CN101887921A - CdMnTe (CMT) thin film solar cell and preparation method thereof - Google Patents
CdMnTe (CMT) thin film solar cell and preparation method thereof Download PDFInfo
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- CN101887921A CN101887921A CN201010215756XA CN201010215756A CN101887921A CN 101887921 A CN101887921 A CN 101887921A CN 201010215756X A CN201010215756X A CN 201010215756XA CN 201010215756 A CN201010215756 A CN 201010215756A CN 101887921 A CN101887921 A CN 101887921A
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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
- 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 relates to a CdMnTe (CMT) thin film solar cell and a preparation method thereof, belonging to the field of inorganic nonmetallic device manufacture processes. The CMT thin film solar cell structurally and sequentially comprises transparent conducting glass, CdS, CdMnTe and a back electrode, or the transparent conducting glass, a CMT cell, a CuInSe2 cell and a laminated cell of the back electrode, wherein the preparation method of a CMT thin film comprises the following steps of: depositing a CdMnTe thin film on a substrate by adopting a near space sublimation method; and carrying out high-temperature annealing on the CMT thin film in a cadmium chloride vapor atmosphere by adopting near-space sublimation equipment after the thin film is deposited. The technology for preparing solar cells by adopting the CMT thin films is beneficial to promoting the development of low-cost, high-stability and high-efficiency laminated solar cells.
Description
Technical field
What the present invention relates to is a kind of CdMnTe thin-film solar cells and manufacture method thereof, belongs to the solar cell fabrication process technical field.
Background technology
The world today, human demand to the energy is more and more, yet primary energy such as oil, coal but peter out, the mankind will face more and more severeer energy crisis and environmental crisis.Solar energy power generating obtains develop rapidly in this case.The solar cell product is mainly crystal silicon cell at present, but because the cost problem, the crystal silicon cell generating also is difficult to compete on price with the generating of traditional fossil energy.
Thin film solar cell is low because of the consumption of material in this case, can prepare the large tracts of land assembly and helps the development trend that advantages such as suitability for industrialized production become solar-energy photo-voltaic cell.At present, the unijunction thin-film solar cells of broad research mainly contains three kinds of amorphous silicon, cadmium telluride (CdTe) and Copper Indium Gallium Selenide (CIGS/CIS).The efficient of amorphous silicon unijunction solar cell has surpassed 10% in the laboratory, and the most effective of unijunction cadmium telluride battery reaches 16.5%, unijunction Copper Indium Gallium Selenide battery most effective then near 20%.But the further raising of these unijunction thin-film solar cells efficient exists many material behavior restrictions, technology and preparation difficulty, has in the past decade only improved 1% such as the efficient of CdTe battery.Having more the thin-film solar cells of high efficiency (20-40%) can or tie laminated cell more and realize by binode.In the battery of this structure, absorb the short light of solar spectrum medium wavelength by top cell, bottom cell absorbs the long light of solar spectrum medium wavelength, thereby makes laminated cell can fully absorb sunlight, improves conversion efficiency.Studies show that the binode laminated cell for high conversion efficiency, the desirable energy gap of top cell and bottom cell material should be respectively about 1.7eV and 1.0eV.At present for the top cell material, everybody broad research mainly be CdZnTe (CZT) film, its energy gap can be adjustable continuously between 1.45 (CdTe)～2.26eV (ZnTe) with not coexisting of Zn content.But this material has difficulties in preparation, and when its energy gap was 1.7, the doping of Zn will reach 40%, and (atomic percent, at.%), it was big to add the segregation coefficient of Zn in CdTe, therefore is easy to cause the component of CZT material inhomogeneous.With respect to the CZT film, CdMnTe (CMT) film then has a lot of advantages, regulates than being easier to such as its energy gap, when its energy gap is 1.7, the doping of Mn only needs 10% (at.%), and Mn in CdTe segregation coefficient near 1, thereby material component is even when mixing.Therefore the CMT film can be used as the ideal material of lamination solar cell top battery.Also almost not about the research of CMT thin-film solar cells, the research of this respect has important academic significance and social economic value at present.
Summary of the invention
The purpose of this invention is to provide a kind of semiconductor CdMnTe (CMT) thin-film solar cells and preparation method thereof, this can provide a kind of new material and new technology for the overlapping thin film solar battery of preparation high conversion efficiency.
The present invention is characterized in the CMT film that obtains among the present invention to have composition uniformity and energy gap controllability preferably, this method depositing of thin film speed is fast simultaneously; The solar cell of better performances that adopted the CMT film preparation; With the CMT hull cell is that the laminated film solar of top battery has been realized high conversion efficiency.
For achieving the above object, the present invention adopts following technical scheme and step:
One, CdMnTe film solar battery structure
A kind of CdMnTe thin-film solar cells adopts the CdMnTe film as p type light absorption layer material.Unijunction CdMnTe thin-film solar cells of the present invention adopts following structure: transparent conducting glass/CdS/CdMnTe/ back electrode.Many knot CdMnTe film solar battery structures are: transparent conducting glass/CMT battery/CuInSe
2Battery/back electrode.
Two, the preparation of CdMnTe (CMT) film
The transparent conducting glass that has deposited the CdS film is put into the sample stage of near space distillation depositing device, deposition CMT film on the CdS film; Earlier sublimation chamber is evacuated to 5～10Pa before the deposit film, with molecular pump reative cell is evacuated to 10 then with vacuum pump
-3Below the Pa; Sublimation source is high-purity CMT crystal, 400-800 ℃ of sublimation source temperature, and 400～700 ℃ of sample substrate temperature, cavity air pressure is 1Pa～10KPa, 0.5～10 minute distillation time.
Three, the heat treatment of CMT film
The CMT film for preparing is put into the sample stage of near space distillation depositing device; Earlier the near space sublimation apparatus is evacuated to 5～10Pa, with molecular pump reative cell is evacuated to 10 then with vacuum pump
-3Below the Pa, sublimation source is high-purity caddy crystal, 350～450 ℃ of sublimation source temperature, 350～450 ℃ of sample substrate temperature; Heat treatment time 5～60 minutes.
Four, the preparation of CMT thin-film solar cells
Adopt magnetron sputtering method or vapour deposition method or cladding process to prepare back electrode on the CMT film, thereby prepare the CMT solar cell, battery structure as shown in Figure 1.Or on the CMT film, deposit other hull cell again, thereby prepare lamination solar cell.
The present invention compares with prior art, has following remarkable advantage:
(1) CMT thin-film solar cells of the present invention adopts p type CMT film as light absorbing zone, has than CdZnTe film more superiority, regulates easily such as CMT film energy gap.The Mn doping is 10%at.%) time CMT film energy gap just can reach about 1.7eV, the energy gap of CMT film just can reach about 1.9eV when the Mn doping was 30% (at.%), and to reach identical energy gap, for the CdZnTe film, the incorporation of Zn will reach 40% (at.%) and 60% (at.%) respectively, and there is difficulty in process in this.
(2) adopting another significant advantage of CMT film is that the CMT film is very even, because the segregation coefficient of Mn in CdTe approaches 1, and the segregation coefficient of Zn in CdTe is bigger, causes the component of CdZnTe film inhomogeneous easily, thereby influences battery performance.
Description of drawings
Fig. 1 is a CdMnTe film solar battery structure schematic diagram of the present invention.
Fig. 2 is CdMnTe/CuInSe of the present invention
2Binode overlapping thin film solar battery structural representation.
Embodiment
After now example of the present invention specifically being described in.
Embodiment 1
(1) preparation of CdMnTe (CMT) film
Transparent conducting glass (the SnO of CdS film will have been deposited
2: F) put into the sample stage of near space distillation depositing device, deposition CMT film on the CdS film, the doping of Mn is 10% (at.%); Earlier sublimation chamber is evacuated to 10Pa before the deposit film, with molecular pump reative cell is evacuated to 7 * 10 then with vacuum pump
-4Pa; Sublimation source be high-purity CMT crystal (99.99%, wt.%), 680 ℃ of sublimation source temperature, 550 ℃ of sample substrate temperature, cavity air pressure is 1Pa～10KPa, the distillation time was 90 seconds.
(2) heat treatment of CMT film
The CMT film for preparing is put into the sample stage of near space distillation depositing device; Earlier the near space sublimation apparatus is evacuated to 10Pa, with molecular pump reative cell is evacuated to 7 * 10 then with vacuum pump
-4Pa, sublimation source be high-purity caddy crystal (99.9%, wt.%), 410 ℃ of sublimation source temperature, 410 ℃ of sample substrate temperature; Heat treatment time 30 minutes.
(3) preparation of CMT thin-film solar cells
Adopt magnetron sputtering method on the CMT film, to prepare Cu/Ni alloy back electrode, thereby prepare the CMT solar cell.
Test by CMT film and battery performance thereof to above preparation, the result shows that the energy gap of film is about 1.68eV, and film crystal grain and component are even; The efficient of this CdS/CMT thin-film solar cells is 13.3%.
Embodiment 2
(1) preparation of CMT film
Transparent conducting glass (the SnO of CdS film will have been deposited
2: F) put into the sample stage of near space distillation depositing device, deposition CMT film on the CdS film, the doping of Mn is 10% (at.%); Earlier sublimation chamber is evacuated to 10Pa before the deposit film, with molecular pump reative cell is evacuated to 7 * 10 then with vacuum pump
-4Pa; Sublimation source be high-purity CMT crystal (99.99%, wt.%), 680 ℃ of sublimation source temperature, 550 ℃ of sample substrate temperature, cavity air pressure is 1Pa～10KPa, the distillation time was 90 seconds.
(2) heat treatment of CMT film
The CMT film for preparing is put into the sample stage of near space distillation depositing device; Earlier the near space sublimation apparatus is evacuated to 10Pa, with molecular pump reative cell is evacuated to 7 * 10 then with vacuum pump
-4Pa, sublimation source be high-purity caddy crystal (99.9%, wt.%), 410 ℃ of sublimation source temperature, 410 ℃ of sample substrate temperature; Heat treatment time 30 minutes.
(3) CMT/CuInSe
2The preparation of binode overlapping thin film solar battery
On the CMT film, prepare CuInSe again
2Thin-film solar cells, thus prepare CMT/CuInSe
2Binode overlapping thin film solar battery, structure are as shown in Figure 2.
Test by the double-junction solar battery to above preparation, the result shows that the efficient of battery reaches 16.1%.Be optimized by preparation technology and parameter to this binode battery, the performance of battery is expected to be largely increased again.
Claims (2)
1. a CdMnTe thin-film solar cells is characterized in that this solar cell adopts the CdMnTe film as p type light absorption layer material.
2. preparation method who is used for the described CdMnTe thin-film solar cells of claim 1 is characterized in that this method has following processing step:
The preparation of a, CdMnTe film
The transparent conducting glass that has deposited the CdS film is put into the sample stage of near space distillation depositing device, deposition CdMnTe film on the CdS film; Earlier sublimation chamber is evacuated to 5～10Pa before the deposit film, with molecular pump reative cell is evacuated to 10 then with vacuum pump
-3Below the Pa; Sublimation source is high-purity CdMnTe crystal, 400～800 ℃ of sublimation source temperature, and 400～700 ℃ of sample substrate temperature, cavity air pressure is 1Pa～10KPa, 0.5～10 minute distillation time;
The heat treatment of b, CdMnTe film
The CdMnTe film for preparing is put into the sample stage of near space distillation depositing device; Earlier the near space sublimation apparatus is evacuated to 5～10Pa, with molecular pump reative cell is evacuated to 10 then with vacuum pump
-3Below the Pa, sublimation source is high-purity caddy crystal, 350～450 ℃ of sublimation source temperature, 350～450 ℃ of sample substrate temperature; Heat treatment time 5～60 minutes;
The preparation of c, CdMnTe thin-film solar cells
Adopt magnetron sputtering method or vapour deposition method or cladding process on the CdMnTe film, to prepare back electrode, thereby prepare the CdMnTe solar cell or on the CdMnTe film, deposit other hull cell again, thereby prepare lamination solar cell.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219423A (en) * | 2013-04-07 | 2013-07-24 | 上海大学 | Preparation method of CdMnTe film ultraviolet light detector |
| CN103474513A (en) * | 2013-09-26 | 2013-12-25 | 上海大学 | Method for manufacturing CdMnTe film ultraviolet-light detector of ohm structure |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101609860A (en) * | 2009-07-16 | 2009-12-23 | 上海联孚新能源科技有限公司 | CdTe thin-film solar cells preparation method |
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- 2010-06-29 CN CN201010215756XA patent/CN101887921A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101609860A (en) * | 2009-07-16 | 2009-12-23 | 上海联孚新能源科技有限公司 | CdTe thin-film solar cells preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 《physica status solidi(c)》 20040205 Sung Hyun Lee et al Polycrystalline sputtered Cd(Zn, Mn)Te films for top cells in PV tandem structures 第1042－1045页 1-2 第1卷, 第4期 2 * |
| 《半导体光电》 20000430 张静全等 CdTe太阳能电池研究进展 88-92 2 第21卷, 第2期 2 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219423A (en) * | 2013-04-07 | 2013-07-24 | 上海大学 | Preparation method of CdMnTe film ultraviolet light detector |
| CN103474513A (en) * | 2013-09-26 | 2013-12-25 | 上海大学 | Method for manufacturing CdMnTe film ultraviolet-light detector of ohm structure |
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Open date: 20101117 |