US20090181179A1 - Sodium/Molybdenum Composite Metal Powders, Products Thereof, and Methods for Producing Photovoltaic Cells - Google Patents
Sodium/Molybdenum Composite Metal Powders, Products Thereof, and Methods for Producing Photovoltaic Cells Download PDFInfo
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- US20090181179A1 US20090181179A1 US12/013,263 US1326308A US2009181179A1 US 20090181179 A1 US20090181179 A1 US 20090181179A1 US 1326308 A US1326308 A US 1326308A US 2009181179 A1 US2009181179 A1 US 2009181179A1
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- United States
- Prior art keywords
- sodium
- metal powder
- molybdenum
- composite metal
- depositing
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- 239000000843 powder Substances 0.000 title claims abstract description 158
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 127
- 239000002184 metal Substances 0.000 title claims abstract description 127
- 239000002131 composite material Substances 0.000 title claims abstract description 106
- 239000011734 sodium Substances 0.000 title claims description 125
- 229910052708 sodium Inorganic materials 0.000 title claims description 121
- 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 title claims description 120
- 229910052750 molybdenum Inorganic materials 0.000 title claims description 90
- 239000011733 molybdenum Substances 0.000 title claims description 90
- 238000000034 method Methods 0.000 title claims description 87
- 239000002002 slurry Substances 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 150000003388 sodium compounds Chemical class 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims description 50
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 48
- 239000011684 sodium molybdate Substances 0.000 claims description 32
- 235000015393 sodium molybdate Nutrition 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 27
- 238000000151 deposition Methods 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000000717 retained effect Effects 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000006096 absorbing agent Substances 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 11
- 238000004544 sputter deposition Methods 0.000 claims description 11
- 238000007639 printing Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 238000001513 hot isostatic pressing Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000009694 cold isostatic pressing Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000007751 thermal spraying Methods 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 description 42
- 239000000047 product Substances 0.000 description 42
- 239000010408 film Substances 0.000 description 39
- 238000002485 combustion reaction Methods 0.000 description 21
- 239000002245 particle Substances 0.000 description 19
- 239000007921 spray Substances 0.000 description 13
- 229940126142 compound 16 Drugs 0.000 description 7
- 238000007596 consolidation process Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 239000000567 combustion gas Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- -1 for example Chemical compound 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- 238000009718 spray deposition Methods 0.000 description 3
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007970 homogeneous dispersion Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 241001279686 Allium moly Species 0.000 description 1
- 229910004616 Na2MoO4.2H2 O Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- QMXBEONRRWKBHZ-UHFFFAOYSA-N [Na][Mo] Chemical compound [Na][Mo] QMXBEONRRWKBHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- FDEIWTXVNPKYDL-UHFFFAOYSA-N sodium molybdate dihydrate Chemical compound O.O.[Na+].[Na+].[O-][Mo]([O-])(=O)=O FDEIWTXVNPKYDL-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
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- H01L31/02—Details
- H01L31/0224—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—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
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03923—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
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- 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
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- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/00—Stock material or miscellaneous articles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/31678—Of metal
Abstract
A method for producing a composite metal powder according to one embodiment of the invention may comprise: Providing a supply of molybdenum metal powder; providing a supply of a sodium compound; combining the molybdenum metal powder and the sodium compound with a liquid to form a slurry; feeding the slurry into a stream of hot gas; and recovering the composite metal powder.
Description
- This invention relates molybdenum-containing materials and coatings in general and more specifically to molybdenum coatings suitable for use in the manufacture of photovoltaic cells.
- Molybdenum coatings are well-known in the art and may be applied by a variety of processes in a wide variety of applications. One application for molybdenum coatings is in the production of photovoltaic cells. More specifically, one type of high-efficiency polycrystalline thin film photovoltaic cell involves an absorber layer comprising CuInGaSe2. Such photovoltaic cells are commonly referred to as “CIGS” photovoltaic cells after the elements comprising the absorber layer. In a common construction, the CuInGaSe2 absorber layer is formed or “grown” on a soda-lime glass substrate having a molybdenum film deposited thereon. Interestingly, it has been discovered that small quantities of sodium from the soda-lime glass substrate diffusing through the molybdenum film serve to increase the efficiency of the cell. See, for example, K. Ramanathan et al., Photovolt. Res. Appl. 11 (2003), 225; John H. Scofield et al., Proc. of the 24th IEEE Photovoltaic Specialists Conference, IEEE, New York, 1995, 164-167. While such efficiency gains are automatically realized in structures wherein the CIGS cell is deposited on soda-lime glass substrates, it has proven considerably more difficult to realize efficiency gains where other types of substrates are used.
- For example, there is considerable interest in forming CIGS cells on flexible substrates so that the cells may be made lighter and may be readily conformed to a variety of shapes. While such cells have been made and are being used, the flexible substrates involved do not contain sodium. Consequently, the performance of CIGS cells manufactured on such substrates may be improved by doping the molybdenum layer with sodium. See, for example, Jae Ho Yun et al., Thin Solid Films, 515, 2007, 5876-5879.
- A method for producing a composite metal powder according to one embodiment of the invention may comprise: Providing a supply of molybdenum metal powder; providing a supply of a sodium compound; combining the molybdenum metal powder and the sodium compound with a liquid to form a slurry; feeding the slurry into a stream of hot gas; and recovering the composite metal powder. Also disclosed is a composite metal powder produced according to this process.
- Another embodiment for producing a composite metal powder may comprise: Providing a supply of molybdenum metal powder; providing a supply of a sodium molybdate powder; combining the molybdenum metal powder and the sodium molybdate powder with water to form a slurry; feeding the slurry into a stream of hot gas; and recovering the composite metal powder. Also disclosed is a composite metal powder produced in accordance with this process.
- Also disclosed is a method for producing a metal article that comprises: Producing a supply of a composite metal powder by: providing a supply of molybdenum metal powder; providing a supply of a sodium compound; combining the molybdenum metal powder and the sodium compound with a liquid to form a slurry; feeding the slurry into a stream of hot gas; and recovering the composite metal powder; and consolidating the composite metal powder to form the metal article, the metal article comprising a sodium/molybdenum metal matrix. Also disclosed is a metal article produced accordance with this method.
- A method for producing a photovoltaic cell in accordance with the teachings provided herein may comprise: Providing a substrate; depositing a sodium/molybdenum metal layer on the substrate; depositing an absorber layer on the sodium/molybdenum metal layer; and depositing a junction partner layer on the absorber layer.
- A method for depositing a sodium/molybdenum film on a substrate may comprise: Providing a supply of a composite metal powder comprising molybdenum and sodium; and depositing the composite metal powder on the substrate by thermal spraying. Another method for depositing a film on a substrate may comprise: Sputtering a target comprising a sodium/molybdenum metal matrix, sputtered material from the target forming the sodium/molybdenum film. Another method for coating a substrate may comprise: Providing a supply of composite metal powder comprising molybdenum and sodium; and evaporating the composited metal powder to form a sodium/molybdenum film. A method for coating a substrate may comprise: Providing a supply of a composite metal powder comprising molybdenum and sodium; mixing the supply of composite metal powder with a vehicle, and depositing the mixture of the composite metal powder and the vehicle on the substrate by printing.
- Illustrative and presently preferred exemplary embodiments of the invention are shown in the drawings in which:
-
FIG. 1 is a schematic representation of one embodiment of basic process steps which may be utilized to produce a sodium/molybdenum composite metal powder; -
FIG. 2 is a process flow chart depicting methods for processing the composite metal powder mixture; -
FIG. 3 is a enlarged cross-section in elevation of a photovoltaic cell having a sodium/molybdenum metal layer; -
FIG. 4 is a scanning electron microscope image of a sodium/molybdenum composite metal powder mixture; -
FIG. 5 a is a spectral map produced by energy dispersive x-ray spectroscopy showing the dispersion of sodium in the image ofFIG. 4 ; -
FIG. 5 b is a spectral map produced by energy dispersive x-ray spectroscopy showing the dispersion of molybdenum in the image ofFIG. 4 ; -
FIG. 6 is a schematic representation of one embodiment of pulse combustion spray dry apparatus; and -
FIG. 7 is a plot showing the screen fraction distributions of exemplary composite metal powders produced in accordance with the teachings provided herein. - A process or
method 10 for producing a sodium/molybdenumcomposite metal powder 12 is illustrated inFIG. 1 and, briefly described, may comprise a supply of amolybdenum metal powder 14 and a supply of asodium compound 16, such as, for example, sodium molybdate (Na2MoO4) powder. Themolybdenum metal powder 14 andsodium molybdate powder 16 are combined with aliquid 18, such as water, to form aslurry 20. Theslurry 20 may then be spray dried, e.g., by a pulsecombustion spray dryer 22, in order to produce the sodium/molybdenumcomposite metal powder 12. - Referring now primarily to
FIG. 2 , the sodium/molybdenumcomposite metal powder 12 may be used in its as-recovered or “green” form as afeedstock 24 for a variety of processes and applications, many of which are shown and described herein, and others of which will become apparent to persons having ordinary skill in the art after having become familiar with the teachings provided herein. Alternatively, the “green”composite metal powder 12 may be further processed, e.g., by sintering 26, byclassification 28, or combinations thereof, before being used asfeedstock 24. The sodium/molybdenum composite metal powder feedstock 24 (e.g., in either the “green” form or in the processed form) may be used in a thermalspray deposition process 30 in order to deposit a sodium/molybdenum film 32 on asubstrate 34, as best seen inFIG. 3 . Such sodium/molybdenum films 32 may be used to advantage in a wide variety of applications. For example, and as will be described in further detail below, the sodium/molybdenum film 32 may comprise a portion of aphotovoltaic cell 36 and may be used to improve the efficiency of thephotovoltaic cell 36. In an alternate deposition process, thecomposite metal powder 12 may also be used as afeedstock 24 in aprinting process 38 which may also be used to form a sodium/molybdenum film or coating 32′ onsubstrate 34. - In still yet another embodiment, the composite
metal powder feedstock 24, again in either its “green” form or in its processed form, may be consolidated atstep 40 in order to produce ametal product 42, such as asputter target 44. Themetal product 42 may be used “as is” directly fromconsolidation 40. Alternatively, the consolidated product may be further processed, e.g., by sintering 46, in which case themetal product 42 will comprise a sintered metal product. In the case where themetal product 42 comprises a sputter target 44 (i.e., in either a sintered form or an un-sintered form), thesputter target 44 may be used, in a sputter deposition apparatus (not shown) in order to deposit a sodium/molybdenum film 32″ onsubstrate 34. SeeFIG. 3 . - Referring now primarily to
FIGS. 4 , 5 a, and 5 b, the sodium/molybdenumcomposite metal powder 12 comprises a plurality of generally spherically-shaped particles that are themselves agglomerations of smaller particles. Accordingly, thecomposite metal powder 12 may be characterized herein in the alternative as “soccer balls” formed of “BB's.” Moreover, and as is evidenced byFIGS. 5 a and 5 b, the sodium is highly dispersed within the molybdenum. That is, the sodium/molybdenum composite powders of the present invention are not mere combinations of sodium metal powders and molybdenum metal powders, but rather comprise substantially homogeneous dispersions or composite mixtures of sodium and molybdenum sub-particles that are fused or agglomerated together. The sodium/molybdenum metal powder composite is also of high density and possesses favorable flow characteristics. As will be discussed in further detail herein, exemplary sodium/molybdenumcomposite metal powders 12 produced in accordance with the teachings provided herein may have Scott densities in a range of about 2 g/cc to about 3 g/cc. Hall flowabilities range from less than about 35 s/50 g to as low as 30 s/50 g for the various example compositions shown and described herein. - A significant advantage of the present invention is that it provides a metallic combination of molybdenum and sodium that is otherwise difficult or impossible to achieve by conventional methods. Moreover, even though the sodium/molybdenum composite metal powder comprises a powdered material, it is not a mere mixture of sodium and molybdenum particles. Instead, the sodium and molybdenum sub-particles are actually fused together, so that individual particles of the powdered metal product comprise both sodium and molybdenum. Accordingly, powdered
feedstocks 24 comprising the sodium/molybdenum composite powders according to the present invention will not separate (e.g., due to specific gravity differences) into sodium particles and molybdenum particles. Furthermore, coatings or films produced from the sodium/molybdenum composite metal powders will have compositions that are similar to the compositions of the sodium/molybdenum metal powders since such deposition processes do not rely on the codeposition of separate molybdenum and sodium particles that would each have different deposition rates. - Besides the advantages associated with the ability to provide a composite metal powder wherein sodium is highly and evenly dispersed throughout molybdenum, the composite metal powders disclosed herein are also characterized by high densities and flowabilities, thereby allowing the composite metal powders to be used to advantage in a wide variety of power metallurgy processes that are now known in the art or that may be developed in the future. For example, the sodium molybdenum composite metal powders may be readily used in a wide variety of thermal spray deposition apparatus and associated processes to deposit sodium/molybdenum films or coatings on various substrates. The powders may also be readily used in a wide variety of consolidation processes, such as cold and hot isostatic pressing processes as well as pressing and sintering processes. The high flowability allows the powders disclosed herein to readily fill mold cavities, whereas the high densities minimizes shrinkage that may occur during subsequent sintering. Sintering can be accomplished by heating in an inert atmosphere or in hydrogen to further reduce oxygen content of the compact.
- In another embodiment, the sodium/molybdenum composite metal powders may be used to form sputter targets, which may then be used in subsequent sputter deposition processes to form sodium/molybdenum films and coatings. In one embodiment, such sodium/molybdenum films may used to increase the energy conversion efficiencies of photovoltaic cells.
- Having briefly described the sodium/molybdenum composite metal powders 12 of one present invention, methods for producing them, and how they may be used to produce sodium/molybdenum coatings or films on substrates, various embodiments of the composite powders, as well as methods for producing and using the composite powders will now be described in detail.
- Referring back now primarily to
FIG. 1 , amethod 10 for producing sodium/molybdenum composite powders 12 may comprise a supply ofmolybdenum metal powder 14 and a supply of asodium compound 16. Themolybdenum metal power 14 may comprise a molybdenum metal powder having a particle size in a range of about 0.1 μm to about 15 μm, although molybdenum metal powders 14 having other sizes may also be used. Molybdenum metal powders suitable for use in the present invention are commercially available from Climax Molybdenum, a Freeport-McMoRan Company, and from Climax Molybdenum Company, a Freeport-McMoRan Company, Ft. Madison Operations, Ft. Madison, Iowa (US). Alternatively, molybdenum metal powders from other sources may be used as well. - The
sodium compound 16 may comprise sodium molybdate, either in its anhydrous form (i.e., Na2MoO4) or as the dihydrate (i.e., Na2MoO4.2H2O), although other sodium-containing materials including, but not limited to elemental sodium, Na2O, and Na(OH), may be used. Sodium molybdate is usually available in powder form and may comprise any of a wide range of sizes. The particle size of thesodium molybdate powder 16 is not particularly critical in embodiments wherein water is used as the liquid 18, because sodium molybdate is soluble in water. Sodium molybdate powders suitable for use in the present invention are commercially available from Climax Molybdenum, a Freeport-McMoRan Company, Ft. Madison Operations, of Ft. Madison, Iowa (US). Alternatively, sodium molybdate may be obtained from other sources. - The
molybdenum metal powder 14 andsodium molybdate 16 may be mixed with a liquid 18 to form aslurry 20. Generally speaking, the liquid 18 may comprise deionized water, although other liquids, such as alcohols, volatile liquids, organic liquids, and various mixtures thereof, may also be used, as would become apparent to persons having ordinary skill in the art after having become familiar with the teachings provided herein. Consequently, the present invention should not be regarded as limited to theparticular liquids 18 described herein. In addition to the liquid 18, abinder 48 may be used as well, although the addition of abinder 48 is not required.Binders 48 suitable for use in the present invention include, but are not limited to, polyvinyl alcohol (PVA), Carbowax, and mixtures thereof. Thebinder 48 may be mixed with the liquid 18 before adding themolybdenum metal powder 14 and thesodium molybdate 16. Alternatively, thebinder 48 could be added to theslurry 20, i.e., after themolybdenum metal 14 andsodium molybdate 16 have been combined withliquid 18. - The
slurry 20 may comprise from about 15% to about 25% by weight liquid (e.g., either liquid 18 alone, or liquid 18 combined with binder 48), with the balance comprising themolybdenum metal powder 14 and thesodium compound 16. The sodium compound 16 (e.g., sodium molybdate) may be added in amounts suitable to provide thecomposite metal powder 12 and/or final product with the desired amount of “retained” sodium. Because the amount of retained sodium will vary depending on a wide range of factors, the present invention should not be regarded as limited to the provision of thesodium compound 16 in any particular amounts. Factors that may affect the amount ofsodium compound 16 that is to be provided inslurry 20 include, but are not limited to, the particular product that is to be produced, the particular “downstream” processes that may be employed, e.g., depending on whether the sodium/molybdenumcomposite metal powder 12 is sintered, and on whether the desired quantity of retained sodium is to be in the powder feedstock (e.g., 24) or in a deposited film or coating (e.g., 32, 32′, 32″). However, by way of example, the mixture ofmolybdenum metal 14 andsodium molybdate 16 may comprise from about 1% by weight to about 15% byweight sodium molybdate 18. Overall, then,slurry 20 may comprise from about 0% by weight (i.e., no binder) to about 2% byweight binder 48. The balance ofslurry 20 may comprise molybdenum metal powder 14 (e.g., in amounts ranging from about 58% by weight to about 84% by weight) and sodium molybdate 16 (e.g., in amounts ranging from about 1% by weight to about 15% by weight). -
Slurry 22 may then be spray dried by any of a wide range of processes that are now known in the art or that may be developed in the future in order to produce the compositemetal powder product 12, as would become apparent to persons having ordinary skill in the art after having become familiar with the teachings provided herein. Consequently, the present invention should not be regarded as limited to any particular drying process. However, by way of example, in one embodiment, theslurry 20 is spray dried in a pulsecombustion spray dryer 22. More specifically, pulsecombustion spray dryer 22 may be of the type shown and described in U.S. Patent Application Publication No. US 2006/0219056, of Larink, Jr., entitled “Metal Powders and Methods for Producing the Same,” which is specifically incorporated herein by reference for all that it discloses. - Referring now to
FIGS. 1 and 6 ,slurry 20 may be fed into pulsecombustion spray dryer 22, whereuponslurry 20 impinges a stream of hot gas (or gases) 50, which are pulsed at or near sonic speeds. The sonic pulses ofhot gas 50 contact theslurry 20 and drive-off substantially all of the water and form the compositemetal powder product 12. The temperature of the pulsating stream ofhot gas 50 may be in a range of about 300° C. to about 800° C., such as about 465° C. to about 537° C., and more preferably about 500° C. Generally speaking, the temperature of the pulsating stream ofhot gas 50 is below the melting point of the slurry constituents, but not below the melting point of elemental sodium. However, theslurry 20 is usually not in contact with thehot gases 50 long enough to transfer a significant amount of heat to theslurry 20, which is significant because of the low melting point of sodium metal. For example, in a typical embodiment, it is estimated that theslurry 20 is generally heated to a temperature in the range of about 93° C. to about 121° C. during contact with the pulsating stream ofhot gas 50. - As mentioned above, the pulsating stream of
hot gas 50 may be produced by apulse combustion system 22 of the type that is well-known in the art and readily commercially available. By way of example, in one embodiment, thepulse combustion system 22 may comprise a pulse combustion system of the type shown and described in U.S. Patent Application Publication No. 2006/0219056. Referring now toFIG. 6 ,combustion air 51 may be fed (e.g., pumped) through, aninlet 52 into theouter shell 54 of thepulse combustion system 22 at low pressure, whereupon it flows through aunidirectional air valve 56. The air then enters a tunedcombustion chamber 58 where fuel is added via fuel valves orports 60. The fuel-air mixture is then ignited by apilot 62, creating a pulsating stream ofhot combustion gases 64 which may be pressurized to a variety of pressures, e.g., in a range of about 15,000 Pa (about 2.2 psi) to about 20,000 Pa (about 3 psi) above the combustion fan pressure. The pulsating stream ofhot combustion gases 64 rushes downtailpipe 66 toward theatomizer 68. Just above theatomizer 68, quenchair 70 may be fed through aninlet 72 and may be blended with thehot combustion gases 64 in order to attain a pulsating stream ofhot gases 50 having the desired temperature. Theslurry 20 is introduced into the pulsating stream ofhot gases 50 via theatomizer 68. The atomized slurry may then disperse in theconical outlet 74 and thereafter enter a conventional tall-form drying chamber (not shown). Further downstream, the compositemetal powder product 12 may be recovered using standard collection equipment, such as cyclones and/or baghouses (also not shown). - In pulsed operation, the
air valve 56 is cycled open and closed to alternately let air into thecombustion chamber 58 and close for the combustion thereof. In such cycling, theair valve 56 may be reopened for a subsequent pulse just after the previous combustion episode. The reopening then allows a subsequent air charge (e.g., combustion air 51) to enter. Thefuel valve 60 then re-admits fuel, and the mixture auto-ignites in thecombustion chamber 58, as described above. This cycle of opening and closing theair valve 56 and combusting the fuel in thechamber 58 in a pulsing fashion may be controllable at various frequencies, e.g., from about 80 Hz to about 110 Hz, although other frequencies may also be used. - The “green” sodium/molybdenum composite
metal powder product 12 produced by the pulse combustion spray drying process described herein is illustrated inFIGS. 4 , 5 a, and 5 b, and comprises a plurality of generally spherically-shaped particles that are themselves agglomerations of smaller particles. As already described, the sodium is highly dispersed within the molybdenum, comprising a substantially homogeneous dispersion or composite mixture of sodium and molybdenum sub-particles that are fused together. More specifically,FIG. 5 a is a spectral map produced by energy dispersive x-ray spectroscopy (“EDS”) that illustrates the presence of sodium within the sample of thecomposite metal material 12 that is shown inFIG. 4 .FIG. 5 b is a spectral map produced by energy dispersive x-ray spectroscopy that shows the presence of molybdenum within the sample. As can be seen by comparingFIGS. 4 and 5 a and 5 b, the sodium is generally evenly and widely dispersed throughout the compositemetal powder product 12. - Generally speaking, the composite metal powder produce 12 produced in accordance with the teachings provided herein will comprise a wide range of sizes, and particles having sizes ranging from about 1 μm to about 100 μm, such as, for example, sizes ranging from about 5 μm to about 45 μm and from about 45 μm to about 90 μm, can be readily produced by the following the teachings provided herein. The composite
metal powder product 12 may be classified e.g., at step 28 (FIG. 2 ), if desired, to provide aproduct 12 having a more narrow size range. Sieve analyses of various exemplary compositemetal powder products 12 are provided inFIG. 7 , which is a plot of the particle size distributions (by U.S. Tyler mesh) of the “green” compositemetal powder product 12 produced by slurry compositions comprising 3, 7, 9, and 15% byweight sodium molybdate 18. - As mentioned above, the sodium/molybdenum
composite metal powder 12 is also of high density and is generally quite flowable. Exemplary compositemetal powder products 12 have Scott densities (i.e., apparent densities) in a range of about 2 g/cc to about 3 g/cc, as identified in the various Examples set forth herein. Hall flowabilities range from about 35 s/50 g to as low as 30 s/50 g, again as identified in the various Examples set forth herein. One example composition (i.e., Example 12) had no flow, however. - As already described, the
pulse combustion system 22 provides a pulsating stream ofhot gases 50 into which is fed theslurry 20. The contact zone and contact time are very short, the time of contact often being on the order of a fraction of a microsecond. Thus, the physical interactions ofhot gas 50, sonic waves, andslurry 20 produces the compositemetal powder product 12. More specifically, theliquid component 18 ofslurry 20 is substantially removed or driven away by the sonic (or near sonic) pulse waves ofhot gas 50. The short contact time also ensures that the slurry components are minimally heated, e.g., to levels on the order of about 93° C. to about 121° C. at the end of the contact time, temperatures which are sufficient to evaporate theliquid component 18. - In certain instances, residual amounts of liquid (e.g., liquid 18 and/or
binder 48, if used) may remain in the resulting “green” compositemetal powder product 12. Any remainingliquid 18 may be driven-off (e.g., partially or entirely), by a subsequent sintering orheating step 26. SeeFIG. 2 . Generally speaking, the heating orsintering process 26 is conducted at a moderate temperatures in order to drive off the liquid components and oxygen, but not substantial quantities of sodium. Some sodium may be lost duringheating 26, which will reduce the amount of retained sodium in the sintered orfeedstock product 24. It is also generally preferred, but not required, to conduct theheating 26 in a hydrogen atmosphere in order to minimize oxidation of thecomposite metal powder 12. Retained oxygen is low, less than about 6%, and generally less than about 2%, as indicated in the Examples provided below.Heating 26 may be conducted at temperatures within a range of about 500° C. to about 825° C. Alternatively, temperatures as high as 1050° C. may be used for short periods of time. However, such higher temperatures will usually reduce the amount of retained sodium in the final product. - It may also be noted that the agglomerations of the metal powder product preferably retain their shapes (in many cases, though not necessarily, substantially spherical), even after the
heating step 26. Flowability data (Hall data) in heated and/or green forms are also generally very good (e.g., in a range of about 30-35 s/50 g), as described relative to the Examples provided herein. - As noted above, in some instances a variety of sizes of agglomerated products may be produced during the drying process, and it may be desirable to further separate or classify the composite
metal powder product 12 into a metal powder product having a size range within a desired product size range. For example, most of the composite metal powder material produced will comprise particle sizes in a wide range (e.g., from about 1 μm to about 150 μm), with a substantial amount of product being in the range of about 5 μm to about 45 μm (i.e., −325 U.S. Tyler mesh) and again in the range of about 45 μm to 90 μm (i.e., −170+325 U.S. Tyler mesh). SeeFIG. 7 . A process hereof may yield a substantial percentage of product in this product size range; however, there may be remainder products, particularly the smaller products, outside the desired product size range which may be recycled through the system, though liquid (e.g., water) would again have to be added to create an appropriate slurry composition. Such recycling is an optional alternative (or additional) step or steps. - The
composite metal powder 12 may be used in its as-recovered or “green” form as afeedstock 24 for a variety of processes and applications, several of which are shown and described herein, and others of which will become apparent to persons having ordinary skill in the art after having become familiar with the teachings provided herein. Alternatively, the “green” compositemetal powder product 12 may be further processed, such as, for example, by heating orsintering 26, by classification 23, and/or combinations thereof, before being used asfeedstock 24. - As mentioned above, the sodium/molybdenum
composite metal powder 12 may be used in various apparatus and processes to deposit sodium/molybdenum films on substrates. In one application, such sodium/molybdenum films can be used to advantage in the fabrication of photovoltaic cells. For example, it is known than the energy conversion efficiency of a CIGS photovoltaic cell can be increased if sodium is allowed to diffuse into the molybdenum layer typically used to form an ohmic contact of the photovoltaic cell. Such efficiency gains are automatically realized in CIGS structures wherein the molybdenum ohmic contact is deposited on a soda-glass substrate. However, they are not realized in structures wherein soda-glass is not used as a substrate. - Referring now to
FIG. 3 , aphotovoltaic cell 36 may comprise asubstrate 34 on which a sodium/molybdenum film substrate 34 may comprise any of a wide range of substrates such as, for example, stainless steel, flexible poly films, or other substrate materials now known in the art or that may be developed in the future that are, or would be, suitable for such devices. A sodium/molybdenum film substrate 34 by any of a wide range of processes now known in the art or that may be developed in the future, but utilizing in some form the sodium/molybdenum compositemetal powder material 12. For example, and as will be described in further detail below, the sodium/molybdenum film may be deposited by thermal spray deposition, by printing, by evaporation, or by sputtering. - Once the sodium/molybdenum film (e.g., 32, 32′, 32″) is deposited on
substrate 34, anabsorber layer 76 may be deposited on the sodium/molybdenum film. By way of example, theabsorber layer 76 may comprise one or more selected from the group consisting of copper, indium, and selenium. Theabsorber layer 76 may be deposited by any of a wide range of methods known in the art or that may be developed in the future that are, or would be, suitable for the intended application. Consequently, the present invention should not be regarded as limited to any particular deposition process. - Next, a
junction partner layer 78 may be deposited on theabsorber layer 76.Junction partner layer 78 may comprise one or more selected from the group consisting of cadmium sulfide and zinc sulfide. Finally, a transparentconductive oxide layer 80 may be deposited onjunction partner layer 78 to form thephotovoltaic cell 36.Junction partner layer 78 and transparentconductive oxide layer 80 may be deposited by any of a wide range processes and methods now known in the art or that may be developed in the future that are, or would be, suitable for depositing these materials. Consequently, the present invention should not be regarded as limited to any particular deposition process. In addition, because processes for fabricating CIGS photovoltaic cells are known in the art (with the exception of providing the sodium/molybdenum film on the substrate) and could be readily implemented by persons having ordinary skill in the art after having become familiar with the teachings of the present invention, the particular fabrication techniques that may be utilized to construct a CIGS photovoltaic cell will not be described in further detail herein. - As mentioned above, the sodium/molybdenum layer or
film feedstock material 24 may be adjusted or varied as necessary in order to provide the desired level of sodium in the resulting sodium/molybdenum film 32. Generally speaking, retained sodium levels ranging from about 0.2% by weight to about 3.5% by weight in thefeedstock material 24 will be sufficient to provide the desired degree of sodium enrichment in the sodium/molybdenum film 32. As indicated in the Examples, such retained sodium levels (e.g., from about 0.2 wt. % to about 3.5 wt. %) may be achieved in “green” and sintered (i.e., heated)feedstock material 24 produced byslurries 20 containing from about 3 wt. % to about 15 wt. % sodium molybdate. - In one embodiment, a sodium/
molybdenum film 32 may be deposited by athermal spray process 30 utilizing thefeedstock material 24.Thermal spray process 30 may be accomplished by using any of a wide variety of thermal spray guns and operated in accordance with any of a wide range of parameters in order to deposit on substrate 34 a sodium/molybdenum film 32 having the desired thickness and properties. However, because thermal spray processes are well known in the art and because persons having ordinary skill in the art would be capable of utilizing such processes after having become familiar with the teachings provided herein, the particularthermal spray process 30 that may be utilized will not be described in further detail herein. - In another embodiment, a sodium/
molybdenum film 32′ may be deposited onsubstrate 34 by aprinting process 38 utilizing thefeedstock material 24.Feedstock material 24 may be mixed with a suitable vehicle (not shown) to form an “ink” or “paint” that may then be deposited onsubstrate 34 by any of a wide range of printing processes. Here again, because such printing processes are well known in the art and could be readily implemented by persons having ordinary skill in the art after having become familiar with the teachings provided herein, theparticular printing process 38 that may be utilized will not be described in further detail herein. - In still another embodiment, a sodium/
molybdenum film 32″ may be deposited onsubstrate 34 by anevaporation process 39 utilizing thefeedstock material 24. By way of example, in one embodiment,evaporation process 39 would involve placing thefeedstock material 24 in a crucible (not shown) of a suitable evaporation apparatus (also not shown). Thefeedstock material 24 could be placed in the crucible either in the form of a loose powder, pressed pellets, or other consolidated forms, or in any combination thereof. Thefeedstock material 24 would the be heated in the crucible until it evaporates, whereupon the evaporated material would be deposited onsubstrate 34, forming the sodium/molybdenum film 32″.Evaporation process 39 may utilize any of a wide range of evaporation apparatus now known in the art or that may be developed in the future that could be used to evaporate thefeedstock material 24 anddeposit film 32″ onsubstrate 34. Consequently, the present invention should not be regarded as limited to use with any particular evaporation apparatus operated in accordance with any particular parameters. Moreover, because such evaporation apparatus are well known in the art and could be readily implemented by persons having ordinary skill in the art after having become familiar with the teachings provided herein, the particular evaporation apparatus that may be utilized will not be described in further detail herein. - In yet another embodiment, a sodium/
molybdenum film 32′″ may be deposited onsubstrate 34 by a sputter deposition process. Thefeedstock material 24 would be processed or formed into asputter target 44, which would then be sputtered in order to form thefilm 32′″. Any of a wide range of sputter deposition apparatus that are now known in the art or that may be developed in the future could be used to sputterdeposit film 32′″ onsubstrate 34. Consequently, the present invention should not be regarded as limited to use with any particular sputter deposition apparatus operated in accordance with any particular parameters. Moreover, because such sputter deposition apparatus are well known in the art and could be readily implemented by persons having ordinary skill in the art after having become familiar with the teachings provided herein, the particular sputter deposition apparatus that may be utilized will not be described in further detail herein. - As mentioned, the sputter target 41 may comprise a
metal product 42 that may be fabricated by consolidating or forming the sodium/molybdenumcomposite metal powder 12 atstep 40. Alternatively, thesputter target 44 could be formed by thermal spraying 30. If thesputter target 44 is to be fabricated byconsolidation 40, thefeedstock material 24, in either its “green” form or processed form, may be consolidated or formed instep 40 to produce the metal product (e.g., sputter target 44). Theconsolidation process 40 may comprise any of a wide range of compaction, pressing, and forming processes now known in the art or that may be developed in the future that would be suitable for the particular application. Consequently, the present invention should not be regarded as limited to any particular consolidation process. - By way of example, the
consolidation process 40 may comprise any of a wide range of cold isostatic pressing processes or any of a wide range of hot isostatic pressing processes that are well-known in the art. As is known, both cold and hot isostatic pressing processes generally involve the application of considerable pressure and heat (in the case of hot isostatic pressing) in order to consolidate or form the composite metalpowder feedstock material 24 into the desired shape. Hot isostatic pressing processes may be conducted at temperatures of 900° C. or greater, depending on the green density of the sodium/molybdenum composite metal powder compact and the retained sodium loss that could be tolerated in the final product. - After
consolidation 40, the resulting metal product 42 (e.g., sputter target 44) may be used “as is” or may be further processed. For example, themetal product 42 may be heated or sintered atstep 46 in order to further increase the density of themetal product 42. It may be desirable to conduct such aheating process 46 in a hydrogen atmosphere in order to minimize the likelihood that themetal product 42 will become oxidized. Generally speaking, it will be preferred to conduct such heating at temperatures below about 825° C. as higher temperatures may result in substantial reductions in the amount of retained sodium, although higher temperatures (e.g., temperatures of 1050° C. or greater) could be used. The resultingmetal product 42 may also be machined if necessary or desired before being placed in service. Such machining could be done regardless of whether thefinal product 42 was sintered. - Several examples have been run using molybdenum metal and sodium molybdate powders 14, 16, specified herein and available from Climax Molybdenum and/or Climax Molybdenum, Ft. Madison Operations. Various ratios of the
powders slurries 20. More specifically, theslurries 20 utilized for the various examples comprised about 20% by weight water (i.e., liquid 18), with the remainder being molybdenum metal and sodium molybdate powders. The ratio of molybdenum metal powder to sodium molybdate was varied in the various examples to range from about 3% by weight to about 15% by weight sodium molybdate. More specifically, the Examples involved amounts of 3, 7, 9, and 15 weight percent sodium molybdate. - The
slurries 20 were then fed into the pulse combustionspray drying system 22 in the manner described herein. The temperature of the pulsating stream ofhot gases 50 was controlled to be within a range of about 465° C. to about 537° C. The pulsating stream ofhot gases 50 produced by thepulse combustion system 22 substantially drove-off the water from theslurry 20 to form the compositemetal powder product 12. The contact zone and contact time were very short, the contact zone on the order of about 5.1 cm and the time of contact being on the order of 0.2 microseconds. - The resulting
metal powder product 12 comprised agglomerations of smaller particles that were substantially solid (i.e., not hollow) and having generally spherical shapes. An SEM photo of a “green” sodium/molybdenumcomposite metal powder 12 produced by aslurry 20 comprising 9% by weight sodium molybdate is presented inFIG. 4 . Data in Tables I and II are presented for the various examples in both “green” form, and after being sintered or heated in a hydrogen atmosphere at the temperatures and for the times specified. Data are also presented for screened green material (+325 mesh moly) as also indicated in Tables I and II. -
TABLE I Molyb- Sodium Hall Ex- denum Molybdate Apparent flow am- metal (SoMo) Density (s/ ple Batch (wt %) (wt %) (g/cc) 50 g) 1 3% SoMo Green 97% 3% 2 7% SoMo Green 93% 7% 2.89 33 3 9% SoMo Green 91% 9% 4 15% SoMo Green 85% 15% 5 3% SoMo + 325 mesh 97% 3% 6 9% SoMo + 325 mesh 91% 9% 7 15% SoMo + 325 mesh 85% 15% 8 9% SoMo Sintered 91% 9% 1 h. 1050° C. 9 7% SoMo Sintered 93% 7% 2.79 32 10 h. 640° C. 10 9% SoMo Sintered 91% 9% 10 h. 640° C. 11 3% SoMo Sintered 97% 3% 6 h. 825° C. 12 9% SoMo Sintered 91% 9% 2.62 No 6 h. 825° C. Flow 13 15% SoMo Sintered 85% 15% 6 h. 825° C. -
TABLE II % Weight Slurry loss Na Viscosity Sodium Conc. during Distribution Example Sec. Zahn#1 (wt. %) % O % N Sintering (EDS) 1 33.8 0.74% 1.23% 0.0020% 2 1.39% 2.14% 0.2500% 3 35 1.74% 2.64% 0.0075% Na varies in particles from 3% to 12% 4 3.11% 5.58% 0.0295% 5 1.22% 0.0016% 6 1.84% 2.93% 0.0101% No Na peak found by EDS 7 3.09% 5.16% 0.196% 8 0.73% No Na peak found by EDS 9 1.36% 1.36% 0.0000% 0.97% 10 1.85% 1.85% 0.0018% 1.85% 4% 11 0.22% 0.22% 0.0011% 1.79% 12 1.32% 1.32% 0.0010% 3.90% 1.86% 13 2.39% 2.39% 0.0015% 4.84% 2.89% - Having herein set forth preferred embodiments of the present invention, it is anticipated that suitable modifications can be made thereto which will nonetheless remain within the scope of the invention. The invention shall therefore only be construed in accordance with the following claims:
Claims (39)
1. A method for producing a composite metal powder, comprising:
providing a supply of molybdenum metal powder;
providing a supply of a sodium compound;
combining said molybdenum metal powder and said sodium compound with a liquid to form a slurry;
feeding said slurry into a stream of hot gas; and
recovering the composite metal powder, said composite metal powder comprising sodium and molybdenum.
2. The method of claim 1 , wherein providing a supply of a sodium compound comprises providing a supply of sodium molybdate powder.
3. The method of claim 1 , wherein feeding said slurry into a stream of hot gas comprises atomizing said slurry and contacting said atomized slurry with the stream of hot gas.
4. The method of claim 1 , wherein combining said molybdenum metal powder and said sodium compound with a liquid comprises combining said molybdenum metal powder and said sodium compound with water to form a slurry.
5. The method of claim 1 , wherein said slurry comprises between about 15% to about 25% by weight liquid.
6. The method of claim 1 , further comprising:
providing a supply of a binder material; and
combining said binder material with said molybdenum metal powder, said sodium compound, and said water to form a slurry.
7. The method of claim 6 , wherein said binder comprises one or more from the selected from the group consisting of polyvinyl alcohol and carbowax.
8. The method of claim 6 , wherein said sodium compound comprises sodium molybdate and wherein said slurry comprises between about 15% to about 25% by weight liquid, from about 0% to about 2% by weight binder, from about 1% by weight to about 15% sodium molybdate, and from about 58% by weight to about 84% by weight molybdenum metal powder.
9. The method of claim 6 , further comprising heating the recovered composite metal powder at a temperature sufficient to drive-off substantially all of said binder.
10. The method of claim 9 , wherein said heating further comprises heating in a hydrogen atmosphere.
11. The method of claim 10 , wherein said heating in a hydrogen atmosphere is conducted at a temperature in a range of about 500° C. to about 825° C.
12. A composite metal powder produced according to the method of claim 1 .
13. A method for producing a composite metal powder, comprising:
providing a supply of molybdenum metal powder;
providing a supply of a sodium molybdate powder;
combining said molybdenum metal powder and said sodium molybdate powder with water to form a slurry;
feeding said slurry into a stream of hot gas; and
recovering the composite metal powder.
14. A composite metal powder produced according to the method of claim 13 .
15. The composite metal powder product of claim 14 comprising a Hall flowability in a range of about 30-35 seconds for 50 grams.
16. The composite metal powder product of claim 14 having a Scott density in a range of about 2 g/cc to about 3 g/cc.
17. The composite metal powder product of claim 14 , comprising from about 0.2% by weight to about 3.5% by weight retained sodium.
18. The composite metal powder product of claim 14 comprising less than about 6% by weight retained oxygen.
19. A method for producing a metal article, comprising:
producing a supply of a composite metal powder by:
providing a supply of molybdenum metal powder;
providing a supply of a sodium compound;
combining said molybdenum metal powder and said sodium compound with a liquid to form a slurry;
feeding said slurry into a stream of hot gas; and
recovering the composite metal powder; and
consolidating said composite metal powder to form the metal article, said metal article comprising a sodium/molybdenum metal matrix.
20. The method of claim 19 , wherein said consolidating said composite metal powder comprises cold isostatic pressing.
21. The method of claim 19 , wherein consolidating comprises pressing said composite metal powder into a shape and sintering the shape.
22. The method of claim 21 , wherein said sintering is conducted in a hydrogen atmosphere.
23. The method of claim 22 , wherein said sintering is conducted at a temperature of less than about 825° C.
24. The method of claim 19 , wherein consolidating comprises hot isostatic pressing.
25. A metal article produced by the method of claim 19 .
26. The metal article of claim 25 , wherein said metal article comprises from about 0.2% by weight to about 3.5% by weight retained sodium.
27. The metal article of claim 25 , wherein said metal article comprises a sputter target.
28. A method for producing a photovoltaic cell, comprising:
providing a substrate;
depositing a sodium/molybdenum metal layer on said substrate;
depositing an absorber layer on said sodium/molybdenum metal layer; and
depositing a junction partner layer on said absorber layer.
29. The method of claim 23 , wherein depositing a sodium/molybdenum metal layer comprises sputtering a target comprising a sodium/molybdenum metal matrix, sputtered material from the target forming said sodium/molybdenum metal layer.
30. The method of claim 28 , wherein depositing a sodium/molybdenum metal layer comprises:
providing a supply of a composite metal powder comprising molybdenum and sodium;
depositing said composite metal powder on said substrate by thermal spraying.
31. The method of claim 28 , wherein depositing a sodium/molybdenum metal layer comprises:
providing a supply of a composite metal powder comprising molybdenum and sodium; and
depositing said composite metal powder on said substrate by printing.
32. The method of claim 28 , wherein depositing a sodium/molybdenum metal layer comprises:
providing a supply of a composite metal powder comprising molybdenum and sodium; and
depositing said composite metal powder on said substrate by evaporation.
33. The method of claim 28 , further comprising depositing a transparent conductive oxide layer on said junction partner layer.
34. The method of claim 33 , wherein said absorber layer comprises one or more selected from the group consisting of copper, indium, and selenium.
35. The method of claim 34 , wherein said junction partner layer comprises one or more selected from the group consisting of cadmium sulfide and zinc sulfide.
36. A method for depositing a film on a substrate, comprising:
providing a supply of a composite metal powder comprising molybdenum and sodium;
depositing said composite metal powder on said substrate by thermal spraying.
37. A method for depositing a film on a substrate, comprising sputtering a target comprising a sodium/molybdenum metal matrix, sputtered material from the target forming said sodium/molybdenum metal layer.
38. A method for forming a coating on a substrate, comprising:
providing a supply of a composite metal powder comprising molybdenum and sodium;
mixing said supply of composite metal powder with a vehicle; and
depositing the mixture of the composite metal powder and the vehicle on said substrate by printing.
39. A method for depositing a film on a substrate, comprising:
providing a supply of a composite metal powder comprising molybdenum and sodium;
depositing said composite metal powder on said substrate by evaporation.
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US12/013,263 US20090181179A1 (en) | 2008-01-11 | 2008-01-11 | Sodium/Molybdenum Composite Metal Powders, Products Thereof, and Methods for Producing Photovoltaic Cells |
CN200980102060.1A CN101919062B (en) | 2008-01-11 | 2009-01-09 | Sodium/molybdenum composite metal powders, products thereof, and methods for producing photovoltaic cells |
EP20090700939 EP2232565B1 (en) | 2008-01-11 | 2009-01-09 | Sodium/molybdenum composite metal powders, products thereof, and methods for producing photovoltaic cells |
JP2010542366A JP5574978B2 (en) | 2008-01-11 | 2009-01-09 | Sodium / molybdenum composite metal powder, product thereof, and method of manufacturing photovoltaic cell |
MYPI2010003217A MY157342A (en) | 2008-01-11 | 2009-01-09 | Sodium/molybdenum composite metal powders, products thereof, and methods for producing photovoltaic cells |
PCT/US2009/030561 WO2009089421A1 (en) | 2008-01-11 | 2009-01-09 | Sodium/molybdenum composite metal powders, products thereof, and methods for producing photovoltaic cells |
KR1020107017378A KR101533133B1 (en) | 2008-01-11 | 2009-01-09 | Sodium/molybdenum composite metal poweders, products thereof and methods for producing photovoltaic cells |
TW98100845A TWI405723B (en) | 2008-01-11 | 2009-01-10 | Sodium/molybdenum composite metal powders, products thereof, and methods for producing photovoltaic cells |
US12/392,792 US8197885B2 (en) | 2008-01-11 | 2009-02-25 | Methods for producing sodium/molybdenum power compacts |
US13/038,578 US8465692B2 (en) | 2008-01-11 | 2011-03-02 | Sodium/molybdenum composite metal articles and methods for producing metal articles |
HK11105387A HK1151389A1 (en) | 2008-01-11 | 2011-05-31 | Sodium molybdenum composite metal powders, products thereof, and methods for producing photovoltaic cells |
US13/245,066 US9103024B2 (en) | 2008-01-11 | 2011-09-26 | Sodium / molybdenum metal articles and powder compacts |
US14/449,514 US20140342497A1 (en) | 2008-01-11 | 2014-08-01 | Sodium/molybdenum composite metal powders, products thereof, and methods for producing photovoltaic cells |
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US12/013,263 US20090181179A1 (en) | 2008-01-11 | 2008-01-11 | Sodium/Molybdenum Composite Metal Powders, Products Thereof, and Methods for Producing Photovoltaic Cells |
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US13/038,578 Division US8465692B2 (en) | 2008-01-11 | 2011-03-02 | Sodium/molybdenum composite metal articles and methods for producing metal articles |
US14/449,514 Continuation US20140342497A1 (en) | 2008-01-11 | 2014-08-01 | Sodium/molybdenum composite metal powders, products thereof, and methods for producing photovoltaic cells |
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US13/038,578 Expired - Fee Related US8465692B2 (en) | 2008-01-11 | 2011-03-02 | Sodium/molybdenum composite metal articles and methods for producing metal articles |
US14/449,514 Abandoned US20140342497A1 (en) | 2008-01-11 | 2014-08-01 | Sodium/molybdenum composite metal powders, products thereof, and methods for producing photovoltaic cells |
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US13/038,578 Expired - Fee Related US8465692B2 (en) | 2008-01-11 | 2011-03-02 | Sodium/molybdenum composite metal articles and methods for producing metal articles |
US14/449,514 Abandoned US20140342497A1 (en) | 2008-01-11 | 2014-08-01 | Sodium/molybdenum composite metal powders, products thereof, and methods for producing photovoltaic cells |
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EP (1) | EP2232565B1 (en) |
JP (1) | JP5574978B2 (en) |
KR (1) | KR101533133B1 (en) |
CN (1) | CN101919062B (en) |
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US8632745B1 (en) | 2012-12-21 | 2014-01-21 | Ut-Battelle, Llc | Method and apparatus for controlling stoichiometry in multicomponent materials |
CN106111994A (en) * | 2016-02-12 | 2016-11-16 | Nep有限公司 | Use the method that ferrous metal nodular powder manufactures ferrous metal part |
Also Published As
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CN101919062B (en) | 2014-02-19 |
US8465692B2 (en) | 2013-06-18 |
TW200942492A (en) | 2009-10-16 |
JP2011511886A (en) | 2011-04-14 |
CN101919062A (en) | 2010-12-15 |
JP5574978B2 (en) | 2014-08-20 |
EP2232565A4 (en) | 2012-07-25 |
US20140342497A1 (en) | 2014-11-20 |
KR20100129268A (en) | 2010-12-08 |
EP2232565B1 (en) | 2014-03-12 |
WO2009089421A1 (en) | 2009-07-16 |
US20110147208A1 (en) | 2011-06-23 |
EP2232565A1 (en) | 2010-09-29 |
KR101533133B1 (en) | 2015-07-01 |
HK1151389A1 (en) | 2012-01-27 |
MY157342A (en) | 2016-05-31 |
TWI405723B (en) | 2013-08-21 |
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