WO2011101993A1 - 太陽電池およびその製造方法 - Google Patents
太陽電池およびその製造方法 Download PDFInfo
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- WO2011101993A1 WO2011101993A1 PCT/JP2010/052652 JP2010052652W WO2011101993A1 WO 2011101993 A1 WO2011101993 A1 WO 2011101993A1 JP 2010052652 W JP2010052652 W JP 2010052652W WO 2011101993 A1 WO2011101993 A1 WO 2011101993A1
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- voltage
- photoelectric conversion
- type semiconductor
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- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
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- 229920000548 poly(silane) polymer Polymers 0.000 description 1
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- 150000004032 porphyrins Chemical class 0.000 description 1
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- 150000003219 pyrazolines Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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
- H10K30/35—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 comprising inorganic nanostructures, e.g. CdSe nanoparticles
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- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035272—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
- H01L31/03529—Shape of the potential jump barrier or surface barrier
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- H—ELECTRICITY
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- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
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- H10K30/80—Constructional details
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- H10K71/421—Thermal treatment, e.g. annealing in the presence of a solvent vapour using coherent electromagnetic radiation, e.g. laser annealing
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- 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
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- 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
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- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
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- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
- H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
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- 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
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- 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
- the present invention relates to a solar cell and a manufacturing method thereof.
- Organic thin-film solar cells are solar cells that use organic thin-film semiconductors that combine conductive polymers, fullerenes, and the like.
- Organic thin-film solar cells can be produced by a simpler method than solar cells based on inorganic materials, and have the advantage of low cost.
- the photoelectric conversion efficiency and life of the organic thin film solar cell have a problem that it is lower than that of a conventional inorganic solar cell. This is because organic semiconductors have many parameters that are difficult to control, such as the purity, molecular weight distribution, and orientation of the semiconductor material.
- Non-Patent Document 1 proposes a method of applying a DC voltage during heat treatment of an organic thin film solar cell element.
- the degree of improvement in photoelectric conversion efficiency by using this method is not so high.
- Patent Document 1 discloses a method for manufacturing an organic thin-film solar cell including an aging step in which a reverse bias voltage is applied to the photoelectric conversion layer. This method is intended to improve the photoelectric conversion efficiency by preventing a local short circuit between the anode and the cathode, but it cannot be said that the photoelectric conversion efficiency is sufficiently improved.
- An object of the present invention is to provide a solar cell with improved photoelectric conversion efficiency and a method for manufacturing the solar cell.
- a heterojunction photoelectric conversion layer including a p-type semiconductor and an n-type semiconductor is formed between a pair of electrodes that are spaced apart from each other, and the photoelectric conversion layer
- a solar cell is manufactured by performing thermal annealing while applying an AC voltage having a frequency of 0.01 kHz or more and less than 1 kHz to control a mixed state of the p-type semiconductor and the n-type semiconductor in the photoelectric conversion layer.
- a heterojunction type photoelectric conversion layer including a p-type semiconductor and an n-type semiconductor is formed between a pair of electrodes arranged apart from each other, and the photoelectric conversion layer
- thermal annealing is performed while applying a DC superimposed AC voltage in which a DC voltage is superimposed on an AC voltage, and the mixed state of the p-type semiconductor and the n-type semiconductor in the photoelectric conversion layer is controlled.
- the p-type semiconductor and the n-type semiconductor are each self-organized to form a microphase separation structure, and the self-organized p-type semiconductor and n-type semiconductor are perpendicular to the pair of electrodes.
- a solar cell manufactured by the method of claim 1 is provided, characterized in that the solar cells are oriented in the direction of and intertwined with each other.
- the present invention it is possible to provide a solar cell with improved photoelectric conversion efficiency and a method for manufacturing the solar cell.
- FIG. 1 is a cross-sectional view of a solar cell according to an embodiment.
- FIG. 2 is a cross-sectional view of a solar cell according to another embodiment.
- FIG. 3 is a conceptual diagram showing the structure of the photoelectric conversion layer of the solar cell according to the embodiment.
- FIG. 4 is a diagram for explaining an operation mechanism of a bulk heterojunction solar cell.
- FIG. 5 is a conceptual diagram of an apparatus that performs thermal annealing while applying a voltage.
- FIG. 6 is a graph comparing photoelectric conversion efficiencies of solar cells of Examples and Comparative Examples.
- FIG. 1 is a cross-sectional view of a solar cell according to an embodiment of the present invention.
- the solar cell shown in FIG. 1 includes a pair of electrodes (anode 11 and cathode 12) arranged apart from each other, and a photoelectric conversion layer 13 arranged between the electrodes 11 and 12, and these are substrates 10. It has a configuration arranged on top.
- a hole transport layer 14 is provided between the anode 11 and the photoelectric conversion layer 13.
- FIG. 2 is a cross-sectional view of a solar cell according to another embodiment of the present invention.
- the solar cell shown in FIG. 2 further includes an electron transport layer 15 between the cathode 12 and the photoelectric conversion layer 13.
- the solar cell according to the embodiment of the present invention is characterized in that an AC voltage is simultaneously applied when performing thermal annealing in the manufacturing stage.
- an AC voltage is simultaneously applied when performing thermal annealing in the manufacturing stage.
- a p-type semiconductor and an n-type semiconductor are uniformly dispersed in the photoelectric conversion layer.
- a path for transporting charges generated by photoexcitation to the electrode is not formed, so that the photoelectric conversion efficiency is significantly reduced.
- the semiconductor material is somewhat oriented due to the self-organizing action, and forms a path for carrying charges, which is incomplete.
- FIG. 3 is a conceptual diagram showing the structure of the photoelectric conversion layer of the solar cell of the present invention.
- FIG. 3 showing the structure when an AC voltage is applied during the thermal annealing, it can be seen that both the p-type semiconductor and the n-type semiconductor form a good transport path. In such a structure, it is possible to guide the carrier smoothly to the electrode. As a result, it is considered that the photoelectric conversion efficiency is improved.
- a DC superimposed AC voltage obtained by superimposing a DC voltage on an AC voltage may be used as the voltage to be applied.
- the photoelectric conversion efficiency tends to be further improved than when an AC voltage that does not superimpose a DC voltage is applied.
- the substrate 10 is for supporting other constituent members.
- the substrate 10 is preferably one that forms an electrode and does not deteriorate by heat or an organic solvent.
- Examples of the material of the substrate 10 include inorganic materials such as alkali-free glass and quartz glass, plastics such as polyethylene, PET, PEN, polyimide, polyamide, polyamideimide, liquid crystal polymer, and cycloolefin polymer, polymer film, SUS, and silicon. And the like, and the like.
- the substrate 10 is not particularly limited, whether it is transparent or opaque. However, when an opaque substrate is used, it is preferable that the electrode opposite to the substrate is transparent or translucent.
- the thickness of the substrate is not particularly limited as long as it has sufficient strength to support other components.
- the anode 11 is disposed on the substrate 10.
- the material of the anode 11 is not particularly limited as long as it has conductivity.
- a transparent or translucent conductive material is formed by vacuum deposition, sputtering, ion plating, plating, coating, or the like.
- the transparent or translucent electrode material include a conductive metal oxide film and a translucent metal thin film.
- a film made of conductive glass made of indium oxide, zinc oxide, tin oxide, or a composite thereof such as indium tin oxide (ITO), FTO, indium zinc oxide, etc. (NESA etc.), gold, platinum, silver, copper, etc. are used.
- ITO or FTO is preferable.
- an electrode material polyaniline and a derivative thereof, which is an organic conductive polymer, polythiophene and a derivative thereof, or the like may be used.
- the thickness of the anode 11 is preferably 30 to 300 nm in the case of ITO. If the thickness is less than 30 nm, the conductivity is lowered, the resistance is increased, and the photoelectric conversion efficiency is lowered. If it is thicker than 300 nm, ITO becomes inflexible and cracks when stress is applied.
- the sheet resistance of the anode 11 is preferably as low as possible, and is preferably 10 ⁇ / ⁇ or less.
- the anode 11 may be a single layer or may be a laminate of layers made of materials having different work functions.
- the hole transport layer 14 is arbitrarily disposed between the anode 11 and the photoelectric conversion layer 13.
- the function of the hole transport layer 14 is to level the unevenness of the lower electrode to prevent a short circuit of the solar cell element, to efficiently transport only holes, and to excitons generated near the interface of the photoelectric conversion layer 13. It is to prevent the disappearance of
- a polythiophene polymer such as PEDOT / PSS (poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonate)), or an organic conductive polymer such as polyaniline or polypyrrole is used. be able to.
- Baytron PH500 manufactured by Starck Co., Ltd. may be mentioned.
- the film thickness is preferably 20 to 100 nm. If it is too thin, the effect of preventing the lower electrode from being short-circuited is lost, and a short circuit occurs. If it is too thick, the film resistance increases and the generated current is limited, so that the light conversion efficiency decreases.
- the method for forming the hole transport layer 14 is not particularly limited as long as it is a method capable of forming a thin film, but it can be applied by, for example, a spin coating method. After applying the material of the hole transport layer 14 to a desired film thickness, it is heated and dried with a hot plate or the like. As the solution to be applied, one previously filtered with a filter may be used.
- the photoelectric conversion layer 13 is disposed between the anode 11 and the cathode 12.
- the solar cell according to the present invention is a heterojunction solar cell.
- a bulk heterojunction type solar cell is characterized in that a p-type semiconductor and an n-type semiconductor are mixed in a photoelectric conversion layer to form a micro layer separation structure.
- a mixed p-type semiconductor and n-type semiconductor form a pn junction having a nano-order size in the photoelectric conversion layer, and a current is obtained by utilizing photocharge separation generated at the junction surface.
- a p-type semiconductor is composed of a material having an electron donating property.
- the n-type semiconductor is made of a material having an electron accepting property.
- at least one of the p-type semiconductor and the n-type semiconductor may be an organic semiconductor.
- Examples of p-type organic semiconductors include polythiophene and derivatives thereof, polypyrrole and derivatives thereof, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof. , Polysiloxane derivatives having an aromatic amine in the side chain or main chain, polyaniline and derivatives thereof, phthalocyanine derivatives, porphyrin and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, and the like, These may be used in combination. These copolymers may be used, and examples thereof include a thiophene-fluorene copolymer, a phenylene ethynylene-phenylene vinylene copolymer, and the like.
- a preferred p-type organic semiconductor is polythiophene, which is a conductive polymer having ⁇ conjugation, and derivatives thereof.
- Polythiophene and its derivatives can ensure excellent stereoregularity and have relatively high solubility in a solvent.
- Polythiophene and derivatives thereof are not particularly limited as long as they are compounds having a thiophene skeleton.
- polythiophene and derivatives thereof include polyalkylthiophenes such as poly-3-methylthiophene, poly-3-butylthiophene, poly-3-hexylthiophene, poly-3-octylthiophene, poly-3-decylthiophene, and poly-3-dodecylthiophene
- Polyarylthiophenes such as poly-3-phenylthiophene and poly-3- (p-alkylphenylthiophene); poly-3-butylisothionaphthene, poly-3-hexylisothionaphthene, poly-3-octylisothionaphthene, poly-3- And polyalkylisothionaphthene such as decylisothionaphthene; polyethylenedioxythiophene and the like.
- These conductive polymers can be formed by applying a solution dissolved in a solvent. Therefore, there is an advantage that a large-area organic thin film solar cell can be manufactured at low cost with inexpensive equipment by a printing method or the like.
- fullerene and its derivatives are preferably used.
- the fullerene derivative used here is not particularly limited as long as it is a derivative having a fullerene skeleton. Specific examples include derivatives composed of C60, C70, C76, C78, C84, etc. as the basic skeleton.
- carbon atoms in the fullerene skeleton may be modified with an arbitrary functional group, and these functional groups may be bonded to each other to form a ring.
- Fullerene derivatives also include fullerene bonded polymers. A fullerene derivative having a functional group with high affinity for the solvent and high solubility in the solvent is preferred.
- Examples of the functional group in the fullerene derivative include hydrogen atom; hydroxyl group; halogen atom such as fluorine atom and chlorine atom; alkyl group such as methyl group and ethyl group; alkenyl group such as vinyl group; cyano group; methoxy group and ethoxy group.
- Alkoxy groups such as phenyl groups, aromatic hydrocarbon groups such as naphthyl groups, and aromatic heterocyclic groups such as thienyl groups and pyridyl groups.
- Specific examples include hydrogenated fullerenes such as C60H36 and C70H36, oxide fullerenes such as C60 and C70, and fullerene metal complexes.
- 60PCBM [6,6] -phenyl C61 butyric acid methyl ester
- 70PCBM [6,6] -phenyl C71 butyric acid methyl ester
- Fullerene C70 has high photocarrier generation efficiency and is suitable for use in organic thin-film solar cells.
- the mixing ratio of the n-type organic semiconductor and the p-type organic semiconductor in the photoelectric conversion layer is preferably such that the content of the n-type organic semiconductor is 30 to 70% by weight.
- the solvent used for the organic semiconductor include toluene, xylene, tetralin, decalin, mesitylene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene.
- Unsaturated hydrocarbon solvents such as, halogenated aromatic hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, chlorohexane, bromohexane, Halogenated saturated hydrocarbon solvents such as chlorocyclohexane and ethers such as tetrahydrofuran and tetrahydropyran. In particular, a halogen-based aromatic solvent is preferable. These solvents can be used alone or in combination.
- the electron transport layer 15 is arbitrarily disposed between the cathode 12 and the photoelectric conversion layer 13.
- a transparent or translucent material is formed by vacuum deposition, sputtering, ion plating, plating, coating, or the like.
- Electron transport layer materials include quinolines such as Alq 3 , phenanthroline derivatives such as BCP, oxadiazole derivatives such as BND, PBD and OXD, oxadiazole dimers, starburst oxadiazoles, triazole derivatives, Examples of the phenylquinoxaline derivative, silole derivative, and inorganic substance include alkali metals such as titanium oxide, fullerenes, and lithium fluoride, halides and oxides of alkaline earth metals.
- the appropriate film thickness of the electron transport layer 15 varies greatly depending on the material and needs to be adjusted, but is generally in the range of 0.1 nm to 100 nm.
- the film thickness When the film thickness is thinner than the above range, the hole blocking effect is reduced, so that the generated excitons are deactivated before dissociating into electrons and holes, and current cannot be efficiently extracted.
- the electron transport layer acts as a resistor and causes a voltage drop.
- the material temperature rises, and the organic layer is damaged and the performance deteriorates.
- the occupation time of the film forming apparatus becomes long, leading to an increase in cost.
- the cathode 12 is laminated on the photoelectric conversion layer 13 (or the electron transport layer 15).
- a conductive material is formed by vacuum deposition, sputtering, ion plating, plating, coating, or the like.
- the electrode material include a conductive metal thin film and a metal oxide film.
- the anode 11 is formed using a material having a high work function, it is preferable to use a material having a low work function for the cathode 12.
- the material having a low work function include alkali metals and alkaline earth metals. Specific examples include Li, In, Al, Ca, Mg, Sm, Tb, Yb, Zr, Na, K, Rb, Cs, Ba, and alloys thereof.
- the cathode 12 may be a single layer or may be a laminate of layers made of materials having different work functions.
- an alloy of one or more of the materials having a low work function with gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, or the like may be used.
- the alloy include a lithium-aluminum alloy, a lithium-magnesium alloy, a lithium-indium alloy, a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum alloy, an indium-silver alloy, and a calcium-aluminum alloy.
- the film thickness of the cathode 12 is 1 nm to 500 nm, preferably 10 nm to 300 nm.
- the film thickness is smaller than the above range, the resistance becomes too large and the generated charge cannot be sufficiently transmitted to the external circuit.
- the film thickness is large, the film formation of the cathode 12 takes a long time, so that the material temperature rises and the organic layer is damaged, and the performance deteriorates. Furthermore, since a large amount of material is used, the occupation time of the film forming apparatus becomes long, leading to an increase in cost.
- the solar cell element manufactured as described above is subjected to thermal annealing.
- the thermal annealing is performed by rapidly heating the substrate to a predetermined temperature by a heating device such as a hot plate and continuing this for an arbitrary time.
- an AC voltage is simultaneously applied to the element.
- the voltage is applied by connecting the output of a power amplifier capable of generating an arbitrary waveform to the anode and cathode of the manufactured element by a signal from a frequency generator.
- Set parameters such as output voltage, frequency, duty ratio, and offset value, and apply voltage to the element.
- the substrate After the thermal annealing treatment for the specified time is completed, the substrate is moved to a metal plate or the like and cooled. After cooling, the applied bias is cut off, and this processing step is completed.
- the applied bias is cut in a state where the substrate temperature is high, the molecular movement of the organic semiconductor material is active, so that the oriented semiconductor layer returns to the original non-arranged state. Therefore, it is preferable to cut the applied bias after the substrate is cooled.
- Heating is preferably performed at 70 to 170 ° C.
- the temperature is lower than 70 ° C.
- the molecules in the photoelectric conversion layer are difficult to move and cannot be sufficiently oriented, so that the photoelectric conversion efficiency decreases.
- temperature exceeds 170 degreeC, the molecular motion in a photoelectric converting layer will become intense too much, and a molecule
- the time for thermal annealing is preferably 10 seconds to 30 minutes. By performing for 10 seconds or more, heat is sufficiently transmitted to the element substrate, the photoelectric conversion layer reaches a predetermined temperature, and an improvement in photoelectric conversion efficiency is observed. On the other hand, if it is carried out for 30 minutes or more, the polymer in the element is deteriorated by heat, so that the photoelectric conversion efficiency is considered to be lowered.
- the frequency of the alternating voltage to be applied is preferably 0.01 kHz or more and less than 1 kHz.
- the frequency is 0.01 kHz or more, it is preferable in that the orientation of the semiconductor material by the application of voltage is promoted and the photoelectric conversion efficiency is improved.
- the frequency is set to 1 kHz or more, the frequency component acts like a DC (direct current) component, thereby reducing the efficiency.
- the duty ratio of forward bias and reverse bias of the applied AC voltage is preferably 1: 1 to 25: 1.
- the duty ratio here is the ratio of the time for applying the forward bias voltage to the time for applying the reverse bias voltage.
- the forward bias is a case where a positive voltage is applied to the anode side
- the reverse bias is a case where a negative voltage is applied to the anode side.
- the reverse bias ratio is large, it is presumed that the photoelectric conversion efficiency is lowered by inhibiting the orientation of the semiconductor material.
- the ratio of the forward bias exceeds the above range, the frequency component acts like a DC component, thereby reducing the photoelectric conversion efficiency.
- the voltage value Vac of the AC voltage to be applied is preferably in the range of 0.5 to 30 Vp-p.
- the applied voltage is 0.5 Vp-p or more, the orientation of the semiconductor material by the application of the voltage is promoted, and the photoelectric conversion efficiency is improved.
- the applied voltage is 30 Vp-p or less, a short circuit due to the voltage being too high does not occur, which is preferable in terms of photoelectric conversion efficiency.
- the applied voltage is expressed by the formula 2.5 ⁇ 10 3 [V / mm] ⁇ Vac / L ⁇ 2 ⁇ 10 5 [V / mm] when converted into the electric field strength with the distance between the anode and the cathode being L. It is preferable that the value satisfies the above.
- a DC superimposed AC voltage obtained by superimposing a DC voltage on the AC voltage as described above may be used as a voltage to be applied during thermal annealing.
- the superimposed DC voltage is preferably -8 to 10V. This is because when the absolute value of the DC voltage is increased, a short circuit of the element may occur and the photoelectric conversion efficiency may be reduced.
- the frequency is preferably 0.01 kHz or more and less than 1 kHz. The reason is the same as in the case where only an AC voltage is applied.
- sealing process Finally, a sealing process is performed to protect the element from oxygen and moisture, and the extraction electrode is taken out from the positive and negative electrodes to form a solar cell. Sealing is performed using glass, metal plate, or inorganic or metal (silica, titania, zirconia, silicon nitride, boron nitride, Al, etc.) on the surface using thermosetting or UV curable epoxy resin as a fixing agent. This is done by protecting the surface with a resin film (PET, PEN, PI, EVOH, CO, EVA, PC, PES, etc.). Furthermore, the lifetime of the element can be expected to improve by putting a desiccant or an oxygen absorbent in the sealed space.
- a resin film PET, PEN, PI, EVOH, CO, EVA, PC, PES, etc.
- the organic electroluminescence device having the configuration in which the anode, the photoelectric conversion layer, and the cathode are disposed on the substrate has been described.
- the cathode, the photoelectric conversion layer, and the anode may be disposed on the substrate.
- FIG. 4 is a diagram for explaining the operation mechanism of a bulk heterojunction solar cell.
- the photoelectric conversion process of an organic thin-film solar cell includes: a) a process in which organic molecules absorb light to generate excitons, b) a process of exciton migration and diffusion, c) a process of exciton charge separation, d) It can be roughly divided into the process of charge transport to both poles.
- step a excitons are generated by absorption of light by the donor or acceptor. Let this generation efficiency be ⁇ 1.
- the generated excitons move to the p / n junction surface by diffusion. This diffusion efficiency is assumed to be ⁇ 2. Since excitons have a lifetime, they can move only about the diffusion length.
- step c) excitons that have reached the p / n junction are separated into electrons and holes. The efficiency of exciton separation is ⁇ 3.
- step d each optical carrier is transported through the p / n material to the electrode and taken out to an external circuit. This transport efficiency is assumed to be ⁇ 4.
- the external extraction efficiency of the generated carriers for the irradiated photons can be expressed by the following equation. This value corresponds to the quantum efficiency of the solar cell.
- ⁇ EQE ⁇ 1, ⁇ 2, ⁇ 3, ⁇ 4.
- Example 1 shows an example in which an organic thin-film solar cell is manufactured by applying an AC voltage during thermal annealing.
- the solid content of the organic semiconductor used as a photoelectric converting layer was prepared. 50 parts by weight of p-type organic semiconductor P3HT (poly-3-hexylthiophene: Plexcore (registered trademark) OS2100 manufactured by Aldrich) and 70-PCBM ([6,6] -phenyl C71 butyric acid methyl ester: SOLENNE, which is an n-type organic semiconductor) 50 parts by weight of 70PCBM fullerene 99% manufactured by the company were mixed.
- P3HT poly-3-hexylthiophene: Plexcore (registered trademark) OS2100 manufactured by Aldrich
- 70-PCBM [6,6] -phenyl C71 butyric acid methyl ester: SOLENNE, which is an n-type organic semiconductor
- the substrate was a glass substrate having a size of 20 mm ⁇ 20 mm and a thickness of 0.7 mm.
- An ITO transparent conductive layer having a thickness of 140 nm was deposited on this glass substrate by a sputtering method, and an ITO glass substrate obtained by patterning the ITO portion into a rectangular shape of 3.2 mm ⁇ 20 mm by a photolithography method was obtained.
- This substrate was ultrasonically cleaned with pure water containing 1% of a surfactant (NCW1001 manufactured by Wako Pure Chemical Industries) for 5 minutes, and then washed with flowing pure water for 15 minutes. Furthermore, after ultrasonically washing with acetone for 5 minutes and ultrasonically washing with IPA for 5 minutes, it was dried in a 120 ° C. constant temperature bath for 60 minutes. Thereafter, the substrate was UV-treated for 10 minutes to make the surface hydrophilic.
- a surfactant NCW1001 manufactured by Wako Pure Chemical Industries
- PEDOT / PSS aqueous solution Poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonate) manufactured by Starck Co., Ltd.
- a hole transport layer on the glass substrate with ITO prepared above, trade name Baytron PH500.
- a PEDOT / PSS aqueous solution used what was previously filtered with the 0.1 micrometer filter.
- a coating solution K serving as a photoelectric conversion layer was dropped on the hole transport layer, and a 100 nm-thick photoelectric conversion layer was formed by a spin coating method.
- an aluminum layer was formed as a cathode by an evaporation method using a vacuum evaporation apparatus.
- the cathode pattern mask had a rectangular slit with a width of 3.2 mm, and was arranged so that the ITO layer and the slit intersected. Therefore, the area of the organic thin film solar cell element is the area of this intersecting portion, and is 0.1024 cm 2 (3.2 mm ⁇ 3.2 mm). Evacuation was performed until the degree of vacuum became 3 ⁇ 10 ⁇ 6 torr, and an Al wire was deposited to a thickness of 80 nm by a resistance heating method.
- FIG. 5 shows a conceptual diagram of an apparatus that performs thermal annealing while applying a voltage.
- a power amplifier 21 is connected to the anode and cathode of the element.
- a hot plate was used as the heating device 20. It is desirable to heat the element substrate so that the heating unit is in direct contact with the element body so that heat is easily transmitted to the element body.
- the waveform was generated by the waveform generator 22 and output from the power amplifier 21.
- a forward bias was applied when a positive voltage was applied to the anode side. Conversely, when a negative voltage is applied to the anode side, a reverse bias is applied.
- the device was annealed on a hot plate at 150 ° C. for 10 minutes while applying a voltage with a power source that generates a sine wave having a voltage of AC 10 Vp-p and a frequency of 0.5 kHz. After the element was cooled on the metal plate, the voltage application was stopped.
- the substrate after annealing was sealed by adhering a sealing glass whose center was cut with an epoxy resin.
- the extraction electrode was taken out from the positive and negative electrodes to obtain an organic thin film solar cell.
- photoelectric conversion efficiency (eta) was measured using the electrical output measuring apparatus (Maki Seisakusho Co., Ltd.).
- the measurement light source is a solar simulator attached to the apparatus, and has an output with an irradiation illuminance of 100 mW / cm 2 .
- the IV characteristics due to the electronic load were measured to determine the photoelectric conversion efficiency.
- the calculated photoelectric conversion efficiency was 3.67%.
- Example 2 An organic thin-film solar cell was fabricated in the same manner as in Example 1 except that the applied voltage was a DC superimposed AC voltage in which DC + 4V was superimposed on AC10Vp-p. The photoelectric conversion efficiency was calculated in the same manner as in Example 1, and it was 4.45%.
- Example 1 An organic thin film solar cell was produced in the same manner as in Example 1 except that only the heat treatment was performed without applying a voltage. The photoelectric conversion efficiency was calculated in the same manner as in Example 1, and it was 3.11%.
- Example 2 An organic thin film solar cell was produced in the same manner as in Example 1 except that a DC voltage of -5 V was applied instead of the AC voltage. The photoelectric conversion efficiency was calculated in the same manner as in Example 1, and it was 3.19%.
- Example 3 An organic thin film solar cell was produced in the same manner as in Example 1 except that a DC voltage +3 V was applied instead of the AC voltage. The photoelectric conversion efficiency was calculated in the same manner as in Example 1, and it was 3.32%.
- the photoelectric conversion efficiency was improved as compared with the case where the voltage was not applied.
- the photoelectric conversion efficiency was greatly improved when an AC voltage was applied, compared to when a DC voltage was applied.
- the improvement in photoelectric conversion efficiency when applying a DC superimposed AC voltage was most remarkable.
- Test Example 1 Examination of optimum frequency range
- the optimum frequency range of the applied AC voltage was examined.
- the frequency of the alternating voltage to apply was changed, the organic thin film solar cell was produced as described in Example 1, and the photoelectric conversion efficiency was compared.
- the results are shown in Table 1.
- the applied voltage was fixed at AC 10 Vp-p.
- Test Example 2 Examination of optimum range of voltage value
- the optimum range of AC voltage to be applied was examined.
- the value of the alternating voltage to apply was changed, the organic thin film solar cell was produced as described in Example 1, and the photoelectric conversion efficiency was compared.
- the results are shown in Table 2.
- the frequency of the voltage was fixed at 0.5 kHz (sine wave).
- the photoelectric conversion efficiency was improved.
- the thickness of the organic layer is 150 nm (PEDOT / PSS 50 nm + photoelectric conversion layer 100 nm), it is in the range of 3.3 ⁇ 10 3 to 2.0 ⁇ 10 5 [V / mm] in terms of electric field strength.
- Test Example 4 Examination of optimum range of annealing temperature
- the optimum range of heat treatment temperature (annealing temperature) during thermal annealing was investigated.
- Organic thin film solar cells were prepared as described in Example 1 by changing the annealing temperature, and the photoelectric conversion efficiencies were compared. The results are shown in Table 4.
- the applied voltage was fixed at AC 10 Vp-p, and the voltage frequency was fixed at 0.5 kHz.
- the annealing temperature up to 40 ° C. was not significantly different from the conversion efficiency without heat treatment.
- the annealing temperature was 70 to 170 ° C., the photoelectric conversion efficiency was improved.
- the efficiency of the annealing process was about 2% up to 5 seconds, but an efficiency of about 3% was observed when annealing was performed for 10 seconds or more.
- the highest photoelectric conversion efficiency was obtained in the range of 10 to 30 minutes. From the above results, it can be said that the optimum range of the annealing time is in the range of 10 seconds to 30 minutes.
- the photoelectric conversion efficiency is improved.
- a DC superimposed AC voltage in which a large DC voltage is superimposed on the minus side is applied, the element tends to be easily destroyed.
- a DC superimposed AC voltage in which a positive DC voltage is superimposed tends to have a larger contribution to the improvement of photoelectric conversion efficiency.
- Test example 7 Examination of optimum frequency of DC superimposed AC current
- the optimum value of the frequency was examined in the case of applying the DC superimposed AC voltage in the thermal annealing process.
- Organic thin film solar cells were produced as described in Example 2 by changing the frequency of the DC superimposed AC voltage, and the photoelectric conversion efficiency was compared. The results are shown in Table 7.
- the applied voltage was fixed to AC 10 Vp-p, and the superimposed DC voltage was fixed to +4 V.
- SYMBOLS 1 P-type semiconductor, 2 ... N-type semiconductor, 10 ... Substrate, 11 ... Anode, 12 ... Cathode, 13 ... Photoelectric conversion layer, 14 ... Hole transport layer, 15 ... Electron transport layer, 20 ... Heating device, 21 ... Power amplifier, 22 ... Waveform generator.
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Abstract
Description
基板10は、他の構成部材を支持するためのものである。この基板10は、電極を形成し、熱や有機溶剤によって変質しないものが好ましい。基板10の材料としては、例えば、無アルカリガラス、石英ガラス等の無機材料、ポリエチレン、PET、PEN、ポリイミド、ポリアミド、ポリアミドイミド、液晶ポリマー、シクロオレフィンポリマー等のプラスチック、高分子フィルム、SUS、シリコン等の金属基板等が挙げられる。基板10は、透明なものであっても不透明なものであっても特に限定されるものではない。しかし不透明な基板を使用する場合、基板とは反対側の電極が透明または半透明であることが好ましい。基板の厚さは、その他の構成部材を支持するために十分な強度があれば、特に限定されない。
陽極11は、基板10の上に配置する。陽極11の材料としては、導電性を有するものであれば特に限定されない。通常は、透明または半透明の導電性を有する材料を、真空蒸着法、スパッタリング法、イオンプレーティング法、メッキ法、塗布法等で成膜する。透明または半透明の電極材料としては、導電性の金属酸化物膜、半透明の金属薄膜等が挙げられる。具体的には、酸化インジウム、酸化亜鉛、酸化スズ、およびそれらの複合体であるインジウム・スズ・オキサイド(ITO)、FTO、インジウム・亜鉛・オキサイド等からなる導電性ガラスを用いて作製された膜(NESA等)や、金、白金、銀、銅等が用いられる。特に、ITOまたはFTOが好ましい。また、電極材料として、有機系の導電性ポリマーであるポリアニリンおよびその誘導体、ポリチオフェンおよびその誘導体等を用いてもよい。陽極11の膜厚は、ITOの場合、30~300nmであることが好ましい。30nmより薄くすると、導電性が低下して抵抗が高くなり、光電変換効率低下の原因となる。300nmよりも厚くすると、ITOに可撓性がなくなり、応力が作用するとひび割れてしまう。陽極11のシート抵抗は可能な限り低いことが好ましく、10Ω/□以下であることが好ましい。陽極11は、単層であってもよく、異なる仕事関数の材料で構成される層を積層したものであってもよい。
正孔輸送層14は、任意に、陽極11と光電変換層13との間に配置される。正孔輸送層14の機能は、下部の電極の凹凸をレベリングして太陽電池素子の短絡を防ぐこと、正孔のみを効率的に輸送すること、光電変換層13の界面近傍で発生した励起子の消滅を防ぐこと等である。正孔輸送層14の材料としては、PEDOT/PSS(ポリ(3,4-エチレンジオキシチオフェン)-ポリ(スチレンスルホネート))等のポリチオフェン系ポリマー、ポリアニリン、ポリピロール等の有機導電性ポリマーを使用することができる。ポリチオフェン系ポリマーの代表的な製品としては、例えば、スタルク社のBaytron PH500が挙げられる。
光電変換層13は、陽極11と陰極12との間に配置される。本発明に係る太陽電池は、ヘテロ接合型の太陽電池である。ヘテロ接合型の中でも特にバルクヘテロ接合型の太陽電池は、p型半導体とn型半導体が光電変換層中で混合してミクロ層分離構造をとることが特徴である。バルクへテロ接合型は、混合されたp型半導体とn型半導体が光電変換層内でナノオーダーのサイズのpn接合を形成し、接合面において生じる光電荷分離を利用して電流を得る。p型半導体は、電子供与性の性質を有する材料で構成される。一方、n型半導体は、電子受容性の性質を有する材料で構成される。本発明の実施形態においては、p型半導体およびn型半導体の少なくとも一方が有機半導体であってよい。
電子輸送層15は、任意に、陰極12と光電変換層13との間に配置される。通常、透明または半透明の材料を真空蒸着法、スパッタリング法、イオンプレーティング法、メッキ法、塗布法等で成膜する。電子輸送層材料としてはAlq3などのキノリン類、BCPなどのフェナンスロリン誘導体、BNDやPBDさらにはOXDなどのオキサジアゾール誘導体、オキサジアゾール二量体、スターバーストオキサジアゾール、トリアゾール誘導体、フェニルキノキサリン誘導体、シロール誘導体、無機物としては酸化チタン、フラーレン類、フッ化リチウム等のアルカリ金属、アルカリ土類金属のハロゲン化物、酸化物等を挙げることができる。電子輸送層15の適正膜厚は材質により大きく異なるため調整が必要であるが、一般的には0.1nm~100nmの範囲である。膜厚が上記範囲より薄い場合は、ホールブロック効果が減少してしまうため、発生したエキシトンが電子とホールに解離する前に失活してしまい、効率的に電流を取り出すことができない。膜厚が厚い場合には、電子輸送層が抵抗体として作用し、電圧降下を招く。また電子輸送層15の成膜に長時間を要するため材料温度が上昇して、有機層にダメージを与えて性能が劣化してしまう。さらに、材料を大量に使用するため、成膜装置の占有時間が長くなり、コストアップにつながる。
陰極12は、光電変換層13(または電子輸送層15)の上に積層される。導電性を有する材料を真空蒸着法、スパッタリング法、イオンプレーティング法、メッキ法、塗布法等で成膜する。電極材料としては、導電性の金属薄膜、金属酸化物膜、等が挙げられる。陽極11を仕事関数の高い材料を用いて形成した場合、陰極12には仕事関数の低い材料を用いることが好ましい。仕事関数の低い材料としては、例えば、アルカリ金属、アルカリ土類金属等が挙げられる。具体的には、Li、In、Al、Ca、Mg、Sm、Tb、Yb、Zr、Na、K、Rb、Cs、Ba、およびこれらの合金を挙げることができる。
上記のように作製した太陽電池素子について、熱アニーリングを行う。熱アニーリングは、ホットプレート等の加熱装置により所定の温度に急速に基板を加熱し、任意の時間これを継続することにより行う。その間、同時に、素子に交流電圧を印加する。電圧の印加は、作製した素子の陽極および陰極に、周波数発生器からの信号により任意の波形を発生できる電源アンプの出力を接続することにより行う。出力電圧、周波数、デューティ比、オフセット値等のパラメータを設定し、素子に電圧を印加する。
最後に、酸素および水分から素子を保護するために封止処理を行い、正負の電極から引き出し電極を取り出し、太陽電池とする。封止は、熱硬化型またはUV硬化型のエポキシ樹脂等を固定剤として、ガラス、金属板、あるいは無機物や金属(シリカ、チタニア、ジルコニア、窒化珪素、窒化ホウ素、Al等)を表面に成膜した樹脂フィルム(PET、PEN、PI、EVOH、CO、EVA、PC、PES等)などで表面を保護することにより行う。さらに、封止空間に乾燥剤や酸素吸収剤を入れることで素子寿命の向上が期待できる。
ηEQE=η1・η2・η3・η4。
実施例1として、熱アニール時に交流電圧を印加して有機薄膜太陽電池を作製した例を示す。
まず、光電変換層となる有機半導体の固形分の調製を行った。p型有機半導体であるP3HT(ポリ3-ヘキシルチオフェン: Aldrich社製 Plexcore(登録商標)OS2100)50重量部と、n型有機半導体である70PCBM([6,6]-フェニルC71酪酸メチルエステル: SOLENNE社製 70PCBMフラーレン99%)50重量部を混合した。
その後、この基板を10分間UV処理し、表面を親水化した。
まず、上記で作製したITO付ガラス基板上に、正孔輸送層となるPEDOT/PSS水溶液(スタルク社製 ポリ(3,4-エチレンジオキシチオフェン)-ポリ(スチレンスルホネート))、商品名Baytron PH500をスピンコート法により50nmの厚さに成膜した。その後、200℃のホットプレート上で5分間加熱乾燥した。なおPEDOT/PSS水溶液は、あらかじめ0.1μmのフィルターで濾過したものを使用した。
電圧AC10Vp-p、周波数0.5kHzのサイン波を発生する電源で電圧を印加しながら、150℃で10分間、ホットプレート上で素子のアニーリングを行った。金属板上で素子を冷却後に、電圧印加を停止した。
最後に、正負の電極から引き出し電極を取り出し、有機薄膜太陽電池とした。
印加する電圧を、AC10Vp-pにDC+4Vを重畳した直流重畳交流電圧としたことを除き、上記実施例1と同様に有機薄膜太陽電池を作製した。実施例1と同様に光電変換効率を算出したところ、4.45%であった。
電圧を印加せずに加熱処理のみを行うことを除き、上記実施例1と同様に有機薄膜太陽電池を作製した。実施例1と同様に光電変換効率を算出したところ、3.11%であった。
交流電圧の代わりに直流電圧-5Vを印加したことを除き、上記実施例1と同様に有機薄膜太陽電池を作製した。実施例1と同様に光電変換効率を算出したところ、3.19%であった。
交流電圧の代わりに直流電圧+3Vを印加したことを除き、上記実施例1と同様に有機薄膜太陽電池を作製した。実施例1と同様に光電変換効率を算出したところ、3.32%であった。
印加する交流電圧の周波数の最適範囲について検討した。印加する交流電圧の周波数を変化させて、実施例1に記載したように有機薄膜太陽電池を作製し、光電変換効率を比較した。その結果を表1に示す。なお、印加する電圧はAC 10Vp-pに固定した。
印加する交流電圧値の最適範囲について検討した。印加する交流電圧の値を変化させて、実施例1に記載したように有機薄膜太陽電池を作製し、光電変換効率を比較した。その結果を表2に示す。なお、電圧の周波数は0.5kHz(サイン波)に固定した。
印加する交流電圧のデューティ比(順バイアス電圧を印加する時間と逆バイアス電圧を印加する時間の比)の最適範囲について検討した。印加する交流電圧のデューティ比を変化させて、実施例1に記載したように有機薄膜太陽電池を作製し、光電変換効率を比較した。その結果を表3に示す。なお、印加する電圧はAC 10Vp-p、電圧の周波数は0.5kHz(サイン波)に固定した。
熱アニーリング時の熱処理温度(アニール温度)の最適範囲について検討した。アニール温度を変化させて、実施例1に記載したように有機薄膜太陽電池を作製し、光電変換効率を比較した。その結果を表4に示す。なお、印加する電圧はAC 10Vp-p、電圧の周波数は0.5kHzに固定した。
電圧を印加しながら行う熱アニール処理の処理時間の最適値について検討した。処理時間を変化させて、実施例1に記載したように有機薄膜太陽電池を作製し、光電変換効率を比較した。その結果を表5に示す。なお、印加する電圧はAC 10Vp-p、電圧の周波数は0.5kHz、アニール温度は150℃に固定した。
熱アニール工程において直流重畳交流電圧を印加する場合について、重畳する直流電圧の電圧値の最適範囲を検討した。重畳する直流電圧の電圧値を変化させて、実施例2に記載したように有機薄膜太陽電池を作製し、光電変換効率を比較した。その結果を表6に示す。なお、印加する電圧はAC 10Vp-p、電圧の周波数は0.5kHzに固定した。
熱アニール工程において直流重畳交流電圧を印加する場合について、周波数の最適値を検討した。直流重畳交流電圧の周波数を変化させて、実施例2に記載したように有機薄膜太陽電池を作製し、光電変換効率を比較した。その結果を表7に示す。なお、印加する電圧はAC 10Vp-p、重畳する直流電圧は+4Vに固定した。
Claims (11)
- 互いに離間して配置された一対の電極の間に、p型半導体とn型半導体とを含むヘテロ接合型の光電変換層を形成し、
前記光電変換層に周波数が0.01kHz以上1kHz未満の交流電圧を印加しながら熱アニーリングを行い、前記光電変換層における前記p型半導体と前記n型半導体の混合状態を制御する
ことを特徴とする太陽電池の製造方法。 - 前記p型半導体および前記n型半導体の少なくとも一方が有機半導体であることを特徴とする、請求項1に記載の太陽電池の製造方法。
- 前記光電変換層がバルクヘテロ接合型であることを特徴とする請求項1に記載の太陽電池の製造方法。
- 前記交流電圧の電圧値Vacは、前記一対の電極間の距離をLとしたとき、式2.5×103[V/mm]<Vac/L<2×105[V/mm]を満たす値であることを特徴とする請求項1に記載の太陽電池の製造方法。
- 前記交流電圧の順バイアスと逆バイアスのデューティ比が1:1~25:1であることを特徴とする請求項1に記載の太陽電池の製造方法。
- 前記熱アニーリングを70~170℃の範囲の温度で行うことを特徴とする請求項1に記載の太陽電池の製造方法。
- 前記熱アニーリングを10秒~30分間の範囲の時間で行うことを特徴とする請求項1に記載の太陽電池の製造方法。
- 互いに離間して配置された一対の電極の間に、p型半導体とn型半導体とを含むヘテロ接合型の光電変換層を形成し、
前記光電変換層に、交流電圧に直流電圧を重畳した直流重畳交流電圧を印加しながら熱アニーリングを行い、前記光電変換層における前記p型半導体と前記n型半導体の混合状態を制御する
ことを特徴とする太陽電池の製造方法。 - 前記重畳する直流電圧の値が-8V~+10Vの範囲にあることを特徴とする請求項8に記載の太陽電池の製造方法。
- 前記直流重畳交流電圧は、周波数が0.01kHz以上1kHz未満の範囲にあることを特徴とする請求項8に記載の太陽電池の製造方法。
- 互いに離間して配置された一対の電極と、
前記電極間に設けられた、p型半導体とn型半導体とを含むヘテロ接合型の光電変換層と
を具備し、
前記p型半導体および前記n型半導体は、それぞれ自己組織化してミクロ相分離構造を形成し、前記自己組織化したp型半導体およびn型半導体は、前記一対の電極に対して垂直方向に配向し、且つ相互に絡み合っていることを特徴とする、請求項1に記載の方法により製造される太陽電池。
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