CN104409535A - A copper zinc tin sulfide thin film solar cell device and preparing method thereof - Google Patents
A copper zinc tin sulfide thin film solar cell device and preparing method thereof Download PDFInfo
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- CN104409535A CN104409535A CN201410528412.2A CN201410528412A CN104409535A CN 104409535 A CN104409535 A CN 104409535A CN 201410528412 A CN201410528412 A CN 201410528412A CN 104409535 A CN104409535 A CN 104409535A
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title abstract description 9
- 239000010409 thin film Substances 0.000 title abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 229920001721 polyimide Polymers 0.000 claims abstract description 17
- 239000004642 Polyimide Substances 0.000 claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims description 53
- 238000001704 evaporation Methods 0.000 claims description 37
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 36
- 230000008020 evaporation Effects 0.000 claims description 34
- 229910052718 tin Inorganic materials 0.000 claims description 19
- 235000013024 sodium fluoride Nutrition 0.000 claims description 18
- 239000011775 sodium fluoride Substances 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- 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 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 238000005096 rolling process Methods 0.000 abstract 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000003860 storage Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 48
- 238000001755 magnetron sputter deposition Methods 0.000 description 20
- 239000011701 zinc Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
- 229910052717 sulfur Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 13
- 238000004062 sedimentation Methods 0.000 description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 11
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 9
- 239000005695 Ammonium acetate Substances 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 229940043376 ammonium acetate Drugs 0.000 description 9
- 235000019257 ammonium acetate Nutrition 0.000 description 9
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 7
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052950 sphalerite Inorganic materials 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 1
- KYRUBSWVBPYWEF-UHFFFAOYSA-N copper;iron;sulfane;tin Chemical compound S.S.S.S.[Fe].[Cu].[Cu].[Sn] KYRUBSWVBPYWEF-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000012360 testing method 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- General Physics & Mathematics (AREA)
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- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a copper zinc tin sulfide thin film solar cell device based on a polyimide flexible substrate. 1. The polyimide flexible substrate thin film solar cell has a higher power to weight ratio, and has advantages of being flexible, foldable and fearless of being fallen or bumped. There is great potentiality in cost reduction in the solar cell device, and thus the solar cell device is suitable for rolling to rolling process in mass production. 2. Composition components of copper zinc tin sulfide are abundant in storage and are free from environmental pollution with low production cost. An energy gap is about 1.45eV which is very close to an ideal bandgap of 1.4eV of a photovoltaic cell. The copper zinc tin sulfide is a direct-bandgap p-type semiconductor material an optical absorption coefficient of which is greater than 104cm-1, and thus is an ideal material for an absorbing layer of the thin film solar cell. The cell has high conversion efficiency, and theoretically reaches the highest conversion efficiency of a single-junction cell. The invention has the following advantages: the cell preparing method is simple, ease to be implemented, and is conducive to massive popularization and application, and the method especially has a very important application prospect in aerospace and special occasions.
Description
Technical field
The present invention relates to thin film solar cell art, particularly a kind of copper-zinc-tin-sulfur film solar cell device based on polyimide flex substrate and preparation thereof.
Background technology
Copper-zinc-tin-sulfur material (CZTS) belongs to I2-III-IV-VI4 race quaternary compound semiconductor, mainly has custerite, stannite and copper-gold alloy structure.Wherein, custerite structure thermodynamically has better stability compared with other structure types.
The feature of copper-zinc-tin-sulfur battery: each component rich reserves of copper-zinc-tin-sulfur and environmentally safe, preparation cost is low; The energy gap of copper-zinc-tin-sulfur at about 1.45eV, the closely ideal bandgap 1.4eV of photovoltaic cell; Copper-zinc-tin-sulfur is a kind of direct band gap p-type semiconductor material, and optical absorption coefficient is more than 10
4cm
-1, be suitable as very much the absorbed layer material of thin film solar cell; Battery conversion efficiency is high, can reach the most high conversion efficiency of single junction cell theoretically.Solar Frontier companies in 2013 and IBM, Tokyo answer the CZTS thin film solar cell conversion efficiency of the charge-coupled common research and development of chemical industry (TOK) to be increased to 12.6% (battery size 0.42cm
2).
Aerospace field needs solar cell to have higher quality than power, namely wishes that the solar cell of unit mass can send more electricity.The surface modeling of ground photovoltaic building and the photovoltaic plant etc. of movable type are required that solar cell has flexibility, foldability and is not afraid of to fall touch, this promotes the development of flexible solar cell.Due to relatively strong heat-resisting ability and the comparatively applicable coefficient of expansion, polyimides (PI) is shown one's talent wherein.
Summary of the invention:
The invention provides a kind of preparation scheme of the copper-zinc-tin-sulfur film solar cell device based on polyimide substrate.Using the polyimide film of flexibility as substrate, prepare back contact, copper zinc tin sulfur absorption layer, cadmium sulfide resilient coating, transparent window layer and aluminium top electrode successively on its surface.
Technical scheme of the present invention
Based on a copper-zinc-tin-sulfur film solar cell for polyimide flex substrate, the thickness of polyimide film used is 25-30 μm; Molybdenum back contact is grown on polyimide film substrate, is divided into resistive formation and low resistivity layer, and wherein the thickness of resistive formation is 80-120nm, and the thickness of low resistivity layer is 600-700nm, adopts DC magnetron sputtering system preparation; Copper zinc tin sulfur absorption layer is grown on molybdenum film, and chemical molecular formula is Cu
2znSnS
4, conduction type is p-type, and thickness is 1-2 μm, adopts DM-700 type coating machine, application coevaporation preparation technology; The film growth of sodium fluoride preformed layer is on copper zinc tin sulfur absorption layer, and chemical molecular formula is NaF, and thickness is 20-30nm, adopts DM-700 type coating machine, application Evaporation preparation technique; Cadmium sulfide buffer growth is in copper zinc tin sulfur absorption layer surface, and chemical molecular formula is CdS, and conduction type is N-shaped, and thickness is 45-50nm, adopts chemical bath method preparation technology; Transparent window layer is grown on cadmium sulfide resilient coating, be divided into high resistant native oxide zinc film and low-resistance zinc oxide aluminum film, conduction type is N-shaped, wherein the thickness of native oxide zinc film is 50-100nm, the thickness of zinc oxide aluminum film is 0.4-0.6 μm, adopts rf magnetron sputtering preparation system and the preparation of magnetically controlled DC sputtering preparation system respectively; Aluminium upper electrode film is grown on transparent window layer, and its thickness is 0.8-1.5 μm, adopts the preparation of coevaporation preparation system.
The preparation process of molybdenum back contact is as follows:
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the Mo of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit the molybdenum film of one deck high resistant and low-resistance respectively at substrate surface.
The described technological parameter depositing one deck high resistance film at substrate surface is: base vacuum: 3.0 × 10
-4pa, operating air pressure is 1-2Pa, and underlayer temperature is room temperature 25-50 DEG C, and radio-frequency power is 500-700W, Ar throughput is 30-50sccm, and the base target speed of travel is 4-6mm/s, and sedimentation time (reciprocal time of base target) is for 2-4 time.
The described technological parameter depositing one deck low-resistance film at substrate surface is: operating air pressure is 0-0.5Pa, underlayer temperature is room temperature 25-50 DEG C, radio-frequency power is 1500-2000W, Ar throughput is 15-20sccm, the base target speed of travel is 4-6mm/s, and sedimentation time (reciprocal time of base target) is for 4-6 time.
The preparation process of copper zinc tin sulfur absorption layer film is as follows:
1. base vacuum is 3.0 × 10
-4pa, underlayer temperature is 450-500 DEG C, Cu source temperature is 1100-1200 DEG C, ZnS source temperature is 1000-1100 DEG C, Sn source temperature be 1000-1100 DEG C, S source temperature is 75-85 DEG C, coevaporation Cu, ZnS, Sn, S tetra-kinds of elements, evaporation time is 30-50min;
2. substrate is cooled, keep Sn and S evaporating temperature constant, evaporation Sn and S two kinds of elements, when underlayer temperature is down to 300 DEG C, closes Sn and S evaporation source, then substrate is cooled to room temperature.The film obtained is p-type direct gap semiconductor, custerite structure.By adjusting substrate, each source temperature and steaming the time altogether, control the rich zinc of the poor copper of copper-zinc-tin-sulfur film, wherein Cu/ (Zn+Sn)=0.8-1.0, Zn/Sn=1.0-1.2, S/ (Cu+Zn+Sn) approximates 1.
The preparation process of sodium fluoride preformed layer film is as follows:
1) base vacuum is 3.0 × 10
-4pa, underlayer temperature is 200-300 DEG C, and evaporation NaF initialization layer, wherein the temperature of NaF evaporation source is 800-850 DEG C, and evaporation time is 1-2min.
2) underlayer temperature is 400-450 DEG C, anneals under Sn and Se atmosphere, and wherein the temperature of Sn evaporation source is the temperature of 1000-1100 DEG C, Se evaporation source is 240-280 DEG C, and annealing time is 5min.
The preparation process of cadmium sulfide resilient coating is as follows:
1) configure solution, prepare thiocarbamide SC (NH
2)
2solution 1L, concentration is 0.01mol/L; Cadmium acetate (CH
3cOO)
2cd and Ammonium Acetate CH
3cOONH
4mixed solution 1L, wherein cadmium acetate solution concentration is 0.001mol/L, and Ammonium Acetate solubility is 0.003mol/L; Ammoniacal liquor NH
3h
2o solubility is 1.3 × 10
-3mol/L.
2) configure reaction solution 1L, get the various solution configured in the first step; Wherein thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL, ammonia spirit 4.Stir.
3) sample is put into beaker, and beaker is put into water-bath.Bath temperature is set to 78-80 DEG C, and preparation time is 50-60min.
4) after having prepared, by clean for sample deionized water rinsing.
The preparation process of native oxide zinc film is as follows:
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the i-ZnO of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit one deck native oxide zinc film at substrate surface.
The described technological parameter depositing one deck zinc oxide aluminum film at substrate surface is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is room temperature 25-50 DEG C, and radio-frequency power is 800-1000W, Ar throughput is 10-20sccm, O
2throughput is 2-6sccm, and the base target speed of travel is 2-6mm/s, and sedimentation time (reciprocal time of base target) is for 6-10 time.
The preparation process of zinc oxide aluminum film is as follows:
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the ZnO:Al of 99.99% be target, adopt DC magnetron sputtering process to deposit layer of ZnO at substrate surface: Al film.
The described technological parameter depositing one deck zinc oxide aluminum film at substrate surface is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is 25-50 DEG C, and direct current power is 1000-1200W, Ar throughput is 12-18sccm, and the base target speed of travel is 2-6mm/s, and sedimentation time (reciprocal time of base target) is for 10-15 time.
The preparation process of aluminium top electrode is as follows:
1) base vacuum: 3.0 × 10
-4pa, gives heater strip 20A electric current, continues 1-2min; Give heater strip 50A electric current, continue 1-2min; Give heater strip 80A electric current, continue 1-2min; Give heater strip 120A electric current, continue 5-8min.
2) after glass pane to be seen is covered completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, cool afterwards.
Accompanying drawing explanation
Accompanying drawing 1 is the schematic diagram of the copper-zinc-tin-sulfur film solar cell device architecture based on polyimide flex substrate.
Embodiment
In order to make those skilled in the art person understand the present invention program better, below in conjunction with drawings and embodiments, the present invention is described in further detail.
Embodiment 1
Based on the preparation of the copper-zinc-tin-sulfur film solar cell of polyimide flex substrate, its preparation process is as follows:
1) preparation of molybdenum back contact
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the Mo of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit the molybdenum film of one deck high resistant and low-resistance respectively at substrate surface.1. base vacuum: 3.0 × 10
-4pa, operating air pressure is 1Pa, and underlayer temperature is room temperature 25 DEG C, and radio-frequency power is 600W, Ar throughput is 40sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 2 times.2. operating air pressure is 0.1Pa, and underlayer temperature is room temperature 25 DEG C, and radio-frequency power is 1500W, Ar throughput is 15sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 6 times.
2) preparation of copper zinc tin sulfur absorption layer
1. base vacuum is 3.0 × 10
-4pa, underlayer temperature is 450 DEG C, and Cu source temperature is 1100 DEG C, and ZnS source temperature is 1000 DEG C, and Sn source temperature is 1000 DEG C, and S source temperature is 75 DEG C, coevaporation Cu, ZnS, Sn, S tetra-kinds of elements, and evaporation time is 30min;
2. substrate is cooled, keep Sn and S evaporating temperature constant, evaporation Sn and S two kinds of elements, when underlayer temperature is down to 300 DEG C, closes Sn and S evaporation source, then substrate is cooled to room temperature.The film obtained is p-type direct gap semiconductor, custerite structure.By adjusting substrate, each source temperature and steaming the time altogether, control the rich zinc of the poor copper of copper-zinc-tin-sulfur film, wherein Cu/ (Zn+Sn)=0.8-1.0, Zn/Sn=1.0-1.2, S/ (Cu+Zn+Sn) approximates 1.
3) preparation process of sodium fluoride preformed layer film is as follows:
1. base vacuum is 3.0 × 10
-4pa, underlayer temperature is 200 DEG C, and evaporation NaF initialization layer, wherein the temperature of NaF evaporation source is 800 DEG C, and evaporation time is 1min.
2. underlayer temperature is 400 DEG C, anneals under Sn and Se atmosphere, and wherein the temperature of Sn evaporation source is 1000 DEG C, and the temperature of Se evaporation source is 240 DEG C, and annealing time is 5min.
4) preparation of cadmium sulfide buffer layer thin film
1. configure solution, prepare thiocarbamide SC (NH
2)
2solution 1L, concentration is 0.01mol/L; Cadmium acetate (CH
3cOO)
2cd and Ammonium Acetate CH
3cOONH
4mixed solution 1L, wherein cadmium acetate solution concentration is 0.001mol/L, and Ammonium Acetate solubility is 0.003mol/L; Ammoniacal liquor NH
3h
2o solubility is 1.3 × 10
-3mol/L.
2. configure reaction solution 1L, get the various solution configured in the first step; Wherein thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL, ammonia spirit 4.Stir.3. sample is put into beaker, and beaker is put into water-bath.Bath temperature is set to 78 DEG C, and preparation time is 60min.4. after having prepared, by clean for sample deionized water rinsing.
5) preparation of native oxide zinc film
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the i-ZnO of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit one deck native oxide zinc film at substrate surface.Technological parameter is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is room temperature 35 DEG C, and radio-frequency power is 800W, Ar throughput is 10sccm, O
2throughput is 3sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 8 times.
6) preparation of zinc oxide aluminum film
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the ZnO:Al of 99.99% be target, adopt DC magnetron sputtering process to deposit layer of ZnO at substrate surface: Al film.Technological parameter is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is room temperature 25 DEG C, and direct current power is 1000W, Ar throughput is 15sccm, and the base target speed of travel is 6mm/s, and sedimentation time (reciprocal time of base target) is 10 times.
7) preparation of aluminium top electrode
1. base vacuum: 3.0 × 10
-4pa, gives heater strip 20A electric current, continues 2min; Give heater strip 50A electric current, continue 2min; Give heater strip 80A electric current, continue 2min; Give heater strip 120A electric current, continue 6min.2. after glass pane to be seen is covered completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, cool afterwards.
Accompanying drawing 1 is the schematic diagram of the copper-zinc-tin-sulfur film solar cell device architecture based on polyimide flex substrate
Embodiment 2
Based on the preparation of the copper-zinc-tin-sulfur film solar cell of polyimide flex substrate, its preparation process is as follows:
1) preparation of molybdenum back contact
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the Mo of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit the molybdenum film of one deck high resistant and low-resistance respectively at substrate surface.1. base vacuum: 3.0 × 10
-4pa, operating air pressure is 1Pa, and underlayer temperature is room temperature 25 DEG C, and radio-frequency power is 600W, Ar throughput is 40sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 2 times.2. operating air pressure is 0.1Pa, and underlayer temperature is room temperature 25 DEG C, and radio-frequency power is 1500W, Ar throughput is 15sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 6 times.
2) preparation of copper zinc tin sulfur absorption layer
1. base vacuum is 3.0 × 10
-4pa, underlayer temperature is 500 DEG C, and Cu source temperature is 1200 DEG C, and ZnS source temperature is 1100 DEG C, and Sn source temperature is 1100 DEG C, and S source temperature is 85 DEG C, coevaporation Cu, ZnS, Sn, S tetra-kinds of elements, and evaporation time is 50min;
2. substrate is cooled, keep Sn and S evaporating temperature constant, evaporation Sn and S two kinds of elements, when underlayer temperature is down to 300 DEG C, closes Sn and S evaporation source, then substrate is cooled to room temperature.The film obtained is p-type direct gap semiconductor, custerite structure.By adjusting substrate, each source temperature and steaming the time altogether, control the rich zinc of the poor copper of copper-zinc-tin-sulfur film, wherein Cu/ (Zn+Sn)=0.8-1.0, Zn/Sn=1.0-1.2, S/ (Cu+Zn+Sn) approximates 1.
3) preparation process of sodium fluoride preformed layer film is as follows:
1. base vacuum is 3.0 × 10
-4pa, underlayer temperature is 300 DEG C, and evaporation NaF initialization layer, wherein the temperature of NaF evaporation source is 850 DEG C, and evaporation time is 2min.
2. underlayer temperature is 450 DEG C, anneals under Sn and Se atmosphere, and wherein the temperature of Sn evaporation source is 1100 DEG C, and the temperature of Se evaporation source is 280 DEG C, and annealing time is 5min.
4) preparation of cadmium sulfide buffer layer thin film
1. configure solution, prepare thiocarbamide SC (NH
2)
2solution 1L, concentration is 0.01mol/L; Cadmium acetate (CH
3cOO)
2cd and Ammonium Acetate CH
3cOONH
4mixed solution 1L, wherein cadmium acetate solution concentration is 0.001mol/L, and Ammonium Acetate solubility is 0.003mol/L; Ammoniacal liquor NH
3h
2o solubility is 1.3 × 10
-3mol/L.
2. configure reaction solution 1L, get the various solution configured in the first step; Wherein thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL, ammonia spirit 4.Stir.3. sample is put into beaker, and beaker is put into water-bath.Bath temperature is set to 78 DEG C, and preparation time is 60min.4. after having prepared, by clean for sample deionized water rinsing.
5) preparation of native oxide zinc film
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the i-ZnO of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit one deck native oxide zinc film at substrate surface.Technological parameter is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is room temperature 35 DEG C, and radio-frequency power is 800W, Ar throughput is 10sccm, O
2throughput is 3sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 8 times.
6) preparation of zinc oxide aluminum film
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the ZnO:Al of 99.99% be target, adopt DC magnetron sputtering process to deposit layer of ZnO at substrate surface: Al film.Technological parameter is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is room temperature 25 DEG C, and direct current power is 1000W, Ar throughput is 15sccm, and the base target speed of travel is 6mm/s, and sedimentation time (reciprocal time of base target) is 10 times.
7) preparation of aluminium top electrode
1. base vacuum: 3.0 × 10
-4pa, gives heater strip 20A electric current, continues 2min; Give heater strip 50A electric current, continue 2min; Give heater strip 80A electric current, continue 2min; Give heater strip 120A electric current, continue 6min.2. after glass pane to be seen is covered completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, cool afterwards.
Testing result is identical with embodiment 1.
In sum, the invention provides a kind of preparation scheme based on polyimide flex substrate copper-zinc-tin-sulfur film solar cell device, using the polyimide film of flexibility as substrate, prepare back contact, copper zinc tin sulfur absorption layer, cadmium sulfide resilient coating, transparent window layer and aluminium top electrode successively on its surface.These preparation method's process conditions are convenient and easy, are conducive to applying on a large scale, especially in space and special occasions, have extremely important application prospect.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (3)
1. the preparation method of the copper-zinc-tin-sulfur film solar cell device of a polyimide flex substrate, it is characterized in that: sodium fluoride preformed layer and copper zinc tin sulfur absorption layer adopt coevaporation film preparing system, mix the preparation technology of sodium after application high temperature one step coevaporation, sodium fluoride preformed layer is grown on copper zinc tin sulfur absorption layer.
2. the preparation method of sodium fluoride preformed layer film according to claim 1, is characterized in that:
1. base vacuum is 3.0 × 10
-4pa, underlayer temperature is 200-300 DEG C, evaporation NaF initialization layer, and wherein the temperature of NaF evaporation source is 800-850 DEG C, and evaporation time is 1-2min;
2. underlayer temperature is 400-450 DEG C, anneals under Sn and Se atmosphere, and wherein the temperature of Sn evaporation source is the temperature of 1000-1100 DEG C, Se evaporation source is 240-280 DEG C, and annealing time is 5min.
3. the preparation method of sodium fluoride preformed layer film according to claim 2, it is characterized in that: preferred, underlayer temperature is 300 DEG C, the temperature of NaF evaporation source is 850 DEG C, evaporation time is 2min, after underlayer temperature is adjusted to 450 DEG C, the temperature of Sn evaporation source is 1100 DEG C, the temperature of Se evaporation source is 280 DEG C, and annealing time is 5min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105679881A (en) * | 2016-03-03 | 2016-06-15 | 上海大学 | Preparation method of copper-indium-sulfur thin-film solar cell |
| CN105895735A (en) * | 2016-02-29 | 2016-08-24 | 云南师范大学 | Method for preparing CZTS (copper zinc tin sulfide) thin-film solar cell through zinc oxide target sputtering |
-
2014
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105895735A (en) * | 2016-02-29 | 2016-08-24 | 云南师范大学 | Method for preparing CZTS (copper zinc tin sulfide) thin-film solar cell through zinc oxide target sputtering |
| CN105679881A (en) * | 2016-03-03 | 2016-06-15 | 上海大学 | Preparation method of copper-indium-sulfur thin-film solar cell |
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