CN103531659B - A kind of method preparing vacuum volume to volume plated film flexible substrate and film - Google Patents
A kind of method preparing vacuum volume to volume plated film flexible substrate and film Download PDFInfo
- Publication number
- CN103531659B CN103531659B CN201310486546.8A CN201310486546A CN103531659B CN 103531659 B CN103531659 B CN 103531659B CN 201310486546 A CN201310486546 A CN 201310486546A CN 103531659 B CN103531659 B CN 103531659B
- Authority
- CN
- China
- Prior art keywords
- volume
- film
- vacuum
- base material
- torr
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 91
- 239000000758 substrate Substances 0.000 title claims abstract description 32
- 239000010408 film Substances 0.000 claims abstract description 118
- 239000000463 material Substances 0.000 claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 36
- 238000000576 coating method Methods 0.000 claims abstract description 36
- IUZNJVILEJRNNP-UHFFFAOYSA-N magnesium;oxozinc Chemical compound [Mg].[Zn]=O IUZNJVILEJRNNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010409 thin film Substances 0.000 claims abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 17
- 239000011888 foil Substances 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 239000004411 aluminium Substances 0.000 claims abstract description 13
- 238000004544 sputter deposition Methods 0.000 claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 120
- 239000007789 gas Substances 0.000 claims description 90
- 229910052786 argon Inorganic materials 0.000 claims description 60
- 238000005086 pumping Methods 0.000 claims description 30
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 28
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 28
- 238000007747 plating Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 229910000838 Al alloy Inorganic materials 0.000 claims description 17
- 239000013077 target material Substances 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 15
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 claims description 14
- 239000004744 fabric Substances 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002048 anodisation reaction Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000012467 final product Substances 0.000 claims description 10
- 239000005030 aluminium foil Substances 0.000 claims description 9
- 239000000470 constituent Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 9
- 239000000956 alloy Substances 0.000 abstract description 9
- 238000007654 immersion Methods 0.000 abstract description 8
- 230000008020 evaporation Effects 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000001771 vacuum deposition Methods 0.000 abstract 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 48
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229960001296 zinc oxide Drugs 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 210000001142 back Anatomy 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 229910000743 fusible alloy Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a kind of method preparing volume to volume vacuum coating flexible base plate and film, entire rolls of aluminum foil or alloy foil is used to be base material, first anode process is carried out for substrate surface before plated film, and add sodium element simultaneously, can enter in CIGS rete by diffusion process sodium element to improve the efficiency of battery during high temperature CIGS evaporation film-forming.Pioneering aluminium or the alloy foil of using is used as base material, resilient coating aspect also uses the zinc-magnesium oxygen rete of sputter to replace the CdS film of traditional immersion method, make CIGS solar cell can realize the production of entire volume, volume to volume sputtering machine is utilized to plate bottom electrode, resilient coating and transparent conductive film layer, volume to volume evaporator is utilized to prepare CIGS absorbed layer, the production realizing CIGS battery completes under the processing procedure of vacuum, guarantee large-area uniformity, significantly improve production efficiency and the productive rate of battery, improve film quality and performance, meet the Production requirement of CIGS thin film solar cell.
Description
Technical field
The present invention relates to the preparation method of a kind of vacuum volume to volume plated film flexible substrate and film, belong to photovoltaic field.
Background technology
Global energy requirements is climbed to a higher point year by year, and under energy-conservation and environmental consciousness come back, the development renewable energy resources are global common target; With the renewable energy resources, no matter waterpower, wind-force, geothermal power generation, all need obtain conversion efficiency with kinetic energy conversion regime, solar power generation is then the electricity generation system utilizing sunlight to convert electric energy to, without moving part in solar power system, rotary machine must be used unlike in the electricity generation systems such as wind-force, waterpower, underground heat, therefore not have the puzzlement such as HTHP and noise, in power generation process, do not cause environmental pressure, be a cleanly green energy resource.In addition, the characteristic that solar source is inexhaustible, makes solar power system can have the large advantage of one of continuous utilization; Although the photoelectric conversion efficiency of solar power generation is still not high now, it is its advantage that solar power system does not need to expend extra energy cost, and in other words, these are not had fraction as power source by the energy that people utilize originally now.The sun is irradiated to the energy on earth's surface every day, and exceed the energy required for the whole mankind 30 years, solar cell has become the main flow of following alternative energy source.Estimating to global energy in 2100 uses the utilance of solar energy to reach 60%.
The huge number of solar cell, and CIGS (Copper Indium Gallium Selenide) thin-film solar cells has high conversion efficiency and development potentiality and is attracted attention, the most high conversion efficiency of current CIGS (Copper Indium Gallium Selenide) thin-film solar cells created by U.S.'s Renewable Energy Laboratory (NREL), and its efficiency reaches 20%.CIGS is developed so far conversion efficiency from nineteen ninety-five and has improved and have 7% more than fully, within the same time CdTe 4%, monocrystalline silicon and polysilicon be respectively 1% of 3% and amorphous silicon, be enough to find out the development potentiality of CIGS in conversion efficiency.CIGS belongs to polycrystalline yellow copper structure (Chalcopyrite) compound of I-III-VI race, be a kind of by II-VI compounds of group zincblende lattce structure (Zinc-BlendStructure) the semi-conducting material that derives, formed by the unit cell storehouse of two zincblende, the lattice position belonging to II race's element originally is replaced by I race and III race and is formed, lattice position residing for the inner In of chalcopyrite then can be the Ga element that adds replace.CIGS (Copper Indium Gallium Selenide) has the P-type characteristic of semiconductor of direct gap (Directband-gap) character, and has quite high absorption coefficient of light α (α=10
4~ 10
5cm
-1), be 100 times of monocrystalline silicon, most solar spectrum can be contained, compared with other solar cell, therefore only need the thickness of 1 ~ 3 μm, be i.e. the incident sunlight of Absorbable rod more than 99%.The most high conversion efficiency of current CIGS thin film solar cell created by U.S.'s Renewable Energy Laboratory (NREL), and its efficiency reaches 20%.And NREL shows in assessment report in 2011, CIGS (Copper Indium Gallium Selenide) up can grow up with annual 0.3% in conversion efficiency.
CIGS (Copper Indium Gallium Selenide) thin-film solar cells be developed so far its modular construction roughly part be made up of top electrode (AL/Ni), anti-reflecting layer (MgF2), optical window layer (AZO/ITO), resilient coating (CdS), absorbed layer (CIGS), back electrode (Mo) and substrate (SS/GLASS/PET), in single rete, the parameter allotment of each material composition ratio, film crystal structure, processing procedure mode and various factorss such as optimizing processing procedure are the challenge on it is prepared, in addition, also need to consider that each rete is stacked into the matching of assembly, the many factors such as to influence each other between each Film preparation mode and processing procedure, especially CIGS (Copper Indium Gallium Selenide) is shown for extremely responsive for component influences various process parameter from pertinent literature, more increase the difficulty of CIGS (Copper Indium Gallium Selenide) thin-film solar cells in preparation, also make technology door relatively improve simultaneously, a kind of solar cell that technical difficulty is larger is thought at international photovoltaic circle.
Target has the mother metal of solid shape for sputter coating.If target can be divided into metal and pottery two large classes simply according to materials classification, if melting processing procedure and the large class of powder metallurgy processing procedure two usually generally can be divided into according to processing procedure classification.Most metals target adopts melting processing procedure, and minority target just adopts powder metallurgy processing procedure in view of the factors such as grain size controls, alloy composition fusing point gap is too large during use.Generally adopt vacuum induction melting to allocate composition for metal or alloy target material, and obtain required target through machining mode such as the forging of back segment and heat treatments.As touch screen, integrated circuit, liquid crystal display screen, building glass, blooming and thin-film solar cells etc. in current photoelectricity and semiconductor industry, be obtain large-area uniformity and production, associated film uses vacuum magnetic control sputter process all in a large number.
Multi-element compounds solar cell is at present by belonging to one of object material, be that the solar battery obsorbing layer formed with I race of race of race-III-IV can the regulation and control of its composition carry out being change and reaching best photoelectric conversion efficiency, wherein, I race is copper (Cu), silver (Ag), gold (Au), III race is aluminium (Al), gallium (Ga), indium (In), IV race is sulphur (S), selenium (Se), antimony (Te), the highest with copper indium gallium selenium solar cell photoelectric conversion efficiency at present.
In CIGS rete, absorbed layer is the important rete affecting battery efficiency and the mode of production, and absorbed layer generally uses vacuum evaporation and vacuum magnetic control sputter to add the heat treated two kinds of main processing procedures of rear selenizing, has the characteristic of large area film forming and the better uniformity of acquisition.Typical case's CIGS solar cell is Mo (molybdenum dorsum electrode layer)/CIGS (CuInGaSe absorbed layer)/CdS (cadmium sulfide resilient coating)/ZnO+AZO (zinc oxide with mix aluminum zinc oxide optical window layer)/Al (aluminium upper electrode layer) according to base material from lower to upper, general dorsum electrode layer, optical window layer adopt vacuum splashing and plating mode, resilient coating adopts chemical waters mode, compared in each rete of modular construction, absorbed layer preparation method is divided into two large classes: 1. vacuum process, comprises common evaporation and sputter precursors and selenizing processing procedure; 2. antivacuum processing procedure, comprises plating and coating etc.; Wherein use that to prepare resilient coating main cause absorbed layer surface made by the current stage in chemical bath mode very thick, need reach complete batch of resilient coating by immersion method is overlying on absorbed layer, but, in whole production CIGS solar cell process, immersion method processing procedure mode is used to have several restriction: 1. do not add for continuous production; 2. large-area uniformity is wayward; 3. need in immersion method manufacturing process to consume large water gaging; 4. immersion method uses chemical solvent subsequent treatment cost high.If the surface planarisation of absorbed layer just can not be able to be adopted waters method to do resilient coating, avoid the discontinuity of producing to enhance productivity and yield, and reduce production cost.
Absorbed layer film is prepared for a large amount of and large area, current processing procedure mode system adopts sputter precursors and rear selenizing processing procedure, wherein, early stage precursors metallic film is designed to single-element or double base alloying metal adopts multiple gun sputter, processing procedure passage is many, time is grown and has the factors such as low-melting alloy processing procedure unsteadiness, but because precursor layer is containing the phosphide element of low melting point, traditional filming parameter is used the predecessor roughness of film made to be become large (>300nm), CIGS surface in the future after high temperature selenizing cannot reach desirable planarization, be unfavorable for the preparation of follow-up resilient coating and optical window layer, and required formation absorbed layer phase change temperature reduces, cause follow-up selenizing cannot continue to diffuse in precursors film and react, make selenizing not exclusively and conversion efficiency cannot effectively promote, improve manufacturing cost because of above-mentioned reason and reduce process rate and productive rate.And CIGS solar cell is mostly adopt one chip to produce before the present invention, volume production rate is low, and required is manually more, and relative production cost also cannot decline to a great extent.Some people adopts the mode of volume to volume evaporation film-forming on PI to make CIGS battery in addition, light-weighted demand can be reached, but because process temperatures cannot be drawn high (<300 DEG C), effectively homogeneous CIGS phase cannot be formed, so battery efficiency rests on 5-10% always, the method that there is no breaks through.
Summary of the invention
The object of this invention is to provide a kind of method preparing vacuum volume to volume plated film flexible base plate and film, entire rolls of aluminum foil or alloy foil is used to be base material, first anode process is carried out for substrate surface before plated film, and be added into the sodium element of inequality simultaneously, can enter in CIGS rete by diffusion process sodium element to improve the efficiency of battery during high temperature CIGS evaporation film-forming.Base material is used as by the pioneering aluminum or aluminum alloy paper tinsel that uses of the present invention, and do not use the CdS resilient coating of immersion method, the zinc-magnesium oxygen of vacuum splashing and plating is used to be used as resilient coating, make CIGS solar cell can realize the production of entire volume vacuum process, volume to volume sputtering machine is utilized to plate molybdenum, zinc oxide and nesa coating (ITO), volume to volume evaporator is utilized to prepare CIGS absorbed layer, significantly improve production efficiency and the productive rate of battery, significantly reduce manpower man-hour, improve film quality and performance, meet the Production requirement of CIGS thin film solar cell.
A kind of method preparing vacuum volume to volume plated film flexible substrate and film, the entire rolls of aluminum foil or the aluminium alloy that use fabric width 15-150cm are base material, the thickness of aluminium foil or aluminium alloy is less than 1.0mm, first anodization is carried out for substrate surface before plated film, anodized technological parameter is: anode is aluminium, negative electrode is plumbous, electrolyte constituent is: the concentrated sulfuric acid and sodium thiosulfate, wherein the volume ratio of the concentrated sulfuric acid and sodium thiosulfate is 2:7-9, sodium thiosulfate is 1-5mol/L, and current density is 1.5-2.0A/dm
2, the reaction time is 30-50min, reaction temperature: 15-25 DEG C, makes the quality of the sodium element added in base material account for the 0.1-10% of base material gross mass; Then base material is inserted in volume to volume vacuum splashing and plating machine cavity, then with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.7 × 10
-5-0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, uses the DC power supply Mo film that sputter ground floor 500nm is thick on base material; And then using the common evaporator of volume to volume to manufacture the thick CIGS absorbed layer film of second layer 2000nm, during common evaporating coating, base material heating is to 300-550 DEG C; Then with vacuum splashing and plating legal system for third layer zinc-magnesium oxygen film, use zinc-magnesium oxygen target to be placed on sputtering machine, with vacuum-pumping system, sputter cavity background pressure be evacuated to 0.7 × 10
-5-0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2.5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, the zinc-magnesium oxygen film of obtained thickness 100nm; Finally be coated with the 4th layer of nesa coating, use tin indium oxide target material to put into vacuum cavity, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.7 × 10
-5-0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, and the transparent conductive oxide indium tin thin film of obtained thickness 100nm, to obtain final product.
After wherein first the manufacture of zinc-magnesium oxygen target uses 61% zinc oxide+6% magnesium oxide powder+25% deionized water wet-mixed, pour in three inches of moulds after grinding 8 hours with zirconia ball, target material blank body is formed through 1450 DEG C of 6 hours sintering, the zinc-magnesium oxygen target needed for becoming through attrition process Deng after drying.
After wherein first the manufacture of indium tin target uses 70% indium oxide powder and the mixing of 5% stannic oxide powder to add the deionized water wet-mixed of 25%, 20 hours are ground with zirconia ball, then pour in three inches of moulds, after to be dried through 1550 DEG C 6 hours sintering and after attrition process become needed for tin indium oxide target material.
Wherein volume to volume vacuum splashing and plating machine is that Taiwan Qin You company manufactures, and volume to volume altogether evaporator extensively continues science and technology manufacture in Taiwan.
Anodization is a kind of metal surface treatment process, and this patent utilizes aluminium foil or alloy foil in electrolyte solution, makes its surface form a kind of material protection adsorption technology of oxide-film by executing anode current outward.Anodic oxidation is generally carried out in acidic electrolysis bath, and in electrolytic process, anion and the aluminum or aluminum alloy effect of oxygen produce oxide-film.Because simultaneously in the process forming oxide-film due to the effect of electric current, this layer of close film is punctured by electric current and defines hole, containing sodium ion material (sodium thiosulfate Na in electrolyte
2s
2o
3.5H
2o) will adsorb by space, thus reach the interpolation of sodium element.
Feature of the present invention is using entire rolls of aluminum foil or alloy foil to be base material, first anode process is carried out for substrate surface before plated film, and be added into sodium (Na) element of inequality simultaneously, in the future again high temperature CIGS evaporation film-forming time can enter in CIGS rete by diffusion process sodium element to improve the efficiency of battery.Pioneering aluminium or the alloy foil of using of the present invention is used as base material, resilient coating aspect also uses the zinc-magnesium oxygen rete (ZnMgO) of sputter to replace the CdS film of traditional immersion method, begin CIGS solar cell can realize the production of entire volume, volume to volume sputtering machine is utilized to plate bottom electrode (Mo), resilient coating (ZnMgO) and nesa coating (ITO) layer, volume to volume evaporator is utilized to prepare CIGS absorbed layer, the production realizing CIGS battery completes under the processing procedure of vacuum, guarantee large-area uniformity, mean sheet surface roughness is made to be less than 150nm, significantly improve production efficiency and the productive rate of battery, significantly reduce manpower man-hour, improve film quality and performance, meet the Production requirement of CIGS thin film solar cell.
embodiment:
Embodiment 1:
A kind of method preparing vacuum volume to volume plated film flexible substrate and film, the entire rolls of aluminum foil using fabric width 15cm is base material, the thickness 0.25mm of aluminium foil, first carry out anodization for substrate surface before plated film, anodized technological parameter is: anode is aluminium, and negative electrode is plumbous, electrolyte constituent is: the concentrated sulfuric acid and sodium thiosulfate, wherein the volume ratio of the concentrated sulfuric acid and sodium thiosulfate is 2:7, and sodium thiosulfate is 1mol/L, and current density is 1.5A/dm
2, the reaction time is 30min, reaction temperature: 15 DEG C, makes the quality of the sodium element added in base material account for 0.1% of base material gross mass; Then base material is inserted in volume to volume vacuum splashing and plating machine cavity, then with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.7 × 10
-5after torr, utilizing argon gas to be used as working gas, is 5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, uses the DC power supply Mo film that sputter ground floor 500nm is thick on base material; And then use the volume to volume CIGS absorbed layer film that evaporator manufacture second layer 2000nm is thick altogether, base material heating to 300 DEG C during evaporating coating altogether; Then with vacuum splashing and plating legal system for third layer zinc-magnesium oxygen film, use zinc-magnesium oxygen target to be placed on sputtering machine, with vacuum-pumping system, sputter cavity background pressure be evacuated to 0.7 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2.5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, the zinc-magnesium oxygen film of obtained thickness 100nm; Finally be coated with the 4th layer of nesa coating, use tin indium oxide target material to put into vacuum cavity, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.7 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, and the transparent conductive oxide indium tin thin film of obtained thickness 100nm, to obtain final product.
After wherein first the manufacture of zinc-magnesium oxygen target uses 61% zinc oxide+6% magnesium oxide powder+25% deionized water wet-mixed, pour in three inches of moulds after grinding 8 hours with zirconia ball, target material blank body is formed through 1450 DEG C of 6 hours sintering, the zinc-magnesium oxygen target needed for becoming through attrition process Deng after drying.
After wherein first the manufacture of indium tin target uses 70% indium oxide powder and the mixing of 5% stannic oxide powder to add the deionized water wet-mixed of 25%, 20 hours are ground with zirconia ball, then pour in three inches of moulds, after to be dried through 1550 DEG C 6 hours sintering and after attrition process become needed for tin indium oxide target material.
Wherein volume to volume vacuum splashing and plating machine is that Taiwan Qin You company manufactures, and volume to volume altogether evaporator extensively continues science and technology manufacture in Taiwan.
Embodiment 2:
A kind of method preparing vacuum volume to volume plated film flexible substrate and film, the entire rolls of aluminum foil using fabric width 80cm is base material, the thickness 0.5mm of aluminium foil, first carry out anodization for substrate surface before plated film, anodized technological parameter is: anode is aluminium, and negative electrode is plumbous, electrolyte constituent is: the concentrated sulfuric acid and sodium thiosulfate, wherein the volume ratio of the concentrated sulfuric acid and sodium thiosulfate is 2:8, and sodium thiosulfate is 3mol/L, and current density is 1.8A/dm
2, the reaction time is 40min, reaction temperature: 20 DEG C, makes the quality of the sodium element added in base material account for 5.0% of base material gross mass; Then base material is inserted in volume to volume vacuum splashing and plating machine cavity, then with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, uses the DC power supply Mo film that sputter ground floor 500nm is thick on base material; And then use the volume to volume CIGS absorbed layer film that evaporator manufacture second layer 2000nm is thick altogether, base material heating to 400 DEG C during evaporating coating altogether; Then with vacuum splashing and plating legal system for third layer zinc-magnesium oxygen film, use zinc-magnesium oxygen target to be placed on sputtering machine, with vacuum-pumping system, sputter cavity background pressure be evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2.5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, the zinc-magnesium oxygen film of obtained thickness 100nm; Finally be coated with the 4th layer of nesa coating, use tin indium oxide target material to put into vacuum cavity, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, and the transparent conductive oxide indium tin thin film of obtained thickness 100nm, to obtain final product.
All the other are with embodiment 1.
Embodiment 3:
A kind of method preparing vacuum volume to volume plated film flexible substrate and film, the entire rolls of aluminum foil using fabric width 150cm is base material, the thickness 0.9mm of aluminium foil or aluminium alloy, first carry out anodization for substrate surface before plated film, anodized technological parameter is: anode is aluminium, and negative electrode is plumbous, electrolyte constituent is: the concentrated sulfuric acid and sodium thiosulfate, wherein the volume ratio of the concentrated sulfuric acid and sodium thiosulfate is 2:9, and sodium thiosulfate is 5mol/L, and current density is 2.0A/dm
2, the reaction time is 50min, reaction temperature: 25 DEG C, makes the quality of the sodium element added in base material account for 10% of base material gross mass; Then base material is inserted in volume to volume vacuum splashing and plating machine cavity, then with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, uses the DC power supply Mo film that sputter ground floor 500nm is thick on base material; And then use the volume to volume CIGS absorbed layer film that evaporator manufacture second layer 2000nm is thick altogether, base material heating to 550 DEG C during evaporating coating altogether; Then with vacuum splashing and plating legal system for third layer zinc-magnesium oxygen film, use zinc-magnesium oxygen target to be placed on sputtering machine, with vacuum-pumping system, sputter cavity background pressure be evacuated to 0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2.5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, the zinc-magnesium oxygen film of obtained thickness 100nm; Finally be coated with the 4th layer of nesa coating, use tin indium oxide target material to put into vacuum cavity, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, and the transparent conductive oxide indium tin thin film of obtained thickness 100nm, to obtain final product.
All the other are with embodiment 1.
Embodiment 4:
A kind of method preparing vacuum volume to volume plated film flexible substrate and film, the entire rolls of aluminum foil using fabric width 100cm is base material, the thickness 0.7mm of aluminium foil, first carry out anodization for substrate surface before plated film, anodized technological parameter is: anode is aluminium, and negative electrode is plumbous, electrolyte constituent is: the concentrated sulfuric acid and sodium thiosulfate, wherein the volume ratio of the concentrated sulfuric acid and sodium thiosulfate is 2:6, and sodium thiosulfate is 8mol/L, and current density is 1.2A/dm
2, the reaction time is 25min, reaction temperature: 30 DEG C, makes the quality of the sodium element added in base material account for 3.0% of base material gross mass; Then base material is inserted in volume to volume vacuum splashing and plating machine cavity, then with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.7 × 10
-5after torr, utilizing argon gas to be used as working gas, is 5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, uses the DC power supply Mo film that sputter ground floor 500nm is thick on base material; And then use the volume to volume CIGS absorbed layer film that evaporator manufacture second layer 2000nm is thick altogether, base material heating to 500 DEG C during evaporating coating altogether; Then with vacuum splashing and plating legal system for third layer zinc-magnesium oxygen film, use zinc-magnesium oxygen target to be placed on sputtering machine, with vacuum-pumping system, sputter cavity background pressure be evacuated to 0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2.5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, the zinc-magnesium oxygen film of obtained thickness 100nm; Finally be coated with the 4th layer of nesa coating, use tin indium oxide target material to put into vacuum cavity, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.7 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, and the transparent conductive oxide indium tin thin film of obtained thickness 100nm, to obtain final product.
All the other are with embodiment 1.
Embodiment 5:
Prepare a method for vacuum volume to volume plated film flexible substrate and film, the entire volume aluminium alloy using fabric width 15cm is base material, and the thickness 0.25mm of aluminium alloy, all the other are with embodiment 1.
Embodiment 6:
Prepare a method for vacuum volume to volume plated film flexible substrate and film, the entire volume aluminium alloy using fabric width 80cm is base material, and the thickness 0.5mm of aluminium alloy, all the other are with embodiment 2.
Embodiment 7:
Prepare a method for vacuum volume to volume plated film flexible substrate and film, the entire volume aluminium alloy using fabric width 150cm is base material, and the thickness 0.9mm of aluminium alloy, all the other are with embodiment 3.
Embodiment 8:
A kind of method preparing vacuum volume to volume plated film flexible substrate and film, the entire volume aluminium alloy using fabric width 90cm is base material, the thickness 0.4mm of aluminium alloy, first carry out anodization for substrate surface before plated film, anodized technological parameter is: anode is aluminium, and negative electrode is plumbous, electrolyte constituent is: the concentrated sulfuric acid and sodium thiosulfate, wherein the volume ratio of the concentrated sulfuric acid and sodium thiosulfate is 2:10, and sodium thiosulfate is 0.5mol/L, and current density is 2.5A/dm
2, the reaction time is 60min, reaction temperature: 13 DEG C, makes the quality of the sodium element added in base material account for 7.0% of base material gross mass; Then base material is inserted in volume to volume vacuum splashing and plating machine cavity, then with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, uses the DC power supply Mo film that sputter ground floor 500nm is thick on base material; And then use the volume to volume CIGS absorbed layer film that evaporator manufacture second layer 2000nm is thick altogether, base material heating to 350 DEG C during evaporating coating altogether; Then with vacuum splashing and plating legal system for third layer zinc-magnesium oxygen film, use zinc-magnesium oxygen target to be placed on sputtering machine, with vacuum-pumping system, sputter cavity background pressure be evacuated to 0.7 × 10
-5after, utilizing argon gas to be used as working gas, is 2.5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, the zinc-magnesium oxygen film of obtained thickness 100nm; Finally be coated with the 4th layer of nesa coating, use tin indium oxide target material to put into vacuum cavity, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, and the transparent conductive oxide indium tin thin film of obtained thickness 100nm, to obtain final product.
Comparative example 1:
Prior art prepares the method for vacuum volume to volume plated film flexible substrate and film, the entire volume PI using fabric width 30 centimeters is material, the thickness 0.3mm of PI paper tinsel, then first with volume to volume vacuum splashing and plating machine sputter molybdenum (Mo) film, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, uses the Mo film that DC power supply sputter ground floor 500nm is thick.Then the volume to volume CIGS absorbed layer film that evaporation manufacture second layer 2000nm is thick is altogether used, base plate heating to 150 DEG C during evaporating coating altogether.Then prepare CdS film (30nm) and vacuum splashing and plating legal system for zinc oxide (ZnO) buffer layer thin film 100nm with immersion method, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2.5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, the zinc-oxide film of obtained film thickness about 100nm.Finally be coated with nesa coating (TCO), with vacuum-pumping system, sputter cavity background pressure be evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, and transparent conductive oxide indium tin (ITO) film of obtained film thickness about 100nm, to obtain final product.
The performance of the soft CIGS solar cell that each embodiment and comparative example obtain is as shown in the table:
| Group | Conversion efficiency (%) | Film roughness (nm) |
| Embodiment 1 | 13.3 | 131 |
| Embodiment 2 | 14.8 | 110 |
| Embodiment 3 | 13.5 | 122 |
| Embodiment 4 | 10.2 | 186 |
| Embodiment 5 | 13.9 | 127 |
| Embodiment 6 | 14.5 | 112 |
| Embodiment 7 | 13.2 | 130 |
| Embodiment 8 | 10.7 | 195 |
| Comparative example 1 | 8 | 450 |
As can be seen from upper table result, embodiment 1-3 within the scope of present invention process and embodiment 5-7, the conversion efficiency of follow-up obtained soft CIGS solar cell and Film roughness are obviously better than the embodiment 4 adopting the extraneous surface anode process of present invention process, embodiment 8 and prior art prepare the comparative example 1 of vacuum volume to volume plated film flexible substrate and film, especially with the best results of embodiment 2 and embodiment 6, the aluminium foil that visible the present invention adopts or alloy foil, by the vacuum volume to volume plated film flexible base plate prepared by surface anode process and interpolation sodium element and film, reduce production cost, improve film quality and performance, meet the Production requirement of CIGS thin film solar cell.
Claims (5)
1. prepare the method for vacuum volume to volume plated film flexible substrate and film for one kind, it is characterized by: use the entire rolls of aluminum foil of fabric width 15-150cm or aluminium alloy to be base material, the thickness of aluminium foil or aluminium alloy is less than 1.0mm, first anodization is carried out for substrate surface before plated film, anodized technological parameter is: anode is aluminium, negative electrode is plumbous, electrolyte constituent is: the concentrated sulfuric acid and sodium thiosulfate, wherein the volume ratio of the concentrated sulfuric acid and sodium thiosulfate is 2:7-9, sodium thiosulfate is 1-5mol/L, and current density is 1.5-2.0A/dm
2, the reaction time is 30-50min, reaction temperature: 15-25 DEG C, makes the quality of the sodium element added in base material account for the 0.1-10% of base material gross mass; Then base material is inserted in volume to volume vacuum splashing and plating machine cavity, then with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.7 × 10
-5-0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, uses the DC power supply Mo film that sputter ground floor 500nm is thick on base material; And then using the common evaporator of volume to volume to manufacture the thick CIGS absorbed layer film of second layer 2000nm, during common evaporating coating, base material heating is to 300-550 DEG C; Then with vacuum splashing and plating legal system for third layer zinc-magnesium oxygen film, use zinc-magnesium oxygen target to be placed on sputtering machine, with vacuum-pumping system, sputter cavity background pressure be evacuated to 0.7 × 10
-5-0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2.5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, the zinc-magnesium oxygen film of obtained thickness 100nm; Finally be coated with the 4th layer of nesa coating, use tin indium oxide target material to put into vacuum cavity, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.7 × 10
-5-0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, and the transparent conductive oxide indium tin thin film of obtained thickness 100nm, to obtain final product.
2. prepare the method for vacuum volume to volume plated film flexible substrate and film for one kind, it is characterized by: the entire rolls of aluminum foil using fabric width 80cm is base material, the thickness 0.5mm of aluminium foil, first carry out anodization for substrate surface before plated film, anodized technological parameter is: anode is aluminium, and negative electrode is plumbous, electrolyte constituent is: the concentrated sulfuric acid and sodium thiosulfate, wherein the volume ratio of the concentrated sulfuric acid and sodium thiosulfate is 2:8, and sodium thiosulfate is 3mol/L, and current density is 1.8A/dm
2, the reaction time is 40min, reaction temperature: 20 DEG C, makes the quality of the sodium element added in base material account for 5.0% of base material gross mass; Then base material is inserted in volume to volume vacuum splashing and plating machine cavity, then with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, uses the DC power supply Mo film that sputter ground floor 500nm is thick on base material; And then use the volume to volume CIGS absorbed layer film that evaporator manufacture second layer 2000nm is thick altogether, base material heating to 400 DEG C during evaporating coating altogether; Then with vacuum splashing and plating legal system for third layer zinc-magnesium oxygen film, use zinc-magnesium oxygen target to be placed on sputtering machine, with vacuum-pumping system, sputter cavity background pressure be evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2.5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, the zinc-magnesium oxygen film of obtained thickness 100nm; Finally be coated with the 4th layer of nesa coating, use tin indium oxide target material to put into vacuum cavity, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, and the transparent conductive oxide indium tin thin film of obtained thickness 100nm, to obtain final product.
3. prepare the method for vacuum volume to volume plated film flexible substrate and film for one kind, it is characterized by: the entire volume aluminium alloy using fabric width 80cm is base material, the thickness 0.5mm of aluminium alloy, first carry out anodization for substrate surface before plated film, anodized technological parameter is: anode is aluminium, and negative electrode is plumbous, electrolyte constituent is: the concentrated sulfuric acid and sodium thiosulfate, wherein the volume ratio of the concentrated sulfuric acid and sodium thiosulfate is 2:8, and sodium thiosulfate is 3mol/L, and current density is 1.8A/dm
2, the reaction time is 40min, reaction temperature: 20 DEG C, makes the quality of the sodium element added in base material account for 5.0% of base material gross mass; Then base material is inserted in volume to volume vacuum splashing and plating machine cavity, then with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, uses the DC power supply Mo film that sputter ground floor 500nm is thick on base material; And then use the volume to volume CIGS absorbed layer film that evaporator manufacture second layer 2000nm is thick altogether, base material heating to 400 DEG C during evaporating coating altogether; Then with vacuum splashing and plating legal system for third layer zinc-magnesium oxygen film, use zinc-magnesium oxygen target to be placed on sputtering machine, with vacuum-pumping system, sputter cavity background pressure be evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2.5 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, the zinc-magnesium oxygen film of obtained thickness 100nm; Finally be coated with the 4th layer of nesa coating, use tin indium oxide target material to put into vacuum cavity, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through choke valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, carries out sputter process with RF power supply, and the transparent conductive oxide indium tin thin film of obtained thickness 100nm, to obtain final product.
4. a kind of method preparing vacuum volume to volume plated film flexible substrate and film as described in claim 1 or 2 or 3, it is characterized by: after first the manufacture of zinc-magnesium oxygen target uses 61% zinc oxide+6% magnesium oxide powder+25% deionized water wet-mixed, pour in three inches of moulds after grinding 8 hours with zirconia ball, target material blank body is formed through 1450 DEG C of 6 hours sintering, the zinc-magnesium oxygen target needed for becoming through attrition process Deng after drying.
5. a kind of method preparing vacuum volume to volume plated film flexible substrate and film as described in claim 1 or 2 or 3, it is characterized by: after first the manufacture of indium tin target uses 70% indium oxide powder and the mixing of 5% stannic oxide powder to add the deionized water wet-mixed of 25%, 20 hours are ground with zirconia ball, then pour in three inches of moulds, after to be dried through 1550 DEG C 6 hours sintering and after attrition process become needed for tin indium oxide target material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310486546.8A CN103531659B (en) | 2013-10-17 | 2013-10-17 | A kind of method preparing vacuum volume to volume plated film flexible substrate and film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310486546.8A CN103531659B (en) | 2013-10-17 | 2013-10-17 | A kind of method preparing vacuum volume to volume plated film flexible substrate and film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103531659A CN103531659A (en) | 2014-01-22 |
| CN103531659B true CN103531659B (en) | 2016-01-13 |
Family
ID=49933512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310486546.8A Active CN103531659B (en) | 2013-10-17 | 2013-10-17 | A kind of method preparing vacuum volume to volume plated film flexible substrate and film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103531659B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104404459B (en) * | 2014-11-10 | 2017-11-07 | 研创应用材料（赣州）股份有限公司 | A kind of preparation method of target material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101764181A (en) * | 2009-12-03 | 2010-06-30 | 郭玉钦 | Method for preparing copper-indium-gallium-selenium (CIGS) flexible solar cell by using combination process of magnetic control sputtering method and co-evaporation method |
| CN101771105A (en) * | 2009-12-01 | 2010-07-07 | 郭玉钦 | Method for preparing CIGS thin film solar cell in continuous production line |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120231574A1 (en) * | 2011-03-12 | 2012-09-13 | Jiaxiong Wang | Continuous Electroplating Apparatus with Assembled Modular Sections for Fabrications of Thin Film Solar Cells |
-
2013
- 2013-10-17 CN CN201310486546.8A patent/CN103531659B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101771105A (en) * | 2009-12-01 | 2010-07-07 | 郭玉钦 | Method for preparing CIGS thin film solar cell in continuous production line |
| CN101764181A (en) * | 2009-12-03 | 2010-06-30 | 郭玉钦 | Method for preparing copper-indium-gallium-selenium (CIGS) flexible solar cell by using combination process of magnetic control sputtering method and co-evaporation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103531659A (en) | 2014-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107871795B (en) | A kind of regulation method of the band gap gradient of the cadmium doping copper zinc tin sulfur selenium film based on flexible molybdenum substrate | |
| Wang et al. | Enhanced photoelectrochemical hydrogen generation in neutral electrolyte using non-vacuum processed CIGS photocathodes with an earth-abundant cobalt sulfide catalyst | |
| CN102054897B (en) | Method for preparing thin film solar cell from multi-element alloy single target material | |
| CN105826425B (en) | A kind of preparation method of copper-zinc-tin-sulfur film solar cell | |
| CN102652368B (en) | Cu-In-Zn-Sn-(Se,S)-based thin film for solar cell and preparation method thereof | |
| CN106653898B (en) | A kind of CZTS solar battery | |
| CN101127371A (en) | A nano structure thin film solar battery and its making method | |
| CN104143579A (en) | Antimony-base compound thin film solar cell and manufacturing method thereof | |
| CN103060861A (en) | Method for preparing copper-zinc-tin-sulfur film through co-electrodeposition | |
| EP2695200B1 (en) | Solar cell | |
| CN104404459B (en) | A kind of preparation method of target material | |
| Mandati et al. | Copper chalcopyrites for solar energy applications | |
| CN102694077B (en) | Preparation method of CIGS (copper indium gallium diselenide) thin-film solar cell | |
| CN103572229B (en) | Preparation method of flexible base material and thin film for vacuum reel-to-reel coating | |
| CN102637777A (en) | Chemical preparation technology for solar cell light absorption layer Cu2O nano film | |
| CN109638096A (en) | A kind of compound semiconductor thin film solar cell preparation method | |
| CN104241439A (en) | Method for preparing cadmium telluride thin-film solar cell | |
| CN101882653B (en) | Preparation method of solar battery based on nano CdS (Cadmium Sulfide) film | |
| CN103531659B (en) | A kind of method preparing vacuum volume to volume plated film flexible substrate and film | |
| CN102856398A (en) | Cu2ZnSnSe4 solar cell and method for manufacturing same | |
| CN109671803A (en) | A kind of thin-film solar cells preparation method | |
| CN102024858B (en) | Ink, thin film solar cell and manufacturing methods thereof | |
| CN103305793B (en) | A kind of method preparing buffer layer oxides target and sull thereof | |
| CN103194726A (en) | Preparation process of cuprum-indium-gallium-selenium film | |
| CN103400899B (en) | A kind of method preparing porousness precursor layer and absorbed layer thin film planarization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 341000 standard factory building, North Zone, Hongkong Industrial Park, Ganzhou Development Zone, Jiangxi, six Applicant after: (Ganzhou) Limited by Share Ltd Address before: 341000 standard factory building, North Zone, Hongkong Industrial Park, Ganzhou Development Zone, Jiangxi, six Applicant before: Applied materials (Ganzhou) Co., Ltd. |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200521 Address after: 341000 building 6, standard workshop, north area, Hong Kong Industrial Park, 168 Xiangjiang Avenue, Ganzhou economic and Technological Development Zone, Ganzhou City, Jiangxi Province Patentee after: Ganzhou Chuangfa Photoelectric Technology Co., Ltd Address before: 341000 standard factory building, North Zone, Hongkong Industrial Park, Ganzhou Development Zone, Jiangxi, six Patentee before: YANCHUANG APPLIED MATERIALS (GANZHOU) INC., Ltd. |
|
| TR01 | Transfer of patent right |