WO2011155131A1 - Dye-adsorbed semiconductor electrode for dye-sensitized solar cell, dye-sensitized solar cell, and process for production of dye-adsorbed semiconductor electrode - Google Patents

Dye-adsorbed semiconductor electrode for dye-sensitized solar cell, dye-sensitized solar cell, and process for production of dye-adsorbed semiconductor electrode Download PDF

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WO2011155131A1
WO2011155131A1 PCT/JP2011/002753 JP2011002753W WO2011155131A1 WO 2011155131 A1 WO2011155131 A1 WO 2011155131A1 JP 2011002753 W JP2011002753 W JP 2011002753W WO 2011155131 A1 WO2011155131 A1 WO 2011155131A1
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dye
solar cell
sensitized solar
metal
semiconductor electrode
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PCT/JP2011/002753
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French (fr)
Japanese (ja)
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早瀬　修二
シャム スデル パンディ
祐二 成冨
晋介 藤田
明理 宮本
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国立大学法人九州工業大学
相互薬工株式会社
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Priority to JP2012519222A priority Critical patent/JP5816620B2/en
Publication of WO2011155131A1 publication Critical patent/WO2011155131A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H01M14/005—Photoelectrochemical storage cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • H01G9/2063—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution comprising a mixture of two or more dyes
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • 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
    • Y02E10/542—Dye sensitized solar 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
    • 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 a dye-adsorbing semiconductor electrode for a dye-sensitized solar cell, a dye-sensitized solar cell, and a method for producing a dye-adsorbing semiconductor electrode.
  • the dye-sensitized solar cell is called a wet solar cell or a Gretzel battery, and is characterized in that it has an electrochemical cell structure typified by an iodine solution without using a silicon semiconductor.
  • porous semiconductors such as titania layers formed by baking titanium dioxide powder or the like on a transparent conductive glass plate (transparent substrate with laminated transparent conductive film: anode substrate) and adsorbing a dye to this powder. It has a simple structure in which an iodine solution or the like is disposed as an electrolytic solution between a counter electrode made of a conductive oxide semiconductor electrode) and a conductive glass plate (conductive substrate: cathode substrate).
  • Electrons are generated by the absorption of sunlight into the dye-sensitized solar cell from the transparent conductive glass plate side.
  • Dye-sensitized solar cells are attracting attention as low-cost next-generation solar cells because they are inexpensive and do not require large-scale equipment for production.
  • a ruthenium complex commonly called N3 has been awarded.
  • the pyridine ligand of the ruthenium complex has a carboxylic acid group (—COOH), and this carboxylic acid group forms an ester bond with the hydroxyl group (—OH group) on the surface of the titania semiconductor particle, and the ruthenium complex is formed on the surface of the titania semiconductor particle.
  • Fixed Due to the strong bond between the ruthenium complex (dye) and the titania semiconductor (porous semiconductor), electrons are efficiently transferred from the ruthenium complex to the titania semiconductor.
  • Other so-called anchor groups such as carboxylic acid groups include phosphoric acid groups and sulfonic acid groups.
  • Non-Patent Document 1 phthalocyanine complexes using zinc or aluminum as a metal to be coordinated have been reported as dyes that are sensitive to the near-infrared region of light and adsorb to titania semiconductors.
  • Non-Patent Document 2 As dyes adsorbed on titania semiconductor, aluminum phthalocyanine and myristic acid (Myristic Acid) has been reported (see Non-Patent Document 2). In the report, it is said that a product in which a predetermined amount of myristic acid is co-adsorbed exhibits better characteristics than when only aluminum phthalocyanine is used.
  • a porphine complex using a silicon derivative as a coordination bond metal has been reported as a dye adsorbed on a metal oxide semiconductor or the like, and pyrrole of the porphine complex includes a carboxylic acid group, a phosphate group, a sulfone group.
  • a basic group is bonded instead of an acidic group such as an acid group (see Patent Document 1).
  • the problem to be solved is that there is a demand for further improvement of a dye that can efficiently use light in a wide wavelength region including a long wavelength.
  • the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present invention is adsorbed with a dye containing one or two or more selected from porphyrin, phthalocyanine, naphthalocyanine, and metal complexes of derivatives of these compounds.
  • the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present invention is preferably characterized in that both the metal of the metal complex and the metal of the metal oxide porous semiconductor are tin.
  • the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present invention is preferably characterized in that a dye different from the dye is co-adsorbed on the metal oxide porous semiconductor.
  • the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present invention is preferably characterized in that the another dye is bonded to a metal atom of the metal complex through an oxygen atom.
  • the dye-sensitized solar cell according to the present invention is characterized by including the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell.
  • a method for producing a dye-adsorbing semiconductor electrode of a dye-sensitized solar cell according to the present invention is a method for producing a dye-adsorbing semiconductor electrode of the dye-sensitized solar cell, wherein the metal oxide porous semiconductor includes porphyrin, It is impregnated with a dye containing one or more selected from metal complexes of phthalocyanine and naphthalocyanine and derivatives of these compounds.
  • the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present invention adsorbs a dye containing one or more selected from porphyrin, phthalocyanine, naphthalocyanine, and metal complexes of derivatives of these compounds, and the dye Since it has a metal oxide porous semiconductor and the metal atoms of the metal complex are bonded to the metal atoms of the metal oxide porous semiconductor through oxygen atoms and are chemically adsorbed, light in a wide wavelength region including long wavelengths Can be used efficiently. Moreover, since the dye-sensitized solar cell according to the present invention includes the above-described dye-adsorbing semiconductor electrode, the effect of the dye-adsorbing semiconductor electrode can be suitably obtained.
  • dye adsorption semiconductor electrode of the dye-sensitized solar cell which concerns on this invention impregnates the pigment
  • dye adsorption semiconductor which concerns on this invention by a simple manufacturing method An electrode can be suitably obtained.
  • FIG. 1 is a graph showing the relationship between the light wavelength of the metal complex of Example 1 and photoelectric conversion efficiency.
  • FIG. 2 is a graph showing the relationship between the light wavelength of the metal complex of Example 2 and photoelectric conversion efficiency.
  • FIG. 3 is a graph showing the relationship between the light wavelength of the metal complex of Example 3 and photoelectric conversion efficiency.
  • FIG. 4 is a graph showing the relationship between the light wavelength of the complex of the comparative example and the photoelectric conversion efficiency.
  • FIG. 5 is a view for explaining the suction mechanism of the seventh embodiment.
  • FIG. 6 is a graph showing the relationship between the light wavelength of the metal complex of Example 7 and photoelectric conversion efficiency.
  • FIG. 7 is a graph showing the relationship between the light wavelength of the metal complex of Example 4 and photoelectric conversion efficiency.
  • FIG. 8 is a graph showing the relationship between the light wavelength of the metal complex of Example 5 and photoelectric conversion efficiency.
  • FIG. 9 is a graph showing the relationship between the light wavelength of the metal complex of Example 6 and photoelectric conversion efficiency.
  • the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present embodiment has a dye containing one or more selected from porphyrin, phthalocyanine, naphthalocyanine, and metal complexes of derivatives of these compounds, and the dye adsorbed Having a metal oxide porous semiconductor.
  • the dye is adsorbed on the surface of the metal oxide nanoparticle of the metal oxide porous semiconductor.
  • metal complexes of porphyrin derivatives include the following. Examples of metal complexes of phthalocyanine derivatives are given in Examples 1 to 3, and examples of metal complexes of naphthalocyanine derivatives are given in Examples 4 to 6, respectively.
  • the metal at the center of the metal complex of the dye and the metal of the metal oxide porous semiconductor may be the same element or different elements.
  • the metal atom of the metal complex is bonded to the metal atom of the metal oxide porous semiconductor through an oxygen atom. That is, it becomes an M1 (metal atom of metal oxide porous semiconductor) -O-M2 (metal atom of metal complex) bond.
  • the oxygen atom is considered to be derived from the OH group present on the surface of the metal oxide porous semiconductor. However, in the case where the OH group is bonded to the metal atom of the metal complex, it may be derived from the OH group.
  • the metal at the center of the metal complex includes one in which a halogen group or a hydroxyl group is bonded to the metal.
  • the metal at the center of the metal complex can realize the above bonding form by, for example, changing the valence, etc., but the bonding form such as a halogen group can more suitably obtain the above bonding form.
  • the metal complex may contain an anchor such as a carboxylic acid group, a phosphoric acid group, or a sulfonic acid group. However, for example, introducing a carboxylic acid group into the complex requires a complicated synthesis process, and in that sense, those that do not contain these anchors are preferable.
  • the metal complex may contain an alkyl group, an aromatic group, a halogenated amide, a nitrile, a nitro group, or the like, and the conjugate length may be extended by an unsaturated bond.
  • the dye-adsorbing semiconductor electrode may contain other components as a dye and a metal oxide porous semiconductor material as long as the function thereof is not impaired.
  • the metal to which the complex is coordinated and the metal of the metal oxide porous semiconductor are, for example, tin (Sn), silicon (Si), lead (Pb), germanium (groups 13 and 14 of the periodic table), respectively. Ge), titanium (Ti), aluminum (Al), gallium (Ga), indium (In), and the like can be given.
  • the metal to which the complex coordinates is tin or silicon
  • tin or titanium can be preferably used as the metal of the metal oxide porous semiconductor, respectively.
  • the metal coordinated by the complex and the metal of the metal oxide porous semiconductor are the same element, the metal species is not particularly limited as long as it is useful as a metal oxide porous semiconductor, but tin Is preferred.
  • the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present embodiment configured as described above can be obtained by a manufacturing method in which the metal oxide porous semiconductor is impregnated with the dye. When impregnating, an appropriate solvent is used, and after impregnation, drying is performed by an appropriate method.
  • the method for producing the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to this embodiment is simple in that it is not essential to introduce carboxylic acid or the like into the dye.
  • a dye different from the above dye is co-adsorbed on the metal oxide porous semiconductor.
  • a conventional dye can be adsorbed as a second layer on a novel dye layer adsorbed on the metal oxide porous semiconductor, and a synergistic effect can be obtained.
  • the other dye is bonded to the metal atom of the metal complex through an oxygen atom, that is, M1 (metal atom of the porous semiconductor) -O-M2 (metal atom of the metal complex)- A bonded form of O- (another dye) is more preferable.
  • the electrons of LUMO in which electron injection occurs are collected at the center of the phthalocyanine, and the dye binds to the porous semiconductor metal at the center of the complex
  • electrons are effectively injected from the dye into the metal oxide porous semiconductor.
  • the dye-sensitized solar cell according to the present embodiment includes the dye-adsorbing semiconductor electrode according to the present embodiment, and includes an anode electrode, a cathode electrode, and an electrolytic solution together with the dye-adsorbing semiconductor electrode.
  • the dye-sensitized solar cell according to the present embodiment can suitably obtain the effects of the dye-adsorbing semiconductor electrode according to the present embodiment.
  • Example 1 ⁇ Production of photoelectric conversion element (dye-sensitized solar cell)> (Example 1) 1 ml of pure water and 1 ml of acetic acid were added to 6 g of tin oxide powder (NanoTek (registered trademark) manufactured by CI Kasei Co., Ltd.), and ultrasonic irradiation was performed for 24 hours. Then, 100 ml of ethanol was added and ultrasonic irradiation was further performed for 3 hours. Further, 1.5 g of ethyl cellulose and 10 ml of ⁇ -terpineol were added and sufficiently stirred, and then concentrated with a rotary evaporator to prepare a tin oxide paste.
  • tin oxide powder Nethyl cellulose and 10 ml of ⁇ -terpineol were added and sufficiently stirred, and then concentrated with a rotary evaporator to prepare a tin oxide paste.
  • a squeegee coating of tin oxide paste is applied on a transparent conductive glass substrate with tin oxide film doped with fluorine, dried at room temperature, and then baked at 450 ° C. for 30 minutes to provide a conductive support (transparent conductive glass substrate with tin oxide film).
  • a porous tin oxide film having a thickness of 5 ⁇ m was formed thereon.
  • a solution in which 0.1 mM of a metal complex of the following formula is dissolved in 30 ml of N-methyl-2-pyrrolidone is prepared, and the semiconductor layer with the above tin oxide film is immersed together with the support, and it is kept at 80 ° C. in the atmosphere for 6 hours. Held.
  • the tin oxide film was washed with ethanol and dried at room temperature three times to produce a photoelectric conversion layer (dye-adsorbing semiconductor electrode).
  • a transparent conductive glass plate carrying platinum on a transparent conductive glass substrate with a tin oxide film was used, and Hi-Milan 25 ⁇ m made by Mitsui DuPont was thermocompression bonded between the two, and 4-tert.
  • a charge transfer layer containing a redox electrolyte in which -butylpyridine 580 mM, iodine 50 mM, and lithium iodide 500 mM were dissolved was prepared to prepare a photoelectric conversion element (dye-sensitized solar cell).
  • Example 2 A photoelectric conversion element (dye-sensitized solar cell) was produced in the same manner as in Example 1 except that the metal complex of the following formula was used.
  • Example 3 A photoelectric conversion element (dye-sensitized solar cell) was produced in the same manner as in Example 1 except that the metal complex of the following formula was used.
  • Example 4 A photoelectric conversion element (dye-sensitized solar cell) was produced in the same manner as in Example 1 except that the metal complex of the following formula was used.
  • Example 5 A photoelectric conversion element (dye-sensitized solar cell) was produced in the same manner as in Example 1 except that the metal complex of the following formula was used.
  • Example 6 A photoelectric conversion element (dye-sensitized solar cell) was produced in the same manner as in Example 1 except that the metal complex of the following formula was used.
  • a photoelectric conversion element (dye-sensitized solar cell) was produced in the same manner as in Example 1 except that the metal complex of the following formula was used.
  • Examples 1 to 6 are excellent in the characteristics of the photoelectric conversion element, and have an absorption wavelength region having a spectral sensitivity of 800 nm or more.
  • Example 7 ⁇ Production and Evaluation of Photoelectric Conversion Element (Dye-sensitized Solar Cell)> (Example 7) 1 ml of pure water and 1 ml of acetic acid were added to 6 g of tin oxide powder (NanoTek (registered trademark) manufactured by CI Kasei Co., Ltd.), and ultrasonic irradiation was performed for 24 hours. Then, 100 ml of ethanol was added and ultrasonic irradiation was further performed for 3 hours. Further, 1.5 g of ethyl cellulose and 10 ml of ⁇ -terpineol were added and sufficiently stirred, and then concentrated with a rotary evaporator to prepare a tin oxide paste.
  • tin oxide powder Nethyl cellulose and 10 ml of ⁇ -terpineol
  • a tin oxide paste is squeegee-coated on a transparent conductive glass substrate with a tin oxide film doped with fluorine, dried at room temperature, then baked at 450 ° C. for 30 minutes, and porous tin oxide having a thickness of 5 ⁇ m on the conductive support.
  • a film was formed.
  • a solution in which 0.1 mM of the metal complex used in Example 1 was dissolved in 30 ml of N-methyl-2-pyrrolidone was prepared, and the semiconductor layer with the tin oxide film was immersed together with the support. Hold under air. This operation was repeated three times. After the reaction, the tin oxide film was washed with ethanol and dried at room temperature three times to produce a photoelectric conversion layer.
  • the substrate photoelectric conversion layer
  • Ru dye N719 Solaronics
  • a counter electrode on a transparent conductive glass substrate with a tin oxide film doped with fluorine, a transparent conductive glass plate carrying platinum, and between the conductive support and the counter electrode, HiMilan 25 ⁇ m made by Mitsui DuPont And a charge transfer layer in which a redox electrolyte in which 4-tert-butylpyridine (580 mM), iodine (50 mM) and lithium iodide (500 mM) were dissolved in an acetonitrile solvent was prepared to produce a photoelectric conversion element.
  • 4-tert-butylpyridine 580 mM
  • iodine 50 mM
  • lithium iodide 500 mM
  • the short-circuit current of the obtained photoelectric conversion element was 12 mA / cm2, which was higher than 8 mA / cm2 when only N719 was adsorbed and 4 mA / cm2 when only the metal complex used in Example 1 was adsorbed. .
  • the immersion time at the time of producing a photoelectric converting layer was changed and the adsorption amount of the metal complex used in Example 1 and the adsorption amount of N719 were compared, the metal complex used in Example 1 was adsorbed over time. Although the amount increased, there was little decrease in the amount of N719 adsorbed.
  • N719 is bonded to the central metal of the metal complex used in Example 1 through an oxygen atom.
  • Ru represents ruthenium
  • TBA represents Tetrabutyl ammonium.
  • FIG. 6 shows the relationship between the light wavelength (horizontal axis: unit nm) of the metal complex (dye) and the photoelectric conversion efficiency (vertical unit: unit%).
  • a dotted line (SPC6) indicates the metal complex used in Example 1
  • N719) indicates N719
  • a solid line (SPC6 (N719)) indicates Example 7.

Abstract

Disclosed are: a dye-adsorbed semiconductor electrode which can efficiently utilize light having a wide wavelength range including a long wavelength such as an infrared region wavelength; a dye-sensitized solar cell equipped with the dye-adsorbed semiconductor electrode; and a process for producing the dye-adsorbed semiconductor electrode. Specifically disclosed is a dye-adsorbed semiconductor electrode for a dye-sensitized solar cell, comprising: a dye which contains at least one component selected from metal complexes of porphyrin, phthalocyanine, naphthalocyanine and a derivative of any one of the aforementioned compounds; and a metal oxide porous semidoncuctor material onto which the dye can be adsorbed. The dye can be adsorbed chemically onto the metal oxide porous semidoncuctor material through the binding of a metal atom in the metal complex to a metal atom in the metal oxide porous semidoncuctor material through an oxygen atom. The metal in the complex and the metal in the metal oxide may be the same as or different from each other.

Description

色素増感太陽電池の色素吸着半導体電極および色素増感太陽電池ならびに色素吸着半導体電極の製造方法Dye-adsorbed semiconductor electrode for dye-sensitized solar cell, dye-sensitized solar cell, and method for producing dye-adsorbed semiconductor electrode
　本発明は、色素増感太陽電池の色素吸着半導体電極および色素増感太陽電池ならびに色素吸着半導体電極の製造方法に関する。 The present invention relates to a dye-adsorbing semiconductor electrode for a dye-sensitized solar cell, a dye-sensitized solar cell, and a method for producing a dye-adsorbing semiconductor electrode.
　色素増感太陽電池は、湿式太陽電池あるいはグレッツェル電池等と呼ばれ、シリコン半導体を用いることなくヨウ素溶液に代表される電気化学的なセル構造を持つ点に特徴がある。具体的には、透明な導電性ガラス板（透明導電膜を積層した透明基板：アノード基板）に二酸化チタン粉末等を焼付け、これに色素を吸着させて形成したチタニア層等の多孔質半導体（多孔質酸化物半導体電極）と導電性ガラス板（導電性基板：カソード基板）からなる対極の間に電解液としてヨウ素溶液等を配置した、簡易な構造を有する。透明な導電性ガラス板の側から色素増感太陽電池セル内に導入される太陽光が色素に吸収されることで電子が発生する。
　色素増感太陽電池は、材料が安価であり、作製に大掛かりな設備を必要としないことから、低コストの次世代太陽電池として注目されている。 The dye-sensitized solar cell is called a wet solar cell or a Gretzel battery, and is characterized in that it has an electrochemical cell structure typified by an iodine solution without using a silicon semiconductor. Specifically, porous semiconductors (such as titania layers) formed by baking titanium dioxide powder or the like on a transparent conductive glass plate (transparent substrate with laminated transparent conductive film: anode substrate) and adsorbing a dye to this powder. It has a simple structure in which an iodine solution or the like is disposed as an electrolytic solution between a counter electrode made of a conductive oxide semiconductor electrode) and a conductive glass plate (conductive substrate: cathode substrate). Electrons are generated by the absorption of sunlight into the dye-sensitized solar cell from the transparent conductive glass plate side.
Dye-sensitized solar cells are attracting attention as low-cost next-generation solar cells because they are inexpensive and do not require large-scale equipment for production.
　色素増感太陽電池の光電変換効率は１０％を超え、さらに１５％を目指した研究が行われている。
　光電変換効率を向上させるための課題のひとつに、タンデム型やハイブリッド型の高効率太陽電池の開発がある。
　これらの高効率太陽電池の開発においては、電極構造等の電池の各構成要素の改良が求められるとともに、使用する色素の改良が大きな課題である。
　すなわち、通常利用される可視光等だけでなく赤外域等の長波長を含む広い波長領域の光を効率的に利用することができる色素が求められる。 Researches aiming at the photoelectric conversion efficiency of dye-sensitized solar cells exceeding 10% and further 15% are being conducted.
One of the challenges for improving photoelectric conversion efficiency is the development of tandem and hybrid type high efficiency solar cells.
In the development of these high-efficiency solar cells, improvement of each component of the battery such as an electrode structure is required, and improvement of the dye used is a major issue.
That is, there is a demand for a dye that can efficiently use light in a wide wavelength region including long wavelengths such as the infrared region as well as the commonly used visible light.
　一般的な色素増感太陽電池の色素として、例えば通称Ｎ３と呼ばれるルテニウム錯体が賞用されている。ルテニウム錯体のピリジン系配位子はカルボン酸基（－ＣＯＯＨ）を持ち、このカルボン酸基がチタニア半導体粒子表面の水酸基（－ＯＨ基）とエステル結合を形成し、ルテニウム錯体はチタニア半導体粒子表面に固定される。このルテニウム錯体（色素）とチタニア半導体（多孔質半導体）の強固な結合により、ルテニウム錯体からチタニア半導体への電子の移動が効率的に行われる。
　カルボン酸基のようないわゆるアンカー基には、このほかにリン酸基、スルホン酸基等がある。 As a dye for a general dye-sensitized solar cell, for example, a ruthenium complex commonly called N3 has been awarded. The pyridine ligand of the ruthenium complex has a carboxylic acid group (—COOH), and this carboxylic acid group forms an ester bond with the hydroxyl group (—OH group) on the surface of the titania semiconductor particle, and the ruthenium complex is formed on the surface of the titania semiconductor particle. Fixed. Due to the strong bond between the ruthenium complex (dye) and the titania semiconductor (porous semiconductor), electrons are efficiently transferred from the ruthenium complex to the titania semiconductor.
Other so-called anchor groups such as carboxylic acid groups include phosphoric acid groups and sulfonic acid groups.
　これに対して、光の近赤外域に感度を有する、チタニア半導体に吸着する色素として、配位結合する金属として亜鉛やアルミニウムを用いたフタロシアニン錯体が報告されており、上記の各アンカー基が例示されている（非特許文献１参照）。 On the other hand, phthalocyanine complexes using zinc or aluminum as a metal to be coordinated have been reported as dyes that are sensitive to the near-infrared region of light and adsorb to titania semiconductors. (See Non-Patent Document 1).
　また、例えば、チタニア半導体に吸着する色素として、アルミニウムフタロシアニンとミリスチン酸（Myristic
Acid）を共吸着したものが報告されている（非特許文献２参照）。その報告の中で、アルミニウムフタロシアニンのみを用いた場合に比べてミリスチン酸を所定量共吸着したものは良好な特性を示すとされている。 In addition, for example, as dyes adsorbed on titania semiconductor, aluminum phthalocyanine and myristic acid (Myristic
Acid) has been reported (see Non-Patent Document 2). In the report, it is said that a product in which a predetermined amount of myristic acid is co-adsorbed exhibits better characteristics than when only aluminum phthalocyanine is used.
　また、例えば、金属酸化物半導体等に吸着する色素として、配位結合する金属としてケイ素の誘導体を用いたポルフィン錯体が報告されており、ポルフィン錯体のピロールにはカルボン酸基、リン酸基、スルホン酸基等の酸性基ではなくて塩基性基が結合されている（特許文献１参照）。 In addition, for example, a porphine complex using a silicon derivative as a coordination bond metal has been reported as a dye adsorbed on a metal oxide semiconductor or the like, and pyrrole of the porphine complex includes a carboxylic acid group, a phosphate group, a sulfone group. A basic group is bonded instead of an acidic group such as an acid group (see Patent Document 1).
特開２００９－１９３７６３号公報JP 2009-193663 A
　解決しようとする問題点は、長波長を含む広い波長領域の光を効率的に利用することができる色素のさらなる改良が求められている点である。 The problem to be solved is that there is a demand for further improvement of a dye that can efficiently use light in a wide wavelength region including a long wavelength.
　本発明に係る色素増感太陽電池の色素吸着半導体電極は、ポルフィリン、フタロシアニンおよびナフタロシアニンならびにこれらの化合物の誘導体の金属錯体のなかから選ばれる１または２以上を含む色素と、該色素が吸着される金属酸化物多孔質半導体を有し、酸素原子を介して該金属錯体の金属原子が該金属酸化物多孔質半導体の金属原子に結合して化学吸着されてなることを特徴とする。 The dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present invention is adsorbed with a dye containing one or two or more selected from porphyrin, phthalocyanine, naphthalocyanine, and metal complexes of derivatives of these compounds. A metal oxide porous semiconductor, wherein the metal atom of the metal complex is bonded to and chemisorbed to the metal atom of the metal oxide porous semiconductor through an oxygen atom.
　また、本発明に係る色素増感太陽電池の色素吸着半導体電極は、好ましくは、前記金属錯体の金属と前記金属酸化物多孔質半導体の金属がいずれもスズであることを特徴とする。 The dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present invention is preferably characterized in that both the metal of the metal complex and the metal of the metal oxide porous semiconductor are tin.
　また、本発明に係る色素増感太陽電池の色素吸着半導体電極は、好ましくは、前記色素とは別の色素が前記金属酸化物多孔質半導体に共吸着されてなることを特徴とする。 The dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present invention is preferably characterized in that a dye different from the dye is co-adsorbed on the metal oxide porous semiconductor.
　また、本発明に係る色素増感太陽電池の色素吸着半導体電極は、好ましくは、前記別の色素が酸素原子を介して前記金属錯体の金属原子に結合してなることを特徴とする。 The dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present invention is preferably characterized in that the another dye is bonded to a metal atom of the metal complex through an oxygen atom.
　また、本発明に係る色素増感太陽電池は、上記の色素増感太陽電池の色素吸着半導体電極を備えてなることを特徴とする。 The dye-sensitized solar cell according to the present invention is characterized by including the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell.
　また、本発明に係る色素増感太陽電池の色素吸着半導体電極の製造方法は、上記の色素増感太陽電池の色素吸着半導体電極の製造方法であって、金属酸化物多孔質半導体に、ポルフィリン、フタロシアニンおよびナフタロシアニンならびにこれらの化合物の誘導体の金属錯体のなかから選ばれる１または２以上を含む色素を含浸することを特徴とする。 A method for producing a dye-adsorbing semiconductor electrode of a dye-sensitized solar cell according to the present invention is a method for producing a dye-adsorbing semiconductor electrode of the dye-sensitized solar cell, wherein the metal oxide porous semiconductor includes porphyrin, It is impregnated with a dye containing one or more selected from metal complexes of phthalocyanine and naphthalocyanine and derivatives of these compounds.
　本発明に係る色素増感太陽電池の色素吸着半導体電極は、ポルフィリン、フタロシアニンおよびナフタロシアニンならびにこれらの化合物の誘導体の金属錯体のなかから選ばれる１または２以上を含む色素と、色素が吸着される金属酸化物多孔質半導体を有し、酸素原子を介して金属錯体の金属原子が金属酸化物多孔質半導体の金属原子に結合して化学吸着されてなるため、長波長を含む広い波長領域の光を効率的に利用することができる。
　また、本発明に係る色素増感太陽電池は上記の色素吸着半導体電極を備えてなるため、色素吸着半導体電極の効果を好適に得ることができる。
　また、本発明に係る色素増感太陽電池の色素吸着半導体電極の製造方法は、金属酸化物多孔質半導体に本発明に係る色素を含浸するため、簡易な製造方法で本発明に係る色素吸着半導体電極を好適に得ることができる。 The dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present invention adsorbs a dye containing one or more selected from porphyrin, phthalocyanine, naphthalocyanine, and metal complexes of derivatives of these compounds, and the dye Since it has a metal oxide porous semiconductor and the metal atoms of the metal complex are bonded to the metal atoms of the metal oxide porous semiconductor through oxygen atoms and are chemically adsorbed, light in a wide wavelength region including long wavelengths Can be used efficiently.
Moreover, since the dye-sensitized solar cell according to the present invention includes the above-described dye-adsorbing semiconductor electrode, the effect of the dye-adsorbing semiconductor electrode can be suitably obtained.
Moreover, since the manufacturing method of the pigment | dye adsorption semiconductor electrode of the dye-sensitized solar cell which concerns on this invention impregnates the pigment | dye which concerns on this invention in a metal oxide porous semiconductor, the pigment | dye adsorption semiconductor which concerns on this invention by a simple manufacturing method An electrode can be suitably obtained.
図１は実施例１の金属錯体の光波長と光電変換効率の関係を示す図である。FIG. 1 is a graph showing the relationship between the light wavelength of the metal complex of Example 1 and photoelectric conversion efficiency. 図２は実施例２の金属錯体の光波長と光電変換効率の関係を示す図である。FIG. 2 is a graph showing the relationship between the light wavelength of the metal complex of Example 2 and photoelectric conversion efficiency. 図３は実施例３の金属錯体の光波長と光電変換効率の関係を示す図である。FIG. 3 is a graph showing the relationship between the light wavelength of the metal complex of Example 3 and photoelectric conversion efficiency. 図４は比較例の錯体の光波長と光電変換効率の関係を示す図である。FIG. 4 is a graph showing the relationship between the light wavelength of the complex of the comparative example and the photoelectric conversion efficiency. 図５は実施例７の吸着機構を説明するための図である。FIG. 5 is a view for explaining the suction mechanism of the seventh embodiment. 図６は実施例７の金属錯体の光波長と光電変換効率の関係を示す図である。FIG. 6 is a graph showing the relationship between the light wavelength of the metal complex of Example 7 and photoelectric conversion efficiency. 図７は実施例４の金属錯体の光波長と光電変換効率の関係を示す図である。FIG. 7 is a graph showing the relationship between the light wavelength of the metal complex of Example 4 and photoelectric conversion efficiency. 図８は実施例５の金属錯体の光波長と光電変換効率の関係を示す図である。FIG. 8 is a graph showing the relationship between the light wavelength of the metal complex of Example 5 and photoelectric conversion efficiency. 図９は実施例６の金属錯体の光波長と光電変換効率の関係を示す図である。FIG. 9 is a graph showing the relationship between the light wavelength of the metal complex of Example 6 and photoelectric conversion efficiency.
　本発明の実施の形態について、以下に説明する。
　本実施の形態に係る色素増感太陽電池の色素吸着半導体電極は、ポルフィリン、フタロシアニンおよびナフタロシアニンならびにこれらの化合物の誘導体の金属錯体のなかから選ばれる１または２以上を含む色素と、色素が吸着される金属酸化物多孔質半導体を有する。色素は金属酸化物多孔質半導体の金属酸化物ナノ粒子表面に吸着される。
　ポルフィリンの誘導体の金属錯体の例は、以下のものを挙げることができる。また、フタロシアニンの誘導体の金属錯体の例は実施例１～３に、ナフタロシアニンの誘導体の金属錯体の例は実施例４～６に、それぞれ挙げる。 Embodiments of the present invention will be described below.
The dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present embodiment has a dye containing one or more selected from porphyrin, phthalocyanine, naphthalocyanine, and metal complexes of derivatives of these compounds, and the dye adsorbed Having a metal oxide porous semiconductor. The dye is adsorbed on the surface of the metal oxide nanoparticle of the metal oxide porous semiconductor.
Examples of metal complexes of porphyrin derivatives include the following. Examples of metal complexes of phthalocyanine derivatives are given in Examples 1 to 3, and examples of metal complexes of naphthalocyanine derivatives are given in Examples 4 to 6, respectively.
Figure JPOXMLDOC01-appb-C000001
  
Figure JPOXMLDOC01-appb-C000001
  
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　色素の金属錯体の中心の金属と金属酸化物多孔質半導体の金属は、同一元素であってもよく、また、異なる元素であってもよい。
　色素は、酸素原子を介して金属錯体の金属原子が金属酸化物多孔質半導体の金属原子に結合する。すなわち、Ｍ１（金属酸化物多孔質半導体の金属原子）－Ｏ－Ｍ２（金属錯体の金属原子）結合となる。酸素原子は金属酸化物多孔質半導体の表面に存在するＯＨ基に由来するものと考えられるが、金属錯体の金属原子にＯＨ基が結合したものの場合、このＯＨ基に由来することも考えられる。 The metal at the center of the metal complex of the dye and the metal of the metal oxide porous semiconductor may be the same element or different elements.
In the dye, the metal atom of the metal complex is bonded to the metal atom of the metal oxide porous semiconductor through an oxygen atom. That is, it becomes an M1 (metal atom of metal oxide porous semiconductor) -O-M2 (metal atom of metal complex) bond. The oxygen atom is considered to be derived from the OH group present on the surface of the metal oxide porous semiconductor. However, in the case where the OH group is bonded to the metal atom of the metal complex, it may be derived from the OH group.
　金属錯体の中心の金属は、金属にハロゲン基または水酸基が結合したものを含む。金属錯体の中心の金属は、例えば価数を変えること等により上記の結合形態を実現することができるが、ハロゲン基等の結合物であると、より好適に上記の結合形態を得ることができる。
　金属錯体は、カルボン酸基、リン酸基、スルホン酸基等のアンカーを含んでいてもよい。ただし、錯体に例えばカルボン酸基を導入することは合成工程が煩雑であるので、その意味ではこれらのアンカーを含まないものが好適である。
　また、金属錯体は、アルキル基、芳香族基、ハロゲン化アミド、ニトリル、ニトロ基等を含んでよいし、また、不飽和結合で共役長が伸びていてもよい。 The metal at the center of the metal complex includes one in which a halogen group or a hydroxyl group is bonded to the metal. The metal at the center of the metal complex can realize the above bonding form by, for example, changing the valence, etc., but the bonding form such as a halogen group can more suitably obtain the above bonding form. .
The metal complex may contain an anchor such as a carboxylic acid group, a phosphoric acid group, or a sulfonic acid group. However, for example, introducing a carboxylic acid group into the complex requires a complicated synthesis process, and in that sense, those that do not contain these anchors are preferable.
In addition, the metal complex may contain an alkyl group, an aromatic group, a halogenated amide, a nitrile, a nitro group, or the like, and the conjugate length may be extended by an unsaturated bond.
　色素吸着半導体電極は、その機能を害さない限度で、色素および金属酸化物多孔質半導体材料として他の成分を含んでもよい。 The dye-adsorbing semiconductor electrode may contain other components as a dye and a metal oxide porous semiconductor material as long as the function thereof is not impaired.
　錯体が配位結合する金属および金属酸化物多孔質半導体の金属は、それぞれ、例えば、周期表の第１３族および第１４の、スズ（Ｓｎ）、ケイ素（Ｓｉ）、鉛（Ｐｂ）、ゲルマニウム（Ｇｅ）、チタン（Ｔｉ）、アルミニウム（Ａｌ）、ガリウム（Ｇａ）、インジウム（Ｉｎ）等を挙げることができる。
　例えば、錯体が配位結合する金属がスズやケイ素の場合、それぞれ金属酸化物多孔質半導体の金属としてスズやチタンを好適に用いることができる。
　また、錯体が配位結合する金属および金属酸化物多孔質半導体の金属が同一元素の場合、金属種は、金属酸化物多孔質半導体として有用なものである限り特に限定するものではないが、スズが好適である。
　上記のように構成される本実施の形態に係る色素増感太陽電池の色素吸着半導体電極は、上記の金属酸化物多孔質半導体に上記の色素を含浸する製造方法により得ることができる。含浸の際は適宜の溶媒を用い、また、含浸した後、適宜の方法で乾燥する。
　この本実施の形態に係る色素増感太陽電池の色素吸着半導体電極の製造方法は、色素にカルボン酸等を導入することが必須でない点で製法が簡易である。 The metal to which the complex is coordinated and the metal of the metal oxide porous semiconductor are, for example, tin (Sn), silicon (Si), lead (Pb), germanium (groups 13 and 14 of the periodic table), respectively. Ge), titanium (Ti), aluminum (Al), gallium (Ga), indium (In), and the like can be given.
For example, when the metal to which the complex coordinates is tin or silicon, tin or titanium can be preferably used as the metal of the metal oxide porous semiconductor, respectively.
Further, when the metal coordinated by the complex and the metal of the metal oxide porous semiconductor are the same element, the metal species is not particularly limited as long as it is useful as a metal oxide porous semiconductor, but tin Is preferred.
The dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present embodiment configured as described above can be obtained by a manufacturing method in which the metal oxide porous semiconductor is impregnated with the dye. When impregnating, an appropriate solvent is used, and after impregnation, drying is performed by an appropriate method.
The method for producing the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to this embodiment is simple in that it is not essential to introduce carboxylic acid or the like into the dye.
　また、本実施の形態に係る色素増感太陽電池の色素吸着半導体電極は、好ましくは、上記の色素とは別の色素が金属酸化物多孔質半導体に共吸着される。金属酸化物多孔質半導体上に吸着される新規な色素の層の上に２層目として例えば従来の色素を吸着することができ、これにより相乗効果を得ることができる。
　このとき、上記別の色素が酸素原子を介して前記金属錯体の金属原子に結合するものであると、すなわち、Ｍ１（多孔質半導体の金属原子）－Ｏ－Ｍ２（金属錯体の金属原子）－Ｏ－（別の色素）の結合形態であると、より好ましい。 In addition, in the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present embodiment, preferably, a dye different from the above dye is co-adsorbed on the metal oxide porous semiconductor. For example, a conventional dye can be adsorbed as a second layer on a novel dye layer adsorbed on the metal oxide porous semiconductor, and a synergistic effect can be obtained.
At this time, if the other dye is bonded to the metal atom of the metal complex through an oxygen atom, that is, M1 (metal atom of the porous semiconductor) -O-M2 (metal atom of the metal complex)- A bonded form of O- (another dye) is more preferable.
　本実施の形態に係る色素増感太陽電池の色素吸着半導体電極は、電子注入が起こるLUMOの電子は、フタロシアニン中心部に集まっており、色素が錯体の中心部で多孔質半導体の金属と結合することにより、色素から金属酸化物多孔質半導体に有効に電子が注入される。これにより、赤外域等の長波長を含む広い波長領域の光を効率的に利用することができ、例えば、タンデム型やハイブリッド型の高効率太陽電池に好適に用いることができる。 In the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to the present embodiment, the electrons of LUMO in which electron injection occurs are collected at the center of the phthalocyanine, and the dye binds to the porous semiconductor metal at the center of the complex Thus, electrons are effectively injected from the dye into the metal oxide porous semiconductor. Thereby, light in a wide wavelength region including a long wavelength such as an infrared region can be efficiently used, and for example, it can be suitably used for a tandem type or hybrid type high efficiency solar cell.
　つぎに、本実施の形態に係る色素増感太陽電池は、本実施の形態に係る色素吸着半導体電極を備えるものであり、色素吸着半導体電極とともに、アノード電極、カソード電極および電解液を有する。
　本実施の形態に係る色素増感太陽電池は、本実施の形態に係る色素吸着半導体電極の作用効果を好適に得ることができる。 Next, the dye-sensitized solar cell according to the present embodiment includes the dye-adsorbing semiconductor electrode according to the present embodiment, and includes an anode electrode, a cathode electrode, and an electrolytic solution together with the dye-adsorbing semiconductor electrode.
The dye-sensitized solar cell according to the present embodiment can suitably obtain the effects of the dye-adsorbing semiconductor electrode according to the present embodiment.
　実施例を挙げて本発明を説明する。なお本発明は、以下に説明する実施例に限定されるものではない。 The present invention will be described with reference to examples. The present invention is not limited to the examples described below.
＜光電変換素子（色素増感太陽電池）の作製＞
 (実施例１)
　酸化スズ粉末（シーアイ化成社製NanoTek（登録商標））６gに純水1mlおよび酢酸1mlを加え、超音波照射を２４時間行った後、エタノール１００mlを加えさらに３時間超音波照射を行った。さらにエチルセルロース１．５g、α-テルピネオール１０ml添加し十分に撹拌を行った後、ロータリエバポレーターで濃縮し酸化スズペーストを調整した。フッ素をドープした酸化スズ膜付き透明導電性ガラス基板上に酸化スズペーストをスキージ塗布し室温乾燥後、４５０℃で３０分焼成を行い、導電性支持体（酸化スズ膜付き透明導電性ガラス基板）上に膜厚５μmの多孔質の酸化スズ膜を形成した。
　N-メチル-2-ピロリドン３０ml中に、下記式の金属錯体を０．１mM溶解した溶液を調製し、上記酸化スズ膜付き半導体層を支持体ごと浸漬し、６時間、８０℃、大気下にて保持した。反応後、酸化スズ膜をエタノールで洗浄し室温乾燥を3回繰り返し、光電変換層（色素吸着半導体電極）を作製した。
　対向電極として、酸化スズ膜付き透明導電性ガラス基板上に、白金を担持した透明導電性ガラス板を用い、両者の間に三井デュポン社製ハイミラン25μmを熱圧着し、アセトニトリル溶媒に、４-tert-ブチルピリジン５８０mM、沃素５０mM,沃化リチウム５００mMを溶解したレドックス電解質を入れた電荷移動層を作製して、光電変換素子（色素増感太陽電池）を作製した。 <Production of photoelectric conversion element (dye-sensitized solar cell)>
(Example 1)
1 ml of pure water and 1 ml of acetic acid were added to 6 g of tin oxide powder (NanoTek (registered trademark) manufactured by CI Kasei Co., Ltd.), and ultrasonic irradiation was performed for 24 hours. Then, 100 ml of ethanol was added and ultrasonic irradiation was further performed for 3 hours. Further, 1.5 g of ethyl cellulose and 10 ml of α-terpineol were added and sufficiently stirred, and then concentrated with a rotary evaporator to prepare a tin oxide paste. A squeegee coating of tin oxide paste is applied on a transparent conductive glass substrate with tin oxide film doped with fluorine, dried at room temperature, and then baked at 450 ° C. for 30 minutes to provide a conductive support (transparent conductive glass substrate with tin oxide film). A porous tin oxide film having a thickness of 5 μm was formed thereon.
A solution in which 0.1 mM of a metal complex of the following formula is dissolved in 30 ml of N-methyl-2-pyrrolidone is prepared, and the semiconductor layer with the above tin oxide film is immersed together with the support, and it is kept at 80 ° C. in the atmosphere for 6 hours. Held. After the reaction, the tin oxide film was washed with ethanol and dried at room temperature three times to produce a photoelectric conversion layer (dye-adsorbing semiconductor electrode).
As the counter electrode, a transparent conductive glass plate carrying platinum on a transparent conductive glass substrate with a tin oxide film was used, and Hi-Milan 25 μm made by Mitsui DuPont was thermocompression bonded between the two, and 4-tert. A charge transfer layer containing a redox electrolyte in which -butylpyridine 580 mM, iodine 50 mM, and lithium iodide 500 mM were dissolved was prepared to prepare a photoelectric conversion element (dye-sensitized solar cell).
Figure JPOXMLDOC01-appb-C000005
  
Figure JPOXMLDOC01-appb-C000005
  
 (実施例２)
　下記式の金属錯体を用いたほかは実施例１と同様の方法で光電変換素子（色素増感太陽電池）を作製した。 (Example 2)
A photoelectric conversion element (dye-sensitized solar cell) was produced in the same manner as in Example 1 except that the metal complex of the following formula was used.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
 (実施例３)
　下記式の金属錯体を用いたほかは実施例１と同様の方法で光電変換素子（色素増感太陽電池）を作製した。 Example 3
A photoelectric conversion element (dye-sensitized solar cell) was produced in the same manner as in Example 1 except that the metal complex of the following formula was used.
Figure JPOXMLDOC01-appb-C000007
  
Figure JPOXMLDOC01-appb-C000007
  
 (実施例４)
　下記式の金属錯体を用いたほかは実施例１と同様の方法で光電変換素子（色素増感太陽電池）を作製した。 Example 4
A photoelectric conversion element (dye-sensitized solar cell) was produced in the same manner as in Example 1 except that the metal complex of the following formula was used.
Figure JPOXMLDOC01-appb-C000008
  
Figure JPOXMLDOC01-appb-C000008
  
 (実施例５)
　下記式の金属錯体を用いたほかは実施例１と同様の方法で光電変換素子（色素増感太陽電池）を作製した。 (Example 5)
A photoelectric conversion element (dye-sensitized solar cell) was produced in the same manner as in Example 1 except that the metal complex of the following formula was used.
Figure JPOXMLDOC01-appb-C000009
  
Figure JPOXMLDOC01-appb-C000009
  
 (実施例６)
　下記式の金属錯体を用いたほかは実施例１と同様の方法で光電変換素子（色素増感太陽電池）を作製した。 Example 6
A photoelectric conversion element (dye-sensitized solar cell) was produced in the same manner as in Example 1 except that the metal complex of the following formula was used.
Figure JPOXMLDOC01-appb-C000010
  
Figure JPOXMLDOC01-appb-C000010
  
 (比較例)
　下記式の金属錯体を用いたほかは実施例１と同様の方法で光電変換素子（色素増感太陽電池）を作製した。 (Comparative example)
A photoelectric conversion element (dye-sensitized solar cell) was produced in the same manner as in Example 1 except that the metal complex of the following formula was used.
Figure JPOXMLDOC01-appb-C000011
  
Figure JPOXMLDOC01-appb-C000011
  
<光電変換素子（色素増感太陽電池）の評価>
　上記で得られた実施例１～６および比較例の光電変換素子を、AM１．５,１００mW/cm2のソーラーシミュレータを用いて、太陽電池特性を測定して得られた短絡電流密度Jsc(mA/cm2)および開放電圧値Voc(V)を表１に示す。これらの値は、同様の方法で作製した４サンプルの光電変換素子についての測定結果の平均値である。なお、標準偏差はいずれも０．１以下であった。
　なお、実施例１～３および比較例の光電変換素子で用いた金属錯体（色素）の光波長（横軸：単位　ｎｍ）と光電変換効率（縦軸：単位　％）の関係をこの順でそれぞれ図１～図４に示す。また、実施例４～６の光電変換素子で用いた金属錯体（色素）の光波長（横軸：単位　ｎｍ）と光電変換効率（縦軸：単位　％）の関係をこの順でそれぞれ図７～図９に示す。 <Evaluation of photoelectric conversion element (dye-sensitized solar cell)>
The photoelectric conversion elements of Examples 1 to 6 and Comparative Example obtained above were measured for the short-circuit current density Jsc (mA / mA) obtained by measuring the solar cell characteristics using a solar simulator of AM1.5, 100 mW / cm2. cm2) and the open circuit voltage value Voc (V) are shown in Table 1. These values are average values of the measurement results for the four samples of photoelectric conversion elements manufactured by the same method. The standard deviations were all 0.1 or less.
The relationship between the light wavelength (horizontal axis: unit nm) and the photoelectric conversion efficiency (vertical unit:%) of the metal complexes (pigments) used in the photoelectric conversion elements of Examples 1 to 3 and Comparative Example, respectively, in this order. It is shown in FIGS. The relationship between the light wavelength (horizontal axis: unit nm) and the photoelectric conversion efficiency (vertical unit:%) of the metal complex (dye) used in the photoelectric conversion elements of Examples 4 to 6 is shown in FIG. As shown in FIG.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
　表１より、実施例１～６は光電変換素子の特性が優れており、吸収波長領域も８００nm以上に分光感度を有していることがわかる。 From Table 1, it can be seen that Examples 1 to 6 are excellent in the characteristics of the photoelectric conversion element, and have an absorption wavelength region having a spectral sensitivity of 800 nm or more.
＜光電変換素子（色素増感太陽電池）の作製および評価＞
（実施例７）
　酸化スズ粉末（シーアイ化成社製NanoTek（登録商標））６gに純水1mlおよび酢酸1mlを加え、超音波照射を２４時間行った後、エタノール１００mlを加えさらに３時間超音波照射を行った。さらにエチルセルロース１．５g、α-テルピネオール１０ml添加し十分に撹拌を行った後、ロータリエバポレーターで濃縮し酸化スズペーストを調整した。フッ素をドープした酸化スズ膜付き透明導電性ガラス基板上に酸化スズペーストをスキージ塗布し室温乾燥後、４５０℃で３０分焼成を行い、導電性支持体上に膜厚５μmの多孔質の酸化スズ膜を形成した。
　N-メチル-2-ピロリドン３０ml中に、実施例１で用いた金属錯体を０．１mM溶解した溶液を調製し、上記酸化スズ膜付き半導体層を支持体ごと浸漬し、６時間、８０℃、大気下にて保持した。この操作を３度くり返した。反応後、酸化スズ膜をエタノールで洗浄し室温乾燥を3回繰り返し、光電変換層を作製した。さらに、本基板（光電変換層）を0.1mMのRu色素(N719　ソラロニクス社製)に浸漬した。
　対向電極として、フッ素をドープした酸化スズ膜付き透明導電性ガラス基板上に、白金を担持した透明導電性ガラス板を用い、前記導電性支持体と対向電極との間に三井デュポン社製ハイミラン25μmを熱圧着し、アセトニトリル溶媒に、４-tert-ブチルピリジン５８０mM、沃素５０mM,沃化リチウム５００mMを溶解したレドックス電解質を入れた電荷移動層を作製して、光電変換素子を作製した。
　得られた光電変換素子の短絡電流は12 mA/cm2で、N719のみを吸着させた場合の8mA/cm2、実施例１で用いた金属錯体のみを吸着させた場合の4mA/cm2よりも高かった。
　なお、光電変換層を作製する際の浸漬時間を変化させ、実施例１で用いた金属錯体の吸着量とN719の吸着量を比較したところ、実施例１で用いた金属錯体は時間経過とともに吸着量が増加したが、これに伴うN719の吸着量の減少は少なかった。これは、実施例１で用いた金属錯体が金属酸化物の吸着サイトを満たしたとしても、吸着サイトが新しく生まれることでＮ７１9の吸着量が減らないことを意味するものと考えられる。このときの吸着機構は、図５に示すものが考えられる。実施例１で用いた金属錯体の中心金属に酸素原子を介してＮ７１9が結合する。なお、図５中、Ｒｕはルテニウムを、ＮＣＳはＮ＝Ｃ＝Ｓを、ＴＢＡはTetrabutyl ammoniumを、それぞれ示す。
　金属錯体（色素）の光波長（横軸：単位　ｎｍ）と光電変換効率（縦軸：単位　％）の関係を図６に示す。図６中、点線（ＳＰＣ６）は実施例１で用いた金属錯体、破線（Ｎ７１９）はＮ７１９および実線（ＳＰＣ６（Ｎ７１９））は実施例７を、それぞれ示す。 <Production and Evaluation of Photoelectric Conversion Element (Dye-sensitized Solar Cell)>
(Example 7)
1 ml of pure water and 1 ml of acetic acid were added to 6 g of tin oxide powder (NanoTek (registered trademark) manufactured by CI Kasei Co., Ltd.), and ultrasonic irradiation was performed for 24 hours. Then, 100 ml of ethanol was added and ultrasonic irradiation was further performed for 3 hours. Further, 1.5 g of ethyl cellulose and 10 ml of α-terpineol were added and sufficiently stirred, and then concentrated with a rotary evaporator to prepare a tin oxide paste. A tin oxide paste is squeegee-coated on a transparent conductive glass substrate with a tin oxide film doped with fluorine, dried at room temperature, then baked at 450 ° C. for 30 minutes, and porous tin oxide having a thickness of 5 μm on the conductive support. A film was formed.
A solution in which 0.1 mM of the metal complex used in Example 1 was dissolved in 30 ml of N-methyl-2-pyrrolidone was prepared, and the semiconductor layer with the tin oxide film was immersed together with the support. Hold under air. This operation was repeated three times. After the reaction, the tin oxide film was washed with ethanol and dried at room temperature three times to produce a photoelectric conversion layer. Further, the substrate (photoelectric conversion layer) was immersed in 0.1 mM Ru dye (N719 Solaronics).
As a counter electrode, on a transparent conductive glass substrate with a tin oxide film doped with fluorine, a transparent conductive glass plate carrying platinum, and between the conductive support and the counter electrode, HiMilan 25 μm made by Mitsui DuPont And a charge transfer layer in which a redox electrolyte in which 4-tert-butylpyridine (580 mM), iodine (50 mM) and lithium iodide (500 mM) were dissolved in an acetonitrile solvent was prepared to produce a photoelectric conversion element.
The short-circuit current of the obtained photoelectric conversion element was 12 mA / cm2, which was higher than 8 mA / cm2 when only N719 was adsorbed and 4 mA / cm2 when only the metal complex used in Example 1 was adsorbed. .
In addition, when the immersion time at the time of producing a photoelectric converting layer was changed and the adsorption amount of the metal complex used in Example 1 and the adsorption amount of N719 were compared, the metal complex used in Example 1 was adsorbed over time. Although the amount increased, there was little decrease in the amount of N719 adsorbed. This is considered to mean that even if the metal complex used in Example 1 satisfies the adsorption site of the metal oxide, the adsorption amount of N719 is not reduced by newly creating the adsorption site. As the adsorption mechanism at this time, the one shown in FIG. 5 can be considered. N719 is bonded to the central metal of the metal complex used in Example 1 through an oxygen atom. In FIG. 5, Ru represents ruthenium, NCS represents N = C = S, and TBA represents Tetrabutyl ammonium.
FIG. 6 shows the relationship between the light wavelength (horizontal axis: unit nm) of the metal complex (dye) and the photoelectric conversion efficiency (vertical unit: unit%). In FIG. 6, a dotted line (SPC6) indicates the metal complex used in Example 1, a broken line (N719) indicates N719, and a solid line (SPC6 (N719)) indicates Example 7.

Claims (14)

  1. 　ポルフィリン、フタロシアニンおよびナフタロシアニンならびにこれらの化合物の誘導体の金属錯体のなかから選ばれる１または２以上を含む色素と、該色素が吸着される金属酸化物多孔質半導体を有し、酸素原子を介して該金属錯体の金属原子が該金属酸化物多孔質半導体の金属原子に結合して化学吸着されてなることを特徴とする色素増感太陽電池の色素吸着半導体電極。 Having a dye containing one or more selected from metal complexes of porphyrin, phthalocyanine and naphthalocyanine, and derivatives of these compounds, and a metal oxide porous semiconductor to which the dye is adsorbed, and through an oxygen atom A dye-adsorbing semiconductor electrode of a dye-sensitized solar cell, wherein the metal atom of the metal complex is bonded to and chemically adsorbed to the metal atom of the metal oxide porous semiconductor.
  2. 　前記色素とは別の色素が前記金属酸化物多孔質半導体に共吸着されてなることを特徴とする請求項１に記載の色素増感太陽電池の色素吸着半導体電極。 The dye-adsorbing semiconductor electrode of a dye-sensitized solar cell according to claim 1, wherein a dye different from the dye is co-adsorbed on the metal oxide porous semiconductor.
  3. 　前記別の色素が酸素原子を介して前記金属錯体の金属原子に結合してなることを特徴とする請求項２記載の色素増感太陽電池の色素吸着半導体電極。 The dye-adsorbing semiconductor electrode of a dye-sensitized solar cell according to claim 2, wherein the another dye is bonded to a metal atom of the metal complex through an oxygen atom.
  4. 　前記金属錯体の金属と前記金属酸化物多孔質半導体の金属がいずれもスズであることを特徴とする請求項１記載の色素増感太陽電池の色素吸着半導体電極。 The dye-adsorbing semiconductor electrode of a dye-sensitized solar cell according to claim 1, wherein the metal of the metal complex and the metal of the metal oxide porous semiconductor are both tin.
  5. 　前記色素とは別の色素が前記金属酸化物多孔質半導体に共吸着されてなることを特徴とする請求項４に記載の色素増感太陽電池の色素吸着半導体電極。 The dye-adsorbing semiconductor electrode of a dye-sensitized solar cell according to claim 4, wherein a dye different from the dye is co-adsorbed on the metal oxide porous semiconductor.
  6. 　前記別の色素が酸素原子を介して前記金属錯体の金属原子に結合してなることを特徴とする請求項５記載の色素増感太陽電池の色素吸着半導体電極。 The dye-adsorbing semiconductor electrode of a dye-sensitized solar cell according to claim 5, wherein the another dye is bonded to a metal atom of the metal complex through an oxygen atom.
  7. 　請求項１に記載の色素増感太陽電池の色素吸着半導体電極を備えてなることを特徴とする色素増感太陽電池。 A dye-sensitized solar cell comprising the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to claim 1.
  8. 　請求項２に記載の色素増感太陽電池の色素吸着半導体電極を備えてなることを特徴とする色素増感太陽電池。 A dye-sensitized solar cell comprising the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to claim 2.
  9. 　請求項３に記載の色素増感太陽電池の色素吸着半導体電極を備えてなることを特徴とする色素増感太陽電池。 A dye-sensitized solar cell comprising the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to claim 3.
  10. 　請求項４に記載の色素増感太陽電池の色素吸着半導体電極を備えてなることを特徴とする色素増感太陽電池。 A dye-sensitized solar cell comprising the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to claim 4.
  11. 　請求項５に記載の色素増感太陽電池の色素吸着半導体電極を備えてなることを特徴とする色素増感太陽電池。 A dye-sensitized solar cell comprising the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to claim 5.
  12. 　請求項６に記載の色素増感太陽電池の色素吸着半導体電極を備えてなることを特徴とする色素増感太陽電池。 A dye-sensitized solar cell comprising the dye-adsorbing semiconductor electrode of the dye-sensitized solar cell according to claim 6.
  13. 　請求項１記載の色素増感太陽電池の色素吸着半導体電極の製造方法であって、金属酸化物多孔質半導体に、ポルフィリン、フタロシアニンおよびナフタロシアニンならびにこれらの化合物の誘導体の金属錯体のなかから選ばれる１または２以上を含む色素を含浸することを特徴とする色素増感太陽電池の色素吸着半導体電極の製造方法。 The method for producing a dye-adsorbing semiconductor electrode of a dye-sensitized solar cell according to claim 1, wherein the metal oxide porous semiconductor is selected from metal complexes of porphyrin, phthalocyanine, naphthalocyanine, and derivatives of these compounds. A method for producing a dye-adsorbing semiconductor electrode of a dye-sensitized solar cell, comprising impregnating a dye containing one or more dyes.
  14. 　請求項４記載の色素増感太陽電池の色素吸着半導体電極の製造方法であって、金属酸化物多孔質半導体に、ポルフィリン、フタロシアニンおよびナフタロシアニンならびにこれらの化合物の誘導体の金属錯体のなかから選ばれる１または２以上を含む色素を含浸することを特徴とする色素増感太陽電池の色素吸着半導体電極の製造方法。 5. The method for producing a dye-adsorbing semiconductor electrode of a dye-sensitized solar cell according to claim 4, wherein the metal oxide porous semiconductor is selected from metal complexes of porphyrin, phthalocyanine and naphthalocyanine and derivatives of these compounds. A method for producing a dye-adsorbing semiconductor electrode of a dye-sensitized solar cell, comprising impregnating a dye containing one or more dyes.
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