WO2010137449A1 - Elément de conversion photoélectrique organique, et pile solaire et ensemble de capteurs optiques l'utilisant chacun - Google Patents

Elément de conversion photoélectrique organique, et pile solaire et ensemble de capteurs optiques l'utilisant chacun Download PDF

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WO2010137449A1
WO2010137449A1 PCT/JP2010/057864 JP2010057864W WO2010137449A1 WO 2010137449 A1 WO2010137449 A1 WO 2010137449A1 JP 2010057864 W JP2010057864 W JP 2010057864W WO 2010137449 A1 WO2010137449 A1 WO 2010137449A1
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photoelectric conversion
organic photoelectric
group
layer
atom
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Japanese (ja)
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大久保　康
北　弘志
野島　隆彦
伊東　宏明
晃矢子 和地
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Konica Minolta Inc
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    • 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
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    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
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    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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    • 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
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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    • C08G2261/90—Applications
    • C08G2261/94—Applications in sensors, e.g. biosensors
    • 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
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to an organic photoelectric conversion element, a solar cell, and an optical sensor array. More specifically, the present invention relates to a bulk heterojunction type organic photoelectric conversion element, a solar cell using the organic photoelectric conversion element, and an optical array sensor.
  • an electron donor layer p-type semiconductor layer
  • an electron acceptor are provided between the transparent electrode and the counter electrode.
  • a bulk heterojunction photoelectric conversion element has been proposed in which a photoelectric conversion layer mixed with a layer (n-type semiconductor layer) is sandwiched (see, for example, Non-Patent Document 1).
  • these bulk heterojunction solar cells are formed by a coating process except for the anode and cathode, it is expected that they can be manufactured at high speed and at low cost, and may solve the above-mentioned problem of power generation cost. . Furthermore, unlike the Si-based solar cells, compound semiconductor-based solar cells, and dye-sensitized solar cells described above, there is no process at a temperature higher than 160 ° C., so that it can be formed on a cheap and lightweight plastic substrate. Is done.
  • Non-Patent Document 1 conversion efficiency exceeding 5% has been achieved. This is achieved by utilizing intramolecular charge transfer between a thiophene ring and a benzothiadiazole ring, which is very long wavelength ( ⁇ 900 nm). This is because it has become possible to absorb a wide range of sunlight until.
  • the solar cell is also required to have durability.
  • Durability was insufficient.
  • Non-Patent Documents 1 and 2 described above, since the donor and acceptor in the molecule are only bonded by a single bond and a double bond, decomposition is likely to occur.
  • some photochromic dye nuclei have a structure in which the Sp1 nitrogen atom is present at the bridgehead position of the two condensed rings and the Sp2 nitrogen atom is located at a position other than the bridgehead position of the condensed ring. is there.
  • long-wave absorption can be obtained by the Sp1 nitrogen atom at the bridgehead position acting as a donor and the Sp2 nitrogen atom other than the bridgehead position acting as an acceptor.
  • the donor and the acceptor formed a ring structure and thus had good durability.
  • a solar cell having high efficiency and high durability can be obtained by using a photoelectric conversion material having a partial structure that can absorb such a long wave and has high durability, and completes the present invention. It came to.
  • This invention is made
  • the objective is to provide a photoelectric conversion element with high photoelectric conversion efficiency and durability, a solar cell using this organic photoelectric conversion element, and an optical array sensor. is there.
  • organic photoelectric conversion element having a transparent electrode, a counter electrode, and a photoelectric conversion layer in which a p-type semiconductor material and an n-type semiconductor material are mixed, the compound having a structure represented by the following general formula (1) in the photoelectric conversion layer
  • An organic photoelectric conversion element comprising:
  • Z 1 and Z 2 are an atomic group forming a 5-membered or 6-membered ring, and at least one of Z 1 and Z 2 is an atomic group having a nitrogen atom in addition to the nitrogen atom at the bridge head position.
  • Z 1 and Z 2 are both heteroaromatic rings having a nitrogen atom in addition to the nitrogen atom at the bridge head position.
  • Y 1 and Y 2 represent a substituted or unsubstituted nitrogen atom, oxygen atom, sulfur atom or silicon atom
  • R 1 to R 5 represent a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group
  • Y 1 and Y 2 are sulfur atoms.
  • Y 3 represents a substituted or unsubstituted nitrogen atom, carbon atom, oxygen atom, sulfur atom, or silicon atom.
  • Y 3 is a silicon atom.
  • a solar cell comprising the organic photoelectric conversion device according to any one of 1 to 11 above.
  • An optical sensor array comprising the organic photoelectric conversion elements according to any one of 1 to 11 arranged in an array.
  • an organic photoelectric conversion element having high photoelectric conversion efficiency and durability, a solar cell using the organic photoelectric conversion element, and an optical array sensor could 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 photoelectric conversion layer. It is a figure which shows the structure of an optical sensor array.
  • the organic photoelectric conversion device of the present invention is characterized in that the photoelectric conversion layer contains a compound having a structure represented by the general formula (1).
  • FIG. 1 is a cross-sectional view showing 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 photoelectric conversion layer 14, an electron transport layer 18, and a counter electrode (generally, on one surface of a substrate 11.
  • Cathode 13 is sequentially laminated.
  • the substrate 11 is a member that holds the transparent electrode 12, the photoelectric conversion layer 14, and the counter electrode 13 that are sequentially stacked. In the present embodiment, since light photoelectrically converted enters from the substrate 11 side, the substrate 11 can transmit the light subjected to photoelectric conversion, that is, transparent to the wavelength of the light to be photoelectrically converted. It is an important 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 layer 14.
  • the photoelectric conversion layer 14 is a layer that converts light energy into electric energy, and includes a photoelectric conversion 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.
  • 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 layer 14 has a so-called pin three-layer configuration (FIG. 2).
  • a normal photoelectric conversion layer is a single 14i layer in which a p-type semiconductor material and an n-type semiconductor layer are mixed, but is sandwiched between a 14p layer made of a single p-type semiconductor material and a 14n layer made of a single n-type semiconductor material. Further, the rectification property of holes and electrons is further increased, loss due to recombination of charge-separated holes and electrons is reduced, and higher photoelectric conversion efficiency can be obtained.
  • FIG. 3 is a cross-sectional view illustrating an organic photoelectric conversion element including a tandem photoelectric conversion layer.
  • the transparent electrode 12 and the first photoelectric conversion layer 14 ′ are sequentially stacked on the substrate 11, the charge recombination layer 15 is stacked, the second photoelectric conversion layer 16, and then the counter electrode 13.
  • the second photoelectric conversion layer 16 may be a layer that absorbs the same spectrum as the absorption spectrum of the first photoelectric conversion layer 14 'or may be a layer that absorbs a different spectrum, but is preferably a layer that absorbs a different spectrum. is there.
  • both the first photoelectric conversion layer 14 ′ and the second photoelectric conversion layer 16 may have the above-described three-layer structure of pin.
  • P-type semiconductor materials In the present invention, as the p-type semiconductor material, a compound having a structure represented by the general formula (1) is used.
  • Z 1 and Z 2 are an atomic group forming a 5-membered or 6-membered ring, and at least one of Z 1 and Z 2 is an atomic group having a nitrogen atom in addition to the nitrogen atom at the bridgehead position It is.
  • Examples of the 5-membered or 6-membered ring formed by Z 1 and Z 2 include pyrrole, pyrazole, imidazole, triazole, thiazole, thiadiazole, oxazole, oxadiazole, triazine, pyrimidine, pyridine, pyrazine, pyridazine and the like. is, preferably Z 1, Z 2 is a heteroaromatic ring together with a nitrogen atom besides the nitrogen atoms of a bridge head position, it is preferably further is Z 1, Z 2 are both nitrogen-containing 5-membered ring . Specific examples include pyrazole, imidazole, and triazole.
  • the 5-membered or 6-membered ring formed by Z 1 and Z 2 may have a substituent.
  • substituents include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to carbon atoms). 12, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, etc.), a cycloalkyl group (preferably Has 4 to 8 carbon atoms, and examples thereof include cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms).
  • alkynyl group preferably having 2 to 20 carbon atoms, more preferably 2 to 1 carbon atoms
  • alkynyl group preferably having 2 to 20 carbon atoms, more preferably 2 to 1 carbon atoms
  • it has 2 to 8 carbon atoms, and examples thereof include propargyl, 3-pentynyl, etc.
  • an aryl group preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably carbon atoms.
  • 6 to 12 for example, phenyl, p-methylphenyl, naphthyl, etc.
  • amino group preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 carbon atoms).
  • To 6 includes, for example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino, etc.), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably carbon atoms). 1 to 8, for example, methoxy, ethoxy, butoxy, etc.), cycloalkyloxy group (preferably carbon 4 to 8, for example, cyclopentyloxy, cyclohexyloxy, etc.), an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms).
  • phenyloxy, 2-naphthyloxy, etc. acyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, , Acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms.
  • aryloxycarbonyl group (preferably having 7 to 2 carbon atoms) 0, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, and examples thereof include phenyloxycarbonyl.
  • An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy), an acylamino group (preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino and benzoylamino), alkoxycarbonylamino group (preferably having 2 carbon atoms) To 20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.), an aryloxycarbonylamino group (preferably 7 to 20 carbon atoms, more Preferably it has 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms.
  • Sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino).
  • a sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl) , Phenylsulfamoyl etc.), carbamoyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, And diethylcarbamoyl, phenylcarbamoyl, etc.), al A ruthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), an arylthio group (preferably having a carbon number of 6 to 20, more preferably 6
  • Phosphoric acid amide groups preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethyl phosphoric acid amide and phenylphosphoric acid amide.
  • X 1 to X 6 represent a substituted or unsubstituted carbon atom or a nitrogen atom, and at least one of X 1 to X 3 and at least one of X 4 to X 6 are nitrogen atoms, X 1 , X 5 and X 6 are preferably nitrogen atoms.
  • the general formula (2) is preferably represented by the general formula (3).
  • the inside of [] represents a repeating unit.
  • Y 1 and Y 2 represent a substituted or unsubstituted nitrogen atom, oxygen atom, sulfur atom, or silicon atom
  • R 1 to R 5 represent a substituted or unsubstituted alkyl group, cycloalkyl group, It represents a substituent selected from an aryl group, a heteroaryl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heteroaryloxy group, and an amino group.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 4 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
  • the cycloalkyl group preferably has 4 to 8 carbon atoms, and examples thereof include cyclopentyl and cyclohexyl.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl.
  • the heteroaryl group preferably has 1 to 12 carbon atoms, more preferably 3 to 9 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, Examples include pyridyl, quinolyl, furyl, benzoxazolyl, benzimidazolyl, and benzthiazolyl.
  • the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 4 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include butoxy, hexyloxy, dodecyloxy and the like.
  • the cycloalkyloxy group preferably has 4 to 8 carbon atoms, and examples thereof include cyclopentyloxy and cyclohexyloxy.
  • the aryloxy group preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy.
  • the heteroaryloxy group preferably has 1 to 12 carbon atoms, more preferably 3 to 9 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl. Examples thereof include oxy, pyridyloxy, quinolyloxy, furyloxy, benzoxazolyloxy, benzimidazolyloxy, benzthiazolyloxy and the like.
  • the amino group preferably has 0 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 6 to 16 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like. It is done.
  • Y 1 and Y 2 are sulfur atoms.
  • Y 3 represents a substituted or unsubstituted nitrogen atom, carbon atom, oxygen atom, sulfur atom, or silicon atom, and is preferably a carbon atom or silicon atom that can be expected to achieve both high mobility and high solubility. Preferably it is a silicon atom.
  • the compound having the structure of the present invention includes a low molecular compound and a high molecular compound.
  • a high molecular compound is easy to control the morphology of the p-type material and the n-type material to obtain a compound having high photoelectric conversion efficiency.
  • the metal catalyst used during polymerization, the reactive group of the monomer, etc. are related to the lifetime of the organic photoelectric conversion element, so it is difficult to improve the lifetime, which is another important characteristic of the photoelectric conversion element. There is a tendency. Therefore, the p-type semiconductor material is preferably a low molecular compound from the viewpoint of lifetime.
  • the low molecular weight compound means a single molecule having no distribution in the molecular weight of the compound.
  • a compound having a molecular weight of less than 5000 is classified as a low molecular compound. More preferably, it is 3000 or less, More preferably, it is 2000 or less.
  • 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 preferably classified as a polymer compound. More preferably, it is 10,000 or more, More preferably, it is 30000 or more.
  • 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). Purification according to molecular weight can also be performed by preparative gel permeation chromatography (GPC).
  • the p-type semiconductor material can be used in combination with the following p-type semiconductor material.
  • examples of p-type semiconductor materials that can be used in combination include various condensed polycyclic aromatic low-molecular compounds and conjugated polymers.
  • condensed polycyclic aromatic low-molecular compound examples include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthracene, bisanthene, zesulene, Compounds such as heptazeslen, pyranslen, violanthene, isoviolanthene, circobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenedithiatetrathiafulvalene (BEDTTTTF) -perchloric acid complex, and derivatives and precursors thereof.
  • TTF tetra
  • Examples of the derivative having the above condensed polycycle include International Publication No. 03/16599, International Publication No. 03/28125, US Pat. No. 6,690,029, Japanese Patent Application Laid-Open No. 2004-107216.
  • conjugated polymer examples include polythiophene such as poly-3-hexylthiophene (P3HT) represented by the following structural formula and oligomers thereof, or Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225.
  • Polythiophene having a polymerizable group Nature Mat. , (2006), vol. 5, p328, polythiophene-thienothiophene copolymer, polythiophene-diketopyrrolopyrrole copolymer described in WO08 / 664, Adv Mater. , 2007, p4160, a polythiophene-thiazolothiazole copolymer, Nature Mat. , Vol.
  • a polythiophene copolymer such as poly (cyclopentadithiophene-benzothiadiazole) copolymer (PCPDTBT), polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its Examples thereof include polymer materials such as oligomers, polythienylene vinylenes and oligomers thereof, ⁇ -conjugated polymers such as polyacetylene, polydiacetylene, polysilane, and polygermane.
  • PCPDTBT cyclopentadithiophene-benzothiadiazole copolymer
  • PCPDTBT cyclopentadithiophene-benzothiadiazole copolymer
  • PCPDTBT cyclopentadithiophene-benzothiadiazole copolymer
  • PCPDTBT cyclopentadithiophene-benzothiadiazole copoly
  • oligomeric materials not polymer materials, include thiophene hexamer ⁇ -seccithiophene ⁇ , ⁇ -dihexyl- ⁇ -sexualthiophene, ⁇ , ⁇ -dihexyl- ⁇ -kinkethiophene, ⁇ , ⁇ -bis (3 Oligomers such as -butoxypropyl) - ⁇ -sexithiophene can be preferably used.
  • the n-type semiconductor material used in the photoelectric conversion layer according to the present invention is not particularly limited.
  • a perfluoro compound perfluoropentacene in which hydrogen atoms of a p-type semiconductor such as fullerene and octaazaporphyrin are substituted with fluorine atoms.
  • naphthalene tetracarboxylic acid anhydride naphthalene tetracarboxylic acid diimide
  • perylene tetracarboxylic acid anhydride perylene tetracarboxylic acid diimide
  • other aromatic carboxylic acid anhydrides and imidized polymers thereof as a skeleton A compound etc. can be mentioned.
  • the n-type semiconductor material is preferably a fullerene derivative capable of efficiently performing charge separation with various p-type semiconductor materials at high speed (up to 50 femtoseconds).
  • 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), and the like.
  • fullerene having a cyclic ether group such as Amer. Chem. Soc. , (2009) vol. 130, p15429, SIMEF, Appl. Phys. Lett. , Vol. 87 (2005), C60MC12 described in p203504, and the like. It is preferable to use a fullerene derivative having a substituent and having improved solubility.
  • Examples of the method for forming a photoelectric conversion 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. Also, the coating method is excellent in production speed.
  • the application method used in this case is not limited, and examples thereof include spin coating, casting from a solution, dip coating, wire bar coating, gravure coating, and spray coating. Furthermore, patterning can also be performed by a printing method such as an ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, or a flexographic printing method.
  • a printing method such as an ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, or a flexographic printing method.
  • annealing is performed at a predetermined temperature during the manufacturing process, a part of the particles is microscopically aggregated or crystallized and the photoelectric conversion layer can have an appropriate phase separation structure. As a result, the mobility of holes and electrons (carriers) in the photoelectric conversion layer is improved, and high efficiency can be obtained.
  • the photoelectric conversion layer may be composed of a single layer in which an electron acceptor and an electron donor are uniformly mixed, or may be composed of a plurality of layers in which the mixing ratio of the electron acceptor and the electron donor is changed. Good. In this case, it can be formed by using a material that can be insolubilized after coating as described above.
  • the electron transport layer is a layer that is located between the cathode and the bulk heterojunction layer and can more efficiently transfer electrons between the bulk heterojunction layer and the electrode. More specifically, a compound having an LUMO level intermediate between the LUMO level of the n-type semiconductor material of the bulk heterojunction 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 in the electron transport layer having a HOMO level deeper than that of the p-type semiconductor material used for the bulk heterojunction layer, holes generated in the bulk heterojunction layer are allowed to flow to the cathode side.
  • a hole blocking function having a rectifying effect is provided.
  • Such an electron transport layer is also referred to as a hole blocking layer.
  • a material having a HOMO level deeper than the HOMO level of the n-type semiconductor is used for the electron transport layer.
  • the electron transport layer As the electron transport layer, octaazaporphyrin, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), carboline compounds described in International Publication No. 04/095889, and the like can be used.
  • the electron transport layer having a HOMO level deeper than the HOMO level of the p-type semiconductor material used for the photoelectric conversion layer has a rectifying effect so that holes generated in the photoelectric conversion layer do not flow to the cathode side.
  • the hole blocking function is imparted.
  • a material deeper than the HOMO level of the n-type semiconductor is used as the electron transport layer.
  • Such an electron transport layer is also called a hole blocking layer, and it is preferable to use an electron transport layer having such a function.
  • examples of such materials include phenanthrene compounds such as bathocuproine, 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.
  • unit used for the photoelectric converting layer can also be used.
  • 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 organic photoelectric conversion element of the present invention has a hole transport layer between the photoelectric conversion layer and the anode, and it is possible to take out charges generated in the photoelectric conversion layer more efficiently. It is preferable.
  • PEDOT poly-3,4-ethylenedioxythiophene
  • PSS polystyrene sulfonic acid
  • cyan compounds described in International Publication No. 06/019270, and the like can be used.
  • the hole transport layer having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the photoelectric conversion layer has a rectifying effect that prevents electrons generated in the photoelectric conversion layer from flowing to the anode side. It has an electronic block function.
  • 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.
  • triarylamine compounds described in JP-A-5-271166 metal oxides such as molybdenum oxide, nickel oxide, and tungsten oxide can be used.
  • a layer made of a single p-type semiconductor material used for the photoelectric conversion 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 a coating film in the lower layer before forming the photoelectric conversion layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.
  • it preferably has a hole mobility higher than 10 ⁇ 4 due to the property of transporting holes, and a compound with electron mobility lower than 10 ⁇ 6 due to the property of blocking electrons. It is preferable to use it.
  • 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 organic photoelectric conversion element of the present invention has at least an anode and a cathode. Moreover, when taking a tandem configuration, the tandem configuration can be achieved by using an intermediate electrode.
  • an electrode through which holes mainly flow is called an anode, and an electrode through which electrons mainly flow is called a cathode.
  • a light-transmitting electrode may be called a transparent electrode
  • a non-light-transmitting electrode may be called a counter electrode.
  • 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.
  • materials include transparent metal oxides such as indium tin oxide (ITO), AZO, FTO, SnO 2 , ZnO, and titanium oxide, very thin metal layers such as Ag, Al, Au, and Pt, metal nanowires, and carbon Nanowires such as nanotubes, layers containing nanoparticles, conductive polymer materials such as PEDOT: PSS, polyaniline, and the like can be used.
  • Conductive polymers 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. Improved and preferable.
  • the cathode may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon nanoparticles, nanowires, nanostructures, or a nanowire dispersion. If so, a transparent and highly conductive cathode can be formed by a coating method, which is preferable.
  • a metal for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.
  • 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, SnO 2 , ZnO and titanium oxide, very thin metal layers such as Ag, Al, Au and Pt, or layers containing nanowires and nanoparticles such as metal nanowires and carbon nanotubes PEDOT: PSS, conductive polymer materials such as polyaniline, etc.
  • conductive polymer materials such as polyaniline, etc.
  • 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. If the resin film transmittance of 80% or more at 0 ⁇ 800 nm), can be preferably applied to a transparent resin film according to the present invention.
  • biaxially stretched polyethylene terephthalate film preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film. More preferred are a stretched polyethylene terephthalate film and a biaxially stretched polyethylene naphthalate film.
  • 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.
  • the light scattering layer examples 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.
  • a method of sealing a cap made of aluminum or glass by bonding with an adhesive, a plastic film on which a gas barrier layer such as aluminum, silicon oxide, or aluminum oxide is formed and an organic photoelectric conversion element are pasted with an adhesive.
  • Method, spin coating of organic polymer material with high gas barrier property (polyvinyl alcohol, etc.), inorganic thin film with high gas barrier property (silicon oxide, aluminum oxide, etc.) or organic film (parylene etc.) are deposited under vacuum. Examples thereof include a method and a method of laminating these in a composite manner.
  • optical sensor array Next, an optical sensor array to which the bulk heterojunction type organic photoelectric conversion element 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 of a photoelectric conversion layer 24b 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 unit 24b, and the cathode 23 have the same configuration and role as the anode 12, the photoelectric conversion layer 14, and the cathode 13 in the bulk heterojunction organic photoelectric conversion element 10 described above.
  • the substrate 21 glass is used for the substrate 21, ITO is used for the anode 22, and aluminum is used for the cathode 23, for example.
  • the exemplified compound 11 is used for the p-type semiconductor material of the photoelectric conversion layer 24b, and for example, PCBM (Nanom Spectra E100H made by Frontier Carbon) is used for the n-type semiconductor material.
  • 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.
  • Example Compound 11 and PCBM were mixed in a chlorobenzene solvent at a ratio of 1: 4, 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 Exemplary Compound 11 and PCBM after the annealing treatment was 70 nm.
  • ITO indium tin oxide
  • the patterned transparent electrode was cleaned in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried by nitrogen blowing, and finally subjected to ultraviolet 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 dried by heating 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.
  • P3HT Plextronics OS, plex core OS2100
  • PCBM Frontier Carbon, Nanom Spectra E100H
  • a liquid was prepared, spin-coated at 700 rpm for 60 seconds and then at 2200 rpm for 1 second while being filtered with a 0.45 ⁇ m filter, and dried at room temperature for 30 minutes to obtain a photoelectric conversion layer.
  • the substrate on which the organic layer was formed was placed in a vacuum evaporation apparatus.
  • 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 0.5 nm of lithium fluoride and 80 nm of Al were evaporated.
  • 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 for all, and the size was 2 mm square.
  • the obtained organic photoelectric conversion element 1 was sealed with an aluminum cap and a UV curable resin (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1) in a nitrogen atmosphere, and then a solar simulator (AM1.5G). ) was irradiated at an irradiation intensity of 100 mW / cm 2 , voltage-current characteristics were measured, and initial conversion efficiency was measured.
  • a UV curable resin manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1
  • AM1.5G solar simulator
  • the obtained organic photoelectric conversion elements 2 to 10 were sealed with an aluminum cap and a UV curable resin in a nitrogen atmosphere and then taken out into the atmosphere, and the light from a solar simulator (AM1.5G) was 100 mW / cm 2.
  • the initial conversion efficiency was measured by measuring the voltage-current characteristics.
  • 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.
  • Formula 1 ⁇ (%) Jsc (mA / cm 2 ) ⁇ Voc (V) ⁇ FF (Durability evaluation)
  • Solar simulator (AM1.5G) light was irradiated at an irradiation intensity of 100 mW / cm 2 , voltage-current characteristics were measured, and initial conversion efficiency was measured. Further, assuming that the initial conversion efficiency at this time is 100, the conversion efficiency after continuous irradiation for 1000 hours at an irradiation intensity of 100 mW / cm 2 with a resistor connected between the anode and the cathode was evaluated, and the relative efficiency reduction was calculated. .

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Abstract

La présente invention se rapporte à un élément de conversion photoélectrique organique qui est doté d'une grande efficacité de conversion photoélectrique et d'une forte durabilité. La présente invention se rapporte également à une pile solaire et à un ensemble de capteurs optiques qui utilisent chacun l'élément de conversion photoélectrique organique. L'élément de conversion photoélectrique organique comprend une électrode transparente, une contre-électrode et une couche de conversion photoélectrique dans laquelle un matériau semi-conducteur de type p et un matériau semi-conducteur de type n sont mélangés. L'élément de conversion photoélectrique organique selon l'invention est caractérisé en ce que la couche de conversion photoélectrique contient un composé qui a une structure représentée par la formule générale (1). (Dans la formule, Z1 et Z2 représentent chacun un groupe atomique formant un anneau à cinq éléments ou à six éléments, et Z1 et/ou Z2 représentent un groupe atomique qui a un atome d'azote autre que l'atome d'azote dans la position de tête de pont.)
PCT/JP2010/057864 2009-05-25 2010-05-10 Elément de conversion photoélectrique organique, et pile solaire et ensemble de capteurs optiques l'utilisant chacun Ceased WO2010137449A1 (fr)

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US8809675B2 (en) 2011-12-16 2014-08-19 Tsinghua University Solar cell system
US9012767B2 (en) 2011-12-16 2015-04-21 Tsinghua University Solar cell system
CN102646794A (zh) * 2012-04-23 2012-08-22 华北电力大学 一种p-i-n型聚合物太阳能电池及其制备方法

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