WO2004017426A1 - Metal-oxyde-semi-conducteur nanoporeux spectralement sensibilise a l'aide de nanoparticules de chalcogenures metalliques - Google Patents

Metal-oxyde-semi-conducteur nanoporeux spectralement sensibilise a l'aide de nanoparticules de chalcogenures metalliques Download PDF

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WO2004017426A1
WO2004017426A1 PCT/EP2003/050313 EP0350313W WO2004017426A1 WO 2004017426 A1 WO2004017426 A1 WO 2004017426A1 EP 0350313 W EP0350313 W EP 0350313W WO 2004017426 A1 WO2004017426 A1 WO 2004017426A1
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nano
metal oxide
chalcogenide
solution
metal
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PCT/EP2003/050313
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Hieronymus Andriessen
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Agfa-Gevaert
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Priority to AU2003262523A priority Critical patent/AU2003262523A1/en
Priority to EP03787807A priority patent/EP1547159A1/fr
Priority to JP2004528512A priority patent/JP2005539349A/ja
Publication of WO2004017426A1 publication Critical patent/WO2004017426A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035272—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
    • H01L31/03529—Shape of the potential jump barrier or surface barrier
    • 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

Definitions

  • the present invention relates to a nano-porous metal oxide semiconductor in-situ spectrally sensitized with a metal chalcogenide .
  • the first type is the regenerative cell which converts light to electrical power leaving no net chemical change behind. Photons of energy exceeding that of the band gap generate electron- hole pairs, which are separated by the electrical field present in the space-charge layer. The negative charge carriers move through the bulk of the semiconductor to the current collector and the external circuit. The positive holes (h + ) are driven to the surface where they are scavenged by the reduced form of the redox relay molecular (R) , oxidizing it: h + + R — 0, the oxidized form. 0 is reduced back to R by the electrons that re-enter the cell from the external circuit.
  • R redox relay molecular
  • photosynthetic cells operate on a similar principle except that there are two redox systems : one reacting with the holes at the surface of the semiconductor electrode and the second reacting with the electrons entering the counter-electrode.
  • water is typically oxidized to oxygen at the semiconductor photoanode and reduced to hydrogen at the cathode.
  • Titanium dioxide has been the favoured semiconductor for these studies.
  • Unfortunately because of its large band-gap (3 to 3.2 eV) , Ti0 2 absorbs only part of the solar emission and so has low conversion efficiencies.
  • Graetzel reported in 2001 in Nature, volume 414, page 338, that numerous attempts to shift the spectral response of Ti0 2 into the visible had so far failed.
  • Mesoscopic or nano-porous semiconductor materials minutely structured materials with an enormous internal surface area, have been developed for the first type of cell to improve the light capturing efficiency by increasing the area upon which the spectrally sensitizing species could adsorb.
  • Arrays of nano- crystals of oxides such as Ti0 2 , ZnO, Sn0 2 and Nb 2 O s or chalcogenides such as CdSe are the preferred semiconductor materials and are interconnected to allow electrical conduction to take place.
  • a wet type solar cell having a porous film of dye-sensitized titanium dioxide semiconductor particles as a work electrode was expected to surpass an amorphous silicon solar cell in conversion efficiency and cost.
  • Mater., volume 7, page 1349 reported an all-solid-state solar cell consisting of a highly structured heterojunction between a p- and n-type semiconductor with a absorber in between in which the p- semiconductor is CuSCN or Cul, the n-semiconductor is nano-porous titanium dioxide and the absorber is an organic dye.
  • EP-A 1 176 646 discloses a solid state p-n heterojunction comprising an electron conductor and a hole conductor, characterized in that if further comprises a sensitizing semiconductor, said sensitizing being located at an interface between said electron conductor and said hole conductor; and its application in a solid state sensitized photovolaic cell.
  • the sensitizing semiconductor is in the form of particles adsorbed at the surface of said electron conductor and in a further preferred embodiment the sensitizing semiconductor is in the form of quantum dots, which according to a particularly preferred embodiment are particles consisting of PbS, CdS, Bi 2 S 3 , Sb 2 S 3 , g 2 S, InAs, CdTe, CdSe or HgTe or solid solutions of HgTe/CdTe or HgSe/CdSe.
  • the electron conductor is a ceramic made of finely divided large band gap metal oxide, with nanocrystalline Ti ⁇ 2 being particularly preferred.
  • EP-A 1 176 646 further includes an example for making a layered heterojunction in which Sn ⁇ 2 _ coated glass was coated with a compact Ti ⁇ 2 layer by spray pyrolysis, PbS quantum dots were deposited upon the Ti ⁇ 2 layer, the hole conductor 2, 2', 7,7'- tetrakis (N, N-di-p-methoxyphenyl-amine) 9,9' -spirobifluorene (OMeTAD) was deposited on the quantum dots and a semitransparent gold back contact was evaporated on the OMeTAD layer.
  • OLED hole conductor 2', 7,7'- tetrakis
  • OMeTAD 9,9' -spirobifluorene
  • aspects of the present invention are realized by a nano-porous metal oxide semiconductor with a band-gap of greater than 2.9 eV in-situ spectrally sensitized on its internal and external surface with metal chalcogenide nano-particles with a band-gap of less than 2.9 eV containing at least one metal chalcogenide, characterized in that the nano-porous metal oxide semiconductor further contains a triazole or diazole compound.
  • aspects of the present invention are also realized by a process for in-situ spectral sensitization of nano-porous metal oxide semiconductor with a band-gap of greater than 2.9 eV on its internal and external surface with metal chalcogenide nano- particles with a band-gap of less than 2.9 eV, containing at least one metal chalcogenide, comprising a metal chalcogenide-forming cycle comprising the steps of: contacting the nano-porous metal oxide with a solution of metal ions; and contacting the nano-porous metal oxide with a solution of chalcogenide ions, wherein the solution of metal ions and/or the solution of chalcogenide ions contains a triazole or diazole compound.
  • aspects of the present invention are also realized by a photovoltaic device comprising the above-mentioned nano-porous metal oxide semiconductor.
  • aspects of the present invention are also realized by a second photovoltaic device comprising a nano-porous metal oxide semiconductor with a band-gap of greater than 2.9 eV on spectrally sensitized on its internal and external surface with metal chalcogenide nano-particles with a band-gap of less than 2.9 eV, containing at least one metal chalcogenide, prepared according to the above-mentioned process.
  • nano-porous metal oxide semiconductor means a metal oxide semiconductor having pores with a size of 100 nm or less and
  • chalcogenide means a binary compound containing a chalcogen and a more electropositive element or radical.
  • a chalcogen is an element from group IV of the periodic table including oxygen, sulphur, selenium, tellurium and polonium.
  • a mixture of two or more metal chalcogenides includes a simple mixture thereof, mixed crystals thereof and doping of a metal chalcogenide by metal or chalcogenide replacement .
  • aqueous for the purposes of the present invention means containing at least 60% by volume of water, preferably at least 80% by volume of water, and optionally containing water- miscible organic solvents such as alcohols e.g. methanol, ethanol,
  • 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.
  • coating is used as a generic term including all means of applying a layer including all techniques for producing continuous layers, such as curtain coating, doctor-blade coating etc., and all techniques for producing non-continuous layers such as screen printing, ink jet printing, flexographic printing, and techniques for producing continuous layers .
  • PEDOT poly (3, 4-ethylenedioxy- thiophene)
  • PSS poly(styrene sulphonic acid) or pol (styrenesulphonate) .
  • aspects of the present invention are realized by a nano-porous metal oxide semiconductor with a band-gap of greater than 2.9 eV in-situ spectrally sensitized on its internal and external surface with metal chalcogenide nano-particles with a band-gap of less than 2.9 eV containing at least one metal chalcogenide, characterized in that the nano-porous metal oxide further contains a triazole or diazole compound.
  • the metal oxide semiconductor is n-type .
  • the metal oxide is selected from the group consisting of titanium oxides, tin oxides, niobium oxides, tantalum oxides, tungsten oxides and zinc oxides.
  • the nano-porous metal oxide semiconductor is titanium dioxide.
  • aspects of the present invention are realized by a nano-porous metal oxide semiconductor with a band-gap of greater than 2.9 eV in-situ spectrally sensitized on its internal and external surface with metal chalcogenide nano-particles with a band-gap of less than 2.9 eV containing at least one metal chalcogenide, characterized in that the nano-porous metal oxide further contains a triazole or diazole compound.
  • the metal chalcogenide is a metal oxide, metal sulphide, metal selenide or a mixture of two or more thereof.
  • the metal chalcogenide is a metal sulphide or a mixture of two or more thereof.
  • the metal chalcogenide is selected from the group consisting of lead sulphide, bismuth sulphide, cadmium sulphide, silver sulphide, antimony sulphide, indium sulphide, copper sulphide, cadmium selenide, copper selenide, indium selenide, cadmium telluride or a mixture of two or more thereof.
  • aspects of the present invention are realized by a nano-porous metal oxide semiconductor with a band-gap of greater than 2.9 eV in-situ spectrally sensitized on its internal and external surface with metal chalcogenide nano-particles with a band-gap of less than 2.9 eV containing at least one metal chalcogenide.
  • the triazole compound is a tetraazaindene .
  • the triazole compound is selected from the group consisting of
  • Suitable triazole or diazole compounds include:
  • the nano-porous metal oxide further contains a phosphoric acid or a phosphate .
  • the phosphoric acid is selected from the group consisting of , orthophosphoric acid, phosphorous acid, hypophosphorous acid and polyphosphoric acids .
  • Polyphosphoric acids include diphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, metaphosphoric acid and "polyphosphoric acid” .
  • the phosphate is selected from the group consisting of orthophosphates , phosphates , phosphites , hypophosphites and polyphosphates .
  • Polyphosphates are linear polyphosphates , cyclic polyphosphates or mixtures thereof .
  • Linear polyphosphates contain 2 to 15 phosphorus atoms and include pyrophosphates , dipolyphosphates , tripolyphosphates and tetrapolyphosphates .
  • Cyclic polyphosphates contain 3 to 8 phosphorus atoms and include trimetaphosphates and tetrametaphosphates and metaphosphates .
  • Polyphosphoric acid may be prepared by heating H 3 PO 4 with sufficient P4O10 (phosphoric anhydride) or by heating H 3 PO 4 to remove water . A P O 10 /H 2 O mixture containing 72 .
  • P 4 O 10 corresponds to pure H 3 PO 4 , but the usual commercial grades of the acid contain more water .
  • P 4 O 10 content H 4 P 2 O 7 pyrophosphoric acid, forms along with P 3 through Ps polyphosphoric acids .
  • Triphosphoric acid appears at 71 . 7% P 2 O 5 (H 5 P 3 O 10 ) and tetraphosphoric acid (H 6 P 4 O 13 ) at about 75 . 5% P 2 O 5 .
  • Such linear polyphosphoric acids have 2 to 15 phosphorus atoms, which each bear a strongly acidic OH group.
  • the two terminal P atoms are each bonded to a weakly acidic OH group.
  • High linear and cyclic polyphosphoric acids are present only at acid concentrations above 82% P 2 O 5 .
  • Commercial phosphoric acid has a 82 to 85% by weight P 2 O 5 content. It consists of about 55% tripolyphosphoric acid, the remainder being H 3 PO 4 and other polyphosphoric acids .
  • a polyphosphoric acid suitable for use according to the present invention is a 84% (as P 2 O 5 ) polyphosphoric acid supplied by ACROS (Cat. No. 19695-0025) .
  • aspects of the present invention are also realized by a process for in-situ spectral sensitization of nano-porous metal oxide semiconductor with a band-gap of greater than 2.9 eV on its internal and external surface with metal chalcogenide nano- particles with a band-gap of less than 2.9 eV, containing at least one metal chalcogenide, comprising a metal chalcogenide-forming cycle comprising the steps of: contacting nano-porous metal oxide with a solution of metal ions; and contacting nano-porous metal oxide with a solution of chalcogenide ions, wherein the solution of metal ions and/or the solution of chalcogenide ions contains a triazole or diazole compound.
  • the contact with a solution of metal ions occurs before the contact with a solution of chalcogenide ions .
  • the metal chalcogenide-forming cycle is repeated.
  • the triazole or diazole compound is tetraazaindene is 5-methyl-l, 2, -triazolo- (1, 5-a) -pyrimidine-7-ol .
  • the metal chalcogenide is rinsed with an aqueous solution containing a phosphoric acid or a phosphate.
  • 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 adjacent layers.
  • Suitable polymeric films are poly (ethylene terephthalate) , poly (ethylene naphthalate) , polystyrene, polyethersulphone, polycarbonate, polyacrylate, polyamide, polyimides, cellulosetriacetate, polyolefins and poly (vinylchloride) , optionally treated by corona discharge or glow discharge or provided with a subbing layer.
  • the photovoltaic device comprises a layer configuration.
  • the photovoltaic device comprises a layer configuration.
  • Photovoltaic devices incorporating the spectrally sensitized nano-porous metal oxide 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, 9' - spirobifluorene (OMeTAD) or triphenylamine compounds or a polymer such as PPV-derivatives, poly (N-vinylcarbazole) etc., or inorganic semiconductors such as Cul, CuSCN etc.
  • the charge transporting process can be ionic as in the case of a liquid electrolyte or gel electrolyte or electronic as in the case of organic or inorganic hole transporting materials .
  • 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 or other means 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 metal oxide 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) ] .
  • at least one of the components 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).
  • Spectrally sensitized nano-porous metal oxide can be used in a both regenerative and photosynthetic photovoltaic devices.
  • Metal solution 1 a 0.6 M Bi -solution, was prepared by mixing 36 mL of deionized water, 6.2 mL of concentrated HNO 3 and 28.75 g of Bi (NO 3 ) 3 .5H 2 O, then adding a solution of 40 g triammonium citrate in
  • Metal solution 2 a 0.96 M Pb ⁇ -solution, was prepared by dissolving 37.65 g of Pb(N ⁇ 3 ) 2 in 100 L of deionized water.
  • Sulphide solution 1 a 0.1 M S 2 solution, was prepared by dissolving 0.78 g of Na 2 S in 100 mL of deionized water.
  • 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 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.
  • a dry layer thickness of 1.4 ⁇ m was obtained as verified by laserprofilometry (DEKTRAKTM profilometer) , mechanically with a diamond-tipped probe (Perthometer) and interferometry .
  • the titanium dioxide-coated glass plates were cooled to 150°C by placing them on a hot plate at 150°C for 10 minutes and then immediately dipped into the metal solution for 1 minute, then rinsed for 10 seconds with deionized water immediately followed by dipping for 1 minute in the sulphide solution and finally rinsing once more with deionized water for 10 seconds.
  • nano-metal sulphides were deposited on the internal and external surface of the nano-porous titanium dioxide. The amount of adsorbed nano-metal sulphide particles could be increased by carrying out multiple dipping cycles.
  • Photovoltaic devices 1 to 5 were prepared by the following procedure: Preparation of the front electrode
  • the electrode was taped off at the borders and was doctor
  • 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 inbetween two pre-patterned layers of Surlyn® (DuPont) (2 x 7 cm
  • the thereby prepared photovoltaic cells were irradiated with a Xenon Arc Discharge lamp with a power of 100 mW/cm .
  • the current generated was recorded with a Keithley electrometer (Type 2420) .
  • the open circuit voltage (V oc ) , short circuit current density (I sc ) and Fill Factor (FF) of the photocell as calculated from the quality of generated current are given in Table 3.
  • 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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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
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Abstract

L'invention concerne un métal-oxyde-semi-conducteur nanoporeux possédant une largeur de bande interdite supérieure à 2,9 eV spectralement sensibilisée in situ sur sa surface interne et externe à l'aide de nanoparticules de chalcogénures métalliques possédant une largeur de bande interdite inférieure à 2,9 eV contenant au moins un chalcogénure métallique, cet oxyde métallique nanoporeux se caractérisant par le fait qu'il contient également une triazole ou une diazole. L'invention concerne également un procédé destiné à la sensibilisation spectrale in situ d'un métal-oxyde-semi-conducteur nanoporeux possédant une largeur de bande interdite supérieure à 2,9 eV sur sa surface interne et externe avec des nanoparticules de chalcogénures métalliques possédant une largeur de bande interdite inférieure à 2,9 eV, contenant au moins un chalcogénure métallique, comprenant un cycle formant un chalcogénure métallique. Ce procédé consiste à mettre l'oxyde métallique nanoporeux en contact avec une solution d'ions métalliques, puis à mettre l'oxyde métallique nanoporeux en contact avec une solution d'ions chalcogénure, ladite solution d'ions métalliques et/ou ladite solution d'ions chalcogénure contenant une triazole ou une diazole.
PCT/EP2003/050313 2002-08-13 2003-07-16 Metal-oxyde-semi-conducteur nanoporeux spectralement sensibilise a l'aide de nanoparticules de chalcogenures metalliques WO2004017426A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2003262523A AU2003262523A1 (en) 2002-08-13 2003-07-16 Nano-porous metal oxide semiconductor spectrally sensitized with metal chalcogenide nano-particles
EP03787807A EP1547159A1 (fr) 2002-08-13 2003-07-16 Metal-oxyde-semi-conducteur nanoporeux spectralement sensibilise a l'aide de nanoparticules de chalcogenures metalliques
JP2004528512A JP2005539349A (ja) 2002-08-13 2003-07-16 金属カルコゲニドナノ−粒子を用いて分光増感されたナノ−多孔質金属酸化物半導体

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EP02102129.0 2002-08-13
EP02102129 2002-08-13

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Cited By (1)

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