CN110224037A - Copper-zinc-tin-sulfur film solar cell and preparation method thereof - Google Patents
Copper-zinc-tin-sulfur film solar cell and preparation method thereof Download PDFInfo
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- CN110224037A CN110224037A CN201910477710.6A CN201910477710A CN110224037A CN 110224037 A CN110224037 A CN 110224037A CN 201910477710 A CN201910477710 A CN 201910477710A CN 110224037 A CN110224037 A CN 110224037A
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- zinc
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000010408 film Substances 0.000 claims abstract description 94
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000010409 thin film Substances 0.000 claims abstract description 24
- IGUWUAGBIVHKDA-UHFFFAOYSA-N cadmium;sulfanylidenezinc Chemical group [Zn].[Cd]=S IGUWUAGBIVHKDA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000151 deposition Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 47
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000011787 zinc oxide Substances 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 229910052793 cadmium Inorganic materials 0.000 claims description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 3
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 16
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 16
- 238000004544 sputter deposition Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 230000031700 light absorption Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 description 1
- YGSCHSPBVNFNTD-UHFFFAOYSA-N [S].[Sn].[Zn] Chemical compound [S].[Sn].[Zn] YGSCHSPBVNFNTD-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007773 growth pattern Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
-
- 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
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar 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
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a kind of copper-zinc-tin-sulfur film solar cells, and including setting gradually first electrode layer, copper-zinc-tin-sulfur film absorbed layer, buffer layer, Window layer and the second electrode lay on substrate, the buffer layer is zinc cadmium sulphur film.In its preparation process, zinc cadmium sulphur thin film buffer layer is prepared by the heating of applied chemistry water-bath depositing operation combination local laser.In copper-zinc-tin-sulfur film solar cell of the invention, buffer layer uses ZnCdS film, on the one hand can promote the efficiency of CZTS thin-film solar cells and improve the short circuit current of battery, can reduce the dosage of Cd on the other hand to lower the pollution to environment.
Description
Technical field
The invention belongs to technical field of solar batteries, and in particular to a kind of copper-zinc-tin-sulfur film solar cell and its system
Preparation Method.
Background technique
In recent years, it is based on CdTe and Cu (In, Ga) Se2The thin film solar cell of (copper indium gallium sulphur, CIGS) absorption layer material
Quick development has been obtained, and has had been realized in commercialization.But since Cd is toxic, In, Ga and Te are rare metal, are led
It causes to be difficult to realize industrialization using the membrane photovoltaic component of these materials.Therefore, it finds a kind of safety and environmental protection and to have reserves rich
The thin-film material of rich raw material source becomes the hot spot of research.Quaternary compound Cu2ZnSnS4(copper-zinc-tin-sulfur, CZTS) semiconductor
All constituent elements rich reserves of material and nontoxic, absorption coefficient is big (to be greater than 104cm-1), it is good to the absorbability of light, most
Excellent unijunction band gap is about 1.5eV, can absorb well sunlight and convert light energy into electric energy, is most potential novel green
One of photovoltaic material.
In the prior art, the structure of CZTS thin-film solar cells generally comprises the first electrode set gradually on substrate
Layer, copper-zinc-tin-sulfur film absorbed layer, buffer layer, Window layer and the second electrode lay, wherein buffer layer is mostly using cadmium sulfide
(CdS) film.Currently, being haveed the defects that using CdS as buffer layer as follows:
(1), the forbidden bandwidth of CZTS and CdS is 1.5eV and 2.5eV respectively, and the energy band matching relationship of the two is not met simultaneously
The requirement of high efficiency battery.
(2), the bandwidth of CdS is 2.4eV or so, and corresponding absorbing wavelength is 520nm or so, be will cause to short wavelength's
Optical absorption loss is unfavorable for the raising of battery short circuit electric current.
(3), Cd is more toxic, and there are problems that environmental pollution, therefore reduces the use of Cd as far as possible.
Summary of the invention
In view of the shortcomings of the prior art, the object of the present invention is to provide a kind of copper-zinc-tin-sulfur film solar electricity
Pond and preparation method thereof, by being improved to the buffer layer in battery structure, to promote the effect of CZTS thin-film solar cells
Rate.
For achieving the above object, present invention employs following technical solutions:
A kind of copper-zinc-tin-sulfur film solar cell, including setting gradually first electrode layer on substrate, copper-zinc-tin-sulfur
Film absorption layer, buffer layer, Window layer and the second electrode lay, wherein the buffer layer is zinc cadmium sulphur film.
Specifically, the buffer layer with a thickness of 20~100nm.
Specifically, intrinsic zinc oxide film layer is additionally provided between the buffer layer and the Window layer.
Specifically, the material of the first electrode layer is metal, and the material of the Window layer is transparent conductive material, described
The material of the second electrode lay is metal.
The present invention also provides a kind of preparation methods of copper-zinc-tin-sulfur film solar cell comprising applied chemistry water-bath is heavy
The step of preparation forms zinc cadmium sulphur thin film buffer layer on copper-zinc-tin-sulfur film absorbed layer, which specifically includes product technique:
It prepares reaction solution: cadmium source, zinc source and sulphur source being dissolved in aqueous solution, prepare reaction solution；
It is passed through the reaction solution into chemical bath reaction vessel, preparation is completed to the substrate of copper-zinc-tin-sulfur film absorbed layer
It is placed in the chemical bath reaction vessel, and at least the copper-zinc-tin-sulfur film absorbed layer is totally submerged in described anti-
It answers in liquid；
It is anti-to control the water-bath of copper-zinc-tin-sulfur film absorbed layer corresponding region to heat the substrate using laser irradiation
Temperature is answered, deposition forms zinc cadmium sulphur thin film buffer layer on the copper-zinc-tin-sulfur film absorbed layer.
Wherein, in the reaction solution, the concentration in the cadmium source is 0.004mol/L~0.008mol/L, the zinc source it is dense
Degree is 0.2mol/L~0.4mol/L, and the concentration of the sulphur source is 0.25mol/L~0.3mol/L.
Wherein, the cadmium source is cadmium sulfate or cadmium acetate or caddy, zinc source zinc sulfate or zinc acetate, the sulphur source
For thiocarbamide or thioacetamide.
Wherein, in the reaction solution also added with ammonium hydroxide and/or citric acid with the pH value for adjusting the reaction solution be 10~
12。
Wherein, when carrying out chemical bath reaction, the temperature setting in the chemical bath reaction vessel is 0~25 DEG C,
Laser irradiation heating makes 80~150 DEG C of water-bath temperature of copper-zinc-tin-sulfur film absorbed layer corresponding region, when reaction
Between be 20~30min.
Specifically, the copper-zinc-tin-sulfur film solar cell preparation method comprising steps of
S10, substrate is provided, prepares to form first electrode layer over the substrate；
S20, preparation forms copper-zinc-tin-sulfur film absorbed layer in the first electrode layer；
S30, applied chemistry water-bath depositing operation prepare on the copper-zinc-tin-sulfur film absorbed layer and form zinc cadmium sulphur film
Buffer layer；
S40, preparation forms intrinsic zinc oxide film layer on the zinc cadmium sulphur thin film buffer layer；
S50, preparation forms Window layer in the intrinsic zinc oxide film layer；
S60, preparation forms the second electrode lay in the Window layer.
Copper-zinc-tin-sulfur film solar cell provided in an embodiment of the present invention and preparation method thereof, applied chemistry water-bath deposition
The heating of technique combination local laser prepares zinc cadmium sulphur (ZnCdS) thin film buffer layer, using ZnCdS buffer layer compared to existing
CdS buffer layer in technology has following advantage:
(1), the forbidden bandwidth of ZnCdS is 2.5-3.37eV, can preferably be matched with CZTS, promotes CZTS film too
The efficiency of positive energy battery；
(2), it since ZnCdS buffer layer has bigger forbidden bandwidth, can reduce compared to CdS buffer layer to visible
The absorption of light is especially the reduction of the light absorption to short wavelength, so that the light-absorption layer of battery has higher light absorption, leads to
Cross the short circuit current for increasing absorption of the battery at shortwave to improve battery；
(3), in the identical situation of the structure size of buffer layer, ZnCdS buffer layer can be reduced compared to CdS buffer layer
The dosage of Cd can not yet avoid completely at present using the pollution that can also lower to a certain extent the case where Cd to environment.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of copper-zinc-tin-sulfur film solar cell provided in an embodiment of the present invention；
Fig. 2 is the flow chart of the preparation method of copper-zinc-tin-sulfur film solar cell provided in an embodiment of the present invention；
Fig. 3 is that applied chemistry water-bath depositing operation prepares formation on copper-zinc-tin-sulfur film absorbed layer in the embodiment of the present invention
The graphical representation of exemplary of the technical process of zinc cadmium sulphur thin film buffer layer.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, with reference to the accompanying drawing to specific reality of the invention
The mode of applying is described in detail.The example of these preferred embodiments is illustrated in the accompanying drawings.Shown in attached drawing and according to
The embodiments of the present invention of attached drawing description are only exemplary, and the present invention is not limited to these embodiments.
Here, it should also be noted that, in order to avoid having obscured the present invention because of unnecessary details, in the accompanying drawings only
Show with closely related structure and/or processing step according to the solution of the present invention, and be omitted little with relationship of the present invention
Other details.
The embodiment of the present invention provides firstly a kind of copper-zinc-tin-sulfur film solar cell, as shown in Figure 1, the copper zinc-tin
S film solar battery includes that substrate 1 and the first electrode layer 2 being arranged on the substrate 1, copper-zinc-tin-sulfur film absorb
Layer 3, zinc cadmium sulphur (ZnCdS) thin film buffer layer 4, Window layer 5 and the second electrode lay 6.In the present embodiment, the ZnCdS buffering
Intrinsic zinc oxide film layer (i-ZnO) 7 is additionally provided between layer 4 and the Window layer 5.
Wherein, the substrate 1 can choose as glass substrate.The material of the first electrode layer 2 is metal, such as molybdenum
(Mo).The material of the Window layer 5 is transparent conductive material, such as the zinc oxide (AZO) of aluminium doping.The second electrode lay
Material is metal, such as aluminium (Al).
In the present embodiment, as shown in Figure 1, the second electrode lay 6 is to include multiple sub-electrode 6a for being spaced apart from each other arrangement
The gate-shaped electrode of composition.Since the surface resistance of the Window layer 5 of transparent conductive material is larger, charge can not be effectively collected, because
This can preferably collect charge by the way that gate-shaped electrode is arranged.In the preferred scheme, the sub-electrode 6a can be set to wrap
The Ni metal layer, Al metal layer and Ni metal layer being successively set in the Window layer 5 are included, the electrode knot of Ni/Al/Ni is formed
Structure: the effect of Ni metal layer mainly increases adhesiveness and anti-oxidant；Al metal layer is critically important to the collection of charge, thickness
Preferably 8 μm or so.
The copper-zinc-tin-sulfur film solar cell provided as described above, buffer layer use ZnCdS film, and ZnCdS film is slow
The forbidden bandwidth for rushing layer is 2.5-3.37eV or so, can preferably be matched with CZTS, and CZTS thin-film solar cells is promoted
Efficiency；And it since ZnCdS buffer layer has bigger forbidden bandwidth, can reduce compared to CdS buffer layer to visible
The absorption of light is especially the reduction of the light absorption to short wavelength, so that the light-absorption layer of battery has higher light absorption, leads to
Cross the short circuit current for increasing absorption of the battery at shortwave to improve battery；Further, buffer layer uses ZnCdS film,
The dosage of Cd can be reduced, can be not yet avoided completely at present using can also lower to a certain extent to environment the case where Cd
Pollution.
The embodiment of the invention also provides the preparation methods of copper-zinc-tin-sulfur film solar cell as described above, refering to figure
2 and combine Fig. 1, the preparation method comprising steps of
S10, substrate 1 is provided, preparation forms first electrode layer 2 on the substrate 1.
Specifically, in the present embodiment, the substrate 1 is selected as glass substrate, the material molybdenum of the first electrode layer 2.It is first
The substrate 1 is first cleaned using deionized water and cleaning agent, by being dried with nitrogen the substrate 1 through over cleaning, is then dried
Described 1 a period of time of substrate is baked, then the substrate 1 is sent to sputtering chamber.After the substrate 1 is placed in sputtering chamber, adopt
First electrode layer 2 is made on the substrate 1 with DC magnetron sputtering process, concrete technology, which may is that, uses molybdenum for target,
Air pressure is to recycle 15 left sides of sputtering on the substrate 1 with the sputtering power of 1000W or so under the argon atmosphere of 0.3Pa~1Pa
The first electrode layer 2 with a thickness of 600nm~450nm is made in the right side.
S20, preparation forms copper-zinc-tin-sulfur film absorbed layer 3 in the first electrode layer 2.
After having made the first electrode layer 2 on the substrate 1, it is heavy using evaporation, sputtering method or solution to may be selected
Area method makes copper-zinc-tin-sulfur film absorbed layer 3 in the first electrode layer 2, in the present embodiment, prepared using sputtering method described in
Copper-zinc-tin-sulfur film absorbed layer 3.
Concrete technology may is that using four sources while sputter, wherein with ZnS, Cu, SnS2Be target with CdS, in argon gas and
H2It is sputtered under S atmosphere, gas flow ratio 20sccm:0.25sccm, thus sputtering 60min or so is prepared about
With a thickness of 1 μm or so of copper-zinc-tin-sulfur film absorbed layer 3.
Further, it is also necessary to which the copper-zinc-tin-sulfur film absorbed layer 3 is made annealing treatment.Concrete technology may is that
The sample that above step is prepared is placed in annealing furnace, by stove evacuation of annealing, is then passed through about 10.5KPa's again
H2S gas, annealing furnace are heated to 270 DEG C from room temperature 15min or so, then 290 DEG C are heated to 5min or so again, 290
75min or so is kept the temperature at DEG C, pumps H after 290 DEG C of heat preservations2S gas；Then pass to the H that flow-rate ratio is 52:2.32S and N2
Mixed gas, then be heated to 515 DEG C from 290 DEG C with 30min or so, 12min or so kept the temperature at 515 DEG C；Finally allow its from
It is so cooling, when temperature drops to 450 DEG C or so, gas in annealing furnace is pumped, is cooled to 80 DEG C or so taking-ups to sample.
S30, applied chemistry water-bath depositing operation prepare on the copper-zinc-tin-sulfur film absorbed layer 3 and form zinc cadmium sulphur film
Buffer layer 4.As shown in connection with fig. 3, step S30 is specifically included:
S31, it prepares reaction solution: cadmium source, zinc source and sulphur source being dissolved in aqueous solution, prepare reaction solution.
Specifically, in the reaction solution, the range of 0.004mol/L~0.008mol/L is arranged in the concentration in the cadmium source
Interior, the concentration in the zinc source is arranged in the range of 0.2mol/L~0.4mol/L, and the concentration setting of the sulphur source exists
In the range of 0.25mol/L~0.3mol/L.Wherein, the cadmium source is cadmium sulfate or cadmium acetate or caddy, zinc source sulphur
Sour zinc or zinc acetate, the sulphur source are thiocarbamide or thioacetamide.
Further, ammonium hydroxide and/or citric acid can also be added in the reaction solution to adjust the pH of the reaction solution
Value is 10~12.It is preferable to use ammonium hydroxide, on the one hand ammonium hydroxide is adjustable pH value, on the other hand can also be to the cadmium in reaction solution
Source, zinc source and sulphur source play the role of complexing.
S32, refering to Fig. 3, the reaction solution 20 is passed through into chemical bath reaction vessel 10, will preparation complete copper-zinc-tin-sulfur
It is anti-that the substrate 1 (structure sheaf between substrate 1 and absorbed layer 3 is omitted in Fig. 3) of film absorption layer 3 is placed in the chemical bath
It answers in container 10, and at least the copper-zinc-tin-sulfur film absorbed layer 3 is totally submerged in the reaction solution 20.
Specifically, the chemical bath reaction is placed in the substrate 1 that copper-zinc-tin-sulfur film absorbed layer 3 is completed in preparation to hold
When in device 10, by the copper-zinc-tin-sulfur film absorbed layer 3 towards the bottom of the chemical bath reaction vessel 10, and substrate 1 is then
Backwards to the bottom of the chemical bath reaction vessel 10, so that more convenient laser irradiation is to the substrate in the subsequent process
1。
In preferred scheme, the copper-zinc-tin-sulfur film absorbed layer 3 is totally submerged in the reaction solution 20, and it is described
Substrate 1 is then exposed from the upper surface of the reaction solution 20, preferably controls heating when so that laser irradiation is to the substrate 1
Temperature.In other some embodiments, it is also possible to for the substrate 1 being also immersed in the reaction solution 20, at this time laser
Irradiation has portion of energy loss when heating the substrate 1, but also can be realized heated perimeter.
S33, refering to Fig. 3, heat the substrate 1 using the irradiation of laser 30 to control the copper-zinc-tin-sulfur film absorbed layer 3
The water-bath temperature of corresponding region, deposition forms zinc cadmium sulphur thin film buffer layer 4 on the copper-zinc-tin-sulfur film absorbed layer 3.
Specifically, when carrying out chemical bath reaction, the whole temperature of reaction solution 20 in the chemical bath reaction vessel 10
Degree is set as 0~25 DEG C, then heats the substrate 1 using the irradiation of laser 30 to control the copper-zinc-tin-sulfur film absorbed layer 3
The temperature of the reaction solution 20 of corresponding region is 80 DEG C or more, so that water-bath occurs for the reaction solution 20 in the region, thus in copper
Deposition forms zinc cadmium sulphur thin film buffer layer 4 on zinc-tin-sulfur film absorbed layer 3.Wherein, water-bath time can for 20~
30min prepares the zinc cadmium sulphur thin film buffer layer 4 with a thickness of 20~100nm.It should be noted that can be swashed by controlling
The light intensity of light irradiation, adjusts the hydrothermal temperature of corresponding region；And it is adjustable by the length of time of control water-bath
The thickness of zinc cadmium sulphur thin film buffer layer 4 is prepared.
Preparation ZnCdS film, growth pattern are heated using local laser (the corresponding region of copper-zinc-tin-sulfur film absorbed layer 3)
Mainly chemical thought (CBD).In chemical thought reaction, reaction temperature starts to be deposited with when being 60 DEG C or so
CdS material, reaction temperature start to be deposited with ZnS material when being 80 DEG C or so, and the too low ZnS of temperature can not be formed, the excessively high CdS of temperature
Deposition velocity is too fast not easy to control, therefore in the embodiment of the present invention, the temperature of conversion zone is made by local laser heating
It is 80 DEG C or more, maximum temperature can be set as 150 DEG C, thus be formed simultaneously CdS material and ZnS material, and it is heavy to solve the two
Accumulated temperature degree difference problem prepares the ZnCdS film of high quality by laser to the local heating of substrate.In preferred scheme, lead to
Crossing laser Local heating method makes the temperature of conversion zone be 90~120 DEG C
It should be noted that the ZnCdS thin film buffer layer prepared in the embodiment of the present invention, CdS material and ZnS material
It deposits to be formed simultaneously, CdS material and ZnS material are that mutual doping forms same layer ZnCdS film layer rather than formed and successively folded
The CdS film layer and ZnS film layer of layer.
Further, chemical bath after reaction, sample is taken out and use ammonium hydroxide (preferred concentration be 3mol/L ammonia
Water) it impregnates five minutes, then rinsed with deionized water, it is dried with nitrogen.
S40, preparation forms intrinsic zinc oxide film layer 7 on the zinc cadmium sulphur thin film buffer layer 4.
Specifically, native oxide zinc layers described in the present embodiment 7 is using r. f. magnetron sputtering in the buffer layer 4
On.Concrete technology may is that using ZnO as target, and in pressure be 0.1Pa or so and the flow-rate ratio of argon gas and oxygen is 20:2's
Under the conditions of, sputtering 20 times or so is recycled on the buffer layer 4 with 220 watts of power, is made with a thickness of the sheet of 50 rans
Levy zinc oxide film 7.
S50, preparation forms Window layer 5 in the intrinsic zinc oxide film layer 7.
Specifically, Window layer 5 described in the present embodiment is using r. f. magnetron sputtering in the intrinsic zinc oxide film
On layer 7.Concrete technology may is that using Al and ZnO as target, in the flow-rate ratio that pressure is 0.1Pa or so and argon gas and hydrogen
Under conditions of 20:4, while sample is heated to 90 DEG C or so, with 850 watts of power in the intrinsic zinc oxide film layer 7
Circulation sputtering 12 times or so, is then cooled to 40~50 DEG C or so taking-up samples to sample, the window with a thickness of 200 nanometers is made
Layer 5.
S60, preparation forms the second electrode lay 6 in the Window layer 5.
In the present embodiment, Ni metal layer, Al metal layer and Ni metal layer are sequentially depositing in Window layer 5 first, is then answered
It is prepared to form the gate-shaped electrode including multiple sub-electrode 6a compositions for being spaced apart from each other arrangement with etching technics, each sub-electrode 6a points
Be not formed as the electrode structure of Ni/Al/Ni.
In conclusion copper-zinc-tin-sulfur film solar cell provided in an embodiment of the present invention and preparation method thereof, application
It learns the heating of water-bath depositing operation combination local laser and prepares zinc cadmium sulphur thin film buffer layer, buffer layer is using ZnCdS film, and one
Aspect can promote the efficiency of CZTS thin-film solar cells and improve the short circuit current of battery, on the other hand can reduce Cd
Dosage to lower pollution to environment.
The above is only the specific embodiment of the application, it is noted that for the ordinary skill people of the art
For member, under the premise of not departing from the application principle, several improvements and modifications can also be made, these improvements and modifications are also answered
It is considered as the protection scope of the application.
Claims (10)
- It is thin including setting gradually first electrode layer on substrate, copper-zinc-tin-sulfur 1. a kind of copper-zinc-tin-sulfur film solar cell Film absorbed layer, buffer layer, Window layer and the second electrode lay, which is characterized in that the buffer layer is zinc cadmium sulphur film.
- 2. copper-zinc-tin-sulfur film solar cell according to claim 1, which is characterized in that the buffer layer with a thickness of 20~100nm.
- 3. copper-zinc-tin-sulfur film solar cell according to claim 1, which is characterized in that the buffer layer and the window Intrinsic zinc oxide film layer is additionally provided between mouth layer.
- 4. copper-zinc-tin-sulfur film solar cell according to claim 1 to 3, which is characterized in that the first electrode The material of layer is metal, and the material of the Window layer is transparent conductive material, and the material of the second electrode lay is metal.
- 5. a kind of preparation method of copper-zinc-tin-sulfur film solar cell, which is characterized in that deposit work including applied chemistry water-bath The step of preparation forms zinc cadmium sulphur thin film buffer layer on copper-zinc-tin-sulfur film absorbed layer, which specifically includes skill:It prepares reaction solution: cadmium source, zinc source and sulphur source being dissolved in aqueous solution, prepare reaction solution；It is passed through the reaction solution into chemical bath reaction vessel, the substrate that copper-zinc-tin-sulfur film absorbed layer is completed in preparation is placed The copper-zinc-tin-sulfur film absorbed layer is totally submerged in the reaction solution in the chemical bath reaction vessel, and at least In；The substrate is heated using laser irradiation to control the water-bath temperature of copper-zinc-tin-sulfur film absorbed layer corresponding region Degree, deposition forms zinc cadmium sulphur thin film buffer layer on the copper-zinc-tin-sulfur film absorbed layer.
- 6. the preparation method of copper-zinc-tin-sulfur film solar cell according to claim 5, which is characterized in that the reaction In liquid, the concentration in the cadmium source is 0.004mol/L~0.008mol/L, and the concentration in the zinc source is 0.2mol/L~0.4mol/ L, the concentration of the sulphur source are 0.25mol/L~0.3mol/L.
- 7. the preparation method of copper-zinc-tin-sulfur film solar cell according to claim 6, which is characterized in that the cadmium source For cadmium sulfate or cadmium acetate or caddy, zinc source zinc sulfate or zinc acetate, the sulphur source are thiocarbamide or thioacetamide.
- 8. the preparation method of copper-zinc-tin-sulfur film solar cell according to claim 5, which is characterized in that the reaction Also added with ammonium hydroxide and/or citric acid to adjust the pH value of the reaction solution as 10~12 in liquid.
- 9. the preparation method of copper-zinc-tin-sulfur film solar cell according to claim 5, which is characterized in that changed When learning water-bath, the temperature setting in the chemical bath reaction vessel is 0~25 DEG C, and laser irradiation heating makes the copper zinc The water-bath temperature of tin sulphur film absorption layer corresponding region is 80~150 DEG C, and the reaction time is 20~30min.
- 10. according to the preparation method of any copper-zinc-tin-sulfur film solar cell of claim 5-9, which is characterized in that The preparation method comprising steps ofS10, substrate is provided, prepares to form first electrode layer over the substrate；S20, preparation forms copper-zinc-tin-sulfur film absorbed layer in the first electrode layer；S30, applied chemistry water-bath depositing operation prepare on the copper-zinc-tin-sulfur film absorbed layer and form zinc cadmium sulphur film damper Layer；S40, preparation forms intrinsic zinc oxide film layer on the zinc cadmium sulphur thin film buffer layer；S50, preparation forms Window layer in the intrinsic zinc oxide film layer；S60, preparation forms the second electrode lay in the Window layer.
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