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WO2010090123A1 - Élément de conversion photoélectrique organique, cellule solaire l'utilisant, et réseau de détecteur optique - Google Patents

Élément de conversion photoélectrique organique, cellule solaire l'utilisant, et réseau de détecteur optique Download PDF

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WO2010090123A1
WO2010090123A1 PCT/JP2010/051119 JP2010051119W WO2010090123A1 WO 2010090123 A1 WO2010090123 A1 WO 2010090123A1 JP 2010051119 W JP2010051119 W JP 2010051119W WO 2010090123 A1 WO2010090123 A1 WO 2010090123A1
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compound
photoelectric conversion
organic photoelectric
general formula
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Japanese (ja)
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大久保　康
野島　隆彦
伊東　宏明
晃矢子 和地
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Konica Minolta Inc
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Konica Minolta Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an organic photoelectric conversion element, a solar cell, and an optical sensor array, and more particularly, to a bulk heterojunction type organic photoelectric conversion element, a solar cell using the organic photoelectric conversion element, and an optical array sensor.
  • These bulk heterojunction solar cells are formed by a coating process except for the anode and cathode, and are expected to be able to be manufactured at high speed and at low cost. There is. Furthermore, unlike the Si solar cells, compound semiconductor solar cells, and dye-sensitized solar cells described above, there is no process at a temperature higher than 160 ° C., so it can be formed on a cheap and lightweight plastic substrate. Is done.
  • Non-Patent Document 1 in order to efficiently absorb the solar spectrum, a long wavelength is used. By using an organic polymer capable of absorbing up to 5%, conversion efficiency exceeding 5% has been achieved.
  • the photoelectric conversion efficiency is calculated by the product of short-circuit current density (Jsc) ⁇ open-circuit voltage (Voc) ⁇ curve factor (FF), and generally includes organic photoelectric conversion including high-efficiency organic thin-film solar cells as described above.
  • the device has only a low fill factor of about 0.55, and if these can be improved to values comparable to silicon solar cells (0.65 to 0.75), further photoelectric conversion efficiency is expected.
  • the curve factor is closely related to the internal resistance of the photoelectric conversion element, and it is known that lowering the resistance of the organic thin film and improving the charge separation efficiency (improving rectification) are effective for improving the curve factor. Yes.
  • the charge separation efficiency can be improved and the photoelectric conversion efficiency can be improved by inserting a hole blocking layer made of bathocuproine (BCP) as in the organic EL element (see, for example, Patent Document 1). Since these materials have high crystallinity and low solubility, there is a problem that it is difficult to apply them to a coating method with high productivity.
  • BCP bathocuproine
  • a TiOx layer is disclosed as a hole blocking layer that can be produced by a coating process (see, for example, Non-Patent Document 2), in order to form a TiOx layer, it is necessary to react moisture with titanium alkoxides. An organic photoelectric conversion element that is deteriorated by moisture is not a preferable manufacturing method, and has a problem in durability.
  • a carboline derivative or a diazacarbazole derivative is used for the hole blocking layer in order to improve the light emission efficiency.
  • a hole blocking layer functions as a hole blocking layer is determined by the relationship with the HOMO level of an adjacent layer.
  • any block layer is not necessarily applicable to an organic photoelectric conversion element, and in particular, since the HOMO and LUMO of a fullerene derivative which is an n-type semiconductor contained in a bulk heterojunction layer are relatively deep, the organic photoelectric conversion element The development of a hole blocking layer that can be effectively formed by a non-aqueous coating method is also awaited. It had.
  • the open-circuit voltage is a HOMO level of a p-type semiconductor material used for a bulk heterojunction layer and an n-type semiconductor. It is said that there is a correlation with the difference from the LUMO level of the material, and it is considered that the higher this value, the higher the open circuit voltage.
  • Non-Patent Document 3 proposes an organic photoelectric conversion element using a carbazole derivative in a bulk heterojunction layer, and an open circuit voltage as high as 0.89 V is obtained.
  • the compound of Non-Patent Document 4 having a structure in which the carbazole structure is converted into a thiophenecarbazole derivative has been able to absorb a longer wave wavelength by reducing the band gap, but the HOMO level has become shallower.
  • the open circuit voltage is reduced by 0.52 V, and the photoelectric conversion efficiency is low.
  • an azacarbazole derivative which is a nitrogen-containing aromatic six-membered ring having a deep HOMO level as in the present invention can be used as a semiconductor material for a bulk heterojunction layer, higher open-circuit voltage and photoelectric conversion efficiency can be obtained. It is estimated to be.
  • An object of the present invention is to provide an organic thin-film solar cell having high fill factor, open-circuit voltage, photoelectric conversion efficiency, and durability, and an organic semiconductor material constituting the organic thin-film solar cell.
  • An organic photoelectric conversion element having a cathode, an anode, and a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are mixed, and is represented by at least the following general formula (1) between the cathode and the anode.
  • An organic photoelectric conversion device comprising a layer containing a compound having a partial structure.
  • Z 1 represents a substituted or unsubstituted nitrogen-containing aromatic 6-membered ring
  • Z 2 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring.
  • R 1 represents a hydrogen atom, halogen, This represents a substituent selected from an atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • X 1 to X 4 represent a substituted or unsubstituted carbon atom or a nitrogen atom.
  • Z 3 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring.
  • R 2 represents a hydrogen atom, It represents a substituent selected from a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • R 3 represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group.
  • X 5 to X 8 are substituted or unsubstituted. Represents a carbon atom or a nitrogen atom.
  • R 4 to R 10 represent a substituent selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • R 4 to R 10 represent a substituent selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • R 11 to R 13 represent a substituent selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • Z 4 represents a substituted or unsubstituted group.
  • a nitrogen-containing aromatic ring, Z 5 represents a substituted or unsubstituted aromatic ring and a heteroaromatic ring, p represents an integer of 0 to 4 and q represents an integer of 2 to 6) 10.
  • the compound having a partial structure represented by the general formula (1), (2a), (2b), (3a), (3b), (4) or (5) is a low molecular weight compound having a molecular weight of less than 5000. 10.
  • R 14 to R 16 represent a substituent selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • Z 6 represents a substituted or unsubstituted group.
  • a nitrogen-containing aromatic ring, Z 7 represents a substituted or unsubstituted aromatic ring and a heteroaromatic ring, r represents an integer of 0 to 4, and s represents an integer of 2 to 10,000) 12 12.
  • the organic photoelectric conversion device as described in 11 above, wherein the compound having a partial structure represented by the general formula (6) is a polymer compound having a molecular weight of 5000 or more.
  • An optical sensor array comprising the organic photoelectric conversion elements according to any one of 1 to 13 arranged in an array.
  • an organic thin-film solar cell material that can achieve a high photoelectric conversion efficiency, has high durability, and can be applied to a coating process that enables inexpensive manufacturing can be provided.
  • FIG. 1 is a cross-sectional view showing a solar cell composed of an organic photoelectric conversion element including a photoelectric conversion layer having a three-layer structure of pin. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer. It is a figure which shows the structure of an optical sensor array.
  • the present inventors can achieve the above-mentioned problems because the layer containing the compound represented by the general formula (1) exists between the cathode and the anode. I found. Furthermore, the effect appears more remarkably when a layer containing the compound represented by the general formula (2) or (3) is present between the bulk heterojunction layer and the cathode.
  • FIG. 1 is a cross-sectional view showing an example of a solar cell composed of a bulk heterojunction organic photoelectric conversion element.
  • a bulk heterojunction type organic photoelectric conversion element 10 includes a transparent electrode (generally an anode) 12, a hole transport layer 17, a bulk heterojunction layer photoelectric conversion unit 14, and an electron transport layer 18 on one surface of a substrate 11.
  • a counter electrode (generally a cathode) 13 are sequentially stacked.
  • the substrate 11 is a member that holds the transparent electrode 12, the photoelectric conversion unit 14, and the counter electrode 13 that are sequentially stacked. In the present embodiment, since light that is photoelectrically converted enters from the substrate 11 side, the substrate 11 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. It is a transparent member.
  • the substrate 11 for example, a glass substrate or a resin substrate is used.
  • the substrate 11 is not essential.
  • the bulk heterojunction type organic photoelectric conversion element 10 may be configured by forming the transparent electrode 12 and the counter electrode 13 on both surfaces of the photoelectric conversion unit 14.
  • the photoelectric conversion unit 14 is a layer that converts light energy into electric energy, and includes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed.
  • the p-type semiconductor material functions relatively as an electron donor (donor)
  • the n-type semiconductor material functions relatively as an electron acceptor (acceptor).
  • the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”.
  • an electron acceptor which does not simply donate or accept electrons like an electrode, but donates or accepts electrons by a photoreaction.
  • FIG. 1 light incident from the transparent electrode 12 through the substrate 11 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the photoelectric conversion unit 14, and electrons move from the electron donor to the electron acceptor.
  • a hole-electron pair charge separation state
  • the generated electric charge is caused by an internal electric field, for example, when the work functions of the transparent electrode 12 and the counter electrode 13 are different, the electrons pass between the electron acceptors due to the potential difference between the transparent electrode 12 and the counter electrode 13, and the holes are The photocurrent is detected as it passes between the donors and is carried to different electrodes.
  • the transport direction of electrons and holes can be controlled.
  • a hole blocking layer such as a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, or a smoothing layer may be included.
  • the photoelectric conversion unit 14 has a so-called pin three-layer structure (FIG. 2).
  • a normal bulk heterojunction layer is a 14i layer composed of a mixture of a p-type semiconductor material and an n-type semiconductor layer, but a 14p layer composed of a single p-type semiconductor material and a 14n layer composed of a single n-type semiconductor material.
  • FIG. 3 is a cross-sectional view showing a solar cell composed of an organic photoelectric conversion element including a tandem bulk heterojunction layer.
  • the transparent electrode 12 and the first photoelectric conversion unit 14 ′ are sequentially stacked on the substrate 11, the charge recombination layer 15 is stacked, the second photoelectric conversion unit 16, and then the counter electrode.
  • stacking 13 a tandem configuration can be obtained.
  • the second photoelectric conversion unit 16 may be a layer that absorbs the same spectrum as the absorption spectrum of the first photoelectric conversion unit 14 'or may be a layer that absorbs a different spectrum, but is preferably a layer that absorbs a different spectrum. is there. Further, both the first photoelectric conversion unit 14 ′ and the second photoelectric conversion unit 16 may have the above-described three-layer structure of pin.
  • the compound having the partial structure represented by the general formula (1) is included between the cathode and the anode.
  • the layer containing the partial structure represented by the general formula (1) is preferably a bulk heterojunction layer.
  • the layer containing the partial structure represented by the general formula (1) is also preferably an electron transport layer.
  • Examples of the p-type semiconductor material used for the bulk heterojunction layer of the present invention include various condensed polycyclic aromatic low molecular compounds and conjugated polymers.
  • condensed polycyclic aromatic low molecular weight compound examples include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthanthene, bisanthene, zeslene.
  • Examples of the derivative having the above condensed polycycle include WO 03/16599 pamphlet, WO 03/28125 pamphlet, US Pat. No. 6,690,029, JP 2004-107216 A.
  • conjugated polymer for example, a polythiophene such as poly-3-hexylthiophene (P3HT) and an oligomer thereof, or a technical group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene, Nature Material, (2006) vol. 5, p328, a polythiophene-thienothiophene copolymer described in WO2008000664, a polythiophene-diketopyrrolopyrrole copolymer described in WO2008000664, a polythiophene-thiazolothiazole copolymer described in Adv Mater, 2007p4160, Nature Mat. vol.
  • P3HT poly-3-hexylthiophene
  • polypyrrole and its oligomer polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, Examples thereof include polymer materials such as ⁇ -conjugated polymers such as polysilane and polygermane.
  • oligomeric materials not polymer materials, include thiophene hexamer ⁇ -seccithiophene ⁇ , ⁇ -dihexyl- ⁇ -sexualthiophene, ⁇ , ⁇ -dihexyl- ⁇ -kinkethiophene, ⁇ , ⁇ -bis (3 Oligomers such as -butoxypropyl) - ⁇ -sexithiophene can be preferably used.
  • compounds that are highly soluble in an organic solvent to the extent that a solution process can be performed, can form a crystalline thin film after drying, and can achieve high mobility are preferable. More preferably, it is a compound (a compound capable of forming an appropriate phase separation structure) having appropriate compatibility with the fullerene derivative which is the n-type organic semiconductor material of the present invention.
  • Such materials include materials that can be insolubilized by polymerizing the coating film after coating, such as polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Or a material in which soluble substituents react and become insoluble (pigmented) by applying energy such as heat, as described in US Patent Application Publication No. 2003/136964, and Japanese Patent Application Laid-Open No. 2008-16834 And so on.
  • Z 1 represents a substituted or unsubstituted nitrogen-containing aromatic 6-membered ring
  • Z 2 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring.
  • R 1 represents a substituent selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • the structure represented by the general formula (1) has a deep HOMO level, and an element having a high open-circuit voltage can be obtained. Among them, a material having a plurality of these structures is effective.
  • the nitrogen-containing aromatic six-membered ring represented by Z 1 in the general formula (1) preferably has a nitrogen atom number range of 1 to 3, but in order to obtain a high open circuit voltage, a carbon atom of the carbazole ring A higher open circuit voltage can be obtained by substituting with more nitrogen atoms.
  • a heteroaromatic ring containing one nitrogen atom for each of the aromatic rings of Z 1 and Z 2 is used. It is preferable.
  • the position occupied by the nitrogen atom in Z 1 of the general formula (1) is a deep HOMO quasi-state when the ⁇ -position, ⁇ -position, ⁇ -position, and ⁇ -position from the side close to the nitrogen atom of the central nitrogen-containing 5-membered ring.
  • the ⁇ -position and the ⁇ -position are preferable, and thus a structure represented by the general formula (2a) or (2b) is more preferable.
  • X 1 to X 4 each represent a substituted or unsubstituted carbon atom or nitrogen atom.
  • R 2 represents a substituent selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • Z 3 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring.
  • the aromatic ring represented by Z 3 is also preferably an aromatic 6-membered ring capable of forming a symmetric structure in order to make the obtained p-type semiconductor material highly crystalline and to have a high mobility. And more preferably a nitrogen-containing aromatic 6-membered ring.
  • the ⁇ -position and the ⁇ -position are preferred as the position where the nitrogen atom is substituted, but in particular, the structure is such that the nitrogen atom is substituted at the ⁇ -position or ⁇ -position of both aromatic rings represented by Z 1 and Z 2. Things are preferable.
  • Z 1 and Z 2 have the same and symmetrical structure. That is, a compound represented by the general formula (3a) or (3b) is preferable.
  • R 3 represents a substituent selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • X 5 to X 8 each represents a substituted or unsubstituted carbon atom or nitrogen atom.
  • the p-type semiconductor material has a diazacarbazole structure in which nitrogen is located at the ⁇ -position where the compound has high symmetry and stability, and the HOMO level is deep and the open circuit voltage (Voc) can be improved. 4).
  • R 4 to R 10 represent a substituent selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • the p-type semiconductor material is more preferably a compound that can absorb a long wavelength of about 800 to 1200 nm so that a wider sunlight spectrum can be used, and therefore has a structure in which the conjugate length of ⁇ electrons is as long as possible. It is preferable. That is, the compound represented by the general formula (6) is preferable.
  • R 14 to R 16 represent a substituent selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • Z 6 represents a substituted or unsubstituted nitrogen-containing aromatic ring
  • Z 7 represents a substituted or unsubstituted aromatic ring or heteroaromatic ring.
  • r represents an integer of 0 to 4, and s represents an integer of 2 to 10,000.
  • n 10 to 100.
  • the bulk heterojunction layer increases the interface area between the p-type semiconductor material and the n-type semiconductor material as much as possible so that the charge separation efficiency is sufficiently high, while the holes and electrons generated at the interface are reduced. It is necessary to have a continuous phase separation structure so that the extraction electrode can be extracted.
  • the p-type semiconductor material is preferably a polymer compound.
  • the low molecular weight compound means a single molecule having no distribution in the molecular weight of the compound.
  • the polymer compound means an aggregate of compounds having a certain molecular weight distribution by reacting a predetermined monomer.
  • a compound having a molecular weight of 5000 or more is classified as a polymer compound. More preferably, it is 10,000 or more, More preferably, it is 30000 or more.
  • the solubility decreases as the molecular weight increases, the molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less.
  • the molecular weight can be measured by gel permeation chromatography (GPC).
  • the n-type semiconductor material used in the bulk heterojunction layer of the present invention is not particularly limited.
  • a perfluoro compound perfluoro compound in which hydrogen atoms of a p-type semiconductor such as fullerene and octaazaporphyrin are substituted with fluorine atoms. Pentacene, perfluorophthalocyanine, etc.), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide and other aromatic carboxylic acid anhydrides and imidized compounds thereof. Examples thereof include molecular compounds.
  • fullerene derivatives that can perform charge separation with various p-type semiconductor materials at high speed (up to 50 fs) and efficiently are preferable.
  • Fullerene derivatives include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), etc.
  • PCBM [6,6] -phenyl C61-butyric acid methyl ester
  • PCBnB [6,6] -phenyl C61-butyric acid-n-butyl ester
  • PCBiB [6,6] -phenyl C61-buty Rick acid-isobutyl ester
  • PCBH [6,6] -phenyl C61-butyric acid-n-hexyl ester
  • Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method).
  • the coating method is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency.
  • the coating method is also excellent in production speed.
  • annealing is performed at a predetermined temperature during the manufacturing process, a part of the particles is microscopically aggregated or crystallized, and the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.
  • the photoelectric conversion part (bulk heterojunction layer) 14 may be composed of a single layer in which the electron acceptor and the electron donor are uniformly mixed, but a plurality of the mixture ratios of the electron acceptor and the electron donor are changed. It may consist of layers. In this case, it can be formed by using a material that can be insolubilized after coating as described above.
  • the organic photoelectric conversion element 10 of the present invention can extract charges generated in the bulk heterojunction layer more efficiently by forming the electron transport layer 18 between the bulk heterojunction layer and the cathode. Therefore, it is preferable to have these layers.
  • the electron transport layer is a layer that is located between the cathode and the bulk heterojunction layer and can transfer electrons between the bulk heterojunction layer and the electrode more efficiently. is there. More specifically, a compound having an LUMO level intermediate between the LUMO level of the n-type semiconductor material of the bulk hetero junction layer and the work function of the cathode is suitable as the electron transporting layer. More preferably, it is a compound having an electron mobility of 10 ⁇ 4 or more.
  • the electron transport layer As the electron transport layer (hole blocking layer) 18, octaazaporphyrin and a p-type semiconductor perfluoro compound (perfluoropentacene, perfluorophthalocyanine, etc.) can be used.
  • the electron transport layer having a HOMO level deeper than the HOMO level of the p-type semiconductor material used has a rectifying effect that prevents holes generated in the bulk heterojunction layer from flowing to the cathode side. Block function is added.
  • Such an electron transport layer is also referred to as a hole blocking layer. More preferably, a material deeper than the HOMO level of the n-type semiconductor is used as the electron transport layer.
  • n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide.
  • N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used.
  • a layer made of a single n-type semiconductor material used for the bulk heterojunction layer can also be used.
  • the HOMO level is deep and the electron mobility is high, and the general formulas (1), (2a), (2b), (3a), (3b), (4), and (6) of the present invention are used.
  • the compound to be used as an electron transporting layer also serving as a hole blocking layer
  • effects such as an improvement in fill factor and photoelectric conversion efficiency can be obtained.
  • the structure is represented by the general formula (5).
  • it can design to the compound which has the above LUMO levels and HOMO levels, and can be set as a more efficient organic thin-film solar cell.
  • R 11 to R 13 represent a substituent selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • Z 4 represents a substituted or unsubstituted nitrogen-containing aromatic ring.
  • Z 5 represents a substituted or unsubstituted aromatic ring and heteroaromatic ring.
  • p represents an integer of 0 to 4
  • q represents an integer of 2 to 6.
  • the nitrogen-containing heterocycle represented by Z 4 is more preferably a substituted or unsubstituted imidazole, pyrazole, triazole, oxazole, thiazole, oxadiazole, thiadiazole, benzimidazole, benzooxadiazole, benzothiadiazole.
  • a substituent having a strong electron-withdrawing property having a plurality of nitrogen atoms is preferable, and among them, benzoxadiazole, benzothiadiazole, pyridothiadiazole, thienopyrazine, and the like are preferable. Most preferred are benzoxadiazole and benzothiadiazole.
  • the electron transport layer is a layer of a single electron transport material, and there is no need to consider the morphology of the mixed state.
  • the electron transport material is preferably a low molecular compound.
  • the low molecular weight compound means a single molecule having no distribution in the molecular weight of the compound.
  • the polymer compound means an aggregate of compounds having a certain molecular weight distribution by reacting a predetermined monomer.
  • a compound having a molecular weight of less than 5000 is classified as a low molecular weight compound. More preferably, it is 3000 or less, More preferably, it is 1500 or less.
  • the molecular weight can be measured by gel permeation chromatography (GPC).
  • the means for forming these layers may be either a vacuum vapor deposition method or a solution coating method, but is preferably a solution coating method.
  • the hole transport layer 17 is provided between the bulk heterojunction layer and the anode, and charges generated in the bulk heterojunction layer can be taken out more efficiently. It is preferable to have these layers.
  • PEDOT such as trade name BaytronP, polyaniline and its doped material, cyan compounds described in WO2006019270, etc. Can be used.
  • An electronic block function having a rectifying effect is provided.
  • Such a hole transport layer is also called an electron block layer, and it is preferable to use a hole transport layer having such a function.
  • unit used for the bulk heterojunction layer can also be used.
  • the means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method. Forming the coating film in the lower layer before forming the bulk heterojunction layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.
  • the intermediate layer include a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, an exciton block layer, a UV absorption layer, a light reflection layer, and a wavelength conversion layer.
  • the photoelectric conversion element according to the present invention has at least an anode and a cathode. Further, when a tandem configuration is adopted, the tandem configuration can be achieved by using an intermediate electrode.
  • an electrode through which holes mainly flow is called an anode
  • an electrode through which electrons mainly flow is called a cathode.
  • a translucent electrode is referred to as a transparent electrode and a non-translucent electrode is referred to as a counter electrode because of the function of whether or not it has translucency.
  • the anode is a translucent transparent electrode
  • the cathode is a non-translucent counter electrode.
  • the anode of the present invention is preferably an electrode that transmits light of 380 to 800 nm.
  • the material for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO 2 and ZnO, metal thin films such as gold, silver and platinum, metal nanowires and carbon nanotubes can be used.
  • a conductive material selected from the group consisting of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene.
  • a functional polymer can also be used. Further, a plurality of these conductive compounds can be combined to form an anode.
  • the cathode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination.
  • a conductive material for the cathode a material having a work function (4 eV or less) metal, alloy, electrically conductive compound, and a mixture thereof as an electrode material is used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of these metals and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the light coming to the cathode side is reflected and reflected to the first electrode side, and this light can be reused and absorbed again by the photoelectric conversion layer, further improving the photoelectric conversion efficiency. It is preferable.
  • the cathode 13 may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), a nanoparticle made of carbon, a nanowire, or a nanostructure.
  • a dispersion is preferable because a transparent and highly conductive cathode can be formed by a coating method.
  • the cathode side is made light transmissive, for example, a conductive material suitable for the cathode such as aluminum and aluminum alloy, silver and silver compound is made thin with a film thickness of about 1 to 20 nm, and then the anode By providing a film of the conductive light-transmitting material mentioned in the description, a light-transmitting cathode can be obtained.
  • a conductive material suitable for the cathode such as aluminum and aluminum alloy
  • silver and silver compound is made thin with a film thickness of about 1 to 20 nm
  • the intermediate electrode material required in the case of the tandem structure as shown in FIG. 3 is preferably a layer using a compound having both transparency and conductivity.
  • Transparent metal oxides such as ITO, AZO, FTO and titanium oxide, very thin metal layers such as Ag, Al and Au, or layers containing nanoparticles / nanowires, conductive polymer materials such as PEDOT: PSS and polyaniline Etc.
  • PEDOT: PSS and polyaniline Etc. conductive polymer materials
  • the substrate is preferably a member that can transmit the light that is photoelectrically converted, that is, a member that is transparent to the wavelength of the light to be photoelectrically converted.
  • a transparent resin film from the viewpoint of light weight and flexibility.
  • the material, a shape, a structure, thickness, etc. can be suitably selected from well-known things.
  • polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, polyolefin resins such as cyclic olefin resin Film, vinyl resin film such as polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate (PC) resin film, A polyamide resin film, a polyimide resin film, an acrylic resin film, a triacetyl cellulose (TAC) resin film, and the like can be given.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PE polyethylene
  • PP polypropylene
  • polystyrene resin film polyolefin resins such as cyclic olefin resin Film
  • the resin film transmittance of 80% or more in ⁇ 800 nm can be preferably applied to a transparent resin film according to the present invention.
  • a transparent resin film according to the present invention it is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched.
  • a polyethylene terephthalate film and a biaxially stretched polyethylene naphthalate film are more preferable.
  • the transparent substrate used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution.
  • a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution.
  • a conventionally well-known technique can be used about a surface treatment or an easily bonding layer.
  • the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
  • Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer.
  • a barrier coat layer may be formed in advance on the transparent substrate, or a hard coat layer may be formed in advance on the opposite side to which the transparent conductive layer is transferred. Good.
  • the organic photoelectric conversion element of the present invention may have various optical functional layers for the purpose of more efficient reception of sunlight.
  • a light condensing layer such as an antireflection film or a microlens array, or a light diffusion layer that can scatter light reflected by the cathode and enter the power generation layer again may be provided. .
  • the antireflection layer can be provided as the antireflection layer.
  • the refractive index of the easy adhesion layer adjacent to the film is 1.57. It is more preferable to set it to ⁇ 1.63 because the transmittance can be improved by reducing the interface reflection between the film substrate and the easy adhesion layer.
  • the method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin.
  • the easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.
  • the condensing layer for example, it is processed so as to provide a structure on the microlens array on the sunlight receiving side of the support substrate, or the amount of light received from a specific direction is increased by combining with a so-called condensing sheet. Conversely, the incident angle dependency of sunlight can be reduced.
  • quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably 10 to 100 ⁇ m. If it is smaller than this, the effect of diffraction is generated and colored.
  • examples of the light scattering layer include various antiglare layers, layers in which nanoparticles or nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer, and the like.
  • the method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like according to the present invention are not particularly limited, and known methods can be appropriately applied.
  • the electrode can be patterned by a known method such as mask vapor deposition during vacuum deposition or etching or lift-off.
  • the pattern may be formed by transferring a pattern formed on another substrate.
  • the produced organic photoelectric conversion element 10 is not deteriorated by oxygen, moisture, or the like in the environment, it is preferable to seal not only the organic photoelectric conversion element but also an organic electroluminescence element by a known method.
  • optical sensor array Next, an optical sensor array to which the bulk heterojunction type organic photoelectric conversion element 10 described above is applied will be described in detail.
  • the optical sensor array is produced by arranging the photoelectric conversion elements in a fine pixel form by utilizing the fact that the bulk heterojunction type organic photoelectric conversion elements generate a current upon receiving light, and projected onto the optical sensor array.
  • FIG. 4 is a diagram showing the configuration of the optical sensor array. 4A is a top view, and FIG. 4B is a cross-sectional view taken along line A-A ′ of FIG. 4A.
  • an optical sensor array 20 is paired with an anode 22 as a lower electrode, a photoelectric conversion unit 24 for converting light energy into electrical energy, and an anode 22 on a substrate 21 as a holding member.
  • the cathode 23 is sequentially laminated.
  • the photoelectric conversion unit 24 includes two layers, a photoelectric conversion layer 24b having a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed, and a buffer layer 24a. In the example shown in FIG. 4, six bulk heterojunction type organic photoelectric conversion elements are formed.
  • the substrate 21, the anode 22, the photoelectric conversion layer 24b, and the cathode 23 have the same configuration and role as the anode 12, the photoelectric conversion unit 14, and the cathode 13 in the bulk heterojunction photoelectric conversion element 10 described above.
  • the buffer layer 24a is made of PEDOT (poly-3,4-ethylenedioxythiophene) -PSS (polystyrene sulfonic acid) conductive polymer (trade name BaytronP, manufactured by Stark Vitec).
  • PEDOT poly-3,4-ethylenedioxythiophene
  • PSS polystyrene sulfonic acid
  • Such an optical sensor array 20 was manufactured as follows.
  • An ITO film was formed on the glass substrate by sputtering and processed into a predetermined pattern shape by photolithography.
  • the thickness of the glass substrate was 0.7 mm
  • the thickness of the ITO film was 200 nm
  • the measurement area (light receiving area) of the ITO film after photolithography was 0.5 mm ⁇ 0.5 mm.
  • P3HT and PCBM were mixed with a chlorobenzene solvent in a ratio of 1: 1, and a mixture obtained by stirring (5 minutes) was used.
  • annealing was performed by heating in an oven at 180 ° C. for 30 minutes in a nitrogen gas atmosphere.
  • the thickness of the mixed film of P3HT and PCBM after the annealing treatment was 70 nm.
  • the optical sensor array 20 was produced as described above.
  • Example 1 (use as a hole blocking layer) ⁇ Preparation of Comparative Organic Photoelectric Conversion Element 1> The transparent electrode patterned on the glass substrate was cleaned in the order of ultrasonic cleaning with surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally UV ozone cleaning. .
  • Baytron P4083 manufactured by Starck Vitec, which is a conductive polymer, was spin-coated with a film thickness of 30 nm, and then heat-dried at 140 ° C. for 10 minutes in the air.
  • the substrate was brought into the glove box and worked in a nitrogen atmosphere.
  • the substrate was heat-treated at 140 ° C. for 3 minutes in a nitrogen atmosphere.
  • a solution was prepared by dissolving 1.5 mass% of plexcores OS2100 manufactured by Plextronics as a p-type semiconductor material and 1.5 mass% of E100 (PCBM) manufactured by Frontier Carbon as an n-type semiconductor material in chlorobenzene. While being filtered through a .45 ⁇ m filter, spin coating was performed at 500 rpm for 60 seconds, then at 2200 rpm for 1 second, and left at room temperature for 30 minutes.
  • the substrate on which the series of organic layers was formed was placed in a vacuum deposition apparatus without being exposed to the atmosphere.
  • the element was set so that the shadow mask with a width of 2 mm was orthogonal to the transparent electrode, and the inside of the vacuum deposition apparatus was depressurized to 10 ⁇ 3 Pa or less, and then 100 nm of Al was deposited.
  • the heating for 30 minutes was performed at 120 degreeC, and the comparative organic photoelectric conversion element 1 was obtained.
  • the vapor deposition rate was 2 nm / second, and the size was 2 mm square.
  • the obtained organic photoelectric conversion element 1 was sealed using an aluminum cap and a UV curable resin (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1) in a nitrogen atmosphere, and then taken out into the atmosphere.
  • a UV curable resin manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1
  • Comparative Organic Photoelectric Conversion Element 2 In the comparative organic photoelectric conversion element 1, instead of 0.5% 2,2,3,3-tetrafluoro-1-propanol solution of batocuproine as a hole blocking layer, Ti-isopropoxide was added to ethanol at 25 mmol / l. After the electrode portion was masked and spin-coated at 2000 rpm, it was taken out into the atmosphere and left for 60 minutes to hydrolyze Ti-isopropoxide, thereby obtaining a film thickness of 10 nm. A comparative organic photoelectric conversion element 2 was produced in the same manner except that a TiOx layer was formed and a hole blocking layer was formed.
  • Photoelectric conversion elements prepared above was irradiated with light having an intensity of 100 mW / cm 2 solar simulator (AM1.5G filter), a superposed mask in which the effective area 4.0 mm 2 on the light receiving portion, the short circuit current density Jsc ( The four light-receiving portions formed on the same element were measured for mA / cm 2 ), open-circuit voltage Voc (V), and fill factor (fill factor) FF, and the average value was obtained. Further, energy conversion efficiency ⁇ (%) was obtained from Jsc, Voc, and FF according to Equation 1.
  • Relative reduction efficiency (%) (1 ⁇ conversion efficiency after exposure / conversion efficiency before exposure) ⁇ 100 (Durability evaluation 2)
  • the conversion efficiency after storage for 300 hours under the condition of 65 degrees and 85% humidity was evaluated, and the relative reduction efficiency was calculated.
  • Relative reduction efficiency (%) (conversion efficiency after 1-300 hours storage / conversion efficiency before storage) ⁇ 100
  • the substrate was similarly brought into the glove box and operated in a nitrogen atmosphere.
  • the substrate was heat-treated at 140 ° C. for 3 minutes in a nitrogen atmosphere.
  • a liquid was prepared by dissolving 0.5% by mass of the comparative p-type semiconductor material 1 and 2.0% by mass of Frontier Carbon E100 (PCBM) as an n-type semiconductor material, While being filtered with a 0.45 ⁇ m filter, spin coating was performed at 2000 rpm for 60 seconds, followed by heating at 50 ° C. for 10 minutes, and then standing at room temperature for 12 hours.
  • PCBM Frontier Carbon E100
  • the substrate on which the series of organic layers was formed was placed in a vacuum deposition apparatus without being exposed to the atmosphere.
  • the element was set so that the shadow mask with a width of 2 mm was orthogonal to the transparent electrode, and the inside of the vacuum deposition apparatus was depressurized to 10 ⁇ 3 Pa or less, and then 0.6 nm of lithium fluoride and 100 nm of Al were evaporated.
  • the heating for 30 minutes was performed at 120 degreeC, and the comparative organic photoelectric conversion element 21 was obtained.
  • the vapor deposition rate was 2 nm / second, and the size was 2 mm square.
  • the obtained organic photoelectric conversion element 21 was sealed using an aluminum cap and a UV curable resin (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1) in a nitrogen atmosphere, and then taken out into the atmosphere. The following conversion efficiency and open circuit voltage were evaluated.
  • a UV curable resin manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1
  • the p-type semiconductor material was replaced with the compound of the present invention described in Table 2 below in place of the comparative compound 1, which was the comparative p-type semiconductor material.
  • the conversion efficiency and the open circuit voltage were similarly evaluated.
  • the p-type semiconductor material is a polymer
  • purification is performed by the same reprecipitation and Soxhlet extraction method as in the comparative p-type semiconductor material 1, and in the case of a low molecular material, silica gel column chromatography and gel permeation chromatography are performed. Purification was performed using The number average molecular weights of the exemplary compounds 102 and 104 used in the organic photoelectric conversion elements 22, 23, and 26 were 7000 to 8000.
  • the said exemplary compounds 16 and 44 are made into 2 in the ratio of 0.5 mass%.
  • a solution mixed with 2,3,3-tetrafluoro-1-propanol was spin-coated at 1500 rpm to form a 10 nm-thick hole blocking layer.
  • the organic photoelectric conversion elements 25 and 26 were produced in the same manner as the organic photoelectric conversion element 23, and the conversion efficiency was evaluated in the same manner as in Example 1.

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Abstract

L'invention porte sur un matériau de cellule solaire en couche mince organique, qui a une solubilité élevée qui permet la formation d'un film épais, qui est capable d'améliorer l'absorption optique, par un procédé de revêtement. Le matériau de cellule solaire en couche mince organique présente une aptitude de transport de porteur suffisante même lorsqu'il est formé sous la forme d'un film épais. Le matériau de cellule solaire en film mince organique est caractérisé en ce qu'il est appliqué entre une électrode négative et une électrode positive, et qu'il contient un composé ayant au moins une structure partielle représentée par la formule générale (1). (Dans la formule, Z1 représente un noyau hétérocyclique aromatique substitué ou non substitué; Z2 représente un noyau d'hydrocarbure aromatique substitué ou non substitué ou un noyau hétérocyclique aromatique substitué ou non substitué; et R1 représente un substituant sélectionné à partir d'un atome d'hydrogène, d'un atome d'halogène, d'un groupe alkyle substitué ou non substitué, d'un groupe cycloalkyle, d'un groupe aryle et d'un groupe hétéroaryle).
PCT/JP2010/051119 2009-02-04 2010-01-28 Élément de conversion photoélectrique organique, cellule solaire l'utilisant, et réseau de détecteur optique Ceased WO2010090123A1 (fr)

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JP2012186343A (ja) * 2011-03-07 2012-09-27 Kyushu Univ 有機薄膜太陽電池
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CN103896931A (zh) * 2012-12-27 2014-07-02 海洋王照明科技股份有限公司 一种有机半导体材料、制备方法和电致发光器件
CN104098591B (zh) * 2013-04-09 2017-05-24 河南师范大学 两个小分子有机半导体材料合成方法
CN104098591A (zh) * 2013-04-09 2014-10-15 河南师范大学 两个小分子有机半导体材料合成方法

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