WO2012029659A1 - Nouveau composé fluorène, colorant pour cellule solaire à pigment photosensible utilisant le composé, électrode contenant ledit colorant et cellule solaire à pigment photosensible - Google Patents

Nouveau composé fluorène, colorant pour cellule solaire à pigment photosensible utilisant le composé, électrode contenant ledit colorant et cellule solaire à pigment photosensible Download PDF

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WO2012029659A1
WO2012029659A1 PCT/JP2011/069317 JP2011069317W WO2012029659A1 WO 2012029659 A1 WO2012029659 A1 WO 2012029659A1 JP 2011069317 W JP2011069317 W JP 2011069317W WO 2012029659 A1 WO2012029659 A1 WO 2012029659A1
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dye
group
solar cell
sensitized solar
electrode
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Japanese (ja)
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岡本　秀二
英樹 羽田
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綜研化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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

Definitions

  • the present invention relates to a novel fluorene compound, a dye-sensitized solar cell dye using the compound, a dye-sensitized solar cell dye-containing electrode adsorbing the fluorene compound, and a dye-sensitized dye having such an electrode. It relates to solar cells.
  • a Ru metal complex dye As the sensitizing dye used in the dye-sensitized solar cell, a Ru metal complex dye is generally used. Such a Ru metal complex dye does not have a very high extinction coefficient and does not have a large light absorption ability as a single molecule. However, in a dye-sensitized solar cell, a nanoporous metal oxide can be used as an electrode. By increasing the film thickness, the amount of dye per unit area can be increased, and high photoelectric conversion efficiency can be realized by using such a function. However, since Ru, which is a rare metal, is used, there is anxiety in terms of stable supply in the future, and the amount of dye used increases in order to maintain high photoelectric conversion efficiency. Based on these backgrounds, organic dyes for dye-sensitized solar cells that do not use rare metals such as Ru complexes have attracted attention.
  • organic sensitizing dyes have a higher molar extinction coefficient than Ru-based dyes, but conversely, even if the thickness of the anode electrode is increased, the photoelectric conversion efficiency is not greatly improved.
  • the skeleton used for organic dyes requires a high conjugated structure in order to achieve both the light absorption ability and the charge transfer ability, but the development of these conjugated structures makes the solubility in solvents worse and the anode. It becomes difficult to dye the electrodes.
  • organic dyes for dye-sensitized solar cells often use a heterocycle containing nitrogen element and / or an amine group as a donor skeleton in order to efficiently transfer charges from iodine anions used as an electrolyte.
  • dye-sensitized solar cells usually use an electrolyte having redox ability such as I ⁇ / I 3 ⁇ (electrolyte capable of redox reaction) by combining iodine and an iodine anion such as lithium iodide. Is done.
  • the solution of I ⁇ / I 3 ⁇ is widely used because of its excellent stability, but such an I ⁇ / I 3 ⁇ solution is related to cell durability. corrosion of the wiring material by iodine, degradation has become a problem, I - / I 3 - is a dye capable of performing redox redox alternative to the solution is required, good ones have been reported little.
  • MK-2 was developed using N-ethylcarbazole as the donor part for the combination of oligo n-hexylthiophene (conjugated bond system) and cyanoacetic acid group (acceptor, anchor). Yes (see Non-Patent Document 1). MK-2 is an excellent dye that has a higher open-circuit voltage and higher conversion efficiency than conventional organic dyes, and has been confirmed to exhibit very high conversion efficiency as an organic dye. The structure of MK-2 is shown below as (MK-2).
  • An object of the present invention is to provide a novel fluorene compound using a fluorene compound containing a nitrogen-containing heterocycle and no amine group as a donor, and has a solubility in a general-purpose solvent such as toluene as a dye dyeing solvent.
  • An object of the present invention is to provide a sensitizing dye for a dye-sensitized solar cell which is good but has a high performance.
  • Another object of the present invention is to provide a dye-containing electrode for a dye-sensitized solar cell having high performance by using the fluorene compound. It is another object of the present invention to provide a dye-containing electrode for a dye-sensitized solar cell that can generate power using a non-iodine redox solution by adjusting the HOMO-LUMO level.
  • an object of the present invention is to provide a dye-sensitized solar cell having an electrode using the fluorene compound.
  • novel fluorene compound of the present invention can be represented by the following formula (I).
  • R 1 and R 2 each independently represents at least one atom or group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and an alkoxy group, and X represents the following formula (1 ), At least one group selected from the group consisting of (2) and (3), and n is an integer from 1 to 12.
  • R 3 and R 4 are each independently at least one atom or group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and an alkoxy group. Represents.
  • the dye for dye-sensitized solar cells of the present invention uses the fluorene compound represented by the above formula (I) as the sensitizing dye of the dye-sensitized solar cell.
  • the fluorene compound-coated metal oxide particles obtained by adsorbing the fluorene compound represented by the above formula (I) on the surface of the metal oxide particles are metal electrodes. It has the structure arrange
  • the dye-sensitized solar cell of the present invention has a transparent electrode having a fluorene compound-coated metal oxide particle disposed on the surface as described above as one electrode and a catalyst electrode as the other electrode. And the catalyst electrode.
  • the fluorene compound of the present invention is a novel compound.
  • This fluorene compound can be effectively used as a dye used in a dye-sensitized solar cell.
  • applying a fluorene compound containing a nitrogen element heterocycle and no amine group as a donor skeleton, and using a conjugated low-molecular oligothiophene having a side chain, etc. imparts solubility to general-purpose solvents such as toluene, dye As a dye to be used in dye-sensitized solar cells by controlling inter-stacking, suppressing charge leakage from photoelectrodes, etc., and adjusting the light absorption wavelength region and charge transferability by adjusting the conjugate length It can be used effectively.
  • the electrode in which the dye comprising the fluorene compound of the present invention is adsorbed on titanium oxide can be effectively used as an electrode for a dye-sensitized solar cell.
  • the dye-sensitized solar cell having this electrode has higher open-circuit voltage and short-circuit current density and higher conversion efficiency than the solar cell using MK-2.
  • the fluorene compound of the present invention has a lower extinction coefficient than that of MK-2, and by utilizing this characteristic, the photoelectrode for dye-sensitized solar cell having high conversion efficiency by increasing the effective area of the photoelectrode Can be provided.
  • an electrode containing a dye comprising the fluorene compound of the present invention it is possible to generate power with a non-iodine-based electrolyte, and in particular, a liquid electrolyte that has been an essential constituent requirement for dye-sensitized solar cells Instead of this, it is possible to generate electric power using a solid electrolyte such as a conductive polymer instead. Accordingly, it is possible to provide a new dye-sensitized solar cell that suppresses corrosion of cell wiring materials due to iodine redox and provides a long-life cell or does not cause leakage of electrolyte from the dye-sensitized solar cell. it can.
  • FIG. 1 is a drawing schematically showing an example of a cross section of a dye-sensitized solar cell ⁇ liquid photoelectric conversion element>.
  • FIG. 2 is a drawing schematically showing an example of a cross section of a dye-sensitized solar cell ⁇ fully solid-state photoelectric conversion element>.
  • FIG. 3 is a 1 H-NMR spectrum of the compound represented by formula (H).
  • FIG. 4 is an LC-MS spectrum of the compound represented by the formula (H).
  • FIG. 5 is a 1 H-NMR spectrum of the compound represented by formula (K).
  • FIG. 6 is an LC-MS spectrum of the compound represented by formula (K).
  • a fluorene compound of the present invention a dye for a dye-sensitized solar cell comprising the fluorene compound, a dye-containing electrode for a dye-sensitized solar cell and a dye-sensitized solar cell using the dye will be specifically described. .
  • the fluorene compound of the present invention can be represented by the following formula (I).
  • R 1 and R 2 are each independently at least one atom or group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an alkoxy group.
  • both R 1 and R 2 are hydrogen atoms or alkyl groups, aryl groups and alkoxy groups having the same carbon number, and R 1 and R 2 are those having 1 to 12 carbon atoms.
  • An alkyl group, an aryl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms is preferable.
  • a compound in which R 1 and R 2 are both hydrogen atoms or alkyl groups is suitable as a fluorene compound that forms an electrode for a dye-sensitized solar cell.
  • a fluorene compound using a substituent is used as a dye compound used as an electrode of a dye-sensitized solar cell
  • an electrolyte that performs a redox reaction of the solar cell is, for example, I ⁇ / I 3 ⁇ .
  • a liquid electrolyte but also a solid electrolyte such as a conductive polymer can be suitably used.
  • n is an integer of 1 to 12, particularly preferably an integer of 2 to 10.
  • X is any group of the following formulas (1), (2), and (3).
  • R 3 and R 4 are each independently at least one atom or group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and an alkoxy group. Represents.
  • R 3 and R 4 is a hydrogen atom
  • the other group is an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
  • the groups Preferably any of the groups.
  • R 3 and R 4 are linear groups. It is preferable.
  • X in the formula (I) is preferably the above formula (1) having a thiophene ring, and in this case, one of R 3 and R 4 bonded to the thiophene ring is It is preferably a hydrogen atom and the other is an alkyl group having 2 to 12 carbon atoms, an aryl group or an alkoxy group, and usually has 2 to 12 thiophene rings having such a substituent, preferably 3 It is particularly desirable that ⁇ 7 are bonded (that is, n in formula (I) is usually 2 to 12, preferably 3 to 7).
  • the dye for a dye-sensitized solar cell of the present invention a compound represented by the following formula can be used.
  • R 1 to R 4 and n are the same as described above.
  • a compound having n of 3 is shown as follows.
  • (II-1) having a thiophene ring is preferred as a dye for a dye-sensitized solar cell.
  • R 1 and R 2 may be hydrogen atoms, but are preferably linear alkyl groups.
  • R 1 and R 2 are alkyl groups having the same carbon number. Is particularly preferred.
  • R 3 and R 4 are at least one atom or group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an alkoxy group, and either one of R 3 and R 4 Is a hydrogen atom, and the other is preferably an alkyl group, an aryl group and an alkoxy group.
  • Such a compound can be synthesized using 2-bromofluorene or a derivative thereof as a starting material.
  • the method for synthesizing the compound of the present invention will be described by taking 2-bromofluorene as an example where R 3 is a hydrogen atom and R 4 is a hexyl group.
  • 2-bromofluorene is converted to 3-hexylthiophene-5-boronic acid ester. React.
  • the mixture is refluxed in dimethoxyethane in the presence of bis (triphenylphosphine) palladium (II) dichloride and an aqueous sodium carbonate solution as a catalyst.
  • the reflux time at this time is usually 3 to 12 hours.
  • one fluorene ring having a hexyl group can be introduced into 2-bromofluorene. Then, using a brominating agent such as N-bromosuccinimide, it can be substituted with the bromine atom of the hydrogen atom to which the thiophene ring of the 3-hexylthiophene group is bonded.
  • a coupling reaction Sudzuki coupling reaction
  • thiophene rings can be bonded one after another.
  • a desired alkyl group, aryl group, and alkoxy group can be introduce
  • a hydrogen atom in the 9-position of the fluorene derivative is first used, by using the fluorene derivative substituted on R 1 and R 2, to give a compound wherein R 1 and R 2 is an alkyl group, an aryl group or an alkoxy group be able to.
  • N, N-dimethylformamide (DMF) is added dropwise to cooled phospholine chloride to prepare a Vilsmeier reagent.
  • An aldehyde group is introduced into the terminal thiophene ring by adding to the fluorene derivative bound with the thiophene ring prepared as described above.
  • the fluorene derivative aldehyde having an aldehyde group introduced into the terminal thiophene ring thus obtained is reacted with cyanoacetic acid in the presence of piperidine, and the reaction product is extracted with chloroform, and the extracted organic phase is extracted with hydrochloric acid or the like.
  • a cyano group and a carboxyl group that are both acceptors and anchors can be introduced into the terminal thiophene ring.
  • Such a compound can be suitably used as a dye for a dye-sensitized solar cell. That is, an electrode in which the fluorene compound of the present invention is dissolved in an organic solvent and adsorbed on a metal oxide layer (for example, a TiO 2 film (or layer)) disposed on the surface of the transparent electrode is used as one electrode. By disposing the other electrode through a layer that performs a redox reaction, the dye-sensitized solar cell of the present invention can be obtained.
  • a metal oxide layer for example, a TiO 2 film (or layer)
  • Such a dye-sensitized solar cell usually has a cross-sectional structure as shown in FIG.
  • a solid electrolyte such as a conductive polymer
  • the metal oxide layer for example, a TiO 2 film (or layer)
  • Such a dye-sensitized solar cell usually has a cross-sectional structure as shown in FIG.
  • photosensitization can be achieved by adsorbing the above-described dye compound in a particle layer of a metal oxide such as titanium oxide laminated on the surface of a transparent electrode disposed on the anode. it can.
  • the thickness (film thickness) of the metal oxide particles such as titanium oxide is usually 1 to 50 ⁇ m, preferably 10 to 30 ⁇ m.
  • One electrode of the dye-sensitized solar cell is an electrode in which the dye is adsorbed on the surface of the transparent electrode as described above, but the other electrode is formed by sputtering or depositing a conductive metal such as Pt on the surface of the substrate.
  • a catalyst electrode made of a laminated body having a thickness of 2 to 100 nm is used.
  • an electrolyte is filled between the electrodes as described above.
  • the electrolyte solution is formed from lithium iodide / iodine / t-butylpyridine / iodide 1,2-dimethyl-3-propyl imidazolium used conventionally I - / I 3 - as redox solution
  • an iodine-based electrolytic solution can be used, in the present invention, by introducing an alkyl group or the like into the fluorene ring, a conductive polymer can be used instead of the liquid electrolytic solution.
  • solid electrolyte examples include conductive polymers (polyaniline, polyethylenedioxythiophene, poly (3-hexylthiophene), polypyrrole, etc.) and international patent applications (PCT / JP2010 / 061514) filed earlier by the present applicant.
  • Composition for solid electrolyte according to the present invention solid electrolyte comprising a polymer compound obtained by polymerizing a monomer containing a monomer having a chelating ability, and a charge transfer material which is a carbon material and / or a ⁇ -conjugated polymer) Composition
  • solid electrolyte comprising a polymer compound obtained by polymerizing a monomer containing a monomer having a chelating ability, and a charge transfer material which is a carbon material and / or a ⁇ -conjugated polymer
  • the width of the gap between the electrodes filled with the above redox solution or conductive polymer usually needs to be determined by the balance with the titania film thickness. It is preferable to adjust within a range of 50 ⁇ m, preferably 10 to 30 ⁇ m.
  • the dye-sensitized solar cell using the conductive polymer as described above has a power generation efficiency equal to or higher than that of a dye-sensitized solar cell using a conventionally used dye.
  • the dye-sensitized solar cell of the present invention will be described from the step of producing a fluorene compound with specific examples. These examples show one embodiment of the present invention, and the present invention is not limited to these examples.
  • MK-2 was prepared according to the description in Example 2 of WO2007 / 119525.
  • Example 1 2.50 g of 2-bromofluorene represented by the following formula (A) (manufactured by Sigma-Aldrich) and 4.29 g of 3-hexylthiophene-5-boronic acid ester represented by the following formula (B) were mixed, The mixture was refluxed with heating in dimethoxyethane for 8 hours in the presence of 0.36 g of bis (triphenylphosphine) palladium (II) dichloride and 13.00 g of 25% aqueous sodium carbonate solution.
  • A 2-bromofluorene represented by the following formula (A) (manufactured by Sigma-Aldrich)
  • 3-hexylthiophene-5-boronic acid ester represented by the following formula (B) were mixed, The mixture was refluxed with heating in dimethoxyethane for 8 hours in the presence of 0.36 g of bis (triphenylphosphine) palladium (II) dichloride and 13.00 g of 25%
  • reaction solution was cooled to room temperature, diluted with ethyl acetate, and the organic phase was washed with water and saturated brine.
  • the obtained washed product was dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
  • DMF N, N-dimethylformamide
  • a fluorene derivative represented by the formula (D) was dissolved in 4 ml of DMF.
  • the Vilsmeier reagent prepared by the above operation was added dropwise at room temperature and stirred at 70 ° C. for 1 hour. Thereafter, 50 g of 10% aqueous sodium acetate solution was added for neutralization, and the mixture was extracted with ethyl acetate.
  • the obtained organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off to obtain a crude product.
  • Example 2 In Example 1, 0.1 ml of phosphoryl chloride was cooled to 5 ° C., 0.21 ml of DMF was added dropwise, and the mixture was stirred for 1 hour to prepare a Vilsmeier reagent. 0.52 g of the fluorene derivative represented by the formula (E) was dissolved in 4 ml of DMF, and the Vilsmeier reagent prepared above was added dropwise thereto at room temperature and stirred at 70 ° C. for 1 hour. Thereafter, 50 g of 10% aqueous sodium acetate solution was added for neutralization, and extraction was performed with ethyl acetate. The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
  • FIG. 5 shows the 1 H-NMR result of the compound represented by the formula (K), and FIG. 6 shows the LC-MS result.
  • Example 3 0.06 ml of phosphoryl chloride was cooled to 5 ° C., 0.12 ml of DMF was added dropwise and stirred for 1 hour to prepare Vilsmeier reagent. 0.35 g of the fluorene derivative represented by the formula (F) was dissolved in 3 ml of DMF, and the Vilsmeier reagent prepared above was added dropwise thereto at room temperature, followed by stirring at 70 ° C. for 1 hour.
  • Example 4 A dimethyl sulfoxide solution of 5.00 g of 2-bromofluorene represented by formula (A) (manufactured by Sigma-Aldrich), 13.79 g of 1-bromooctane represented by formula (N), and 0.66 g of tetrabutylammonium bromide was added with 10 ml of 50 wt% sodium hydroxide aqueous solution and stirred at 70 ° C. for 12 hours for reaction. After the reaction, ethyl acetate was added, and the organic phase was washed with 2N hydrochloric acid, water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (solvent: hexane) to obtain 7.09 g of a 9,9-di-n-octylfluorene derivative represented by the formula (O). The yield was 70%.
  • A 2-bromoflu
  • Example 5 0.09 ml of phosphoryl chloride was cooled to 5 ° C., 0.18 ml of DMF was added dropwise and stirred for 1 hour to prepare Vilsmeier reagent.
  • Example 6 0.06 ml of sulforyl hydrochloride was cooled to 5 ° C., 0.12 m of DMF was added dropwise and stirred for 1 hour to prepare Vilsmeier reagent.
  • the organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
  • Example 7 (Creation of dye-sensitized solar cell using liquid electrolyte) (1) ⁇ Creation of photoelectrode> Using a FTO glass with an FTO electrode coating formed on one side as a transparent electrode substrate, a commercially available titanium oxide paste (manufactured by Solaronix) was applied to the FTO surface of this transparent electrode by a screen printing method. The average particle diameter of this titanium oxide is 13 ⁇ m. This was fired in air at 450 ° C. to prepare a titanium oxide porous film layer, and this was treated with titanium tetrachloride to prepare a titanium oxide photoelectrode.
  • a commercially available titanium oxide paste manufactured by Solaronix
  • Table 1 shows the performance of the dye-sensitized solar cell using a liquid electrolyte depending on the dye used.
  • Jsc, Voc, FF, and Eff represent a short-circuit current, an open-circuit voltage, a fill factor, and conversion efficiency, respectively.
  • the dye MK-2 shown in the above table is a compound having the following structure.
  • Example 8 (Preparation of dye-sensitized solar cell using solid electrolyte) (1) ⁇ Creation of photoelectrode> Using FTO glass with an FTO electrode coating formed on one side as a transparent electrode substrate, an IPA solution of titanium alkoxide was applied to the FTO surface of this transparent electrode and heated to 120 ° C. to create a short-circuit prevention layer. On top of that, a commercially available titanium oxide paste (manufactured by Solaronix) was applied by screen printing. The average particle type of this titanium oxide is 37 ⁇ m. This was fired in air at 450 ° C. to prepare a titanium oxide porous film layer, and this was treated with titanium tetrachloride to prepare a titanium oxide photoelectrode.
  • IPA solution of titanium alkoxide was applied to the FTO surface of this transparent electrode and heated to 120 ° C. to create a short-circuit prevention layer.
  • a commercially available titanium oxide paste manufactured by Solaronix
  • Jsc, Voc, FF, and Eff represent a short-circuit current, an open-circuit voltage, a fill factor, and conversion efficiency, respectively.

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Abstract

La présente invention concerne un nouveau composé fluorène répondant par exemple à la formule (I), et un dérivé fluorène. L'invention concerne en outre la fabrication d'une électrode pour cellule solaire à pigment photosensible et d'une cellule solaire à pigment photosensible comprenant ladite électrode, le composé fluorène ou l'un de ses dérivés étant adsorbé sur des particules d'oxyde métallique (oxyde de titane, par exemple) afin de constituer une cellule solaire à pigment photosensible. Ladite cellule solaire à pigment photosensible utilisant le composé fluorène selon l'invention, ou l'un de ses dérivés, est capable de fonctionner avec un rendement élevé. (Dans la formule (I), R1 et R2 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle ou un groupe alkoxy ; X représente une structure cyclique, par exemple un cycle thiophène tel que représenté dans les formules ; et n représente un entier de 1 à 12).
PCT/JP2011/069317 2010-08-31 2011-08-26 Nouveau composé fluorène, colorant pour cellule solaire à pigment photosensible utilisant le composé, électrode contenant ledit colorant et cellule solaire à pigment photosensible WO2012029659A1 (fr)

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WO2013042699A1 (fr) * 2011-09-20 2013-03-28 日本電気株式会社 Composé de spirobifluorène, colorant pour transducteur photoélectrique, et transducteur photoélectrique les utilisant

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JP2006004736A (ja) * 2004-06-17 2006-01-05 Sumitomo Chemical Co Ltd 光電変換素子及び光電変換素子用色素
WO2007119525A1 (fr) * 2006-03-31 2007-10-25 National Institute Of Advanced Industrial Science And Technology Compose organique, electrode a couche mince semi-conductrice l'utilisant, transducteur photoelectrique et pile solaire photoelectrochimique
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JP2006004736A (ja) * 2004-06-17 2006-01-05 Sumitomo Chemical Co Ltd 光電変換素子及び光電変換素子用色素
WO2007119525A1 (fr) * 2006-03-31 2007-10-25 National Institute Of Advanced Industrial Science And Technology Compose organique, electrode a couche mince semi-conductrice l'utilisant, transducteur photoelectrique et pile solaire photoelectrochimique
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WO2013042699A1 (fr) * 2011-09-20 2013-03-28 日本電気株式会社 Composé de spirobifluorène, colorant pour transducteur photoélectrique, et transducteur photoélectrique les utilisant

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