CN104835869B - Copper-indium-galliun-selenium film solar cell and preparation method thereof - Google Patents
Copper-indium-galliun-selenium film solar cell and preparation method thereof Download PDFInfo
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- CN104835869B CN104835869B CN201510241668.XA CN201510241668A CN104835869B CN 104835869 B CN104835869 B CN 104835869B CN 201510241668 A CN201510241668 A CN 201510241668A CN 104835869 B CN104835869 B CN 104835869B
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- indium
- galliun
- solar cell
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- 239000011669 selenium Substances 0.000 title claims abstract description 138
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 210000001142 back Anatomy 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 47
- 238000005245 sintering Methods 0.000 claims description 45
- 238000005477 sputtering target Methods 0.000 claims description 39
- 238000000137 annealing Methods 0.000 claims description 38
- 238000004544 sputter deposition Methods 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 33
- 238000000498 ball milling Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 230000007423 decrease Effects 0.000 claims 1
- 239000010408 film Substances 0.000 description 58
- 239000010409 thin film Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 230000005611 electricity Effects 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 239000005083 Zinc sulfide Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- 229910000928 Yellow copper Inorganic materials 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000007096 poisonous effect Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 3
- 229910000058 selane Inorganic materials 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000010307 cell transformation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- BDVZHDCXCXJPSO-UHFFFAOYSA-N indium(3+) oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].[In+3] BDVZHDCXCXJPSO-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 238000000053 physical method Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a kind of copper-indium-galliun-selenium film solar cell, including substrate, dorsum electrode layer, the light absorbing layer being arranged on the dorsum electrode layer, the cushion being arranged on the light absorbing layer and the Window layer being arranged on the cushion of setting on this substrate, it is characterized in that, the light absorbing layer includes copper (Cu), phosphide element (In), gallium element (Ga) and selenium element (Se), and the light absorbing layer is Cuy(In1‑xGax)Se2Situ adulterates Se elements, and the mol ratio between element is 1.0<Se:(Cu+In+Ga)≤1.5.The invention further relates to a kind of preparation method of copper-indium-galliun-selenium film solar cell.
Description
Technical field
The present invention relates to field of photoelectric technology, more particularly to copper-indium-galliun-selenium film solar cell and preparation method thereof.
Background technology
CIS（CuInSe2, abbreviation CIS）Representative of the series film solar battery as third generation solar cell, tool
There are electricity conversion height, stable performance, radiation resistance good and prepare the advantages such as cost is low.CIS energy gap is 1.04
EV, copper gallium selenium（CuGaSe2, abbreviation CGS）Energy gap be 1.68 eV.A certain amount of Ga is set to substitute In in CIS, can be with
Form CIGS（Cu(In1-xGax)Se2）Quaternary semiconductor material, it can be adjusted by the content for adjusting Ga in CIGS
The energy gap of battery, further improve the electricity conversion of thin-film solar cells.Copper-indium-galliun-selenium film solar cell
Typical structure be：Antireflection layer/transparent electrode layer/Window layer/transition zone/light absorbing layer（CIGS layer）/ metal back of the body electricity
Pole/substrate.Wherein the quality of CIGS layer directly determines the transformation efficiency of thin-film solar cells.
The preparation method of CuInGaSe absorbed layer has antivacuum method and the class of vacuum method two.Wherein antivacuum method mainly includes electricity
The processes such as deposition, silk-screen printing, but oxygen impurities content is high in the CIGS thin-film being prepared using these methods, into
Sub-control low precision, cause the copper-indium-galliun-selenium film solar cell transformation efficiency that is prepared low, therefore antivacuum method can not
Meet industrialization production requirements.Vacuum method mainly includes coevaporation, copper and indium gallium（CuInGa, abbreviation CIG）Metal prefabricated membrane selenizing
The methods of with CIGS quaternary target as sputter after annealing.The cell photoelectric transformation efficiency highest that coevaporation method is prepared, but
This method cost is high, and complex process, large-area uniformity is poor, is unsuitable for preparing area battery.CIG metal prefabricated membrane selenizing methods
The thin film surface planeness being prepared is poor, and component distributing is uneven, while selenylation reaction is needed in poisonous H2In Se atmosphere
Carry out.To obtain the CIGS thin-film of large-area high-quality, the method for quaternary CIGS target material sputtering after annealing is extensive
Using to suppress the loss of Se in annealing process, reaction is needed in H2Completed in Se atmosphere, so as to obtain with ideal composition
CIGS thin-film, but H2The use of Se gases limits the application of this method.H2Se is inflammable, hypertoxicity gas, and cost
Height, preservation and operation to gas are required for strictly being limited, and hinder the practical application of the process.
The content of the invention
In view of this, it is necessory to provide a kind of copper-indium-galliun-selenium film solar cell and preparation method thereof, preparing
In journey atmosphere or H are evaporated without using Se simple substance2Se atmosphere.
A kind of copper-indium-galliun-selenium film solar cell, including substrate, dorsum electrode layer on this substrate is set, is arranged on this
Light absorbing layer, the cushion being arranged on the light absorbing layer and the Window layer being arranged on the cushion on dorsum electrode layer, should
Light absorbing layer includes copper (Cu), phosphide element (In), gallium element (Ga) and selenium element (Se), and the light absorbing layer is Cuy(In1- xGax)Se2Situ adulterates Se elements, and the mol ratio between element is 1.0<Se:(Cu+In+Ga)≤1.5.
The preparation method of one copper-indium-galliun-selenium film solar cell, including：1）The dorsum electrode layer is prepared on this substrate；
2）Sputtered using a sputtering target on the dorsum electrode layer and form the amorphous materials film containing Se, Cu, In and Ga, the sputtering target
Preparation method include Cuy(In1-xGax)Se2Powder and simple substance Se powder carry out ball milling mixing in liquid medium, then by ball
Mixture drying after mill removes the liquid medium；And using hot pressed sintering, normal pressure-sintered or HIP sintering technique, it is right
The mixture obtained after ball milling is sintered at 400 °C ~ 900 °C；And the amorphous materials film is made annealing treatment,
The atmosphere of the annealing is at least one of vacuum, rare gas and nitrogen, and annealing temperature is 300 °C ~ 600 °C, heating
Speed is 1 °C/min ~ 100 °C/min, and annealing time is 0.1 hour ~ 3 hours, obtains thin-film solar cells light absorbing layer；
3）The amorphous materials film is made annealing treatment, the atmosphere of the annealing is vacuum, rare gas（Preferably argon gas）
And at least one of nitrogen, annealing temperature are 300 °C ~ 600 °C, heating rate is 1 °C/min ~ 100 °C/min, annealing time
For 0.1 hour ~ 3 hours, the light absorbing layer is obtained；4）Cushion is formed on the light absorbing layer；And 5）In the cushion
Upper formation Window layer.
Compared with prior art, the present invention is with high-purity Cuy(In1-xGax)Se2Powder and Se powder are as raw material, first to Cuy
(In1-xGax)Se2Powder and Se powder carry out mixing and ball milling, then are obtained by normal pressure-sintered, hot pressed sintering or HIP sintering
Quaternary sputtering target with high Se content.Vacuum magnetic-control sputtering is carried out using the sputtering target, can disposably obtain high Se content
Quaternary film, the can that need to only anneal afterwards in the vacuum or protective atmosphere completion crystallization of film and growing up for crystal grain, together
When can ensure that there is sufficient Se contents in light absorbing layer.During film subsequent anneal being avoided by using the sputtering target
Use harmful simple substance Se evaporation sources or poisonous H2Se gases, greatly improve the safety of thin-film solar cells preparation technology
Property, the preparation cost of thin-film solar cells can be effectively reduced, accelerates its industrial applications.
Brief description of the drawings
Fig. 1 is the structural representation of copper-indium-galliun-selenium film solar cell of the embodiment of the present invention.
Fig. 2 is the flow chart of the preparation method of copper-indium-galliun-selenium film solar cell of the embodiment of the present invention.
Fig. 3 is the XRD spectrum of sputtering target of the embodiment of the present invention.
Fig. 4 is the XRD spectrum of light absorbing layer of the embodiment of the present invention.
Fig. 5 is the stereoscan photograph of the cross section of 2-1 light absorbing layers of the embodiment of the present invention.
Main element symbol description
| Copper-indium-galliun-selenium film solar cell | 1 |
| Substrate | 10 |
| Dorsum electrode layer | 20 |
| Light absorbing layer | 30 |
| Cushion | 40 |
| Window layer | 50 |
| Transparent electrode layer | 60 |
| Antireflection layer | 70 |
Following embodiment will combine above-mentioned accompanying drawing and further illustrate the present invention.
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments to copper-indium-galliun-selenium film solar cell provided by the invention and its system
Preparation Method is described in further detail.
Referring to Fig. 1, the embodiment of the present invention provides a kind of copper-indium-galliun-selenium film solar cell 1, including substrate 10, setting
Dorsum electrode layer 20 in the substrate 10, the light absorbing layer 30 being arranged on the dorsum electrode layer 20, it is arranged on the light absorbing layer 30
On cushion 40 and the Window layer 50 that is arranged on the cushion 40.The light absorbing layer 30 includes copper (Cu), phosphide element
(In), gallium element (Ga) and selenium element (Se), specially Cuy(In1-xGax)Se2Situ adulterates Se elements, rubbing between element
You are than being 1.0<Se:(Cu+In+Ga)≤1.5.
The substrate 10 is preferably glass substrate, stainless steel foil, titanium metal foil or Kapton.
The dorsum electrode layer 20 is arranged on the surface of substrate 10.The material of the dorsum electrode layer 20 is preferably molybdenum, titanium, aluminium or tungsten.
The thickness of the dorsum electrode layer 20 is preferably the nm of 50 nm ~ 1000.
The light absorbing layer 30 is arranged on the surface of dorsum electrode layer 20.
The cushion 40 is arranged on the surface of light absorbing layer 30, and the light absorbing layer 30 is sandwiched in the dorsum electrode layer 20 and the buffering
Between layer 40.The material of the cushion 40 is preferably cadmium sulfide (CdS), zinc sulphide (ZnS) or zinc selenide (ZnSe).The buffering
The thickness of layer 40 is preferably the nm of 20 nm ~ 200.
The Window layer 50 is arranged on the surface of the cushion 40, and the cushion 40 is sandwiched in the light absorbing layer 30 and the Window layer
Between 50.The material of the Window layer 50 is preferably zinc oxide (i-ZnO).The thickness of the Window layer 50 is preferably 0.1 μm ~ 1 μm.
The copper-indium-galliun-selenium film solar cell 1 can further comprise the transparent electrode layer being arranged in the Window layer 50
60.The material of the transparent electrode layer 60 is preferably zinc oxide aluminum (ZAO), tin indium oxide (ITO), indium oxide titanium (ITiO) or oxidation
Indium gallium zinc (IGZO).The thickness of the transparent electrode layer 60 is preferably 0.1 μm ~ 1 μm.
The copper-indium-galliun-selenium film solar cell 1 can further comprise the antireflection layer being arranged on the transparent electrode layer 60
70.The material of the antireflection layer 70 is preferably magnesium fluoride (MgF2).The thickness of the antireflection layer 70 is preferably 50 nm ~ 500
nm。
The light absorbing layer 30 includes copper (Cu), phosphide element (In), gallium element (Ga) and selenium element (Se), the Se and Cu
+ In+Ga mol ratio is 1.0<Se:(Cu+In+Ga)≤1.5, Ga and In+Ga mol ratio is 0<Ga:(In+Ga)≤0.8.
The phase composition of light absorbing layer 30 is yellow copper structure, and specially crystalline state CIGS situs adulterate a small amount of Se.
The chemical formula of light absorbing layer 30 can be by Cuy(In1-xGax)Se2+zRepresent, wherein 0<x≤0.8；0.5<y<1.2, it is excellent
Elect 0.7 as<y<1.0；And 0<z<0.5.
Preferably, the light absorbing layer 30 only contains trace impurity in addition to Se, Cu, In, Ga element, the content of the impurity
Preferably less than 10ppm.
The thickness of the light absorbing layer 30 is preferably 0.2 μm ~ 5.0 μm.
The resistivity of the light absorbing layer 30 is preferably the Ω cm of 1 Ω cm ~ 1000.
The carrier concentration of the light absorbing layer 30 is preferably 1 × 1015cm-3~1×1018cm-3。
The carrier mobility of the light absorbing layer 30 is preferably 0.1cm2V-1s-1~100cm2V-1s-1。
The light absorbing layer 30 can be sputtered by sputtering method by using sputtering target and anneal to obtain, in annealing process
In without selenization.
The sputtering target is by Cuy(In1-xGax)Se2Sinter and formed after (abbreviation CIGS) powder and the mixing of simple substance Se powder, its
In 0<x≤0.8；0.5<y<1.2, preferably 0.7<y<1.0.Se adulterates in CIGS situs in the sputtering target, and being formed has Huang
The Cu of copper mine structurey(In1-xGax)Se2+z, wherein 0<x≤0.8；0.5<y<1.2, preferably 0.7<y<1.0；And 0<z<0.5.
In addition, when Se contents are more, Se can exist with simple substance form simultaneously.Contain (1) Cu i.e. in the sputtering targety(In1-xGax)
Se2+zOr (2) Cuy(In1-xGax)Se2+zWith simple substance Se combination.Preferably, compound Cuy(In1-xGax)Se2+zFor crystalline substance
State.
The atomic percent of the Se elements in the sputtering target is preferably 57% ~ 60%.
Molar percentages of the simple substance Se in the sputtering target is preferably 15% ~ 20%.
In one embodiment, the sputtering target only contains by sintering the material that is formed and micro miscellaneous after CIGS and simple substance Se mixing
Matter, the content of the impurity are preferably less than 10ppm.
In another embodiment, the sputtering target is except containing (1) Cuy(In1-xGax)Se2+zOr (2) Cuy(In1-xGax)
Se2+zOnly contain trace impurity outside combination with simple substance Se, the content of the impurity is preferably less than 10ppm.
The relative density of the sputtering target is preferably greater than or equal to 90%, the relative density=sputtering target actual density:CIGS is managed
By density × 100%.
The bulk resistor of the sputtering target is preferably 10-2Ωcm ~100Ωcm。
The roughness on the sputtering target surface is preferably lower than or equal to 2 microns, more preferably less than or equal to 0.5 micron.
Referring to Fig. 2, the embodiment of the present invention provides a kind of preparation method of the copper-indium-galliun-selenium film solar cell 1,
Comprise the following steps：
1）The dorsum electrode layer 20 is prepared in the substrate 10；
2）Sputter on the dorsum electrode layer 20 that to form the amorphous materials containing Se, Cu, In and Ga thin using a sputtering target
Film；And
3）The amorphous materials film is made annealing treatment, the atmosphere of the annealing is vacuum, rare gas（It is preferred that
For argon gas）And at least one of nitrogen, annealing temperature are 300 °C ~ 600 °C, heating rate is 1 °C/min ~ 100 °C/min,
Annealing time is 0.1 hour ~ 3 hours, obtains the light absorbing layer 30；
4）Cushion 40 is formed on the light absorbing layer 30；And
5）Window layer 50 is formed on the cushion 40.
Specifically, in the step 1）In, can be by physical method, such as evaporation or sputtering method, or chemical method, such as
The method of plating or chemical plating prepares the dorsum electrode layer 20 on the surface of substrate 10.It is preferred that back of the body electricity is prepared using magnetron sputtering method
Pole layer 20.Before the dorsum electrode layer 20 is prepared, the step of can further comprising cleaning substrate 10, to remove substrate surface
10 impurity.
In the step 2）In, the preparation method of the sputtering target comprises the following steps：
2-1）CIGS powder and simple substance Se powder are subjected to ball milling mixing in liquid medium, then by the mixture after ball milling
Drying removes the liquid medium；And
2-2）Using hot pressed sintering（Non- isostatic pressed）, normal pressure-sintered or HIP sintering technique, to what is obtained after ball milling
Mixture is sintered at 400 °C ~ 900 °C.
The CIGS powder has yellow copper structure.In step 2-1）In, the CIGS powder and simple substance Se powder are preferably pressed
Mol ratio 1.0:(0.6 ~ 1.0) is mixed.It is micro- that the particle diameter of the CIGS powder and simple substance Se powder is preferably less than or equal to 10
Rice, more preferably 0.05 micron ~ 2 microns.The CIGS powder and the purity of simple substance Se powder are preferably 3N (mass percents
99.9%) ~ 5N (mass percent 99.999%).
The CIGS powder and simple substance Se powder can be in air or protective gas（Such as Ar gas or N2Gas）Middle carry out ball milling.
The liquid medium passes through baking step afterwards not reacted with raw material CIGS powder and simple substance Se powder
It can remove, other impurity are not introduced into mixture.The liquid medium for example can be at least one in water, ethanol and acetone
Kind.The CIGS powder and the gross mass of simple substance Se powder and mill ball quality ratio are preferably 1:(1~20).
The ball milling is carried out in ball mill, and the liquid medium, abrading-ball, CIGS powder and simple substance Se powder insert the ball milling
In machine.The rotating speed of the ball mill is preferably 100 rpm ~ 600rpm., on the one hand can be by the CIGS powder during ball milling
It is sufficiently mixed uniformly with simple substance Se powder, on the other hand the particle diameter of powder can be refined, obtains the material powder of required particle diameter.
The Ball-milling Time is reached requirement and is defined by well mixed and raw material granularity.Preferably, the Ball-milling Time is 0.5 ~ 20 hour.Should
The mixture obtained after ball milling is the mechanical impurity of CIGS powder and simple substance Se powder.
The temperature of the drying is preferably 30 °C ~ 60 °C, and the baking step can be in air or protective gas（Such as Ar gas or N2
Gas）Middle progress, preferably dried in high-purity (3N ~ 5N) protective gas.
In step 2-2）In, when using hot-pressing sintering technique, the sintering temperature of the hot pressed sintering can be 400 °C ~
900 °C, sintering pressure can be 30MPa ~ 100MPa, and sintering time can be 1 hour ~ 40 hours.Burnt when using high temperature insostatic pressing (HIP)
When tying technique, the sintering temperature of the HIP sintering can be 400 °C ~ 900 °C, sintering pressure can be 100MPa ~
300MPa, sintering time can be 1 hour ~ 40 hours.When using normal pressure-sintered technique, the normal pressure-sintered sintering time can
Think 1 hour ~ 40 hours.
The sintering process is carried out in protective gas, and the protective gas can be Ar gas or N2Gas, preferably purity be 3N ~
5N Ar gas or N2Gas.
When applying pressure simultaneously in sintering process, the mixture can be molded in sintering process, to form preboarding
The sputtering target of shape, used suitable for follow-up sputtering.Can be specifically that the mixture is put into the mould with predetermined shape to carry out
Hot pressed sintering or isostatic sintering.
When this is sintered to it is normal pressure-sintered when, the mixture can be first molded before sintering, to form predetermined shape
Sputtering target, used suitable for follow-up sputtering.Can be specifically that the mixture is put into the mould with predetermined shape to be suppressed.
Pressure used in the compacting can be 50MPa ~ 300MPa.
, can be to mixture progress preforming step in addition, before be sintered using any sintering processing, such as can be with
Make mixture preforming using modes such as mould, casting or injections, bonding can be added in mixture in preform process
Agent and/or solvent.The binding agent and/or solvent can be completely removed in follow-up sintering step.
It can be used after the sintered body for obtaining that there is predetermined shape after sintering directly as the sputtering target, one can also be entered
Step carries out the steps such as machine-shaping, polishing.
It can see referring to Fig. 3, the sputtering target obtained after sintering is carried out into XRD tests, the sputtering target main component is
Cuy(In1-xGax)Se2+z, and simple substance Se diffraction maximum can be seen.
The embodiment of the present invention is first mixed using high-purity CIGS powder and Se powder as raw material to CIGS powder and Se powder
Ball milling is closed, then the quaternary sputtering target with high Se content is obtained by normal pressure-sintered, hot pressed sintering or HIP sintering.Use
The sputtering target carries out vacuum magnetic-control sputtering, can disposably obtain selenium atom ratio higher than in former CIGS selenium atom ratio it is thin
Film, the can that need to only be annealed afterwards in vacuum or protective atmosphere completes the crystallization of film and growing up for crystal grain, while can protect
Demonstrate,proving has sufficient Se contents in light absorbing layer 30.Avoided by using the sputtering target during film subsequent anneal using having
Evil simple substance Se evaporation sources or poisonous H2Se gases, the security of thin-film solar cells preparation technology is greatly improved, can be with
The preparation cost of thin-film solar cells is effectively reduced, accelerates its industrial applications.
In the step 2）In, the sputter procedure is sputtered using single target, and the sputtering method can be magnetron sputtering method, as direct current splashes
Penetrate method or exchange sputtering method（Such as medium frequency magnetron sputtering method or radio-frequency magnetron sputter method）, preferably medium frequency magnetron sputtering method or radio frequency
Magnetron sputtering method.The electric current of the sputtering is preferably 0.1A ~ 2.0A.The time of the sputtering is preferably 1 minute ~ 120 minutes.
Before carrying out sputtering and preparing the amorphous materials film, it can further comprise carrying out substrate together with the dorsum electrode layer
The step of cleaning, to remove the impurity of substrate and dorsum electrode layer surface.
The temperature of the sputtering can be normal temperature or high temperature, and the base reservoir temperature is preferably 20 °C ~ 700 °C.When using high temperature,
The step of preparation method can further comprise preheating the substrate in a vacuum before sputtering.
The carrier gas used in the sputtering method can be argon gas, and the purity of carrier gas is preferably 3N ~ 5N.
Base vacuum in the sputter procedure is 1 × 10-4Pa~1×10-2Pa。
The pressure during sputtering in sputtering chamber is preferably 0.1Pa ~ 2.0Pa.
The substrate can be parallel to each other with the sputtering target, can also be in an angle, and the angle is preferably between 20o ~ 85o.
The distance between the substrate and the sputtering target are preferably lower than or equal to 8cm.
The mol ratio for containing Se, Cu, In and Ga element, Se and Cu+In+Ga by sputtering the amorphous materials film formed
For 1.0<Se:(Cu+In+Ga)≤1.5.
In the step 3）In, the purity for making annealing treatment rare gas used and nitrogen is both preferably 3N ~ 5N.At the annealing
Without to the amorphous materials film selenization, the content of Se elements is less than in the atmosphere of the annealing during reason
10ppm.The base vacuum of the annealing process is preferably 1 × 10-4Pa~1×10-2Pa.The annealing process makes the amorphous materials thin
Membrane crystallization, referring to Fig. 4, the film after annealing is carried out into XRD tests, it can be seen that being formd by the annealing process has
The CIGS situs of yellow copper structure adulterate a small amount of Se single crystalline phase film.
It is appreciated that because selenium has higher vapour pressure and fusing point relatively low, easily evaporated in heating process.Se is in shape
Into the content highest in the mixed-powder of sputtering target, the Se in the preparation of follow-up sputtering target and the preparation process of light absorbing layer 30
Content gradually reduces, wherein the annealing process after sputtering is the step of Se contents are greatly reduced, but due in sputtering target
Se contents are higher, can make up the loss amount of Se in annealing process so that in the light absorbing layer 30 finally given Se content
It is higher, without carrying out selenization to film in annealing.The obtained light absorbing layer 30 need not carry out selenization, can be direct
Applied to thin film solar cell device, obtained device electricity conversion can reach more than 8%.The embodiment of the present invention is by making
With above-mentioned sputtering target sputter and can disposably obtain the sufficiently large amorphous materials film of selenium atom ratio, in the film
Se content can make crystallization and the crystal grain that can complete film in annealing process without selenization in vacuum or protective atmosphere
Grow up, while can ensure that there is sufficient Se contents in light absorbing layer 30.The light absorbing layer that this method is not only prepared
30 electricity conversions are high, while avoid harmful Se simple substance evaporation atmosphere and hypertoxic H2The use of Se gases, behaviour was both improved
The security and production efficiency of work, reduce production cost again, suitable for the application of industrialized production.
In the step 4）In, the cushion 40 is preferably prepared by chemical thought (CBD) method.
In the step 5）In, it is preferred to use magnetron sputtering method prepares the Window layer 50.It is to pass through magnetic control in the present embodiment
Sputtering method prepares intrinsic zinc oxide（i-ZnO）As the Window layer 50.
The preparation method of the copper-indium-galliun-selenium film solar cell can further comprise in the Window layer 50 described in formation
The step of transparent electrode layer 60.The transparent electrode layer 60 is preferably prepared using magnetron sputtering method.
The preparation method of the copper-indium-galliun-selenium film solar cell 1 can further comprise being formed on the transparent electrode layer 60
The step of antireflection layer 70.It is preferred that the antireflection layer 70 is prepared using magnetron sputtering method.
Embodiment 1：Sputtering target and preparation method thereof
Embodiment 1-1
Weighing component ratio is Cu/ (In+Ga)=0.9 (i.e. y=0.9), Ga/ (In+Ga)=0.3（That is x=0.3）CIGS powder
290 g, the g of simple substance Se powder 50, the g of abrading-ball 1800, are put into ball grinder and mix.Ball-milling medium elects absolute ethyl alcohol, rotational speed of ball-mill as
300 rpm, the h of Ball-milling Time 8.Drying obtains mixed-powder after ball milling.Target is prepared using normal pressure-sintered, mixed-powder is put
Enter in press, suppressed in a mold, the MPa of pressure 100, the min of dwell time 15.Sintering furnace is put into after the demoulding, high-purity
It is sintered in argon atmosphere, the oC of sintering temperature 600, the oC/min of heating rate 10, the h of sintering time 5.After terminating with
Stove is cooled to room temperature sampling.The defects of target flawless ftractures, percent compaction reach 95.7 %, and Se molar percentage is in target
55%。
Embodiment 1-2
Weighing component ratio is Cu/ (In+Ga)=0.7 (i.e. y=0.7), Ga/ (In+Ga)=0.5（That is x=0.5）CIGS powder
280 g, the g of simple substance Se powder 60, the g of abrading-ball 1000, are put into ball grinder and mix.Ball-milling medium elects absolute ethyl alcohol, rotational speed of ball-mill as
500 rpm, the h of Ball-milling Time 4.Target is prepared using hot pressed sintering, powder is put into graphite jig in high pure nitrogen atmosphere to enter
Row sintering.The oC of sintering temperature 700, the oC/min of heating rate 15, the MPa of sintering pressure 70, the h of sintering time 4.After terminating
Cool to room temperature sampling with the furnace.The defects of target flawless ftractures, percent compaction reach 99.4 %, Se molar percentage in target
For 59%.
Embodiment 1-3
Weighing component ratio is Cu/ (In+Ga)=0.8 (i.e. y=0.8), Ga/ (In+Ga)=0.7（That is x=0.7）CIGS powder
270 g, the g of simple substance Se powder 70, the g of abrading-ball 800, are put into ball grinder and mix.Ball-milling medium elects deionized water, rotational speed of ball-mill as
200 rpm, the h of Ball-milling Time 6.Target is prepared using HIP sintering, after powder is wrapped up, is put into isostatic pressing machine
Forming and sintering.The oC of sintering temperature 500, the oC/min of heating rate 5, the MPa of sintering pressure 240, the h of sintering time 8.Sintering terminates
After cool to the furnace room temperature sampling.The defects of target material surface is smooth, and flawless ftractures, percent compaction reach 99.8 %, Se in target
Molar percentage be 60%.
Embodiment 2：Copper-indium-galliun-selenium film solar cell
Embodiment 2-1
0.8 μ m-thick metal Mo films are deposited using vacuum magnetic-control sputtering method on soda-lime glass, with embodiment 1-1 systems
Standby sputtering target carries out vacuum magnetic-control sputtering, and the amorphous materials film of one layer of 1.5 μ m-thick is deposited on Mo films.Sputtering is originally
Bottom vacuum 2.0 × 10-3Pa, sputtering working gas are high-purity argon gas, the Pa of sputtering pressure 1.2,500 °C of base reservoir temperature.Annealing
Vacuum annealing is carried out to sample in stove, 580 °C are warming up to 20 °C/min heating rate, keeps the min of constant temperature 60, then with
Stove is cooled to room temperature, obtains light absorbing layer.Se atomic ratios reach 52% in the light absorbing layer, and conduction type is p-type, resistivity
60.6 Ω cm, the cm of carrier mobility 4.302•V-1•s-1, carrier concentration is 2.4 × 1016 cm-3.To the light absorbing layer
Cross section be scanned Electronic Speculum test, stereoscan photograph is as shown in Figure 5.Using vacuum magnetic-control sputtering method in the light absorbs
Cushion, Window layer, transparent electrode layer and antireflection layer are sequentially depositing on layer.The cushion is ZnS films, and the Window layer is
ZnO film, the transparent electrode layer are ZAO films, and the antireflection layer is MgF2Film.The CIGS thin film solar-electricity being prepared
The mV of pond open-circuit voltage 523.3, the mA/cm of short-circuit current density 22.52, fill factor, curve factor is 52.7 %, electricity conversion 6.2
%。
Embodiment 2-2
0.5 μ m-thick metal Al films are deposited using vacuum magnetic-control sputtering method in stainless steel base, with embodiment 1-2
The sputtering target of preparation carries out vacuum magnetic-control sputtering, and the amorphous materials film of one layer of 2.0 μ m-thick is deposited on Al films.Sputtering
Base vacuum 1.0 × 10-3Pa, sputtering working gas are high-purity argon gas, the Pa of sputtering pressure 0.7,20 °C of base reservoir temperature.Moving back
Sample is annealed in stove, annealing atmosphere is 50 KPa high pure nitrogens, and 550 are warming up to 10 °C/min heating rate
°C, the min of constant temperature 30 is kept, then cool to room temperature with the furnace, obtain light absorbing layer.Se atomic ratios reach in light absorbing layer after annealing
To 54 %, Thin film conductive type is p-type, Ω cm of resistivity 140.0, the cm of carrier mobility 5.652•V-1•s-1, carrier
Concentration is 7.9 × 1015 cm-3.Be sequentially depositing using vacuum magnetic-control sputtering method on the light absorbing layer cushion, Window layer,
Transparent electrode layer and antireflection layer.The cushion is CdS film, and the Window layer is ZnO film, and the transparent electrode layer is that ITO is thin
Film, the antireflection layer are MgF2Film.The mV of CIGS thin film solar cell open-circuit voltage 449.4 being prepared, short circuit current
The mA/cm of density 31.32, fill factor, curve factor is 61.8 %, and electricity conversion is 8.7 %.
Embodiment 2-3
0.8 μ m-thick metal Mo films are deposited using vacuum magnetic-control sputtering method on polyimide, with embodiment 1-3 systems
Standby sputtering target carries out vacuum magnetic-control sputtering, and the CIGS thin film of one layer of 1.0 μ m-thick is deposited on Mo films.Sputter base vacuum
2.0×10-4Pa, sputtering working gas are high-purity argon gas, the Pa of sputtering pressure 0.5,100 °C of base reservoir temperature.It is right in the lehr
Sample is annealed, and annealing atmosphere is 50 KPa high pure nitrogens, and 500 °C are warming up to 5 °C/min heating rate, keeps permanent
90 min of temperature, then cool to room temperature with the furnace, obtain CIGS solar cell absorbed layers.Se atomic ratios reach 55 in annealing rear film
%, Thin film conductive type are p-type, Ω cm of resistivity 27.5, the cm of carrier mobility 7.12•V-1•s-1, carrier concentration be
3.2×1016cm-3.Cushion, Window layer, transparency electrode are sequentially depositing on the light absorbing layer using vacuum magnetic-control sputtering method
Layer and antireflection layer.The cushion is ZnS films, and the Window layer is ZnO film, and the transparent electrode layer is ITiO films, and this subtracts
Reflecting layer is MgF2Film.The mV of CIGS solar batteries 509.0 being prepared, the mA/ of short-circuit current density 25.9
cm2, fill factor, curve factor is 52.1 %, and electricity conversion is 6.9 %.
In addition, those skilled in the art can also do other changes in spirit of the invention, certainly, these are according to present invention essence
The change that god is done, it should all be included within scope of the present invention.
Claims (11)
1. a kind of copper-indium-galliun-selenium film solar cell, including substrate, dorsum electrode layer on this substrate is set, is arranged on the back of the body
Light absorbing layer, the cushion being arranged on the light absorbing layer and the Window layer being arranged on the cushion on electrode layer, the light
Absorbed layer includes copper (Cu), phosphide element (In), gallium element (Ga) and selenium element (Se), it is characterised in that the light absorbing layer
For Cuy(In1-xGax)Se2Situ adulterates Se elements, and the mol ratio between element be Se: (Cu+In+Ga) equal to 1.5.
2. copper-indium-galliun-selenium film solar cell as claimed in claim 1, it is characterised in that the light absorbing layer chemical formula is by Cuy
(In1-xGax)Se2+zRepresent.
3. copper-indium-galliun-selenium film solar cell as claimed in claim 2, it is characterised in that 0 ＜ x≤0.8,0.5 ＜ y ＜
1.2, and O ＜ z ＜ 0.5.
4. copper-indium-galliun-selenium film solar cell as claimed in claim 1, it is characterised in that the carrier of the light absorbing layer is dense
Spend for 1 × 1015cm-3~1 × 1018cm-3, carrier mobility 0.1cm2V-1s-1~100cm2V-1s-1。
5. copper-indium-galliun-selenium film solar cell as claimed in claim 1, it is characterised in that the thickness of the light absorbing layer is
0.2 μm~5.0 μm.
6. the preparation method of a copper-indium-galliun-selenium film solar cell, including：
1) dorsum electrode layer is prepared in a substrate；
2) sputtered using a sputtering target on the dorsum electrode layer and form the amorphous materials film containing Se, Cu, In and Ga, this splashes
The preparation method shot at the target includes：
By Cuy(In1-xGax)Se2Powder and simple substance Se powder carry out ball milling mixing in liquid medium, then by the mixing after ball milling
Thing drying removes the liquid medium；And using hot pressed sintering, normal pressure-sintered or HIP sintering technique, to being obtained after ball milling
Mixture be sintered at 400 DEG C~900 DEG C, wherein, Cuy(In1-xGax)Se2The particle diameter of powder and simple substance Se powder is less than
Or equal to 10 microns；
3) the amorphous materials film is made annealing treatment, the atmosphere of the annealing is in vacuum, rare gas and nitrogen
At least one, annealing temperature is 300 DEG C~600 DEG C, and heating rate is 1 DEG C/min~100 DEG C/min, annealing time 0.1
Hour~3 hours, light absorbing layer is obtained, the light absorbing layer is Cuy(In1-xGax)Se2Situ adulterates Se elements, between element
Mol ratio be Se: (Cu+In+Ga) be equal to 1.5；
4) cushion is formed on the light absorbing layer；And
5) Window layer is formed on the cushion.
7. the preparation method of copper-indium-galliun-selenium film solar cell as claimed in claim 6, it is characterised in that the annealing
Atmosphere in the contents of Se elements be less than 10ppm.
8. the preparation method of copper-indium-galliun-selenium film solar cell as claimed in claim 6, it is characterised in that the base reservoir temperature
For 20 DEG C~700 DEG C.
9. the preparation method of copper-indium-galliun-selenium film solar cell as claimed in claim 6, it is characterised in that the sputtering method is
Medium frequency magnetron sputtering method or radio-frequency magnetron sputter method.
10. the preparation method of copper-indium-galliun-selenium film solar cell as claimed in claim 6, it is characterised in that this was sputtered
Base vacuum in journey is 1 × 10-4Pa~1 × 10-2Pa。
11. the preparation method of copper-indium-galliun-selenium film solar cell as claimed in claim 6, it is characterised in that this is annealed
The Se contents of amorphous materials film decline in journey.
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| CN108389934A (en) * | 2018-03-08 | 2018-08-10 | 西南石油大学 | A method of preparing CIGS solar cell with a step sputtering method |
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