CA2540723C - Spherical or grain-shaped semiconductor element for use in solar cells and method for producing the same; method for producing a solar cell comprising said semiconductor element and solar cell - Google Patents
Spherical or grain-shaped semiconductor element for use in solar cells and method for producing the same; method for producing a solar cell comprising said semiconductor element and solar cell Download PDFInfo
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- CA2540723C CA2540723C CA2540723A CA2540723A CA2540723C CA 2540723 C CA2540723 C CA 2540723C CA 2540723 A CA2540723 A CA 2540723A CA 2540723 A CA2540723 A CA 2540723A CA 2540723 C CA2540723 C CA 2540723C
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- semiconductor
- solar cell
- semiconductor elements
- spherical
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 187
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000011669 selenium Substances 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 229910052711 selenium Inorganic materials 0.000 claims description 16
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000004020 conductor Substances 0.000 claims description 8
- -1 copper indium gallium sulfides Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000005361 soda-lime glass Substances 0.000 claims description 7
- 150000002483 hydrogen compounds Chemical class 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 claims description 5
- 238000010348 incorporation Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical class [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 claims description 3
- 238000010410 dusting Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- PKLGPLDEALFDSB-UHFFFAOYSA-N [SeH-]=[Se].[In+3].[Cu+2].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se] Chemical class [SeH-]=[Se].[In+3].[Cu+2].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se] PKLGPLDEALFDSB-UHFFFAOYSA-N 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- NMHFBDQVKIZULJ-UHFFFAOYSA-N selanylideneindium Chemical class [In]=[Se] NMHFBDQVKIZULJ-UHFFFAOYSA-N 0.000 claims 1
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical class [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims 1
- 239000012815 thermoplastic material Substances 0.000 claims 1
- 238000005987 sulfurization reaction Methods 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 188
- 210000004027 cell Anatomy 0.000 description 45
- 229940108928 copper Drugs 0.000 description 10
- 239000011521 glass Substances 0.000 description 7
- 235000016768 molybdenum Nutrition 0.000 description 7
- 238000005240 physical vapour deposition Methods 0.000 description 7
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 229910052729 chemical element Inorganic materials 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000000224 chemical solution deposition Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
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- 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
- H01L31/06—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 characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—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 characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0749—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 characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- H—ELECTRICITY
- 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
- H01L31/0352—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
- H01L31/035281—Shape of the body
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
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- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a spherical or grain-shaped semiconductor element for use in solar cells and to a method for producing said semiconductor element.
The invention also relates to a solar cell comprising an integrated spherical semiconductor element, to a method for producing said solar cell and to a photovoltaic module comprising at least one solar cell. The semiconductor element is characterized in that a back contact layer and a I-III-VI compound semiconductor are deposited on a spherical or grain-shaped substrate core. The I-III-VI compound semiconductor is produced by applying precursor layers and subsequent selenization or sulfurization. For producing a solar cell, a plurality of the inventive semiconductor elements is introduced into a substrate layer from which they project on at least one face thereof. The substrate layer is stripped on one side, thereby exposing the back contact layer of most of the semiconductor elements. This back contact layer can be contacted to the back contact of the solar cell while a front contact is provided on the side of the semiconductor elements that was not stripped.
The invention also relates to a solar cell comprising an integrated spherical semiconductor element, to a method for producing said solar cell and to a photovoltaic module comprising at least one solar cell. The semiconductor element is characterized in that a back contact layer and a I-III-VI compound semiconductor are deposited on a spherical or grain-shaped substrate core. The I-III-VI compound semiconductor is produced by applying precursor layers and subsequent selenization or sulfurization. For producing a solar cell, a plurality of the inventive semiconductor elements is introduced into a substrate layer from which they project on at least one face thereof. The substrate layer is stripped on one side, thereby exposing the back contact layer of most of the semiconductor elements. This back contact layer can be contacted to the back contact of the solar cell while a front contact is provided on the side of the semiconductor elements that was not stripped.
Description
SPHERICAL OR GRAIN-SHAPED SEMICONDUCTOR ELEMENT FOR USE
IN SOLAR CELLS AND METHOD FOR PRODUCING THE SAME;
METHOD FOR PRODUCING A SOLAR CELL COMPRISING SAID
SEMICONDUCTOR ELEMENT AND SOLAR CELL
Description:
The invention relates to a spherical or grain-shaped semiconductor element for use in solar cells and to a method for the production of said semiconductor element.
The invention also relates to a solar cell having integrated spherical or grain-shaped semiconductor elements and to a method for the production of said solar cell.
The invention also relates to a photovoltaic module having at least one solar cell having integrated semiconductor elements.
In photovoltaic cells, the photovoltaic effect is utilized in order to convert solar radiation energy into electric energy. Solar cells used for this purpose are made primarily of planar wafers in which a conventional p-n junction is realized.
In order to produce a p-n junction and other function layers, in addition to applying and processing individual continuous layer surfaces, it has proven to be practical to apply semiconductor material in spherical or grain-shaped form since this entails a number of advantages.
For example, when it comes to producing electronic devices, it has long since been a known procedure to incorporate electronically active material as particles into a layer in order to increase the activity of the material. This is described, for example, in U.S. Pat. No. 3,736,476. In an embodiment disclosed therein, a core and a layer surrounding the core are configured in such a way as to create a p-n junction. Several of the particles produced in this manner are incorporated into an insulating support layer in such a way that they protrude from the surface on both sides of the layer and can be contacted by further layers, Moreover, German Preliminary Published Application DE 100 52 914 Al describes a semiconductor device that is made up of a layer structure consisting of an electrically conductive support layer, an insulating layer, semiconductor parti-cles and an electrically conductive cover layer, whereby the semiconductor parti-cies are incorporated into the insulating layer and they touch the support layer that is underneath it as well as the cover layer that is above it. The semiconductor particles can consist, for example, of silicon or semiconductor particles that are coated with II-VI compounds.
The background for the use of compound semiconductors such as copper indium diselenide, copper indium sulfide, copper indium gallium sulfide and cop-per indium gallium diselenide can be found, for example, in U.S. Pat. Nos.
4,335,266 (Mickelsen et al.) and 4,581,108 (ICapur) in which this type of semiconductor and methods for their production are described in depth. 1411-V1 compound semiconductors are also referred to below as chalcopyrites or CIS or C1GS (Copper Indium Gallium diSelenide) semiconductors.
It is also a known procedure to configure independent spherical semiconductor elements that constitute complete semiconductors, including the requisite elec-trades, For example, European patent application EP 0 940 860 Al describes using a spherical core to make a spherical semiconductor element by means of masking, etching steps and the application of various material layers. Such semiconductor elements can be used as solar cells if the p-n junction is selected in such a way that it can convert incident light into energy. If the p-n junction is configured in such a way that it can convert an applied voltage into light, then the semiconductor element can be employed as a light-emitting element.
IN SOLAR CELLS AND METHOD FOR PRODUCING THE SAME;
METHOD FOR PRODUCING A SOLAR CELL COMPRISING SAID
SEMICONDUCTOR ELEMENT AND SOLAR CELL
Description:
The invention relates to a spherical or grain-shaped semiconductor element for use in solar cells and to a method for the production of said semiconductor element.
The invention also relates to a solar cell having integrated spherical or grain-shaped semiconductor elements and to a method for the production of said solar cell.
The invention also relates to a photovoltaic module having at least one solar cell having integrated semiconductor elements.
In photovoltaic cells, the photovoltaic effect is utilized in order to convert solar radiation energy into electric energy. Solar cells used for this purpose are made primarily of planar wafers in which a conventional p-n junction is realized.
In order to produce a p-n junction and other function layers, in addition to applying and processing individual continuous layer surfaces, it has proven to be practical to apply semiconductor material in spherical or grain-shaped form since this entails a number of advantages.
For example, when it comes to producing electronic devices, it has long since been a known procedure to incorporate electronically active material as particles into a layer in order to increase the activity of the material. This is described, for example, in U.S. Pat. No. 3,736,476. In an embodiment disclosed therein, a core and a layer surrounding the core are configured in such a way as to create a p-n junction. Several of the particles produced in this manner are incorporated into an insulating support layer in such a way that they protrude from the surface on both sides of the layer and can be contacted by further layers, Moreover, German Preliminary Published Application DE 100 52 914 Al describes a semiconductor device that is made up of a layer structure consisting of an electrically conductive support layer, an insulating layer, semiconductor parti-cles and an electrically conductive cover layer, whereby the semiconductor parti-cies are incorporated into the insulating layer and they touch the support layer that is underneath it as well as the cover layer that is above it. The semiconductor particles can consist, for example, of silicon or semiconductor particles that are coated with II-VI compounds.
The background for the use of compound semiconductors such as copper indium diselenide, copper indium sulfide, copper indium gallium sulfide and cop-per indium gallium diselenide can be found, for example, in U.S. Pat. Nos.
4,335,266 (Mickelsen et al.) and 4,581,108 (ICapur) in which this type of semiconductor and methods for their production are described in depth. 1411-V1 compound semiconductors are also referred to below as chalcopyrites or CIS or C1GS (Copper Indium Gallium diSelenide) semiconductors.
It is also a known procedure to configure independent spherical semiconductor elements that constitute complete semiconductors, including the requisite elec-trades, For example, European patent application EP 0 940 860 Al describes using a spherical core to make a spherical semiconductor element by means of masking, etching steps and the application of various material layers. Such semiconductor elements can be used as solar cells if the p-n junction is selected in such a way that it can convert incident light into energy. If the p-n junction is configured in such a way that it can convert an applied voltage into light, then the semiconductor element can be employed as a light-emitting element.
In view of the wide array of envisaged areas of application for such semiconduc-tor elements, the elements have to be completely independent components with electrode connections that can be installed in other applications. This calls for a high complexity of the semiconductor elements and of the requisite production processes. Due to the small dimensions amounting to a few millimeters on the part of the spherical shapes employed, the production of the spherical elements with all of the function layers and processing steps is very expensive.
Moreover, U.S. Pat. No. 5,578,503 discloses a method for the rapid production of chalcopyrite semiconductor layers on a substrate in which individual layers of the elements copper, indium or gallium and sulfur or selenium arc applied onto a sub-strate in elemental form or as a binary interelemental compound. The substrate with the layer structure is then quickly heated up and kept at a temperature of 350 C 662 F] for between 10 seconds and one hour.
Moreover, U.S. Pat. No. 4,173,494 describes a semiconductor system with spheri-cal semiconductors that are incorporated into a glass layer. The spherical elements protrude from the surface of the layer on both sides of the glass layer, whereby on one side, a metal layer is applied that joins all of the elements to each other. The spherical elements have a surface consisting of one conductor type and a core of amendments - 3a -the opposite conductor type. Thus, some elements have a core made of a material of the p-type, whereas other elements have a core made of a material of the n-type, resulting in p-n spheres and n-p spheres. Such semiconductor systems are especially well-suited for use in solar cells.
The invention provides a semiconductor element having a high activity that is suitable for flexible use in various solar cells.
The invention provides an efficient method for the production of a semiconductor element for use in solar cells.
The invention provides a method for incorporating a semiconductor element into a solar cell.
The invention provides a solar cell having integrated semiconductor elements and a photovoltaic module having at least one solar cell.
According to an aspect of the invention, there is provided a method for the production of a spherical or grain-shaped semiconductor element for use in a solar cell, characterized by the following steps: application of a conductive back contact layer onto a spherical or grain-shaped substrate core; application of a first precursor layer made of copper or copper gallium;
application of a second precursor layer made of indium; reaction of the precursor layers with sulfur and/or selenium to form a I-III-VI compound semiconductor, whereby the reaction of the layer structure is carried out in a melt of the reaction element sulfur or selenium, or the reaction of the layer structure is carried out in hydrogen compounds of the reaction element sulfur or selenium, whereby the reaction in hydrogen compounds is carried out at atmospheric pressure or at a pressure lower than atmospheric pressure.
According to another aspect of the invention, there is provided a spherical or grain-shaped semiconductor element for use in solar cells, characterized in that the semiconductor element has a spherical or grain-shaped substrate core that consists of soda-lime glass and that is coated - 3b -at least with one back contact layer made of molybdenum and with one compound semiconductor.
According to another aspect of the invention, there is provided a method for the production of a solar cell having integrated spherical or grain-shaped semiconductor elements, characterized by the following features: incorporation of several spherical or gain-shaped semiconductor elements into an insulating support layer, whereby the semiconductor elements protrude from the surface of the support layer on at least one side of the support layer, and the semiconductor elements each consist of a spherical or grain-shaped substrate core that is coated at least with one conductive back contact layer and with one compound semiconductor layer;
removal of parts of the semiconductor elements on one side of the support layer so that a surface of the conductive back contact layer of the semiconductor elements is exposed;
application of a back contact layer onto the side of the support layer on which parts of the semiconductor elements have been removed; and application of a front contact layer onto the side of the support layer on which no semiconductor elements have been removed.
According to another aspect of the invention, there is provided a solar cell having integrated spherical or grain-shaped semiconductor elements, characterized in that the solar cell has at least the following features: an insulating support layer into which the spherical or grain-shaped semiconductor elements are incorporated, whereby the semiconductor elements protrude from the layer on at least one side of the support layer, and the semiconductor elements each consist of a spherical or grain-shaped substrate core that is coated at least with one conductive back contact layer and with one compound semiconductor layer; a back contact layer on one side of the support layer, whereby several semiconductor elements on this side of the support layer have a surface that is free of compound semiconductors; and a front contact layer on the side of the support layer on which the semiconductor elements do not have a surface that is free of compound semiconductors.
Moreover, U.S. Pat. No. 5,578,503 discloses a method for the rapid production of chalcopyrite semiconductor layers on a substrate in which individual layers of the elements copper, indium or gallium and sulfur or selenium arc applied onto a sub-strate in elemental form or as a binary interelemental compound. The substrate with the layer structure is then quickly heated up and kept at a temperature of 350 C 662 F] for between 10 seconds and one hour.
Moreover, U.S. Pat. No. 4,173,494 describes a semiconductor system with spheri-cal semiconductors that are incorporated into a glass layer. The spherical elements protrude from the surface of the layer on both sides of the glass layer, whereby on one side, a metal layer is applied that joins all of the elements to each other. The spherical elements have a surface consisting of one conductor type and a core of amendments - 3a -the opposite conductor type. Thus, some elements have a core made of a material of the p-type, whereas other elements have a core made of a material of the n-type, resulting in p-n spheres and n-p spheres. Such semiconductor systems are especially well-suited for use in solar cells.
The invention provides a semiconductor element having a high activity that is suitable for flexible use in various solar cells.
The invention provides an efficient method for the production of a semiconductor element for use in solar cells.
The invention provides a method for incorporating a semiconductor element into a solar cell.
The invention provides a solar cell having integrated semiconductor elements and a photovoltaic module having at least one solar cell.
According to an aspect of the invention, there is provided a method for the production of a spherical or grain-shaped semiconductor element for use in a solar cell, characterized by the following steps: application of a conductive back contact layer onto a spherical or grain-shaped substrate core; application of a first precursor layer made of copper or copper gallium;
application of a second precursor layer made of indium; reaction of the precursor layers with sulfur and/or selenium to form a I-III-VI compound semiconductor, whereby the reaction of the layer structure is carried out in a melt of the reaction element sulfur or selenium, or the reaction of the layer structure is carried out in hydrogen compounds of the reaction element sulfur or selenium, whereby the reaction in hydrogen compounds is carried out at atmospheric pressure or at a pressure lower than atmospheric pressure.
According to another aspect of the invention, there is provided a spherical or grain-shaped semiconductor element for use in solar cells, characterized in that the semiconductor element has a spherical or grain-shaped substrate core that consists of soda-lime glass and that is coated - 3b -at least with one back contact layer made of molybdenum and with one compound semiconductor.
According to another aspect of the invention, there is provided a method for the production of a solar cell having integrated spherical or grain-shaped semiconductor elements, characterized by the following features: incorporation of several spherical or gain-shaped semiconductor elements into an insulating support layer, whereby the semiconductor elements protrude from the surface of the support layer on at least one side of the support layer, and the semiconductor elements each consist of a spherical or grain-shaped substrate core that is coated at least with one conductive back contact layer and with one compound semiconductor layer;
removal of parts of the semiconductor elements on one side of the support layer so that a surface of the conductive back contact layer of the semiconductor elements is exposed;
application of a back contact layer onto the side of the support layer on which parts of the semiconductor elements have been removed; and application of a front contact layer onto the side of the support layer on which no semiconductor elements have been removed.
According to another aspect of the invention, there is provided a solar cell having integrated spherical or grain-shaped semiconductor elements, characterized in that the solar cell has at least the following features: an insulating support layer into which the spherical or grain-shaped semiconductor elements are incorporated, whereby the semiconductor elements protrude from the layer on at least one side of the support layer, and the semiconductor elements each consist of a spherical or grain-shaped substrate core that is coated at least with one conductive back contact layer and with one compound semiconductor layer; a back contact layer on one side of the support layer, whereby several semiconductor elements on this side of the support layer have a surface that is free of compound semiconductors; and a front contact layer on the side of the support layer on which the semiconductor elements do not have a surface that is free of compound semiconductors.
According to another aspect of the invention, there is provided a photovoltaic module, characterized in that it has at least one solar cell as described above.
According to the invention, this is achieved by a spherical or grain-shaped semiconductor element for use in a solar cell. The method for the production of such a semiconductor element is characterized by the application of a conductive back contact layer onto a spherical or grain-shaped substrate core, by the application of a first precursor layer made of copper or copper gallium, by the application of a second precursor layer made of indium and by the reaction of the precursor layers with sulfur and/or selenium to form a I-III-VI compound semiconductor.
The reaction of the precursor layers takes place in the presence of selenium and/or sulfur and is referred to as selenization or sulfurization. These processes can be carried out in various ways with parameters that are coordinated with the given process. These include These parameters include, for example, temperature, time, atmosphere and pressure. The selenization or sulfurization can take place, for example, in the vapor, melts or salt melts of the reaction element in question or in the salt melts with admixtures of sulfur and/or selenium. The elements sulfur and selenium can be used simultaneously as well as consecutively for reaction purposes. In an especially preferred embodiment of the invention, the reaction takes place in hydrogen compounds of sulfur or selenium.
In order to obtain a I-III-VI compound semiconductor layer with defined properties, certain parameters of the precursor layers have to be set. Aside from the composition, these parameters also include the thicknesses of the individual layers. Here, due to the spherical shape and the consequently varying diameter, if applicable, layer thickness ratios should be selected that are different from those of prior-art methods in order to create planar 1-Ill-VI
compound semiconductors.
- 4a -In an especially preferred embodiment of the invention, the substrate core that is to be coated consists of glass, especially soda-lime glass, since this is a good source of sodium for the layer structuring. The main constituent of the conductive back contact layer is preferably molybdenum. In an especially preferred embodiment of the invention, the back contact layer contains up to 20% by weight of gallium in order to improve the adhesion. The individual layers can each be applied by means of physical vapor deposition (PVD) methods such as sputtering or evaporation coating or else by means of chemical vapor deposition (CVD) methods.
=
The precursor layers can be alloyed at temperatures of typically > 220 C j>
428 F]
prior to the reaction to form a 1-TIT-VI compound semiconductor, Additional processing steps or coatings can be implemented after the reaction of the precur-Consequently, the spherical or grain-shaped semiconductor element according to the invention for use in solar cells has a spherical or grain-shaped substrate core that is coated at least with one back contact layer and with one I-1II-VI
compound semiconductor. The substrate core preferably consists of glass, metal or ceramics Spherical or grain-shaped semiconductor elements produced with the described process steps constitute elements for further use in the production of solar cells.
call for correspondingly large reactors in which, for instance, large total masses have to be heated up and cooled off again during the reaction under the influence of heat. This entails a high energy demand. In contrast, the production of spherical or grain-shaped semiconductor elements for subsequent incorporation into solar cells requires far less energy since relatively small volumes have to be reacted in the reactors in question.
Another advantage is the higher flexibility during the production process. If, for example, with conventional solar cell surfaces, larger or smaller structures are to be reacted in a reactor, an appropriate new reactor has to be provided in order to be able to precisely set the requisite parameters. This is very cost-intensive. The production of such conventional thin-layer modules is thus limited by the appara-tuses employed for manufacturing the semiconductor layer. In contrast, in the production of the spherical semiconductor elements according to the invention, an existing reactor can be augmented by additional reactors in order to produce the necessary quantity of elements. Hence, this greatly simplifies the later production of solar cells for which no reactor is needed but rather only systems for applying additional layers.
Moreover, thanks to the spherical shape, practical layer systems can be achieved that might not be obtainable with flat semiconductor structures. For example, the required thickness of the deposited layers is less, As a result, for example, a back contact layer made of molybdenum and gallium can be used without the resistance of the layer becoming too great, which is the case with flat structures.
Thc method according to the invention for the production of a solar cell having integrated spherical or grain-shaped semiconductor elements is used to subse-quently incorporate semiconductor elements into a solar cell. The method pro-vides for incorporating spherical semiconductor elements into an insulating sup-port layer, whereby the semiconductor elements protrude from the surface of the support layer on at least one side of the support layer, and the spherical or grain-shaped semiconductor elements each consist of a substrate core that is coated at least with one conductive back contact layer and with one 1-HI-VI compound semiconductor layer. Parts of the semiconductor elements are removed on one side of the support layer so that preferably a surface of the back contact layer of In an especially preferred embodiment of the invention, the semiconductor ele-ments are applied onto the support layer by means of scattering, dusting and/or printing and they are subsequently pressed into the support layer so that they become embedded to a certain extent in the support layer. if the support layer is a The support layer can also be configured as a matrix with recesses into which the When parts of the semiconductor elements are removed, part of the support layer can also be removed along with it. The removal can be done, for example, by PC17E1'2004/010615 Thus, the solar cell according to the invention having integrated spherical or grain-shaped semiconductor elements has an insulating support layer into which the semiconductor elements are incorporated, whereby the semiconductor ele-ments protrude from the layer on at least one side of the support layer. The solar cell also has a front contact layer on one side and a back contact layer on the other side. On the side of the back contact layer, several semiconductor elements have a surface that is free of I-III-VI compound semiconductors and that thus frees the back contact layer of the semiconductor element. These surfaces are in direct con-tact with the back contact layer of the solar cell.
In an especially preferred embodiment of the invention, the support layer consists of an insulating material such as, for example, a polymer. The spherical semiconductor elements were preferably produced by means of the method according to the invention and the front contact layer consists, for example, of a transparent conductive oxide (TCO). The back contact layer consists of a conduc-tive material such as a metal, a TCO or a polymer having conductive particles.
The solar cell can have other function layers in addition to the front contact layer and the back contact layer.
Once all of the process steps have been completed, a solar cell having integrated semiconductor elements has been made that entails a number of advantages, espe-cially in comparison to planar semiconductor structures. The essential advantage ¨
in addition to the simplified production ¨ lies in the curved surfaces of the semiconductor elements which can be struck by incident light, irrespective of the incidence direction. Thus, even diffuse light can be used more efficiently in order to generate electricity.
Further advantages, special features and advantageous embodiments of the inven-tion can be gleaned from the subordinate claims and from the presentation below of preferred embodiments making reference to the figures.
The figures show the following:
Figure 1 in illustration (a), an especially preferred embodiment of a layer struc-ture for the production of a spherical semiconductor element and in illustration (b), a semiconductor element produced by means of the method according to the invention; and Figure 2 in illustrations (a) to (d), the process steps according to the invention during the incorporation of a spherical semiconductor element into a solar cell, Figure 1, illustration (a), shows an especially preferred embodiment of a layer structure 10 for the production of a spherical or grain-shaped semiconductor ele-ment Ii. The layer structure 10 can also be seen as the precursor layer structure for the later reaction to form a I-III-VI compound semiconductor. In the first step of the method according to the invention for the production of a spherical semiconductor element Ii, a spherical substrate core 20 is coated with a back con-tact 30. The spherical substrate preferably consists of glass, but it can also be made of other materials such as metals or ceramics. When glass is employed, for example, soda-lime glass can be used, which is a good source of sodium for the later layer structuring. Other glass compositions can also be used.
The substrate is essentially spherical, but the shape can also diverge from a pure spherical shape. Depending on the production process, the resultant spheres can also be designated as being grain-shaped. Hollow bodies made of the above-men-tioned materials can also be used. The diameter of the spheres is in the order of magnitude of 0.5 mm to 1 mm, a diameter of approximately 0.2 mm preferably being selected.
The back contact 30 is applied onto the spherical substrate in such a way that the entire surface of the sphere is coated. The material for the back contact is prefera-bly molybdenum, but other suitable conductive materials such as, for instance, tungsten or vanadium can also be used.
The semiconductor core 20 can be coated by means of PVD methods such as 5 sputtering or evaporation coating. CVD methods can also be used; in this context, it must be pointed out that sputtering a large number of small substrate spheres is a very time-consuming process that, in view of the attainable throughput rate, is less suitable than other methods. The thickness of the back contact layer is in the order of magnitude of 0.1 gm to I gm.
In order to improve the adhesion of subsequent layers to the back contact layer, a gallium layer can be applied onto the molybdenum layer. In an especially pre-ferred embodiment of the invention, the gallium is incorporated into the molybde-num layer in order to increase the adhesion. This can involve a gallium content of up to 20% by weight. In actual practice, this approach is normally avoided for flat solar cells since it increases the resistance of the back contact in a detrimental manner. However, a gallium-molybdenum layer has proven to be advantageous for the production of the semiconductor elements according to the invention, since thinner layers can be achieved than with flat semiconductors and their greater resistance does not entail any serious drawbacks.
According to the invention, a 1-11.1-VI compound semiconductor is selected as the semiconductor compound. These semiconductors, which are also referred to as chalcopyrites, also include, for example, copper indium diselenide, copper indium sulfide, copper indium gallium sulfide and copper indium gallium diselenide.
In order to produce such a CuGa/InS/Se2 layer on the substrate, first of all, precur-sor layers made of copper, gallium and/or indium are applied and these are reacted in a subsequent selenization or sulfurization process to form the envisaged semiconductors. The precursor layers can be applied with the same methods as the back contact so that here, too, PVD methods such as sputtering and evaporation coating or CVD methods can be employed. As the first precursor layer 40, in an especially preferred embodiment of the invention, the spherical substrate is coated with copper. In order to improve the adhesion between this first layer and the back contact, a thin copper-gallium layer can be applied ahead of time as an adhesive.
In a first embodiment of the invention, a second precursor layer 50 in the form of indium is deposited onto the copper layer. An alternating application of Cu/In layer packets (e.g. Cugn/Cu/In) is likewise possible. The Cu/In layers are subse-quently sulfurized with sulfur to form CuInS and a so-called CIS layer is formed.
The CIS layer 60 resulting from the precursors and the sulfurization process is shown on the semiconductor element 11 in illustration (b). The precursor layer system consisting of copper and indium can optionally be alloyed at an elevated temperature of typically T> 220 C (428 F] prior to the sulfurization, which is advantageous for the adhesion and the later reaction with selenium and/or sulfur.
This step, however, is not absolutely necessary.
The layer thicknesses of the Cu and In layers are determined by the envisaged layer thickness of the CIS semiconductor, Preferably, the thickness of the CIS
layer 60 is in the order of magnitude of 1 gm to 3 gm. Moreover, it has proven to be advantageous for the atomic ratio of Cu to ln to be in the order of magnitude of to 2. Special preference is given to atomic ratios of copper to indium of between 1.2 and 1.8.
In a second embodiment of the invention, a copper layer or a copper-gallium layer is applied onto the back contact layer 30 as a first precursor layer 40. This first precursor layer is, in turn, followed by a second precursor 50 in the form of an indium layer, whereby the two layers are subsequently selenized into CuIn/GaSe2 and form a CIGS layer. The copper-indium/gallium layer system here can also optionally be alloyed at an elevated temperature of typically T> 220 C [428 F].
In this embodiment, the layer thicknesses are likewise dependent on the envisaged atomic ratio Cugln+Ga) after the selenization. It has proven to be advantageous for this ratio to be < 1. The layer thickness of the CIGS layer after the selenization is preferably in the order of magnitude of 1 gm to 3 gm. It has turned out that the copper content of the finished CIGS layer can be set smaller than the stoichiometrically necessary value.
The spheres coated with the precursors can be reacted by means of selenization with selenium anclior by means of sulfurization with sulfur. Various methods can be used for this purpose. In an especially preferred embodiment of the invention, the spheres are reacted in a vacuum or at atmospheric pressure with a vapor of the element in question (Sc and/or S). This reaction takes place employing certain parameters such as, for instance, temperature, time, process duration, pressure and partial pressure. The reaction can also take place in a melt made up of the ele-ments. Another possibility for the reaction is the salt melt containing S
and/or Se.
In another embodiment of the invention, the spheres are reacted to form hydrogen compounds of sulfur and/or of selenium. This can take place, for example, at atmospheric pressure or at a pressure that is less than atmospheric pressure.
Sulfur as well as selenium can be used consecutively or simultaneously during the reac-tion.
In an especially preferred embodiment of the invention, the next process step after the reaction of the spheres is to remove surface layers that have a detrimental effect. These can be, for example, CuS compounds that were formed during the reaction process. One way to remove such layers is through a treatment with a KCN solution. If a sulfurization was carried out, this treatment step is necessary, whereas it can be considered to be optional after selenization.
In a preferred embodiment, the next step is to deposit a buffer layer onto the CIS
or CIGS semiconductor. For example, CdS, ZnS, ZnSe, ZnO or CdZnS can be used as the layer materials. Other possible materials are In-Se compounds or In-S
compounds. These buffer layers can be deposited by means of coating methods such as CVD, PVD, or by wet-chemical (chemical bath deposition) methods or other suitable methods. The deposition by means of chemical bath deposition has In another especially preferred embodiment of the invention, the next step is to deposit high-resistance ZnO (i-ZnO) onto the layer structure. The deposition of After the deposition of high-resistance ZnO (approx. 50 nm), in an especially pre-for further use in the production of solar cells. The semiconductor elements according to the invention can be subsequently incorporated in various ways into solar cells. For example, in another aspect of the invention, the spherical semiconductor elements are embedded in a solar cell as is shown in illustrations (a) 25 to (d) of Figure 2.
Illustration (a) of Figure 2 shows the incorporation of the semiconductor elements 11 into an insulating support layer 70. Here, it has proven to be advantageous to use a flexible film as the support layer. The support layer preferably consists of a 30 thermoplastic polymer which can be, for instance, a polymer from the group of the polycarbonates or polyesters. Pre-polymerized resins from the group of the epox.
ides, polyurethanes, polyactylies and/or polyimides can be used. Moreover, a liq-uid polymer can be used into which the spheres are pressed and which subse-quently hardens, The semiconductor elements 11 are preferably incorporated into the support layer 70 in such a way that they protrude from the surface of the layer on at least one side of the support layer. For this purpose, the particles can be applied, for exam-ple, by means of scattering, dusting and/or printing, after which they are pressed in. In order to press the bodies into the support layer, the latter can, for instance, be heated up.
In another embodiment of the invention, the particles are incorporated into a pre-pared matrix of a support layer having recesses into which the particles are incorporated. In order to attach the bodies to the support layer, a heating and/or pressing procedure can be carried out, If the semiconductor elements are supposed to protrude on both sides of the sup-port layer, the support layer can be situated on a flexible base when the elements are incorporated, so that the semiconductor elements can be pressed so far into the support layer that parts of them emerge from the bottom of the support layer.
In an especially preferred embodiment of the invention, the next step is to remove parts of the semiconductor elements on one side of the support layer. Parts of the support layer can also be removed in this process. This is shown in the illustration (b) of Figure 2 by an arrow. Here, the support layer 70 is preferably removed down to a layer thickness at which parts of the incorporated bodies are also removed. In the embodiment shown, the removal extends all the way to the back contact layer 30 of the semiconductor element 11 as shown by a dotted line. If the semiconductor elements are incorporated into the support layer in such a way that they protrude from both sides of the layer, it is also possible to process the semiconductor elements on one side without additional removal of the support layer so that, after the removal procedure, the semiconductor elements either pro-trude further from the support layer or are flush with it.
The removal of the semiconductor elements or of the support layer can also be 5 carried out at different points in time before the application of a later back contact 80 on this side. The removal of the semiconductor elements and/or of the support layer can be done by mechanical procedures such as grinding or polishing, etching, thermal energy input such as, for instance, using a laser or radiation or else by means of photolithographic processes.
In another process step, a conductive back contact layer 80 is applied onto the side on which the semiconductor elements had been removed. Examples of conductive material for this back contact include substances from various classes of polymers.
Especially well-suited materials are epoxy resins, polyurethanes and/or poly-imides that have been provided with suitable conductive particles such as carbon, indium, nickel, molybdenum, iron, nickel chromium, silver, aluminum and/or the corresponding alloys or oxides. Another possibility comprises intrinsic conductive polymers. These include, for example, polymers from the group of the PANis.
Other materials that can be employed are TCOs or suitable metals, In the case of TCOs and metals, the back contact can be applied with PVD or CVD methods.
In another process step, a conductive front contact layer 90 is applied onto the side of the support layer on which no semiconductor elements have been removed.
This can also be carried out with methods such as PVD or CVD. Various transpar-ent conductive oxides (TCOs) can be used as the conductive material of the front contact.
Other function layers can be deposited before or after the deposition of a front contact and a back contact. The selection of the other function layers depends especially on the semiconductor elements employed, Function layers such as, for example, buffer layers that have already been deposited onto the semiconductor elements do not necessarily have to be deposited any more for the production of the solar cell having integrated semiconductor elements. All of the required deposition and processing steps yield a solar cell from which a photovoltaic mod-ule can be made. One or more of the solar cells can be connected in series, for example, and joined to form a module at which the generated current is tapped.
List of reference numerals layer structure, precursor layer structure 11 semiconductor element 5 20 substrate, substrate core 30 back contact layer of a semiconductor element 40 rust precursor layer 50 second precursor layer 60 I-III-VI compound semiconductor, CIS or CIGS layer 10 70 support layer, insulating 80 back contact layer of a solar cell 90 front contact layer of a solar cell
According to the invention, this is achieved by a spherical or grain-shaped semiconductor element for use in a solar cell. The method for the production of such a semiconductor element is characterized by the application of a conductive back contact layer onto a spherical or grain-shaped substrate core, by the application of a first precursor layer made of copper or copper gallium, by the application of a second precursor layer made of indium and by the reaction of the precursor layers with sulfur and/or selenium to form a I-III-VI compound semiconductor.
The reaction of the precursor layers takes place in the presence of selenium and/or sulfur and is referred to as selenization or sulfurization. These processes can be carried out in various ways with parameters that are coordinated with the given process. These include These parameters include, for example, temperature, time, atmosphere and pressure. The selenization or sulfurization can take place, for example, in the vapor, melts or salt melts of the reaction element in question or in the salt melts with admixtures of sulfur and/or selenium. The elements sulfur and selenium can be used simultaneously as well as consecutively for reaction purposes. In an especially preferred embodiment of the invention, the reaction takes place in hydrogen compounds of sulfur or selenium.
In order to obtain a I-III-VI compound semiconductor layer with defined properties, certain parameters of the precursor layers have to be set. Aside from the composition, these parameters also include the thicknesses of the individual layers. Here, due to the spherical shape and the consequently varying diameter, if applicable, layer thickness ratios should be selected that are different from those of prior-art methods in order to create planar 1-Ill-VI
compound semiconductors.
- 4a -In an especially preferred embodiment of the invention, the substrate core that is to be coated consists of glass, especially soda-lime glass, since this is a good source of sodium for the layer structuring. The main constituent of the conductive back contact layer is preferably molybdenum. In an especially preferred embodiment of the invention, the back contact layer contains up to 20% by weight of gallium in order to improve the adhesion. The individual layers can each be applied by means of physical vapor deposition (PVD) methods such as sputtering or evaporation coating or else by means of chemical vapor deposition (CVD) methods.
=
The precursor layers can be alloyed at temperatures of typically > 220 C j>
428 F]
prior to the reaction to form a 1-TIT-VI compound semiconductor, Additional processing steps or coatings can be implemented after the reaction of the precur-Consequently, the spherical or grain-shaped semiconductor element according to the invention for use in solar cells has a spherical or grain-shaped substrate core that is coated at least with one back contact layer and with one I-1II-VI
compound semiconductor. The substrate core preferably consists of glass, metal or ceramics Spherical or grain-shaped semiconductor elements produced with the described process steps constitute elements for further use in the production of solar cells.
call for correspondingly large reactors in which, for instance, large total masses have to be heated up and cooled off again during the reaction under the influence of heat. This entails a high energy demand. In contrast, the production of spherical or grain-shaped semiconductor elements for subsequent incorporation into solar cells requires far less energy since relatively small volumes have to be reacted in the reactors in question.
Another advantage is the higher flexibility during the production process. If, for example, with conventional solar cell surfaces, larger or smaller structures are to be reacted in a reactor, an appropriate new reactor has to be provided in order to be able to precisely set the requisite parameters. This is very cost-intensive. The production of such conventional thin-layer modules is thus limited by the appara-tuses employed for manufacturing the semiconductor layer. In contrast, in the production of the spherical semiconductor elements according to the invention, an existing reactor can be augmented by additional reactors in order to produce the necessary quantity of elements. Hence, this greatly simplifies the later production of solar cells for which no reactor is needed but rather only systems for applying additional layers.
Moreover, thanks to the spherical shape, practical layer systems can be achieved that might not be obtainable with flat semiconductor structures. For example, the required thickness of the deposited layers is less, As a result, for example, a back contact layer made of molybdenum and gallium can be used without the resistance of the layer becoming too great, which is the case with flat structures.
Thc method according to the invention for the production of a solar cell having integrated spherical or grain-shaped semiconductor elements is used to subse-quently incorporate semiconductor elements into a solar cell. The method pro-vides for incorporating spherical semiconductor elements into an insulating sup-port layer, whereby the semiconductor elements protrude from the surface of the support layer on at least one side of the support layer, and the spherical or grain-shaped semiconductor elements each consist of a substrate core that is coated at least with one conductive back contact layer and with one 1-HI-VI compound semiconductor layer. Parts of the semiconductor elements are removed on one side of the support layer so that preferably a surface of the back contact layer of In an especially preferred embodiment of the invention, the semiconductor ele-ments are applied onto the support layer by means of scattering, dusting and/or printing and they are subsequently pressed into the support layer so that they become embedded to a certain extent in the support layer. if the support layer is a The support layer can also be configured as a matrix with recesses into which the When parts of the semiconductor elements are removed, part of the support layer can also be removed along with it. The removal can be done, for example, by PC17E1'2004/010615 Thus, the solar cell according to the invention having integrated spherical or grain-shaped semiconductor elements has an insulating support layer into which the semiconductor elements are incorporated, whereby the semiconductor ele-ments protrude from the layer on at least one side of the support layer. The solar cell also has a front contact layer on one side and a back contact layer on the other side. On the side of the back contact layer, several semiconductor elements have a surface that is free of I-III-VI compound semiconductors and that thus frees the back contact layer of the semiconductor element. These surfaces are in direct con-tact with the back contact layer of the solar cell.
In an especially preferred embodiment of the invention, the support layer consists of an insulating material such as, for example, a polymer. The spherical semiconductor elements were preferably produced by means of the method according to the invention and the front contact layer consists, for example, of a transparent conductive oxide (TCO). The back contact layer consists of a conduc-tive material such as a metal, a TCO or a polymer having conductive particles.
The solar cell can have other function layers in addition to the front contact layer and the back contact layer.
Once all of the process steps have been completed, a solar cell having integrated semiconductor elements has been made that entails a number of advantages, espe-cially in comparison to planar semiconductor structures. The essential advantage ¨
in addition to the simplified production ¨ lies in the curved surfaces of the semiconductor elements which can be struck by incident light, irrespective of the incidence direction. Thus, even diffuse light can be used more efficiently in order to generate electricity.
Further advantages, special features and advantageous embodiments of the inven-tion can be gleaned from the subordinate claims and from the presentation below of preferred embodiments making reference to the figures.
The figures show the following:
Figure 1 in illustration (a), an especially preferred embodiment of a layer struc-ture for the production of a spherical semiconductor element and in illustration (b), a semiconductor element produced by means of the method according to the invention; and Figure 2 in illustrations (a) to (d), the process steps according to the invention during the incorporation of a spherical semiconductor element into a solar cell, Figure 1, illustration (a), shows an especially preferred embodiment of a layer structure 10 for the production of a spherical or grain-shaped semiconductor ele-ment Ii. The layer structure 10 can also be seen as the precursor layer structure for the later reaction to form a I-III-VI compound semiconductor. In the first step of the method according to the invention for the production of a spherical semiconductor element Ii, a spherical substrate core 20 is coated with a back con-tact 30. The spherical substrate preferably consists of glass, but it can also be made of other materials such as metals or ceramics. When glass is employed, for example, soda-lime glass can be used, which is a good source of sodium for the later layer structuring. Other glass compositions can also be used.
The substrate is essentially spherical, but the shape can also diverge from a pure spherical shape. Depending on the production process, the resultant spheres can also be designated as being grain-shaped. Hollow bodies made of the above-men-tioned materials can also be used. The diameter of the spheres is in the order of magnitude of 0.5 mm to 1 mm, a diameter of approximately 0.2 mm preferably being selected.
The back contact 30 is applied onto the spherical substrate in such a way that the entire surface of the sphere is coated. The material for the back contact is prefera-bly molybdenum, but other suitable conductive materials such as, for instance, tungsten or vanadium can also be used.
The semiconductor core 20 can be coated by means of PVD methods such as 5 sputtering or evaporation coating. CVD methods can also be used; in this context, it must be pointed out that sputtering a large number of small substrate spheres is a very time-consuming process that, in view of the attainable throughput rate, is less suitable than other methods. The thickness of the back contact layer is in the order of magnitude of 0.1 gm to I gm.
In order to improve the adhesion of subsequent layers to the back contact layer, a gallium layer can be applied onto the molybdenum layer. In an especially pre-ferred embodiment of the invention, the gallium is incorporated into the molybde-num layer in order to increase the adhesion. This can involve a gallium content of up to 20% by weight. In actual practice, this approach is normally avoided for flat solar cells since it increases the resistance of the back contact in a detrimental manner. However, a gallium-molybdenum layer has proven to be advantageous for the production of the semiconductor elements according to the invention, since thinner layers can be achieved than with flat semiconductors and their greater resistance does not entail any serious drawbacks.
According to the invention, a 1-11.1-VI compound semiconductor is selected as the semiconductor compound. These semiconductors, which are also referred to as chalcopyrites, also include, for example, copper indium diselenide, copper indium sulfide, copper indium gallium sulfide and copper indium gallium diselenide.
In order to produce such a CuGa/InS/Se2 layer on the substrate, first of all, precur-sor layers made of copper, gallium and/or indium are applied and these are reacted in a subsequent selenization or sulfurization process to form the envisaged semiconductors. The precursor layers can be applied with the same methods as the back contact so that here, too, PVD methods such as sputtering and evaporation coating or CVD methods can be employed. As the first precursor layer 40, in an especially preferred embodiment of the invention, the spherical substrate is coated with copper. In order to improve the adhesion between this first layer and the back contact, a thin copper-gallium layer can be applied ahead of time as an adhesive.
In a first embodiment of the invention, a second precursor layer 50 in the form of indium is deposited onto the copper layer. An alternating application of Cu/In layer packets (e.g. Cugn/Cu/In) is likewise possible. The Cu/In layers are subse-quently sulfurized with sulfur to form CuInS and a so-called CIS layer is formed.
The CIS layer 60 resulting from the precursors and the sulfurization process is shown on the semiconductor element 11 in illustration (b). The precursor layer system consisting of copper and indium can optionally be alloyed at an elevated temperature of typically T> 220 C (428 F] prior to the sulfurization, which is advantageous for the adhesion and the later reaction with selenium and/or sulfur.
This step, however, is not absolutely necessary.
The layer thicknesses of the Cu and In layers are determined by the envisaged layer thickness of the CIS semiconductor, Preferably, the thickness of the CIS
layer 60 is in the order of magnitude of 1 gm to 3 gm. Moreover, it has proven to be advantageous for the atomic ratio of Cu to ln to be in the order of magnitude of to 2. Special preference is given to atomic ratios of copper to indium of between 1.2 and 1.8.
In a second embodiment of the invention, a copper layer or a copper-gallium layer is applied onto the back contact layer 30 as a first precursor layer 40. This first precursor layer is, in turn, followed by a second precursor 50 in the form of an indium layer, whereby the two layers are subsequently selenized into CuIn/GaSe2 and form a CIGS layer. The copper-indium/gallium layer system here can also optionally be alloyed at an elevated temperature of typically T> 220 C [428 F].
In this embodiment, the layer thicknesses are likewise dependent on the envisaged atomic ratio Cugln+Ga) after the selenization. It has proven to be advantageous for this ratio to be < 1. The layer thickness of the CIGS layer after the selenization is preferably in the order of magnitude of 1 gm to 3 gm. It has turned out that the copper content of the finished CIGS layer can be set smaller than the stoichiometrically necessary value.
The spheres coated with the precursors can be reacted by means of selenization with selenium anclior by means of sulfurization with sulfur. Various methods can be used for this purpose. In an especially preferred embodiment of the invention, the spheres are reacted in a vacuum or at atmospheric pressure with a vapor of the element in question (Sc and/or S). This reaction takes place employing certain parameters such as, for instance, temperature, time, process duration, pressure and partial pressure. The reaction can also take place in a melt made up of the ele-ments. Another possibility for the reaction is the salt melt containing S
and/or Se.
In another embodiment of the invention, the spheres are reacted to form hydrogen compounds of sulfur and/or of selenium. This can take place, for example, at atmospheric pressure or at a pressure that is less than atmospheric pressure.
Sulfur as well as selenium can be used consecutively or simultaneously during the reac-tion.
In an especially preferred embodiment of the invention, the next process step after the reaction of the spheres is to remove surface layers that have a detrimental effect. These can be, for example, CuS compounds that were formed during the reaction process. One way to remove such layers is through a treatment with a KCN solution. If a sulfurization was carried out, this treatment step is necessary, whereas it can be considered to be optional after selenization.
In a preferred embodiment, the next step is to deposit a buffer layer onto the CIS
or CIGS semiconductor. For example, CdS, ZnS, ZnSe, ZnO or CdZnS can be used as the layer materials. Other possible materials are In-Se compounds or In-S
compounds. These buffer layers can be deposited by means of coating methods such as CVD, PVD, or by wet-chemical (chemical bath deposition) methods or other suitable methods. The deposition by means of chemical bath deposition has In another especially preferred embodiment of the invention, the next step is to deposit high-resistance ZnO (i-ZnO) onto the layer structure. The deposition of After the deposition of high-resistance ZnO (approx. 50 nm), in an especially pre-for further use in the production of solar cells. The semiconductor elements according to the invention can be subsequently incorporated in various ways into solar cells. For example, in another aspect of the invention, the spherical semiconductor elements are embedded in a solar cell as is shown in illustrations (a) 25 to (d) of Figure 2.
Illustration (a) of Figure 2 shows the incorporation of the semiconductor elements 11 into an insulating support layer 70. Here, it has proven to be advantageous to use a flexible film as the support layer. The support layer preferably consists of a 30 thermoplastic polymer which can be, for instance, a polymer from the group of the polycarbonates or polyesters. Pre-polymerized resins from the group of the epox.
ides, polyurethanes, polyactylies and/or polyimides can be used. Moreover, a liq-uid polymer can be used into which the spheres are pressed and which subse-quently hardens, The semiconductor elements 11 are preferably incorporated into the support layer 70 in such a way that they protrude from the surface of the layer on at least one side of the support layer. For this purpose, the particles can be applied, for exam-ple, by means of scattering, dusting and/or printing, after which they are pressed in. In order to press the bodies into the support layer, the latter can, for instance, be heated up.
In another embodiment of the invention, the particles are incorporated into a pre-pared matrix of a support layer having recesses into which the particles are incorporated. In order to attach the bodies to the support layer, a heating and/or pressing procedure can be carried out, If the semiconductor elements are supposed to protrude on both sides of the sup-port layer, the support layer can be situated on a flexible base when the elements are incorporated, so that the semiconductor elements can be pressed so far into the support layer that parts of them emerge from the bottom of the support layer.
In an especially preferred embodiment of the invention, the next step is to remove parts of the semiconductor elements on one side of the support layer. Parts of the support layer can also be removed in this process. This is shown in the illustration (b) of Figure 2 by an arrow. Here, the support layer 70 is preferably removed down to a layer thickness at which parts of the incorporated bodies are also removed. In the embodiment shown, the removal extends all the way to the back contact layer 30 of the semiconductor element 11 as shown by a dotted line. If the semiconductor elements are incorporated into the support layer in such a way that they protrude from both sides of the layer, it is also possible to process the semiconductor elements on one side without additional removal of the support layer so that, after the removal procedure, the semiconductor elements either pro-trude further from the support layer or are flush with it.
The removal of the semiconductor elements or of the support layer can also be 5 carried out at different points in time before the application of a later back contact 80 on this side. The removal of the semiconductor elements and/or of the support layer can be done by mechanical procedures such as grinding or polishing, etching, thermal energy input such as, for instance, using a laser or radiation or else by means of photolithographic processes.
In another process step, a conductive back contact layer 80 is applied onto the side on which the semiconductor elements had been removed. Examples of conductive material for this back contact include substances from various classes of polymers.
Especially well-suited materials are epoxy resins, polyurethanes and/or poly-imides that have been provided with suitable conductive particles such as carbon, indium, nickel, molybdenum, iron, nickel chromium, silver, aluminum and/or the corresponding alloys or oxides. Another possibility comprises intrinsic conductive polymers. These include, for example, polymers from the group of the PANis.
Other materials that can be employed are TCOs or suitable metals, In the case of TCOs and metals, the back contact can be applied with PVD or CVD methods.
In another process step, a conductive front contact layer 90 is applied onto the side of the support layer on which no semiconductor elements have been removed.
This can also be carried out with methods such as PVD or CVD. Various transpar-ent conductive oxides (TCOs) can be used as the conductive material of the front contact.
Other function layers can be deposited before or after the deposition of a front contact and a back contact. The selection of the other function layers depends especially on the semiconductor elements employed, Function layers such as, for example, buffer layers that have already been deposited onto the semiconductor elements do not necessarily have to be deposited any more for the production of the solar cell having integrated semiconductor elements. All of the required deposition and processing steps yield a solar cell from which a photovoltaic mod-ule can be made. One or more of the solar cells can be connected in series, for example, and joined to form a module at which the generated current is tapped.
List of reference numerals layer structure, precursor layer structure 11 semiconductor element 5 20 substrate, substrate core 30 back contact layer of a semiconductor element 40 rust precursor layer 50 second precursor layer 60 I-III-VI compound semiconductor, CIS or CIGS layer 10 70 support layer, insulating 80 back contact layer of a solar cell 90 front contact layer of a solar cell
Claims (40)
1. A method for the production of a spherical or grain-shaped semiconductor element (11) for use in a solar cell, characterized by the following steps:
.cndot. application of a conductive back contact layer (30) onto a spherical or grain-shaped substrate core (20) that consists of soda-lime glass;
.cndot. application of a first precursor layer (40) made of copper or copper gallium;
.cndot. application of a second precursor layer (50) made of indium;
.cndot. reaction of the precursor layers (40) and (50) with sulfur and/or selenium to form a I-III-VI compound semiconductor, whereby the reaction of the layer structure (10) is carried out in a melt of the reaction element sulfur or selenium, or the reaction of the layer structure (10) is carried out in hydrogen compounds of the reaction element sulfur or selenium, whereby the reaction in hydrogen compounds is carried out at atmospheric pressure or at a pressure lower than atmospheric pressure.
.cndot. application of a conductive back contact layer (30) onto a spherical or grain-shaped substrate core (20) that consists of soda-lime glass;
.cndot. application of a first precursor layer (40) made of copper or copper gallium;
.cndot. application of a second precursor layer (50) made of indium;
.cndot. reaction of the precursor layers (40) and (50) with sulfur and/or selenium to form a I-III-VI compound semiconductor, whereby the reaction of the layer structure (10) is carried out in a melt of the reaction element sulfur or selenium, or the reaction of the layer structure (10) is carried out in hydrogen compounds of the reaction element sulfur or selenium, whereby the reaction in hydrogen compounds is carried out at atmospheric pressure or at a pressure lower than atmospheric pressure.
2. The method according to claim 1, characterized in that the main constituent of the conductive back contact layer (30) is molybdenum.
3. The method according to claim 2, characterized in that the conductive back contact layer (30) contains up to 20% by weight of gallium in order to improve the adhesion.
4. The method according to any one of claims 1 to 3, characterized in that the layers (30; 40; 50) are each applied by means of PVD or CVD methods.
5. The method according to any one of claims 1 to 4, characterized in that a layer structure (10) comprising precursor layers (40; 50) is alloyed at a temperature of T > 220°C (> 428°F] prior to the reaction to form a l-Ill-VI
compound semiconductor.
compound semiconductor.
6. The method according to any one of claims 1 to 5, characterized in that a treatment with a KCN solution is carried out after the reaction of the layer structure (10) to form a I-III-VI compound semiconductor.
7. The method according to any one of claims 1 to 6, characterized in that a buffer layer is deposited after the reaction of the layer structure (10) to form a l-lII-VI
compound semiconductor.
compound semiconductor.
8. The method according to any one of claims 1 to 7, characterized in that a high-resistance ZnO layer and a low-resistance ZnO layer are deposited after the reaction of the layer structure (10) to form a l-lll-VI compound semiconductor.
9. The method according to either claim 7 or 8, characterized in that the buffer layer and/or the high-resistance and the low-resistance layers are deposited by means of PVD or CVD methods.
10. A spherical or grain-shaped semiconductor element for use in solar cells, characterized in that the semiconductor element (11) has a spherical or grain-shaped substrate core (20) that consists of soda-lime glass and that is coated at least with one back contact layer (30) made of molybdenum and with one l-lll-VI
compound semiconductor.
compound semiconductor.
11. The semiconductor element according to claim 10, characterized in that the diameter of the substrate core (20) is in the range of 0.1 mm to 1 mm, especially approximately 0.2 mm.
12. The semiconductor element according to either claim 10 or 11, characterized in that the thickness of the back contact layer (30) is in the range of 0.1 µm to 1 µm.
13. The semiconductor element according to any one of claims 10 to 12, characterized in that the l-lll-Vl compound semiconductor layer (60) consists of a compound from the group of the copper indium sulfides, copper indium diselenides, copper indium gallium sulfides or copper indium gallium diselenides.
14. The semiconductor element according to any one of claims 10 to 13, characterized in that the thickness of the l-lll-Vl compound semiconductor layer (60) is in the range of 1 µm to 3 µm.
15. The semiconductor element according to any one of claims 10 to 14, characterized in that the semiconductor element (11) has a buffer layer above the l-lII-Vl compound semiconductor layer (60).
16. The semiconductor element according to claim 15, characterized in that the buffer layer consists of a material from the group comprising CdS, ZnS, ZnSe, ZnO, indium selenium compounds or indium sulfur compounds.
17. The semiconductor element according to either claim 15 or 16, characterized in that the thickness of the buffer layer is in the range of 20 nm to 200 nm.
18. The semiconductor element according to any one of claims 10 to 17, characterized in that the semiconductor element has a high-resistance and a low-resistance ZnO layer above the compound semiconductor layer (60).
19. The semiconductor element according to claim 18, characterized in that the thickness of the high-resistance layer is in the range of 10 nm to 100 nm, whereas the thickness of the low-resistance ZnO layer is in the range of 0.1 µm to 2 µm.
20. The semiconductor element according to any one of claims 10 to 19, characterized in that the semiconductor element (11) was produced by a method according to any one of claims 1 to 9.
21. A method for the production of a solar cell having integrated spherical or grain-shaped semiconductor elements, characterized by the following features:
.cndot. incorporation of several spherical or grain-shaped semiconductor elements (11) into an insulating support layer (70), whereby the semiconductor elements (11) protrude from the surface of the support layer on at least one side of the support layer, and the semiconductor elements (11) each consist of a spherical or grain-shaped substrate core (20) that consists of soda-lime glass and that is coated at least with one conductive back contact layer (30) and with one l-lII-VI compound semiconductor layer (60);
.cndot. removal of parts of the semiconductor elements (11) on one side of the support layer (70) so that a surface of the conductive back contact layer (30) of the semiconductor elements (11) is exposed;
.cndot. application of a back contact layer (80) onto the side of the support layer (70) on which parts of the semiconductor elements (11) have been removed; and .cndot. application of a front contact layer (90) onto the side of the support layer (70) on which no semiconductor elements (11) have been removed.
.cndot. incorporation of several spherical or grain-shaped semiconductor elements (11) into an insulating support layer (70), whereby the semiconductor elements (11) protrude from the surface of the support layer on at least one side of the support layer, and the semiconductor elements (11) each consist of a spherical or grain-shaped substrate core (20) that consists of soda-lime glass and that is coated at least with one conductive back contact layer (30) and with one l-lII-VI compound semiconductor layer (60);
.cndot. removal of parts of the semiconductor elements (11) on one side of the support layer (70) so that a surface of the conductive back contact layer (30) of the semiconductor elements (11) is exposed;
.cndot. application of a back contact layer (80) onto the side of the support layer (70) on which parts of the semiconductor elements (11) have been removed; and .cndot. application of a front contact layer (90) onto the side of the support layer (70) on which no semiconductor elements (11) have been removed.
22. The method according to claim 21, characterized in that, in addition to parts of the semiconductor elements (11), part of the support layer (70) is also removed.
23. The method according to either claim 21 or 22, characterized in that the semiconductor elements (11) are applied onto the support layer (70) by means of scattering, dusting and/or printing and they are subsequently incorporated into the support layer.
24. The method according to any one of claims 21 to 23, characterized in that the support layer (70) is configured as a matrix with recesses into which the semiconductor elements (11) are incorporated.
25. The method according to any one of claims 21 to 24, characterized in that the semiconductor elements (11) are incorporated into the support layer (70) by means of a heating and/or pressing procedure.
26. The method according to any one of claims 21 to 25, characterized in that the removal of the semiconductor elements (11) and/or of the support layer (70) is done by grinding, polishing, etching, thermal energy input and/or by photolithographic processes.
27. The method according to any one of claims 21 to 26, characterized in that the back contact layer (80) and/or the front contact layer (90) are deposited by PVD or CVD methods or by other methods adapted to the material of the layer in question.
28. A solar cell having integrated spherical or grain-shaped semiconductor elements, characterized in that the solar cell has at least the following features:
.cndot. an insulating support layer (70) into which the spherical or grain-shaped semiconductor elements (11) are incorporated, whereby the semiconductor elements (11) protrude from the layer on at least one side of the support layer (70), and the semiconductor elements (11) each consist of a spherical or grain-shaped substrate core (20) that consists of soda-lime glass and that is coated at least with one conductive back contact layer (30) and with one compound semiconductor layer;
.cndot. a back contact layer (80) on one side of the support layer (70), whereby several semiconductor elements (11) on this side of the support layer have a surface that is free of l-lll-Vl compound semiconductors; and .cndot. a front contact layer (90) on the side of the support layer (70) on which the semiconductor elements (11) do not have a surface that is free of l-lll-Vl compound semiconductors.
.cndot. an insulating support layer (70) into which the spherical or grain-shaped semiconductor elements (11) are incorporated, whereby the semiconductor elements (11) protrude from the layer on at least one side of the support layer (70), and the semiconductor elements (11) each consist of a spherical or grain-shaped substrate core (20) that consists of soda-lime glass and that is coated at least with one conductive back contact layer (30) and with one compound semiconductor layer;
.cndot. a back contact layer (80) on one side of the support layer (70), whereby several semiconductor elements (11) on this side of the support layer have a surface that is free of l-lll-Vl compound semiconductors; and .cndot. a front contact layer (90) on the side of the support layer (70) on which the semiconductor elements (11) do not have a surface that is free of l-lll-Vl compound semiconductors.
29. The solar cell according to claim 28, characterized in that it is produced by means of a method according to any one of claims 21 to 27.
30. The solar cell according to either claim 28 or 29, characterized in that the insulating support layer (70) consists of a thermoplastic material.
31. The solar cell according to any one of claims 28 to 30, characterized in that the support layer (10) consists of a polymer from the group of the epoxides, polycarbonates, polyesters, polyurethanes, polyacrylics and/or polyimides.
32. The solar cell according to any one of claims 28 to 31, characterized in that the spherical or grain-shaped semiconductor elements (11) are semiconductor elements according to one or more of claims 10 to 20.
33. The solar cell according to any one of claims 28 to 32, characterized in that the semiconductor elements (11) are coated with a compound semiconductor from the group of the copper indium diselenides, copper indium disulfides, copper indium gallium diselenides and copper indium gallium diselenide disulfides.
34. The solar cell according to any one of claims 28 to 33, characterized in that the front contact layer (90) consists of a conductive material.
35. The solar cell according to claim 34, characterized in that the front contact layer (90) consists of a transparent conductive oxide (TCO).
36. The solar cell according to any one of claims 28 to 35, characterized in that the back contact layer (80) consists of a conductive material.
37. The solar cell according to claim 36, characterized in that the back contact layer (80) consists of a metal, a transparent conductive oxide (TCO) or a polymer having conductive particles.
38. The solar cell according to claim 37, characterized in that the back contact layer (80) consists of a polymer from the group of the epoxy resins, polyurethanes and/or polyimides having conductive particles from a group comprising carbon, indium, nickel, molybdenum, iron, nickel chromium, silver, aluminum and/or the corresponding alloys or oxides.
39. The solar cell according to claim 38, characterized in that the back contact layer (80) consists of an intrinsic conductive polymer.
40. A photovoltaic module, characterized in that it has at least one solar cell according to any one of claims 28 to 39.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03022301.0 | 2003-10-02 | ||
| EP03022301A EP1521308A1 (en) | 2003-10-02 | 2003-10-02 | Ball or grain-shaped semiconductor element to be used in solar cells and method of production; method of production of a solar cell with said semiconductor element and solar cell |
| PCT/EP2004/010615 WO2005034149A2 (en) | 2003-10-02 | 2004-09-22 | Spherical or grain-shaped semiconductor element for use in solar cells and method for producing the same; method for producing a solar cell comprising said semiconductor element and solar cell |
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| Publication Number | Publication Date |
|---|---|
| CA2540723A1 CA2540723A1 (en) | 2005-04-14 |
| CA2540723C true CA2540723C (en) | 2014-08-05 |
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| CA2540723A Expired - Fee Related CA2540723C (en) | 2003-10-02 | 2004-09-22 | Spherical or grain-shaped semiconductor element for use in solar cells and method for producing the same; method for producing a solar cell comprising said semiconductor element and solar cell |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20070089782A1 (en) |
| EP (3) | EP1521308A1 (en) |
| JP (2) | JP2007507867A (en) |
| KR (2) | KR101168260B1 (en) |
| CN (1) | CN100517764C (en) |
| CA (1) | CA2540723C (en) |
| WO (1) | WO2005034149A2 (en) |
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| US9105776B2 (en) * | 2006-05-15 | 2015-08-11 | Stion Corporation | Method and structure for thin film photovoltaic materials using semiconductor materials |
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| EP2341550A1 (en) | 2011-07-06 |
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| KR20120034826A (en) | 2012-04-12 |
| US20070089782A1 (en) | 2007-04-26 |
| KR20060115994A (en) | 2006-11-13 |
| KR101168260B1 (en) | 2012-07-30 |
| CN1860617A (en) | 2006-11-08 |
| WO2005034149A3 (en) | 2005-05-26 |
| EP1671336A2 (en) | 2006-06-21 |
| CA2540723A1 (en) | 2005-04-14 |
| JP2007507867A (en) | 2007-03-29 |
| EP1521308A1 (en) | 2005-04-06 |
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