CN103258896A - Manufacturing technology of soft CIGS thin film solar cell absorbing layer - Google Patents
Manufacturing technology of soft CIGS thin film solar cell absorbing layer Download PDFInfo
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- CN103258896A CN103258896A CN2012100358065A CN201210035806A CN103258896A CN 103258896 A CN103258896 A CN 103258896A CN 2012100358065 A CN2012100358065 A CN 2012100358065A CN 201210035806 A CN201210035806 A CN 201210035806A CN 103258896 A CN103258896 A CN 103258896A
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- preparation
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- 239000010409 thin film Substances 0.000 title claims abstract description 19
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 10
- 239000010935 stainless steel Substances 0.000 claims abstract description 10
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 29
- 239000010408 film Substances 0.000 claims description 19
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 238000009834 vaporization Methods 0.000 claims 1
- 230000008016 vaporization Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000010549 co-Evaporation Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000011669 selenium Substances 0.000 description 20
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 240000002329 Inga feuillei Species 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
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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
- H01L31/036—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
- H01L31/03926—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 comprising a flexible substrate
- H01L31/03928—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 comprising a flexible substrate including AIBIIICVI compound, e.g. CIS, CIGS deposited on metal or polymer foils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses manufacturing technology of a soft CIGS thin film solar cell absorbing layer. Reel-to-reel production technology is utilized, and stainless steel with the thickness of 25 microns to 100 microns is taken as a substrate. Firstly, a back electrode molybdenum layer is deposited on the substrate, and secondly, a three-step co-evaporation method is utilized for depositing a CIGS absorbing layer. In the first step, when the temperature of the substrate is 300 DEG C to 400 DEG C, elements of In, Ga and Se are evaporated together; in the second step, when the temperature of the substrate is 550 DEG C to 580 DEG C, elements of Cu and Se are evaporated together till a thin film is rich in copper; in the third step, when the temperature of the substrate is 550 DEG C to 580 DEG C, elements of In, Ga and Se are evaporated together, and a CIGS thin film meeting a chemical measuring ratio is finally obtained. Mass industrialized production of CIGS solar cells is achieved with the reel-to-reel production technology, and the soft CIGS solar cells which are good in conversion efficiency are manufactured with the manufacturing technology of the soft CIGS thin film solar cell absorbing layer.
Description
Technical field
The present invention is a kind of preparation technology of flexible CIGS thin-film solar cell absorbed layer, belongs to the photoelectric cell field, more precisely belongs to the photovoltaic solar field of batteries.
Background technology
As the solar cell of clear energy sources develop rapidly in recent years thin-film solar cells because of have cost low, can be mass-produced and be easy to the developing direction that advantage such as integrated will become following solar cell.Wherein copper-indium-galliun-selenium film solar cell has the high absorption coefficient of light, high transformation efficiency, adjustable energy gap, high stability, stronger advantages such as capability of resistance to radiation, be considered to third generation solar cell main material (first generation monocrystalline silicon, second generation polysilicon, amorphous silicon), and existing procucts enter solar cell market.
The highest transformation efficiency of small sample CIGS thin-film solar cells reaches 19.9% in March, 2008, adopts the evaporation preparation of three steps by U.S. regenerative resource laboratory.At present, the conversion efficiency peak of CIGS class solar cell be German ZSW in August, 2010 announce 20.3% but its area has only 0.5cm
2Because Copper Indium Gallium Selenide solar cell element proportioning is difficult to control, uniformity of film is difficult to characteristics such as realization, large-area CIGS thin film solar cell prepares that difficulty is very big, conversion efficiency is on the low side and manufacturing equipment is expensive.
Summary of the invention
The present invention is a kind of preparation technology of flexible CIGS thin-film solar cell absorbed layer.Utilize the preparation method of volume to volume, can realize the production in enormous quantities of CIGS thin-film solar cell.Adopt described preparation method can improve the stability of large tracts of land CIGS thin film preparation process and the equal and property of film.Adopt the method for winding type, by backrush and rolling combination, utilize the method for three step coevaporations, the rate of finished products height of the film quality height of preparation, good uniformity, battery is the optimal path of industrial mass production.
The present invention is a kind of preparation technology of flexible CIGS thin-film solar cell absorbed layer.At first at the bottom of flexible stainless steel lining, utilize magnetically controlled sputter method sputter separator chromium and bottom electrode layer molybdenum.Adopt the technology of volume to volume then, utilize the method evaporation absorbed layer CIGS of three step coevaporations.
The preparation technology of flexible CIGS thin-film solar cell absorbed layer.Three-step approach may further comprise the steps:
At first, when 300～400 ℃ of underlayer temperatures, coevaporation In, Ga and Se element form (In
1-xGa
x)
2Se
3Initialization layer, element ratio is that Se/ (In+Ga) flow-rate ratio is greater than 3 in the preparation process.
(In，Ga)+Se→(In
1-xGa
x)
2Se
3
Secondly, when 550～580 ℃ of underlayer temperatures, coevaporation Cu and Se element adopt constant power heated substrate, finish this and go on foot in preparation when substrate temperature has quick decline, can form the CIGS film of rich copper.
(In
1-xGa
x)
2Se
3+Cu+Se→Cu(InGa)Se
After the ratio of component of Cu and Se reaches the amount that generates CIGS, continue deposition Cu and Se, when temperature is higher than 523 °, CuxSe exists with liquid form, it has stronger thermal radiation, make the thermal radiation of substrate greater than absorption, cause underlayer temperature to descend fast, therefore can be with substrate fast cooling point as second end point that goes on foot.
At last, keep the temperature that sinks to the bottom in second step, evaporate In, Ga, Se element at the film of rich a little copper, form the film of rich In at film surface, and finally obtain meeting the CuIn of required stoichiometric proportion
1-xGa
xSe
2Film.
Description of drawings
Fig. 1 is preparation technology's schematic diagram of a kind of flexible CIGS thin-film solar cell absorbed layer of the present invention.Wherein: substrate heater 1, baffle plate 2, vacuum pump 3, inner cover 4, device housings 5, stainless steel lining tail band 6.
Fig. 2 is for scheming in the scanning electron microscopy (SEM) that with the stainless steel is the CIGS solar cell of substrate preparation.
Embodiment
For further understanding the feasibility of aspect of the present invention characteristics, usability and industrial mass production, enumerate embodiment now, and conjunction with figs. is described in detail as follows:
At first at the bottom of the thick flexible stainless steel lining of 25～100 μ m, utilize magnetically controlled sputter method sputter separator chromium and bottom electrode layer molybdenum.Adopt the technology of volume to volume then, utilize the method evaporation absorbed layer CIGS of three step coevaporations.The first step: when 300～400 ℃ of underlayer temperatures, coevaporation In, Ga and Se element form (In
1-xGa
x)
2Se
3Initialization layer, element ratio is that Se/ (In+Ga) flow-rate ratio is greater than 3 in the preparation process.Second step: when 550～580 ℃ of underlayer temperatures, coevaporation Cu and Se element adopt constant power heated substrate, finish this and go on foot in preparation when substrate temperature has quick decline, can form the CIGS film of rich copper.The 3rd step: keep the temperature that sinks to the bottom in second step, evaporate In, Ga, Se element at the film of rich a little copper, form the film of rich In at film surface, and finally obtain near stoichiometric proportion CuIn
07Ga
03Se
2The CIGS film
In the first step, stainless-steel roll 6 is by accurate electrode control rate, by the fixed-direction uniform motion.
In second one, stainless-steel roll carries out the backrush sputter, round about motion.
In the 3rd step, stainless-steel roll backrush campaign again realizes that finally three step coevaporations satisfy the CIGS film of stoichiometric proportion.
Claims (8)
1. the preparation technology of a flexible CIGS thin-film solar cell absorbed layer, it is characterized in that: utilizing the production technology of volume to volume, is substrate deposition back electrode molybdenum layer with the stainless steel, utilizes the method deposition CIGS absorbed layer of three-step approach coevaporation then.
2. preparation method according to claim 1, it is characterized in that: the substrate of flexible CIGS thin-film solar cell is the thick stainless steel bands of 25～100 μ m.
3. preparation method according to claim 1 is characterized in that: the preparation form adopts the plated film mode of volume to volume (Roll-To-Roll), and the technology of this winding type is to realize the optimal path of large area film, production in enormous quantities.
4. preparation method according to claim 3, it is characterized in that: it is wide that the thin film solar cell width of preparation can be 300～100mm, the long 500～1000m of winding.
5. preparation method according to claim 1, it is characterized in that: the initial pressure of vaporization chamber is 2 * 10
-4Pa.
6. preparation method according to claim 1 is characterized in that: three-step approach is adopted in the preparation of absorbed layer, specifically comprises following processing step:
(1) when 300～400 ℃ of underlayer temperatures, coevaporation In, Ga and Se element, evaporation time are 15～25 minutes.
(2) when 550～580 ℃ of underlayer temperatures, coevaporation Cu and Se element finish when the rich copper of film.
(3) when 550～580 ℃ of underlayer temperatures, coevaporation In, Ga and Se element finally are met the CIGS film of stoichiometric proportion.
7. preparation method according to claim 1 is characterized in that: the thickness of the CIGS absorbed layer of final preparation is 1.5～2.5 μ m.
8. preparation method according to claim 1, it is characterized in that: the hull cell stoichiometric proportion of preparation is near CuIn
1-xGa
xSe
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100358065A CN103258896A (en) | 2012-02-17 | 2012-02-17 | Manufacturing technology of soft CIGS thin film solar cell absorbing layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100358065A CN103258896A (en) | 2012-02-17 | 2012-02-17 | Manufacturing technology of soft CIGS thin film solar cell absorbing layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103258896A true CN103258896A (en) | 2013-08-21 |
Family
ID=48962708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100358065A Pending CN103258896A (en) | 2012-02-17 | 2012-02-17 | Manufacturing technology of soft CIGS thin film solar cell absorbing layer |
Country Status (1)
| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104011879A (en) * | 2012-07-13 | 2014-08-27 | 韩国Energy技术硏究院 | Method for forming cigs light absorption layer for solar cell and cigs solar cell |
| CN104377273A (en) * | 2014-11-14 | 2015-02-25 | 厦门惟华光能有限公司 | Roll-to-roll production equipment and method for perovskite thin film solar cell assembly |
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|---|---|---|---|---|
| US20040063320A1 (en) * | 2002-09-30 | 2004-04-01 | Hollars Dennis R. | Manufacturing apparatus and method for large-scale production of thin-film solar cells |
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| CN101165923A (en) * | 2006-10-19 | 2008-04-23 | 中国电子科技集团公司第十八研究所 | Flexible copper-indium-gallium-selenium film solar cell and its preparation method |
| CN101908583A (en) * | 2010-07-26 | 2010-12-08 | 中国电子科技集团公司第十八研究所 | Preparation method of CIGS (Copper, Indium, Gallium and Selenide) thin film solar cell window layer |
| CN102201456A (en) * | 2011-03-30 | 2011-09-28 | 株洲永盛电池材料有限公司 | Flexible metal substrate connected with back electrode of solar battery and fabrication method thereof |
-
2012
- 2012-02-17 CN CN2012100358065A patent/CN103258896A/en active Pending
Patent Citations (5)
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| US20040063320A1 (en) * | 2002-09-30 | 2004-04-01 | Hollars Dennis R. | Manufacturing apparatus and method for large-scale production of thin-film solar cells |
| CN1836338A (en) * | 2003-08-12 | 2006-09-20 | 山特维克知识产权股份有限公司 | New metal strip product |
| CN101165923A (en) * | 2006-10-19 | 2008-04-23 | 中国电子科技集团公司第十八研究所 | Flexible copper-indium-gallium-selenium film solar cell and its preparation method |
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| Title |
|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104011879A (en) * | 2012-07-13 | 2014-08-27 | 韩国Energy技术硏究院 | Method for forming cigs light absorption layer for solar cell and cigs solar cell |
| CN104011879B (en) * | 2012-07-13 | 2016-06-22 | 韩国Energy技术硏究院 | Form method and the CIGS solaode of the CIGS light absorbing zone for solaode |
| CN104377273A (en) * | 2014-11-14 | 2015-02-25 | 厦门惟华光能有限公司 | Roll-to-roll production equipment and method for perovskite thin film solar cell assembly |
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Application publication date: 20130821 |