CN102903766A - Cadmium-free copper indium gallium selenium (CIGS) thin-film solar cell and preparation method thereof - Google Patents
Cadmium-free copper indium gallium selenium (CIGS) thin-film solar cell and preparation method thereof Download PDFInfo
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- CN102903766A CN102903766A CN201210390494XA CN201210390494A CN102903766A CN 102903766 A CN102903766 A CN 102903766A CN 201210390494X A CN201210390494X A CN 201210390494XA CN 201210390494 A CN201210390494 A CN 201210390494A CN 102903766 A CN102903766 A CN 102903766A
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Abstract
The invention relates to a cadmium-free copper indium gallium selenium (CIGS) thin-film solar cell. According to the cadmium-free CIGS thin-film solar cell, a structure comprising a metal gate layer, a transparent electrode layer, a buffering layer, a light absorption layer, a back electrode layer and a substrate is adopted; and the intrinsic ZnO window layer in the typical CIGS thin-film solar structure is removed. The invention also provides a full-sputtering preparation method for the cell. According to the cadmium-free CIGS thin-film solar cell and the full-sputtering preparation method, the intrinsic ZnO window layer is removed, so that the technical preparation steps can be simplified, and the producing cost can be reduced.
Description
Technical field
The invention belongs to the photoelectric material technical field of new energies, be specifically related to a kind of cadmium-free copper-indium-gallium-selenium thin-film solar cells and preparation method thereof.
Background technology
Copper Indium Gallium Selenide (CIGS) solar cell is as one of most potential thin-film solar cells, has high absorption coefficient, band gap is adjustable, capability of resistance to radiation is strong, and stable performance, low light level performance are good, low cost and other advantages.Typical structure is multi-layer film structure; from incidence surface; comprise successively: metal gate layers (Al)/transparency conducting layer (AZO)/Window layer (ZnO)/resilient coating (CdS)/light absorbing zone (CIGS)/dorsum electrode layer (Mo)/glass; wherein coevaporation method or sputtering and selenization technique method are mainly adopted in the preparation of CIGS absorbed layer; such as CN02104073 and CN201110367960; these two kinds of methods have technical process complicated, are difficult to the shortcoming of scale.CdS generally adopts chemical bath deposition method as resilient coating, this exists some shortcomings: (1) Cd is harmful, contaminated environment (2) chemical bath deposition method belongs to wet preparation method, has destroyed and has adopted vacuum deposition method to prepare the integrality of copper-indium-galliun-selenium film solar cell.Therefore people are devoted to the exploitation of dry process cadmium-free copper-indium-gallium-selenium thin film solar resilient coating, prepare the CdS resilient coating as preparing the traditional water-bath sedimentation of zinc sulphide (ZnS) resilient coating replacement with sputtering method among the patent CN201110294472, but this patent still uses intrinsic ZnO as Window layer, technical process is complicated, and production cost is higher.
Summary of the invention
The purpose of this invention is to provide a kind of cadmium-free copper-indium-gallium-selenium thin-film solar cells and preparation method thereof, removed intrinsic ZnO Window layer, simplified the technique preparation process, reduced production cost.
The present invention is achieved through the following technical solutions:
A kind of cadmium-free copper-indium-gallium-selenium thin-film solar cells, it is comprised of transparency conducting layer, resilient coating, light absorbing zone, metal back electrode layer and substrate from top to bottom successively.
Described metal back electrode layer is metal M o layer, and described light absorbing zone is Copper Indium Gallium Selenide (CuIn
xGa
1-xSe
2) film, described resilient coating is the ZnS film, described transparency conducting layer is doped zinc oxide aluminium AZO film.
A kind of cadmium-free copper-indium-gallium-selenium thin-film solar cells adopts full sputtering method, comprises following preparation process:
(1) Mo target, CuIn are installed in the magnetron sputtering cavity
xGa
1-xSe
2Target (0≤x≤1), ZnS target and AZO target, and cleaned soda lime glass substrates is installed, then cavity is evacuated to 1 * 10
-3Below the Pa.At the high-purity Ar gas that passes into 99.999%, using radio-frequency power supply sputter thickness on substrate is the Mo film of 0.5 μ m-1.5 μ m, back electrode as thin-film solar cells, sputtering condition is: substrate temperature is 25-600 ℃, target-substrate distance is 5-10cm, and the flow of Ar gas is 10-100SCCM, and the sputtering pressure of Mo is 1-5mTorr, sputtering power is 100-400W, and corresponding sputtering time is 20-90min.
(2) prepare the Mo layer after, sputter thickness is the CIGS film of 1.5-3 μ m on the soda lime glass substrates of Mo being coated with to use radio-frequency power supply, absorbed layer as thin-film solar cells, sputtering condition is: substrate temperature is 25-600 ℃, target-substrate distance is 5-10cm, and the flow of Ar gas is 10-100SCCM, and sputtering pressure is 0.5-4mTorr, sputtering power is 100-400W, and sputtering time is 1-4h.
(3) prepare cigs layer after, use radio-frequency power supply sputter thickness to be the ZnS film of 30-100nm, resilient coating as thin-film solar cells, sputtering condition is: substrate temperature is 25-600 ℃, target-substrate distance is 5-10cm, and the flow of Ar gas is 10-100SCCM, and sputtering pressure is 1-5mTorr, sputtering power is 100W-400W, and sputtering time is 2-15min.
(4) prepare the ZnS layer after, use radio-frequency power supply sputter thickness to be the AZO film of 500-1000nm, transparency conducting layer as thin-film solar cells, sputtering condition is: substrate temperature is 25-600 ℃, target-substrate distance is 5-10cm, and the flow of Ar gas is 20-100SCCM, and sputtering pressure is 1-4mTorr, sputtering power is 100W-400W, and sputtering time is 10-60min.
(5) cover aluminium lead wire at transparency conducting layer at last, make solar cell.
Al in the described AZO target of step (1)
2O
3Doping ratio is 1.5%-3%.
Technique effect of the present invention is embodied in:
Prior art it has been generally acknowledged that the cadmium-free copper-indium-gallium-selenium thin-film solar cells must include Window layer (intrinsic ZnO), can prevent battery short circuit like this, but it causes whole solar battery process process complicated, and production cost is higher.The present invention has overcome the prejudice of prior art, removed the Window layer (intrinsic ZnO) in the typical Copper Indium Gallium Selenide film solar battery structure, evidence, the battery for preparing is normal steady operation still, and simple in structure, simplified its preparation technology, decrease cost, improved yields.
Description of drawings
Fig. 1 is solar battery structure schematic diagram of the present invention.
Fig. 2 is the section SEM figure of cadmium-free copper-indium-gallium-selenium (CIGS) thin-film solar cells prepared in the invention process case one.
Fig. 3 is the I-V performance diagram of cadmium-free copper-indium-gallium-selenium (CIGS) thin-film solar cells prepared in the invention process case one.
Embodiment
Below by the elaboration of specific embodiment and Fig. 1 ~ 3, improve with significant to further specify substantive distinguishing features of the present invention, but the present invention absolutely not only is confined to embodiment.
Embodiment one
A kind of cadmium-free copper-indium-gallium-selenium thin-film solar cells, preparation process is as follows:
(1) Mo target, CuIn are installed in the magnetron sputtering cavity
0.3Ga
0.7Se
2Target, ZnS target and AZO(Al
2O
3Doping ratio is 2%) target, and cleaned soda lime glass substrates is installed, then cavity is evacuated to 1 * 10
-3Below the Pa.At the high-purity Ar gas that passes into 99.999%, using radio-frequency power supply sputter thickness on substrate is the Mo film of 1.2 μ m, back electrode as thin-film solar cells, sputtering condition is: substrate temperature is 25 ℃, target-substrate distance is 9cm, and the flow of Ar gas is 30SCCM, and the sputtering pressure of Mo is 4mTorr, sputtering power is 300W, and corresponding sputtering time is 60min.
(2) prepare the Mo layer after, sputter thickness is the CIGS film of 2 μ m on the soda lime glass substrates of Mo being coated with to use radio-frequency power supply, absorbed layer as thin-film solar cells, sputtering condition is: substrate temperature is 350 ℃, target-substrate distance is 9cm, and the flow of Ar gas is 30SCCM, and sputtering pressure is 1mTorr, sputtering power is 200W, and sputtering time is 3h.
(3) prepare cigs layer after, use radio-frequency power supply sputter thickness to be the ZnS film of 50nm, resilient coating as thin-film solar cells, sputtering condition is: substrate temperature is 25 ℃, target-substrate distance is 9cm, and the flow of Ar gas is 30SCCM, and sputtering pressure is 3.75mTorr, sputtering power is 100W, and sputtering time is 5min.
(4) prepare the ZnS layer after, use radio-frequency power supply sputter thickness to be the AZO film of 700nm, transparency conducting layer as thin-film solar cells, sputtering condition is: substrate temperature is 25 ℃, target-substrate distance is 9cm, and the flow of Ar gas is 30SCCM, and sputtering pressure is 3mTorr, sputtering power is 200W, and sputtering time is 35min.
(5) cover aluminium lead wire at transparency conducting layer at last, make solar cell.
Fig. 2 is the section SEM photo of the prepared cadmium-free copper-indium-gallium-selenium of the present embodiment (CIGS) thin-film solar cells, and thin film crystallization is in good condition as can be seen from Figure.Fig. 3 is the I-V performance diagram of the prepared cadmium-free copper-indium-gallium-selenium of the present embodiment (CIGS) thin-film solar cells, and the battery open circuit voltage for preparing is 627mV, and short-circuit current density is 15.6mA/cm
2Fill factor, curve factor is 0.37, and electricity conversion is 3.61%.
Embodiment two
(1) Mo target, CuIn are installed in the magnetron sputtering cavity
0.2Ga
0.8Se
2Target, ZnS target and AZO(Al
2O
3Doping ratio is 2%) target, and cleaned soda lime glass substrates is installed, then cavity is evacuated to 1 * 10
-3Below the Pa.At the high-purity Ar gas that passes into 99.999%, using radio-frequency power supply sputter thickness on substrate is the Mo film of 0.5 μ m, back electrode as thin-film solar cells, sputtering condition is: substrate temperature is 25 ℃, target-substrate distance is 10cm, and the flow of Ar gas is 10SCCM, and the sputtering pressure of Mo is 1Torr, sputtering power is 100W, and corresponding sputtering time is 90min.
(2) prepare the Mo layer after, sputter thickness is the CIGS film of 1.5 μ m on the soda lime glass substrates of Mo being coated with to use radio-frequency power supply, absorbed layer as thin-film solar cells, sputtering condition is: substrate temperature is 25 ℃, target-substrate distance is 10cm, and the flow of Ar gas is 10SCCM, and sputtering pressure is 0.5mTorr, sputtering power is 100W, and sputtering time is 4h.
(3) prepare cigs layer after, use radio-frequency power supply sputter thickness to be the ZnS film of 30nm, resilient coating as thin-film solar cells, sputtering condition is: substrate temperature is 25 ℃, target-substrate distance is 10cm, and the flow of Ar gas is 10SCCM, and sputtering pressure is 1Torr, sputtering power is 100W, and sputtering time is 15min.
(4) prepare the ZnS layer after, use radio-frequency power supply sputter thickness to be the AZO film of 500nm, transparency conducting layer as thin-film solar cells, sputtering condition is: substrate temperature is 25 ℃, target-substrate distance is 10cm, and the flow of Ar gas is 10SCCM, and sputtering pressure is 1mTorr, sputtering power is 100W, and sputtering time is 60min.
(5) cover aluminium lead wire at transparency conducting layer at last, make solar cell.
Embodiment three
(1) Mo target, CuIn are installed in the magnetron sputtering cavity
0.4Ga
0.6Se
2Target, ZnS target and AZO(Al
2O
3Doping ratio is 2%) target, and cleaned soda lime glass substrates is installed, then cavity is evacuated to 1 * 10
-3Below the Pa.At the high-purity Ar gas that passes into 99.999%, using radio-frequency power supply sputter thickness on substrate is the Mo film of 1.5 μ m, back electrode as thin-film solar cells, sputtering condition is: substrate temperature is 600 ℃, target-substrate distance is 5cm, and the flow of Ar gas is 100SCCM, and the sputtering pressure of Mo is 5mTorr, sputtering power is 400W, and corresponding sputtering time is 20min.
(2) prepare the Mo layer after, sputter thickness is the CIGS film of 3 μ m on the soda lime glass substrates of Mo being coated with to use radio-frequency power supply, absorbed layer as thin-film solar cells, sputtering condition is: substrate temperature is 600 ℃, target-substrate distance is 5cm, and the flow of Ar gas is 100SCCM, and sputtering pressure is 4mTorr, sputtering power is 400W, and sputtering time is 1h.
(3) prepare cigs layer after, use radio-frequency power supply sputter thickness to be the ZnS film of 100nm, resilient coating as thin-film solar cells, sputtering condition is: substrate temperature is 600 ℃, target-substrate distance is 10cm, and the flow of Ar gas is 100SCCM, and sputtering pressure is 5mTorr, sputtering power is 400W, and sputtering time is 15min.
(4) prepare the ZnS layer after, use radio-frequency power supply sputter thickness to be the AZO film of 1000nm, transparency conducting layer as thin-film solar cells, sputtering condition is: substrate temperature is 600 ℃, target-substrate distance is 10cm, and the flow of Ar gas is 100SCCM, and sputtering pressure is 4mTorr, sputtering power is 400W, and sputtering time is 10min.
(5) cover aluminium lead wire at transparency conducting layer at last, make solar cell.
Above-described embodiment only is better embodiment of the present invention; describe technical conceive of the present invention and essential implementation in detail; be not that protection scope of the present invention is limited; all any simple modification that Spirit Essence is done according to the present invention and equivalent structure transformation or modification all are encompassed within protection scope of the present invention.
Claims (3)
1. a cadmium-free copper-indium-gallium-selenium thin-film solar cells is characterized in that, it is comprised of transparency conducting layer, resilient coating, light absorbing zone, metal back electrode layer and substrate from top to bottom successively.
2. cadmium-free copper-indium-gallium-selenium thin-film solar cells according to claim 1, it is characterized in that, described metal back electrode layer is metal M o layer, and described light absorbing zone is CIGS thin-film, described resilient coating is the ZnS film, and described transparency conducting layer is doped zinc oxide aluminium AZO film.
3. prepare the method for claim 1 or 2 described cadmium-free copper-indium-gallium-selenium thin-film solar cells, be specially:
(1) Mo target, CuIn are installed in the magnetron sputtering cavity
xGa
1-xSe
2Target, ZnS target and AZO target, and cleaned soda lime glass substrates is installed, 0≤x≤1;
(2) the magnetron sputtering cavity is vacuumized, pass into Ar gas, use Mo target sputter Mo film at soda lime glass substrates, as the metal back electrode of thin-film solar cells;
(3) use CuIn at the soda lime glass substrates that is coated with the Mo film
xGa
1-xSe
2Target sputter CIGS film is as the light absorbing zone of thin-film solar cells;
(4) prepare light absorbing zone after, use ZnS target sputter ZnS film, as the resilient coating of thin-film solar cells;
(5) prepare resilient coating after, use AZO target sputter AZO film, as the transparency conducting layer of thin-film solar cells.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474487A (en) * | 2013-09-02 | 2013-12-25 | 深圳先进技术研究院 | Copper-zinc-tin-sulfur solar battery device and preparation method thereof |
| CN105355716A (en) * | 2015-11-18 | 2016-02-24 | 北京四方创能光电科技有限公司 | Method for manufacturing CIGS thin-film solar cell by using dry buffer layer |
| CN105471076A (en) * | 2016-01-20 | 2016-04-06 | 深圳先进技术研究院 | Composite power supply device adopting solar cell and all-solid-state secondary cell |
| CN106129188A (en) * | 2016-09-08 | 2016-11-16 | 京东方科技集团股份有限公司 | Thin-film solar cells and preparation method thereof |
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| US20110220198A1 (en) * | 2010-03-31 | 2011-09-15 | Stion Corporation | Method and Device Utilizing Strained AZO Layer and Interfacial Fermi Level Pinning in Bifacial Thin Film PV Cells |
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| US20110220198A1 (en) * | 2010-03-31 | 2011-09-15 | Stion Corporation | Method and Device Utilizing Strained AZO Layer and Interfacial Fermi Level Pinning in Bifacial Thin Film PV Cells |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474487A (en) * | 2013-09-02 | 2013-12-25 | 深圳先进技术研究院 | Copper-zinc-tin-sulfur solar battery device and preparation method thereof |
| CN105355716A (en) * | 2015-11-18 | 2016-02-24 | 北京四方创能光电科技有限公司 | Method for manufacturing CIGS thin-film solar cell by using dry buffer layer |
| CN105471076A (en) * | 2016-01-20 | 2016-04-06 | 深圳先进技术研究院 | Composite power supply device adopting solar cell and all-solid-state secondary cell |
| CN106129188A (en) * | 2016-09-08 | 2016-11-16 | 京东方科技集团股份有限公司 | Thin-film solar cells and preparation method thereof |
| CN106129188B (en) * | 2016-09-08 | 2017-08-08 | 京东方科技集团股份有限公司 | Thin-film solar cells and preparation method thereof |
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Application publication date: 20130130 |