WO2010114159A1 - Dispositif de conversion photoélectrique et procédé de fabrication de celui-ci, cellule solaire et cible - Google Patents

Dispositif de conversion photoélectrique et procédé de fabrication de celui-ci, cellule solaire et cible Download PDF

Info

Publication number
WO2010114159A1
WO2010114159A1 PCT/JP2010/056139 JP2010056139W WO2010114159A1 WO 2010114159 A1 WO2010114159 A1 WO 2010114159A1 JP 2010056139 W JP2010056139 W JP 2010056139W WO 2010114159 A1 WO2010114159 A1 WO 2010114159A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkali
target
photoelectric conversion
group
layer
Prior art date
Application number
PCT/JP2010/056139
Other languages
English (en)
Inventor
Hiroyuki Kobayashi
Shinya Suzuki
Toshiaki Fukunaga
Hiroshi Kubo
Original Assignee
Fujifilm Corporation
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 Fujifilm Corporation filed Critical Fujifilm Corporation
Publication of WO2010114159A1 publication Critical patent/WO2010114159A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—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 the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—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 crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—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 crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03923—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 crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02614—Transformation of metal, e.g. oxidation, nitridation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • 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
    • Y02E10/541—CuInSe2 material PV 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

  • Photoelectric conversion devices having a laminated structure of a lower electrode (back contact electrode) , a photoelectric conversion semiconductor layer that generates a current by absorbing light, and an upper electrode are used in various applications, such as solar cells and the like.
  • Most of the conventional solar cells are Si-based cells that use bulkmonocrystalline Si, polycrystalline Si, or thin film amorphous Si. Recently, however, research and development of compound semiconductor-based solar cells that do not depend on Si has been carried out.
  • glass substrates are currently used. But, glass substrates are not flexible and, therefore, unable to be used in a continuous process (roll to roll process) of solar cells . Further, glass substrates are liable to breakage because of inflexibility and also causing difficulty in reducing the thickness and weight of solar cells .
  • Japanese Unexamined Patent Publication No. 2000-349320 proposes the use of an anodized substrate formed of an Al base having an anodized filia (AI2O3 film) on a surface thereof. Suchmethod allows, even when a large area substrate is used, easy formation of an insulation film without any pinhole over the entire surface of the substrate .
  • CIS or CIGS photoelectric conversion devices it is known that the crystallization of the photoelectric conversion layer is improved and photoelectric conversion efficiency is increased by diffusing an alkali (earth) metal, preferably Na, into the photoelectric conversion layer.
  • an alkali (earth) metal preferably Na
  • the diffusion of Na into photoelectric conversion layer has been effected by the used of a soda-lime glass (SLG) substrate containing Na.
  • an alkali metal layer for supplying an alkali metal to the photoelectric conversion layer because the substrate does not include an alkali (earth) metal.
  • AIST, 23 rd EU-PVSEC 3BV.5.43 describes provision of a soda-lime glass layer, as an alkali metal supply layer, between a substrate and a Mo lower electrode by RF sputtering using soda-lime glass (SLG) as the target.
  • SSG soda-lime glass
  • International Patent Publication No. WO2003/069684 describes a method of forming Na 2 S alkali metal supply layer on a Mo lower electrode by a dipping method.
  • a method of forming an alkali metal supply layer on a Mo lower electrode by a spray method is also known.
  • the dipping method described in International Patent Publication No. WO2003/069684 or the spray method is a wet process.
  • the lower electrode andphotoelectric conversion layer formed before and after the alkali metal supply layer are normally formed by dry processes. The introduction of the wet process between the dry processes causes decreased productivity.
  • the present invention has been developed in view of the circumstances described above, and it is an object of the present invention to provide aphotoelectric conversiondevicemanufacturing method capable of forming alkali (earth) metal layers with high productivity and manufacturing photoelectric conversion devices having excellent photoelectric conversion efficiency with high productivity. It is a further object of the present invention to provide a photoelectric conversion device manufactured by the method described above. Disclosure of the Invention
  • a first photoelectric conversion device manufacturing method of the present invention is a method of manufacturing a photoelectric conversion device having a laminated structure of a lower electrode, a photoelectric conversion semiconductor layer that generates a current by absorbing light, and an upper electrode on a substrate and an alkali (earth) metal supply layer, provided between the substrate and lower electrode, which includes one or more types of alkali metals and/or alkali earth metals and supplies the one or more types of alkali metals and/or alkali earth metals to the photoelectric conversion semiconductor layer when the layer is formed, wherein: a major component of the photoelectric conversion semiconductor layer is at least one type of compound semiconductor having a chalcopyrite structure formed of a group Ib element, a group IIIb element, and a group VIb element; and the alkali (earth) metal supply layer is formedby a sputtering method using a semi-conductive or conductive target that includes the one or more types of alkali metals and/or alkali earth metals.
  • Asecondphotoelectric conversion device manufacturingmethod of the present invention is a method of manufacturing a photoelectric conversion device having a laminated structure of a lower electrode, a photoelectric conversion semiconductor layer that generates a current by absorbing light, and an upper electrode on a substrate and an alkali (earth) metal supply layer, provided between the substrate and lower electrode, which includes one or more types of alkali metals and/or alkali earth metals and supplies the one or more types of alkali metals and/or alkali earth metals to the photoelectric conversion semiconductor layer when the layer is formed, wherein: a major component of the photoelectric conversion semiconductor layer is at least one type of compound semiconductor having a chalcopyrite structure formed of a group Ib element, a group IHb element, and a group VIb element; and the alkali (earth) metal supply layer is formed by a reactive sputtering method in the presence of oxygen and/or nitrogen using a semi-conductive or conductive target that includes the one or more types of alkali metals and/or al
  • sensing as used herein is defined as having a resistivity of 10 ⁇ 3 to 10 8 ( ⁇ /cm) .
  • conductive as used herein is defined as having a resistivity less than of ICf 3 ( ⁇ /cm) .
  • a solar cell of the present invention is a solar cell having the photoelectric conversion device described above.
  • Atarget of the present invention is a target for use in sputter forming an alkali (earth) metal supply layer of a photoelectric conversion device, which is semi-conductive or conductive and includes one or more types of alkali metals and/or alkali earth metals.
  • a photoelectric conversion device manufacturing method capable of forming an alkali
  • Figure 1 is a schematic view of a DC sputtering apparatus, illustrating the construction thereof.
  • Figure 2 is a schematic view of a RF sputtering apparatus, illustrating the construction thereof.
  • Figure 3 a schematic view of a magnetron sputtering apparatus, illustrating the construction thereof.
  • Figure 4 a schematic view of a dual magnetron sputtering apparatus, illustrating the construction thereof.
  • Figure 5 is a schematic sectional view of a photoelectric conversion device according to an embodiment of the present invention taken along a longitudinal direction.
  • Figure 6 illustrates sectional views of anodized substrates, illustrating constructions thereof.
  • Figure 7 a perspective view of an anodized substrate, illustrating a manufacturing method thereof.
  • Figure 8 is a schematic cross-sectional view of an anodized substrate using two layer clad material, illustrating the construction thereof.
  • Figure 9 is an XPS spectrum of a thin film obtained in Example 5.
  • Figure 10 illustrates the relationship between the lattice constant and band gap of I-III-VI compound semiconductors.
  • a first photoelectric conversion device manufacturing method of the present invention is a method of manufacturing a photoelectric conversion device having a laminated structure of a lower electrode, a photoelectric conversion semiconductor layer that generates a current by absorbing light, and an upper electrode on a substrate and an alkali (earth) metal supply layer, provided between the substrate and lower electrode, which includes one or more types of alkali metals and/or alkali earth metals and supplies the one or more types of alkali metals and/or alkali earth metals to the photoelectric conversion semiconductor layer when the layer is formed, wherein: a major component of the photoelectric conversion semiconductor layer is at least one type of compound semiconductor having a chalcopyrite structure formed of a group Ib element, a group IIIb element, and a group VIb element; and the alkali (earth) metal supply layer is formedby a sputtering method using a semi-conductive or conductive target that includes the one or more types of alkali
  • a secondphotoelectric conversion device manufacturingmethod of the present invention is a method of manufacturing a photoelectric conversion device having a laminated structure of a lower electrode, a photoelectric conversion semiconductor layer that generates a current by absorbing light, and an upper electrode on a substrate and an alkali (earth) metal supply layer, provided between the substrate and lower electrode, which includes one or more types of alkali metals and/or alkali earth metals and supplies the one or more types of alkali metals and/or alkali earth metals to the photoelectric conversion semiconductor layer when the layer is formed, wherein: a major component of the photoelectric conversion semiconductor layer is at least one type of compound semiconductor having a chalcopyrite structure formed of a group Ib element, a group 11Ib element, and a group VIb element; and the alkali (earth) metal supply layer is formed by a reactive sputtering method in the presence of oxygen and/or nitrogen using a semi-conductive or conductive target that includes the one or more types of alkali metals and/or al
  • the sputtering method or reactive sputtering method is abbreviated as the (reactive) sputtering method and alkali metals and/or alkali earth metals are abbreviated as alkali (earth) metals.
  • substrates for photoelectric conversion devices may include, for example, glass substrates, such as soda-lime glass substrates, metal substrates, such as Al, Cu, Ti, stainless-steel substrates, anodized substrates constituted by an Al based metal base having an anodized film on at least one of the sides, and resin substrates such as polyimide substrates.
  • a flexible substrate such as an anodized substrate, a metal substrate with an insulation film formed thereon, or a resin substrate.
  • a resin substrate such as a polyimide substrate
  • the difference in thermal expansion coefficient between a substrate and each layer formed thereon is small in order to prevent warpage of the substrate due to thermal stress .
  • an anodized substrate constituted by an Al based metal base having an anodized filmon at least one of the sides is particularlypreferable.
  • the "major component of the metal base” as used herein refers to a component that accounts for 98% by mass or more.
  • the metal base may be a pure Al base that may include a trace element or an alloy base of Al with another metal element.
  • the anodized substrate constituted by an Al based metal base having an anodized film on at least one surface side has a comparatively small difference in thermal expansion coefficient with the photoelectric conversion layer and lower electrode. If a semiconductor film is formed at a high temperature exceeding 500 0 C, however, cracks and detachment may occur due to thermal stress at the time of film forming. Further, the photoelectric conversion efficiency may possibly be reduced due to strong internal stress within the compound semiconductor arising from the difference in thermal expansion coefficient with the base material.
  • a preferable substrate may be provided by using a metal substrate (cladmaterial) integrally formed of Al base (first metal base) and a second metal base having a thermal expansion coefficient comparable to that of the photoelectric conversion semiconductor layer 30 with a high rigidity and a high heat resistance, and providing an anodized film on the Al base.
  • the "major component" of an electrode or a photoelectric conversion layer formed on a substrate, or any other layer provided refers to a component that accounts for 80% by mass or more.
  • the alkali (earth) metal supply layer formed is semi-conductive or conductive like the target.
  • film forming is performed by the reactive sputtering under the presence of oxygen and/or nitrogen, which causes oxidation and/or nitridization and the alkali (earth) metal supply layer formed is insulative.
  • the insulative alkali (earth) metal supply layer is preferable because it increases the insulation between the substrate and lower electrode, whereby a dielectric breakdown of the substrate may be prevented.
  • the major component of the photoelectric conversion semiconductor layer is at least one type of compound semiconductor formed of a group Ib element, a group 11Ib element, and a group VIb element.
  • the alkali metals may include Li, Na, K, Rb, and Cs and the alkali earth metals may include Be, Mg, Ca, Sr, and Ba.
  • at least one type of alkali metal selected from the group consisting of Na, K, Rb, and Cs is preferable, Na and/or K is more preferable, and Na is particularly preferable from the viewpoint of easy acquisition of chemically stable and easy-to-handle compound, can be easily released from the alkali (earth) metal supply layer by heating, and advantageous effect of improving the crystallization of the photoelectric conversion layer.
  • the target may include an alkali (earth) metal singly or in the form of a compound.
  • Alkali metal compounds may include inorganic salts, such as sodium fluoride, potassium fluoride, sodium sulfide, potassium sulfide, sodium selenide, potassium selenide, sodium chloride, sodium carbonate, sodium molybdate (including hydrates) , potassium chloride, andthe like. Among them, sodium fluoride, sodium carbonate, and sodium molybdate are preferable, and sodium fluoride is more preferable .
  • Alkali earthmetal compounds may include inorganic salts, such as calcium fluoride, magnesium fluoride, calcium sulfide, magnesium sulfide, calcium selenide, and the like.
  • the total amount of the one or more types of alkali metals and/or alkali earth metals in the target is preferable to be 1 to 30 at. % , more preferable to be 5 to 20 at.%, and further preferable to be 10 to 15 at.% in view of the stable supply of the alkali earth metals from the alkali (earth) metal supply layer to the photoelectric conversion layer at a suitable level. It is known that an excess amount of these may possibly become a cause of preventing stable electric discharge at the time of DC sputtering.
  • Si target that includes one or two or more alkali metals and/or alkali earth metals is preferably used.
  • the alkali (earth) metal supply layer is formedby a sputtering method or a reactive sputtering method, which allows the alkali (earth) metal supply layer, and the subsequent lower electrode and photoelectric conversion layer to be formed by a dry process .
  • a sputtering method or a reactive sputtering method which allows the alkali (earth) metal supply layer, and the subsequent lower electrode and photoelectric conversion layer to be formed by a dry process .
  • this is far more productive.
  • 23 rd EU-PVSEC 3BV.5.43, cited under the "BackgroundArt” there is no choice but to use RF sputtering, if film forming is to be performed by sputtering, because the soda-lime glass (SLG) is insulative.
  • the present invention uses a semi-conductive or conductive target so that the alkali (earth) metal supply layer can be formed by a sputtering method other than the RF sputtering.
  • the alkali (earth) metal supply layer can be formed by DC
  • the film forming can be performed by pulse DC (reactive) sputtering, magnetron (reactive) sputtering, or dual magnetron (reactive) sputtering.
  • a film forming may be performed favorably by DC (reactive) sputtering.
  • the film forming by DC (reactive) sputtering is facilitated by improving the conductivity (reducing the specific resistance) by adding at least one type element selected from the group consisting of Al, Ga, and B thereto.
  • the film forming can be performed by DC (reactive) sputtering, pulse DC (reactive) sputtering, magnetron (reactive) sputtering, or dual magnetron (reactive) sputtering.
  • the total amount of at least one element selected from the group consisting of Al, Ga, and B in the Si target is not any specific restriction on the total amount of at least one element selected from the group consisting of Al, Ga, and B in the Si target as long as it is within a range that can reduce the specific resistance of the target to 1 ⁇ /cm or less, which may be not less than 10 ⁇ 4 at.% but a larger amount is more preferable in order to make the thermal expansion coefficient comparable to those of the substrate and photoelectric conversion layer.
  • the total amount is preferable to be 1 to 30 at.%, and more preferable to be 10 to 20 at.%.
  • the alkali (earth) metal supplied to the photoelectric conversion layer Na is particularly preferable. Accordingly, it is preferable that the Si target used includes simple Na or a Na compound.
  • the Si target used includes at least one type of sodium salt selected from the group consisting of sodium fluoride, sodium carbonate, and sodium molybdate. Above all, it is preferable that the Si target used includes sodium fluoride (NaF) .
  • an alkali metal and an alkali earth metal such as Mg, Ca, and the like, are included in the Si target.
  • the inventor of the present invention has actually succeeded in preparing these targets (Examples to be described later) .
  • the target of soda-lime glass described in AIST, 23 rd EU-PVSEC 3BV.5.43 include many impurities, has quality variations, and the impurities may adversely affect the formation of the photoelectric conversion layer, thereby degrading the photoelectric conversion efficiency.
  • soda-lime glass manufactured by a floating method which is a main manufacturing method of soda lime glass, tents to include Sn as an impurity.
  • a high purity target may be prepared by the use of high puritymaterials for the sinteredbodies described above.
  • (earth) metal layer can be prevented and photoelectric conversion devices having excellent photoelectric conversion efficiency can be manufactured stably.
  • alkali (earth) metal supply layers can be formed with high productivity and photoelectric conversion devices having excellent photoelectric conversion efficiency can be manufactured with high productivity.
  • DC Sputtering Apparatus Pulse DC Sputtering Apparatus
  • a gas G introduced into the inside of vacuum vessel 110 is plasmatizedby the discharge of plasma electrode 112 andpositive ions, such asAr and the like, are generated.
  • the generated positive ions sputter the target T, and a constituent element of the target T is released from the target and deposited on the substrate B in the neutral or ionized state.
  • reference symbol P schematically illustrates the plasma space.
  • Film forming apparatus 101 has a gas introducing means for introducing the gas G to be plasmatized.
  • the gas introducing means includes a supply source (not shown) of gas G to be plasmatized and gas introducing pipe 118.
  • film forming apparatus 101 has gas exhaust pipe 119 to be connected to an exhausting means (not shown) , such as a vacuum pump or the like, to exhaust a gas V in the vacuum vessel.
  • an exhausting means such as a vacuum pump or the like
  • the DC reactive sputtering uses the same apparatus and a mixed gas, as the gas G, of, for example, an Ar gas to be plasmatized and oxygen and/or nitrogen.
  • magnetron sputtering apparatus 103 An example construction of a magnetron sputtering apparatus will be described with reference to Figure 3. Components identical to those of DC sputtering apparatus 101 and RF sputtering apparatus 102 are given the same reference symbols and will not be elaborated upon further here.
  • the basic construction of magnetron sputtering apparatus 103 is identical to that of the RF sputtering apparatus and only differs in that magnet unit 115 having a plurality of magnets 115M is attached to plasma electrode 112 and the target T is mounted thereon.
  • a high frequency AC voltage is applied to plasma electrode 112 with a magnetic field being generated adjacent to the target T by magnet unit 115.
  • a DC voltage may be applied to plasma electrode 112.
  • the magnetron sputtering may implement sputtering of the target T efficiently by keeping the plasma ions away from the substrate B.
  • dual magnetron sputtering apparatus 104 The basic construction of dual magnetron sputtering apparatus 104 is identical to that of magnetron sputtering apparatus 103 and only differs in that two sets of plasma electrode 112 and magnet unit 115 are provided. Two plasma electrodes 112 are connected to common high frequency AC power source 116, in which either of the electrodes is driven as the cathode and the other is driven as the anode. In the dual magnetron sputtering, a high frequency AC voltage is applied between two plasma electrodes 112 and film forming is performed by changing the polarity of each plasma electrode 112. The dual magnetron sputtering may perform film forming with a target having a low conductivity. Further, the method may use an insulative target.
  • the dual magnetron reactive sputtering uses the same apparatus as that of the dual magnetron reactive sputtering arid a mixed gas, as the gas G, of, for example, an Ar gas to be plasmatized and oxygen and/or nitrogen, as in the DC reactive sputtering.
  • the gas G of, for example, an Ar gas to be plasmatized and oxygen and/or nitrogen, as in the DC reactive sputtering.
  • the vacuum of the background is, for example, about IxIO "5 to about 1OxIO "5 Pa.
  • the DC (reactive) sputtering or the pulse DC (reactive) sputtering it is preferable to perform film forming after obtaining optimum conditions for film forming speed, film quality, film forming stability, and the like by changing the flow rate of introduction gas, application voltage, and further, for the pulse DC sputtering, the pulse period and pulse width according to the structure and size of the apparatus, type of gas used, and the like.
  • the temperature of the substrate When a film is formed, the temperature of the substrate generally increased to 100 to 300 0 C by the heat accumulation so that it is not necessary to heat the substrate, whichmay sometimes be cooled as required though.
  • the DC magnetron (reactive) sputtering When a film is formed, the temperature of the substrate generally increased to 100 to 300 0 C by the heat accumulation so that it is not necessary to heat the substrate, whichmay sometimes be cooled as required though. The same is true for the DC magnetron (reactive) sputtering.
  • a target (sputtering target) itself used in the first and second photoelectric conversion device manufacturing methods of the present invention is also novel and included in the present invention.
  • the target of the present invention is a target used for sputter forming an alkali (earth) metal supply layer to be provided in a photoelectric conversion device, the target being semi-conductive or conductive and including one or more types of alkali metals and/or alkali earth metals.
  • the total amount of the one or two or more alkali metals and/or alkali earth metals in the target of thepresent invention is preferable to be 1 to 30 at.%, more preferable to be 5 to 20 at. %, and further preferable to be 10 to 15 at.%. It is known that an excess amount of these may possibly become a cause of preventing stable electric discharge at the time of DC sputtering.
  • the matrix of target of the present invention is a semi-conductive substance.
  • the target of the present invention is a Si target that includes one or more types of alkali metals and/or alkali earth metals.
  • the film forming can be performed by DC (reactive) sputtering, pulse DC (reactive) sputtering, magnetron (reactive) sputtering, or dual magnetron (reactive) sputtering.
  • the total amount of at least one element selected from the group consisting of Al, Ga, and B in a Si target is not any specific restriction on the total amount of at least one element selected from the group consisting of Al, Ga, and B in a Si target as long as it is within a range that can reduce the specific resistance of the target to 1 ⁇ /cm or less, which may be not less than 10 ⁇ 4 at.% but a larger amount is more preferable. Therefore, the total amount is preferable to be 1 to 30 at.%, and more preferable to be 10 to 20 at.%.
  • the target of the present invention includes at least one type of sodium salt selected from the group consisting of sodium fluoride, sodium carbonate, and sodium molybdate . It is known that an excess amount of these may possibly become a cause of preventing stable electric discharge at the time of DC sputtering.
  • the target of the present invention is a sintered body obtained by casting and sintering a mixed powder of a sodium salt powder, such as a NaF powder, and a Si powder (which may include an unavoidable impurity) . More preferably, the target of the present invention is a sintered body obtained by casting and sintering a mixed powder that includes a sodium salt powder and a Si powder and further includes an Al containing powder, Ga containing powder, and
  • FIG. 5 is a schematic sectional view of the photoelectric conversion device in a longitudinal direction.
  • Figure 6 is a schematic sectional view of an anodized substrate, illustrating the structure thereof, and
  • Figure 7 is a perspective view of an anodized substrate, illustrating a manufacturing method thereof.
  • each component is not drawn to scale in order to facilitate visual recognition.
  • Photoelectric conversion device 1 is a device manufactured by the first or secondphotoelectric conversion device manufacturing method of the present invention described above.
  • Photoelectric conversion device 1 is a device having a laminated structure as the basic structure thereof in which lower electrode (back contact electrode) 20, photoelectric conversion semiconductor layer 30, buffer layer 40, and upper electrode 50 are stacked on substrate 10 in this order.
  • the photoelectric conversion semiconductor layer is abbreviated as "photoelectric conversion layer”.
  • Photoelectric conversion device 1 includes alkali (earth) metal supply layer 70 between substrate 10 and lower electrode 20 which includes one or more types of alkali metals and/or alkali earth metals and supplies the one or more types of alkali metals and/or alkali earth metals to photoelectric conversion layer 30 when the layer is formed.
  • alkali (earth) metal supply layer 70 between substrate 10 and lower electrode 20 which includes one or more types of alkali metals and/or alkali earth metals and supplies the one or more types of alkali metals and/or alkali earth metals to photoelectric conversion layer 30 when the layer is formed.
  • Photoelectric conversion device 1 has first separation grooves 61 that run through lower electrode 20, second separation grooves 62 that run through photoelectric conversion layer 30 and buffer layer 40, and third separation grooves 63 that run through photoelectric conversion layer 30, buffer layer 40, and upper electrode layer 50 in a longitudinal sectional view.
  • anodized substrate 10 is a substrate obtained by anodizing at least one of the sides of metal substrate 14 of Al based metal base 11 (Al base 11) .
  • Anodized substratelO may be Al base 11 with anodized film 12 formed on each side, as illustrated on the left of Figure 6 orAl base 11 with anodized film 12 formed on either one of the sides, as illustrated on the right of Figure 6.
  • Anodized film 12 is a film mainly consisting of Al 2 O 3 .
  • anodized film 12 is formed on each side of anodized substrate 10, it is preferable that two anodized films are formed to have substantially the same film thickness or anodized film 12 on which a photoelectric conversion layer and some other layers are not provided is formed to have a slightly thicker film thickness than that of the anodized film 12 on the other side considering heat stress balance between each side.
  • Anodization may be performed by immersing Al base 11, which is cleaned, smoothed by polishing, and the like as required, as an anode together with a cathode in an electrolyte, and applying a voltage between the anode and cathode.
  • the cathode carbon, aluminum, or the like is used.
  • an acid electrolyte that includes one type or two or more types of acids, such as sulfuric acid, phosphoric acid, chromic acid, oxalic acid, malonic acid, sulfamic acid, benzenesulfonic acid, amido-sulfonic acid, and the like, is preferably used.
  • the electrolyte a sulfuric acid, a phosphoric acid, an oxalic acid, or a mixture thereof may preferably be used.
  • electrolyte concentration 4 to 30% by mass
  • current density 0.05 to 0.30 A/cm 2
  • voltage 30 to 150 V.
  • Anodized film 12 generated by the anodization has a structure in which multiple fine columnar bodies, each having a substantially regular hexagonal shape in plan view, are tightly arranged.
  • Each fine columnar body 12a has a fine pore 12b, substantially in the center, extending substantially linearly in a depth direction from surface 11s, and the bottom surface of each fine columnar body 12a has a rounded shape.
  • a barrier layer without any fine pore 12b is formed (generally, with a thickness of 0.01 to 0.4 ⁇ m) at a bottom area of fine columnar bodies 12a.
  • the diameter of fine pore 12b of anodized film 12 Preferably the diameter of fine pore 12b is 200nm or less, and more preferably lOOnm or less from the viewpoint of surface smoothness and insulation properties. It is possible to reduce the diameter of fine pore 12b to about lOnm.
  • the pore density of fine pores 12b is 100 to 10000/ ⁇ m 2 , and more preferably 100 to 5000/ ⁇ m 2 , and particularly preferably 100 to 1000/ ⁇ m 2 from the viewpoint of insulation properties.
  • Aporous anodized film has a low Young' s modulus in comparison with a non-porous aluminum oxide single layer film, resulting in a high resistance against bending and a high resistance against a crack that occurs due to difference in thermal expansion coefficient at a high temperature. Note that any known pore sealing process may be performed on fine pores 12b of anodized film 12.
  • electrolytic treatment using a neutral electrolyte, such as boric acid, instead of an acid electrolyte results in a dense anodized film (non-porous alumina single layer film) insteadof an anodized film inwhichporous fine columnar bodies are disposed.
  • An anodized film having a thicker barrier layer may be formed by first forming a porous anodized film using an acid electrolyte and then performing pore filling in which the porous film is subjected to electrolytic treatment using a neural electrolyte.
  • Athicker barrier layer may result in a filmof excellent insulating properties. There is not any specific restriction on the surface roughness
  • the preferable thickness of anodized film 12 is in the range from 0.5 to 50 ⁇ m.
  • the thickness may be controlled based on the magnitude of current or voltage in constant-current electrolysis or constant-voltage electrolysis and electrolyzing time.
  • the thickness of metal base 11 prior to anodization is, for example, 0.05 to 0.6 mm, and more preferably 0.1 to 0.3 mm in consideration of the mechanical strength of substrate 10, and reduction in the thickness and weight.
  • a preferable range of the thickness of anodized film 12 is 0.1 to 100 ⁇ m.
  • a preferable substrate may be provided by using a metal substrate (clad material) 14 integrally formed of Al base (first metal base) and a second metal base 13 having a thermal expansion coefficient comparable to that of the photoelectric conversion semiconductor layer 30 with a high rigidity and a high heat resistance, and providing an anodized film 12 on the Al base ( Figure 8) .
  • Anodized substrate 10' shown in Figure 8 includes metal substrate 14 (clad material 14) , formed of metal base 13 with Al base 11 integrated on one surface of metal base 13, and Al anodized film 12 having a porous structure formed as an electrical insulating layer by anodizing the surface of Al base 11. Accordingly, anodized substrate 10' has a three-layer structure of metal base 13/Al base 11/anodized film 12.
  • the material of metal base 13 may be any metal as long as it has a smaller linear thermal expansion coefficient, a higher rigidity, and a higher heat resistance than Al. The material may be selected appropriately from stress calculation results based on substrate 10' and the configuration andmaterial property of the photoelectric conversion circuit provided on the substrate.
  • metal base 13 In the case of a compound semiconductor layer, such as CI (G) S, a steel material, an alloy steel, or the like may be cited as the material of metal base 13.
  • a steel material, an alloy steel, or the like may be cited as the material of metal base 13.
  • the carbon steel and austenitic-ferritic stainless steel described, for example, in Japanese Unexamined Patent Publication No. 2009-132996 are preferably used.
  • metal base 13 is thicker than Al base 11.
  • linear thermal expansion coefficients of principal compound semiconductors used as the photoelectric conversion layer are 5.8 ⁇ lO ⁇ 6 /°C for GaAs representing group III-V compounds, 4.5 ⁇ lO "6 /°C for CdTe representing group 11-VI compounds, and 10 ⁇ l0 ⁇ 6 /°C for Cu (InGa) Se2 representing group I-III-VI compounds.
  • the thickness of metal base 13 may be set arbitrarily based on the handlability (strength and flexibility) of the semiconductor device at the manufacturing process and operation, but is preferable to be 10 ⁇ m to 1 mm.
  • Al base 11 may be bonded to metal base 13 by any method as long as it is capable of integrally bonding them and ensuring adhesiveness.
  • they may be bonded together by depositing Al on metal base 13, vapor phase process, such as sputtering, hot-dip plating in which metal base 13 is dipped in molten Al, aluminum electroplating using non-aqueous electrolyte, or pressure bonding after surface cleaning.
  • Anodization of clad material 14 may be performed by immersing clad material 14, as an anode, together with a cathode in an electrolyte, and applying a voltage between the anode and cathode.
  • metal base 13 contacts the electrolyte
  • a local battery is formed by metal base 13 and Al base 11, so that metal base 13 contacting the electrolyte needs to be mask insulated.
  • metal base 13 contacting the electrolyte needs to be mask insulated.
  • clad material 14 having a two-layer structure of metal base 13 andAl base 11, it is necessary to insulate the surface of steel base 13, as well as the end face thereof.
  • the anodization processing is identical to that described above.
  • anodized substrate 10' includes clad material 14, formed of metal base 13 with Al base 11 integrated on one surface of metal base 13, and an anodized film formed on the surface of Al base 11 of clad material 14. Consequently, anodized substrate 10' may prevent crack generation in anodized film 12 even in a film forming process of a photoelectric conversion layer 30 of a compound semiconductor on the substrate which accompanies a high temperature (not less than 500°C) , whereby a high insulating power may be maintained.
  • Photoelectric conversion layer 30 is a layer that generates a current by absorbing light.
  • the main component of the layer preferably the main component is at least one type of compound semiconductor having a chalcopyrite structure.
  • the main component of photoelectric conversion layer 30 is at least one type of compound semiconductor formed of a group Ib element, a group IHb element, and a group VIb element.
  • the major component of the photoelectric conversion layer is at least one type of compound semiconductor formed of at least one type of group Ib element selected from the group consisting of Cu and Ag, at least one type of group IHb element selected from the group consisting of Al, Ga, and In, and at least one type of group VIb element selected from the group consisting of S, Se, and Te.
  • photoelectric conversion layer 30 includes CuInSe 2 (CIS) , or a compound solidified with Ga, i.e, Cu(In,Ga)S 2 (CIGS) .
  • CIS and CIGS are semiconductors having chalcopyrite structures and it is reported that they have high light absorption rates and high energy conversion efficiencies. Further, they are excellent in the durability with less deterioration in the conversion efficiency due to light exposure and the like.
  • Photoelectric conversion layer 30 may have a concentration distributionof constituent elements of group I-III-VI semiconductor and/or an impurity, and may have a plurality of layer regions of different semi-conductivities, such as n-type, p-type, i-type, and the like. For example, ina CIGS system, if Ga content ofphotoelectric conversion layer 30 is distributed in the thickness direction, band gap width/carrier mobility and the like can be controlled, whereby a higher photoelectric conversion efficiency value can be designed.
  • Photoelectric conversion layer 30 may include one or more types of semiconductors other than the group I-III-VI semiconductor.
  • Semiconductors other than the group I-III-VI semiconductor may- include a semiconductor of group IVb element, such as Si (group IV semiconductor) , a semiconductor of group IHb element and group Vb element such as GaAs (group 111-V semiconductor) , and a semiconductor of group lib element and group VIb element, such as CdTe (group 11-VI semiconductor) .
  • Photoelectric conversion layer 30 may include any arbitrary component other than semiconductors and an impurity for causing the semiconductors to become an intended conductivity type within a limit that does not affect the properties.
  • Modifications of the methods described above for improving crystallization of a CIGS film include the following: a) a method that uses ionized Ga (H. Miyazaki et al., "Growth of high-quality CuGaSe 2 thin films using ionized Ga precursor", Physica status solidi (a), Vol. 203, No. 11, pp. 2603-2608, 2006, and the like) ; b) a method that uses cracked Se (M.
  • gradedband gap CIGS film formingmethod amethod in which a Cu-Ga alloy film is deposited first, then an In film is deposited thereon, and, when selenizing the film, Ga concentration in the film thickness direction is graded by the natural thermal diffusion is known (K. Kushiya et al., Tech. Digest 9 th Photovoltaic
  • the following methods are known: a) a method the uses CuInSe 2 multicrystal as the target; b) a two-source sputtering method that uses Cu2Se and In 2 Se3 as the target and H 2 Se/Ar mixed gas as the sputtering gas (J.H.
  • hybrid sputtering a hybrid sputtering method in which Cu and In metals are DC sputtered and only Se is deposited in the sputtering method described above is known (T. Nakada et al. , "Microstructural Characterization for Sputter-Deposited CuInSe 2 Films and Photovoltaic Devices", Japanese Journal ofApplied Physics, Vol. 34, Part 1, No. 9A, pp. 4715-4721, 1995, and the like) .
  • CIGS film forming methods include screen printing, proximity sublimation, MOCVD, spraying, and the like.
  • a crystal having a desired composition may be obtained by forming a particle filmthat includes a group Ib element, a group IHb element, and a group VIb element on a substrate and performing pyrolytic processing (which may be performed under the group VIb element atmosphere) on the particle film (Japanese Unexamined Patent
  • Figure 10 illustrates the relationship between the lattice constant and band gap of major I-III-VI compound semiconductors.
  • Figure 8 shows that various band gaps may be obtained by changing the composition ratio.
  • a photon having a greater energy than the band gap is incident on a semiconductor, the amount of energy exceeding the band gap becomes heat loss. It has been known by a theoretical calculation that the conversion efficiency becomes maximal at about 1.4 to 1.5 eV in the combination between solar spectrum and band gap.
  • the band structure may be graded by varying the composition ratio in the film thickness direction.
  • Two types of graded structures are known, one of which is a single graded band gap in which the band gap increases from the light entrance window side toward the electrode side on the opposite and the other of which is a double gradedband gap inwhich the bandgap decreases from the light entrance window side toward the PN junction and increases after passing the PN junction (T. Dullweber et al., "Anew approach to high-efficiency solar cells by band gap grading in Cu(In, Ga)Se 2 chalcopyrite semiconductors", Solar Energy Materials and Solar Cells, Vol. 67, pp. 145-150, 2001, and the like) .
  • the use of a plurality of semiconductors having different band gaps with respect to each spectrum range may reduce heat loss due to discrepancy between photon energy and band gap and increase the power generation efficiency.
  • the use of a plurality of such photoelectric conversion layers stacked on top of each other is referred to as tandem type.
  • the power generation efficiency may be increased, for example, by the use of a combination of 1.1 eV and 1.7 eV. (Electrodes, Buffer Layer)
  • Each of lower electrode 20 and upper electrode 50 is made of a conductive material.
  • Upper electrode 50 on the light input side needs to be transparent.
  • lower electrode 20 There is not any specific restriction on the major component of lower electrode 20 and Mo, Cr, W, or a combination thereof is preferably used, in which Mo is particularly preferable. There is not any specific restriction on the thickness of lower electrode 20 and a value of 0.3 to l.O ⁇ m is preferably used.
  • upper electrode 50 There is not any specific restriction on the major component of upper electrode 50 and ZnO, ITO (indium tin oxide) , Sn ⁇ 2, or a combination thereof is preferably used. There is not any specific restriction on the thickness of upper electrode 50 and a value of 0.6 to l.O ⁇ m is preferably used.
  • Lower electrode 20 and/or upper electrode 50 may have a single layer structure or a laminated structure, such as a two-layer structure .
  • buffer layer 40 There is not any specific restriction on the major component of buffer layer 40 and CdS, ZnS, ZnO, ZnMgO, ZnS(O, OH), or a combination thereof is preferably used. There is not any specific restriction on the thickness of buffer layer 40 and a value of 0.03 to O.l ⁇ m is preferably used.
  • Apreferable combination of the compositions is, for example, Mo lower electrode/CdS buffer layer/CIGS photoelectric conversion layer/ZnO upper electrode.
  • photoelectric conversion layer 30 is a p-layer
  • buffer layer 40 is an n-layer (n-CdS, or the like)
  • upper electrode 50 is an n-layer (n-ZnO layer, or the like) or has a laminated structure of i-layer and n-layer (i-ZnO layer and n-ZnO, or the like) . It is believed that such conductivity types form a p-n junction or a p-i-n junction between photoelectric conversion layer 30 andupper electrode 50.
  • CdS buffer layer 40 on photoelectric conversion layer 30 results in an n-layer to be formed in a surface layer of photoelectric conversion layer 30 by Cd diffusion, whereby a p-n junction is formed inside of photoelectric conversion layer 30. It is also conceivable that an i-layer may be provided below the n-layer inside of photoelectric conversion layer 30 to form a p-i-n junction inside of photoelectric conversion layer 30. (Alkali (Earth) Metal Supply Layer)
  • Alkali (earth) metal supply layer 70 is a layer that includes one or more types of alkali metals and/or alkali earth metals and is provided for supplying the alkali metals and/or alkali earth metals to photoelectric conversion layer 30 when the layer is formed.
  • Alkali (earth) metal supply layer 70 mayhave a single layer structure or a laminated structure of different compositions.
  • alkali (earth) metal supply layer 70 is a layer formed by a sputtering method using a semi-conductive or conductive target that includes one or more types of alkali metals and/or alkali earthmetals (firstmanufacturingmethodof the present invention) or by a reactive sputtering method under the presence of oxygen and/or nitrogen using a semi-conductive or conductive target that includes one or more types of alkali metals and/or alkali earthmetals (secondmanufacturingmethod of the present invention) .
  • alkali (earth) metal supply layer 70 is patterned in the same manner as that of lower electrode 20.
  • alkali (earth) metal supply layer 70 When alkali (earth) metal supply layer 70 is conductive / , such patterning is required in order to prevent short-circuiting between adjacent cells. If alkali (earth) metal supply layer 70 is insulative, such patterning is not required. (Other Layers)
  • Photoelectric conversion device 1 may further includes, as required, any layer other than those described above.
  • a diffusion prevention layer may be provided between anodized substrate 10 and alkali (earth) metal supply layer 70 for preventing the diffusion of alkali (earth) metals included in alkali (earth) metal supply layer 70 into substrate 10.
  • a adhesive layer may be provided, as required, between substrate 10 and lower electrode 20, and/or between lower electrode 20 and photoelectric conversion layer 30 for enhancing the adhesion of the layers .
  • Photoelectric conversion device 1 is structured in the manner as described above.
  • Photoelectric conversion device 1 is a device that uses anodized substrate 10 so that it is lightweight and flexible, and can be manufactured at low cost.
  • alkali (earth) metal supply layer 70 is provided between substrate 10 and photoelectric conversion layer 30, so that an alkali (earth) metal may be effectively diffuse-supplied to photoelectric conversion layer 30 when the layer is formed.
  • an alkali metal of desired concentration is stably supplied to photoelectric conversion layer 30, whereby the crystallization of photoelectric conversion layer is improved and photoelectric conversion device 1 having excellent conversion efficiency may be provided.
  • alkali (earth) metal supply layer 70 is a layer formed by a sputtering method using a semi-conductive or conductive target that includes one or more types of alkali metals and/or alkali earth metals or by a reactive sputtering method under the presence of oxygen and/or nitrogen using a semi-conductive or conductive target that includes one or more types of alkali metals and/or alkali earth metals.
  • alkali (earth) metal supply layer 70 may be formed with high productivity and photoelectric conversion device 1 having excellent conversion efficiency may be manufactured with high productivity.
  • Photoelectric conversion device 1 may preferably be used as a solar cell. It can be turned into a solar cell by attaching, as required, a cover glass, a protection film, 'and the like. [Design Changes]
  • Al alloy 1050 Al purity of 99.5%, 0.30mm thickness
  • the base material was anodized to form an anodized filmon each side of the basematerial, whichwas then cleaned with water and dried, whereby an anodized substrate was obtained.
  • the thickness of the anodized film was 9.0 ⁇ m (including a barrier layer thickness of 0.38 ⁇ m) with a pore diameter of about lOOnm.
  • the anodization conditions are as follows:
  • Electrolytic Solution l ⁇ °C aqueous solution which includes 0.5M- of oxalic acid; DC Voltage Source; Voltage of 40.
  • an alkali metal supply layer was formed on the anodized substrate.
  • a mixed powder of NaF powder (purity of 99.99%) and Si powder (purity of 99.999%) was cast and sintered to obtain a sintered body (Na content of 10 at.%) .
  • an alkali metal supply layer was formed by dual magnetron sputtering using the sintered body as the target.
  • the film forming conditions were as follows. In this example, an alkali metal supply layer was formed for about three minutes with high productivity. ⁇ Film Forming Conditions>
  • Pa by providing a Cu deposition source, an In deposition source, a Ga deposition source, and a Se deposition source inside of a vacuum vessel.
  • the film forming was implemented by controlling the deposition rate from each deposition source with a maximum substrate temperature of 540 0 C.
  • a CdS film was deposited by chemical deposition with a thickness of about 50 nm.
  • a high resistance ZnO film (not shown in Figure 5) was formed on the buffer layer by RF sputtering with a thickness of O.l ⁇ m and, as an upper electrode, a ZnO:Al film was formed in succession with a thickness of 0.6 ⁇ m.
  • an Al grid electrode was deposited on the substrate and the substrate was cut into a plurality of 10 x 5 mm rectangular devices, whereby a total of 20 photoelectric conversion devices were produced.
  • an alkali metal supply layer can also be formed by pulse DC sputtering andmagnetron sputtering using an identical target to that of Example 1. (Example 2)
  • Photoelectric conversion devices were obtained in the same manner as that of Example 1 except that the alkali metal supply layer was formed by pulse DC reactive sputtering under an oxygen flow.
  • the film forming conditions were as follows. The film forming time was about 5 minutes. ⁇ Film Forming Conditions>
  • an alkali metal supply layer can also be formed by magnetron reactive sputtering and dual magnetron reactive sputtering using an identical target to that of Example 2. (Example 3)
  • Photoelectric conversion devices were obtained in the same manner as that of Example 1 except that a mixed powder of NaF powder (purity of 99.99%), Si powder (purity of 99.999%), and Al powder (purity of 99.99%) was cast and sintered to obtain a sintered body
  • the alkali metal supply layer was formed by pulse DC reactive sputtering under oxygen flow using the sintered body as the target.
  • the film forming conditions were as follows. The film forming time was about 4 minutes .
  • an alkali metal supply layer can also be formedby DC reactive sputtering, magnetron reactive sputtering, and dual magnetron reactive sputtering using an identical target to that of Example 3.
  • Phtoelectric conversion devices were obtained in the same manner as that of Example 3 except that the alkali metal supply layer was formed by RF sputtering using soda lime glass (Na content 9 at.%) as the target. Film forming conditions are as follows, which are identical to those of Example 3 other than RF power. Consequently, the film forming time was 40 minutes, i.e., the film forming speed was reduced to 1/10 of that in Example 3.
  • Table 1 shows the evaluation result of the presence or absence of arcing in a period of five minutes from the start of the film forming, since actual film forming time is three minutes.
  • x indicates that arcing occurred in each of five times of film forming
  • O indicates that stable discharge was maintained in each of five times of film forming
  • ⁇ indicates that arcing occurred one to four times of the five times of film forming.
  • a mixed powder of NaF powder (purity of 99.99%) , Si powder (purity of 99.999%) , Al powder (purity of 99.99%) , Mg powder (purity of 99.99%) , and Ca powder (purity of 99.99%) were cast and sintered to obtain a sintered body (Na content of 10 at.%, Al content of 10 at.%, Mg content of 2 at.%, and Ca content of 2 at.%). Then film forming was performed in the same manner as that of Example 3 using the sintered body as the target and a favorable film was formed successfully as in Example 3.
  • the photoelectric conversion devices of the present invention and manufacturing methods thereof may preferably be applied to solar cells, infrared sensors, and the like.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Sustainable Energy (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne la formation d'une couche de métal alcalin (terreux) d'un dispositif de conversion photoélectrique avec une productivité élevée. Dans la fabrication d'un dispositif de conversion photoélectrique comportant une couche de conversion photoélectrique qui comprend, comme composant principal, un semi-conducteur composé présentant une structure de chalcopyrite formée à partir d'un élément du groupe Ib, d'un élément du groupe IIIb et d'un élément du groupe VIb, une couche d'apport de métal alcalin (terreux) est formée par un procédé de pulvérisation utilisant une cible conductrice ou semi-conductrice qui comprend un ou plusieurs types de métaux alcalins et/ou de métaux alcalino-terreux. Dans un autre mode de réalisation, une couche d'apport de métal alcalin (terreux) est formée par un procédé de pulvérisation réactif, en présence d'oxygène et/ou d'azote, qui utilise une cible semi-conductrice ou conductrice comprenant un ou plusieurs types de métaux alcalins et/ou alcalino-terreux.
PCT/JP2010/056139 2009-03-30 2010-03-30 Dispositif de conversion photoélectrique et procédé de fabrication de celui-ci, cellule solaire et cible WO2010114159A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009081803 2009-03-30
JP2009-081803 2009-03-30

Publications (1)

Publication Number Publication Date
WO2010114159A1 true WO2010114159A1 (fr) 2010-10-07

Family

ID=42828442

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/056139 WO2010114159A1 (fr) 2009-03-30 2010-03-30 Dispositif de conversion photoélectrique et procédé de fabrication de celui-ci, cellule solaire et cible

Country Status (3)

Country Link
JP (1) JP4745449B2 (fr)
TW (1) TWI482301B (fr)
WO (1) WO2010114159A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120286219A1 (en) * 2010-01-07 2012-11-15 Jx Nippon Mining & Metals Corporation Sputtering target, semiconducting compound film, solar cell comprising semiconducting compound film, and method of producing semiconducting compound film
JP2013028836A (ja) * 2011-07-28 2013-02-07 Ulvac Japan Ltd ＣｕＧａＮａ系スパッタリング用ターゲット及びその製造方法
JP2013028837A (ja) * 2011-07-28 2013-02-07 Ulvac Japan Ltd ＣｕＧａＮａ系スパッタリング用ターゲット及びその製造方法
WO2017137523A1 (fr) * 2016-02-11 2017-08-17 Flisom Ag Fabrication haute vitesse de dispositifs à cellules solaires à rubidium et/ou césium ajouté
CN108456853A (zh) * 2018-03-12 2018-08-28 广东欧珀移动通信有限公司 制备电子设备壳体的方法、电子设备壳体和电子设备

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014185339A1 (fr) 2013-05-17 2014-11-20 日本碍子株式会社 Élément photovoltaïque
JP2015135899A (ja) * 2014-01-17 2015-07-27 国立研究開発法人産業技術総合研究所 太陽電池の製造方法及び太陽電池

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5581147A (en) * 1978-12-13 1980-06-18 Glyco Metall Werke Laminated material* sliding or friction material* and method of making said materials
JPH10151696A (ja) * 1996-02-16 1998-06-09 Mitsui Chem Inc 積層体及びその製造方法
JPH10230558A (ja) * 1996-12-17 1998-09-02 Asahi Glass Co Ltd 光吸収性反射防止膜付き有機基体とその製造方法
JPH11312817A (ja) * 1998-04-28 1999-11-09 Honda Motor Co Ltd 太陽電池
JP2004047860A (ja) * 2002-07-15 2004-02-12 Matsushita Electric Ind Co Ltd 薄膜太陽電池およびその製造方法
JP2004158556A (ja) * 2002-11-05 2004-06-03 Matsushita Electric Ind Co Ltd 太陽電池
JP2006080370A (ja) * 2004-09-10 2006-03-23 Matsushita Electric Ind Co Ltd 太陽電池
JP2008063636A (ja) * 2006-09-11 2008-03-21 Canon Inc 成膜装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW473400B (en) * 1998-11-20 2002-01-21 Asahi Chemical Ind Modified photocatalyst sol
TW572925B (en) * 2000-01-24 2004-01-21 Mitsui Chemicals Inc Urethane resin composition for sealing optoelectric conversion devices

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5581147A (en) * 1978-12-13 1980-06-18 Glyco Metall Werke Laminated material* sliding or friction material* and method of making said materials
JPH10151696A (ja) * 1996-02-16 1998-06-09 Mitsui Chem Inc 積層体及びその製造方法
JPH10230558A (ja) * 1996-12-17 1998-09-02 Asahi Glass Co Ltd 光吸収性反射防止膜付き有機基体とその製造方法
JPH11312817A (ja) * 1998-04-28 1999-11-09 Honda Motor Co Ltd 太陽電池
JP2004047860A (ja) * 2002-07-15 2004-02-12 Matsushita Electric Ind Co Ltd 薄膜太陽電池およびその製造方法
JP2004158556A (ja) * 2002-11-05 2004-06-03 Matsushita Electric Ind Co Ltd 太陽電池
JP2006080370A (ja) * 2004-09-10 2006-03-23 Matsushita Electric Ind Co Ltd 太陽電池
JP2008063636A (ja) * 2006-09-11 2008-03-21 Canon Inc 成膜装置

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120286219A1 (en) * 2010-01-07 2012-11-15 Jx Nippon Mining & Metals Corporation Sputtering target, semiconducting compound film, solar cell comprising semiconducting compound film, and method of producing semiconducting compound film
JP2013028836A (ja) * 2011-07-28 2013-02-07 Ulvac Japan Ltd ＣｕＧａＮａ系スパッタリング用ターゲット及びその製造方法
JP2013028837A (ja) * 2011-07-28 2013-02-07 Ulvac Japan Ltd ＣｕＧａＮａ系スパッタリング用ターゲット及びその製造方法
WO2017137523A1 (fr) * 2016-02-11 2017-08-17 Flisom Ag Fabrication haute vitesse de dispositifs à cellules solaires à rubidium et/ou césium ajouté
CN108456853A (zh) * 2018-03-12 2018-08-28 广东欧珀移动通信有限公司 制备电子设备壳体的方法、电子设备壳体和电子设备

Also Published As

Publication number Publication date
TWI482301B (zh) 2015-04-21
JP2010258429A (ja) 2010-11-11
JP4745449B2 (ja) 2011-08-10
TW201044626A (en) 2010-12-16

Similar Documents

Publication Publication Date Title
JP4629151B2 (ja) 光電変換素子及び太陽電池、光電変換素子の製造方法
JP5229901B2 (ja) 光電変換素子、及び太陽電池
TWI482301B (zh) 光電轉換裝置及其製造方法、太陽電池以及靶材
US20130230943A1 (en) Solar cell device and solar cell device manufacturing method
US20110186102A1 (en) Photoelectric conversion element, thin-film solar cell, and photoelectric conversion element manufacturing method
WO2011040645A1 (fr) Dispositif de conversion photoélectrique, procédé de production associé, et batterie solaire
EP2532029A1 (fr) Substrat métallique isolant et dispositif à semi-conducteurs
JP2010212336A (ja) 光電変換素子とその製造方法、及び太陽電池
US20110186103A1 (en) Photoelectric conversion element, thin-film solar cell, and photoelectric conversion element manufacturing method
US8686281B2 (en) Semiconductor device and solar battery using the same
KR101241708B1 (ko) 태양광 발전장치 및 이의 제조방법
JP2010242116A (ja) 成膜方法と成膜装置、マスク、パターン膜、光電変換素子、及び太陽電池
JP2011159796A (ja) 絶縁層付基板および薄膜太陽電池
JP5512219B2 (ja) 太陽電池
JP2010232427A (ja) 光電変換素子、その製造方法、それに用いられる陽極酸化基板及び太陽電池
JP2010258255A (ja) 陽極酸化基板、それを用いた光電変換素子の製造方法、光電変換素子及び太陽電池
JP2011124538A (ja) 絶縁層付金属基板、それを用いた半導体装置および太陽電池の製造方法、並びに太陽電池
JP4550928B2 (ja) 光電変換素子、及びこれを用いた太陽電池
JP2011176286A (ja) 光電変換素子、薄膜太陽電池および光電変換素子の製造方法
JP2011159685A (ja) 太陽電池の製造方法
EP2940737A1 (fr) Procédé de fabrication de cellule solaire à couches minces à base de composé

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: 10758923

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10758923

Country of ref document: EP

Kind code of ref document: A1