The organic electroluminescent element of the present invention has an organic layer having at least one organic semiconductor compound between a pair of electrodes.
Between the pair of electrodes, a hole injection layer, a hole transport layer, an electron transport layer, and the like may be disposed as an organic layer in addition to the light emitting layer, and each of these layers has another function. It may be. Preferably, it is a dye-dispersed element in which an organic semiconductor compound is added as a light emitting material in a polymer having charge transporting ability.

  The compound emitting light in the present invention is preferably a condensed ring aromatic compound. Examples of the condensed aromatic compound include compounds having a condensed aromatic hydrocarbon ring (for example, naphthalene, anthracene, phenanthrene, acenaphthylene, pyrene, perylene, fluoranthene, tetracene, chrysene, pentacene, coronene, and these Derivatives (tetra-t-butylpyrene, binaphthyl, rubrene, benzopyrene, benzoanthracene, etc.), compounds having a condensed aromatic heterocycle (quinoline, quinoxaline, benzimidazole, benzoxazole, benzimidazole, imidazopyridine, azaindole, and These derivatives (for example, bisbenzoxazolylbenzene, benzoquinoline, etc.), etc. are mentioned, and a compound having a condensed aromatic hydrocarbon ring is preferable.

As the compound having a condensed aromatic hydrocarbon ring, naphthalene, anthracene, phenanthrene, acenaphthylene, pyrene, perylene, fluoranthene, tetracene, pentacene, and derivatives thereof are preferable from the viewpoint of durability and efficiency. Anthracene, fluoranthene, pyrene, perylene, tetracene, and derivatives thereof are more preferable, fluoranthene derivatives, pyrene derivatives, perylene derivatives, and tetracene derivatives are more preferable, and tetracene derivatives are particularly preferable.
These compounds may be used alone or in combination.

  As the compound having the condensed aromatic hydrocarbon ring, a compound represented by any one of the following general formulas (1) to (5) is preferable, and the compound represented by the following general formula (3), (4) or (5) The compound represented by either is more preferable, the compound represented by the following general formula (4) or (5) is more preferable, and the compound represented by the following general formula (4) is particularly preferable.

Hereinafter, the general formula (1) will be described.
R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹⁰ each represents a hydrogen atom or a substituent.
Examples of the substituent include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert- Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as propargyl and 3-pentynyl), aryl group (preferably carbon 6 to 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc.), amino group (preferably 0 carbon atoms) -30, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc.), alkoxy Group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like), aryl Oxy group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably A prime number of 6 to 12, for example, phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), a heterocyclic oxy group (preferably having a carbon number of 1 to 30, more preferably a carbon number of 1 to 20, particularly Preferably it is C1-C12, for example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy etc.), an acyl group (preferably C1-C30, more preferably C1-C20, especially preferably carbon) 1 to 12, for example, acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 2 carbon atoms). 12 such as methoxycarbonyl and ethoxycarbonyl), aryl An oxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyloxy), an acylamino group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino, benzoylamino, and the like, and an alkoxycarbonylamino group (preferably having 2-2 carbon atoms). 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.), aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino). ), A sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenyl Sulfamoyl, etc.), a carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, Phenylcarbamoyl etc.), alkylthio group ( Preferably, it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio, ethylthio and the like, and an arylthio group (preferably 6 to 30 carbon atoms). , More preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 to carbon atoms). 20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, and a sulfonyl group (preferably having 1 carbon atom). To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl). Sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl. ), A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid. An amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenylphosphoric acid amide), a hydroxy group , Mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group ( Preferably it is C1-C30, More preferably, it is C1-C12, As a hetero atom, for example, a nitrogen atom, oxygen Children, sulfur atoms, specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, etc.), silyl group (preferably). Has 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl, triphenylsilyl, and the like, and a silyloxy group (preferably 3 to 40 carbon atoms). More preferably, it has 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyloxy, triphenylsilyloxy, and the like. These substituents may be further substituted.

Substituents represented by R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹⁰ are bonded together to form a condensed ring structure (for example, a benzo condensed ring). It may be formed. ^R101 , ^R102 , ^R103 , ^R104 , ^R105 , ^R106 , ^R107 , ^R108 , ^R109 , ^R110 are each a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkenyl group, a fluorine atom, A cyano group and an amino group are preferable, a hydrogen atom, an alkyl group, an aryl group, and an amino group are more preferable, and a hydrogen atom and an aryl group are further preferable.

R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ and R ¹¹⁰ are each preferably a hydrogen atom or an aryl group, more preferably a hydrogen atom.

R ¹⁰⁴ and R ¹⁰⁹ are each preferably a hydrogen atom, an aryl group, a heteroaryl group or an amino group, more preferably a heteroaryl group, an aryl group or an amino group, and even more preferably an aryl group.

Hereinafter, the general formula (2) will be described.
^{R 201, R 202, R 203} , R 204, R 205, R 206, R 207, R 208 each represents a hydrogen atom or a substituent. Examples of the substituent include the groups described for R ¹⁰¹ . The substituents represented by R ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , and R ²⁰⁸ may be bonded to form a ring structure (for example, a benzo condensed ring).

^{R 201, R 202, R 203} , R 204, R 205, R 206, R 207, R 208 are each a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkenyl group, a fluorine atom, a cyano group, an amino group ( And a group in which substituents are bonded to form a ring structure (for example, benzo condensed ring), and a hydrogen atom, an alkyl group, an aryl group, a diarylamino group, and substituents are bonded to each other. Thus, a group that forms a ring structure (for example, a benzo-condensed ring) is more preferable, and a group that forms a ring structure (for example, a benzo-condensed ring) by combining a hydrogen atom, an aryl group, or a substituent is more preferable.

R ²⁰¹ and R ²⁰² are each preferably a hydrogen atom, an aryl group, or a group that combines to form a condensed ring structure, more preferably an aryl group or a group that combines to form a condensed ring structure. Groups that form are more preferred.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁷ and R ²⁰⁸ are each preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an aryl group, and even more preferably a hydrogen atom.

R ²⁰⁵ and R ²⁰⁶ are each preferably a hydrogen atom, an aryl group, a group that combines to form a condensed ring structure (such as a benzo-condensed ring), or an amino group (including a diarylamino group). A group that forms a condensed ring structure (such as a benzo-condensed ring) and a diarylamino group are more preferable, and a group that forms a condensed ring structure (such as a benzo-condensed ring) by bonding with a hydrogen atom is more preferable.

Hereinafter, the general formula (3) will be described.
R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ , R ³⁰⁵ , R ³⁰⁶ , R ³⁰⁷ , R ³⁰⁸ , R ³⁰⁹ , R ³¹⁰ , R ³¹¹ , R ³¹² each represents a hydrogen atom or a substituent. Examples of the substituent include the groups described for R ¹⁰¹ . The substituents represented by R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ , R ³⁰⁵ , R ³⁰⁶ , R ³⁰⁷ , R ³⁰⁸ , R ³⁰⁹ , R ³¹⁰ , R ³¹¹ , R ³¹² are bonded to each other to form a ring structure (for example, Benzo-fused ring) may be formed.

R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ , R ³⁰⁵ , R ³⁰⁶ , R ³⁰⁷ , R ³⁰⁸ , R ³⁰⁹ , R ³¹⁰ , R ³¹¹ , R ³¹² are each a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, An alkenyl group, a fluorine atom, a cyano group, and an amino group (including a diarylamino group) are preferable, a hydrogen atom, an alkyl group, an aryl group, and a diarylamino group are more preferable, and a hydrogen atom and an aryl group are further preferable.

R ³⁰² , R ³⁰⁵ , R ³⁰⁸ and R ³¹¹ are preferably a hydrogen atom, an aryl group or an alkyl group, more preferably a hydrogen atom or an alkyl group.

R ³⁰¹ , R ³⁰⁶ , R ³⁰⁷ and R ³¹² are preferably a hydrogen atom, an aryl group or an amino group (including a diarylamino group), more preferably a hydrogen atom or a diarylamino group.

R ³⁰² , R ³⁰³ , R ³⁰⁴ , R ³⁰⁵ , R ³⁰⁸ , R ³⁰⁹ , R ³¹⁰ , and R ³¹¹ are preferably a hydrogen atom, an aryl group, or an alkyl group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom.

Hereinafter, the general formula (4) will be described.
R ⁴⁰¹ , R ⁴⁰² , R ⁴⁰³ , R ⁴⁰⁴ , R ⁴⁰⁵ , R ⁴⁰⁶ , R ⁴⁰⁷ , R ⁴⁰⁸ , R ⁴⁰⁹ , R ⁴¹⁰ , R ⁴¹¹ , R ⁴¹² each represents a hydrogen atom or a substituent. Examples of the substituent include the groups described for R ¹⁰¹ . The substituents represented by R ⁴⁰¹ , R ⁴⁰² , R ⁴⁰³ , R ⁴⁰⁴ , R ⁴⁰⁵ , R ⁴⁰⁶ , R ⁴⁰⁷ , R ⁴⁰⁸ , R ⁴⁰⁹ , R ⁴¹⁰ , R ⁴¹¹ , R ⁴¹² are bonded to each other to form a ring structure (for example, Benzo-fused ring) may be formed.

R ⁴⁰¹ , R ⁴⁰² , R ⁴⁰³ , R ⁴⁰⁴ , R ⁴⁰⁵ , R ⁴⁰⁶ , R ⁴⁰⁷ , R ⁴⁰⁸ , R ⁴⁰⁹ , R ⁴¹⁰ , R ⁴¹¹ , R ⁴¹² are a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, An alkenyl group, a fluorine atom, a cyano group, and an amino group (including a diarylamino group) are preferable, a hydrogen atom, an alkyl group, an aryl group, and a diarylamino group are more preferable, and a hydrogen atom and an aryl group are further preferable.

R ⁴⁰¹ , R ⁴⁰² , R ⁴⁰⁵ , R ⁴⁰⁶ , R ⁴⁰⁷ , R ⁴⁰⁸ , R ⁴¹¹ , and R ⁴¹² are each preferably a hydrogen atom, an aryl group, or an alkyl group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom. .

R ⁴⁰³ , R ⁴⁰⁴ , R ⁴⁰⁹ and R ⁴¹⁰ are each preferably a hydrogen atom, an aryl group or a heteroaryl group, more preferably an aryl group or a heteroaryl group, and even more preferably an aryl group.

Hereinafter, the general formula (5) will be described.
R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R ⁵⁰⁵ , R ⁵⁰⁶ , R ⁵⁰⁷ , R ⁵⁰⁸ , R ⁵⁰⁹ , R ⁵¹⁰ each represents a hydrogen atom or a substituent. Examples of the substituent include the groups described for R ¹⁰¹ . The substituents represented by R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R ⁵⁰⁵ , R ⁵⁰⁶ , R ⁵⁰⁷ , R ⁵⁰⁸ , R ⁵⁰⁹ , R ⁵¹⁰ are bonded to form a ring structure (for example, a benzo-fused ring). You may do it.

R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R ⁵⁰⁵ , R ⁵⁰⁶ , R ⁵⁰⁷ , R ⁵⁰⁸ , R ⁵⁰⁹ , and R ⁵¹⁰ are a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkenyl group, and a fluorine atom, respectively. , A cyano group, and an amino group (including a diarylamino group) are preferable, a hydrogen atom, an alkyl group, an aryl group, and a diarylamino group are more preferable, and a hydrogen atom and an aryl group are further preferable.

R ⁵⁰² , R ⁵⁰⁵ , R ⁵⁰⁷ and R ⁵¹⁰ are each preferably a hydrogen atom, an aryl group, an alkyl group or an amino group (including a diarylamino group), more preferably a hydrogen atom, an aryl group or a diarylamino group, More preferred are a hydrogen atom and an aryl group.

R ⁵⁰¹ , R ⁵⁰³ , R ⁵⁰⁴ , R ⁵⁰⁶ , R ⁵⁰⁸ and R ⁵⁰⁹ are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an aryl group, and even more preferably a hydrogen atom.

  The light emitting device of the present invention preferably contains at least one host material in the light emitting layer, and the host material is a complex. The ions in the complex are preferably boron ions or metal ions, more preferably boron ions, magnesium ions, beryllium ions, zinc ions, aluminum ions, gallium ions, indium ions, boron ions, zinc ions, aluminum ions, gallium. Ions are more preferable, and zinc ions and aluminum ions are particularly preferable.

  Although it does not specifically limit as a ligand in a complex, It is preferable to have a bidentate ligand, a bidentate ligand coordinated by oxygen-nitrogen, a bidentate ligand coordinated by oxygen-oxygen. More preferably, the ligand has a bidentate ligand coordinated with nitrogen-nitrogen, a bidentate ligand coordinated with oxygen-nitrogen, and a bidentate coordinated with nitrogen-nitrogen It is more preferable to have a child, and it is particularly preferable to have a bidentate ligand coordinated by oxygen-nitrogen.

  The complex of the host material in the present invention is preferably a compound represented by any of the following general formulas (11), (12) or (13) (more preferably represented by the following general formula (11) or (12)). Compound, more preferably a compound represented by the following general formula (11)), a compound represented by the following general formula (15) or (16) is more preferred (more preferably represented by the following general formula (15)). And a compound represented by the following general formula (17) is more preferable.

The general formula (11) will be described. M ¹¹ represents a boron ion or a metal ion. Boron ions, magnesium ions, beryllium ions, zinc ions, aluminum ions, gallium ions, and indium ions are preferable, boron ions, zinc ions, aluminum ions, and gallium ions are more preferable, and zinc ions and aluminum ions are further preferable.

Y ¹¹ represents an oxygen atom, a sulfur atom, or a substituted or unsubstituted nitrogen atom. Examples of the substituent on nitrogen include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, especially Preferably it has 2 to 10 carbon atoms, such as vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, especially Preferably it has 2 to 10 carbon atoms, and examples thereof include propargyl and 3-pentynyl), an aryl group (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc.), acyl group (preferably carbon 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 2 carbon atoms). 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (preferably 7 to 30 carbon atoms, more preferably Has 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl ), A sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms such as mesyl and tosyl), hetero A cyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, Thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably Has 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl. And so on. These substituents may be further substituted.

Y ¹¹ is preferably an oxygen atom or a substituted nitrogen atom (the substituent is preferably an acyl group, a sulfonyl group or a phosphonyl group), more preferably an oxygen atom.

Q ¹¹ represents an atomic group necessary for forming an aromatic ring. Examples of the aromatic ring formed by Q ¹¹ include a benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, Examples include a furan ring, a thiophene ring, and condensed rings thereof (such as benzothiophene). A benzene ring and a pyridine ring are preferable, and a benzene ring is more preferable.

The aromatic ring formed by Q ¹¹ may have a substituent. Examples of the substituent include the groups described for R ¹⁰¹ .

As the substituent on Q ¹¹ , an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, a fluorine atom and an alkoxy group are preferable, an alkyl group and an aryl group are more preferable, and an alkyl group is further preferable.

Q ¹² represents an atomic group necessary for forming a nitrogen-containing heterocycle. The nitrogen-containing heterocycle formed by Q ¹² is not particularly limited. For example, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, thiazole ring, oxazole ring, pyrrole ring, imidazole ring, pyrazole ring, triazole Ring, oxadiazole ring, thiadiazole ring, and condensed ring containing them (for example, quinoline ring, benzoxazole ring, benzimidazole ring, indolenine ring, imidazopyridine ring, etc.), pyridine ring, benzoxazole A ring, a benzimidazole ring, and an imidazopyridine ring are preferable, a pyridine ring, a benzimidazole ring, and an imidazopyridine ring are more preferable, and an imidazopyridine ring is more preferable.

The nitrogen-containing heterocycle formed by Q ¹² may have a substituent, and examples of the substituent include the groups described in Q ¹¹ above, and the preferred ranges are also the same.

L ¹¹ represents a ligand. Examples of the ligand include “Photochemistry and Photophysics of Coordination Compounds”, Springer-Verlag, H. et al. The ligands described in Yersin, published in 1987, “Organometallic Chemistry-Fundamentals and Applications-”, Hankabosha, Yamamoto Akio, published in 1982, and the like, preferably substituted oxy ligands (metal oxo) Ligands (for example, aluminum oxo ligands substituted with ligands), siloxy ligands (such as triphenylsiloxy ligands), aryloxy ligands (such as biphenyloxy ligands), alkoxy coordination Child (isopropoxy ligand, etc.), arylthio ligand (phenylthio ligand, etc.), alkylthio ligand (t-butylthio group, etc.), halogen ligand (chlorine ligand, fluorine ligand, etc.) ), Nitrogen-containing heterocyclic ligands (eg bipyridyl ligand, phenanthroline ligand, phenylpyridine ligand, pyrazolylpyridine ligand, benzimidazolylpyridine coordination) , Picolinic acid ligands, thienylpyridine ligands, pyrazolylpyridine ligands, imidazolylpyridine ligands, triazolylpyridine ligands, pyrazolylbenzoxazole ligands, and their condensed rings (eg, phenylquinoline) Ligand, benzothienylpyridine ligand, biquinoline ligand, etc.), diketone ligand (eg acetylacetone ligand), nitrile ligand (eg acetonitrile ligand etc.), CO ligand , Isonitrile ligands (eg t-butyl isonitrile ligands), phosphorus ligands (eg phosphine derivatives, phosphite derivatives, phosphinine derivatives etc.), carboxylic acid ligands (eg acetic acid ligands etc.) More preferably a diketone ligand, a bidentate nitrogen-containing heterocyclic ligand, a substituted oxy ligand, Preferably the al, the bidentate nitrogen-containing heterocyclic ligands, substituted oxy ligands.

X ¹¹ represents a counter ion. The counter ion is not particularly limited, but is preferably an alkali metal ion, alkaline earth metal ion, halogen ion, perchlorate ion, PF ₆ ion, ammonium ion (eg, tetramethylammonium ion, etc.), borate ion, phosphonium ion. More preferably, perchlorate ions or PF ₆ ions.

m ¹¹ represents an integer of 1 to 4, 1 to 3 are preferred, 2,3 is more preferred. When m ¹¹ is plural, the plural bidentate ligands may be the same or different.

m ¹² represents an integer of 0 to 4, preferably from 0 to 2, more preferably 0 or 1, 0 is more preferred. When m ¹² is plural, the plural L ¹¹ may be the same or different.

m ¹³ represents an integer of 0 to 3, preferably 0 or 1, more preferably 0.

The general formula (12) will be described below.
M ²¹ , Q ²² , L ²¹ , X ²¹ , m ²¹ , m ²² , and m ²³ have the same meanings as M ¹¹ , Q ¹² , L ¹¹ , X ¹¹ , m ¹¹ , m ¹² , and m ¹³ , and preferred ranges are also included. The same.

Q ²¹ represents an atomic group necessary for forming a nitrogen-containing aromatic ring. The nitrogen-containing heterocycle formed by Q ²¹ is not particularly limited. For example, a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, and a condensed ring containing them (for example, an indole ring, a benzimidazole ring, a benzine) A pyrrole ring, an imidazole ring, a pyrazole ring, an indole ring and a benzimidazole ring are preferred, a pyrazole ring, an indole ring and a benzimidazole ring are more preferred, and a pyrazole ring is more preferred.

The general formula (13) will be described below.
M ³¹ , Y ³¹ , Q ³¹ , Q ³² , L ³¹ , X ³¹ , m ³¹ , m ³² , and m ³³ are M ¹¹ , Y ¹¹ , Q ¹¹ , Q ¹² , L ¹¹ , X ¹¹ , m ¹¹ , respectively. m ^12, m ¹³ and have the same meanings, and the preferred range is also the same.

The general formula (15) will be described below.
M ⁵¹ , Y ⁵¹ , L ⁵¹ , X ⁵¹ , m ⁵¹ , m ⁵² , and m ⁵³ have the same meanings as M ¹¹ , Y ¹¹ , L ¹¹ , X ¹¹ , m ¹¹ , m ¹² , and m ¹³ , respectively. Is the same.

R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each represent a hydrogen atom or a substituent. The substituents may be bonded to each other to form a ring structure (for example, a benzene ring, a pyridine ring, a naphthalene ring, a phenanthrene ring). Examples of the substituent include the groups described for the substituent on Q ¹¹ . R ⁵¹ , R ⁵² , R ⁵³ , and R ⁵⁴ are preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, or a group that combines to form an aromatic ring, and a hydrogen atom, an alkyl group, or a combined aromatic ring. Is more preferable, and a hydrogen atom is more preferable.

R ⁵⁵ and R ⁵⁶ represent a substituent. The substituents may be bonded to form a ring structure. R ⁵⁵ and R ⁵⁶ are preferably an alkyl group, an aryl group, a heteroaryl group, or a group that combines to form an aromatic ring, more preferably an aryl group or a group that combines to form an aromatic ring. The group which forms is more preferable, and the group which couple | bonds together and forms a nitrogen-containing heterocycle is especially preferable.

Y ⁵² represents an oxygen atom, a sulfur atom, or a substituted or unsubstituted nitrogen atom. Y ⁵² is preferably an oxygen atom or a substituted nitrogen atom (the substituent on the nitrogen atom is preferably an alkyl group, an aryl group or a heteroaryl group, more preferably an alkyl group or an aryl group, more preferably an aryl group), and a substituted nitrogen atom An atom is more preferable, and an aryl group-substituted nitrogen atom is more preferable.

Hereinafter, the general formula (16) will be described.
M ⁶¹ , L ⁶¹ , X ⁶¹ , m ⁶¹ , m ⁶² , and m ⁶³ have the same meanings as M ⁵¹ , L ⁵¹ , X ⁵¹ , m ⁵¹ , m ⁵² , and m ⁵³ , respectively, and the preferred ranges are also the same.

R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each represents a hydrogen atom or a substituent. The substituents may be bonded to each other to form a ring structure (for example, a benzene ring, a pyridine ring, a naphthalene ring, a phenanthrene ring). Examples of the substituent include the groups described for the substituent on Q ¹¹ . R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, or a group that combines to form an aromatic ring, and a hydrogen atom, an alkyl group, or a combined aromatic ring. Is more preferable, and a hydrogen atom is more preferable.

Y ⁶¹ , Y ⁶² and Y ^{63 each} represent a nitrogen atom or a substituted or unsubstituted carbon atom. Examples of the substituent on the carbon atom include the groups described above for the substituent on Q ¹¹ . Y ⁶¹ is preferably a nitrogen atom. Y ⁶² is preferably a substituted or unsubstituted carbon atom (the alkyl group or aryl group is preferred as the substituent), and more preferably a substituted carbon atom. Y ⁶³ is preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom.

Hereinafter, the general formula (17) will be described.
M ⁷¹ , Y ⁷¹ , L ⁷¹ , X ⁷¹ , m ⁷¹ , m ⁷² , m ⁷³ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ are the same as M ⁵¹ , Y ⁵¹ , L ⁵¹ , X ⁵¹ , m ⁵¹ , ^{m 52, m 53, R 51} , R 52, R 53, have the same meaning as R ^54, and preferred ranges are also the same.

R ⁷⁹ represents a substituent, preferably an alkyl group, an aryl group, or a heteroaryl group, more preferably an alkyl group or an aryl group, and even more preferably an aryl group.

R ⁷⁶ , R ⁷⁷ and R ⁷⁸ each represent a hydrogen atom or a substituent. The substituents may be bonded to form a ring structure. Examples of the substituent include the groups described for the substituent on Q ¹¹ . R ⁷⁶ , R ⁷⁷ and R ⁷⁸ are preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or a group in which substituents are bonded to each other to form a ring structure, more preferably a hydrogen atom, an alkyl group or an aryl group, A hydrogen atom and an alkyl group are more preferable, and a hydrogen atom is particularly preferable.

  The light-emitting device of the present invention preferably contains an electron transport layer, and the electron transport layer is preferably a non-complex compound. Although it does not specifically limit as a non-complex compound, A nitrogen-containing heterocyclic compound is preferable.

  The nitrogen-containing heterocyclic compound is not particularly limited, but a 6-membered aromatic nitrogen-containing heterocyclic compound or a 5-membered aromatic nitrogen-containing heterocyclic compound is preferable, and pyridine, pyrazine, pyrimidine, triazine, quinoxaline, quinoline, Pyrrole, pyrazole, imidazole, oxazole, thiazole, oxadiazole, thiadiazole, and derivatives thereof (for example, tetraphenylpyridine, benzimidazole, imidazopyridine, etc.) are more preferable, imidazole derivatives are more preferable, and imidazopyridine derivatives are particularly preferable. .

  The nitrogen-containing heterocyclic compound constituting the electron transport layer used in the present invention is preferably a compound represented by the following general formula (18) or (19), more preferably a compound represented by the following general formula (19). The compound represented by the following general formula (20) is more preferable.

The general formula (18) will be described below.
R ⁸¹ , R ⁸² and R ⁸³ each represent a hydrogen atom or a substituent. Examples of the substituent include the groups described for R ¹⁰¹ .

R ⁸¹ is preferably an alkyl group, an aryl group, or a heteroaryl group, more preferably an alkyl group or an aryl group, and still more preferably an alkyl group.

R ⁸² and R ⁸³ are each preferably an alkyl group, an aryl group, a heteroaryl group, or a group that combines to form an aromatic ring, and more preferably a group that combines to form an aromatic ring.

L ⁸¹ represents a linking group. L ⁸¹ is preferably an aryl linking group, a heteroaryl linking group, or an alkyl linking group, more preferably an aryl linking group or a heteroaryl linking group, and still more preferably a nitrogen-containing heteroaryl linking group.

n ⁸¹ represents an integer of 2 or more. n ⁸¹ is 2 to 6 is preferred, 3-4 is more preferable.

L ⁸² represents a divalent linking group. ^L82 is preferably an alkylene group, an arylene group, a heteroarylene group, an oxygen linking group, a carbonyl linking group or an amino linking group, more preferably an alkylene group or an arylene group.

n ⁸² represents an integer of 0 to 6, preferably from 0 to 3, 0 or 1 are more preferable. When ⁿ⁸² is plural, the plural ^L82s may be the same or different.

The general formula (19) will be described. R ⁹² and R ⁹³ each represent a hydrogen atom or a substituent. Examples of the substituent include the groups described for R ¹⁰¹ .

R ⁹² and R ⁹³ are each preferably an alkyl group, an aryl group, a heteroaryl group, or a group that combines to form an aromatic ring, more preferably a group that combines to form an aromatic ring, and combines to form a nitrogen-containing aromatic ring. Groups that form are more preferred.

R ⁹⁴ represents a hydrogen atom or a substituent. Examples of the substituent include the groups described for the substituent on the nitrogen atom. R ⁹⁴ is preferably an alkyl group, an aryl group, or a heteroaryl group, more preferably an aryl group or a heteroaryl group, and even more preferably an aryl group.

L ⁹¹ , L ⁹² , n ⁹¹ and n ⁹² have the same meanings as L ⁸¹ , L ⁸² , n ⁸¹ and n ⁸² , respectively, and the preferred ranges are also the same.

Hereinafter, the general formula (20) will be described.
R ²¹ , R ²² and R ²³ each represent a substituent. Examples of the substituent include the groups described for R ¹⁰¹ . R ²¹ , R ²² and R ²³ are preferably an alkyl group, an aryl group, a heteroaryl group or a fluorine atom, more preferably an alkyl group or an aryl group, and even more preferably an aryl group.

n ²¹ , n ²² and n ²³ each represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0. When there are a plurality of n ²¹ , n ²² and n ²³ , the plurality of R ²¹ , R ²² and R ²³ may be the same or different.

R ²⁴ , R ²⁵ and R ²⁶ each represent a substituent. Examples of the substituent include the groups described for the substituent on the nitrogen atom. R ²⁴ , R ²⁵ and R ²⁶ are preferably an alkyl group, an aryl group or a heteroaryl group, more preferably an aryl group or a heteroaryl group, and even more preferably an aryl group.

R ²⁷ , R ²⁸ and R ²⁹ each represent a hydrogen atom or a substituent. Examples of the substituent include the groups described for R ¹⁰¹ . R ²⁷ , R ²⁸ and R ²⁹ are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an aryl group, and even more preferably a hydrogen atom.

The light-emitting device of the present invention has at least a hole transport layer, a light-emitting layer, and an electron transport layer, and has a compound that emits fluorescence when a voltage is applied in the light-emitting layer, and the fluorescent light emission contained in the light-emitting layer The light emission from the compound is preferably 80% or more of the total light emission obtained from the device from the viewpoint of light emission response and durability, more preferably 85% or more, and 90% or more. Particularly preferred.
The light emission obtained from the element includes light emission from the amplifying agent, light emission from the host material, light emission from the electron transport layer, light emission from the hole transport layer, and the like in addition to the fluorescent light emitting compound contained in the light emitting layer.

There are no particular restrictions on the method for producing a single crystal, but there are no particular restrictions, such as a recrystallization method from a supersaturated solution, a crystallization method from a gas phase such as vapor deposition onto a solid substrate, or a physical vapor in an inert gas such as argon. A method using physical transport (physical vapor transport) or the like is preferably used.
About the thickness of a single crystal, it is the range of 0.01 nm-1 micrometer, Preferably, it is the range of 0.1 nm-0.5 micrometer. More preferably, it is the range of 1.0 nm-200 nm.

  The single crystal of the organic semiconductor compound having an aspect ratio of 2 or more is preferably a single crystal of the condensed ring aromatic compound, and any one of the general formulas (1), (2), (3), (4), or (5). It is preferable that it is a single crystal of the compound represented by these. Particularly preferred are single crystals of pentacene and rubrene.

  When introducing a single crystal of an organic semiconductor compound into a light emitting element, a method of dispersing in a binder is preferable. As a binder having a charge transporting ability, poly (N-vinylcarbazole), polythiophene derivatives, poly (p-phenylene vinylene) (PPV) derivatives, poly (2,5-thienylene vinylene) derivatives, polyaniline derivatives, etc. Is mentioned. Examples of the binder having no charge transporting ability include gelatin, polyvinyl alcohol, siloxane polymer, polymethacrylate, and polystyrene. Poly (N-vinylcarbazole) is preferable. As the dispersion medium, it is preferable to use a dispersion medium that does not dissolve the single crystal of the organic semiconductor compound and is compatible with the binder. When poly (N-vinylcarbazole) is used as the binder, an alcohol solvent is preferably used.

  The method for forming the organic layer in the light emitting device of the present invention is not particularly limited, but resistance heating vapor deposition, electron beam, sputtering, molecular lamination method, coating method (spray coating method, dip coating method, impregnation method, roll) Coating method, gravure coating method, reverse coating method, roll brush method, air knife coating method, curtain coating method, spin coating method, flow coating method, bar coating method, micro gravure coating method, air doctor coating, blade coating method, squeeze Coating methods, transfer roll coating methods, kiss coating methods, cast coating methods, extrusion coating methods, wire bar coating methods, screen coating methods, etc.), inkjet methods, printing methods, transfer methods, etc. Resistance heating vapor deposition on the surface, coating method, Copy method is preferred.

  The light-emitting device of the present invention is a device in which a light-emitting layer or a plurality of organic compound films including a light-emitting layer is formed between a pair of anode and cathode electrodes. In addition to the light-emitting layer, a hole injection layer, a hole transport layer, an electron An injection layer, an electron transport layer, a protective layer, and the like may be provided, and each of these layers may have other functions. Various materials can be used for forming each layer.

The anode supplies holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like, and a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. The material preferably has a work function of 4 eV or more.
Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), metals such as gold, silver, chromium and nickel, and these metals and conductive metal oxides. Inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, preferably conductive metals It is an oxide, and ITO is particularly preferable from the viewpoint of productivity, high conductivity, transparency, and the like.
The thickness of the anode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm to 500 nm.

The anode used is usually a layer formed on soda-lime glass, non-alkali glass, a transparent resin substrate or the like. When glass is used, it is preferable to use non-alkali glass as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength, but when glass is used, a thickness of 0.2 mm or more, preferably 0.7 mm or more is usually used.
Various methods are used for the production of the anode. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (such as a sol-gel method), a dispersion of indium tin oxide is used. A film is formed by a method such as coating.
The anode can be driven to lower the driving voltage of the element or increase the light emission efficiency by washing or other processing. For example, in the case of ITO, UV-ozone treatment, plasma treatment, etc. are effective.

The cathode supplies electrons to an electron injection layer, an electron transport layer, a light emitting layer, and the like. Adhesion between the cathode and adjacent layers such as an electron injection layer, an electron transport layer, and a light emitting layer, ionization potential, and stability The material is selected in consideration of properties and the like.
As the material of the cathode, a metal, an alloy, a metal halide, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Specific examples include alkali metals (for example, Li, Na, K, etc.) And fluorides or oxides thereof, alkaline earth metals (eg Mg, Ca, etc.) and fluorides or oxides thereof, gold, silver, lead, aluminum, sodium-potassium alloys or mixed metals thereof, lithium-aluminum alloys or These mixed metals, magnesium-silver alloys or mixed metals thereof, rare earth metals such as indium, ytterbium, etc. are mentioned, preferably materials having a work function of 4 eV or less, more preferably aluminum, lithium-aluminum alloys or those Mixed metal, magnesium-silver alloy or mixed metal of them That.
The cathode can take not only a single layer structure of the compound and the mixture but also a laminated structure including the compound and the mixture. For example, a laminated structure of aluminum / lithium fluoride and aluminum / lithium oxide is preferable. The thickness of the cathode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 1 μm.
For production of the cathode, a method such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a coating method, or a transfer method is used, and a metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. . Furthermore, a plurality of metals can be vapor-deposited simultaneously to form an alloy electrode, or a previously prepared alloy may be vapor-deposited.
The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less.

The material of the light emitting layer is capable of injecting holes from an anode, a hole injection layer, or a hole transport layer when an electric field is applied, and a function capable of injecting electrons from a cathode, an electron injection layer, or an electron transport layer. Any compound can be used as long as it can form a layer having a function of transferring injected charges and a function of emitting light by providing a recombination field of holes and electrons. In addition, for example, benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin, perylene, perinone, oxadiazole, aldazine, pyralidine, cyclopentadiene, bisstyrylanthracene, Quinacridone, pyrrolopyridine, thiadiazolopyri , Cyclopentadiene, styrylamine, aromatic dimethylidin compounds, various metal complexes represented by 8-quinolinol metal complexes and rare earth complexes, polythiophene, polyphenylene, polyphenylene vinylene and other polymer compounds, organosilanes, iridium trisphenylpyridine complexes, Examples of the transition metal complexes represented by platinum porphyrin complexes and derivatives thereof other than the amplifying agent and the host material can be given.
Although the film thickness of the said light emitting layer is not specifically limited, The thing of the range of 1 nm-5 micrometers is preferable normally, More preferably, it is 5 nm-1 micrometer, More preferably, it is 10 nm-500 nm.
The method for forming the light emitting layer is not particularly limited, and methods such as resistance heating vapor deposition, electron beam, sputtering, molecular lamination method, coating method, ink jet method, printing method, LB method, and transfer method are used. Preferably, resistance heating vapor deposition or coating method is used.

  The light emitting layer may be formed of a single compound or a plurality of compounds. In addition, the light emitting layer may be a single layer or a plurality of layers, and each layer may emit light with a different emission color, for example, white light. White light may be emitted from a single light emitting layer. When there are a plurality of light emitting layers, each light emitting layer may be formed of a single material or may be formed of a plurality of compounds.

The material of the hole injection layer and hole transport layer (hereinafter also referred to as “hole injection transport material”) has the function of injecting holes from the anode, the function of transporting holes, and the electrons injected from the cathode. It may be any one having any function of blocking the above. Specific examples include carbazole, triazole, oxazole, oxadiazole, imidazole, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone, stilbene, silazane, aromatic group Tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole), aniline copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, organic Examples thereof include silane, a carbon film, the organic semiconductor compound, and derivatives thereof. The thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 500 nm. It is. The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. .
The hole injection layer and hole transport layer can be formed by vacuum deposition, LB, coating by dissolving or dispersing the hole injection / transport material in a solvent, ink jet, printing, or transfer. Used. In the case of the coating method, examples of the resin component that can be dissolved or dispersed together with the hole injecting and transporting material include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, and polybutadiene. , Poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, etc. It is done.

The material of the electron injection layer and the electron transport layer (hereinafter also referred to as “electron injection / transport material”) has a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. Any of the above may be used. Specific examples include fragrances such as triazole, oxazole, oxadiazole, imidazole, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyrandioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, naphthalene, and perylene. Various metal complexes represented by metal complexes of cyclic tetracarboxylic anhydride, phthalocyanine, 8-quinolinol, metal phthalocyanine, benzoxazole and benzothiazole as ligands, organic silanes, and derivatives thereof Can be mentioned. The film thicknesses of the electron injection layer and the electron transport layer are not particularly limited, but are usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 500 nm. The electron injection layer and the electron transport layer may have a single-layer structure made of one or more of the materials described above, or may have a multi-layer structure made of a plurality of layers having the same composition or different compositions.
As a method for forming the electron injection layer and the electron transport layer, a vacuum vapor deposition method, an LB method, a method in which the electron injection transport material is dissolved or dispersed in a solvent, a coating method, an ink jet method, a printing method, a transfer method, and the like are used. In the case of the coating method, examples of the resin component that can be dissolved or dispersed together with the electron injecting and transporting material include those exemplified in the case of the hole injecting and transporting layer.

As the material for the protective layer in the present invention, any material may be used as long as it has a function of suppressing the entry of elements that promote element deterioration such as moisture and oxygen into the element. Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O. ₃ , metal oxides such as Y ₂ O ₃ , TiO ₂ , metal fluorides such as MgF ₂ , LiF, AlF ₃ , CaF ₂ , nitrides such as SiN _x , SiO _x N _y , polyethylene, polypropylene, polymethyl methacrylate A monomer mixture comprising polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer Copolymer obtained by copolymerization, fluorine-containing copolymer having a cyclic structure in the main chain Polymer, 1% by weight of the water absorbing water absorption material, water absorption of 0.1% or less of moisture-proof material, and the like.

  There is no particular limitation on the method for forming the protective layer. For example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency excitation ions) Plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, and transfer method can be applied.

  The light emitting device of the present invention can be suitably used in the fields of display devices, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, substance amounts and ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

Example 1
As a single crystal of an organic semiconductor compound, a single crystal of copper phthalocyanine is produced using a horizontal physical gas transport method in an argon gas. The single crystal is a flat single crystal having a length of 200 μm and an aspect ratio of 50.
As shown in FIG. 1, a PEDOT / PSS aqueous dispersion (Stark) is applied on a glass substrate with ITO (10 cm square, manufactured by Eetchy) as a transparent electrode to produce a PEDOT layer having a thickness of 100 nm. To do. In addition, a toluene dispersion solution in which the same amount of the single crystal of copper phthalocyanine and the fullerene derivative C60-PCBM (Aldrich, Exemplified Compound No. 1) is mixed is attached by spin coating so as to have a thickness of 100 nm. After drying for 2 hours, an electrode made of LiF (thickness 1.0 nm) and Al (thickness 60 nm) is attached on the organic semiconductor layer by vapor deposition.
The produced photoelectrochemical cell is irradiated with simulated sunlight at 45 ° C., and the generated electricity is measured with a current-voltage measuring device (Keutley SMU238 type, trade name) to obtain the conversion efficiency (η).

  The device of the present invention has high photoelectric conversion efficiency (η). That is, a solar cell using an organic semiconductor single crystal having a large aspect ratio has an advantage of having high photoelectric conversion efficiency. Although the reason for this is not necessarily clear, (1) since single crystals are used, charge mobility is high, (2) there are fewer interfaces compared to the microcrystalline state, and there are few defect structures. Therefore, efficient charge transfer is possible. (3) Since the flat crystals are arranged in the horizontal direction, light can be efficiently absorbed.

Example 2
A single crystal of rubrene as an organic semiconductor compound is produced using a horizontal physical gas transport method in argon gas. The single crystal is a flat single crystal having an average thickness of 120 nm and a length of 5 μm, and has an aspect ratio of 42.
A methanol dispersion of poly (N-vinylcarbazole) (manufactured by Aldrich) in which the above rubrene single crystal is dispersed on a cleaned ITO substrate (ratio of rubrene and poly (N-vinylcarbazole) = 0.5: 100) Is spin-coated and dried to form a light-emitting layer having a thickness of about 250 nm. Next, lithium fluoride was vapor-deposited by 3 nm, and aluminum was vapor-deposited by 200 nm thereon. Using a source measure unit 2400 type (trade name) manufactured by Toyo Technica, a DC constant voltage is applied to the EL element to emit light, and the luminance is measured using a luminance meter BM-8 (trade name) manufactured by Topcon Corporation. The emission spectrum of the device is measured with a photonic multichannel analyzer PMA-11 (trade name) manufactured by Hamamatsu Photonics.

Comparative Example 2
The device of the present invention has high external quantum efficiency. That is, an organic EL element using an organic semiconductor single crystal having a large aspect ratio has a merit that it has a high external quantum efficiency. Although the reason for this is not necessarily clear, (1) since single crystals are used, charge mobility is high, (2) there are fewer interfaces compared to the microcrystalline state, and there are few defect structures. Therefore, efficient charge transfer is possible. (3) Since the plate-like crystals are arranged in the horizontal direction, light can be emitted efficiently and light extraction efficiency is improved. Conceivable.

FIG. 1 is a schematic diagram showing the configuration of the solar cell produced in Example 1. FIG.

Claims (11)

  A photoelectric conversion element comprising at least one single crystal of an organic semiconductor compound having an aspect ratio of 2 or more.   The photoelectric conversion element according to claim 1, wherein the single crystal of the organic semiconductor compound has a flat plate shape and is oriented in a horizontal direction with respect to the substrate.   A solar cell comprising the photoelectric conversion element according to claim 1.   The solar cell according to claim 3, wherein the organic semiconductor compound is a phthalocyanine compound.   The solar cell according to claim 3 or 4, wherein the solar cell is a bulk heterojunction solar cell containing a p-type organic semiconductor compound and an n-type organic semiconductor compound as the organic semiconductor compound.   6. The solar cell according to claim 5, wherein the p-type organic semiconductor is a single crystal of a phthalocyanine compound, and the n-type organic semiconductor is a fullerene compound.   An organic EL device comprising the photoelectric conversion device according to claim 1.   The photoelectric conversion element of Claim 7 whose thickness of the single crystal of the said organic-semiconductor compound is the range of 0.1 nm-1 micrometer.   The organic EL element according to claim 7 or 8, wherein the organic semiconductor compound is a compound having a condensed aromatic hydrocarbon ring.   The organic EL device according to claim 7, wherein the organic EL device is a dye-dispersed light-emitting device, and the single crystal of the organic semiconductor compound is a light-emitting material.   The organic EL element according to any one of claims 7 to 10, wherein poly (N-vinylcarbazole) is used as a binder.

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