EP1540679A1 - Process for preparing nano-porous metal oxide semiconductor layers - Google Patents

Process for preparing nano-porous metal oxide semiconductor layers

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Publication number
EP1540679A1
EP1540679A1 EP02769994A EP02769994A EP1540679A1 EP 1540679 A1 EP1540679 A1 EP 1540679A1 EP 02769994 A EP02769994 A EP 02769994A EP 02769994 A EP02769994 A EP 02769994A EP 1540679 A1 EP1540679 A1 EP 1540679A1
Authority
EP
European Patent Office
Prior art keywords
nano
metal oxide
oxide semiconductor
particles
layer
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Withdrawn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
EP02769994A
Other languages
German (de)
English (en)
French (fr)
Inventor
Hieronymus AGFA-GEVAERT ANDRIESSEN
Joop Van Deelen
Jan Kroon
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
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 EP1540679A1 publication Critical patent/EP1540679A1/en
Withdrawn legal-status Critical Current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
    • H01G9/2027—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
    • 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
    • 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 process for preparing nano- porous metal oxide semiconductor layers .
  • 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 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.
  • 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.
  • 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.
  • a drawback in the manufacture of nano-porous metal oxide semiconductor layers for Graetzel photovoltaic cells is the high temperature needed for making the nano-porous metal oxide semiconductor layer. This is apparently needed to obtain sufficient contact between the nano-porous metal oxide particles to create a conductive pathway for the photogenerated charges (electrons) .
  • the term sintering is not the appropriate one in this context, this term is often used to describe this heating process. Usually temperatures between 300 and 550°C are applied for 15 to 90 minutes . Such high temperatures are prohibitive for making photovoltaic cells on plastic and flexible substrates. Such cells would offer a myriad of advantages for this type of photovoltaic cell.
  • WO 00/72373 discloses a method for manufacturing a nanostructured porous film electrode, the method characterized by the steps of: preparing a binder-free suspension (21) of electrode material particles (11) in a volatile suspending agent (13), said particles substantially having a size within the nanometer scale, depositing the binder-free particle suspension (21) on a substrate (22) covered with a conducting film, removing the suspending agent (31) by evaporation, and compressing the particles to form an electrically conducting and mechanically stable nanostructured porous film.
  • the process of WO 00/72373 enables the realization of the same solar cell performance with high pressure sintered nano- porous titanium dioxide layers as with conventional high temperature sintering. This finding was confirmed in 2000 by Pichot et al .
  • layers of nano-porous metal oxide semiconductors can be prepared with nano-particles prepared by a wet precipitation process on supports by a process involving preheating the nano-particles at a temperature of 250 to 600°C, applying a coating of these preheated nano-particles to the support and subjecting the coating to a pressure of 100 to 1000 bar, without the application of the high temperatures needed for conventional sintering of titanium dioxide nano-particles i.e. 300 to 550°C.
  • aspects of the present invention are realized by a process for preparing a layer of a nano-porous metal oxide semiconductor comprising the steps of: (i) providing metal oxide semiconductor nano-particles prepared by a wet precipitation process, (ii) heating said nano-particles at a temperature in the range of 250 to 600°C, (iii) preparing a dispersion of the heat-treated nano- particles from step (ii) , (iv) applying the dispersion of step (iii) to a support to produce a coating; and (v) subjecting said coating to a pressure in the range of 100 to 1000 bar at a temperature below 250°C.
  • An electrically conducting and mechanically stable nano-porous metal oxide semiconductor layer is thereby prepared.
  • aspects of the present invention are also realized by a layer of a nano-porous metal oxide semiconductor obtainable by the above- mentioned process.
  • a photovoltaic device comprising a layer of a nano-porous metal oxide semiconductor obtainable by 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 having an internal surface area of at least 5 m 2 /g and not more than 300 m7g.
  • 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.
  • 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 represents poly (3 , 4-ethylenedioxy- thiophene) .
  • PSS poly(styrene sulphonic acid) or poly (styrenesulphonate) .
  • a process for preparing a layer of a nano-porous metal oxide semiconductor comprising the steps of: (i) providing metal oxide semiconductor nano-particles prepared by a wet precipitation process, (ii) heating said nano-particles at a temperature in the range of 250 to 600°C, (iii) preparing a dispersion of the heat-treated nano- particles from step (ii) , (iv) applying the dispersion of step (iii) to a support to produce a coating; and (v) subjecting said coating to a pressure in the range of 100 to 1000 bar at a temperature below 250°C.
  • the metal oxide semiconductor is n-type.
  • the nano-porous metal oxide semiconductor has a band-gap of greater than 2.9 eV.
  • the nano-porous metal oxide semiconductor nano-particle have a mean number averaged particle size ⁇ 20 run.
  • the nano-porous metal oxide semiconductor 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.
  • the nano-porous metal oxide semiconductor is titanium dioxide and between 80 and 100% thereof has an anatase morphology.
  • the nano-porous metal oxide semiconductor is titanium dioxide and between 90 and 100% thereof has an anatase morphology.
  • the pretreatment temperature is in the range of 300 to 500°C.
  • the pretreatment temperature is in the range of 350 to 450°C.
  • the sintering pressure is in the range of 300 to 700 bar. According to an eleventh embodiment of the process, according to the present invention, the sintering pressure is in the range of 400 to 600 bar.
  • the process further comprises heating the coating subjected to pressure from step (v) at a temperature of 100 to 200°C.
  • the process further comprises heating the coating subjected to pressure from step (v) at a temperature of 125 to 170°C.
  • step (v) is carried out at a temperature above 0°C.
  • Step (ii) of the process, according to the present invention is carried out under the atmosphere and pressure necessary to obtain metal oxide nano-particles with semiconducting properties.
  • step (ii) is carried out at under an ambient atmosphere i.e. at the pertaining ambient pressure and under the pertaining ambient atmosphere.
  • the sintering pressure for a particular layer of a nano-porous metal oxide semiconductor is dependent upon the nature of the support, a sintering pressure of 300 to 700 bar being suitable for glass supports and sintering pressures up to 1000 bar being suitable for polymeric film supports.
  • 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.
  • Step (i) of the process, according to the present invention provides metal oxide semiconductor nano-particles prepared by a wet precipitation process.
  • the expression "wet precipitation process” distinguishes the metal oxide semiconductor nano-particles used in the process, according to the present invention, from those prepared by non-wet chemical processes such as flame pyrolysis processes such as that operated by Degussa.
  • Suitable titanium dioxide nano-particles produced by wet precipitation processes include:
  • the layer contains at least one spectral sensitizer for the nano-porous metal oxide semiconductor selected from the group consisting of metal chalcogenide nano-particles with a band-gap between 1.5 and 2.9 eV, organic dyes, and metallo- organic dyes .
  • the layer contains at least one spectral sensitizer for the nano-porous metal oxide semiconductor selected from the group consisting of metal oxides, metal sulphides and metal selenides.
  • the layer contains at least one spectral sensitizer for the nano-porous metal oxide semiconductor which is a metal sulphide.
  • the layer contains at least one spectral sensitizer for the nano-porous metal oxide semiconductor 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.
  • EP-A 1 176 646, herein incorporated by reference, 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 , Ag 2 S, InAs, CdTe, CdSe or HgTe or solid solutions of HgTe/CdTe or HgSe/CdSe.
  • Suitable spectrally sensitizing organic dyes include cyanine, merocyanine and anionic dyes, such as:
  • Suitable spectrally sensitizing metallo-organic dyes allowing for broad absorption of the solar spectrum include:
  • Ruthenium 470 a ruthenium tris (2,2'bipyridyl-4, 4' dicarboxylato) dye from Solaronix ruthenium (II) dichloride
  • Ruthenium 505 a ruthenium cis-bis (isocyanato) (2,2 'bipyridyl-4, 4' dye from Solaronix dicarboxylato) ruthenium (II)
  • Ruthenium 535 a ruthenium cis-bis (isothiocyanato)bis (2,2' -bipyridyl- dye from Solaronix 4,4' -dicarboxylato) -ruthenium (II)
  • Ruthenium 535 bis-TBA cis-bis (isothiocyanato)bis (2, 2 ' -bipyridyl- ruthenium dye from 4,4' -dicarboxylato) -ruthenium(II) bis- Solaronix tetrabutylammonium
  • Ruthenium 620 Black Dye, (anion only) tris (isothiocyanato) - a ruthenium dye from ruthenium (II) -2 , 2 ' : 6 ' , 2 " -terpyridine-4 , 4 ' , 4 " • Solaronix tricarboxylic acid
  • 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 layer configuration, according to the present invention.
  • Suitable polymeric films are poly(ethylene terephthalate) , pol (ethylene naphthalate) , polystyrene, polyethersulphone, polycarbonate, polyacrylate, polyamide, polyimides, cellulosetriacetate, polyolefins and poly (vinyl chloride) , optionally treated by corona discharge or glow discharge or provided with a subbing layer.
  • a photovoltaic device comprising a layer of a nano-porous metal oxide semiconductor obtainable by a process, according to the present invention.
  • Photovoltaic devices comprising a layer of a nano-porous metal oxide semiconductor prepared by a process, according to the present invention, 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.
  • 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 (OMeTA
  • 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 materials.
  • 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 lo 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 layer of a nano-porous metal oxide semiconductor prepared by a process, according to the present invention 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,
  • Dispersion 2 P25 a nano-sized titanium dioxide with a mean particle size of 40 25 nm and a specific surface of 55 m 2 /g from DEGUSSA was mixed with ethanol to give a 25% by weight of solid material and then treated ultrasonically to produce Dispersion 1.
  • Dispersion 2 P25 a nano-sized titanium dioxide with a mean particle size of 40 25 nm and a specific surface of 55 m 2 /g from DEGUSSA was mixed with ethanol to give a 25% by weight of solid material and then treated ultrasonically to produce Dispersion 1.
  • Dispersion 2 P25 a nano-sized titanium dioxide with a mean particle size of 40 25 nm and a specific surface of 55 m 2 /g from DEGUSSA was mixed with ethanol to give a 25% by weight of solid material and then treated ultrasonically to produce Dispersion 1.
  • Dispersion 2
  • Ti-NanoxideTM T from SOLARONIX having a mean particle size of
  • dispersion 3 a specific surface of 120 m2/g and containing 11% by weight of titanium oxide is called dispersion 3.
  • Dispersions 2 or 3 were dried in a rotary evaporator, ground, spread on a sheet of glass and heated at 200, 350, 400 or 450°C, depending on the experiment, for 30 minutes in a rotary tube furnace. The resulting powders were then cooled, ground again and converted into a paste by adding water, ethanol and 10-20 UL of nitric acid. To prevent material loss, the paste was diluted with water and put in a bottle. The excess liquid was evaporated at a temperature of 100-150°C prior to use.
  • Photovoltaic devices 1-46 were prepared by the following procedure:
  • 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 2) with the titanium dioxide colloidal dispersion with or without dilution with ethanol depending upon the desired layer thickness.
  • the layer thickness was determined mechanically with a diamond-tipped probe (Perthometer) and interferometry and are given in Tables 1 to 4.
  • Coated glass electrodes with the nano titanium dioxide dispersions were heated at 450°C for 30 minutes, then cooled to
  • Coated glass electrodes with the nano titanium dioxide dispersions were first dried at 110°C for 5 minutes, then, after cooling to room temperature (25°C) , a pressure of 500 bars was applied for 5 seconds. These pressure sintered coatings were then heated to 110-150°C, then immediately immersed in a 2 x 10 "4 M
  • the back electrode (consisting of Sn0 2 :F glass (Pilkington TEC15/3) evaporated with platinum to catalyze reduction of the electrolyte)
  • electrolyte was added through holes in the counter electrode.
  • the electrolyte used was a solution of 0.5 M Lil, 0.05 M I 2 and 0.4 M t-butylpyridine in acetonitrile and was injected into the cell during cell assembly. The holes were then sealed with Surlyn® and a thin piece of glass. Conductive tape was attached on both long sides of the cell to collect the electricity during measurement. Measurements were performed immediately after cell assembly.
  • 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 electricity generated was recorded with a Type 2400 SMU Keithley electrometer.
  • the most relevant parameter for these experiments was the short circuit current (I sc ) which is given for the examples in Tables 1 to 4.
  • the open circuit voltage was in all cases almost the same (0.640 to 0.680), which was also the case for the fill factor (FF) (0.5 to 0.6). Cells with lower open circuit voltages than 0.640 V or fill factors lower than 0.5 were not considered.
  • the short circuit currents, l ac for photovoltaic devices incorporating front electrodes with sintered titanium dioxide layers prepared with Dispersion 2 are given in Table 2 together with information concerning the heat pretreatment of Dispersion 2 and the sintering conditions used.
  • the short circuit currents, I so device parameters for the photovoltaic devices of reference Devices 2, 8 and 9 are also included in Table 2 by way of reference.
  • Dispersion 2 pretreated at 450°C was used, according to the present invention, instead of Dispersion 2 without pretreatment, then short circuit currents comparable with that observed with Device 14 incorporating a high temperature sintered layer of Dispersion 2 without pretreatment were observed, whether high pressure sintering was used, as in the case of Device 17, or high temperature sintering was used, as in the case of Device 16.
  • Table 3 gives the results obtained with further photovoltaic devices with front electrodes prepared with Dispersion 2 for different titanium dioxide layer thicknesses, together with information regarding the heat pretreatment and sintering conditions.
  • the short circuit currents, I sc , device parameters for the photovoltaic devices of comparative Device 14 and invention device 17 are also included in Table 3 for the sake of comparison.
  • the short circuit currents, I sc for photovoltaic devices with front electrodes incorporating sintered titanium dioxide layers prepared with Dispersion 3 sintered at different pretreatment temperatures are given in Table 4 together with information concerning the heat treatment of the Dispersion and of the sintering conditions used.
  • the short circuit currents, I sc device parameters for the photovoltaic devices of comparative Devices 14 and 15 are also included in Table 4 for the sake of comparison. Table 4 :
  • Photovoltaic devices were prepared as described for Device numbers 46 to 49 except that the titanium dioxide layer thicknesses were different and that after sintering the titanium dioxide layers were heated for 5 minutes at 150°C before drying.
  • the short circuit currents obtained with these devices, Devices 50 to 52, together with details over their titanium dioxide layer thickness and processing are given in Table 5 together with the results for Devices 46 to 49.
  • 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)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
EP02769994A 2002-09-12 2002-09-12 Process for preparing nano-porous metal oxide semiconductor layers Withdrawn EP1540679A1 (en)

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WO1995029509A1 (en) * 1994-04-20 1995-11-02 Valence Technology, Inc. Method for producing low porosity electrode
DE19839454A1 (de) * 1998-08-29 2000-03-02 Agfa Gevaert Ag Aufzeichnungsmaterial aus einem Träger und einer auf einer Oberfläche des Trägers aufgebrachten Keramikschicht
SE514600C2 (sv) * 1999-05-25 2001-03-19 Forskarpatent I Uppsala Ab Metod för tillverkning av nanostrukturerade tunnfilmselektroder
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