EP1540680A1 - Semi-conducteur a oxyde metallique de type n spectralement sensibilise par un sensibilisateur spectral cationique - Google Patents

Semi-conducteur a oxyde metallique de type n spectralement sensibilise par un sensibilisateur spectral cationique

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Publication number
EP1540680A1
EP1540680A1 EP02772296A EP02772296A EP1540680A1 EP 1540680 A1 EP1540680 A1 EP 1540680A1 EP 02772296 A EP02772296 A EP 02772296A EP 02772296 A EP02772296 A EP 02772296A EP 1540680 A1 EP1540680 A1 EP 1540680A1
Authority
EP
European Patent Office
Prior art keywords
metal oxide
oxide semiconductor
type metal
cationic
dihydroxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02772296A
Other languages
German (de)
English (en)
Inventor
Hieronymus c/o AGFA-GEVAERT Andriessen
Paul c/o AGFA-GEVAERT Callant
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Agfa Gevaert AG
Original Assignee
Agfa Gevaert NV
Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV, Agfa Gevaert AG filed Critical Agfa Gevaert NV
Publication of EP1540680A1 publication Critical patent/EP1540680A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • H10K85/652—Cyanine 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
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • 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 nano-porous n-type metal oxide semiconductor spectrally sensitized with a catio ⁇ ic spectral sensitizer.
  • a wet type solar cell having a nano-porous film of dye-sensitized titanium dioxide semiconductor particles as a work electrode has been expected to surpass an amorphous silicon solar cell in conversion efficiency and cost.
  • These fundamental techniques were disclosed in 1991 by Graetzel et al. in Nature, volume 353, pages 737-740 and in US 4,927,721, US 5,350,644 and JP-A 05-504023.
  • One approach is to improve the adsorption of dye sensitizers on the semiconductor layer.
  • EP-A 1 137 022 discloses semiconductor particles having a dye adsorbed thereby in the presence of an anionic sulfo ⁇ ic acid derivative, preferably represented by formula (I) :
  • R represents a hydrogen atom or a substituted or unsubstituted alkyl group
  • Ar represents a substituted or unsubstituted arylene group
  • m represents 0 or 1
  • Li represents a single bond or a divalent linking group
  • M represents a cation; provided that a combination of a hydrogen atom as Ri, 0 as , and a single bond Li is excluded; or by formula (II) :
  • R 2 represents a straight chain or branched alkyl group
  • Ph represents a phenylene group
  • n represents an integer of 0 to 50
  • L 2 represents a single bond, a substituted or unsubstituted alkylene group or a substituted or unsubstituted alkyleneoxy group
  • M represents a cation.
  • JP-A 2001-024252 discloses a photo-electric conversion material containing a semiconductor sensitized with a pigment or dye whose adsorption thereon is assisted by a compound A represented by general formula (I) : R-L-Z, wherein R is an optionally substituted alkyl, alkenyl or aryl group; L is a single bond or a divalent linking group; and Z is an acidic group (which dissociates a proton), or its alkali metal salt.
  • the photo-electric conversion material may also contain a high molecular weight polymer B represented by general formula (II) : X
  • X is a hydrogen atom or a C 1 - 4 alkyl group
  • Y is a single bond or a divalent linking group
  • E is a repeat unit derived from a compound with ethylenic unsaturation
  • Z is an acidic group (which dissociates a proton), or its alkali metal salt
  • j,k are the weight composition ratio of the repeat units.
  • Preferred acidic groups which dissociate a proton are carboxylic acid and sulfonic groups, although boric acid, phenolic and hydroxy groups are also mentioned. All the specific compounds according to formula (I) disclosed in JP-A 2001-024252 have a carboxy group as their acidic group which dissociates a proton and several compounds have more than one carboxy group.
  • a critical feature of photovoltaic devices based on nano- porous titanium dioxide is their spectral sensitization, which in large measure determines their efficiency.
  • Organic metal complex dyes preferably including ruthenium
  • Pure anionic organic dye compounds e.g. merocyanines
  • Spectral sensitization of titanium dioxide semiconductors with cationic dye sensitizers is, to our knowledge, unknown.
  • aspects of the present invention are realized by a layer configuration comprising a layer of a nano-porous n-type metal oxide semiconductor with a band-gap of greater than 2.7 eV, an adsorbed cationic spectral sensitizer and a coadsorber capable of enhancing the adsorption of a cationic spectral sensitizer on a n- type metal oxide semiconductor.
  • aspects of the present invention are also realized by a process for preparing the above-mentioned layer configuration comprising the steps of: providing a layer of a nano-porous n-type metal oxide semiconductor with a band-gap of greater than 2.7 eV, adsorbing the coadsorber on the nano-porous n-type metal oxide semiconductor layer and adsorbing a cationic spectral sensitizer on the n-type metal oxide semiconductor layer.
  • nano-porous metal oxide semiconductor means a metal oxide semiconductor having pores with a size of 100 nm or less and
  • anionic spectral sensitizer means a dye with an overall negative charge having spectral sensitizing properties, such as cyanine dyes with at least two covalently-bonded acidic group either as a free acid or as a salt and merocyanine dyes with at least one covalently-bonded acidic group either as a free acid or as a salt.
  • Covalently bonded acidic groups include a hydroxy group on an aromatic ring system and sulpho [-S0 3 ⁇ ] , sulphato [-0-SOJ] , carboxy [-C0 2 " ] and phosphoric acid groups.
  • Anionic dyes exhibit an ionic interaction with positively charged sites on surfaces, such as on certain natural and artificial fibres.
  • cationic spectral sensitizer means a dye with an overall positive charge having spectral sensitizing properties, such as merocyanine dye with at least one covalently-bonded positively charged group, such as a quaternary ammonium group or a ternary sulfonium group, and cyanine dyes.
  • Cationic dyes exhibit an ionic interaction with negatively charged sites on surfaces, such as on certain natural and artificial fibres.
  • ortho-dihydroxy-benzene compound includes 1,2- dihydroxybenzene, also known as cathechol, and substituted ortho- dihydroxy-benzene compounds, such substitution also including carbocyclic and heterocyclic rings systems annelated (i.e. sharing two carbon atoms) with a ortho-dihydroxy-benzene nucleus for example aromatic and heteroaromatic ring systems.
  • alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e.
  • support means a "self-supporting material" so as to distinguish it from a "layer” which may be coated on a support, but which is itself not self-supporting. It also includes any treatment necessary for, or layer applied to aid, adhesion to the support .
  • continuous layer refers to a layer in a single plane covering the whole area of the support and not necessarily in direct contact with the support.
  • non-continuous layer refers to a layer in a single plane not covering the whole area of the support and not necessarily in direct contact with the support.
  • a layer configuration comprising a layer of a nano-porous n-type metal oxide semiconductor with a band-gap of greater than 2.7 eV, an adsorbed cationic spectral sensitizer and a coadsorber capable of enhancing the adsorption of a cationic spectral sensitizer on a n- type metal oxide semiconductor.
  • the n-type metal oxide semiconductor is selected from the group consisting of titanium oxides, tin oxides, niobium oxides, tantalum oxides and zinc oxides .
  • the n-type metal oxide semiconductor is titanium dioxide.
  • the coating of the nano-porous Ti02 should be between 8 and 12 ⁇ m in order to have sufficient light absorption for generating power conversion efficiencies up to 5 to 8%.
  • the thicker the titanium dioxide coating the longer the pathway for the charges (electrons) have to be transported to the charge collecting electrode and the greater the probability of recombination occurring with resultant power conversion efficiency loss.
  • smaller titanium dioxide nano-particles can be used, having a larger specific surface and hence enabling thinner layers to be realized with the same light absorbance values. In this way, photovoltaic cells with higher efficiencies can be obtained due to the fact that the probability of recombination is reduced due to the path traversed by the electrons to the charge collecting electrode being shorter.
  • the metal oxide semiconductor nano-particles with a band-gap of greater than 2.7 eV used in the process, according to the present invention can be prepared by wet precipitation and non- wet-precipitation processes.
  • Non-wet-precipitation processes include such processes as the flame pyrolysis process operated by DEGUSSA.
  • Titanium dioxide nano-particles produced according to wet-chemical process are commercially available from SOLARONIX SA as Ti-NanoxideTM T, a nano-sized titanium dioxide with a mean particle size of 13 nm and a specific surface of 120 m 2 /g, and Ti- NanoxideTM HT, a nano-sized titanium dioxide with a mean particle size 9 nm and specific surface of 165 m 2 /g, which are often used as n-type semi-conductor nano-particles in making Graetzel-type photovoltaic cells, or can be readily synthesized using fairly straightforward precipitation techniques as disclosed in 1997 by Barbe et al .
  • the metal oxide is titanium dioxide prepared by a non-wet-precipitation process.
  • a layer configuration comprising a layer of a nano-porous n-type metal oxide semiconductor with a band-gap of greater than 2.7 eV, an adsorbed cationic spectral sensitizer and a coadsorber capable of enhancing the adsorption of a cationic spectral sensitizer on a n- type metal oxide semiconductor.
  • the cationic spectral sensitizer is a cyanine dye.
  • Cationic spectral sensitizers suitable for use in the present invention include:
  • a layer configuration comprising a layer of a nano-porous n-type metal oxide semiconductor with a band-gap of greater than 2.7 eV, an adsorbed cationic spectral sensitizer and a coadsorber capable of enhancing the adsorption of a cationic spectral sensitizer on a n- type metal oxide semiconductor.
  • the coadsorber is an ortho- dihydroxy-benzene compound.
  • the coadsorber is an ortho- dihydroxy-benzene compound with a group having a Hammett ⁇ value of at least 0.60 and below 1.00.
  • the coadsorber is an ortho- dihydroxy-benzene compound with a group having a Hammett ⁇ value of at least 0.60 and below 1.00, wherein the ortho-dihydroxy-benzene compound has the ortho-dihydroxy-groups and the group having a Hammett ⁇ value of at least 0.60 and below 1.00 on the same benzene ring.
  • the coadsorber is an ortho- dihydroxy-benzene compound with a nitrile group substituted on the same benzene ring as the ortho-dihydroxy-groups.
  • the coadsorber is selected from the group consisting of 2 , 3-dihydroxy-benzonitrile, 3 , 4-dihydroxy- benzonitrile, 3 , 4, 5-trihydroxy-benzonitrile, 3 , 4-dihydroxy-4 ' - cyano-benzophenone, 4-nitro-catechol, (3 , 4-dihydroxy-phenyl)methyl- sulphone, 1, 2-dihydroxy-anthraquinone, 3 , 4-dihydroxy-anthraquinone- 2-sulphonic acid, 4, 5-dihydroxy-benzene-l, 3-disulphonic acid, 6,7- dihydroxy-naphthalene-2-sulphonic acid, 3 , 4-dihydroxy-benzoic acid and catechol.
  • the coadsorber is selected from the group consisting of 3 , 4-dihydroxy-benzonitrile, 3,4,5- trihydroxy-benzonitrile, 1, 2-dihydroxy-anthraquinone, (3,4- dihydroxy-phenyl) methylsulphone, 4 , 5-dihydroxy-benzene-l , 3- disulphonic acid and catechol.
  • Coadsorbers suitable for use in the present invention include:
  • aspects of the present invention are realized by a process for preparing a layer configuration, according to the present invention, comprising the steps of: providing a layer of a nano- porous n-type metal oxide semiconductor with a band-gap of greater than 2.7 eV, adsorbing a coadsorber on the nano-porous n-type metal oxide semiconductor layer and adsorbing a cationic spectral sensitizer on the nano-porous n-type metal oxide semiconductor layer.
  • the adsorption of the cationic spectral sensitizer on the nano-porous n-type metal oxide semiconductor layer is carried out simultaneously with the adsorption of the coadsorber on the nano- porous n-type metal oxide semiconductor layer.
  • complex formation between the coadsorber and the cationic spectral sensitizer takes place before adsorption on the nano-porous n-type metal oxide semiconductor layer i.e. that a complex is adsorbed rather than the two components individually.
  • the adsorption of the cationic spectral sensitizer on the nano-porous n-type metal oxide semiconductor layer is carried out after the adsorption of the coadsorber on the nano-porous n-type metal oxide semiconductor layer.
  • Supports for use according to the present invention include polymeric films, silicon, ceramics, oxides, glass, polymeric film reinforced glass, glass/plastic laminates, metal/plastic laminates, paper and laminated paper, optionally treated, provided with a subbing layer or other adhesion promoting means to aid adhesion to the light-exposure differentiable element.
  • Suitable polymeric films are poly (ethylene terephthalate) , poly (ethylene naphthalate) , polystyrene, polyethersulphone, polycarbonate, polyacrylate, polya ide, polyimides, cellulose triacetate, polyolefins and poly (vinylchloride) , optionally treated by corona discharge or glow discharge or provided with a subbing layer.
  • aspects of the present invention are also realized by a photovoltaic device comprising the layer configuration, according to the present invention, or produced according to the process, according to the present invention.
  • Photovoltaic devices incorporating the spectrally sensitized nano-porous n-type metal oxide semiconductor can be of two types: the regenerative type which converts light into electrical power leaving no net chemical change behind in which current-carrying electrons are transported to the anode and the external circuit and the holes are transported to the cathode where they are oxidized by the electrons from the external circuit and the photosynthetic type in which there are two redox systems one reacting with the holes at the surface of the semiconductor electrode and one reacting with the electrons entering the counter-electrode, for example, water is oxidized to oxygen at the semiconductor photoanode and reduced to hydrogen at the cathode.
  • the hole transporting medium may be a liquid electrolyte supporting a redox reaction, a gel electrolyte supporting a redox reaction, an organic hole transporting material, which may be a low molecular weight material such as 2 , 2 ' , 7 , 7 ' -tetrakis (N,N-di-p-methoxyphenyl-amine) , 9 ' - spirobifluorene (OMeTAD) or triphenylamine compounds or a polymer such as PPV-derivatives, pol (N-vinylcarbazole) etc., or inorganic semiconductors such as Cul, CuSCN etc.
  • the charge transporting process can be ionic as, for example, in the case of a liquid electrolyte or gel electrolyte or electronic as, for example, in the case of organic or inorganic hole transporting
  • Such regenerative photovoltaic devices can have a variety of internal structures in conformity with the end use. Conceivable forms are roughly divided into two types: structures which receive light from both sides and those which receive light from one side.
  • An example of the former is a structure made up of a transparently conductive layer e.g. an ITO-layer or a PEDOT/PSS-containing layer and a transparent counter electrode electrically conductive layer e.g. an ITO-layer or a PEDOT/PSS-containing layer having interposed therebetween a photosensitive layer and a charge transporting layer.
  • Such devices preferably have their sides sealed with a polymer, an adhesive etc. to prevent deterioration or volatilization of the inside substances.
  • the external circuit connected to the electrically-conductive substrate and the counter electrode via the respective leads is well-known.
  • the spectrally sensitized nano-porous n-type metal oxide semiconductor can be incorporated in hybrid photovoltaic compositions such as described in 1991 by Graetzel et al . in Nature, volume 353, pages 737-740, in 1998 by U. Bach et al. [see Nature, volume 395, pages 583-585 (1998)] and in 2002 by W. U. Huynh et al . [see Science, volume 295, pages 2425-2427 (2002)]. In all these cases, at least one of the components (light absorber, electron transporter or hole transporter) is inorganic (e.g.
  • nano-Ti ⁇ 2 as electron transporter CdSe as light absorber and electron transporter
  • at least one of the components is organic (e.g. triphenylamine as hole transporter or poly (3-hexylthiophene) as hole transporter).
  • Layer configurations can be used in photovoltaic devices and solar cells.
  • a glass substrate (FLACHGLAS AG) was ultrasonically cleaned in ethanol for 5 minutes and then dried.
  • a layer of a nano-Ti02 dispersion (Ti-nanoxide HT from Solaronix SA) was applied to the glass substrate using a doctor blade coater. This titanium dioxide- coated glass was heated to 450°C for 30 minutes. This results in a highly transparent nano-porous Ti ⁇ 2 layer.
  • the titanium dioxide-coated glass plates were cooled to 150°C by placing it on a hot plate at 150°C for 10 minutes and then immediately immersed in a dye-containing solution optionally containing an ortho-dihydroxy-benzene compound where they remained for 15 to 17 hours. After immersion in the dye solution, the titanium dioxide layers were rinsed with acetonitrile to remove non-adsorbed dye and then dried at 50°C for several mins .
  • Photovoltaic devices 1 to 8 were prepared as follows:
  • a glass plate (2 x 7 cm ) coated with conductive Sn0 2 :F (Pilkington TEC15/3) with a surface conductivity of ca 15 Ohm/square was ultrasonically cleaned in isopropanol for 5 minutes and then dried.
  • the electrode was taped off at the borders and was doctor blade-coated in the middle (0.7 x 4.5 cm ) with the above-described Solaronix disperion of Ti ⁇ 2 to give layer thicknesses after sintering of 1.8 or 5 ⁇ m to ensure comparable optical absorbances of the cells.
  • the sintering procedure and cationic spectral sensitizer adsorption procedure in the presence of a coadsorber were as described for EXAMPLE 1.
  • the front electrode was thereby produced, which was immediately used in assembling the cell.
  • the back electrode (consisting of Sn ⁇ 2 :F glass (Pilkington TEC15/3) evaporated with platinum to catalyse the reduction of the electrolyte) was sealed together with the front electrode with two
  • the cell was irradiated with a Steuernagel Solar Constant 575 solar simulator with a metal halide 1 AM light source. The simulator was adjusted to about 1 sunequivalent .
  • the generated electricity was recorded with a Keithley electrometer (Type 2400 SMU) .
  • the open circuit voltage (V oc ) short circuit current, density (I sc ) and Fill Factor (FF) of the photocell calculated from the quantity of electricity generated are shown in table 6.
  • Photovoltaic cells were prepared as described in EXAMPLE 3 with the cationic spectral sensitizers separately and with a mixtures of the cationic spectral sensitizers.
  • Degussa P25 Ti ⁇ 2 nano-colloid a nano-titanium dioxide produced by a non- wet-precipitation process i.e. by flame pyrolysis, was used instead of the Ti-nanoxide HT from Solaronix, a nano-titanium dioxide produced by a wet-precipitation process, 5 g of Degussa P25 being added to 15 mL of water with 1 mL of Triton X-100 being subsequently added.
  • the resulting titanium dioxide colloidal dispersion was cooled in ice and ultrasonically treated for 5 minutes. This titanium dioxide colloidal dispersion was then further used as described above for the Ti-nanoxide HT dispersion.
  • the dye adsorption was carried out with a cationic spectral sensitizer concentration of 1 x 10 -4 M and a CA-1 concentration of
  • the present invention may include any feature or combination of features disclosed herein either implicitly or explicitly or any generalisation thereof irrespective of whether it relates to the presently claimed invention.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Hybrid Cells (AREA)

Abstract

L'invention concerne une configuration de couche comprenant une couche semi-conductrice à oxyde métallique de type n nanoporeux, dont la bande interdite dépasse 2.7 eV, un sensibilisateur spectral cationique adsorbé et un coadsorbant capable d'améliorer l'adsorption d'un sensibilisateur spectral cationique sur un semi-conducteur à oxyde métallique de type n. La présente invention porte également sur un procédé pour réaliser cette configuration de couche, ce procédé comportant les opérations suivantes : préparer une couche semi-conductrice à oxyde métallique de type n nanoporeux, dont la bande interdite dépasse 2.7 eV, adsorber un coadsorbant sur la couche semi-conductrice à oxyde métallique de type n nanoporeux, et adsorber un sensibilisateur spectral cationique sur la couche semi-conductrice à oxyde métallique de type n nanoporeux.
EP02772296A 2002-09-12 2002-09-12 Semi-conducteur a oxyde metallique de type n spectralement sensibilise par un sensibilisateur spectral cationique Withdrawn EP1540680A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2002/010269 WO2004025674A1 (fr) 2002-09-12 2002-09-12 Semi-conducteur a oxyde metallique de type n spectralement sensibilise par un sensibilisateur spectral cationique

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EP1540680A1 true EP1540680A1 (fr) 2005-06-15

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EP (1) EP1540680A1 (fr)
JP (1) JP2005538519A (fr)
AU (1) AU2002337090A1 (fr)
WO (1) WO2004025674A1 (fr)

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KR101137701B1 (ko) 2009-10-22 2012-04-25 한양대학교 산학협력단 고분자 공흡착제를 갖는 염료감응형 태양전지용 광전극
KR20120113107A (ko) * 2011-04-04 2012-10-12 포항공과대학교 산학협력단 다공성 박막이 형성된 금속 산화물 반도체 전극 및 이를 이용한 염료 감응 태양전지 및 그 제조 방법
KR101286075B1 (ko) * 2011-04-04 2013-07-15 포항공과대학교 산학협력단 이온층을 포함하는 염료 감응형 태양전지 및 그 제조 방법
JP5520258B2 (ja) * 2011-06-29 2014-06-11 東京エレクトロン株式会社 色素吸着装置及び色素吸着方法

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US6245988B1 (en) * 1997-05-07 2001-06-12 Ecole Polytechnique Federale De Lausanne Metal complex photosensitizer and photovoltaic cell
EP1091373B1 (fr) * 1997-10-23 2004-05-06 Fuji Photo Film Co., Ltd. Dispositif de conversion photoélectrique et cellule photoélectrochimique
JP4443713B2 (ja) * 2000-03-24 2010-03-31 富士フイルム株式会社 半導体微粒子、光電変換素子および光電池

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EP0333641A1 (fr) * 1988-02-12 1989-09-20 Ecole Polytechnique Féderale de Lausanne (EPFL) Cellule photoélectrochimique, procédé de fabrication d'une telle cellule et utilisation de la cellule

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Title
H. TRIBUTSH, BER. BUNSENGES., vol. 73, no. 6, 1969, pages 582 - 590 *
See also references of WO2004025674A1 *

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AU2002337090A1 (en) 2004-04-30
WO2004025674A1 (fr) 2004-03-25

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