CN102044577A - Flexible thin film solar cell and production method thereof - Google Patents
Flexible thin film solar cell and production method thereof Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 239000010409 thin film Substances 0.000 title claims abstract description 38
- 239000010408 film Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 238000004544 sputter deposition Methods 0.000 claims abstract description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 18
- 239000011733 molybdenum Substances 0.000 claims abstract description 18
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 16
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 copper-indium-aluminum-selenium Chemical compound 0.000 claims abstract description 14
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 13
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 20
- 239000011669 selenium Substances 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 claims description 7
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000007669 thermal treatment Methods 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 229910018565 CuAl Inorganic materials 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000031700 light absorption Effects 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 abstract 2
- 230000000873 masking effect Effects 0.000 abstract 1
- 231100000701 toxic element Toxicity 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 7
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- 239000013078 crystal Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
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- 239000002994 raw material Substances 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- DWGQLIHNAWNSTB-UHFFFAOYSA-N [AlH3].[Se] Chemical compound [AlH3].[Se] DWGQLIHNAWNSTB-UHFFFAOYSA-N 0.000 description 2
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000000197 pyrolysis Methods 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- 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 invention discloses a flexible thin film solar cell and a production method thereof. The thin film solar cell provided by the invention is prepared from polyacidamide, a molybdenum back electrode, a copper-indium-aluminum-selenium light absorption layer, a zinc sulfide buffer layer, a zinc-aluminum oxide window layer and a nickel-aluminum top electrode successively from bottom to top. The invention also discloses a preparation method of the flexible thin film solar cell, which comprises the following steps: 1) depositing the molybdenum back electrode of 0.3-3.0 mu m on the polyacidamide substrate by adopting a direct current magnetic control sputtering method; 2) depositing a copper-indium-aluminum-selenium thin film of 0.5-5.0 mu m on the molybdenum back electrode by adopting a sputtering selenization method; 3) growing a zinc sulfide thin film on the copper-indium-aluminum-selenium thin film by adopting a radio frequency reaction sputtering method; 4) growing a zinc-aluminum oxide thin film on the zinc sulfide thin film by adopting the direct current magnetic control sputtering method; and 5) depositing a nickel-aluminum alloy thin film though a masking film by adopting an evaporation method. The invention greatly reduces the use of rare metals and toxic elements and has the advantages of simple structure and production process, high photoelectric conversion efficiency, good stability and the like.
Description
Technical field
The invention belongs to photoelectric material and technical field of new energies, be specifically related to a kind of flexible thin-film solar cell and manufacture method thereof.
Background technology
Utilize in the mode the various of solar energy, the solar cell generating is field with fastest developing speed, most active and that attract most attention, is expected to become the effective way of serious day by day energy crisis of solution and problem of environmental pollution.The solar cell industry from nineteen ninety for having entered Rapid development stage latter half, the annual average rate of increase of nearest 10 years solar cells is 41.3%, nearest 5 years annual average rate of increase is 49.5%.Though development speed is so fast, the ratio of solar cell generating at present in entire society's energy resource structure is still very little, less than 1%.Therefore, the development potentiality of solar cell is extremely huge, and market prospects are wide.
The solar cell that is at present leading position on industrial production and market is based on the first generation solar cell of crystalline silicon (monocrystalline silicon and polysilicon), its electricity conversion height (can reach 24.7% and 20.3% respectively), technology is comparative maturity also, and output accounts for whole solar cell about 90% (monocrystalline silicon 43.4%, polysilicon 46.5%).But owing to need to consume a large amount of expensive high-purity crystal silicon raw materials, cost of material accounts for total cost 60%～80%, causes holding at high price, and has become the major obstacle that photovoltaic industry development and solar cell are applied.In order to save raw material, effectively reduce the cost of solar cell, the second generation solar cell of based thin film technology demonstrates huge advantage and development potentiality gradually, becomes the research focus in solar cell field in the last few years.
In various thin film solar cells, though the amorphous silicon film solar battery cost is lower, efficient is also lower, and exists the light decay effect to be difficult to solve; Though the dye-sensitized solar cells cost is low, but owing to adopt liquid electrolyte and organic dyestuff, make manufacturing and encapsulation difficulty, efficient instability, though cadmium-Te solar battery efficient can reach requirement, but need to use the rare element tellurium, also contain hypertoxic heavy metal element cadmium, Copper Indium Gallium Selenide is that thin film solar cell has advantages such as environmental friendliness, with low cost and function admirable, but, how to avoid and the use that reduces these rare metals is one and has very much one of problem of using sight because the use of indium, gallium is not expected its development sight.
Traditional inorganic thin film semiconductor solar cell structure adopts rigid material such as soda-lime glass to do substrate, and this has limited the large tracts of land deposition of each layer film material, the use field of also having limited battery simultaneously.Reduction along with the solar cell cost, this kind battery more and more comes many application spaces such as roof that solar panel, packsack power supply or the like are installed, this just requires its use to have the substrate of flexible characteristic, flexible substrates has high-specific-power, light weight, it is folding to curl, be not afraid of the characteristics such as bump, capability of resistance to radiation is strong of falling, and can also deposit with the takeup type serialization, its material and production cost have bigger reduction space, no matter, all have vast market prospect and huge demand background military or civilian.
Summary of the invention
In order to overcome the deficiency of thin film solar cells such as remedying existing amorphous silicon, dye sensitization, cadmium telluride and Copper Indium Gallium Selenide, the invention provides that a kind of structure and manufacturing process are simple, with low cost, environmental friendliness, stable performance, flexible thin-film solar cell and manufacture method thereof that transformation efficiency is high.
Flexible thin-film solar cell of the present invention is solved by the following technical programs:
Described flexible thin-film solar cell, from top to bottom successively by substrate, back electrode, light absorbing zone, resilient coating, Window layer and top electrode constitute, described resilient coating is a zinc sulfide film, its thickness is 20～100nm, described Window layer is the zinc oxide aluminum film, its thickness is 0.2～5.0 μ m, described top electrode is the nickel alumin(i)um alloy film, and its thickness is 0.2～5.0 μ m, and described substrate is pi (polyimides, initialism is PI), its thickness is 10～100 μ m, and described light absorbing zone is Cu-In-Al-Se (CIAS) film, and its thickness is 0.5～5.0 μ m, described back electrode is molybdenum (Mo) film, and its thickness is 0.3～3.0 μ m.
Advantage such as that pi has is collapsible, density is little, in short time high temperature deposit film technical process, have radiation hardness simultaneously, difficult wear out, do not absorb water, performance such as good insulation preformance, it is a kind of one of comparatively desirable flexible base material of flexible thin-film solar cell for preparing, light absorbing zone adopts the Cu-In-Al-Se film, can reduce the use of rare metal indium, gallium, and in the pi substrate, deposit the molybdenum back electrode, can make light absorption layer material and substrate keep good bonding force.
Preferably, described molybdenum film is pure molybdenum film, or the molybdenum-copper film, and wherein the percentage by weight of copper content is 2～40%.
The method of manufacturing flexible thin-film solar cell of the present invention is solved by the following technical programs:
The manufacture method of described flexible thin-film solar cell may further comprise the steps:
1) back electrode manufacturing: deposit back electrode on substrate surface, described substrate is a pi, and its thickness is 10～100 μ m, and described back electrode is the molybdenum film, and its thickness is 0.3～3.0 μ m;
2) light absorbing zone manufacturing: deposit light absorbing zone on described back electrode, described light absorbing zone is the Cu-In-Al-Se film, and its thickness is 0.5～5.0 μ m;
3) resilient coating manufacturing: deposit resilient coating on described Cu-In-Al-Se film, described resilient coating is a zinc sulfide film, and its thickness is 20～100nm;
4) Window layer manufacturing: deposit Window layer on described zinc sulfide film, described Window layer is the zinc oxide aluminum film, and its thickness is 0.2～5.0 μ m, and wherein the percentage by weight of alumina doped amount is 1～5%;
5) manufacturing of top electrode: deposit top electrode on described zinc oxide aluminum film, described top electrode is the nickel alumin(i)um alloy film, and its thickness is 0.2～5.0 μ m, wherein the aluminium content 1-100% that is weight percentage.
Preferably, direct current magnetron sputtering process is adopted in the manufacturing of described step 1) back electrode, adopt pure molybdenum or molybdenum-copper alloy target or molybdenum, the two target magnetically controlled DC sputterings of copper to make at described substrate surface, the working gas of its sputter is a high-purity argon gas, operating air pressure is 0.05～10.00Pa, sputtering power is 40～250W, and heat treatment temperature is 300～450 ℃.
Preferably, described step 2) sputter selenizing method is adopted in the manufacturing of light absorbing zone, and it comprises step by step following:
2.1) adopt the method for substep sputter or cosputtering to form copper-indium-aluminium alloy preformed layer: adopt Cu target, In target and Al target while or sputter successively, or employing CuIn alloys target and CuAl alloys target while or sputter successively, or adopt the sputter of CuInAl alloys target, form copper-indium-aluminium alloy preformed layer;
2.2) handle by in elemental selenium atmosphere, carrying out selenizing, the selenizing temperature is 300～450 ℃, diffuses to form the Cu-In-Al-Se film.
In further preferred version, described step by step 2.2) selenizing is handled and is adopted quick thermal treatment process, and it comprises following substep:
2.2.1) described copper-indium-aluminium alloy preformed layer is placed the selenizing stove, feed the air in the Ar eliminating pipeline;
2.2.2) at Ar/H
2Under the mixed atmosphere of Se (gas ratio is adjustable), be rapidly heated to 300～450 ℃, the described technological parameter that is rapidly heated is: heating rate is 0 ~ 100 ℃/s, and the heating-up time is 8 ~ 40s, outlet temperature is 300～450 ℃, is incubated 10-300s after reaching outlet temperature;
2.2.3) at Ar/H
2Be cooled to room temperature under the mixed atmosphere of Se;
For CuInSe
2It is chalcopyrite family thin-film material, its crystallization temperature generally will could obtain crystallinity preferably more than 450 ℃, and adopt PI to do the technology that flexible base material has greatly limited heat treatment stages employing high temperature, at high temperature melt pyrolysis for fear of the PI substrate and can obtain the crystallinity good film again simultaneously, adopt rapid thermal treatment (Rapid Treatment Process, initialism is RTP) technology solved this technological difficulties, makes heat treatment temperature be lower than the crystal property of light absorbing zone film of 450 ℃ and gained and good with the adhesion of substrate.
Further in the RTP technology of optimizing: heating rate is 10-50 ℃/s described substep 2.2.2), and outlet temperature is 400 ℃, and temperature retention time is 10-180s; Described substep 2.2.3) be 30 ~ 45min cooling time in.
Preferably, described quick thermal treatment process adopts the tungsten halogen lamp Fast Heating.
Preferably, the radio frequency reaction magnetron sputtering method is adopted in the manufacturing of described step 3) resilient coating, the working gas of its sputter is the mist of high-pure hydrogen sulfide and high-purity argon gas, wherein the content of hydrogen sulfide is 1～100%, operating air pressure is 0.05～10.00Pa, target is high purity zinc target or zinc sulphide target, sputtering power is 40～250W, base reservoir temperature is 200～400 ℃, thereby preparation one deck zinc sulfide film on described light absorbing zone, direct current magnetron sputtering process is adopted in the manufacturing of described step 4) Window layer, the working gas of its sputter is a high-purity argon gas, and operating air pressure is 0.05～10.00Pa, and sputtering power is 40～250W, base reservoir temperature is 150～400 ℃, and the manufacturing of described step 5) top electrode is by the method for mask with evaporation.
The beneficial effect that the present invention is compared with the prior art is: the various materials of the solar cell of manufacturing of the present invention are inorganic crystal material, reduced the use of rare your element, poisonous element, the material that does not also contain liquid electrolyte and be difficult for encapsulating, have raw material sources extensively, structure and technology is simple, with low cost, environmental protection, functional advantage such as stable, be easy to large-scale production and application.
Description of drawings
Fig. 1 is a Cu-In-Al-Se thin film solar cell cross-sectional view in the embodiment of the invention;
Fig. 2 is the I-V characteristic curve of the Cu-In-Al-Se flexible thin-film solar cell made in the embodiment of the invention.
Embodiment
The contrast accompanying drawing also is described in further detail the present invention in conjunction with the preferred embodiments below.
Flexible thin-film solar cell of the present invention is a flexible copper indium aluminium selenium film solar battery, as shown in Figure 1, is made of pi substrate 1, back electrode 2, light absorbing zone 3, resilient coating 4, Window layer 5 and top electrode 6 successively from top to bottom.The thickness of pi substrate 1 is 10～100 μ m; Back electrode 2 is the molybdenum film, and its thickness is 0.3～3.0 μ m, and present embodiment adopts the molybdenum-copper film, and wherein copper content is 2～40%; Light absorbing zone 3 is the CIAS film, and its thickness is 0.5～5.0 μ m; Resilient coating 4 is a zinc sulfide film, and its thickness is 20～100nm; Window layer 5 is zinc oxide aluminum (ZAO) film, and its thickness is 0.2～5.0 μ m; Top electrode 6 is the nickel alumin(i)um alloy film, and its thickness is 0.2～5.0 μ m, and wherein the percentage by weight of aluminium content is 1～100%.
The manufacture method of flexible copper indium aluminium selenium film solar battery of the present invention is carried out according to the following step:
1) back electrode 2 is made: use molybdenum-copper alloy target magnetically controlled DC sputtering or molybdenum, the two target magnetically controlled DC sputterings of copper on pi substrate 1 surface, deposition molybdenum-copper film;
2) light absorbing zone 3 is made: adopt sputter selenizing method to deposit one deck Cu-In-Al-Se film on back electrode 2;
3) resilient coating 4 is made: adopt the RF-reactively sputtered titanium method to deposit one deck zinc sulfide film on light absorbing zone 3;
4) Window layer 5 is made: the zinc oxide target that adopts magnetically controlled DC sputtering aluminium oxide (1～5%) to mix, deposition preparation one deck zinc oxide aluminum film;
5) manufacturing of top electrode 6: on the zinc oxide aluminum film, deposit one deck nickel alumin(i)um alloy film with the method for evaporating by mask.
Above-mentioned steps 1) working gas of magnetically controlled DC sputtering is a high-purity argon gas in the manufacturing of back electrode 2, and operating air pressure is 0.05～10.00Pa, and sputtering power is 40～250W, and heat treatment temperature is 300～450 ℃.
Above-mentioned steps 2) sputter sulfuration method is adopted in the manufacturing of light absorbing zone, and it comprises step by step following:
2.1) adopt the method for substep sputter or cosputtering to form copper-indium-aluminium alloy preformed layer: adopt Cu target, In target and Al target while or sputter successively, or employing CuIn alloys target and CuAl alloys target while or sputter successively, or adopt the sputter of CuInAl alloys target, form copper-indium-aluminium alloy preformed layer;
2.2) handle by in elemental selenium atmosphere, carrying out selenizing, the selenizing temperature is 300～450 ℃, diffuses to form the Cu-In-Al-Se film.
Further preferred, step by step 2.2) selenizing is handled and is adopted quick thermal treatment process, and it comprises following substep:
2.2.1) described copper-indium-aluminium alloy preformed layer is placed the selenizing stove, feed the air in the Ar eliminating pipeline;
2.2.2) at Ar/H
2Under the mixed atmosphere of Se (gas ratio is adjustable), be rapidly heated to 300～450 ℃, the described technological parameter that is rapidly heated is: heating rate is 0 ~ 100 ℃/s, preferred heating rate is 10-50 ℃/s, heating-up time is 8 ~ 40s, outlet temperature is 300～450 ℃, and preferred outlet temperature is 400 ℃, is incubated 10-300s after reaching outlet temperature;
2.2.3) at Ar/H
2Be cooled to room temperature under the mixed atmosphere of Se, be 30 ~ 45min cooling time, preferred 40min.
Above-mentioned steps 3) in the radio frequency reaction magnetron sputtering method of resilient coating 4, the working gas of its sputter is the mist of high-pure hydrogen sulfide and high-purity argon gas, wherein the content of hydrogen sulfide is 1～100%, operating air pressure is 0.05～10Pa, target is high purity zinc target or zinc sulphide target, sputtering power is 40～250W, and base reservoir temperature is 200～400 ℃.
Above-mentioned steps 4) in the direct current magnetron sputtering process of Window layer 5, the working gas of its sputter is a high-purity argon gas, and operating air pressure is 0.05～10.00Pa, and sputtering power is 40～250W, and base reservoir temperature is 150～400 ℃.
With the Cu-In-Al-Se flexible thin-film solar cell of the 1cm*1cm that makes at spectrum grade AM1.5, irradiance 100mW/cm
Down test of simulated solar irradiation, obtain the I-V test curve shown in Fig. 2, short-circuit current density is 36.39mA/cm
2, open circuit voltage is 669mV, cell conversion efficiency is 5.17%.
Each alphabetical physical meaning among Fig. 2: transverse axis V is a voltage, the Volts(of unit volt), V
OcBe open circuit voltage; Longitudinal axis J is a current density, and unit is mA/cm
2, J
ScBe short-circuit current density, FF is a fill factor, curve factor, and Eff is a transformation efficiency, and Area is a sample area.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, make some substituting or obvious modification without departing from the inventive concept of the premise, and performance or purposes are identical, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. flexible thin-film solar cell, from top to bottom successively by substrate, back electrode, light absorbing zone, resilient coating, Window layer and top electrode constitute, described resilient coating is a zinc sulfide film, its thickness is 20～100nm, described Window layer is the zinc oxide aluminum film, its thickness is 0.2～5.0 μ m, described top electrode is the nickel alumin(i)um alloy film, its thickness is 0.2～5.0 μ m, it is characterized in that: described substrate is a pi, and its thickness is 10～100 μ m, described light absorbing zone is the Cu-In-Al-Se film, its thickness is 0.5～5.0 μ m, and described back electrode is the molybdenum film, and its thickness is 0.3～3.0 μ m.
2. flexible thin-film solar cell according to claim 1 is characterized in that: described molybdenum film is pure molybdenum film, or the molybdenum-copper film, and wherein the percentage by weight of copper content is 2～40%.
3. the manufacture method of a flexible thin-film solar cell is characterized in that may further comprise the steps:
1) back electrode manufacturing: deposit back electrode on substrate surface, described substrate is a pi, and its thickness is 10～100 μ m, and described back electrode is the molybdenum film, and its thickness is 0.3～3.0 μ m;
2) light absorbing zone manufacturing: adopt sputter selenizing method to deposit light absorbing zone on described back electrode, described light absorbing zone is the Cu-In-Al-Se film, and its thickness is 0.5～5.0 μ m;
3) resilient coating manufacturing: deposit resilient coating on described Cu-In-Al-Se film, described resilient coating is a zinc sulfide film, and its thickness is 20～100nm;
4) Window layer manufacturing: deposit Window layer on described zinc sulfide film, described Window layer is the zinc oxide aluminum film, and its thickness is 0.2～5.0 μ m, and wherein the percentage by weight of alumina doped amount is 1～5%;
5) manufacturing of top electrode: deposit top electrode on described zinc oxide aluminum film, described top electrode is the nickel alumin(i)um alloy film, and its thickness is 0.2～5.0 μ m, wherein the aluminium content 1-100% that is weight percentage.
4. flexible thin-film solar cell manufacture method according to claim 3, it is characterized in that: direct current magnetron sputtering process is adopted in the manufacturing of described step 1) back electrode, adopt pure molybdenum or molybdenum-copper alloy target or molybdenum, the two target magnetically controlled DC sputterings of copper to make at described substrate surface, the working gas of its sputter is a high-purity argon gas, operating air pressure is 0.05～10.00Pa, sputtering power is 40～250W, and heat treatment temperature is 300～450 ℃.
5. flexible thin-film solar cell manufacture method according to claim 3 is characterized in that: sputter selenizing method described step 2), and it comprises step by step following:
2.1) adopt the method for substep sputter or cosputtering to form copper-indium-aluminium alloy preformed layer: adopt Cu target, In target and Al target while or sputter successively, or employing CuIn alloys target and CuAl alloys target while or sputter successively, or adopt the sputter of CuInAl alloys target, form copper-indium-aluminium alloy preformed layer;
2.2) handle by in elemental selenium atmosphere, carrying out selenizing, the selenizing temperature is 300～450 ℃, diffuses to form the Cu-In-Al-Se film.
6. flexible thin-film solar cell manufacture method according to claim 5 is characterized in that: described step by step 2.2) selenizing is handled and is adopted quick thermal treatment process, and it comprises following substep:
2.2.1) described copper-indium-aluminium alloy preformed layer is placed the selenizing stove, feed the air in the Ar eliminating pipeline;
2.2.2) at Ar/H
2Under the mixed atmosphere of Se, be rapidly heated to 300～450 ℃, the described technological parameter that is rapidly heated is: heating rate is 0 ~ 100 ℃/s, and the heating-up time is 8 ~ 40s, and outlet temperature is 300～450 ℃, is incubated 10-300s after reaching outlet temperature;
2.2.3) at Ar/H
2Be cooled to room temperature under the mixed atmosphere of Se.
7. flexible thin-film solar cell manufacture method according to claim 6 is characterized in that: heating rate is 10-50 ℃/s described substep 2.2.2), and outlet temperature is 400 ℃, and temperature retention time is 10-180s.
8. flexible thin-film solar cell manufacture method according to claim 6 is characterized in that: be 30 ~ 45min cooling time described substep 2.2.3).
9. according to claim 6 or 7 described flexible thin-film solar cell manufacture methods, it is characterized in that: described quick thermal treatment process adopts the tungsten halogen lamp Fast Heating.
10. flexible thin-film solar cell manufacture method according to claim 3, it is characterized in that: the radio frequency reaction magnetron sputtering method is adopted in the manufacturing of described step 3) resilient coating, the working gas of its sputter is the mist of high-pure hydrogen sulfide and high-purity argon gas, wherein the content of hydrogen sulfide is 1～100%, operating air pressure is 0.05～10.00Pa, target is high purity zinc target or zinc sulphide target, sputtering power is 40～250W, base reservoir temperature is 200～400 ℃, thereby preparation one deck zinc sulfide film on described light absorbing zone, the alumina doped zinc oxide target of magnetically controlled DC sputtering is adopted in the manufacturing of described step 4) Window layer, the working gas of its sputter is a high-purity argon gas, operating air pressure is 0.05～10.00Pa, and sputtering power is 40～250W, and base reservoir temperature is 150～400 ℃; The manufacturing of described step 5) top electrode is by the method for mask with evaporation.
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| CN102515561A (en) * | 2011-12-16 | 2012-06-27 | 大连交通大学 | Preparation technology of Cu (In, al) Se2thin film |
| CN102903766A (en) * | 2012-10-12 | 2013-01-30 | 华中科技大学 | Cadmium-free copper indium gallium selenium (CIGS) thin-film solar cell and preparation method thereof |
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