US20060213550A1 - Thin-film photoelectric conversion device and a method of manufacturing the same - Google Patents
Thin-film photoelectric conversion device and a method of manufacturing the same Download PDFInfo
- Publication number
- US20060213550A1 US20060213550A1 US11/422,570 US42257006A US2006213550A1 US 20060213550 A1 US20060213550 A1 US 20060213550A1 US 42257006 A US42257006 A US 42257006A US 2006213550 A1 US2006213550 A1 US 2006213550A1
- Authority
- US
- United States
- Prior art keywords
- thin
- silicon film
- film
- semiconductor film
- crystalline silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 title description 10
- 239000010408 film Substances 0.000 claims abstract description 230
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 92
- 239000000758 substrate Substances 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 22
- 239000011574 phosphorus Substances 0.000 claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 72
- 239000004065 semiconductor Substances 0.000 claims description 58
- 229910052759 nickel Inorganic materials 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract description 71
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 38
- 238000010438 heat treatment Methods 0.000 abstract description 37
- 229910052710 silicon Inorganic materials 0.000 abstract description 37
- 239000010703 silicon Substances 0.000 abstract description 37
- 238000002425 crystallisation Methods 0.000 abstract description 28
- 230000008025 crystallization Effects 0.000 abstract description 28
- 238000000151 deposition Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 78
- 239000005360 phosphosilicate glass Substances 0.000 description 28
- 230000008569 process Effects 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 22
- 239000012299 nitrogen atmosphere Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 238000004544 sputter deposition Methods 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
- 238000005247 gettering Methods 0.000 description 12
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229940078494 nickel acetate Drugs 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- -1 phosphorus ions Chemical class 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018503 SF6 Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
Images
Classifications
-
- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1872—Recrystallisation
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022441—Electrode arrangements specially adapted for back-contact 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
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
-
- 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
- H01L31/068—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 homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
- H01L31/0682—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 homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
-
- 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
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a thin-film photoelectric conversion device, especially a solar cell which is formed on a substrate, and more particularly to a thin-film solar cell having a photoelectric conversion layer formed of a crystalline silicon film.
- a solar cell or a solar battery can be manufactured using a variety of semiconductor materials or organic compound materials.
- silicon is mainly used for the solar cell.
- the solar cells using silicon can be classified into a bulk solar cell using a wafer of monocrystal silicon or polycrystal silicon and a thin-film solar cell having a silicon film formed on a substrate. Reduction of manufacturing costs is required, and the thin-film solar cell is expected to have the effect of reducing the costs because less raw materials are used for the thin-film solar cell than for the bulk solar cell.
- an amorphous silicon solar cell In the field of thin-film solar cells, an amorphous silicon solar cell has been placed into practical use. However, since the amorphous silicon solar cell is lower in conversion efficiency compared with the monocrystal silicon or polycrystal silicon solar cell and also suffers from problems such as deterioration due to light exposure and so on, the use thereof is limited. For that reason, as another means, a thin-film solar cell using a crystalline silicon film has been also developed.
- a melt recrystallization method and a solid-phase growth method are used for obtaining a crystalline silicon film in the thin-film solar cell.
- an amorphous silicon layer is formed on a substrate and recrystallized, thereby obtaining a crystalline silicon film.
- the substrate is required to withstand the crystallization temperature, whereby usable materials are limited.
- the substrate has been limited to a material that withstands 1,412° C., which is the melting point of silicon.
- the solid-phase growth method is a method in which an amorphous silicon film is formed on the substrate and crystallized thereafter through a heat treatment.
- a solid-phase growth method in general, as the temperature becomes high, the processing time may be shortened more.
- the amorphous silicon film is hardly crystallized at a temperature of 500° C. or lower.
- the heat treatment is conducted at the temperature of 550° C., 100 hours or longer is required for the heat treatment.
- the substrate of the thin-film solar cell For the above reason, a high heat resistance has been required for the substrate of the thin-film solar cell. Therefore, glass, carbon, or ceramic was used for the substrate.
- those substrates are not always proper, and it has been desired that the solar cell be fabricated on a substrate which is most generally used and inexpensive.
- the #7059 glass substrate made by Corning which is generally used, has a strain point of 593° C., and the conventional crystallization technique allows the substrate to be strained and largely deformed. For that reason, such a substrate could not be used.
- the concentration of the catalyst material is as low as possible.
- the concentration of catalyst material necessary for accelerating crystallization was 1 ⁇ 10 17 /cm 3 to 1 ⁇ 10 20 /cm 3 .
- the concentration is relatively low, since the above catalyst materials are heavy metal elements, the material contained in silicon forms a defect level, thereby lowering the characteristics of a fabricated element.
- the principle of operation of a solar cell containing a p-n junction can be roughly described as follows.
- the solar cell absorbs light and generates electron/hole charge pairs due to absorbed light energy.
- the electrons move toward the n-layer side of the junction, and the holes move toward the p-layer side due to drift caused by the junction electric field and diffusion.
- the defect levels are high in silicon, the charges are trapped by the defect levels while they are moving in the silicon, thereby disappearing. In other words, the photoelectric conversion characteristics are lowered.
- the period of time from when the electrons/holes are generated until they disappear is called the “life time”. In the solar cell, it is desirable that the lifetime is long. Hence, it has been necessary to reduce as much as possible the heavy metal elements that generate the defect levels in silicon.
- the present invention has been made in view of the above circumstances, and therefore an object of the present invention is to provide a method of manufacturing a thin-film solar cell, which retains the feature of crystallization due to the above catalyst material and removes the catalyst material after the crystallization has been completed.
- Another object of the present invention is to provide a solar cell which has an excellent photoelectric conversion characteristic, using the above method.
- a method of manufacturing a photoelectric conversion device includes a step of forming a gettering layer on a crystallized semiconductor layer obtained by using a catalyst metal such as nickel.
- the gettering layer may be either insulative or semiconductive and contains phosphorus to absorb the catalyst metal such as nickel from the semiconductor layer after it is crystallized, thereby reducing the concentration of the catalyst metal in the semiconductor layer.
- the method includes the steps of:
- metal element it is possible to use one or more elements chosen from Ni, Fe, Co, Ru, Rh, Pd, Os, Ir, Pt, Cu, and Au.
- the gettering layer may be a silicon layer to which phosphorus is added during the deposition thereof onto the crystallized semiconductor layer.
- the gettering layer may be a phosphorus doped region formed within the crystallized semiconductor layer, namely, a method of the present invention includes a step of introducing phosphorus ions into a surface region of the crystallized semiconductor layer by ion doping after crystallizing the semiconductor layer by the use of the catalyst metal.
- the gettering layer may be a phospho-silicate glass (PSG) layer deposited on the crystallized semiconductor layer.
- PSG phospho-silicate glass
- the catalyst metal is provided by disposing the metal containing layer in contact with an upper or lower surface of a non-single crystalline semiconductor layer to be crystallized.
- the metal containing layer may be used also as a lower electrode of the photoelectric conversion device.
- a solar cell comprises a substrate, a first crystalline silicon film having conductivity type formed on the substrate, and a second crystalline silicon film having another conductivity type adjacent to the first crystalline silicon film, wherein the first crystalline silicon film contains a catalyst element for promoting crystallization of silicon at a concentration not higher than 5 ⁇ 10 18 atoms/cm 3 .
- concentration value disclosed in the present invention is determined by secondary ion mass spectroscopy and corresponds to a maximum value of the measured values.
- the concentration of the catalyst contained in the second crystalline silicon film is higher than the concentration of the catalyst contained in the first crystalline silicon film.
- the crystalline semiconductor film obtained by using the catalyst metal such as nickel has a plurality of crystal grains in the form of needles.
- the lifetime of carriers in the crystalline silicon film is increased, and the excellent characteristics of the thin-film solar cell are obtained.
- FIGS. 1A to 1 D are schematic diagrams showing a method of manufacturing a thin-film solar cell in accordance with the present invention
- FIGS. 2A to 2 D are schematic diagrams showing a method of manufacturing a thin-film solar cell in accordance with the present invention.
- FIG. 3 is a diagram showing an example of a cross-sectional structure of a thin-film solar cell in accordance with the present invention.
- FIG. 4 is a diagram showing an example of a cross-sectional structure of a thin-film solar cell in accordance with the present invention.
- the first embodiment shows a process of manufacturing a thin-film solar cell through a method of forming an amorphous silicon film in close contact with a metal element that accelerates the crystallization of silicon, crystallizing said amorphous silicon film through a heat treatment, and removing said metal element remaining in the amorphous silicon film after the crystallization.
- nickel is used as a metal element having a catalyst action that accelerates the crystallization of silicon.
- a silicon oxide film 102 having a thickness of 0.3 ⁇ m is formed on a glass substrate (for example, Corning 7059 glass substrate) 101 as an underlying layer.
- the silicon oxide film 102 is formed through a plasma CVD technique using tetra ethoxy silane (TEOS as a raw material), and also can be formed through a sputtering technique as another method.
- TEOS tetra ethoxy silane
- an amorphous silicon film 103 is formed using silane gas as a raw material through a plasma CVD technique.
- the formation of the amorphous silicon film 103 may be conducted using a low pressure thermal CVD technique, a sputtering technique, or an evaporation method.
- the above amorphous silicon film 103 may be a substantially-intrinsic amorphous silicon film or may contain boron (B) at 0.001 to 0.1 atms %.
- the thickness of the amorphous silicon film 103 is set at 10 ⁇ m. However, the thickness may be set at a required value ( FIG. 1A ).
- the substrate is immersed in an ammonium hydroxide, hydrogen peroxide mixture and then held at 70° C. for 5 minutes, to thereby form an oxide film (not shown) on the surface of the amorphous silicon film 103 .
- the silicon oxide film is formed in order to improve wettability in the next step process of coating with a nickel acetate solution.
- the nickel acetate solution is coated on the surface of the amorphous silicon film 103 by spin coating.
- the nickel functions as an element that accelerates the crystallization of the amorphous silicon film 103 .
- the amorphous silicon film 103 is held at a temperature of 450° C. for one hour in a nitrogen atmosphere, thereby eliminating hydrogen from the amorphous silicon film 103 . This is because dangling bonds are intentionally produced in the amorphous silicon film, to thereby lower the threshold energy in subsequent crystallizing. Then, the amorphous silicon film 103 is subjected to a heat treatment at 550° C. for 4 to 8 hours in the nitrogen atmosphere, to thereby crystallize the amorphous silicon film 103 .
- the temperature during crystallizing can be set to 550° C. because of the action of the nickel. 0.001 atms % to 5 atms % hydrogen is contained in crystallized silicon film 104 . During the above heat treatment, nickel accelerates the crystallization of the silicon film while it is moving in the silicon film.
- the crystalline silicon film 104 is formed on the glass substrate.
- a phospho-silicate glass (PSG) 105 is formed on the crystalline silicon film 104 .
- the phospho-silicate glass (PSG) 105 is formed, using a gas mixture consisting of silane, phosphine, and oxygen, at a temperature of 450° C. through an atmospheric CVD technique.
- the concentration of phosphorus in the phospho-silicate glass is set to 1 to 30 wt %, preferably 7 wt %.
- the phospho-silicate glass (PSG) 105 is used to getter nickel remaining in the crystalline silicon film.
- the phospho-silicate glass 105 is formed at only 450° C., its effect is obtained. More effectively, the phospho-silicate glass 105 may be subjected to a heat treatment at a temperature of 500 to 800° C., preferably 550° C. for 1 to 4 hours in a nitrogen atmosphere. As another method, the phospho-silicate glass 105 can be replaced by a silicon film to which phosphorus of 0.1 to 10 wt % has been added with the same effect ( FIG. 1B ).
- the phospho-silicate glass 105 is etched using an aqueous hydrogen fluoride solution so as to be removed from the surface of the crystalline silicon film 104 .
- the surface of the crystalline silicon film 104 is exposed.
- an n-type crystalline silicon film 106 On that surface there is formed an n-type crystalline silicon film 106 .
- the n-type crystalline silicon film 106 may be formed through a plasma CVD technique or through a low pressure thermal CVD technique.
- the n-type crystalline silicon film 106 is desirably formed at a thickness of 0.02 to 0.2 ⁇ m, and in this embodiment, it is formed at a thickness of 0.1 ⁇ m ( FIG. 1C ).
- a transparent electrode 107 is formed through a sputtering technique on the above n-type crystalline silicon film 106 .
- the transparent electrode 107 is made of indium tin oxide alloy (ITO) and has a thickness of 0.08 ⁇ m.
- ITO indium tin oxide alloy
- a process of providing output electrodes 103 is conducted.
- a negative side electrode is disposed on the transparent electrode 107
- a positive side electrode is disposed on the crystalline silicon film 104 by removing parts of the transparent electrode 107 , the n-type crystalline silicon film 106 , and the crystalline silicon film 104 .
- the output electrodes 108 can be formed by sputtering or vacuum evaporation, or using an aluminum or silver paste or the like. Furthermore, after the provision of the output electrodes 108 , the product is subjected to a heat treatment at 150° C. to 300° C. for several minutes with the result that the adhesion between the output electrodes 108 and the underlying layer becomes high, thereby obtaining an excellent electric characteristic. In this embodiment, the product is subjected to a heat treatment at 200° C. for 30 minutes in a nitrogen atmosphere using an oven.
- a thin-film solar cell which is formed in a process where a metal element that accelerates the crystallization of crystalline silicon is removed after crystallization, through a method where phosphorus is implanted into the surface of the crystalline silicon film via a plasma doping method.
- Nickel is used in this embodiment as a metal element functioning as a catalyst to accelerate the crystallization to accellerate the crystallization of silicon.
- a silicon oxide film 202 having a thickness of 0.3 ⁇ m is formed on a glass substrate (for example, Corning 7059 glass substrate) 201 as an underlying layer.
- the silicon oxide film 202 is formed by plasma CVD with tetra ethoxy silane (TEOS as a raw material), and also can be formed through a sputtering technique as another method.
- TEOS tetra ethoxy silane
- an amorphous silicon film 203 is formed with silane gas as a raw material through a plasma CVD technique.
- the formation of the amorphous silicon film 203 may be conducted using a low pressure thermal CVD technique, a sputtering technique, or an evaporation method.
- the above amorphous silicon film 203 may be a substantially-intrinsic amorphous silicon film or an amorphous silicon film to which boron (B) of 0.001 to 0.1 atms % has been added.
- B boron
- the thickness of the amorphous silicon film 203 is set at 20 ⁇ m. However, the thickness may be set at any required value ( FIG. 2A ).
- the substrate is immersed in an ammonium hydroxide, hydrogen peroxide mixture at 70° C. for 5 minutes, to thereby form an oxide film (not shown) on the surface of the amorphous silicon film 203 .
- the silicon oxide film is formed in order to improve wettability in the next step of coating with a nickel acetate solution.
- the nickel acetate solution is coated on the surface of the amorphous silicon film 203 by spin coating.
- the nickel element functions as an element that accelerates the crystallization of the amorphous silicon film 203 .
- the amorphous silicon film 203 is held at a temperature of 450° C. for one hour in a nitrogen atmosphere, thereby eliminating hydrogen from the amorphous silicon film 203 . This is because dangling bonds are intentionally produced in the amorphous silicon film, to thereby lower the threshold energy in subsequent crystallizing. Then, the amorphous silicon film 203 is subjected to a heat treatment at 550° C. for 4 to 8 hours in a nitrogen atmosphere, to thereby crystallize the amorphous silicon film 203 .
- the temperature during crystallizing can be set to 550° C. because of the action of the nickel. 0.001 atms % to 5 atms % hydrogen is contained in a crystallized silicon film 204 . During the above heat treatment, nickel accelerates the crystallization of the silicon film 204 while it is moving in the silicon film.
- the crystalline silicon film 204 can be formed on the glass substrate.
- the implantation of phosphorus (P) ions is conducted by a plasma doping method.
- the dose amount may be set to 1 ⁇ 10 14 to 1 ⁇ 10 17 /cm 2 , and in this embodiment, it is set to 1 ⁇ 10 16 /cm 2 .
- the accelerating voltage is set to 20 keV.
- a layer containing phosphorus at a high concentration is formed within a region of 0.1 to 0.2 ⁇ m depthwise from the surface of the crystalline silicon film 204 .
- a heat treatment is conducted on the crystalline silicon film 204 in order to getter nickel remaining in the crystalline silicon film 204 .
- the crystalline silicon film 204 may be subjected to a heat treatment at 500 to 800° C., preferably 550° C. for 1 to 4 hours in a nitrogen atmosphere ( FIG. 2B ).
- the crystalline silicon film 204 since the region into which phosphorus ions have been implanted has its crystallinity destroyed, it becomes of a substantially amorphous structure immediately after the ions have been implanted thereinto. Thereafter, since that region is crystallized through said heat treatment, it is usable as the n-type layer of the solar cell even in this state. In this case, the concentration of nickel in the i-type or p-type layer 204 is lower than in the phosphorus doped n-type layer.
- the phosphorus implanted region is more desirably removed since nickel that has functioned as a catalyst element is segregated in this region.
- the removing method after a thin natural oxide film on the surface has been etched using an aqueous hydrogen fluoride aqueous solution, it is removed via dry etching using sulfur hexafluoride and nitric trifluoride. With this process, the surface of the crystalline silicon film 204 is exposed. An n-type crystalline silicon film 205 is formed on that surface.
- the n-type crystalline silicon film 205 may be formed by plasma CVD or low pressure thermal CVD.
- the n-type crystalline silicon film 205 is desirably formed at a thickness of 0.02 to 0.2 ⁇ m, and in this embodiment, it is formed at a thickness of 0.1 ⁇ m ( FIG. 2C ).
- a transparent electrode 206 is formed via a sputtering technique on the above n-type crystalline silicon film 205 .
- the transparent electrode 206 is made of indium tin oxide alloy (ITO) and has a thickness of 0.08 ⁇ m.
- ITO indium tin oxide alloy
- a process of providing output lead electrodes 207 is conducted. In providing the output electrodes 207 , as shown in FIG. 2D , a negative side electrode is disposed on the transparent electrode 206 , and a positive side electrode is disposed on the crystalline silicon film 204 by removing parts of the transparent electrode 206 , the n-type crystalline silicon film 205 , and the crystalline silicon film 204 .
- the output electrodes 207 can be formed through a sputtering technique or an evaporation method, or by using aluminum or silver paste or the like. Furthermore, after the provision of the output lead electrodes 207 , the substrate is subjected to a heat treatment at 150° C. to 300° C. for several minutes with the result that the adhesion between the output electrodes 207 and the underlying layer becomes high, thereby obtaining excellent electric characteristics. In this embodiment, the substrate is subjected to a heat treatment at 200° C. for 30 minutes in a nitrogen atmosphere using an oven.
- a third embodiment shows an example where in the process of manufacturing the thin-film solar cell described with reference to the first and second embodiments, the surface of the crystalline silicon film is subjected to an anisotropic etching process so as to make the surface of the solar cell irregular as shown in FIG. 3 .
- a technique by which that surface is made irregular so that reflection from the surface of the solar cell is reduced is called a “texture technique”.
- a silicon oxide film 302 having a thickness of 0.3 ⁇ m is formed on a glass substrate (for example, Corning 7059 glass substrate) 301 as an underlying layer.
- the silicon oxide film 302 is formed by plasma CVD with tetra ethoxy silane (TEOS as a raw material), and also can be formed by sputtering as another method.
- TEOS tetra ethoxy silane
- an amorphous silicon film is formed by plasma CVD.
- the formation of the amorphous silicon film may be conducted by low pressure thermal CVD, sputtering, evaporation, or the like.
- the above amorphous silicon film 303 may be a substantially-intrinsic amorphous silicon film or an amorphous silicon film to which of 0.001 to 0.1 atms % boron (B) has been added. Also, the thickness of the amorphous silicon film is set at 20 ⁇ m. However, the thickness may be set at any required value.
- the substrate is immersed in an ammonium hydroxide and hydrogen peroxide mixture and then held at 70° C. for 5 minutes, to thereby form an oxide film on the surface of the amorphous silicon film.
- the silicon oxide film is formed in order to improve wettability in the next step of coating nickel acetate solution.
- the nickel acetate solution is coated on the surface of the amorphous silicon film by spin coating.
- the nickel functions as an element that accelerates the crystallization of the amorphous silicon film.
- the amorphous silicon film is held at a temperature of 450° C. for one hour in a nitrogen atmosphere, thereby eliminating hydrogen from the amorphous silicon film. This is because dangling bonds are intentionally produced in the amorphous silicon film, to thereby lower the threshold energy in subsequent crystallizing.
- the amorphous silicon film is subjected to a heat treatment at 550° C. for 4 to 8 hours in a nitrogen atmosphere, to thereby crystalline the amorphous silicon film to obtain a crystalline silicon film 303 .
- the temperature during crystallizing can be set to 550° C. because of the action of nickel. 0.001 atms % to 5 atms % of hydrogen is contained in the crystalline silicon film 303 .
- nickel accelerates the crystallization of the silicon film 303 while it is moving in the silicon film.
- the crystalline silicon film 303 can be formed on the glass substrate. Then, a gettering process is conducted on the crystalline silicon film 304 in order to remove nickel remaining in the crystalline silicon film 304 .
- a method of conducting the gettering process may include forming a phospho-silicate glass (PSG) on the crystalline silicon film 303 , or implanting phosphorus ions into the surface of the crystalline silicon film 303 .
- PSG phospho-silicate glass
- the phospho-silicate glass film is formed via atomspheric CVD, using a gas mixture consisting of silane, phosphine, and oxygen, at a temperature of 450° C.
- the gettering process is then conducted by subjecting the crystalline silicon film to a heat treatment at 550° C. for 1 to 4 hours in a nitrogen atmosphere.
- the phospho-silicate glass film is desirably etched using an aqueous hydrogen fluoride aqueous solution so as to be removed.
- the implantation of ions can be conducted through plasma doping.
- the dose amount may be set to 1 ⁇ 10 14 to 1 ⁇ 10 17 /cm 2 , and in this embodiment, it is set to 1 ⁇ 10 16 /cm 2 .
- the accelerating voltage is set to 20 keV.
- a layer containing phosphorus at a high concentration is formed within a region of 0.1 to 0.2 ⁇ m depthwise from the surface of the crystalline silicon film.
- a heat treatment is conducted on the crystalline silicon film in order to getter nickel remaining in the crystalline silicon film.
- the heat treatment is conducted at a temperature of 500 to 800° C., preferably 550° C. for 1 to 4 hours in a nitrogen atmosphere.
- the texture process is conducted on the surface of the crystalline silicon film.
- the texture process can be conducted using hydrazine or sodium hydroxide aqueous solution.
- sodium hydroxide a case of using sodium hydroxide will be described.
- the texture process is conducted by heating a 2% aqueous solution of sodium hydroxide to 80° C. Under this condition, the etching rate of the crystalline silicon film thus obtained in this embodiment is about 1 ⁇ m/min. The etching is conducted for five minutes, and thereafter the crystalline silicon film is immersed in boiling water in order to immediately cease the reaction and then the film is sufficiently cleaned by flowing water. As a result of observing the surface of the crystalline silicon film which has been subjected to the texture process through an electron microscope, an unevenness of about 0.1 to 5 ⁇ m is found on the surface although it is at random.
- n-type crystalline silicon film 304 is formed on that surface.
- the n-type crystalline silicon film 304 may be formed through a plasma CVD technique or through a low pressure thermal CVD technique.
- the n-type crystalline silicon film 304 is desirably formed at a thickness of 0.02 to 0.2 ⁇ m, and in this embodiment, it is formed at a thickness of 0.1 ⁇ m.
- a transparent electrode 305 is formed by sputtering on the above n-type crystalline silicon film 304 .
- the transparent electrode 305 is made of indium tin oxide alloy (ITO) and has a thickness of 0.08 ⁇ m.
- ITO indium tin oxide alloy
- a process of providing output electrodes 307 is conducted. In providing the output electrodes 307 , as shown by the structure in FIG. 3D , a negative side electrode is disposed on the transparent electrode 305 , and a positive side electrode is disposed on the crystalline silicon film 303 by removing parts of the transparent electrode 305 , the n-type crystalline silicon film 304 , and the crystalline silicon film 303 .
- the output electrodes 306 can be formed by sputtering or vacuum evaporation, or using an aluminum or silver paste or the like. Furthermore, after the provision of the output lead electrodes 307 , the entire structure is subjected to a heat treatment at 150° C. to 300° C. for several minutes with the result that the adhesion between the lead electrodes 207 and the underlying layers becomes high, thereby obtaining excellent electric characteristics. In this embodiment, the heat treatment was conducted at 200° C. for 30 minutes in a nitrogen atmosphere using an oven.
- a fourth embodiment is a process of manufacturing a thin-film solar cell, as shown in FIG. 4 , in which a coating of a metal element that accelerates the crystallization of silicon is formed on a substrate, an amorphous silicon film is formed on the coating of metal element, the amorphous silicon film is crystallized through a heat treatment, and after crystallization, the metal element diffused in the silicon film is removed therefrom.
- a coating of the metal element that accelerates the crystallization of silicon is formed on a substrate.
- Nickel is used as the metal element.
- a silicon oxide film having a thickness of 0.3 ⁇ m is first formed on a glass substrate (for example, Corning 7059 glass substrate) 401 as an underlying layer 402 .
- the silicon oxide film is formed through a plasma CVD technique with of tetra ethoxy silane (TEOS) as a raw material, and also can be formed through a sputtering technique as another method.
- TEOS tetra ethoxy silane
- a nickel film 407 is formed on the substrate.
- the nickel film 407 having 0.1 ⁇ m is formed through an electron beam evaporation method using a tablet made of pure nickel.
- an amorphous silicon film is formed through a plasma CVD technique.
- the formation of the amorphous silicon film may be conducted through low pressure thermal CVD, sputtering, evaporation, or the like.
- the above amorphous silicon film may be a substantially-intrinsic amorphous silicon film or an amorphous silicon film to which 0.001 to 0.1 atms % boron (B) has been added.
- the thickness of the amorphous silicon film is set at 10 ⁇ m. However, the thickness may be set at any required value.
- the amorphous silicon film is held at a temperature of 450° C. for one hour in a nitrogen atmosphere, thereby eliminating hydrogen from the amorphous silicon film. This is because dangling bonds are intentionally produced in the amorphous silicon film, to thereby lower the threshold energy in subsequent crystallizing. Then, the amorphous silicon film is subjected to a heat treatment at 550° C. for 4 to 8 hours in a nitrogen atmosphere, to thereby crystallize the amorphous silicon film to obtain a crystalline silicon film 403 .
- the temperature during crystallizing can be set to 550° C. because of the action of the nickel.
- 0.001 atms % hydrogen to 5 atms % is contained in a the crystalline silicon film 403 .
- a small amount of nickel diffuses into the silicon film from the nickel film disposed under the amorphous silicon film, and accelerates the crystallization of the crystalline silicon film 403 while it is moving in the silicon film.
- the crystalline silicon film 403 is formed on the glass substrate.
- a phospho-silicate glass (PSG) is formed on the crystalline silicon film 403 .
- the phospho-silicate glass (PSG) is formed by atmospheric CVD gas, using a mixture consisting of silane, phosphine, and oxygen, at a temperature of 450° C.
- the concentration of phosphorus in the phospho-silicate glass is set to 1 to 30 wt %, preferably 7 wt %.
- the phospho-silicate glass is used to getter nickel remaining in the crystalline silicon film. Even though the phospho-silicate glass is formed at only 450° C., its effect is obtained.
- the phospho-silicate glass may be subjected to a heat treatment at a temperature of 500 to 800° C., preferably 550° C. for 1 to 4 hours in the nitrogen atmosphere.
- the phospho-silicate glass can be replaced with the same effect by a silicon film to which 0.1 to 10 wt % phosphorus has been added with the same effect.
- the phospho-silicate class is etched using an aqueous hydrogen fluoride solution so as to be removed from the surface of the crystalline silicon film.
- an n-type crystalline silicon film 404 is formed on that surface.
- the r-type crystalline silicon film 404 may be formed by plasma CVD or low pressure thermal CVD.
- the n-type crystalline silicon film 404 is desirably formed at a thickness of 0.02 to 0.2 ⁇ m, and in this embodiment, it is formed at a thickness of 0.1 ⁇ m.
- a transparent electrode 405 is formed by sputtering on the above n-type crystalline silicon film 404 .
- the transparent electrode 405 is made of indium tin oxide alloy (ITO) and has a thickness of 0.08 ⁇ m.
- ITO indium tin oxide alloy
- a process of providing output electrodes 406 is conducted. In providing the output electrodes, as shown in FIG. 4 , a negative side electrode is disposed on the transparent electrode 405 , and a positive side electrode is disposed on the crystalline silicon film 403 by removing parts of the transparent electrode 405 , the n-type crystalline silicon film 404 and the crystalline silicon film 403 .
- the output electrodes 406 can be formed by sputtering or vacuum evaporation, or by using aluminum or silver paste or the like.
- the substrate is subjected to a heat treatment at 150° C. to 300° C., for example at 200° C. for 30 minutes in a nitrogen atmosphere, with the result that the adhesion between the output electrodes and the underlying layer becomes high, thereby obtaining excellent electric characteristics.
- the method of manufacturing the thin-film solar cell in accordance with the present invention in a process of crystallizing an amorphous silicon film by a heat treatment, a catalyst material such as nickel is used, thereby making it possible to obtain a crystalline silicon film at a heat treatment temperature lower than in the conventional methods. Furthermore, the method of the present invention enables the concentration of the catalyst material remaining in the crystalline silicon film obtained to be lowered. As a result, a thin-film solar cell that uses an inexpensive glass substrate and is excellent in photoelectric conversion characteristic can be obtained.
Abstract
A method of manufacturing a thin-film solar cell, comprising the steps of: forming an amorphous silicon film on a substrate; placing a metal element that accelerates the crystallization of silicon in contact with the surface of the amorphous silicon film; subjecting the amorphous silicon film to a heat treatment to obtain a crystalline silicon film; depositing a silicon film to which phosphorus has been added in contact with the crystalline silicon film; and subjecting the crystalline silicon film and the silicon film to which phosphorus has been added to a heat treatment to getter the metal element from the crystalline film.
Description
- 1. Field of the Invention
- The present invention relates to a thin-film photoelectric conversion device, especially a solar cell which is formed on a substrate, and more particularly to a thin-film solar cell having a photoelectric conversion layer formed of a crystalline silicon film.
- 2. Description of the Related Art
- A solar cell or a solar battery can be manufactured using a variety of semiconductor materials or organic compound materials. However, from an industrial viewpoint, silicon is mainly used for the solar cell. The solar cells using silicon can be classified into a bulk solar cell using a wafer of monocrystal silicon or polycrystal silicon and a thin-film solar cell having a silicon film formed on a substrate. Reduction of manufacturing costs is required, and the thin-film solar cell is expected to have the effect of reducing the costs because less raw materials are used for the thin-film solar cell than for the bulk solar cell.
- In the field of thin-film solar cells, an amorphous silicon solar cell has been placed into practical use. However, since the amorphous silicon solar cell is lower in conversion efficiency compared with the monocrystal silicon or polycrystal silicon solar cell and also suffers from problems such as deterioration due to light exposure and so on, the use thereof is limited. For that reason, as another means, a thin-film solar cell using a crystalline silicon film has been also developed.
- A melt recrystallization method and a solid-phase growth method are used for obtaining a crystalline silicon film in the thin-film solar cell. In both the methods an amorphous silicon layer is formed on a substrate and recrystallized, thereby obtaining a crystalline silicon film. In any event, the substrate is required to withstand the crystallization temperature, whereby usable materials are limited. In particular, in the melt recrystallization method, the substrate has been limited to a material that withstands 1,412° C., which is the melting point of silicon.
- The solid-phase growth method is a method in which an amorphous silicon film is formed on the substrate and crystallized thereafter through a heat treatment. In such a solid-phase growth method, in general, as the temperature becomes high, the processing time may be shortened more. However, the amorphous silicon film is hardly crystallized at a temperature of 500° C. or lower. For example, when the amorphous silicon film which has been grown through a gas-phase growth method is heated at 600° C. so as to be crystallized, 10 hours are required. Also, when the heat treatment is conducted at the temperature of 550° C., 100 hours or longer is required for the heat treatment.
- For the above reason, a high heat resistance has been required for the substrate of the thin-film solar cell. Therefore, glass, carbon, or ceramic was used for the substrate. However, from the viewpoint of reducing the costs of the solar cell, those substrates are not always proper, and it has been desired that the solar cell be fabricated on a substrate which is most generally used and inexpensive. However, for example, the #7059 glass substrate made by Corning, which is generally used, has a strain point of 593° C., and the conventional crystallization technique allows the substrate to be strained and largely deformed. For that reason, such a substrate could not be used. Also, since a substrate made of a material essentially different from silicon is used, monocrystal cannot be obtained even through crystallization is conducted on the amorphous silicon film through the above means, and silicon having large crystal grains is hard to obtain. Consequently, this causes a limit to an improvement in the efficiency of the solar cell.
- In order to solve the above problems, a method of crystallizing an amorphous silicon film through a heat treatment is disclosed in U.S. Pat. No. 5,403,772. According to the method disclosed in this patent, in order to accelerate crystallization at a low temperature, a small amount of a metal element is added to the amorphous silicon film as a catalyst material. Further, it is therein disclosed that a lowering of the heat treatment temperature and a reduction of the treatment time are enabled. Also, it is disclosed therein that a simple elemental metal substance, e.g. nickel (Ni), iron (Fe), cobalt (Co), or platinum (Pt), or a compound of any one of those metals and silicon, or the like is suitable for the catalyst material.
- However, since the catalyst materials used for accelerating crystallization are naturally undesirable for crystalline silicon, it has been desired that the concentration of the catalyst material is as low as possible. The concentration of catalyst material necessary for accelerating crystallization was 1×1017/cm3 to 1×1020/cm3. However, even when the concentration is relatively low, since the above catalyst materials are heavy metal elements, the material contained in silicon forms a defect level, thereby lowering the characteristics of a fabricated element.
- The principle of operation of a solar cell containing a p-n junction can be roughly described as follows. The solar cell absorbs light and generates electron/hole charge pairs due to absorbed light energy. The electrons move toward the n-layer side of the junction, and the holes move toward the p-layer side due to drift caused by the junction electric field and diffusion. However, when the defect levels are high in silicon, the charges are trapped by the defect levels while they are moving in the silicon, thereby disappearing. In other words, the photoelectric conversion characteristics are lowered. The period of time from when the electrons/holes are generated until they disappear is called the “life time”. In the solar cell, it is desirable that the lifetime is long. Hence, it has been necessary to reduce as much as possible the heavy metal elements that generate the defect levels in silicon.
- The present invention has been made in view of the above circumstances, and therefore an object of the present invention is to provide a method of manufacturing a thin-film solar cell, which retains the feature of crystallization due to the above catalyst material and removes the catalyst material after the crystallization has been completed.
- Another object of the present invention is to provide a solar cell which has an excellent photoelectric conversion characteristic, using the above method.
- In accordance with the primary feature of the present invention, a method of manufacturing a photoelectric conversion device includes a step of forming a gettering layer on a crystallized semiconductor layer obtained by using a catalyst metal such as nickel. The gettering layer may be either insulative or semiconductive and contains phosphorus to absorb the catalyst metal such as nickel from the semiconductor layer after it is crystallized, thereby reducing the concentration of the catalyst metal in the semiconductor layer. Specifically, the method includes the steps of:
-
- disposing a metal containing layer in contact with an upper or lower surface of a non-single crystalline silicon semiconductor layer;
- crystallizing the non-single crystalline silicon semiconductor layer by heating, wherein the metal functions to promote the crystallization;
- forming a gettering layer on or within said semiconductor layer after crystallized, the gettering layer containing phosphorus; and
- heating said semiconductor layer and the gettering layer in order to getter the metal contained in the semiconductor layer.
- As the metal element, it is possible to use one or more elements chosen from Ni, Fe, Co, Ru, Rh, Pd, Os, Ir, Pt, Cu, and Au.
- In accordance with a preferred embodiment of the invention, the gettering layer may be a silicon layer to which phosphorus is added during the deposition thereof onto the crystallized semiconductor layer. In an alternative, the gettering layer may be a phosphorus doped region formed within the crystallized semiconductor layer, namely, a method of the present invention includes a step of introducing phosphorus ions into a surface region of the crystallized semiconductor layer by ion doping after crystallizing the semiconductor layer by the use of the catalyst metal. In a further alternative, the gettering layer may be a phospho-silicate glass (PSG) layer deposited on the crystallized semiconductor layer.
- In accordance with another aspect of the invention, the catalyst metal is provided by disposing the metal containing layer in contact with an upper or lower surface of a non-single crystalline semiconductor layer to be crystallized. In the case of disposing the metal containing layer under the non-single crystalline semiconductor layer, the metal containing layer may be used also as a lower electrode of the photoelectric conversion device.
- In accordance with still another aspect of the invention, a solar cell comprises a substrate, a first crystalline silicon film having conductivity type formed on the substrate, and a second crystalline silicon film having another conductivity type adjacent to the first crystalline silicon film, wherein the first crystalline silicon film contains a catalyst element for promoting crystallization of silicon at a concentration not higher than 5×1018 atoms/cm3. The concentration value disclosed in the present invention is determined by secondary ion mass spectroscopy and corresponds to a maximum value of the measured values.
- In accordance with a further aspect of the invention, in the above mentioned solar cell, the concentration of the catalyst contained in the second crystalline silicon film is higher than the concentration of the catalyst contained in the first crystalline silicon film.
- In accordance with a still further aspect of the invention, the crystalline semiconductor film obtained by using the catalyst metal such as nickel has a plurality of crystal grains in the form of needles.
- According to the present invention, the lifetime of carriers in the crystalline silicon film is increased, and the excellent characteristics of the thin-film solar cell are obtained.
- The above and other objects and features of the present invention will be more apparent from the following description taken in conjunction with the accompanying drawings.
-
FIGS. 1A to 1D are schematic diagrams showing a method of manufacturing a thin-film solar cell in accordance with the present invention; -
FIGS. 2A to 2D are schematic diagrams showing a method of manufacturing a thin-film solar cell in accordance with the present invention; -
FIG. 3 is a diagram showing an example of a cross-sectional structure of a thin-film solar cell in accordance with the present invention; and -
FIG. 4 is a diagram showing an example of a cross-sectional structure of a thin-film solar cell in accordance with the present invention. - Now, a description will be given in more detail of embodiments of the present invention with reference to the accompanying drawings.
- The first embodiment shows a process of manufacturing a thin-film solar cell through a method of forming an amorphous silicon film in close contact with a metal element that accelerates the crystallization of silicon, crystallizing said amorphous silicon film through a heat treatment, and removing said metal element remaining in the amorphous silicon film after the crystallization.
- This embodiment will be described with reference to
FIGS. 1A to 1D. In this embodiment, nickel is used as a metal element having a catalyst action that accelerates the crystallization of silicon. First, asilicon oxide film 102 having a thickness of 0.3 μm is formed on a glass substrate (for example, Corning 7059 glass substrate) 101 as an underlying layer. Thesilicon oxide film 102 is formed through a plasma CVD technique using tetra ethoxy silane (TEOS as a raw material), and also can be formed through a sputtering technique as another method. Subsequently, anamorphous silicon film 103 is formed using silane gas as a raw material through a plasma CVD technique. The formation of theamorphous silicon film 103 may be conducted using a low pressure thermal CVD technique, a sputtering technique, or an evaporation method. The aboveamorphous silicon film 103 may be a substantially-intrinsic amorphous silicon film or may contain boron (B) at 0.001 to 0.1 atms %. Also, the thickness of theamorphous silicon film 103 is set at 10 μm. However, the thickness may be set at a required value (FIG. 1A ). - Subsequently, the substrate is immersed in an ammonium hydroxide, hydrogen peroxide mixture and then held at 70° C. for 5 minutes, to thereby form an oxide film (not shown) on the surface of the
amorphous silicon film 103. The silicon oxide film is formed in order to improve wettability in the next step process of coating with a nickel acetate solution. The nickel acetate solution is coated on the surface of theamorphous silicon film 103 by spin coating. The nickel functions as an element that accelerates the crystallization of theamorphous silicon film 103. - Subsequently, the
amorphous silicon film 103 is held at a temperature of 450° C. for one hour in a nitrogen atmosphere, thereby eliminating hydrogen from theamorphous silicon film 103. This is because dangling bonds are intentionally produced in the amorphous silicon film, to thereby lower the threshold energy in subsequent crystallizing. Then, theamorphous silicon film 103 is subjected to a heat treatment at 550° C. for 4 to 8 hours in the nitrogen atmosphere, to thereby crystallize theamorphous silicon film 103. The temperature during crystallizing can be set to 550° C. because of the action of the nickel. 0.001 atms % to 5 atms % hydrogen is contained in crystallizedsilicon film 104. During the above heat treatment, nickel accelerates the crystallization of the silicon film while it is moving in the silicon film. - In this way, the
crystalline silicon film 104 is formed on the glass substrate. Subsequently, a phospho-silicate glass (PSG) 105 is formed on thecrystalline silicon film 104. The phospho-silicate glass (PSG) 105 is formed, using a gas mixture consisting of silane, phosphine, and oxygen, at a temperature of 450° C. through an atmospheric CVD technique. The concentration of phosphorus in the phospho-silicate glass is set to 1 to 30 wt %, preferably 7 wt %. The phospho-silicate glass (PSG) 105 is used to getter nickel remaining in the crystalline silicon film. Even though the phospho-silicate glass 105 is formed at only 450° C., its effect is obtained. More effectively, the phospho-silicate glass 105 may be subjected to a heat treatment at a temperature of 500 to 800° C., preferably 550° C. for 1 to 4 hours in a nitrogen atmosphere. As another method, the phospho-silicate glass 105 can be replaced by a silicon film to which phosphorus of 0.1 to 10 wt % has been added with the same effect (FIG. 1B ). - Thereafter, the phospho-
silicate glass 105 is etched using an aqueous hydrogen fluoride solution so as to be removed from the surface of thecrystalline silicon film 104. As a result, the surface of thecrystalline silicon film 104 is exposed. On that surface there is formed an n-typecrystalline silicon film 106. The n-typecrystalline silicon film 106 may be formed through a plasma CVD technique or through a low pressure thermal CVD technique. The n-typecrystalline silicon film 106 is desirably formed at a thickness of 0.02 to 0.2 μm, and in this embodiment, it is formed at a thickness of 0.1 μm (FIG. 1C ). - Then, a
transparent electrode 107 is formed through a sputtering technique on the above n-typecrystalline silicon film 106. Thetransparent electrode 107 is made of indium tin oxide alloy (ITO) and has a thickness of 0.08 μm. Finally, a process of providingoutput electrodes 103 is conducted. In providing theoutput electrodes 108, as shown inFIG. 1D , a negative side electrode is disposed on thetransparent electrode 107, and a positive side electrode is disposed on thecrystalline silicon film 104 by removing parts of thetransparent electrode 107, the n-typecrystalline silicon film 106, and thecrystalline silicon film 104. Theoutput electrodes 108 can be formed by sputtering or vacuum evaporation, or using an aluminum or silver paste or the like. Furthermore, after the provision of theoutput electrodes 108, the product is subjected to a heat treatment at 150° C. to 300° C. for several minutes with the result that the adhesion between theoutput electrodes 108 and the underlying layer becomes high, thereby obtaining an excellent electric characteristic. In this embodiment, the product is subjected to a heat treatment at 200° C. for 30 minutes in a nitrogen atmosphere using an oven. - Through the above-mentioned processes, a thin-film solar cell is completed.
- In a second embodiment, there is described a thin-film solar cell which is formed in a process where a metal element that accelerates the crystallization of crystalline silicon is removed after crystallization, through a method where phosphorus is implanted into the surface of the crystalline silicon film via a plasma doping method.
- The second embodiment will be described with reference to
FIGS. 2A to 2D. Nickel is used in this embodiment as a metal element functioning as a catalyst to accelerate the crystallization to accellerate the crystallization of silicon. First, asilicon oxide film 202 having a thickness of 0.3 μm is formed on a glass substrate (for example, Corning 7059 glass substrate) 201 as an underlying layer. Thesilicon oxide film 202 is formed by plasma CVD with tetra ethoxy silane (TEOS as a raw material), and also can be formed through a sputtering technique as another method. Subsequently, anamorphous silicon film 203 is formed with silane gas as a raw material through a plasma CVD technique. The formation of theamorphous silicon film 203 may be conducted using a low pressure thermal CVD technique, a sputtering technique, or an evaporation method. The aboveamorphous silicon film 203 may be a substantially-intrinsic amorphous silicon film or an amorphous silicon film to which boron (B) of 0.001 to 0.1 atms % has been added. Also, the thickness of theamorphous silicon film 203 is set at 20 μm. However, the thickness may be set at any required value (FIG. 2A ). - Thereafter, the substrate is immersed in an ammonium hydroxide, hydrogen peroxide mixture at 70° C. for 5 minutes, to thereby form an oxide film (not shown) on the surface of the
amorphous silicon film 203. The silicon oxide film is formed in order to improve wettability in the next step of coating with a nickel acetate solution. The nickel acetate solution is coated on the surface of theamorphous silicon film 203 by spin coating. The nickel element functions as an element that accelerates the crystallization of theamorphous silicon film 203. - Subsequently, the
amorphous silicon film 203 is held at a temperature of 450° C. for one hour in a nitrogen atmosphere, thereby eliminating hydrogen from theamorphous silicon film 203. This is because dangling bonds are intentionally produced in the amorphous silicon film, to thereby lower the threshold energy in subsequent crystallizing. Then, theamorphous silicon film 203 is subjected to a heat treatment at 550° C. for 4 to 8 hours in a nitrogen atmosphere, to thereby crystallize theamorphous silicon film 203. The temperature during crystallizing can be set to 550° C. because of the action of the nickel. 0.001 atms % to 5 atms % hydrogen is contained in a crystallizedsilicon film 204. During the above heat treatment, nickel accelerates the crystallization of thesilicon film 204 while it is moving in the silicon film. - In this way, the
crystalline silicon film 204 can be formed on the glass substrate. In this state, the implantation of phosphorus (P) ions is conducted by a plasma doping method. The dose amount may be set to 1×1014 to 1×1017/cm2, and in this embodiment, it is set to 1×1016/cm2. The accelerating voltage is set to 20 keV. Through this process, a layer containing phosphorus at a high concentration is formed within a region of 0.1 to 0.2 μm depthwise from the surface of thecrystalline silicon film 204. Thereafter, a heat treatment is conducted on thecrystalline silicon film 204 in order to getter nickel remaining in thecrystalline silicon film 204. Thecrystalline silicon film 204 may be subjected to a heat treatment at 500 to 800° C., preferably 550° C. for 1 to 4 hours in a nitrogen atmosphere (FIG. 2B ). - In the
crystalline silicon film 204, since the region into which phosphorus ions have been implanted has its crystallinity destroyed, it becomes of a substantially amorphous structure immediately after the ions have been implanted thereinto. Thereafter, since that region is crystallized through said heat treatment, it is usable as the n-type layer of the solar cell even in this state. In this case, the concentration of nickel in the i-type or p-type layer 204 is lower than in the phosphorus doped n-type layer. - In accordance with a preferred embodiment of the invention, the phosphorus implanted region is more desirably removed since nickel that has functioned as a catalyst element is segregated in this region. As the removing method, after a thin natural oxide film on the surface has been etched using an aqueous hydrogen fluoride aqueous solution, it is removed via dry etching using sulfur hexafluoride and nitric trifluoride. With this process, the surface of the
crystalline silicon film 204 is exposed. An n-typecrystalline silicon film 205 is formed on that surface. The n-typecrystalline silicon film 205 may be formed by plasma CVD or low pressure thermal CVD. The n-typecrystalline silicon film 205 is desirably formed at a thickness of 0.02 to 0.2 μm, and in this embodiment, it is formed at a thickness of 0.1 μm (FIG. 2C ). - Then, a
transparent electrode 206 is formed via a sputtering technique on the above n-typecrystalline silicon film 205. Thetransparent electrode 206 is made of indium tin oxide alloy (ITO) and has a thickness of 0.08 μm. Finally, a process of providing output lead electrodes 207 is conducted. In providing the output electrodes 207, as shown inFIG. 2D , a negative side electrode is disposed on thetransparent electrode 206, and a positive side electrode is disposed on thecrystalline silicon film 204 by removing parts of thetransparent electrode 206, the n-typecrystalline silicon film 205, and thecrystalline silicon film 204. The output electrodes 207 can be formed through a sputtering technique or an evaporation method, or by using aluminum or silver paste or the like. Furthermore, after the provision of the output lead electrodes 207, the substrate is subjected to a heat treatment at 150° C. to 300° C. for several minutes with the result that the adhesion between the output electrodes 207 and the underlying layer becomes high, thereby obtaining excellent electric characteristics. In this embodiment, the substrate is subjected to a heat treatment at 200° C. for 30 minutes in a nitrogen atmosphere using an oven. - Through the above-mentioned processes, a thin-film solar cell is completed.
- A third embodiment shows an example where in the process of manufacturing the thin-film solar cell described with reference to the first and second embodiments, the surface of the crystalline silicon film is subjected to an anisotropic etching process so as to make the surface of the solar cell irregular as shown in
FIG. 3 . A technique by which that surface is made irregular so that reflection from the surface of the solar cell is reduced is called a “texture technique”. - A
silicon oxide film 302 having a thickness of 0.3 μm is formed on a glass substrate (for example, Corning 7059 glass substrate) 301 as an underlying layer. Thesilicon oxide film 302 is formed by plasma CVD with tetra ethoxy silane (TEOS as a raw material), and also can be formed by sputtering as another method. Subsequently, an amorphous silicon film is formed by plasma CVD. The formation of the amorphous silicon film may be conducted by low pressure thermal CVD, sputtering, evaporation, or the like. The aboveamorphous silicon film 303 may be a substantially-intrinsic amorphous silicon film or an amorphous silicon film to which of 0.001 to 0.1 atms % boron (B) has been added. Also, the thickness of the amorphous silicon film is set at 20 μm. However, the thickness may be set at any required value. - Subsequently, the substrate is immersed in an ammonium hydroxide and hydrogen peroxide mixture and then held at 70° C. for 5 minutes, to thereby form an oxide film on the surface of the amorphous silicon film. The silicon oxide film is formed in order to improve wettability in the next step of coating nickel acetate solution. The nickel acetate solution is coated on the surface of the amorphous silicon film by spin coating. The nickel functions as an element that accelerates the crystallization of the amorphous silicon film.
- Subsequently, the amorphous silicon film is held at a temperature of 450° C. for one hour in a nitrogen atmosphere, thereby eliminating hydrogen from the amorphous silicon film. This is because dangling bonds are intentionally produced in the amorphous silicon film, to thereby lower the threshold energy in subsequent crystallizing. Then, the amorphous silicon film is subjected to a heat treatment at 550° C. for 4 to 8 hours in a nitrogen atmosphere, to thereby crystalline the amorphous silicon film to obtain a
crystalline silicon film 303. The temperature during crystallizing can be set to 550° C. because of the action of nickel. 0.001 atms % to 5 atms % of hydrogen is contained in thecrystalline silicon film 303. During the above heat treatment, nickel accelerates the crystallization of thesilicon film 303 while it is moving in the silicon film. - In this way, the
crystalline silicon film 303 can be formed on the glass substrate. Then, a gettering process is conducted on thecrystalline silicon film 304 in order to remove nickel remaining in thecrystalline silicon film 304. A method of conducting the gettering process may include forming a phospho-silicate glass (PSG) on thecrystalline silicon film 303, or implanting phosphorus ions into the surface of thecrystalline silicon film 303. - In the method comprising of forming the phospho-silicate glass (PSG), the phospho-silicate glass film is formed via atomspheric CVD, using a gas mixture consisting of silane, phosphine, and oxygen, at a temperature of 450° C. The gettering process is then conducted by subjecting the crystalline silicon film to a heat treatment at 550° C. for 1 to 4 hours in a nitrogen atmosphere. Thereafter, the phospho-silicate glass film is desirably etched using an aqueous hydrogen fluoride aqueous solution so as to be removed.
- In the method comprising implanting phosphorus ions into the surface of the crystalline silicon film, the implantation of ions can be conducted through plasma doping. The dose amount may be set to 1×1014 to 1×1017/cm2, and in this embodiment, it is set to 1×1016/cm2. The accelerating voltage is set to 20 keV. Through this process, a layer containing phosphorus at a high concentration is formed within a region of 0.1 to 0.2 μm depthwise from the surface of the crystalline silicon film. Thereafter, a heat treatment is conducted on the crystalline silicon film in order to getter nickel remaining in the crystalline silicon film. The heat treatment is conducted at a temperature of 500 to 800° C., preferably 550° C. for 1 to 4 hours in a nitrogen atmosphere.
- After the gettering process has been completed, a texture process is conducted on the surface of the crystalline silicon film. The texture process can be conducted using hydrazine or sodium hydroxide aqueous solution. Hereinafter, a case of using sodium hydroxide will be described.
- The texture process is conducted by heating a 2% aqueous solution of sodium hydroxide to 80° C. Under this condition, the etching rate of the crystalline silicon film thus obtained in this embodiment is about 1 μm/min. The etching is conducted for five minutes, and thereafter the crystalline silicon film is immersed in boiling water in order to immediately cease the reaction and then the film is sufficiently cleaned by flowing water. As a result of observing the surface of the crystalline silicon film which has been subjected to the texture process through an electron microscope, an unevenness of about 0.1 to 5 μm is found on the surface although it is at random.
- An n-type
crystalline silicon film 304 is formed on that surface. The n-typecrystalline silicon film 304 may be formed through a plasma CVD technique or through a low pressure thermal CVD technique. The n-typecrystalline silicon film 304 is desirably formed at a thickness of 0.02 to 0.2 μm, and in this embodiment, it is formed at a thickness of 0.1 μm. - Then, a
transparent electrode 305 is formed by sputtering on the above n-typecrystalline silicon film 304. Thetransparent electrode 305 is made of indium tin oxide alloy (ITO) and has a thickness of 0.08 μm. Finally, a process of providing output electrodes 307 is conducted. In providing the output electrodes 307, as shown by the structure inFIG. 3D , a negative side electrode is disposed on thetransparent electrode 305, and a positive side electrode is disposed on thecrystalline silicon film 303 by removing parts of thetransparent electrode 305, the n-typecrystalline silicon film 304, and thecrystalline silicon film 303. Theoutput electrodes 306 can be formed by sputtering or vacuum evaporation, or using an aluminum or silver paste or the like. Furthermore, after the provision of the output lead electrodes 307, the entire structure is subjected to a heat treatment at 150° C. to 300° C. for several minutes with the result that the adhesion between the lead electrodes 207 and the underlying layers becomes high, thereby obtaining excellent electric characteristics. In this embodiment, the heat treatment was conducted at 200° C. for 30 minutes in a nitrogen atmosphere using an oven. - Through the above-mentioned processes, a thin-film solar cell having the texture structure on the surface is completed.
- A fourth embodiment is a process of manufacturing a thin-film solar cell, as shown in
FIG. 4 , in which a coating of a metal element that accelerates the crystallization of silicon is formed on a substrate, an amorphous silicon film is formed on the coating of metal element, the amorphous silicon film is crystallized through a heat treatment, and after crystallization, the metal element diffused in the silicon film is removed therefrom. - First, a coating of the metal element that accelerates the crystallization of silicon is formed on a substrate. Nickel is used as the metal element. A silicon oxide film having a thickness of 0.3 μm is first formed on a glass substrate (for example, Corning 7059 glass substrate) 401 as an
underlying layer 402. The silicon oxide film is formed through a plasma CVD technique with of tetra ethoxy silane (TEOS) as a raw material, and also can be formed through a sputtering technique as another method. Subsequently, anickel film 407 is formed on the substrate. Thenickel film 407 having 0.1 μm is formed through an electron beam evaporation method using a tablet made of pure nickel. Then, an amorphous silicon film is formed through a plasma CVD technique. The formation of the amorphous silicon film may be conducted through low pressure thermal CVD, sputtering, evaporation, or the like. The above amorphous silicon film may be a substantially-intrinsic amorphous silicon film or an amorphous silicon film to which 0.001 to 0.1 atms % boron (B) has been added. Also, the thickness of the amorphous silicon film is set at 10 μm. However, the thickness may be set at any required value. - Subsequently, the amorphous silicon film is held at a temperature of 450° C. for one hour in a nitrogen atmosphere, thereby eliminating hydrogen from the amorphous silicon film. This is because dangling bonds are intentionally produced in the amorphous silicon film, to thereby lower the threshold energy in subsequent crystallizing. Then, the amorphous silicon film is subjected to a heat treatment at 550° C. for 4 to 8 hours in a nitrogen atmosphere, to thereby crystallize the amorphous silicon film to obtain a
crystalline silicon film 403. The temperature during crystallizing can be set to 550° C. because of the action of the nickel. 0.001 atms % hydrogen to 5 atms % is contained in a thecrystalline silicon film 403. During the above heat treatment, a small amount of nickel diffuses into the silicon film from the nickel film disposed under the amorphous silicon film, and accelerates the crystallization of thecrystalline silicon film 403 while it is moving in the silicon film. - In this way, the
crystalline silicon film 403 is formed on the glass substrate. Subsequently, a phospho-silicate glass (PSG) is formed on thecrystalline silicon film 403. The phospho-silicate glass (PSG) is formed by atmospheric CVD gas, using a mixture consisting of silane, phosphine, and oxygen, at a temperature of 450° C. The concentration of phosphorus in the phospho-silicate glass is set to 1 to 30 wt %, preferably 7 wt %. The phospho-silicate glass is used to getter nickel remaining in the crystalline silicon film. Even though the phospho-silicate glass is formed at only 450° C., its effect is obtained. More effectively, the phospho-silicate glass may be subjected to a heat treatment at a temperature of 500 to 800° C., preferably 550° C. for 1 to 4 hours in the nitrogen atmosphere. As another method, the phospho-silicate glass can be replaced with the same effect by a silicon film to which 0.1 to 10 wt % phosphorus has been added with the same effect. - Thereafter, the phospho-silicate class is etched using an aqueous hydrogen fluoride solution so as to be removed from the surface of the crystalline silicon film. As a result, the surface of the
crystalline silicon film 403 is exposed. An n-typecrystalline silicon film 404 is formed on that surface. The r-typecrystalline silicon film 404 may be formed by plasma CVD or low pressure thermal CVD. The n-typecrystalline silicon film 404 is desirably formed at a thickness of 0.02 to 0.2 μm, and in this embodiment, it is formed at a thickness of 0.1 μm. - Then, a
transparent electrode 405 is formed by sputtering on the above n-typecrystalline silicon film 404. Thetransparent electrode 405 is made of indium tin oxide alloy (ITO) and has a thickness of 0.08 μm. Finally, a process of providingoutput electrodes 406 is conducted. In providing the output electrodes, as shown inFIG. 4 , a negative side electrode is disposed on thetransparent electrode 405, and a positive side electrode is disposed on thecrystalline silicon film 403 by removing parts of thetransparent electrode 405, the n-typecrystalline silicon film 404 and thecrystalline silicon film 403. Theoutput electrodes 406 can be formed by sputtering or vacuum evaporation, or by using aluminum or silver paste or the like. Furthermore, after the provision of the output electrodes, the substrate is subjected to a heat treatment at 150° C. to 300° C., for example at 200° C. for 30 minutes in a nitrogen atmosphere, with the result that the adhesion between the output electrodes and the underlying layer becomes high, thereby obtaining excellent electric characteristics. - Through the above-mentioned processes, a thin-film solar cell is completed.
- As was described above, in the method of manufacturing the thin-film solar cell in accordance with the present invention, in a process of crystallizing an amorphous silicon film by a heat treatment, a catalyst material such as nickel is used, thereby making it possible to obtain a crystalline silicon film at a heat treatment temperature lower than in the conventional methods. Furthermore, the method of the present invention enables the concentration of the catalyst material remaining in the crystalline silicon film obtained to be lowered. As a result, a thin-film solar cell that uses an inexpensive glass substrate and is excellent in photoelectric conversion characteristic can be obtained.
- The foregoing description of a preferred embodiment of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention. The embodiment was chosen and described in order to explain the principles of the invention and its practical application to enable one skilled in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto, and their equivalents.
Claims (33)
1. A thin-film device comprising:
a semiconductor film formed over a substrate; and
an n-type semiconductor film formed over the semiconductor film, wherein the n-type semiconductor film contains a metal element.
2. A thin-film device according to claim 1 , wherein the semiconductor film comprises a crystalline silicon.
3. A thin-film device according to claim 1 , further comprising silicon oxide between the substrate and the semiconductor film.
4. A thin-film device according to claim 1 , wherein the metal element comprises at least one selected from the group consisting of nickel, iron, cobalt and platinum.
5. A thin-film device according to claim 1 , wherein the thin-film device is a solar cell.
6. A thin-film device comprising:
a semiconductor film formed over a substrate, wherein the semiconductor film contains a metal element at a concentration not higher than 5×1018 atoms/cm3; and
an n-type semiconductor film formed over the semiconductor film, wherein the n-type semiconductor film contains the metal element.
7. A thin-film device according to claim 6 , wherein the semiconductor film comprises a crystalline silicon.
8. A thin-film device according to claim 6 , further comprising silicon oxide between the substrate and the semiconductor film.
9. A thin-film device according to claim 6 , wherein the metal element comprises at least one selected from the group consisting of nickel, iron, cobalt and platinum.
10. A thin-film device according to claim 6 , wherein the thin-film device is a solar cell.
11. A thin-film device comprising:
a semiconductor film formed over a substrate; and
an n-type semiconductor film formed over the semiconductor film, wherein the n-type semiconductor film contains phosphorus and a metal element.
12. A thin-film device according to claim 11 , wherein the semiconductor film comprises a crystalline silicon.
13. A thin-film device according to claim 11 , further comprising silicon oxide between the substrate and the semiconductor film.
14. A thin-film device according to claim 11 , wherein the metal element comprises at least one selected from the group consisting of nickel, iron, cobalt and platinum.
15. A thin-film device according to claim 11 , wherein the thin-film device is a solar cell.
16. A thin-film device comprising:
a semiconductor film formed over a substrate;
an n-type semiconductor film formed over the semiconductor film, wherein the n-type semiconductor film contains a metal element; and
a transparent electrode formed over the n-type semiconductor film.
17. A thin-film device according to claim 16 , wherein the semiconductor film comprises a crystalline silicon.
18. A thin-film device according to claim 16 , further comprising silicon oxide between the substrate and the semiconductor film.
19. A thin-film device according to claim 16 , wherein the metal element comprises at least one selected from the group consisting of nickel, iron, cobalt and platinum.
20. A thin-film device according to claim 16 , wherein the transparent electrode comprises indium tin oxide.
21. A thin-film device according to claim 16 , wherein the thin-film device is a solar cell.
22. A thin-film device comprising:
a semiconductor film formed over a substrate, wherein the semiconductor film contains a metal element at a concentration not higher than 5×1018 atoms/cm3;
an n-type semiconductor film formed over the semiconductor film, wherein the n-type semiconductor film contains the metal element; and
a transparent electrode formed over the n-type semiconductor film.
23. A thin-film device according to claim 22 , wherein the semiconductor film comprises a crystalline silicon.
24. A thin-film device according to claim 22 , further comprising silicon oxide between the substrate and the semiconductor film.
25. A thin-film device according to claim 22 , wherein the metal element comprises at least one selected from the group consisting of nickel, iron, cobalt and platinum.
26. A thin-film device according to claim 22 , wherein the transparent electrode comprises indium tin oxide.
27. A thin-film device according to claim 22 , wherein the thin-film device is a solar cell.
28. A thin-film device comprising:
a semiconductor film formed over a substrate;
an n-type semiconductor film formed over the semiconductor film, wherein the n-type semiconductor film contains phosphorus and a metal element; and
a transparent electrode formed over the n-type semiconductor film.
29. A thin-film device according to claim 28 , wherein the semiconductor film comprises a crystalline silicon.
30. A thin-film device according to claim 28 , further comprising silicon oxide between the substrate and the semiconductor film.
31. A thin-film device according to claim 28 , wherein the metal element comprises at least one selected from the group consisting of nickel, iron, cobalt and platinum.
32. A thin-film device according to claim 28 , wherein the transparent electrode comprises indium tin oxide.
33. A thin-film device according to claim 28 , wherein the thin-film device is a solar cell.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/422,570 US20060213550A1 (en) | 1995-03-27 | 2006-06-06 | Thin-film photoelectric conversion device and a method of manufacturing the same |
Applications Claiming Priority (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12986495 | 1995-03-27 | ||
JP07129864 | 1995-03-27 | ||
JP12986595 | 1995-03-27 | ||
JP07129865 | 1995-03-27 | ||
JP07110121 | 1995-04-11 | ||
JP11012195 | 1995-04-11 | ||
US08/623,336 US5700333A (en) | 1995-03-27 | 1996-03-27 | Thin-film photoelectric conversion device and a method of manufacturing the same |
US08/907,182 US7075002B1 (en) | 1995-03-27 | 1997-08-06 | Thin-film photoelectric conversion device and a method of manufacturing the same |
US11/422,570 US20060213550A1 (en) | 1995-03-27 | 2006-06-06 | Thin-film photoelectric conversion device and a method of manufacturing the same |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/623,336 Continuation US5700333A (en) | 1995-03-27 | 1996-03-27 | Thin-film photoelectric conversion device and a method of manufacturing the same |
US08/907,182 Continuation US7075002B1 (en) | 1995-03-27 | 1997-08-06 | Thin-film photoelectric conversion device and a method of manufacturing the same |
Publications (1)
Publication Number | Publication Date |
---|---|
US20060213550A1 true US20060213550A1 (en) | 2006-09-28 |
Family
ID=27469796
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/907,182 Expired - Fee Related US7075002B1 (en) | 1995-03-27 | 1997-08-06 | Thin-film photoelectric conversion device and a method of manufacturing the same |
US11/422,570 Abandoned US20060213550A1 (en) | 1995-03-27 | 2006-06-06 | Thin-film photoelectric conversion device and a method of manufacturing the same |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/907,182 Expired - Fee Related US7075002B1 (en) | 1995-03-27 | 1997-08-06 | Thin-film photoelectric conversion device and a method of manufacturing the same |
Country Status (1)
Country | Link |
---|---|
US (2) | US7075002B1 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090139558A1 (en) * | 2007-11-29 | 2009-06-04 | Shunpei Yamazaki | Photoelectric conversion device and manufacturing method thereof |
US20090165854A1 (en) * | 2007-12-28 | 2009-07-02 | Semiconductor Energy Laboratory Co., Ltd. | Photoelectric conversion device and manufacturing method thereof |
CN104051563A (en) * | 2013-03-14 | 2014-09-17 | 北京北方微电子基地设备工艺研究中心有限责任公司 | Preparation method of solar cell |
US8994009B2 (en) | 2011-09-07 | 2015-03-31 | Semiconductor Energy Laboratory Co., Ltd. | Photoelectric conversion device |
US20160126395A1 (en) * | 2014-11-03 | 2016-05-05 | First Solar, Inc. | Photovoltaic devices and method of manufacturing |
US10062800B2 (en) | 2013-06-07 | 2018-08-28 | First Solar, Inc. | Photovoltaic devices and method of making |
US10141463B2 (en) | 2013-05-21 | 2018-11-27 | First Solar Malaysia Sdn. Bhd. | Photovoltaic devices and methods for making the same |
US10243092B2 (en) | 2013-02-01 | 2019-03-26 | First Solar, Inc. | Photovoltaic device including a p-n junction and method of manufacturing |
US11876140B2 (en) | 2013-05-02 | 2024-01-16 | First Solar, Inc. | Photovoltaic devices and method of making |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE43450E1 (en) * | 1994-09-29 | 2012-06-05 | Semiconductor Energy Laboratory Co., Ltd. | Method for fabricating semiconductor thin film |
US6994083B2 (en) * | 2001-12-21 | 2006-02-07 | Trudell Medical International | Nebulizer apparatus and method |
US20070044832A1 (en) * | 2005-08-25 | 2007-03-01 | Fritzemeier Leslie G | Photovoltaic template |
JP2011503847A (en) * | 2007-11-02 | 2011-01-27 | ワコンダ テクノロジーズ, インコーポレイテッド | Crystalline thin film photovoltaic structure and method for forming the same |
US8236603B1 (en) | 2008-09-04 | 2012-08-07 | Solexant Corp. | Polycrystalline semiconductor layers and methods for forming the same |
US8415187B2 (en) * | 2009-01-28 | 2013-04-09 | Solexant Corporation | Large-grain crystalline thin-film structures and devices and methods for forming the same |
Citations (66)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4038104A (en) * | 1976-06-07 | 1977-07-26 | Kabushiki Kaisha Suwa Seikosha | Solar battery |
US4124410A (en) * | 1977-11-21 | 1978-11-07 | Union Carbide Corporation | Silicon solar cells with low-cost substrates |
US4389534A (en) * | 1980-12-22 | 1983-06-21 | Messerschmitt-Bolkow-Blohm Gmbh | Amorphous silicon solar cell having improved antireflection coating |
US4443652A (en) * | 1982-11-09 | 1984-04-17 | Energy Conversion Devices, Inc. | Electrically interconnected large area photovoltaic cells and method of producing said cells |
US4464823A (en) * | 1982-10-21 | 1984-08-14 | Energy Conversion Devices, Inc. | Method for eliminating short and latent short circuit current paths in photovoltaic devices |
US4561171A (en) * | 1982-04-06 | 1985-12-31 | Shell Austria Aktiengesellschaft | Process of gettering semiconductor devices |
US4571448A (en) * | 1981-11-16 | 1986-02-18 | University Of Delaware | Thin film photovoltaic solar cell and method of making the same |
US4781766A (en) * | 1985-10-30 | 1988-11-01 | Astrosystems, Inc. | Fault tolerant thin-film photovoltaic cell and method |
US5085711A (en) * | 1989-02-20 | 1992-02-04 | Sanyo Electric Co., Ltd. | Photovoltaic device |
US5244819A (en) * | 1991-10-22 | 1993-09-14 | Honeywell Inc. | Method to getter contamination in semiconductor devices |
US5275851A (en) * | 1993-03-03 | 1994-01-04 | The Penn State Research Foundation | Low temperature crystallization and patterning of amorphous silicon films on electrically insulating substrates |
US5328519A (en) * | 1990-05-07 | 1994-07-12 | Canon Kabushiki Kaisha | Solar cells |
US5330918A (en) * | 1992-08-31 | 1994-07-19 | The United States Of America As Represented By The Secretary Of The Navy | Method of forming a high voltage silicon-on-sapphire photocell array |
US5360748A (en) * | 1992-01-24 | 1994-11-01 | Kabushiki Kaisha Toshiba | Method of manufacturing a semiconductor device |
US5380372A (en) * | 1991-10-11 | 1995-01-10 | Nukem Gmbh | Solar cell and method for manufacture thereof |
US5403772A (en) * | 1992-12-04 | 1995-04-04 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing semiconductor device |
US5426061A (en) * | 1994-09-06 | 1995-06-20 | Midwest Research Institute | Impurity gettering in semiconductors |
US5426064A (en) * | 1993-03-12 | 1995-06-20 | Semiconductor Energy Laboratory Co., Ltd. | Method of fabricating a semiconductor device |
US5461002A (en) * | 1990-05-30 | 1995-10-24 | Safir; Yakov | Method of making diffused doped areas for semiconductor components |
US5501989A (en) * | 1993-03-22 | 1996-03-26 | Semiconductor Energy Laboratory Co., Ltd. | Method of making semiconductor device/circuit having at least partially crystallized semiconductor layer |
US5529937A (en) * | 1993-07-27 | 1996-06-25 | Semiconductor Energy Laboratory Co., Ltd. | Process for fabricating thin film transistor |
US5543352A (en) * | 1993-12-01 | 1996-08-06 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing a semiconductor device using a catalyst |
US5569610A (en) * | 1993-03-12 | 1996-10-29 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing multiple polysilicon TFTs with varying degrees of crystallinity |
US5575862A (en) * | 1993-11-30 | 1996-11-19 | Canon Kabushiki Kaisha | Polycrystalline silicon photoelectric conversion device and process for its production |
US5595944A (en) * | 1993-03-12 | 1997-01-21 | Semiconductor Energy Laboratory Co., Inc. | Transistor and process for fabricating the same |
US5604360A (en) * | 1992-12-04 | 1997-02-18 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device including a plurality of thin film transistors at least some of which have a crystalline silicon film crystal-grown substantially in parallel to the surface of a substrate for the transistor |
US5608232A (en) * | 1993-02-15 | 1997-03-04 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor, semiconductor device, and method for fabricating the same |
US5614426A (en) * | 1993-08-10 | 1997-03-25 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing semiconductor device having different orientations of crystal channel growth |
US5624851A (en) * | 1993-03-12 | 1997-04-29 | Semiconductor Energy Laboratory Co., Ltd. | Process of fabricating a semiconductor device in which one portion of an amorphous silicon film is thermally crystallized and another portion is laser crystallized |
US5644156A (en) * | 1994-04-14 | 1997-07-01 | Kabushiki Kaisha Toshiba | Porous silicon photo-device capable of photoelectric conversion |
US5696003A (en) * | 1993-12-20 | 1997-12-09 | Sharp Kabushiki Kaisha | Method for fabricating a semiconductor device using a catalyst introduction region |
US5700333A (en) * | 1995-03-27 | 1997-12-23 | Semiconductor Energy Laboratory Co., Ltd. | Thin-film photoelectric conversion device and a method of manufacturing the same |
US5741615A (en) * | 1992-04-24 | 1998-04-21 | Canon Kabushiki Kaisha | Light receiving member with non-single-crystal silicon layer containing Cr, Fe, Na, Ni and Mg |
US5789284A (en) * | 1994-09-29 | 1998-08-04 | Semiconductor Energy Laboratory Co., Ltd. | Method for fabricating semiconductor thin film |
US5843225A (en) * | 1993-02-03 | 1998-12-01 | Semiconductor Energy Laboratory Co., Ltd. | Process for fabricating semiconductor and process for fabricating semiconductor device |
US5915174A (en) * | 1994-09-30 | 1999-06-22 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and method for producing the same |
US5932893A (en) * | 1993-06-12 | 1999-08-03 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device having doped polycrystalline layer |
US5962871A (en) * | 1993-05-26 | 1999-10-05 | Semiconductor Energy Laboratory Co., Ltd. | Method for producing semiconductor device |
US6066518A (en) * | 1997-07-22 | 2000-05-23 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing semiconductor devices using a crystallization promoting material |
US6090646A (en) * | 1993-05-26 | 2000-07-18 | Semiconductor Energy Laboratory Co., Ltd. | Method for producing semiconductor device |
US6133119A (en) * | 1996-07-08 | 2000-10-17 | Semiconductor Energy Laboratory Co., Ltd. | Photoelectric conversion device and method manufacturing same |
US6156628A (en) * | 1997-07-22 | 2000-12-05 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and method of manufacturing the same |
US6162704A (en) * | 1997-02-12 | 2000-12-19 | Semiconductor Energy Laboratory Co., Ltd. | Method of making semiconductor device |
US6177302B1 (en) * | 1990-11-09 | 2001-01-23 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a thin film transistor using multiple sputtering chambers |
US6197626B1 (en) * | 1997-02-26 | 2001-03-06 | Semiconductor Energy Laboratory Co. | Method for fabricating semiconductor device |
US6232205B1 (en) * | 1997-07-22 | 2001-05-15 | Semiconductor Energy Laboratory Co., Ltd. | Method for producing a semiconductor device |
US6242290B1 (en) * | 1997-07-14 | 2001-06-05 | Semiconductor Energy Laboratory Co., Ltd. | Method of forming a TFT by adding a metal to a silicon film promoting crystallization, forming a mask, forming another silicon layer with group XV elements, and gettering the metal through opening in the mask |
US6251712B1 (en) * | 1995-03-27 | 2001-06-26 | Semiconductor Energy Laboratory Co., Ltd. | Method of using phosphorous to getter crystallization catalyst in a p-type device |
US6261875B1 (en) * | 1993-03-12 | 2001-07-17 | Semiconductor Energy Laboratory Co., Ltd. | Transistor and process for fabricating the same |
US6300558B1 (en) * | 1999-04-27 | 2001-10-09 | Japan Energy Corporation | Lattice matched solar cell and method for manufacturing the same |
US6303415B1 (en) * | 1997-06-10 | 2001-10-16 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and method of fabricating same |
US6348368B1 (en) * | 1997-10-21 | 2002-02-19 | Semiconductor Energy Laboratory Co., Ltd. | Introducing catalytic and gettering elements with a single mask when manufacturing a thin film semiconductor device |
US6355509B1 (en) * | 1997-01-28 | 2002-03-12 | Semiconductor Energy Laboratory Co., Ltd. | Removing a crystallization catalyst from a semiconductor film during semiconductor device fabrication |
US6399454B1 (en) * | 1997-07-14 | 2002-06-04 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a semiconductor film and method of manufacturing a semiconductor device |
US6420246B1 (en) * | 1997-02-17 | 2002-07-16 | Semiconductor Energy Laboratory Co., Ltd. | Method of gettering a metal element for accelerating crystallization of silicon by phosphorous |
US6432756B1 (en) * | 1997-07-24 | 2002-08-13 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and fabricating method thereof |
US6436745B1 (en) * | 1999-11-02 | 2002-08-20 | Sharp Kabushiki Kaisha | Method of producing a semiconductor device |
US20020115271A1 (en) * | 2001-02-16 | 2002-08-22 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a semiconductor device |
US6458637B1 (en) * | 1996-02-23 | 2002-10-01 | Semiconductor Energy Laboratory Co., Ltd. | Thin film semiconductor and method for manufacturing the same, semiconductor device and method for manufacturing the same |
US6479333B1 (en) * | 1997-03-03 | 2002-11-12 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a semiconductor device |
US6544826B1 (en) * | 1997-06-17 | 2003-04-08 | Semiconductor Energy Laboratory Co., Ltd. | Method for producing semiconductor device |
US6548370B1 (en) * | 1999-08-18 | 2003-04-15 | Semiconductor Energy Laboratory Co., Ltd. | Method of crystallizing a semiconductor layer by applying laser irradiation that vary in energy to its top and bottom surfaces |
US6670225B2 (en) * | 1997-07-30 | 2003-12-30 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a semiconductor device |
US6777273B1 (en) * | 1998-05-16 | 2004-08-17 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor display device |
US6821710B1 (en) * | 1998-02-11 | 2004-11-23 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing semiconductor device |
US6858480B2 (en) * | 2001-01-18 | 2005-02-22 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing semiconductor device |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS49134276A (en) | 1973-04-27 | 1974-12-24 | ||
DE3049226A1 (en) | 1975-05-20 | 1982-03-11 | Pao Hsien Dr. 02178 Belmont Mass. Fang | Thin film solar cell prodn. - uses a substrate of thin metal with semiconductor covering layer |
JPH02296377A (en) | 1989-05-10 | 1990-12-06 | Sanyo Electric Co Ltd | Formation of polycrystalline semiconductor layer and manufacture of photoelectromotive force device |
JPH03218683A (en) | 1990-01-24 | 1991-09-26 | Sanyo Electric Co Ltd | Photovoltaic element |
JP3249508B2 (en) | 1990-09-25 | 2002-01-21 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor device |
JP2794678B2 (en) * | 1991-08-26 | 1998-09-10 | 株式会社 半導体エネルギー研究所 | Insulated gate semiconductor device and method of manufacturing the same |
JP2889718B2 (en) | 1991-03-20 | 1999-05-10 | 三洋電機株式会社 | Method for manufacturing photovoltaic device |
JPH04360518A (en) | 1991-06-07 | 1992-12-14 | Sanyo Electric Co Ltd | Manufacture of photovoltaic device |
JPH05109737A (en) | 1991-10-18 | 1993-04-30 | Casio Comput Co Ltd | Manufacture of thin film transistor |
JP2852853B2 (en) | 1993-07-27 | 1999-02-03 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor device |
JP3241515B2 (en) | 1992-12-04 | 2001-12-25 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor device |
JP3497198B2 (en) | 1993-02-03 | 2004-02-16 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor device and thin film transistor |
JPH06244103A (en) | 1993-02-15 | 1994-09-02 | Semiconductor Energy Lab Co Ltd | Manufacture of semiconductor |
JP3359690B2 (en) | 1993-03-12 | 2002-12-24 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor circuit |
JP3137797B2 (en) | 1993-03-12 | 2001-02-26 | 株式会社半導体エネルギー研究所 | Thin film transistor and manufacturing method thereof |
JP3431681B2 (en) | 1993-03-12 | 2003-07-28 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor circuit |
JP3329512B2 (en) | 1993-03-22 | 2002-09-30 | 株式会社半導体エネルギー研究所 | Semiconductor circuit and manufacturing method thereof |
JP3190483B2 (en) | 1993-05-21 | 2001-07-23 | 株式会社半導体エネルギー研究所 | Semiconductor device manufacturing method |
JP3190482B2 (en) * | 1993-05-21 | 2001-07-23 | 株式会社半導体エネルギー研究所 | Semiconductor device and manufacturing method thereof |
JP3190518B2 (en) | 1993-05-26 | 2001-07-23 | 株式会社半導体エネルギー研究所 | Semiconductor device manufacturing method |
JP3076490B2 (en) | 1993-12-20 | 2000-08-14 | シャープ株式会社 | Method for manufacturing semiconductor device |
-
1997
- 1997-08-06 US US08/907,182 patent/US7075002B1/en not_active Expired - Fee Related
-
2006
- 2006-06-06 US US11/422,570 patent/US20060213550A1/en not_active Abandoned
Patent Citations (97)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4038104A (en) * | 1976-06-07 | 1977-07-26 | Kabushiki Kaisha Suwa Seikosha | Solar battery |
US4124410A (en) * | 1977-11-21 | 1978-11-07 | Union Carbide Corporation | Silicon solar cells with low-cost substrates |
US4389534A (en) * | 1980-12-22 | 1983-06-21 | Messerschmitt-Bolkow-Blohm Gmbh | Amorphous silicon solar cell having improved antireflection coating |
US4571448A (en) * | 1981-11-16 | 1986-02-18 | University Of Delaware | Thin film photovoltaic solar cell and method of making the same |
US4561171A (en) * | 1982-04-06 | 1985-12-31 | Shell Austria Aktiengesellschaft | Process of gettering semiconductor devices |
US4464823A (en) * | 1982-10-21 | 1984-08-14 | Energy Conversion Devices, Inc. | Method for eliminating short and latent short circuit current paths in photovoltaic devices |
US4443652A (en) * | 1982-11-09 | 1984-04-17 | Energy Conversion Devices, Inc. | Electrically interconnected large area photovoltaic cells and method of producing said cells |
US4781766A (en) * | 1985-10-30 | 1988-11-01 | Astrosystems, Inc. | Fault tolerant thin-film photovoltaic cell and method |
US5085711A (en) * | 1989-02-20 | 1992-02-04 | Sanyo Electric Co., Ltd. | Photovoltaic device |
US5328519A (en) * | 1990-05-07 | 1994-07-12 | Canon Kabushiki Kaisha | Solar cells |
US5461002A (en) * | 1990-05-30 | 1995-10-24 | Safir; Yakov | Method of making diffused doped areas for semiconductor components |
US6177302B1 (en) * | 1990-11-09 | 2001-01-23 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a thin film transistor using multiple sputtering chambers |
US5380372A (en) * | 1991-10-11 | 1995-01-10 | Nukem Gmbh | Solar cell and method for manufacture thereof |
US5244819A (en) * | 1991-10-22 | 1993-09-14 | Honeywell Inc. | Method to getter contamination in semiconductor devices |
US5360748A (en) * | 1992-01-24 | 1994-11-01 | Kabushiki Kaisha Toshiba | Method of manufacturing a semiconductor device |
US5741615A (en) * | 1992-04-24 | 1998-04-21 | Canon Kabushiki Kaisha | Light receiving member with non-single-crystal silicon layer containing Cr, Fe, Na, Ni and Mg |
US5330918A (en) * | 1992-08-31 | 1994-07-19 | The United States Of America As Represented By The Secretary Of The Navy | Method of forming a high voltage silicon-on-sapphire photocell array |
US5563426A (en) * | 1992-12-04 | 1996-10-08 | Semiconductor Energy Laboratory Co., Ltd. | Thin film transistor |
US5888857A (en) * | 1992-12-04 | 1999-03-30 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and method for manufacturing the same |
US5403772A (en) * | 1992-12-04 | 1995-04-04 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing semiconductor device |
US5604360A (en) * | 1992-12-04 | 1997-02-18 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device including a plurality of thin film transistors at least some of which have a crystalline silicon film crystal-grown substantially in parallel to the surface of a substrate for the transistor |
US5843225A (en) * | 1993-02-03 | 1998-12-01 | Semiconductor Energy Laboratory Co., Ltd. | Process for fabricating semiconductor and process for fabricating semiconductor device |
US5956579A (en) * | 1993-02-15 | 1999-09-21 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor, semiconductor device, and method for fabricating the same |
US5897347A (en) * | 1993-02-15 | 1999-04-27 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor, semiconductor device, and method for fabricating the same |
US6084247A (en) * | 1993-02-15 | 2000-07-04 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device having a catalyst enhanced crystallized layer |
US5639698A (en) * | 1993-02-15 | 1997-06-17 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor, semiconductor device, and method for fabricating the same |
US5608232A (en) * | 1993-02-15 | 1997-03-04 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor, semiconductor device, and method for fabricating the same |
US5275851A (en) * | 1993-03-03 | 1994-01-04 | The Penn State Research Foundation | Low temperature crystallization and patterning of amorphous silicon films on electrically insulating substrates |
US5580792A (en) * | 1993-03-12 | 1996-12-03 | Semiconductor Energy Laboratory Co., Ltd. | Method of removing a catalyst substance from the channel region of a TFT after crystallization |
US5646424A (en) * | 1993-03-12 | 1997-07-08 | Semiconductor Energy Laboratory Co., Ltd. | Transistor device employing crystallization catalyst |
US5773846A (en) * | 1993-03-12 | 1998-06-30 | Semiconductor Energy Laboratory Co., Ltd. | Transistor and process for fabricating the same |
US5614733A (en) * | 1993-03-12 | 1997-03-25 | Semiconductor Energy Laboratory Co., Inc. | Semiconductor device having crystalline thin film transistors |
US5624851A (en) * | 1993-03-12 | 1997-04-29 | Semiconductor Energy Laboratory Co., Ltd. | Process of fabricating a semiconductor device in which one portion of an amorphous silicon film is thermally crystallized and another portion is laser crystallized |
US5426064A (en) * | 1993-03-12 | 1995-06-20 | Semiconductor Energy Laboratory Co., Ltd. | Method of fabricating a semiconductor device |
US6060725A (en) * | 1993-03-12 | 2000-05-09 | Semiconductor Energy Laboratory Co., Ltd. | Thin film transistor using a semiconductor film |
US5783468A (en) * | 1993-03-12 | 1998-07-21 | Semiconductor Energy Laboratory Co. Ltd. | Semiconductor circuit and method of fabricating the same |
US5677549A (en) * | 1993-03-12 | 1997-10-14 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device having a plurality of crystalline thin film transistors |
US5595944A (en) * | 1993-03-12 | 1997-01-21 | Semiconductor Energy Laboratory Co., Inc. | Transistor and process for fabricating the same |
US6261875B1 (en) * | 1993-03-12 | 2001-07-17 | Semiconductor Energy Laboratory Co., Ltd. | Transistor and process for fabricating the same |
US5569610A (en) * | 1993-03-12 | 1996-10-29 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing multiple polysilicon TFTs with varying degrees of crystallinity |
US5589694A (en) * | 1993-03-22 | 1996-12-31 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device having a thin film transistor and thin film diode |
US5744822A (en) * | 1993-03-22 | 1998-04-28 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device/circuit having at least partially crystallized semiconductor layer |
US5501989A (en) * | 1993-03-22 | 1996-03-26 | Semiconductor Energy Laboratory Co., Ltd. | Method of making semiconductor device/circuit having at least partially crystallized semiconductor layer |
US6090646A (en) * | 1993-05-26 | 2000-07-18 | Semiconductor Energy Laboratory Co., Ltd. | Method for producing semiconductor device |
US5962871A (en) * | 1993-05-26 | 1999-10-05 | Semiconductor Energy Laboratory Co., Ltd. | Method for producing semiconductor device |
US6121076A (en) * | 1993-05-26 | 2000-09-19 | Semiconductor Energy Laboratory Co., Ltd. | Method for producing semiconductor device |
US6475840B1 (en) * | 1993-06-12 | 2002-11-05 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and method for manufacturing the same |
US5932893A (en) * | 1993-06-12 | 1999-08-03 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device having doped polycrystalline layer |
US5529937A (en) * | 1993-07-27 | 1996-06-25 | Semiconductor Energy Laboratory Co., Ltd. | Process for fabricating thin film transistor |
US5696388A (en) * | 1993-08-10 | 1997-12-09 | Semiconductor Energy Laboratory Co., Ltd. | Thin film transistors for the peripheral circuit portion and the pixel portion |
US5614426A (en) * | 1993-08-10 | 1997-03-25 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing semiconductor device having different orientations of crystal channel growth |
US5575862A (en) * | 1993-11-30 | 1996-11-19 | Canon Kabushiki Kaisha | Polycrystalline silicon photoelectric conversion device and process for its production |
US5543352A (en) * | 1993-12-01 | 1996-08-06 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing a semiconductor device using a catalyst |
US5821562A (en) * | 1993-12-20 | 1998-10-13 | Sharp Kabushiki Kaisha | Semiconductor device formed within asymetrically-shaped seed crystal region |
US5696003A (en) * | 1993-12-20 | 1997-12-09 | Sharp Kabushiki Kaisha | Method for fabricating a semiconductor device using a catalyst introduction region |
US5644156A (en) * | 1994-04-14 | 1997-07-01 | Kabushiki Kaisha Toshiba | Porous silicon photo-device capable of photoelectric conversion |
US5426061A (en) * | 1994-09-06 | 1995-06-20 | Midwest Research Institute | Impurity gettering in semiconductors |
US6071766A (en) * | 1994-09-29 | 2000-06-06 | Semiconductor Energy Laboratory Co., Ltd. | Method for fabricating semiconductor thin film |
US5789284A (en) * | 1994-09-29 | 1998-08-04 | Semiconductor Energy Laboratory Co., Ltd. | Method for fabricating semiconductor thin film |
USRE38266E1 (en) * | 1994-09-29 | 2003-10-07 | Semiconductor Energy Laboratory Co., Ltd. | Method for fabricating semiconductor thin film |
US5915174A (en) * | 1994-09-30 | 1999-06-22 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and method for producing the same |
US5700333A (en) * | 1995-03-27 | 1997-12-23 | Semiconductor Energy Laboratory Co., Ltd. | Thin-film photoelectric conversion device and a method of manufacturing the same |
US5961743A (en) * | 1995-03-27 | 1999-10-05 | Semiconductor Energy Laboratory Co., Ltd. | Thin-film photoelectric conversion device and a method of manufacturing the same |
US6251712B1 (en) * | 1995-03-27 | 2001-06-26 | Semiconductor Energy Laboratory Co., Ltd. | Method of using phosphorous to getter crystallization catalyst in a p-type device |
US6458637B1 (en) * | 1996-02-23 | 2002-10-01 | Semiconductor Energy Laboratory Co., Ltd. | Thin film semiconductor and method for manufacturing the same, semiconductor device and method for manufacturing the same |
US6133119A (en) * | 1996-07-08 | 2000-10-17 | Semiconductor Energy Laboratory Co., Ltd. | Photoelectric conversion device and method manufacturing same |
US6624049B1 (en) * | 1996-07-08 | 2003-09-23 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and method of manufacturing the same |
US6355509B1 (en) * | 1997-01-28 | 2002-03-12 | Semiconductor Energy Laboratory Co., Ltd. | Removing a crystallization catalyst from a semiconductor film during semiconductor device fabrication |
US6162704A (en) * | 1997-02-12 | 2000-12-19 | Semiconductor Energy Laboratory Co., Ltd. | Method of making semiconductor device |
US6461943B1 (en) * | 1997-02-12 | 2002-10-08 | Semiconductor Energy Laboratory Co., Ltd. | Method of making semiconductor device |
US6420246B1 (en) * | 1997-02-17 | 2002-07-16 | Semiconductor Energy Laboratory Co., Ltd. | Method of gettering a metal element for accelerating crystallization of silicon by phosphorous |
US6448118B2 (en) * | 1997-02-26 | 2002-09-10 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor film manufacturing with selective introduction of crystallization promoting material |
US6197626B1 (en) * | 1997-02-26 | 2001-03-06 | Semiconductor Energy Laboratory Co. | Method for fabricating semiconductor device |
US6479333B1 (en) * | 1997-03-03 | 2002-11-12 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a semiconductor device |
US6303415B1 (en) * | 1997-06-10 | 2001-10-16 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and method of fabricating same |
US20020006712A1 (en) * | 1997-06-10 | 2002-01-17 | Shunpei Yamazaki | Semiconductor device and method of fabricating same |
US6544826B1 (en) * | 1997-06-17 | 2003-04-08 | Semiconductor Energy Laboratory Co., Ltd. | Method for producing semiconductor device |
US6242290B1 (en) * | 1997-07-14 | 2001-06-05 | Semiconductor Energy Laboratory Co., Ltd. | Method of forming a TFT by adding a metal to a silicon film promoting crystallization, forming a mask, forming another silicon layer with group XV elements, and gettering the metal through opening in the mask |
US6399454B1 (en) * | 1997-07-14 | 2002-06-04 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a semiconductor film and method of manufacturing a semiconductor device |
US6664144B2 (en) * | 1997-07-14 | 2003-12-16 | Semiconductor Energy Laboratory Co., Ltd. | Method of forming a semiconductor device using a group XV element for gettering by means of infrared light |
US6962837B2 (en) * | 1997-07-14 | 2005-11-08 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a semiconductor film and method of manufacturing a semiconductor device |
US6426276B1 (en) * | 1997-07-22 | 2002-07-30 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and method of manufacturing the same |
US6368904B1 (en) * | 1997-07-22 | 2002-04-09 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and method of manufacturing the same |
US6232205B1 (en) * | 1997-07-22 | 2001-05-15 | Semiconductor Energy Laboratory Co., Ltd. | Method for producing a semiconductor device |
US6066518A (en) * | 1997-07-22 | 2000-05-23 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing semiconductor devices using a crystallization promoting material |
US6156628A (en) * | 1997-07-22 | 2000-12-05 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and method of manufacturing the same |
US6432756B1 (en) * | 1997-07-24 | 2002-08-13 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and fabricating method thereof |
US6670225B2 (en) * | 1997-07-30 | 2003-12-30 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a semiconductor device |
US6348368B1 (en) * | 1997-10-21 | 2002-02-19 | Semiconductor Energy Laboratory Co., Ltd. | Introducing catalytic and gettering elements with a single mask when manufacturing a thin film semiconductor device |
US6821710B1 (en) * | 1998-02-11 | 2004-11-23 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing semiconductor device |
US6777273B1 (en) * | 1998-05-16 | 2004-08-17 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor display device |
US6300558B1 (en) * | 1999-04-27 | 2001-10-09 | Japan Energy Corporation | Lattice matched solar cell and method for manufacturing the same |
US6548370B1 (en) * | 1999-08-18 | 2003-04-15 | Semiconductor Energy Laboratory Co., Ltd. | Method of crystallizing a semiconductor layer by applying laser irradiation that vary in energy to its top and bottom surfaces |
US6436745B1 (en) * | 1999-11-02 | 2002-08-20 | Sharp Kabushiki Kaisha | Method of producing a semiconductor device |
US6858480B2 (en) * | 2001-01-18 | 2005-02-22 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing semiconductor device |
US6808968B2 (en) * | 2001-02-16 | 2004-10-26 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a semiconductor device |
US20020115271A1 (en) * | 2001-02-16 | 2002-08-22 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a semiconductor device |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090139558A1 (en) * | 2007-11-29 | 2009-06-04 | Shunpei Yamazaki | Photoelectric conversion device and manufacturing method thereof |
US20090165854A1 (en) * | 2007-12-28 | 2009-07-02 | Semiconductor Energy Laboratory Co., Ltd. | Photoelectric conversion device and manufacturing method thereof |
US8994009B2 (en) | 2011-09-07 | 2015-03-31 | Semiconductor Energy Laboratory Co., Ltd. | Photoelectric conversion device |
US10243092B2 (en) | 2013-02-01 | 2019-03-26 | First Solar, Inc. | Photovoltaic device including a p-n junction and method of manufacturing |
US11769844B2 (en) | 2013-02-01 | 2023-09-26 | First Solar, Inc. | Photovoltaic device including a p-n junction and method of manufacturing |
CN104051563A (en) * | 2013-03-14 | 2014-09-17 | 北京北方微电子基地设备工艺研究中心有限责任公司 | Preparation method of solar cell |
US11876140B2 (en) | 2013-05-02 | 2024-01-16 | First Solar, Inc. | Photovoltaic devices and method of making |
US10141463B2 (en) | 2013-05-21 | 2018-11-27 | First Solar Malaysia Sdn. Bhd. | Photovoltaic devices and methods for making the same |
US10784397B2 (en) | 2013-06-07 | 2020-09-22 | First Solar, Inc. | Photovoltaic devices and method of making |
US10141473B1 (en) | 2013-06-07 | 2018-11-27 | First Solar, Inc. | Photovoltaic devices and method of making |
US10062800B2 (en) | 2013-06-07 | 2018-08-28 | First Solar, Inc. | Photovoltaic devices and method of making |
US11164989B2 (en) | 2013-06-07 | 2021-11-02 | First Solar, Inc. | Photovoltaic devices and method of making |
US11588069B2 (en) | 2013-06-07 | 2023-02-21 | First Solar, Inc. | Photovoltaic devices and method of making |
US11784278B2 (en) | 2013-06-07 | 2023-10-10 | First Solar, Inc. | Photovoltaic devices and method of making |
US10461207B2 (en) * | 2014-11-03 | 2019-10-29 | First Solar, Inc. | Photovoltaic devices and method of manufacturing |
US10529883B2 (en) * | 2014-11-03 | 2020-01-07 | First Solar, Inc. | Photovoltaic devices and method of manufacturing |
US20160126396A1 (en) * | 2014-11-03 | 2016-05-05 | First Solar, Inc. | Photovoltaic devices and method of manufacturing |
US11817516B2 (en) | 2014-11-03 | 2023-11-14 | First Solar, Inc. | Photovoltaic devices and method of manufacturing |
US20160126395A1 (en) * | 2014-11-03 | 2016-05-05 | First Solar, Inc. | Photovoltaic devices and method of manufacturing |
Also Published As
Publication number | Publication date |
---|---|
US7075002B1 (en) | 2006-07-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5700333A (en) | Thin-film photoelectric conversion device and a method of manufacturing the same | |
US20060213550A1 (en) | Thin-film photoelectric conversion device and a method of manufacturing the same | |
US4468853A (en) | Method of manufacturing a solar cell | |
US7736960B2 (en) | Process for producing a photoelectric conversion device | |
US6459034B2 (en) | Multi-junction solar cell | |
JP3628108B2 (en) | Manufacturing method of solar cell | |
US20110073175A1 (en) | Photovoltaic cell comprising a thin lamina having emitter formed at light-facing and back surfaces | |
EP2051307A2 (en) | Method of fast hydrogen passivation to solar cells made of crystalline silicon | |
KR100224553B1 (en) | Solar cell and its manufacture | |
JP3578539B2 (en) | Solar cell manufacturing method and solar cell structure | |
JPS6184075A (en) | Photovoltaic solar cell | |
JP3394646B2 (en) | Thin film solar cell and method of manufacturing thin film solar cell | |
US20100224238A1 (en) | Photovoltaic cell comprising an mis-type tunnel diode | |
US8536448B2 (en) | Zener diode within a diode structure providing shunt protection | |
EP0007192A1 (en) | Process for preparing hetrojunction solar-cell devices | |
JPS59175170A (en) | Hetero junction solar battery and manufacture thereof | |
JP2002261305A (en) | Thin-film polycrystalline silicon solar cell and manufacturing method therefor | |
US20120258561A1 (en) | Low-Temperature Method for Forming Amorphous Semiconductor Layers | |
CN116435398A (en) | Solar cell with differentiated P-type and N-type region architecture | |
US10923618B2 (en) | Method for manufacturing a photovoltaic device | |
JP3983492B2 (en) | Method for producing crystalline silicon film | |
JP4159592B2 (en) | Solar cell | |
US5242504A (en) | Photovoltaic device and manufacturing method therefor | |
JP2000114558A (en) | Method of forming polycrystalline silicon film | |
JP3434256B2 (en) | Crystalline silicon film and method for manufacturing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: SEMICONDUCTOR ENERGY LABORATORY CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YAMAZAKI, SHUNPEI;ARAI, YASUYUKI;REEL/FRAME:033337/0312 Effective date: 19960319 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |