[go: up one dir, main page]

WO2010059498A2 - Cellule photovoltaïque sensibilisée par colorant - Google Patents

Cellule photovoltaïque sensibilisée par colorant Download PDF

Info

Publication number
WO2010059498A2
WO2010059498A2 PCT/US2009/064156 US2009064156W WO2010059498A2 WO 2010059498 A2 WO2010059498 A2 WO 2010059498A2 US 2009064156 W US2009064156 W US 2009064156W WO 2010059498 A2 WO2010059498 A2 WO 2010059498A2
Authority
WO
WIPO (PCT)
Prior art keywords
article
layer
active layer
photovoltaically active
nanoparticles
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.)
Ceased
Application number
PCT/US2009/064156
Other languages
English (en)
Other versions
WO2010059498A3 (fr
Inventor
Christoph Brabec
Kethinni G. Chittibabu
David Waller
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.)
Konarka Technologies Inc
Original Assignee
Konarka Technologies Inc
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 Konarka Technologies Inc filed Critical Konarka Technologies Inc
Priority to JP2011536457A priority Critical patent/JP5580325B2/ja
Publication of WO2010059498A2 publication Critical patent/WO2010059498A2/fr
Publication of WO2010059498A3 publication Critical patent/WO2010059498A3/fr
Priority to US13/106,068 priority patent/US20110220188A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This disclosure relates to dye sensitized photovoltaic cells (e.g., hybrid dye sensitized photovoltaic cells), as well as related components, systems, and methods.
  • dye sensitized photovoltaic cells e.g., hybrid dye sensitized photovoltaic cells
  • Photovoltaic cells sometimes called solar cells, can convert light, such as sunlight, into electrical energy.
  • Atypical photovoltaic cell includes a photovoltaically active material disposed between two electrodes. Generally, light passes through one or both of the electrodes to interact with the photovoltaically active material, which generates excited electrons that are eventually transferred to an external load in the form of electrical energy.
  • One type of photovoltaic cell is a dye sensitized solar cell (DSSC).
  • this disclosure features articles that include first and second electrodes, and a photovoltaically active layer between the first and second electrodes.
  • the photovoltaically active layer includes titanium oxide nanoparticles. The nanoparticles have an average particle diameter of at least about 20 run.
  • the article is configured as a solid state photovoltaic cell.
  • this disclosure features articles that include first and second electrodes, and a photovoltaically active layer between the first and second electrodes.
  • the photovoltaically active layer includes a metal oxide, a dye, and a proton scavenger.
  • the article is configured as a photovoltaic cell.
  • this disclosure features methods that include (1) disposing a dye composition onto a first layer including metal oxide nanoparticles to form a photovoltaically active layer, and (2) disposing additional components onto the photovoltaically active layer to provide a photovoltaic cell.
  • the dye composition contains a dye and a solvent.
  • the solvent can include an alcohol.
  • Embodiments can include one or more of the following features.
  • the nanoparticles can have an average particle diameter of at most 100 nm (e.g., between about 25 nm and about 60 nm).
  • the photo voltaically active layer can have a thickness of at least about 500 nm and/or at most about 10 microns.
  • the photovoltaically active layer can further include a dye.
  • the dye has a molar extinction coefficient of at least about 8,000.
  • the photovoltaically active layer and/or dye composition can further include a proton scavenger.
  • the proton scavenger includes a guanidino-alkanoic acid (e.g., a guanidino-butyric acid).
  • the articles described above can further include a hole carrier layer between the photovoltaically active layer and the second electrode.
  • the hole carrier layer can include a material selected from the group consisting of spiro-MeO-TAD, triaryl amines, polythiophenes, polyanilines, polycarbazoles, polyvinylcarbazoles, polyphenylenes, polyphenylvinylenes, polysilanes, polythienylenevinylenes, polyisothianaphthanenes, and copolymers or mixtures thereof.
  • the hole carrier layer can include poly(3-hexylthiophene) (P3HT) or poly(3,4-ethylenedioxythiophene) (PEDOT).
  • the articles described above can further include a hole blocking layer between the photovoltaically active layer and the first electrode.
  • the hole blocking layer can include LiF, metal oxides, or amines.
  • the hole blocking layer includes a non-porous metal oxide (e.g., TiO 2 ) layer.
  • the articles described above can be configured as a solid state photovoltaic cell.
  • the metal oxide in the photovoltaically active layer can be in the form of nanoparticles.
  • the metal oxide nanoparticles can be formed from a composition containing a base and a precursor of the metal oxide.
  • the metal oxide is selected from the group consisting of titanium oxides, tin oxides, niobium oxides, tungsten oxides, zinc oxides, zirconium oxides, lanthanum oxides, tantalum oxides, terbium oxides, and combinations thereof.
  • the alcohol can include a primary alcohol, a secondary alcohol, or a tertiary alcohol.
  • the alcohol can include methanol, ethanol, propanol, or 2-methoxy propanol.
  • the solvent can further include a cyclic ester (e.g., ⁇ -butyrolactone).
  • the dye composition can further include a proton scavenger (e.g., a guanidino-alkanoic acid).
  • a proton scavenger e.g., a guanidino-alkanoic acid
  • the first layer can be supported by a first electrode.
  • the methods described above can further include disposing a hole blocking layer between the first electrode and the first layer prior to disposing the dye composition.
  • Disposing additional components can include disposing a hole carrier layer onto the photovoltaically active layer. In some embodiments, disposing additional components further includes disposing a second electrode onto the hole carrier layer. Embodiments can include one or more of the following advantages.
  • a photovoltaically active layer containing nanoparticles with a relatively large average diameter (e.g., larger than about 20 ⁇ m) or a photovoltaically active layer containing nanoparticles and having a relatively large porosity (e.g., at least about 40%) can facilitate filling of solid state hole carrier materials into pores between nanoparticles, thereby improving separation of the charges generated in the photovoltaically active layer.
  • Such nanoparticles can also improve electron diffusion due to reduced particle-particle interfaces, which limit electron conduction.
  • forming a dye monolayer on metal oxide nanoparticles in a photovoltaically active layer can prevent direct contact between the metal oxide (e.g., TiO 2 ) with a conjugated semiconductor polymer in a hole carrier layer, thereby reducing the recombination between electrons and holes generated in a photovoltaically active layer during use and increasing the open circuit voltage and efficiency of a photovoltaic cell.
  • the metal oxide e.g., TiO 2
  • a proton scavenger facilitates removing protons on the metal oxide surface, thereby reducing electron-hole recombination rates and increase the open circuit voltage and efficiency of a photovoltaic cell.
  • FIG. 1 is a cross-sectional view of a solid state dye sensitized photovoltaic cell.
  • FIG. 2 is a schematic of a system containing multiple photovoltaic cells electrically connected in series.
  • FIG. 3 is a schematic of a system containing multiple photovoltaic cells electrically connected in parallel.
  • FIG.1 shows a dye sensitized photovoltaic cell 100 having a substrate 110, an electrode 120, a hole blocking layer 130, a photovoltaically active layer 140, a hole carrier layer 150, an electrode 160, a substrate 170, an electrical connection between electrodes 120 and 160, and an external load electrically connected to photovoltaic cell 100 via electrodes 120 and 160.
  • Photovoltaically active layer 140 can include a semiconductor material (e.g., TiO 2 particles) and a dye associated with the semiconductor material.
  • photovoltaically active layer 140 includes an inorganic semiconductor (e.g., dye sensitized TiO 2 ) and hole carrier layer 150 includes an organic hole carrier material (e.g., P3HT or PEDOT).
  • Such a photovoltaic cell is generally known as an organic-inorganic hybrid solar cell.
  • photovoltaic cell 100 is a solid state photovoltaic cell (e.g., a solid state dye sensitized photovoltaic cell).
  • Photovoltaically active layer 140 generally includes a semiconductor material and a dye associated with the semiconductor material.
  • the semiconductor material includes metal oxides, such as titanium oxides, tin oxides, niobium oxides, tungsten oxides, zinc oxides, zirconium oxides, lanthanum oxides, tantalum oxides, terbium oxides, or combinations thereof.
  • the metal oxides include a titanium oxide, a zinc stannate, or a niobium titanate.
  • Other suitable semiconductor materials have been described in, for example, commonly-owned co-pending U.S. Application Publication Nos. 2006-0130895 and 2007-0224464, the contents of which are hereby incorporated by reference.
  • the metal oxide is in the form of nanoparticles.
  • the nanoparticles can have an average diameter of at least about 20 run (e.g., at least about 25 nm, at least about 30 nm, or at least about 50 nm) and/or at most about 100 nm (e.g., at most about 80 nm or at most about 60 nm).
  • the nanoparticles can have an average diameter between about 25 nm and about 60 nm.
  • nanoparticles with a relatively large average diameter can facilitate filling of solid state hole carrier materials into pores between nanoparticles, thereby improving separation of the charges generated in photo voltaically active layer 140.
  • nanoparticles with a relatively large average diameter e.g., larger than about 20 nm
  • nanoparticles with a relatively large average diameter can improve electron diffusion due to reduced particle-particle interfaces, which limit electron conduction.
  • nanoparticles with an average diameter larger than a certain size may reduce the surface area of the nanoparticles and thereby reducing the short circuit current.
  • the metal oxide nanoparticles can be formed by treating (e.g., heating) a precursor composition containing a precursor of the metal oxide and an acid or a base.
  • a precursor composition containing a precursor of the metal oxide and an acid or a base Preferably, the metal oxide nanoparticles are formed from the precursor composition containing a base.
  • the precursor composition can further include a solvent (e.g., water or an aqueous solvent).
  • the base can include an amine, such as tetraalkyl ammonium hydroxide (e.g., tetramethyl ammonium hydroxide (TMAH), tetraethyl ammonium hydroxide, or tetra cetyl ammonium hydroxide), triethanolamine, diethylenetriamine, ethylenediamine, trimethylenediamine, or triethylenetetramine.
  • TMAH tetramethyl ammonium hydroxide
  • TMAH tetraethyl ammonium hydroxide
  • TMAH tetra cetyl ammonium hydroxide
  • triethanolamine diethylenetriamine
  • ethylenediamine trimethylenediamine
  • triethylenetetramine triethylenetetramine.
  • the composition contains at least about 0.05 M (e.g., at least about 0.2 M, at least about 0.5 M, or at least about 1 M) and/or at most about 2 M (e.g., at most about 1.5 M, at most about 1
  • the morphology of metal oxide nanoparticles can be affected by the pH of the precursor composition. For example, when triethanolamine is used as a base, the morphology of TiO 2 nanoparticles can change from cuboidal to ellipsoidal at pH above about 11.
  • the morphology OfTiO 2 nanoparticles can change into ellipsoidal at pH above about 9.5.
  • metal oxide nanoparticles are formed in the presence of an acid, the nature and amount of the acid would not affect the morphology of the nanoparticles.
  • metal oxide nanoparticles with a large length to width aspect ratio could facilitate electron transport, thereby increasing the efficiency of a photovoltaic cell.
  • metal oxide nanoparticles in photovoltaically active layer 140 has a length to width aspect ratio of at least about 1 (e.g., at least about 5, at least about 10, least about 50, at least about 100, or at least about 500).
  • the metal oxide precursor can include a material selected from the group consisting of metal alkoxides, polymeric derivatives of metal alkoxides, metal diketonates, metal salts, and combinations thereof.
  • metal alkoxides include titanium alkoxides (e.g., titanium tetraisopropoxide), tungsten alkoxides, zinc alkoxides, or zirconium alkoxides.
  • Exemplary polymeric derivatives of metal alkoxides include poly(n-butyl titanate).
  • Exemplary metal diketonates include titanium oxyacetylacetonate or titanium bis(ethyl acetoacetato)diisopropoxide.
  • Exemplary metal salts include metal halides (e.g., titanium tetrachloride), metal bromides, metal fluorides, metal sulfates, or metal nitrates.
  • the precursor composition contains at least about 0.1 M (e.g., at least about 0.2 M, at least about 0.3 M, or at least about 0.5 M) and/or at most about 2 M (e.g., at most about 1 M, at most about 0.7 M, or at most about 0.5 M) of the metal oxide precursor.
  • Methods of forming the precursor composition can vary as desired, hi some embodiments, the precursor composition can be formed by adding an aqueous solution of a metal oxide precursor (e.g., titanium tetraisopropoxide) into an aqueous solution of a base (e.g., TMAH).
  • a metal oxide precursor e.g., titanium tetraisopropoxide
  • the precursor composition After the precursor composition is formed, it can undergo thermal treatment to form metal oxide nanoparticles.
  • the composition can first be heated to an intermediate temperature from about 60°C to about 100°C (e.g., about 80°C) for a sufficient period of time (e.g., from about 7 hours to 9 hours, such as 8 hours) to form a peptized sol.
  • an intermediate temperature from about 60°C to about 100°C (e.g., about 80°C) for a sufficient period of time (e.g., from about 7 hours to 9 hours, such as 8 hours) to form a peptized sol.
  • a sufficient period of time e.g., from about 7 hours to 9 hours, such as 8 hours
  • the peptized sol can be further heated at a high temperature from about 200°C to about 250°C (e.g., about 23O 0 C) for a sufficient period of time (e.g., from about 10 hours to 14 hours, such as 12 hours) to form metal oxide nanoparticles with a desired average particle size (e.g., an average diameter between about 25 nm and about 60 nm).
  • a high temperature from about 200°C to about 250°C (e.g., about 23O 0 C) for a sufficient period of time (e.g., from about 10 hours to 14 hours, such as 12 hours) to form metal oxide nanoparticles with a desired average particle size (e.g., an average diameter between about 25 nm and about 60 nm).
  • a desired average particle size e.g., an average diameter between about 25 nm and about 60 nm.
  • the metal oxide nanoparticles in photovoltaically active layer 140 can be interconnected, for example, by high temperature sintering or by a reactive polymeric linking agent, such as poly(n-butyl titanate).
  • a polymeric linking agent can enable the fabrication of an interconnected nanoparticle layer at relatively low temperatures (e.g., less than about 300°C) and in some embodiments at room temperature.
  • the polymeric linking agent can be added to the precursor composition.
  • the relatively low temperature interconnection process can be amenable to continuous manufacturing processes (e.g., a roll-to-roll manufacturing process) using polymer substrates.
  • the precursor composition can be converted into a printable paste.
  • the printable paste can be obtained by concentrating the precursor composition containing the metal oxide nanoparticles formed above and then adding an additive (e.g., terpineol and/or ethyl cellulose) to the concentrated composition.
  • the printable paste can then be applied onto another layer in a photovoltaic cell (e.g., an electrode or a hole blocking layer) to form photovoltaically active layer 140.
  • the printable paste can be applied by a liquid- based coating processing discussed in more detail below.
  • photovoltaically active layer 140 is a porous layer containing metal oxide nanoparticles.
  • photovoltaically active layer 140 can have a porosity of at least about 40% (e.g., at least about 50% or at least about 60%) and/or at most about 70% (e.g., at most about 60% or at most about 50%).
  • a photovoltaically active layer containing nanoparticles and having a relatively large porosity e.g., larger than about 40%
  • the semiconductor material in photoactive layer 140 is generally photosensitized by at least a dye (e.g., two or more dyes).
  • the dye facilitates conversion of incident light into electricity to produce the desired photovoltaic effect. It is believed that a dye absorbs incident light, resulting in the excitation of electrons in the dye. The excited electrons are then transferred from the excitation levels of the dye into a conduction band of the semiconductor material. This electron transfer results in an effective separation of charge and the desired photovoltaic effect. Accordingly, the electrons in the conduction band of the semiconductor material are made available to drive an external load.
  • the dyes suitable for use in photovoltaic cell 100 can have a molar extinction coefficient ( ⁇ ) of at least about 8,000 (e.g., at least about 10,000, at least about 13,000, at least 14,000, at least about 15,000, at least about 18,000, at least about 20,000, at least about 23,000, at least about 25,000, at least about 28,000, and at least about 30,000) at a given wavelength (e.g., A m3x ) within the visible light spectrum.
  • a molar extinction coefficient e.g., at least about 10,000, at least about 13,000, at least 14,000, at least about 15,000, at least about 18,000, at least about 20,000, at least about 23,000, at least about 25,000, at least about 28,000, and at least about 30,000
  • a given wavelength e.g., A m3x
  • suitable dyes include black dyes (e.g., tris(isothiocyanato)-ruthenium (II)- 2,2':6',2"-terpyridine-4,4',4"-tricarboxylic acid, tris-tetrabutylammonium salt), orange dyes (e.g., tris(2,2'-bipyridyl-4,4'-dicarboxylato) ruthenium (II) dichloride, purple dyes (e.g., cis- bis(isothiocyanato)bis-(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium (H)), red dyes (e.g., an eosin), green dyes (e.g., a merocyanine) and blue dyes (e.g., a cyanine).
  • black dyes e.g., tris(isothiocyanato)-ruthenium (
  • black dyes have also been described in commonly-owned co-pending U.S. Application No. 12/236,150, the contents of which are hereby incorporated by reference.
  • additional dyes include anthocyanines, porphyrins, phthalocyanines, squarates, and certain metal-containing dyes.
  • Commercially available dyes and dyes reported in the literature include Z907, Kl 9, K51, K60, K68, K77, K78, N3, and N719. Combinations of dyes can also be used within a given region so that a given region can include two or more (e.g., two, three, four, five, six, seven) different dyes.
  • the dye can be sorbed (e.g., chemisorbed and/or physisorbed) onto the semiconductor material.
  • the dye can be selected, for example, based on its ability to absorb photons in a wavelength range of operation (e.g., within the visible spectrum), its ability to produce free electrons (or holes) in a conduction band of the nanoparticles, its effectiveness in complexing with or sorbing to the nanoparticles, and/or its color.
  • the dye can be sorbed onto the semiconductor material (e.g., a metal oxide) by immersing an intermediate article (e.g., an article containing a substrate, an electrode, a hole blocking layer, and a semiconductor material) into a dye composition for a sufficient period of time (e.g., at least about 12 hours).
  • the dye composition can form a monolayer on metal oxide nanoparticles.
  • forming a dye monolayer can prevent direct contact between the metal oxide (e.g., TiO 2 ) with a conjugated semiconductor polymer in hole carrier layer 150, thereby reducing recombination between electrons and holes generated in photovoltaically active layer 140 during use and increasing the open circuit voltage and efficiency of photovoltaic cell 100.
  • the metal oxide e.g., TiO 2
  • a conjugated semiconductor polymer in hole carrier layer 150 thereby reducing recombination between electrons and holes generated in photovoltaically active layer 140 during use and increasing the open circuit voltage and efficiency of photovoltaic cell 100.
  • the dye composition includes a solvent, such as an organic solvent.
  • suitable solvents for the photosensitizing agent composition include alcohols (e.g., primary alcohols, secondary alcohols, or tertiary alcohols). Examples of suitable alcohols include methanol, ethanol, propanol, and 2-methoxy propanol.
  • the solvent can further include a cyclic ester, such as a ⁇ -butyrolactone.
  • a solvent e.g., an alcohol
  • a solubility of at most about 8 niM at room temperature facilitates formation of a dye monolayer on the metal oxide layer, thereby reducing the recombination between electrons and holes generated in photovoltaically active layer 140 during use.
  • suitable solvents are those in which the dye has a solubility of at most about 8 mM (e.g., at most about 1 mM) at room temperature.
  • the dye composition further includes a proton scavenger.
  • proton scavenger refers to any agent that is capable of binding to a proton.
  • An example of a proton scavenger is a guanidino-alkanoic acid (e.g., 3-guanidino-propionic acid or guanidine-butyric acid).
  • a proton scavenger facilitates removing protons on the metal oxide surface, thereby reducing electron- hole recombination rates and increase the open circuit voltage and efficiency of photovoltaic cell 100.
  • photovoltaically active layer 140 can generally vary as desired.
  • photovoltaically active layer 140 can have a thickness of at least about 500 run (e.g., at least about 1 micron, at least about 2 microns, or at least about 5 microns) and/or at most about 10 microns (e.g., at most about 8 microns, at most about 6 microns, or at most about 4 microns).
  • photovoltaically active layer 140 having a relative large thickness e.g., larger than about 2 microns
  • photovoltaically active layer 140 having a relative large thickness can have improved light absorption, thereby improving the current density and performance of a photovoltaic cell.
  • photovoltaically active layer 140 having a relative large thickness e.g., larger than about 2 microns
  • a thickness larger than a certain size may exhibit reduced charge separation as the thickness can be larger than the diffusion length of the charges generated by the photovoltaic cell during use.
  • photovoltaically active layer 140 can be formed by applying a composition containing metal oxide nanoparticles onto a substrate by a liquid-based coating process.
  • liquid-based coating process refers to a process that uses a liquid-based coating composition.
  • liquid-based coating compositions include solutions, dispersions, and suspensions (e.g., printable pastes).
  • the liquid-based coating process can be carried out by using at least one of the following processes: solution coating, ink jet printing, spin coating, dip coating, knife coating, bar coating, spray coating, roller coating, slot coating, gravure coating, flexographic printing, or screen printing.
  • solution coating ink jet printing, spin coating, dip coating, knife coating, bar coating, spray coating, roller coating, slot coating, gravure coating, flexographic printing, or screen printing.
  • roll-to-roll processes have been described in, for example, commonly-owned co-pending U.S. Application Publication No. 2005-0263179, the contents of which are hereby incorporated by reference.
  • the liquid-based coating process can be carried out either at room temperature or at an elevated temperature (e.g., at least about 50°C, at least about 100°C, at least about 200°C, or at least about 300°C).
  • the temperature can be adjusted depending on various factors, such as the coating process and the coating composition used.
  • nanoparticles in the coated paste can be sintered at a high temperature (e.g., at least about 300°C) to form interconnected nanoparticles.
  • the sintering process can be carried out at a lower temperature (e.g., below about 300 0 C).
  • a polymeric linking agent e.g., poly(n-butyl titanate)
  • photo voltaically active layer 140 can be prepared as follows: Metal oxide nanoparticles (e.g., TiO 2 nanoparticles) can be formed by treating (e.g., heating) a composition (e.g., a dispersion) containing a precursor of the metal oxide (e.g., a titanium alkoxide such as titanium tetraisopropoxide) in the presence of an acid or a base.
  • a composition e.g., a dispersion
  • a precursor of the metal oxide e.g., a titanium alkoxide such as titanium tetraisopropoxide
  • the composition typically includes a solvent (e.g., such as water or an aqueous solvent). After the treatment, the composition can be converted into a printable paste.
  • the printable paste can be obtained by concentrating the composition containing the metal oxide nanoparticles formed above and then adding an additive (e.g., terpineol and/or ethyl cellulose) to the concentrated composition.
  • the printable paste can then be coated onto another layer in a photovoltaic cell (e.g., an electrode or a hole blocking layer) and then be treated (e.g., by high temperature sintering) to form a porous layer containing interconnected metal oxide nanoparticles.
  • Photo voltaically active layer 140 can subsequently be formed by adding a dye composition (e.g., containing a dye, a solvent, and a proton scavenger) to the porous layer to sensitize the metal oxide nanoparticles.
  • a dye composition e.g., containing a dye, a solvent, and a proton scavenger
  • substrate 110 is generally formed of a transparent material.
  • a transparent material is a material which, at the thickness used in a photovoltaic cell 100, transmits at least about 60% (e.g., at least about 70%, at least about 75%, at least about 80%, or at least about 85%) of incident light at a wavelength or a range of wavelengths used during operation of the photovoltaic cell.
  • Exemplary materials from which substrate 110 can be formed include glass, polyethylene terephthalates, polyimides, polyethylene naphthalates, polymeric hydrocarbons, cellulosic polymers, polycarbonates, polyamides, polyethers, and polyether ketones.
  • the polymer can be a fluorinated polymer.
  • combinations of polymeric materials are used, hi certain embodiments, different regions of substrate 110 can be formed of different materials.
  • substrate 110 can be flexible, semi-rigid or rigid (e.g., glass), hi some embodiments, substrate 110 has a flexural modulus of less than about 5,000 megaPascals (e.g., less than about 1,000 megaPascals or less than about 500 megaPascals). In certain embodiments, different regions of substrate 110 can be flexible, semi-rigid, or inflexible (e.g., one or more regions flexible and one or more different regions semi-rigid, one or more regions flexible and one or more different regions inflexible).
  • substrate 110 is at least about one micron (e.g., at least about five microns or at least about 10 microns) thick and/or at most about 1,000 microns (e.g., at most about 500 microns thick, at most about 300 microns thick, at most about 200 microns thick, at most about 100 microns, or at most about 50 microns) thick.
  • microns e.g., at least about five microns or at least about 10 microns
  • 1,000 microns e.g., at most about 500 microns thick, at most about 300 microns thick, at most about 200 microns thick, at most about 100 microns, or at most about 50 microns
  • substrate 110 can be colored or non-colored. In some embodiments, one or more portions of substrate 110 is/are colored while one or more different portions of substrate 110 is/are non-colored.
  • Substrate 110 can have one planar surface (e.g., the surface on which light impinges), two planar surfaces (e.g., the surface on which light impinges and the opposite surface), or no planar surfaces.
  • Anon-planar surface of substrate 110 can, for example, be curved or stepped.
  • a non-planar surface of substrate 110 is patterned (e.g., having patterned steps to form a Fresnel lens, a lenticular lens or a lenticular prism).
  • Electrode 120 is generally formed of an electrically conductive material.
  • Exemplary electrically conductive materials include electrically conductive metals, electrically conductive alloys, electrically conductive polymers, and electrically conductive metal oxides.
  • Exemplary electrically conductive metals include gold, silver, copper, aluminum, nickel, palladium, platinum, and titanium.
  • Exemplary electrically conductive alloys include stainless steel (e.g., 332 stainless steel, 316 stainless steel), alloys of gold, alloys of silver, alloys of copper, alloys of aluminum, alloys of nickel, alloys of palladium, alloys of platinum and alloys of titanium.
  • Exemplary electrically conducting polymers include polythiophenes (e.g., doped poly(3,4- ethylenedioxythiophene) (doped PEDOT)), polyanilines (e.g., doped polyanilines), polypyrroles (e.g., doped polypyrroles).
  • Exemplary electrically conducting metal oxides include indium tin oxide, fluorinated tin oxide, tin oxide and zinc oxide, hi some embodiments, combinations of electrically conductive materials are used.
  • electrode 120 can include a mesh electrode. Examples of mesh electrodes are described in co-pending U.S. Patent Application Publication Nos. 2004-0187911 and 2006-0090791, the entire contents of which are hereby incorporated by reference.
  • photovoltaic cell 100 can include a hole blocking layer 130.
  • the hole blocking layer is generally formed of a material that, at the thickness used in photovoltaic cell 100, transports electrons to electrode 120 and substantially blocks the transport of holes to electrode 120.
  • materials from which the hole blocking layer can be formed include LiF, metal oxides (e.g., zinc oxide, titanium oxide), and amines (e.g., primary, secondary, or tertiary amines). Examples of amines suitable for use in a hole blocking layer have been described, for example, in commonly-owned co-pending U.S. Application Publication No. 2008- 0264488, the entire contents of which are hereby incorporated by reference.
  • hole blocking layer 130 is at least 0.02 micron (e.g., at least about 0.03 micron, at least about 0.04 micron, or at least about 0.05 micron) thick and/or at most about 0.5 micron (e.g., at most about 0.4 micron, at most about 0.3 micron, at most about 0.2 micron, or at most about 0.1 micron) thick.
  • hole blocking layer 130 can be a non-porous layer. In such embodiments, hole blocking layer 130 can be a compact layer with a small thickness (e.g., less than about 0.1 microns).
  • Hole carrier layer 150 is generally formed of a material that, at the thickness used in photovoltaic cell 100, transports holes to electrode 160 and substantially blocks the transport of electrons to electrode 160.
  • materials from which layer 150 can be formed include spiro-MeO-TAD, triaryl amines, polythiophenes (e.g., PEDOT doped with poly(styrene- sulfonate)), polyanilines, polycarbazoles, polyvinylcarbazoles, polyphenylenes, polyphenylvinylenes, polysilanes, polythienylenevinylenes, polyisothianaphthanenes, and copolymers thereof.
  • hole carrier layer 150 can include combinations of hole carrier materials.
  • the thickness of hole carrier layer 150 (i.e., the distance between the surface of hole carrier layer 150 in contact with photoactive layer 140 and the surface of electrode 160 in contact with hole carrier layer 150) can vary as desired.
  • the thickness of hole carrier layer 150 is at least 0.01 micron (e.g., at least about 0.05 micron, at least about 0.1 micron, at least about 0.2 micron, at least about 0.3 micron, or at least about 0.5 micron) and/or at most about five microns (e.g., at most about three microns, at most about two microns, or at most about one micron).
  • the thickness of hole carrier layer 150 is from about 0.01 micron to about 0.5 micron.
  • Electrode 160 is generally formed of an electrically conductive material, such as one or more of the electrically conductive materials that can be used to form electrode 120 described above. In some embodiments, electrode 160 is formed of a combination of electrically conductive materials. In certain embodiments, electrode 160 can be formed of a mesh electrode.
  • each of electrode 120, hole blocking layer 130, hole carrier layer 150, and electrode 160 can be prepared by a liquid-based coating process, such as one of the processes described above.
  • the liquid-based coating process can be carried out by (1) mixing the nanoparticles with a solvent (e.g., an aqueous solvent or an anhydrous alcohol) to form a dispersion, (2) coating the dispersion onto a substrate, and (3) drying the coated dispersion.
  • a solvent e.g., an aqueous solvent or an anhydrous alcohol
  • a liquid-based coating process for preparing a layer containing inorganic metal oxide nanoparticles can be carried out by (1) dispersing a precursor (e.g., a titanium salt) in a suitable solvent (e.g., an anhydrous alcohol) to form a dispersion, (2) coating the dispersion on a photoactive layer, (3) hydrolyzing the dispersion to form an inorganic metal oxide nanoparticles layer (e.g., a titanium oxide nanoparticles layer), and (4) drying the inorganic metal oxide layer.
  • the liquid-based coating process can include a sol-gel process.
  • the liquid-based coating process used to prepare a layer containing an organic material can be the same as or different from that used to prepare a layer containing an inorganic material.
  • a layer e.g., one of layers 120, 130, 150, and 160
  • the liquid-based coating process can be carried out by mixing the organic material with a solvent (e.g., an organic solvent) to form a solution or a dispersion, coating the solution or dispersion on a substrate, and drying the coated solution or dispersion.
  • a solvent e.g., an organic solvent
  • Substrate 170 can be identical to or different from substrate 110. hi some embodiments, substrate 170 can be formed of one or more suitable polymers, such as the polymers used in substrate 110 described above.
  • photovoltaic cell 100 undergoes cycles of excitation, oxidation, and reduction that produce a flow of electrons across the external load. Specifically, incident light passes through at least one of substrates 110 and 170 and excites the dye in photovoltaically active layer 140. The excited dye then injects electrons into the conduction band of the semiconductor material in photovoltaically layer active 140, which leaves the dye oxidized. The injected electrons flow through the semiconductor material and hole blocking layer 130, to electrode 120, then to the external load. After flowing through the external load, the electrons flow to electrode 160, hole carrier layer 150, and photovoltaically active layer 140, where the electrons reduce the oxidized dye molecules back to their neutral state. This cycle of excitation, oxidation, and reduction is repeated to provide continuous electrical energy to the external load.
  • incident light passes through at least one of substrates 110 and 170 and excites the dye in photovoltaically active layer 140.
  • the excited dye then injects electrons into the conduction band of the semiconductor material in photovoltaically layer active 140, which leaves
  • photovoltaic cell 100 includes a cathode as a bottom electrode and an anode as a top electrode.
  • photovoltaic cell 100 can include an anode as a bottom electrode and a cathode as a top electrode.
  • photovoltaic cell 100 can include the layers shown in FIG. 1 in a reverse order. In other words, photovoltaic cell 100 can include these layers from the bottom to the top in the following sequence: a substrate 170, an electrode 160, a hole carrier layer 150, a photoactive layer 140, a hole blocking layer 130, an electrode 120, and a substrate 110.
  • tandem photovoltaic cells have been described above, in some embodiments, the compositions and methods described herein can be used in tandem photovoltaic cells. Examples of tandem photovoltaic cells have been described in, for example, commonly-owned co-pending U.S. Application Publication Nos. 2007-0181179 and 2007-0246094, the entire contents of which are hereby incorporated by reference.
  • FIG. 2 is a schematic of a photovoltaic system 200 having a module 210 containing photovoltaic cells 220. Cells 220 are electrically connected in series, and system 200 is electrically connected to a load 230.
  • FIG. 3 is a schematic of a photovoltaic system 300 having a module 310 that contains photovoltaic cells 320. Cells 320 are electrically connected in parallel, and system 300 is electrically connected to a load 330.
  • some (e.g., all) of the photovoltaic cells in a photovoltaic system can have one or more common substrates.
  • some photovoltaic cells in a photovoltaic system are electrically connected in series, and some of the photovoltaic cells in the photovoltaic system are electrically connected in parallel.
  • photovoltaic cells have been described above, in some embodiments, the compositions and methods described herein can be used in other electronic devices and systems. For example, they can be used in field effect transistors, photodetectors (e.g., IR detectors), photovoltaic detectors, imaging devices (e.g., RGB imaging devices for cameras or medical imaging systems), light emitting diodes (LEDs) (e.g., organic LEDs or IR or near IRLEDs), lasing devices, conversion layers (e.g., layers that convert visible emission into IR emission), amplifiers and emitters for telecommunication (e.g., dopants for fibers), storage elements (e.g., holographic storage elements), and electrochromic devices (e.g., electrochromic displays).
  • field effect transistors e.g., photodetectors (e.g., IR detectors), photovoltaic detectors, imaging devices (e.g., RGB imaging devices for cameras or medical imaging systems), light emitting diodes (LEDs) (e
  • a first type of solid state dye sensitized solar cell was prepared as follows: A solution containing 0.5 M titanium tetra-isopropoxide in ethanol was spin-coated at 2,000 rpm onto a fluorinated tin oxide (FTO) coated glass slide, followed by sintering at 450 0 C for 5 minutes to form a compact titanium oxide layer with a thickness of about 30-100 nm, which served as an electron conducting hole blocking layer. An acidic colloid dispersion containing titanium oxide nanoparticles with an average diameter of about 20 nm was deposited onto the compact hole blocking layer, followed by sintering at 45O 0 C for 30 minutes.
  • FTO fluorinated tin oxide
  • the sintered film was treated with a solution containing 0.05 M TiCl 4 in water for 30 minutes at 65°C to improve necking between the nanoparticles and to reduce surface traps, followed by re-sintering at 45O 0 C for 2-5 minutes to form a porous titanium oxide nanoparticles layer with a thickness of about 2 microns.
  • the sintered porous titanium oxide nanoparticles layer was sensitized by a dye composition containing Z907 and a guanidinobutyric acid (GBA) to form a photovoltaically active layer.
  • a solution containing 1-5% poly(3-hexylthiophene) in chlorobenzne was deposited on the photovoltaically active layer to form a hole carrier layer.
  • a 50-100 nm of gold electrode was then vacuum evaporated on top of dried hole carrier layer.
  • a second type of SSDSSC was prepared by the same method described above except that the porous titanium oxide nanoparticles layer was prepared by mixing Showa Denko's F2
  • the SSDSSCs containing TiO 2 with an average diameter of about 60 nm exhibited significantly better performance compared to the SSDSSCs containing TiO 2 with an average diameter of about 20 nm.
  • the SSDSSCs were prepared in a manner similar to that of Example 1 except that an alkaline dispersion containing titanium oxide nanoparticles having an average diameter of about 30 nm was used to prepare the photovoltaically active layer. A SSDSSC containing no dye was used as a control. Each type of solar cells were replicated 3-6 times. The performance of the SSDSSCs was measured at simulated 1 sun light under AM 1.5 conditions. The average test results are summarized in Table 3 below. Table 3
  • the effect of a proton scavenger was determined by comparing the performance of SSDSSCs containing a GBA with that of SSDSSCs without a GBA.
  • the SSDSSCs were prepared in a manner similar to that of Example 1 except that an alkaline dispersion containing titanium oxide nanoparticles having an average diameter of about 30 nm was used to prepare the photovoltaically active layer. Each type of solar cells was replicated 4 or 5 times. The performance of the SSDSSCs was measured at simulated 1 sun light under AM 1.5 conditions. The test results are summarized in Tables 4 and 5 below.
  • the SSDSSCs containing a GBA exhibited better performance compared to the SSDSSCs without a GBA.
  • the effect of the dye solvent was determined by comparing the performance of SSDSSCs prepared by using DMF (a good solvent for the Z907 dye) as a dye solvent with that of SSDSSCs prepared by using a mixture of 2-methoxypropanol and a ⁇ -butyrolactone (a poor solvent for the Z907 dye) as a dye solvent.
  • the SSDSSCs were prepared in a manner similar to that of Example 1 except that an alkaline dispersion containing titanium oxide nanoparticles having an average diameter of about 30 nm was used to prepare the photo voltaically active layer. Each type of solar cells was replicated 3 or 5 times.
  • the performance of the SSDSSCs was measured at simulated 1 sun light under AM 1.5 conditions. The test results are summarized in Tables 6 and 7 below.
  • the SSDSSCs prepared by using 2-methoxypropanol and ⁇ - butyrolactone as a dye solvent exhibited significantly better performance compared to the SSDSSCs prepared by using DMF as a dye solvent.

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne des cellules photovoltaïques solides sensibilisées par colorant, ainsi que les composants, systèmes et procédés associés.
PCT/US2009/064156 2008-11-18 2009-11-12 Cellule photovoltaïque sensibilisée par colorant Ceased WO2010059498A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2011536457A JP5580325B2 (ja) 2008-11-18 2009-11-12 色素増感光電セル
US13/106,068 US20110220188A1 (en) 2008-11-18 2011-05-12 Dye Sensitized Photovoltaic Cell

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11564808P 2008-11-18 2008-11-18
US61/115,648 2008-11-18

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/106,068 Continuation US20110220188A1 (en) 2008-11-18 2011-05-12 Dye Sensitized Photovoltaic Cell

Publications (2)

Publication Number Publication Date
WO2010059498A2 true WO2010059498A2 (fr) 2010-05-27
WO2010059498A3 WO2010059498A3 (fr) 2011-01-06

Family

ID=42198749

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/064156 Ceased WO2010059498A2 (fr) 2008-11-18 2009-11-12 Cellule photovoltaïque sensibilisée par colorant

Country Status (3)

Country Link
US (1) US20110220188A1 (fr)
JP (1) JP5580325B2 (fr)
WO (1) WO2010059498A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012116824A (ja) * 2010-11-12 2012-06-21 Everlight Usa Inc 新規のルテニウム錯体及びそれを用いた光電部品
EP2509113A4 (fr) * 2010-12-09 2017-05-17 Korea Institute Of Machinery & Materials Batterie solaire transmettant sélectivement la lumière pourvue d'une unité de filtration de la lumière
NL2021912B1 (en) * 2018-11-01 2020-05-14 Univ Delft Tech Organically engineered solar cells

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2826070A4 (fr) * 2012-03-14 2015-11-04 Univ Princeton Hétérojonction silicium/oxyde de titane bloquant les trous pour les dispositifs photovoltaïques au silicium
US10727001B2 (en) * 2014-04-16 2020-07-28 Ricoh Company, Ltd. Photoelectric conversion element
WO2020107131A1 (fr) * 2018-11-28 2020-06-04 Pontificia Universidad Católica De Chile Accumulateurs rechargeables à l'énergie solaire, basés sur des polymères nanostructurés

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030109588A1 (en) * 1994-04-06 2003-06-12 Helmut Schmidt Method of producing homogeneous multicomponent dispersions and products derived from such dispersions
US20030192585A1 (en) * 2002-01-25 2003-10-16 Konarka Technologies, Inc. Photovoltaic cells incorporating rigid substrates
US7022910B2 (en) * 2002-03-29 2006-04-04 Konarka Technologies, Inc. Photovoltaic cells utilizing mesh electrodes
JP4937438B2 (ja) * 2000-07-19 2012-05-23 富士フイルム株式会社 光電変換用半導体、光電変換素子および光電池
WO2003038909A1 (fr) * 2001-10-31 2003-05-08 Sony Corporation Element de conversion photoelectrique et son procede de fabrication
CN101572193B (zh) * 2001-12-21 2011-08-03 索尼德国有限责任公司 聚合物凝胶混杂太阳能电池
JP4010170B2 (ja) * 2002-04-11 2007-11-21 ソニー株式会社 光電変換素子の製造方法
US20070204904A1 (en) * 2004-07-20 2007-09-06 Keith Brooks Photoactive layer containing macroparticles
EP1915785B1 (fr) * 2005-08-15 2016-04-20 Merck Patent GmbH Cellules photovoltaïques avec des interconnexions sur un circuit externe
EP1920468B1 (fr) * 2005-09-01 2014-02-26 Merck Patent GmbH Cellules photovoltaiques integrees a une diode en parallele
GB2432721B (en) * 2005-11-25 2011-06-22 Seiko Epson Corp Electrochemical cell structure and method of fabrication
JP4201035B2 (ja) * 2006-09-05 2008-12-24 セイコーエプソン株式会社 電池素子および電子機器
WO2008134492A1 (fr) * 2007-04-27 2008-11-06 Konarka Technologies, Inc. Cellules photovoltaïques organiques

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012116824A (ja) * 2010-11-12 2012-06-21 Everlight Usa Inc 新規のルテニウム錯体及びそれを用いた光電部品
EP2509113A4 (fr) * 2010-12-09 2017-05-17 Korea Institute Of Machinery & Materials Batterie solaire transmettant sélectivement la lumière pourvue d'une unité de filtration de la lumière
NL2021912B1 (en) * 2018-11-01 2020-05-14 Univ Delft Tech Organically engineered solar cells
WO2020091593A3 (fr) * 2018-11-01 2020-08-20 Technische Universiteit Delft Cellules solaires organiquement modifiées

Also Published As

Publication number Publication date
US20110220188A1 (en) 2011-09-15
JP2012509579A (ja) 2012-04-19
WO2010059498A3 (fr) 2011-01-06
JP5580325B2 (ja) 2014-08-27

Similar Documents

Publication Publication Date Title
JP5877149B2 (ja) 色素増感光電池のための金属基板
Martinson et al. Dynamics of charge transport and recombination in ZnO nanorod array dye-sensitized solar cells
KR101430139B1 (ko) 페로브스카이트 기반 메조다공 박막 태양전지 제조 기술
Fan et al. Effects of paste components on the properties of screen-printed porous TiO2 film for dye-sensitized solar cells
KR101553104B1 (ko) 광전 변환 소자, 광 전기 화학 전지, 광전 변환 소자용 색소 및 광전 변환 소자용 색소 용액
WO2015159192A1 (fr) Procédé de production d'une cellule solaire sensibilisée par colorant solide ou d'une cellule solaire à pérovskite
US20060225782A1 (en) Photovoltaic cells having a thermoelectric material
JP2012113942A (ja) 多層型光電変換素子およびその製造方法
US20230104362A1 (en) Dye sensitized photovoltaic cells
Suri et al. Photovoltaic performance of dye-sensitized ZnO solar cell based on Eosin-Y photosensitizer
US20110220188A1 (en) Dye Sensitized Photovoltaic Cell
Nursam et al. Analysis of Catalytic Material Effect on the Photovoltaic Properties of Monolithic Dye-sensitized Solar Cells
JP4454007B2 (ja) 導電性支持体及びこれを用いた光電変換素子
CN102013324A (zh) 染料敏化太阳能电池及其制造方法
Xie et al. Structural effects of core-modified porphyrins in dye-sensitized solar cells
KR20130044462A (ko) 염소 이온이 흡착된 이산화티탄 나노입자 및 이의 제조방법
Cosar et al. Photovoltaic performance of bifacial dye sensitized solar cell using chemically healed binary ionic liquid electrolyte solidified with SiO2 nanoparticles
Xie et al. Preparation of porous nanocrystalline TiO2 electrode by screen-printing technique
Sakamoto et al. Near-infrared light harvesting of upconverting Y2O3: Er3+ nanoparticles and their photovoltaic application
KR101585031B1 (ko) 광파장 변환 형광체를 포함하는 염료감응 태양전지
CN102136374A (zh) 染料敏化太阳能电池及其制造方法
Nazeeruddin et al. Mesoscopic Dye‐Sensitized Solar Cells
Kalyanasundaram Photochemical energy conversion
de Jong Emerging Solar Cell Technology: Advances in Solid-state Polymer Hybrid Dye-sensitized Solar Cells
Holliman et al. Rapid, low-temperature processing of dye-sensitized solar cells

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09752086

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 2011536457

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09752086

Country of ref document: EP

Kind code of ref document: A2