US20030062082A1 - Photovoltaic device and method for preparing the same - Google Patents

Photovoltaic device and method for preparing the same Download PDF

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Publication number
US20030062082A1
US20030062082A1 US10/234,488 US23448802A US2003062082A1 US 20030062082 A1 US20030062082 A1 US 20030062082A1 US 23448802 A US23448802 A US 23448802A US 2003062082 A1 US2003062082 A1 US 2003062082A1
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Prior art keywords
photovoltaic device
layer
evaporated
oxide layer
semiconductor oxide
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Abandoned
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US10/234,488
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English (en)
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Tzenka Miteva
Gabriele Nelles
Akio Yasuda
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Sony Deutschland GmbH
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Sony International Europe GmbH
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Assigned to SONY INTERNATIONAL (EUROPE) GMBH reassignment SONY INTERNATIONAL (EUROPE) GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MITEVA, TZENKA, YASUDA, AKIO, NELLES, GABRIELE
Publication of US20030062082A1 publication Critical patent/US20030062082A1/en
Priority to US11/211,358 priority Critical patent/US8003884B2/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/30—Doping active layers, e.g. electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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 photovoltaic device, especially a solar cell, and methods for the preparation of such devices.
  • a dye sensitized semiconductor-electrolyte solar cell was developed by Grätzel et al consisting of titanium dioxide nanoparticles with a ruthenium complex adsorbed on the surface of an iodine-iodide electrolyte as disclosed in WO91/16719.
  • the ruthenium complex acts as a sensitizer, which absorbs light and injects an electron into titanium dioxide; the dye is then regenerated by electron transfer from the iodine-iodide redox couple.
  • the advantage of such a solar cell results from the fact that no crystalline semiconductors have to be used anymore while already providing conversion efficiencies of light into electrical energy of up to 12% (O'Reagan, B. et al; Nature (1991), 353, page 737).
  • a problem with organic devices having a solid conjugated semiconductor is that all interfaces are sources for energy potential losses, for example by introducing serial resistances. Lots of efforts are done to modify the interfaces, for example in solar cells. Desired effects of such modifications are to avoid diffusion of atoms from the back-electrode material into the layer system, to enhance charge carrier transfer or to block it, to fill pinholes to avoid undesired recombination, and to influence the workfunction of electrodes in the desired direction, etc.
  • a major factor limiting the energy conversion efficiencies in such devices is the low photo-voltage, wherein charge recombination at the TiO 2 -electrolyte interface plays a significant role.
  • Interface modifications that were done, e.g. in hybrid solar cells, are for example: Nb 2 O 5 coating of TiO 2 porous layer to match the energy levels, as disclosed in Guo, P. et al., Thin Solid Films 351, 1999, 290; introducing the adsorption of benzoic acid derivatives to improve the charge injection in heterojunctions for dye sensitized solid state solar cells, as disclosed in Krüger et al., Advanced Materials 12, 2000, 447.
  • a further object of the present invention is to provide a method for preparation of a device showing photovoltaic characteristic, more particularly of a device exhibiting the favorable characteristics as defined above.
  • the first object of the invention is solved by a photovoltaic device comprising at least one layer containing evaporated fluoride and/or acetate.
  • the evaporated fluoride is an alkali or alkaline earth metal fluoride.
  • the evaporated acetate is an alkali metal acetate.
  • the device further comprises a semiconductor oxide layer sensitized with a dye, preferably a ruthenium complex dye.
  • the evaporated layer containing fluoride and/or acetates is evaporated on top of the semiconductor oxide layer and/or on top of a layer of the hole transport material and/or on top of a transparent conductive electrode.
  • the semiconductor oxide layer is titanium dioxide.
  • the evaporated layer has a thickness of about 0.5 to about 30 nm, preferably about 0.5 to about 15 nm.
  • the evaporated layer which is evaporated on the semiconductor oxide layer comprises lithium fluoride having a thickness of about 5 nm, and the evaporated layer which is evaporated on the hole transport material comprises cesium fluoride having a thickness of about 15 nm.
  • the hole transport material is represented by formula (I)
  • R in each occurrence is dependently selected from hexyl and ethylhexyl within the wt % ratio of hexyl:ethylhexyl being about 40:about 60, or represented by formula (II)
  • the semiconductor oxide layer is porous.
  • the semiconductor oxide layer comprises nanoparticles, preferably nanoparticles of TiO 2 .
  • the second object of the invention is solved by a method for preparing of a photovoltaic device, preferably a device according to the invention, comprising the step of evaporating at least one layer containing fluoride and/or acetate on at least one layer of the photovoltaic device.
  • the method preferably comprises the additional steps of:
  • At least one layer comprising fluoride and/or acetate is evaporated on top of a dye sensitized semiconductor oxide layer and/or on top of a layer of the hole transport material and/or on top of a transparent conductive electrode.
  • the method further comprises at least one of the following steps:
  • the object of the invention is also solved by a solar cell according to claim 18 and especially to a solar cell comprising an organic and/or polymer blend, and/or organic and/or polymeric semiconductor bilayer structure containing solar cells.
  • the solar cell is an organic or polymeric solid state hybrid solar cell.
  • devices according to the present invention show higher energy conversion efficiencies than the ones without fluoride and/or acetate layer.
  • open circuit voltage V OC and fill factor FF were increased, which yield to the higher efficiency.
  • evaporation of an additional layer is a simpler technique than a wet-chemical process.
  • hole transport materials already disclosed in the application, other compounds are as well suitable and may comprise linear as well as branched or starburst structures and polymers carrying long alkoxy groups as sidechains or in the backbone.
  • Such hole transport materials are in principle disclosed in EP 0 901 175 A2, the disclosure of which is incorporated herein by reference.
  • TDAB hole transport material
  • any of the known TDAB may be—further—derivatized such as by using substitutions such as alkoxy, alkyl, silyl at the end-standing phenyl rings which could be in p-, m- and opposition mono-, bi-, or tri-substituted.
  • substitutions such as alkoxy, alkyl, silyl at the end-standing phenyl rings which could be in p-, m- and opposition mono-, bi-, or tri-substituted.
  • the guidelines disclosed herein apply not only to single organic hole transport materials but also to mixtures thereof.
  • dopant all agents may be used which are suitable to be used in organic devices and which are known to a person skilled in the art.
  • a preferable dopant is, for example, oxidized hole transport material and doping agents disclosed in EP 111 493.3, the disclosure of which is incorporated herein by reference.
  • Dyes which can be used for sensitizing a semiconductor oxide layer are known in the art such as EP 0 887 817 A2 the disclosure of which is incorporated herein by reference.
  • dyes to be used are also Ru(II) dyes.
  • the dyes used to sensitize the semiconductor oxide layer may be attached thereto by chemisorption, adsorption or by any other suitable ways.
  • the semiconductor oxide layer used in the inventive device is preferably a nanoparticulate one.
  • the material can be a metal oxide and more preferably an oxide of the transition metals or of the elements of the third main group, the fourth, fifth and sixth subgroup of the periodic system. These and any other suitable materials are known to those skilled in the art and are, e.g. disclosed in EP 0 333 641 A1, the disclosure of which is incorporated herein by reference.
  • the semiconductor oxide layer material may exhibit a porous structure. Due to this porosity the surface area is increased which allows for a bigger amount of sensitizing dye to be immobilized on the semiconductor oxide layer and thus for an increased performance of the device. Additionally, the rough surface allows the trapping of light which is reflected from the surface and directed to neighbouring surface which in turn increases the yield of the light.
  • HTM concentration (5-60 mg/substrate)
  • oxidized HTM ca. 0.2 mol % of hole conductor concentration, to be added from a solution in acetonitrile
  • Salt Li((CF 3 SO 2 ) 2 N), (ca. 9 mol %)
  • FIG. 1 shows an embodiment of a basic design of an inventive photovoltaic device, namely the hybrid solar cell, described above;
  • FIG. 2 shows the I/V curve of the first type of solar cell according to the present invention and having 5 nm LiF at TiO 2 /dye interface and 15 nm CsF at HTM/back electrode interface evaporated.
  • FIG. 3 shows an embodiment of a basic design of an inventive photovoltaic device, comprising an organic and/or polymer blend, and/or organic and/or polymeric semiconductor bilayer structure.
  • a solar cell according to the present invention is built of a substrate, followed by a FTO layer, a blocking TiO 2 layer, dye-sensitized TiO 2 with a fluoride layer, hole transport material (HTM), a second fluoride layer, and a gold (Au) layer.
  • FIG. 3 shows an embodiment of a basic design of an inventive photovoltaic device, comprising a substrate, a TCO-layer, a counter-electrode, especially an Al electrode as well as two fluoride layers, enclosing a blend or bilayer of p- or n-type organic/or polymeric semiconductors.

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  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)
US10/234,488 2001-09-04 2002-09-03 Photovoltaic device and method for preparing the same Abandoned US20030062082A1 (en)

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EP01121178A EP1289028B1 (de) 2001-09-04 2001-09-04 Solarzelle und Herstellungsmethode
EP01121178.6 2001-09-04

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EP (2) EP1289028B1 (de)
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KR (1) KR20030020854A (de)
AU (1) AU2002300573B2 (de)
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