CN105679881A - Preparation method of copper-indium-sulfur thin-film solar cell - Google Patents
Preparation method of copper-indium-sulfur thin-film solar cell Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical compound [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 title abstract 4
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000004888 barrier function Effects 0.000 claims abstract description 19
- 229910004576 Cd1-xZnxS Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims description 77
- 239000010408 film Substances 0.000 claims description 23
- 238000000137 annealing Methods 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 229910052738 indium Inorganic materials 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MODGUXHMLLXODK-UHFFFAOYSA-N [Br].CO Chemical compound [Br].CO MODGUXHMLLXODK-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910010037 TiAlN Inorganic materials 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 238000002061 vacuum sublimation Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 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
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 238000005234 chemical deposition Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- -1 wherein Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000002207 thermal evaporation Methods 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 238000004544 sputter deposition Methods 0.000 description 14
- 238000007738 vacuum evaporation Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000928 Yellow copper Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910002708 Au–Cu Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—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
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
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Abstract
The invention discloses a preparation method of a copper-indium-sulfur thin-film solar cell. The structure of the cell is as follows from bottom to top successively: a substrate, a Ti-TiN-Mo back electrode, a Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2 absorbing layer, a Cd1-xZnxS barrier layer, an i-ZnO/an Al:ZnO window layer, and an Al(Ni) front electrode. The method comprises the following steps: (1) cleaning and pretreating the substrate; (2) preparing the Ti-TiN-Mo back electrode on the substrate; (3) preparing the Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2 absorbing layer on the Ti-TiN-Mo back electrode; (4) preparing the Cd1-xZnxS barrier layer on the absorbing layer; (5) successively depositing an i-ZnO thin film and an Al:ZnO thin film on the Cd1-xZnxS barrier layer so as to prepare the i-ZnO/an Al:ZnO window layer; (6) using a vacuum thermal evaporation method to evaporate the Al(Ni) front electrode on the i-ZnO/an Al:ZnO window layer so as to obtain the copper-indium-sulfur thin-film solar cell. According to the copper-indium-sulfur thin-film solar cell prepared by the invention, the adhesion between the back electrode of the cell and the glass substrate and between the back electrode of the cell and the absorbing layer thin film is high, the cell is unlikely to peel off, the reliability is high, series resistors among the layers are little, and the electro-optical energy conversion efficiency can be improved.
Description
Technical field
The preparation method that the present invention relates to a kind of copper and indium sulfenyl thin-film solar cells, belongs to solar cell fabrication process technical field.
Background technology
In recent years, semiconductor nano has discontinuous band structure and the characteristic of many excitons, than crystal silicon solar energy battery, there is cost advantage becoming present aspect thin-film solar cells, wherein, thin-film solar cells is with semiconductive thin film for light absorbing zone, the consumption of raw material less, price low, be beneficial to reduction cost, therefore thin-film solar cells becomes main R&D direction. CuInS2Belonging to I-III-VI system ternary compound, its energy gap is between 1.3-1.7ev, and close to the theoretical best energy gap of solaode, and energy gap is insensitive to the change of temperature, and the absorption coefficient of light reaches 105cm-1. It addition, its stability is high, within 7 years, without significant change, capability of resistance to radiation is strong, is adapted for use as the battery material of spacecraft in outdoor illumination. Work as CuInS2Will producing point defect during chemical composition deviation chemical dosage ratio, the kind such as room, gap and dislocation reaches 12 kinds, and these point defects can produce new energy level in forbidden band. It addition, CuInS2Allow composition nonstoichiometry than wider range, wherein, unijunction CuInS2The theoretical conversion efficiencies of homojunction solar cell reaches as high as 32%.
At present, existing CuInS2The composition of thin film solar cell includes CuInS2, CdS, ZnO, its structure is followed successively by: CuInS2/ CdS/ZnO, or its composition includes CuInS2, CuI, ZnO, its structure is followed successively by: CuInS2/ CuI/ZnO. Owing to the contact resistance between different layers is relatively big, causes that the series resistance between each layer increases, affect the efficiency of light absorption of solaode.
Summary of the invention
For the defect that prior art exists, the preparation method that it is an object of the invention to provide a kind of copper and indium sulfenyl thin-film solar cells, the series resistance in solar cell prepared by the method is little, can improve the absorption efficiency of battery.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
The preparation method of a kind of copper and indium sulfenyl thin-film solar cells, described film solar battery structure is followed successively by from bottom to top: substrate/Ti-TiN-Mo back electrode/Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer/Cd1-xZnxS barrier layer/i-ZnO/Al:ZnO Window layer/Al (Ni) front electrode, the method has following processing step:
(1). substrate cleans and pretreatment: adopts acetone, ethanol and deionized water to each ultrasonic cleaning 15min of substrate successively, then adopts Ar plasma that substrate is performed etching;
(2). on substrate, prepare Ti/TiN/Mo back electrode: adopt magnetron sputtering method to be sequentially prepared the bottom Ti thin film of Ti/TiN/Mo back electrode, TiAlN thin film, Mo thin film on substrate, make Ti/TiN/Mo back electrode;
(3). on Ti/TiN/Mo back electrode, prepare Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer:
Cu is prepared respectively first by Bridgman method1-xNaxInS2、CuInS2And Cu1-xAgxInS2Polycrystal silicon ingot, after pulverizing, weighs 1g respectively and puts in tungsten boat and make evaporation source; Then conventional vacuum thermal evaporation is adopted to deposit Cu on Ti/TiN/Mo back electrode successively1-xNaxInS2Thin film, CuInS2Thin film, wherein, Cu1-xNaxInS2Film thickness is 50-100nm, CuInS2Film thickness is 2-3um, then by the Cu after deposit1-xNaxInS2/CuInS2Thin film is placed in the annealing device under sulfur-bearing atmosphere and is annealed, and forms Cu1-xNaxInS2/CuInS2Laminated film, adopts bromine methanol solution to Cu1-xNaxInS2/CuInS2Laminated film corrodes; Adopt conventional vacuum thermal evaporation Cu after corrosion1-xNaxInS2/CuInS2Laminated film deposits Cu1- xAgxInS2Thin layer, then by the Cu after deposit1-xNaxInS2/CuInS2/Cu1-xAgxInS2Put in annealing device and be annealed, then adopt bromine methanol solution to corrode, form Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer;
(4). on absorbed layer, prepare Cd1-xZnxS barrier layer: with cadmium acetate, zinc acetate, ammonium acetate and ammonia spirit for raw material, adopts chemical deposition at Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer deposits Cd1-xZnxS thin film is as barrier layer;
(5). at Cd1-xZnxS barrier layer deposits i-ZnO thin film, Al:ZnO thin film successively, make i-ZnO/Al:ZnO Window layer: adopt magnetron sputtering method to deposit i-ZnO thin film, Al:ZnO thin film over the barrier layer successively, form i-ZnO/Al:ZnO Window layer, wherein, i-ZnO film thickness is 10-50nm, Al:ZnO film thickness is 500-700nm;
(6). electrode before preparation in i-ZnO/Al:ZnO Window layer: adopt Vacuum Heat to steam method evaporating Al (Ni) front electrode in i-ZnO/Al:ZnO Window layer, place into and vacuum annealing equipment carries out vacuum annealing, annealing temperature 300～450 DEG C, annealing time 60～120 minutes, final acquisition copper and indium sulfenyl thin-film solar cells.
Compared with prior art, the present invention has following prominent advantage:
1. the copper and indium sulfenyl thin-film solar cells that prepared by the method for the present invention, owing to the adhesiveness bonding with between glass substrate and absorbed layer thin film of the back electrode of this battery is strong, not easily peel off, the reliability of stability and the device being electrically connected can be improve, and series resistance between each layer is little, photovoltaic energy conversion efficiency can be improved.
2., in the copper and indium sulfenyl thin-film solar cells that prepared by the method for the present invention, adopt bromine methanol solution to remove Cu1- xNaxInS2/CuInS2/Cu1-xAgxInS2The Cu on laminated film surfacexS-phase and AgxS-phase, methanol solution instead of poisonous cyanide caustic, optimizes production environment, and laminated film surface is finer and close, and efficiency of light absorption is higher.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of present configuration.
Fig. 2 (a) be the method for the present invention when vacuum evaporation, substrate tilting angle is 0oCuInS2SEM collection of illustrative plates.
Fig. 2 (b) be the method for the present invention in vacuum evaporation, substrate tilting angle is 40oCuInS2SEM collection of illustrative plates.
Fig. 2 (c) be the method for the present invention in vacuum evaporation, substrate tilting angle is 60oCuInS2SEM collection of illustrative plates.
Fig. 3 (a) is without annealing, substrate tilt angle respectively 0o、40oWith 60oCuInS2The Raman collection of illustrative plates of thin film.
Fig. 3 (b) is after 400 DEG C of annealing temperatures process, substrate tilt angle respectively 0o、40oWith 60oCuInS2The Raman collection of illustrative plates of thin film.
Detailed description of the invention
Below in conjunction with accompanying drawing 1, the present invention is described in more detail.
As it is shown in figure 1, a kind of copper and indium sulfenyl film solar battery structure, 1 is substrate, and 2 is Ti/TiN/Mo back electrode, and 3 is Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer, 4 is Cd1-xZnxS barrier layer, 5 is i-ZnO/Al:ZnO Window layer, and 6 is Al (Ni) front electrode.
The preferred embodiments of the present invention, the preparation method of a kind of multilamellar cascade copper and indium sulfenyl solaode, the method has following processing step:
(1). substrate 1 cleans and pretreatment: select sheet glass as substrate, substrate is cut into 1.5cm × 2cm; Adopting successively goes acetone, ethanol and ionized water to each ultrasonic cleaning 15min of substrate, then adopts high pure nitrogen to dry up, and then adopts Ar plasma that substrate performs etching cleaning, and Ar plasma apparatus voltage is 720V, electric current is 25mA, and etch period is 30min.
(2). preparation Ti/TiN/Mo back electrode 2 on 1 on substrate: first start magnetron sputtering apparatus, installing target is Ti target, and sputtering pressure is 0.5pa, d.c. sputtering power is 160W, sputtering time 15min, forms bottom Ti thin film on 1 on substrate; Then changing target is TiN target, and adjusting substrate 1 inclination angle is 45 °, and sputtering pressure is 0.5pa, d.c. sputtering power is 160W, and sputtering time 10min sputters, and forms TiAlN thin film at Ti thin film; Finally changing target is Mo target, and sputtering pressure is 0.5Pa, sputtering power 60W, and sputtering time 10min forms Mo thin film in TiAlN thin film, prepares into Ti/TiN/Mo back electrode 2;
(3). on Ti/TiN/Mo back electrode 2, prepare Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer 3:
(3-1). Cu it is sequentially prepared respectively by Bridgman method1-xNaxInS2、CuInS2、Cu1-xAgxInS copper and indium sulfur powder, weighs the Cu that weight is 1g respectively successively1-xNaxInS2、CuInS2、Cu1-xAgxInS2Copper and indium sulfur powder is put in the tungsten boat in vacuum evaporation equipment as evaporation source, and described vacuum evaporation equipment, operating air pressure is 3 × 10-6Torr, the inclination angle of substrate is the normal angle with incident steam of substrate, adjusts inclination angle respectively 0o, 40oWith 60, deposition voltage is 10kV, and deposition current is 5～200mA;
(3-2). adopt Vacuum sublimation to deposit Cu on Ti/TiN/Mo back electrode successively1-xNaxInS2Thin film, CuInS2Thin film, obtains Cu1-xNaxInS2/CuInS2, wherein, Cu1-xNaxInS2The thickness of thin film is 50-100nm, CuInS2The thickness of thin film is 2-3um, and test substrate tilting angle is 0o、40o、60o、CuInS2SEM scheme respectively, shown in Fig. 2 (a), Fig. 2 (b), Fig. 2 (c); CuInS by preparation2Thin film carries out Raman test, as shown in Fig. 3 (a), Fig. 3 (b), in Raman collection of illustrative plates, and 290cm-1Place and 304cm-1The diffraction maximum at place is corresponding yellow copper structure CuInS respectively2A1Mould and Au-Cu phase CuInS2A1 *Mould, by the A without annealing1The diffraction maximum of mould and the A after 400 ° of C annealing temperatures1 *The diffraction maximum of mould is compared and is shown, the CuInS of Cu-Au phase2It is converted into yellow copper structure CuInS2, the crystallinity of thin film is higher;
(3-3). by the Cu after deposit1-xNaxInS2/CuInS2Thin film is placed in the annealing device under sulfur-bearing atmosphere and is annealed, and forms Cu1-xNaxInS2/CuInS2Laminated film, adopts bromine methanol solution to Cu1-xNaxInS2/CuInS2Laminated film corrodes;
(3-4). adopt Vacuum sublimation Cu after corrosion1-xNaxInS2/CuInS2Laminated film deposits Cu1- xAgxInS2Thin layer;
(3-5). by the Cu after deposit1-xNaxInS2/CuInS2/Cu1-xAgxInS2Being annealed in sulfur-bearing atmosphere, annealing temperature is 400 DEG C, annealing time 30min-60min, the solution corrosion mixed for the ratio of 1:10000 by ratio of weight and the number of copies with methanol by bromine, and etching time is 1min, removes surface sulfide thing (CuxS), Cu is obtained1-xNaxInS2/CuInS2/Cu1-xAgxInS thin film 3;
(4). on absorbed layer 3, prepare Cd1-xZnxS barrier layer 4: weigh 20mL concentration to be the cadmium acetate of 0.2mol/L, 20mL concentration be 0.1mol/L zinc acetate, 2mL concentration is 1mol/L ammonium acetate and 0.5ml concentration is 1mol/L ammonia spirit, with temperature control magnetic stirring apparatus at 65 DEG C, magnetic agitation 1min under the rotating speed of 200r/min; Solution after stirring is dripped at Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer 3 surface, being subsequently adding 20mL concentration is 0.2mol/L thiourea, under magnetic stirring, keeps 10-20min, takes out substrate, and with deionized water rinsing, vacuum drying obtains Cd1-xZnxS barrier layer 4;
(5). adopt magnetron sputtering method at Cd1-xZnxS barrier layer 4 deposits i-ZnO thin film, Al:ZnO thin film successively, makes i-ZnO/Al:ZnO/Al(Ni) Window layer 5:
At Cd1-xZnxDepositing i-ZnO thin film, Al:ZnO thin film on S barrier layer 4 successively, form i-ZnO/Al:ZnO, described magnetron sputtering method is: intrinsic ZnO target is put into the sputtering target position in magnetron sputtering apparatus, by Cd1-xZnxS barrier layer 4 is placed on plated film platform on 4 sputtering 10min and forms i-ZnO thin film, and wherein, sputtering pressure is 0.5Pa, sputtering power is 100W; Then taking out intrinsic ZnO target, be loaded on Al:ZnO target, sputtering 15min obtains i-ZnO/Al:ZnO Window layer 5, and wherein sputtering pressure is 1pa, magnetron sputtering power 95W;
(6). in i-ZnO/Al:ZnO Window layer 5, prepare Al(Ni) front electrode 6: weigh the Al(Ni of 0.1g mass), it is placed in the evaporation tungsten boat in vacuum evaporation coating machine, i-ZnO/Al:ZnO Window layer 5 is placed on the gate mask version on work rest, heating is to preset temperature, stablize 10-30min and control vacuum evaporation coating machine parameter, evaporation is started with default evaporation rate, until the Al(Ni in evaporation tungsten boat) be evaporated, Al(Ni is formed in i-ZnO/Al:ZnO Window layer 5) front electrode 6, carry out vacuum annealing again, so that electrode has good contact.
Claims (1)
1. the preparation method of a copper and indium sulfenyl thin-film solar cells, it is characterised in that described film solar battery structure is followed successively by from bottom to top: substrate/Ti-TiN-Mo back electrode/Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer/Cd1- xZnxS barrier layer i-ZnO/Al:ZnO Window layer/Al (Ni) front electrode, the method has steps of:
(1). substrate cleans and pretreatment: adopts acetone, ethanol and deionized water to each ultrasonic cleaning 15min of substrate successively, then adopts Ar plasma that substrate is performed etching;
(2). on substrate, prepare Ti/TiN/Mo back electrode: adopt magnetron sputtering method to be sequentially prepared the bottom Ti thin film of Ti/TiN/Mo back electrode, TiAlN thin film, Mo thin film on substrate, make Ti/TiN/Mo back electrode;
(3). on Ti/TiN/Mo back electrode, prepare Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer:
Cu is prepared respectively first by Bridgman method1-xNaxInS2、CuInS2And Cu1-xAgxInS2Polycrystal silicon ingot, after pulverizing, weighs 1g respectively and puts in tungsten boat and make evaporation source; Then adopt conventional or tiltedly plunder Vacuum sublimation on Ti/TiN/Mo back electrode, deposit Cu successively1-xNaxInS2Thin film, CuInS2Thin film, wherein, Cu1-xNaxInS2Film thickness is 50-100nm, CuInS2Film thickness is 2-3um, then by the Cu after deposit1-xNaxInS2/CuInS2Thin film is placed in the annealing device under sulfur-bearing atmosphere and is annealed, and forms Cu1-xNaxInS2/CuInS2Laminated film, adopts bromine methanol solution to Cu1-xNaxInS2/CuInS2Laminated film corrodes; Adopt conventional or tiltedly plunder Vacuum sublimation Cu after corrosion1-xNaxInS2/CuInS2Laminated film deposits Cu1-xAgxInS2Thin layer, then by the Cu after deposit1-xNaxInS2/CuInS2/Cu1-xAgxInS2Put in annealing device and be annealed, then adopt bromine methanol solution to corrode, form Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer;
(4). on absorbed layer, prepare Cd1-xZnxS barrier layer: with cadmium acetate, zinc acetate, ammonium acetate and ammonia spirit for raw material, adopts chemical deposition at Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer deposits Cd1-xZnxS thin film is as barrier layer;
(5). at Cd1-xZnxS barrier layer deposits i-ZnO thin film, Al:ZnO thin film successively, make i-ZnO/Al:ZnO Window layer: adopt magnetron sputtering method to deposit i-ZnO thin film, Al:ZnO thin film over the barrier layer successively, form i-ZnO/Al:ZnO Window layer, wherein, i-ZnO film thickness is 10-50nm, Al:ZnO film thickness is 500-700nm;
(6). electrode before preparation in i-ZnO/Al:ZnO Window layer: adopt Vacuum Heat to steam method evaporating Al (Ni) front electrode in i-ZnO/Al:ZnO Window layer, place into and vacuum annealing equipment carries out vacuum annealing, annealing temperature 300～450 DEG C, annealing time 60～120 minutes, it is thus achieved that copper and indium sulfenyl thin-film solar cells.
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| CN101944541A (en) * | 2009-07-08 | 2011-01-12 | 深圳先进技术研究院 | Thin-film photovoltaic cell and manufacturing method thereof |
| CN104409535A (en) * | 2014-09-30 | 2015-03-11 | 天津理工大学 | A copper zinc tin sulfide thin film solar cell device and preparing method thereof |
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| CN101944541A (en) * | 2009-07-08 | 2011-01-12 | 深圳先进技术研究院 | Thin-film photovoltaic cell and manufacturing method thereof |
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