CN105679881B - A kind of preparation method of indium sulphur based thin film solar cell - Google Patents
A kind of preparation method of indium sulphur based thin film solar cell Download PDFInfo
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- CN105679881B CN105679881B CN201610120003.8A CN201610120003A CN105679881B CN 105679881 B CN105679881 B CN 105679881B CN 201610120003 A CN201610120003 A CN 201610120003A CN 105679881 B CN105679881 B CN 105679881B
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- 239000010409 thin film Substances 0.000 title claims abstract description 25
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000010408 film Substances 0.000 claims abstract description 64
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000004888 barrier function Effects 0.000 claims abstract description 19
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 229910004576 Cd1-xZnxS Inorganic materials 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000000137 annealing Methods 0.000 claims description 19
- 210000004027 cell Anatomy 0.000 claims description 19
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- 238000007738 vacuum evaporation Methods 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 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
- 238000005260 corrosion Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 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
- 238000002207 thermal evaporation Methods 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical class N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 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
- 210000002381 plasma Anatomy 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 235000013904 zinc acetate Nutrition 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 235000015096 spirit Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- -1 wherein Substances 0.000 claims description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 2
- 230000003628 erosive effect Effects 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 46
- 238000004544 sputter deposition Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000928 Yellow copper Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002061 vacuum sublimation Methods 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 229910002708 Au–Cu Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 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
- 238000005234 chemical deposition Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000004246 zinc acetate Substances 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
- H01L31/032—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)
- Physical Vapour Deposition (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a kind of preparation method of indium sulphur based thin film solar cell, the battery structure is followed successively by from bottom to top：Substrate/Ti TiN Mo back electrodes/Cu1‑xNaxInS2/CuInS2/Cu1‑ xAgxInS2Absorbed layer/Cd1‑xZnxS barrier layers i ZnO/Al:Electrode before ZnO Window layers/Al (Ni), this method step is：(1) substrate cleaning and pretreatment；(2) Ti/TiN/Mo back electrodes are prepared on substrate；(3) Cu is prepared on Ti/TiN/Mo back electrodes1‑xNaxInS2/CuInS2/Cu1‑xAgxInS2Absorbed layer；(4) Cd is prepared on absorbed layer1‑xZnxS barrier layers；(5) in Cd1‑xZnxI ZnO films, Al are deposited on S barrier layers successively：ZnO film, is made i ZnO/Al:ZnO Window layers；(6) method is steamed in i ZnO/Al using Vacuum Heat:Electrode before evaporating Al (Ni) in ZnO Window layers, obtains indium sulphur based thin film solar cell.The indium sulphur based thin film solar cell that prepared by the present invention, the adhesiveness be bonded between glass substrate and absorption layer film of the back electrode of the battery is strong, is difficult to peel off, reliability is high, the series resistance between each layer is small, can improve photovoltaic energy conversion efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of indium sulphur based thin film solar cell, belong to solar cell fabrication process
Technical field.
Background technology
In recent years, semiconductor nano has the characteristic of discontinuous band structure and many excitons, the film in terms of cost
Solar cell has cost advantage than crystal silicon solar energy battery, wherein, thin-film solar cells is using semiconductive thin film as light
Absorbed layer, the consumption of raw material less, price it is low, beneficial to reducing cost, therefore thin-film solar cells turns into main R＆D direction.
CuInS2Belong to I-III-VI systems ternary compound, its energy gap is between 1.3-1.7ev, close to the theory of solar cell
Optimal energy gap, and change of the energy gap to temperature is insensitive, the absorption coefficient of light is up to 105cm-1.In addition, its stability
Height, without significant change, capability of resistance to radiation is strong, is adapted for use as the battery material of spacecraft within 7 years for outdoor illumination.Work as CuInS2
Chemical composition will produce point defect when deviateing chemical dosage ratio, and such as species of room, gap and dislocation is up to 12 kinds, these points
Defect can produce new energy level in forbidden band.In addition, CuInS2Allow composition nonstoichiometry than wider range, wherein, unijunction
CuInS2The theoretical conversion efficiencies of homojunction solar cell reach 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 include CuInS2, CuI, ZnO, its structure is followed successively by：CuInS2/CuI/ZnO.Due to not
It is larger with the contact resistance between layer, cause the series resistance between each layer to increase, the light absorbs effect of influence solar cell
Rate.
The content of the invention
The defect existed for prior art, it is an object of the invention to provide a kind of indium sulphur based thin film solar cell
Preparation method, this method prepare solar cell in series resistance it is small, the absorption efficiency of battery can be improved.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of preparation method of indium sulphur based thin film solar cell, the film solar battery structure from bottom to top according to
It is secondary to be：Substrate/Ti-TiN-Mo back electrodes/Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer/Cd1-xZnxS barrier layers/
i-ZnO/Al:Electrode before ZnO Window layers/Al (Ni), this method has following processing step：
(1) cleaning of substrates and pretreatment：Successively using acetone, ethanol and deionized water ultrasonic cleaning each to substrate
15min, then substrate is performed etching using Ar plasmas；
(2) prepares Ti/TiN/Mo back electrodes on substrate：Ti/TiN/ is sequentially prepared on substrate using magnetron sputtering method
Bottom Ti films, TiAlN thin film, the Mo films of Mo back electrodes, are made Ti/TiN/Mo back electrodes；
(3) prepares Cu on Ti/TiN/Mo back electrodes1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer：
Cu is prepared respectively first by Bridgman method1-xNaxInS2、CuInS2And Cu1-xAgxInS2Polycrystal silicon ingot, is crushed
Afterwards, 1g is weighed respectively and is put into tungsten boat make evaporation source；Then using conventional vacuum thermal evaporation on Ti/TiN/Mo back electrodes according to
Secondary deposit Cu1-xNaxInS2Film, CuInS2Film, wherein, Cu1-xNaxInS2Film thickness is 50-100nm, CuInS2Film
Thickness is 2-3um, then by the Cu after deposit1-xNaxInS2/CuInS2Film is placed in the annealing device under sulfur-bearing atmosphere
Annealed, form Cu1-xNaxInS2/CuInS2Laminated film, using bromine methanol solution to Cu1-xNaxInS2/CuInS2It is compound
Thin film corrosive；Using Cu of the conventional vacuum thermal evaporation after corrosion1-xNaxInS2/CuInS2Cu is deposited on laminated film1- xAgxInS2Film layer, then by the Cu after deposit1-xNaxInS2/CuInS2/Cu1-xAgxInS2It is put into annealing device and is moved back
Fire, then using the corrosion of bromine methanol solution, form Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer；
(4) prepares Cd on absorbed layer1-xZnxS barrier layers：With cadmium acetate, zinc acetate, ammonium acetate and ammonia spirit are original
Material, using chemical deposition in Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Cd is deposited on absorbed layer1-xZnxS films are used as resistance
Barrier；
(5) is in Cd1-xZnxI-ZnO films, Al are deposited on S barrier layers successively：ZnO film, is made i-ZnO/Al:ZnO windows
Mouth layer：I-ZnO films, Al are deposited using magnetron sputtering method successively over the barrier layer：ZnO film, forms i-ZnO/Al:ZnO windows
Mouth layer, wherein, i-ZnO film thicknesses are 10-50nm, Al：ZnO film thickness is 500-700nm；
(6) is in i-ZnO/Al:Electrode before being prepared in ZnO Window layers：Method is steamed in i-ZnO/Al using Vacuum Heat:ZnO windows
Electrode before evaporating Al (Ni), is placed into and vacuum annealing is carried out in vacuum annealing equipment on layer, and 300~450 DEG C of annealing temperature is moved back
It is fiery 60~120 minutes time, final to obtain indium sulphur based thin film solar cell.
Compared with prior art, the present invention has the advantages that to protrude as follows：
1. indium sulphur based thin film solar cell prepared by the method for the present invention, due to the back electrode and glass of the battery
The substrate and adhesiveness that is bonded is strong between absorbing layer film, is difficult to peel off, and can improve the stability being electrically connected and device
Series resistance between reliability, and each layer is small, can improve photovoltaic energy conversion efficiency.
2. in indium sulphur based thin film solar cell prepared by the method for the present invention, Cu is removed using bromine methanol solution1- xNaxInS2/CuInS2/Cu1-xAgxInS2The Cu on laminated film surfacexS-phase and AgxS-phase, methanol solution instead of poisonous cyaniding
Thing corrosive agent, optimizes production environment, and laminated film surface is finer and close, and efficiency of light absorption is higher.
Brief description of the drawings
Fig. 1 is the schematic diagram of structure of the present invention.
Fig. 2 (a) be the present invention method in vacuum evaporation, substrate tilting angle be 0oCuInS2SEM spectrum.
Fig. 2 (b) be the present invention method in vacuum evaporation, substrate tilting angle be 40oCuInS2SEM spectrum.
Fig. 2 (c) be the present invention method in vacuum evaporation, substrate tilting angle be 60oCuInS2SEM spectrum.
Fig. 3 (a) is that substrate tilt angle is respectively 0 without annealingo、40oWith 60oCuInS2The Raman of film
Collection of illustrative plates.
Fig. 3 (b) is that substrate tilt angle is respectively 0 after 400 DEG C of annealing temperature processingo、40oWith 60oCuInS2It is thin
The Raman collection of illustrative plates of film.
Embodiment
1 the present invention is described in more detail below in conjunction with the accompanying drawings.
As shown in figure 1, a kind of indium sulphur based thin film solar cell structure, 1 is substrate, and 2 be Ti/TiN/Mo back electrodes, 3
For Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer, 4 be Cd1-xZnxS barrier layers, 5 be i-ZnO/Al:ZnO Window layers,
6 be electrode before Al (Ni).
A kind of the preferred embodiments of the present invention, multilayer cascades the preparation method of indium sulphur based solar battery, this method tool
There is following processing step：
(1) substrates 1 are cleaned and pre-processed：From sheet glass as substrate, substrate is cut into 1.5cm × 2cm；Successively
Using acetone, ethanol and ionized water ultrasonic cleaning 15min each to substrate, then use high pure nitrogen drying is gone, then using Ar etc.
Gas ions perform etching cleaning to substrate, and Ar plasma apparatus voltages are that 720V, electric current are 25mA, and etch period is 30min.
(2) 1 on substrate on prepare Ti/TiN/Mo back electrodes 2：Start magnetron sputtering apparatus first, installation target is Ti
Target, sputtering pressure is that 0.5pa, sputtering power are 160W, sputtering time 15min, 1 on substrate on to form bottom Ti thin
Film；Then it is TiN targets to change target, and adjustment substrate 1 inclination angle is 45 °, and sputtering pressure is that 0.5pa, sputtering power are
160W, sputtering time 10min are sputtered, in Ti films formation TiAlN thin film；It is Mo targets finally to change target, and sputtering pressure is
0.5Pa, sputtering power 60W, sputtering time 10min are prepared into Ti/TiN/Mo back electrodes 2 in TiAlN thin film formation Mo films；
(3) prepares Cu on Ti/TiN/Mo back electrodes 21-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer 3：
(3-1) is sequentially prepared Cu respectively by Bridgman method1-xNaxInS2、CuInS2、Cu1-xAgxInS copper and indium sulphur powders
Not, the Cu that weight is 1g is weighed successively respectively1-xNaxInS2、CuInS2、Cu1-xAgxInS2Indium sulphur powder is put into as evaporation source
In tungsten boat in vacuum evaporation equipment, described vacuum evaporation equipment, operating air pressure is 3 × 10-6Torr, the inclination angle of substrate is
The angle of the normal of substrate and incident steam, adjustment inclination angle is respectively 0o, 40oWith 60, deposition voltage is 10kV, deposition current
For 5~200mA；
(3-2) deposits Cu successively using Vacuum sublimation on Ti/TiN/Mo back electrodes1-xNaxInS2Film,
CuInS2Film, obtains Cu1-xNaxInS2/CuInS2, wherein, Cu1-xNaxInS2The thickness of film is 50-100nm, CuInS2It is thin
The thickness of film is 2-3um, and test substrate inclination angle is 0o、40o、60o、CuInS2SEM figures be respectively, Fig. 2 (a), Fig. 2 (b),
Shown in Fig. 2 (c)；By the CuInS of preparation2Film carries out Raman tests, shown in such as Fig. 3 (a), Fig. 3 (b), in Raman collection of illustrative plates,
290cm-1Place and 304cm-1The diffraction maximum at place corresponds to yellow copper structure CuInS respectively2A1Mould and Au-Cu phases CuInS2A1 *
Mould, passes through the A without annealing1The diffraction maximum of mould and the A after 400 °C of annealing temperatures1 *The diffraction maximum of mould compares table
It is bright, the CuInS of Cu-Au phases2It is converted into yellow copper structure CuInS2, the crystallinity of film is stronger；
(3-3) is by the Cu after deposit1-xNaxInS2/CuInS2Film is placed in the annealing device under sulfur-bearing atmosphere and carried out
Annealing, forms Cu1-xNaxInS2/CuInS2Laminated film, using bromine methanol solution to Cu1-xNaxInS2/CuInS2Laminated film
Corrosion；
(3-4) uses Cu of the Vacuum sublimation after corrosion1-xNaxInS2/CuInS2Cu is deposited on laminated film1- xAgxInS2Film layer；
(3-5) is by the Cu after deposit1-xNaxInS2/CuInS2/Cu1-xAgxInS2Annealed, annealed in sulfur-bearing atmosphere
Temperature is 400 DEG C, annealing time 30min-60min, is 1 by ratio of weight and the number of copies by bromine and methanol:10000 ratio is mixed
Solution corrosion, etching time is 1min, removes surface sulfide thing (CuxS), Cu is obtained1-xNaxInS2/CuInS2/Cu1- xAgxInS films 3；
(4) prepares Cd on absorbed layer 31-xZnxS barrier layers 4：Weigh 20mL concentration be 0.2mol/L cadmium acetate,
20mL concentration is that 0.1mol/L zinc acetates, 2mL concentration are 1mol/L ammonium acetates and 0.5ml concentration is 1mol/L ammonia spirits, is used
Temperature control magnetic stirring apparatus magnetic agitation 1min under 65 DEG C, 200r/min rotating speed；Solution after stirring is added dropwise in Cu1- xNaxInS2/CuInS2/Cu1-xAgxInS2The surface of absorbed layer 3, it is 0.2mol/L thiocarbamides then to add 20mL concentration, is stirred in magnetic force
Mix down, keep 10-20min, take out substrate, with deionized water rinsing, vacuum drying obtains Cd1-xZnxS barrier layers 4；
(5) uses magnetron sputtering method in Cd1-xZnxI-ZnO films, Al are deposited on S barrier layers 4 successively:ZnO film, system
Into i-ZnO/ Al:ZnO/Al（Ni）Window layer 5：
In Cd1-xZnxI-ZnO films, Al are deposited on S barrier layers 4 successively：ZnO film, forms i-ZnO/Al:ZnO, it is described
Magnetron sputtering method be：Intrinsic ZnO target is put into the sputtering target position in magnetron sputtering apparatus, by Cd1-xZnxS barrier layers 4 are placed on
10min formation i-ZnO films are sputtered on 4 on plated film platform, wherein, sputtering pressure is that 0.5Pa, sputtering power are 100W；Then take
Go out intrinsic ZnO target, be loaded on Al:ZnO target, sputtering 15min obtains i-ZnO/ Al:ZnO Window layers 5, wherein sputtering pressure are
1pa, magnetron sputtering power 95W；
(6) is in i-ZnO/ Al:Al is prepared in ZnO Window layers 5（Ni）Preceding electrode 6：Weigh the Al of 0.1g mass（Ni）,
It is placed in the evaporation tungsten boat in vacuum evaporation coating machine, by i-ZnO/ Al:ZnO Window layers 5 are placed on the gate mask on work rest
Version, is heated to after preset temperature, stable 10-30min controls vacuum evaporation coating machine parameter, starts to steam with default evaporation rate
Plating, until the Al in evaporation tungsten boat（Ni）It is evaporated, in i-ZnO/ Al:The formation of ZnO Window layers 5 Al（Ni）Preceding electrode 6, then enter
Row vacuum annealing, so that electrode has good contact.
Claims (1)
1. a kind of preparation method of indium sulphur based thin film solar cell, it is characterised in that the film solar battery structure
It is followed successively by from bottom to top：Substrate/Ti/TiN/Mo back electrodes/Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer/Cd1- xZnxS barrier layers i-ZnO/Al:Electrode before ZnO Window layers/Al (Ni), this method has steps of：
(1) cleaning of substrates and pretreatment：Acetone, ethanol and deionized water ultrasonic cleaning 15min each to substrate are used successively, then
Substrate is performed etching using Ar plasmas；
(2) prepares Ti/TiN/Mo back electrodes on substrate：The Ti/TiN/Mo back ofs the body are sequentially prepared on substrate using magnetron sputtering method
Bottom Ti films, TiAlN thin film, the Mo films of electrode, are made Ti/TiN/Mo back electrodes；
(3) prepares Cu on Ti/TiN/Mo back electrodes1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer：
Cu is prepared respectively first by Bridgman method1-xNaxInS2、CuInS2And Cu1-xAgxInS2Polycrystalline ingot, after crushing, respectively
Weigh 1g and be put into tungsten boat and make evaporation source；Then deposited successively on Ti/TiN/Mo back electrodes using conventional vacuum thermal evaporation
Cu1-xNaxInS2Film, CuInS2Film, wherein, Cu1-xNaxInS2Film thickness is 50-100nm, CuInS2Film thickness is
2-3um, then by the Cu after deposit1-xNaxInS2/CuInS2Moved back in the annealing device that film is placed under sulfur-bearing atmosphere
Fire, forms Cu1-xNaxInS2/CuInS2Laminated film, using bromine methanol solution to Cu1-xNaxInS2/CuInS2Laminated film is rotten
Erosion；Using Cu of the conventional vacuum thermal evaporation after corrosion1-xNaxInS2/CuInS2Cu is deposited on laminated film1-xAgxInS2It is thin
Film layer, then by the Cu after deposit1-xNaxInS2/CuInS2/Cu1-xAgxInS2It is put into annealing device and is annealed, then uses
Bromine methanol solution corrodes, and forms Cu1-xNaxInS2/CuInS2/Cu1-xAgxInS2Absorbed layer；
(4) prepares Cd on absorbed layer1-xZnxS barrier layers：Weighing cadmium acetate, 20mL concentration that 20mL concentration is 0.2mol/L is
0.1mol/L zinc acetates, 2mL concentration are 1mol/L ammonium acetates and 0.5ml concentration is 1mol/L ammonia spirits, are stirred with temperature control magnetic force
Mix device magnetic agitation 1min under 65 DEG C, 200r/min rotating speed；Solution after stirring is added dropwise in Cu1-xNaxInS2/
CuInS2/Cu1-xAgxInS2Layer surface is absorbed, it is 0.2mol/L thiocarbamides then to add 20mL concentration, under magnetic stirring, is kept
10-20min, takes out substrate, with deionized water rinsing, vacuum drying obtains Cd1-xZnxS barrier layers；
(5) is in Cd1-xZnxI-ZnO films, Al are deposited on S barrier layers successively：ZnO film, is made i-ZnO/Al:ZnO Window layers：
I-ZnO films, Al are deposited using magnetron sputtering method successively over the barrier layer：ZnO film, forms i-ZnO/Al:ZnO Window layers,
Wherein, i-ZnO film thicknesses are 10-50nm, Al：ZnO film thickness is 500-700nm；
(6) is in i-ZnO/Al:Electrode before being prepared in ZnO Window layers：The Al (Ni) of 0.1g mass is weighed, vacuum evaporation coating is placed on
In evaporation tungsten boat in machine, by i-ZnO/Al:ZnO Window layers are placed in the gate mask version on work rest, are heated to default temperature
After degree, stable 10-30min controls vacuum evaporation coating machine parameter starts evaporation with default evaporation rate, until in evaporation tungsten boat
Al (Ni) be evaporated, in i-ZnO/Al:Electrode before Al (Ni) is formed in ZnO Window layers, places into and enters in vacuum annealing equipment
Row vacuum annealing, 300~450 DEG C of annealing temperature, annealing time 60~120 minutes obtains indium sulphur based thin film solar cell.
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