CN105810764A - Method for preparing photoelectric absorption and conversion layers of copper, indium, gallium and selenium thin film solar cells - Google Patents
Method for preparing photoelectric absorption and conversion layers of copper, indium, gallium and selenium thin film solar cells Download PDFInfo
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- CN105810764A CN105810764A CN201610410939.4A CN201610410939A CN105810764A CN 105810764 A CN105810764 A CN 105810764A CN 201610410939 A CN201610410939 A CN 201610410939A CN 105810764 A CN105810764 A CN 105810764A
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- 239000010409 thin film Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000011669 selenium Substances 0.000 title claims abstract description 42
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 40
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 27
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 24
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 24
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 17
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 21
- 239000010949 copper Substances 0.000 title abstract description 21
- 229910052802 copper Inorganic materials 0.000 title abstract description 19
- 229910000807 Ga alloy Inorganic materials 0.000 claims abstract description 29
- 238000004544 sputter deposition Methods 0.000 claims abstract description 13
- 238000007738 vacuum evaporation Methods 0.000 claims abstract description 6
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 25
- 238000001704 evaporation Methods 0.000 claims description 23
- 230000008020 evaporation Effects 0.000 claims description 21
- 239000010408 film Substances 0.000 claims description 18
- 229940065287 selenium compound Drugs 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000000427 thin-film deposition Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 abstract description 7
- 229910000881 Cu alloy Inorganic materials 0.000 abstract 2
- 238000005922 selenation reaction Methods 0.000 abstract 2
- 238000010549 co-Evaporation Methods 0.000 abstract 1
- 239000007888 film coating Substances 0.000 abstract 1
- 238000009501 film coating Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910001370 Se alloy Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000058 selane Inorganic materials 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
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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
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- 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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- 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
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses a method for preparing photoelectric absorption and conversion layers of copper, indium, gallium and selenium thin film solar cells.The method sequentially includes basic steps of 1), depositing each copper and gallium alloy thin film by the aid of processes for physically sputtering and depositing thin films under vacuum conditions; 2), carrying out selenation treatment on the copper and gallium alloy thin films in vacuum evaporation film coating selenium steam environments; 3), depositing indium and selenium elements on the thin films by the aid of vacuum co-evaporation processes after the thin films are subjected to selenation treatment; 4), depositing a small quantity of gallium on the thin films by the aid of vacuum evaporation processes to regulate electric properties of the photoelectric absorption and conversion layers of the copper, indium, gallium and selenium thin film solar cells.
Description
Technical field
The present invention relates to the preparation method that a kind of solar cell photoelectric absorbs conversion layer.
Background technology
Copper-indium-galliun-selenium film solar cell is a kind of efficient thin-film solar cell, the photoelectric absorption conversion layer of this solaode is the compound semiconductor film four kinds elementary composition by copper, indium, gallium and selenium, and the existing method preparing this solar cell photoelectric absorption conversion layer has coevaporation method and sputtering and selenization technique method two ways.
nullCoevaporation method prepares the method for copper-indium-gallium-selenium compound semiconductive thin film: by copper、Indium、Gallium、Four kinds of solid matters of selenium are individually positioned in each independent evaporation source，Each independent evaporation source is heated separately the solid matter that can make to be placed in and is melted on the temperature of liquid，The evaporation source wherein placing copper needs heating to 1300 DEG C to 1400 DEG C，The evaporation source placing indium needs heating to 1000 DEG C to 1100 DEG C，The evaporation source placing gallium needs heating to 1150 DEG C to 1250 DEG C，The evaporation source placing selenium needs heating to 300 DEG C to 350 DEG C，After each independent evaporation source reaches above respective temperature，The solid matter being placed in is melted into the liquid of molten condition and produces the steam containing respective element，The steam of various elements arrives the substrate surface being heated to 500 DEG C～600 DEG C in vacuum chamber、And it is attached thereto，There is chemical reaction on the surface of a substrate in various elements，Ultimately form copper-indium-gallium-selenium compound semiconductive thin film.The advantage of coevaporation method is: prepared thin film one step completes, and raw materials is less costly；Copper, indium, gallium, the proportioning of four kinds of elements of selenium and graded elemental concentrations can accurately control.The deficiency of coevaporation method is: the evaporating temperature of three kinds of metallic element especially copper is too high, and the design of evaporation source is complicated, manufacture difficulty；Due to copper, indium, gallium evaporating temperature all more than 1000 degrees Celsius and temperature difference relatively big, thus easily interfere between different evaporation sources, cause the difficulty of technology controlling and process and device structure design to strengthen further.
Sputtering and selenization technique method prepare the method for copper-indium-gallium-selenium compound semiconductive thin film be under vacuum conditions by copper, indium, three kinds of element magnetron sputterings of gallium method sputter to the alloy firm forming copper and indium gallium in deposition substrate, then deposition substrate and the copper and indium gallium alloy thin film that deposits above are put into the H of 400 DEG C～500 DEG C2Se(Selenium hydride .) or Se(selenium) selenization 30 to 60 minutes in steam, obtain copper-indium-gallium-selenium compound semiconductive thin film after selenizing.Sputtering and selenization technique method prepares the advantage of copper-indium-gallium-selenium compound semiconductive thin film: equipment is simple, it is easy to manufacture on a large scale.Its deficiency is: the target needed for thin film deposition is expensive；Selenization process is it is generally required to use the hydrogen selenide gas of severe toxicity, it is easy to human body and environmental pollution, and the control of this technique is extremely complex, has raised the manufacturing cost of copper-indium-galliun-selenium film solar cell further.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of copper-indium-galliun-selenium film solar cell photoelectric absorption conversion layer, vacuum evaporatation and sputter coating method are combined by the method, prepare copper-indium-galliun-selenium film solar cell opto-electronic conversion absorbed layer.
For achieving the above object, the present invention adopts below scheme:
1, the preparation method of a kind of copper-indium-galliun-selenium film solar cell photoelectric absorption conversion layer, it is characterised in that have steps of:
A) on substrate, the copper gallium alloy thin film of one layer of 0.2 ~ 2.5 μ m-thick, is sputtered by the method for vacuum sputtering；
B), the substrate having sputtered copper gallium alloy thin film is positioned over 500 ~ 600 DEG C rich in the environment of selenium steam, copper gallium alloy thin film is carried out selenization；
C), by the substrate after selenization it is placed in the coevaporation vacuum chamber being provided with indium evaporation source and selenium evaporation source, by indium and selenium hydatogenesis to copper gallium alloy thin film at 500 ~ 600 DEG C, forms copper-indium-gallium-selenium compound semiconductive thin film；
D), substrate and copper-indium-gallium-selenium compound semiconductive thin film thereon are placed in the vacuum evaporation chamber being provided with gallium evaporation source, the gallium that copper-indium-gallium-selenium compound semiconductive thin film deposition is a small amount of.
Additionally, as making the preferred of copper-indium-galliun-selenium film solar cell assembly, after above-mentioned a) step copper gallium alloy thin film is formed, by the method for laser scribing, copper gallium alloy thin film and the substrate surface that is in contact with it are delineated together, to cook up each sub-solaode of solaode.
Above scheme is adopted to prepare having the active effect that of photoelectric absorption conversion layer
1, above-mentioned a) step utilizes sputtering vacuum deposition copper gallium alloy thin film, copper gallium element is provided for copper-indium-gallium-selenium alloy thin film, make later use coevaporation method only need to evaporate indium, gallium and selenium element, avoid the evaporation of copper, thus avoiding technique and equipment complexity that evaporation copper brings.
2, above-mentioned b), c) step advantage of the method method of preparing CIGS thin-film relative to sputtering and selenization technique method of selenization copper gallium alloy thin film and deposition indium, gallium element in selenium steam ambient be in that, the atomic number ratio of copper in copper-indium-gallium-selenium alloy thin film, indium, gallium and four kinds of elements of selenium is easier to accurate control, and can be obtained the copper-indium-gallium-selenium alloy thin film of required different atomic concentrations distribution by the adjustment of technique.
The inventive method is reasonable, be beneficial to large-scale production, given full play to coevaporation method prepare copper indium gallium selenium solar cell can accurately control element ratio thus obtaining more high conversion efficiency and the simple advantage of sputtering method device structure, the present invention can convenient utilization and extention aborning, it is thus achieved that the copper-indium-galliun-selenium film solar cell product of high performance-price ratio.
Accompanying drawing explanation
Fig. 1 is the procedure of processing schematic diagram of one embodiment of the invention.
Detailed description of the invention
The present invention is further illustrated below in conjunction with embodiment and accompanying drawing.
Embodiment
First selecting the substrate shown in Fig. 1, this substrate includes a piece of board-like material 01 having flat surface and the one layer of molybdenum film 02 deposited on board-like material.As manufacturing the preferred of thin-film solar cells, board-like material 01 can be plate glass or treated corrosion resistant plate or treated polyimide plate.Above-described substrate is a kind of existing structure.After substrate has selected, implement step as follows:
1, on substrate, the copper gallium alloy thin film of one layer of 0.2 ~ 2.5 μ m-thick is sputtered by the method for vacuum sputtering.Concrete way is, the above substrate is positioned in the vacuum sputtering chamber being provided with copper gallium alloy target, the mode utilizing sputter deposition thin film deposits one layer of copper gallium alloy thin film, copper and two kinds of elements of gallium of described copper gallium alloy thin film come from same copper gallium alloy target, and copper and the gallium element atomic quantity ratio of copper gallium alloy target are 2 ~ 8.After this step completes, copper gallium alloy thin film 03 is deposited on molybdenum film 02.
2, the substrate having sputtered copper gallium alloy thin film is positioned in the environment rich in selenium steam of 500 ~ 600 DEG C, copper gallium alloy thin film is carried out selenization.The selenization time is 20 ~ 60 minutes.As preferably, described selenization can carry out in the vacuum evaporation chamber that placed selenium evaporation source.
3, the substrate after selenization and copper gallium thin film thereon are placed in the coevaporation vacuum chamber being provided with indium evaporation source and selenium evaporation source, by on indium and selenium hydatogenesis to copper gallium alloy thin film at 500 ~ 600 DEG C, form copper-indium-gallium-selenium compound semiconductive thin film 04.In the process of indium and selenium hydatogenesis, copper, gallium, indium, four kinds of elements of selenium inter-diffusion reaction simultaneously, form copper-indium-gallium-selenium compound semiconductive thin film 04.
4, after above-mentioned indium and selenium hydatogenesis, again substrate and copper-indium-gallium-selenium compound semiconductive thin film 04 thereon are placed in the vacuum evaporation chamber being provided with gallium evaporation source, the gallium 05 that copper-indium-gallium-selenium compound semiconductive thin film deposition is a small amount of, the deposit thickness of described gallium is 5 ~ 50 nanometers.It is intended that regulate the electric property of copper-indium-galliun-selenium film solar cell photoelectric absorption conversion layer, improve the efficiency of copper-indium-galliun-selenium film solar cell.
Additionally, as making the preferred of copper-indium-galliun-selenium film solar cell assembly, after above-mentioned 1 step copper gallium alloy thin film is formed, by the method for laser scribing, copper gallium alloy thin film and substrate surface both molybdenum films of being in contact with it are delineated together, to cook up each sub-solaode of copper-indium-galliun-selenium film solar cell.The purpose of these means is in that, reduces the leakage current of solar photovoltaic assembly.Copper-indium-gallium-selenium alloy thin film is just divided the way come by the method because relative to traditional fabrication copper indium gallium selenium solar photovoltaic module after second time line, copper gallium is just divided when first time delineation and comes by the said method described in patent of the present invention so that on the substrate of dashed part, the leakage current of remaining copper element contribution is less.
Claims (2)
1. the preparation method of a copper-indium-galliun-selenium film solar cell photoelectric absorption conversion layer, it is characterised in that have steps of:
A) on substrate, the copper gallium alloy thin film of one layer of 0.2～2.5 μ m-thick, is sputtered by the method for vacuum sputtering；
B), the substrate having sputtered copper gallium alloy thin film is positioned over 500～600 DEG C rich in the environment of selenium steam, copper gallium alloy thin film is carried out selenization；
C), by the substrate after selenization it is placed in the coevaporation vacuum chamber being provided with indium evaporation source and selenium evaporation source, by indium and selenium hydatogenesis to copper gallium alloy thin film at 500～600 DEG C, forms copper-indium-gallium-selenium compound semiconductive thin film；
D), substrate and copper-indium-gallium-selenium compound semiconductive thin film thereon are placed in the vacuum evaporation chamber being provided with gallium evaporation source, the gallium that copper-indium-gallium-selenium compound semiconductive thin film deposition is a small amount of.
2. the preparation method of copper-indium-galliun-selenium film solar cell photoelectric absorption conversion layer according to claim 1, it is characterized in that: after above-mentioned a) step copper gallium alloy thin film is formed, by the method for laser scribing, copper gallium alloy thin film and the substrate surface that is in contact with it are delineated together, to cook up each sub-solaode of solaode.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116497330A (en) * | 2023-04-28 | 2023-07-28 | 华中科技大学 | High-strength and high-toughness titanium alloy and magnetron sputtering-based titanium alloy component screening method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116497330A (en) * | 2023-04-28 | 2023-07-28 | 华中科技大学 | High-strength and high-toughness titanium alloy and magnetron sputtering-based titanium alloy component screening method |
| CN116497330B (en) * | 2023-04-28 | 2024-01-05 | 华中科技大学 | High-strength and high-toughness titanium alloy and magnetron sputtering-based titanium alloy component screening method |
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