CN103872154B - A kind of containing sodium molybdenum film and its preparation method and application - Google Patents
A kind of containing sodium molybdenum film and its preparation method and application Download PDFInfo
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- CN103872154B CN103872154B CN201410123303.2A CN201410123303A CN103872154B CN 103872154 B CN103872154 B CN 103872154B CN 201410123303 A CN201410123303 A CN 201410123303A CN 103872154 B CN103872154 B CN 103872154B
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- molybdenum
- sodium
- molybdenum layer
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- pure
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- QMXBEONRRWKBHZ-UHFFFAOYSA-N [Na][Mo] Chemical compound [Na][Mo] QMXBEONRRWKBHZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 51
- 239000011733 molybdenum Substances 0.000 claims abstract description 51
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011734 sodium Substances 0.000 claims abstract description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 18
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 8
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 claims abstract description 7
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 4
- 239000010959 steel Substances 0.000 claims abstract description 4
- 238000004544 sputter deposition Methods 0.000 claims description 29
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000013077 target material Substances 0.000 claims description 8
- 238000010276 construction Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 2
- 239000011669 selenium Substances 0.000 abstract description 5
- 229910052711 selenium Inorganic materials 0.000 abstract description 5
- 238000010348 incorporation Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 28
- 239000010409 thin film Substances 0.000 description 6
- 150000002751 molybdenum Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar 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
- H01L31/0248—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
- H01L31/036—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 their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03923—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
-
- 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
- H01L31/06—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 characterised by potential barriers
- H01L31/072—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 characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0749—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 characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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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
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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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Abstract
The invention discloses a kind of containing sodium molybdenum film and its preparation method and application, this contain sodium molybdenum film include the most successively thick for 10nm 1um the first pure molybdenum layer, 10nm 1um thick containing sodium molybdenum layer, the second thick for 100nm 2um pure molybdenum layer and substrate, the wherein Na content 1 20% [at] containing sodium molybdenum layer, Mo content 80 99% [at], the molybdenum content of the first pure molybdenum layer and the second pure molybdenum layer is 99.9 99.9999% [at].Compared with prior art, present invention molybdenum film in sodium meets the requirement of copper-indium-galliun-selenium film solar cell at the aspect such as adhesiveness, electric conductivity, may be used for preparing the copper-indium-galliun-selenium film solar cell of high-quality；The present invention can prepare and mixes sodium molybdenum film containing appropriate sodium element, it is ensured that the incorporation of the sodium element positive influences relative maximum to the efficiency of copper indium gallium selenium solar cell；The molybdenum film containing sodium prepared by the present invention is applied widely, can commonly use substrate based on copper-indium-galliun-selenium film solar cells such as glass, PI, rustless steel or potteries and be prepared.
Description
Technical field
Present invention relates particularly to a kind of containing sodium molybdenum film and its preparation method and application.
Background technology
After entering 21 century, human society is faced with more acute Energy situation, with oil, coal
Traditional fossil energy reserves for representing reduce day by day, and the problems such as the environmental pollution that it brings are the tightest
Weight, the requirement that human society finds alternative energy source safe and clean, efficient is extremely urgent.At high speed development
All kinds of new forms of energy in the middle of, solar energy is safe and pollution-free with it, inexhaustible, without geographical restrictions etc.
Advantage, becomes a member important in New Energy Industry, and will certainly will become the energy of the mankind in the near future
In the domain of source irreplaceable one piece.
Wherein, CIGS (CIGS) solaode has multinomial advantage, as high in efficiency, stability
Good, cost is relatively low, can development space big etc., there is vast potential for future development.The CIGS of laboratory
The present conversion efficiency of solaode has been over 20%, in obtaining the making of device of world record,
Sodium plays vital role.Generally, high efficiency CIGS battery sputters on SLG glass,
Under high growth temperature (about 600 DEG C), sodium is diffused into CIGS thin film by molybdenum back electrode from glass
In, this makes the efficiency of solaode be largely dependent upon the quality of molybdenum back electrode, but existing skill
Molybdenum back electrode in art cannot meet such demand.
Summary of the invention
It is an object of the invention to overcome prior art defect, it is provided that a kind of molybdenum film in sodium.
Another object of the present invention is to provide the above-mentioned preparation method containing sodium molybdenum film.
It is still another object of the present invention to provide the above-mentioned application containing sodium molybdenum film.
The concrete technical scheme of the present invention is as follows:
A kind of molybdenum film in sodium, this contains sodium molybdenum film and includes the first thick pure molybdenum of 10nm-1um the most successively
Layer, 10nm-1um thick containing sodium molybdenum layer, the second thick for 100nm-2um pure molybdenum layer and substrate, Qi Zhonghan
Na content 1-20% [at] of sodium molybdenum layer, Mo content 80-99% [at], the first pure molybdenum layer and the second pure molybdenum
The molybdenum content of layer is 99.9-99.9999% [at].
In a preferred embodiment of the invention, include that thick for 100nm first is pure the most successively
Molybdenum layer, 80nm thick containing sodium molybdenum layer, the second thick for 800nm pure molybdenum layer and substrate.
In a preferred embodiment of the invention, the material of described substrate is glass, PI, rustless steel
Or pottery.
A kind of above-mentioned preparation method containing sodium molybdenum film, comprises the steps:
(1) described first pure molybdenum layer is prepared on the substrate with direct current magnetron sputtering process；
(2) on described first pure molybdenum layer, the described molybdenum layer in sodium is prepared with direct current magnetron sputtering process；
(3) with direct current magnetron sputtering process described containing preparing described second pure molybdenum layer on sodium molybdenum layer.
The application in preparing copper indium gallium selenium solar cell of a kind of above-mentioned molybdenum film containing sodium.
The invention has the beneficial effects as follows:
1, compared with prior art, present invention molybdenum film in sodium meets copper and indium at the aspect such as adhesiveness, electric conductivity
The requirement of gallium selenium thin-film solar cells, may be used for preparing the copper-indium-galliun-selenium film solar cell of high-quality；
2, the present invention can prepare and mixes sodium molybdenum film containing appropriate sodium element, it is ensured that the incorporation pair of sodium element
The positive influences relative maximum of the efficiency of copper indium gallium selenium solar cell；
3, the molybdenum film containing sodium that prepared by the present invention is applied widely, can be based on glass, PI, rustless steel or pottery
Commonly use substrate Deng copper-indium-galliun-selenium film solar cell to be prepared.
Accompanying drawing explanation
Fig. 1 is the I-V characteristic curve of the copper indium gallium selenium solar cell of embodiment 1 preparation；
Fig. 2 is the X-ray diffraction result figure of the CIGS thin-film of embodiment 2 preparation；
Fig. 3 is the stereoscan photograph on the surface of the CIGS thin-film of embodiment 2 preparation；
Fig. 4 is the stereoscan photograph of the cross section of the CIGS thin-film of embodiment 2 preparation.
Detailed description of the invention
Combine accompanying drawing below by way of detailed description of the invention technical scheme is further detailed
And description.
Embodiment 1
Utilize direct current magnetron sputtering process, pure molybdenum film thick for one layer of 800nm of sputtering on the glass substrate, sputtering
Molybdenum target material Mo content used is 99.95% [at], target diameter 50.8mm, thickness 3.175mm, this molybdenum
Film uses laminated construction, and the sputtering power of employing is 180W, deposits 4min under the conditions of sputtering pressure 8mTorr,
36min is deposited under the conditions of 5mTorr；Recycling one layer of 80nm of Deposited By Dc Magnetron Sputtering thick containing sodium molybdenum film,
The sodium molybdenum target material of mixing used is Na content 10% [at], Mo content 90% [at], target diameter 50.8mm,
Thickness 6.35mm, the sputtering power of employing is 100W, and sputtering pressure is 100W, sputtering time 10min；
Sputtering the thick pure molybdenum film of one layer of 100nm again, sputtering molybdenum target material Mo content used is 99.95% [at], target
Material diameter 50.8mm, thickness 3.175mm, this molybdenum film uses laminated construction, and the sputtering power of employing is 180W,
5min is deposited under the conditions of sputtering pressure 5mTorr.Above step is utilized to obtain containing sodium molybdenum film, then containing sodium
After using on molybdenum film, selenizing method prepares CuInGaSe absorbed layer, and immersion method prepares cadmium sulfide cushion, radio frequency
Magnetron sputtering method prepares ZnO Window layer, and direct current magnetron sputtering process prepares gate electrode, obtains CIGS too
Sun can battery.
Obtained the I-V characteristic curve (as shown in Figure 1) of battery by mensuration, be calculated solaode
Efficiency, with use pure molybdenum electrode compared with copper indium gallium selenium solar cell prepared by batch, improved efficiency
16.5%.
Embodiment 2
Utilize direct current magnetron sputtering process, pure molybdenum film thick for one layer of 800nm of sputtering on the glass substrate, this molybdenum
Film uses laminated construction, and the sputtering power of employing is 180W, deposits 4min under the conditions of sputtering pressure 8mTorr,
36min is deposited under the conditions of 5mTorr；Recycling one layer of 80nm of Deposited By Dc Magnetron Sputtering thick containing sodium molybdenum film,
The sodium molybdenum target material of mixing used is Na content 10% [at], and Mo content 90% [at], the sputtering power of employing is
100W, sputtering pressure is 100W, sputtering time 10min；Sputter the thick pure molybdenum film of one layer of 100nm again,
This molybdenum film uses laminated construction, and the sputtering power of employing is 180W, and sputtering pressure 5mTorr condition is sunk
Long-pending 5min, obtains containing sodium molybdenum film.Again prefabricated containing using magnetron sputtering method to prepare CuGa/In on sodium molybdenum film
Rotating fields, recycles annealing furnace selenizing, obtains CIGS thin-film.
By using X-ray diffraction (XRD) to analyze its crystal structure, such as crystal formation, crystal orientation, crystalline substance
The crystalline qualities (as shown in Figure 2) such as the suffered stress of grain.Scanning electron microscope (SEM) observes them
Surface and cross section (as shown in Figure 3 and Figure 4).
The above, only presently preferred embodiments of the present invention, therefore the present invention can not be limited according to this and implement
Scope, i.e. according to the scope of the claims of the present invention and description made equivalence change with modify, all should be still
In the range of the genus present invention contains.
Claims (2)
1. a molybdenum film in sodium, it is characterized in that: this contain sodium molybdenum film include the most successively thick for 100nm the first pure molybdenum layer, 80nm thick containing sodium molybdenum layer, the second thick for 800nm pure molybdenum layer and substrate, the wherein Na content 10% [at] containing sodium molybdenum layer, Mo content 90% [at], the molybdenum content of the first pure molybdenum layer and the second pure molybdenum layer is 99.9-99.9999% [at], the material of substrate is glass, PI, rustless steel or pottery
Its preparation method comprises the steps:
(1) prepare described first pure molybdenum layer on the substrate with direct current magnetron sputtering process, use stepped construction, sputtering molybdenum target material diameter 50.8mm used, thickness 3.175mm, sputtering power is 180W, deposits 4min under the conditions of sputtering pressure 8mTorr, deposits 36min under the conditions of 5mTorr；
(2) on described first pure molybdenum layer, the described molybdenum layer in sodium is prepared with direct current magnetron sputtering process, mixing sodium molybdenum target material used by sputtering is Na content 10% [at], Mo content 90% [at], diameter 50.8mm, thickness 6.35mm, the sputtering power used is 100W, and sputtering pressure is 100W, sputtering time 10min；
(3) with direct current magnetron sputtering process described containing preparing described second pure molybdenum layer on sodium molybdenum layer, use stepped construction, sputtering used molybdenum target material diameter 50.8mm, thickness 3.175mm, sputtering power is 180W, deposits 5min under the conditions of sputtering pressure 5mTorr.
2. the application in preparing copper indium gallium selenium solar cell of the molybdenum film containing sodium described in a claim 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410123303.2A CN103872154B (en) | 2014-03-28 | 2014-03-28 | A kind of containing sodium molybdenum film and its preparation method and application |
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| CN201410123303.2A CN103872154B (en) | 2014-03-28 | 2014-03-28 | A kind of containing sodium molybdenum film and its preparation method and application |
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| CN103872154B true CN103872154B (en) | 2016-08-17 |
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| CN106558628A (en) * | 2015-09-30 | 2017-04-05 | 常德汉能薄膜太阳能科技有限公司 | A kind of preparation method of CIGS thin film window layer of solar battery |
| CN108914070A (en) * | 2018-06-08 | 2018-11-30 | 研创应用材料（赣州）股份有限公司 | A kind of CIGS titanium electrode aluminium alloy compound target material and preparation method thereof |
| CN110079767B (en) * | 2019-04-26 | 2021-03-19 | 潮州市亿加光电科技有限公司 | Metal Na-doped target material, back electrode layer preparation method and CIGS solar cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101859812A (en) * | 2010-04-30 | 2010-10-13 | 浙江大学 | Method for preparing flexible copper indium gallium selenide thin-film solar cell |
| EP2693496A1 (en) * | 2012-03-12 | 2014-02-05 | Korea Institute of Energy Research | Method for manufacturing cigs thin-film solar cells using substrates not containing na, and solar cell manufactured thereby |
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2014
- 2014-03-28 CN CN201410123303.2A patent/CN103872154B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101859812A (en) * | 2010-04-30 | 2010-10-13 | 浙江大学 | Method for preparing flexible copper indium gallium selenide thin-film solar cell |
| EP2693496A1 (en) * | 2012-03-12 | 2014-02-05 | Korea Institute of Energy Research | Method for manufacturing cigs thin-film solar cells using substrates not containing na, and solar cell manufactured thereby |
Non-Patent Citations (1)
| Title |
|---|
| sodium-doped molybdenum targets for controllable sodium incorporation in CIGS solar cells;Lorelle M.Mansfield et al.;《37th IEEE photovoltaic specialists conference》;20111231;说明书第003636页右栏第2段至第003640页右栏第2段，附图1-8 * |
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