CN112853264B - Method for preparing copper indium gallium selenide thin-film solar cell in selenium-free atmosphere - Google Patents
Method for preparing copper indium gallium selenide thin-film solar cell in selenium-free atmosphere Download PDFInfo
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- CN112853264B CN112853264B CN202011560558.7A CN202011560558A CN112853264B CN 112853264 B CN112853264 B CN 112853264B CN 202011560558 A CN202011560558 A CN 202011560558A CN 112853264 B CN112853264 B CN 112853264B
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- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000010409 thin film Substances 0.000 title claims abstract description 17
- 238000004544 sputter deposition Methods 0.000 claims abstract description 180
- 239000001257 hydrogen Substances 0.000 claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000010521 absorption reaction Methods 0.000 claims abstract description 35
- 230000004888 barrier function Effects 0.000 claims abstract description 32
- 239000013077 target material Substances 0.000 claims abstract description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 108
- 239000007789 gas Substances 0.000 claims description 104
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 60
- 229910052786 argon Inorganic materials 0.000 claims description 54
- 239000010408 film Substances 0.000 claims description 46
- 239000008367 deionised water Substances 0.000 claims description 43
- 229910021641 deionized water Inorganic materials 0.000 claims description 43
- 239000000758 substrate Substances 0.000 claims description 35
- 239000011787 zinc oxide Substances 0.000 claims description 31
- QMXBEONRRWKBHZ-UHFFFAOYSA-N [Na][Mo] Chemical compound [Na][Mo] QMXBEONRRWKBHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000004140 cleaning Methods 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 239000011733 molybdenum Substances 0.000 claims description 13
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical group OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000012459 cleaning agent Substances 0.000 claims description 11
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 10
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004642 Polyimide Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005083 Zinc sulfide Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 2
- 239000005361 soda-lime glass Substances 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 16
- 239000011669 selenium Substances 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 9
- 239000011684 sodium molybdate Substances 0.000 description 9
- 235000015393 sodium molybdate Nutrition 0.000 description 9
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000010965 430 stainless steel Substances 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 239000001509 sodium citrate Substances 0.000 description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052711 selenium Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 4
- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention discloses a method for preparing a copper indium gallium selenide thin-film solar cell in a selenium-free atmosphere. The method comprises the following steps: a. preparing a barrier layer; b. preparing a back electrode layer; c. preparing a copper indium gallium selenide absorption layer: introducing hydrogen in the process of sputtering the copper indium gallium selenide absorption layer, or sputtering the copper indium gallium selenide target material for 1-5min at low power after the copper indium gallium selenide absorption layer is sputtered, and simultaneously introducing hydrogen; d. preparing a buffer layer; e. preparing a high-resistance layer; f. and preparing a window layer. The method has the advantages of simple process, good consistency, small defect density of the prepared absorption layer, excellent front-back contact, capability of preparing and obtaining high-efficiency batteries and wide application prospect.
Description
Technical Field
The invention relates to the technical field of thin film solar cell preparation, in particular to a method for preparing a copper indium gallium selenide thin film solar cell in a selenium-free atmosphere.
Background
In the world of today, energy is a common concern all over the world and all over the human, and is also an important material basis for social progress and human activities, which plays a crucial role in the healthy and continuous development of the global economy and the daily life of people. At present, fossil energy such as petroleum and coal is exhausted, and the use of the fossil energy generates a large amount of harmful gas, so that the ecological environment is irreversibly damaged and the survival of human beings is endangered. From the perspective of sustainable development, clean and pollution-free renewable energy sources, such as tidal energy, wind energy, geothermal energy, solar energy, etc., are vigorously developed. With the enhancement of environmental awareness of people, the development of solar cells becomes the key direction in the research field of renewable energy resources at home and abroad.
Photovoltaic power generation is an important development direction for renewable energy utilization, and a Copper Indium Gallium Selenide (CIGS) thin film material is a research hotspot in the field of photovoltaic technology, has the advantages of rich raw materials, low cost, high light absorption coefficient, high theoretical conversion efficiency, adjustable forbidden bandwidth and the like, and the preparation research of the current high-efficiency CIGS solar cell has attracted extensive attention, and the highest conversion efficiency of the current high-efficiency CIGS solar cell is reported to reach 23.4 percent and is 1 percent higher than that of a polysilicon technical cell.
By using vacuum magnetron sputtering technology, which is known for its high deposition rate and good large surface uniformity, many companies have been able to prepare high efficiency modules: MiaSol é 16.5%, 17.5% from Solar Frontier and 18.2% from AVANCIS. The solar Frontier produced CIGS without cadmium in 2019 to a single point world maximum efficiency of 23.3%. Although these companies can produce high-efficiency battery modules, highly toxic H is inevitably used in the production process thereof 2 Se gas or Se vapor. Based on H 2 The high toxicity of Se gas, the high energy consumption of Se vapor, the generated waste treatment and other practical problems, and the excessive selenium can be enriched on the inner wall of the vacuum chamber, which increases the equipment maintenance cost and maintenance frequency, so the selenium-free atmosphere high-temperature direct sputtering method becomes the key point of researchExternal selenium atmospheres and annealing are receiving increasing attention from many research groups. However, in the absence of a selenium atmosphere, a large number of VSe vacancies and InCu substitutional defects are formed by volatilization of selenium element in a high-temperature preparation process, and the internal defects of the prepared absorber layer are high, so that the preparation of a high-efficiency CIGS battery by directly sputtering a quaternary alloy target has great challenges.
Disclosure of Invention
The invention aims to provide a method for preparing a copper indium gallium selenide thin-film solar cell in a selenium-free atmosphere, and the method is used for solving the problem that the defects in the copper indium gallium selenide thin film prepared by the existing direct sputtering method in the selenium-free atmosphere are high.
The technical scheme adopted by the invention is as follows: a method for preparing a copper indium gallium selenide thin-film solar cell in a selenium-free atmosphere comprises the following steps:
a. preparation of a barrier layer: depositing a barrier layer with the thickness of 50-800nm on the pretreated substrate by adopting a magnetron sputtering or plasma enhanced chemical vapor deposition method;
b. preparing a back electrode layer: depositing a back electrode layer with the thickness of 600-1000nm on the barrier layer by adopting a magnetron sputtering method;
c. preparing a copper indium gallium selenide absorption layer: b, heating the substrate processed in the step b to 400-600 ℃ by using an annular graphite device, and preparing the copper indium gallium selenide absorption layer with the thickness of 1.3-1.7 mu m by using a magnetron sputtering method; introducing hydrogen in the process of sputtering the CIGS absorbing layer, wherein the introduced hydrogen is 0.1-20% of the argon flow, and preferably 3-9%; or after the copper indium gallium selenide absorption layer is sputtered, keeping the temperature of the substrate unchanged, and sputtering at the sputtering pressure of 0.5-2pa and the sputtering power of 0.1-0.5w/cm 2 Under the condition, sputtering the copper indium gallium selenide target material for 1-5min, and introducing hydrogen, wherein the introduced hydrogen is 0.1-100% of the argon flow;
d. preparing a buffer layer: preparing a buffer layer with the thickness of 40-100nm on the copper indium gallium selenide absorption layer by adopting a chemical water bath or magnetron sputtering method;
e. preparing a high-resistance layer: preparing an intrinsic zinc oxide high-resistance layer with the thickness of 80-120nm on the buffer layer by adopting a magnetron sputtering method;
f. preparation of a window layer: and preparing an aluminum-doped zinc oxide window layer with the thickness of 200-500nm on the high-resistance layer by adopting a magnetron sputtering method.
In the step a, the substrate is one of a stainless steel sheet with the thickness of 50-300 μm, a soda-lime glass sheet with the thickness of 1-3.2mm and a polyimide substrate with the thickness of 25-200 μm, and the cleaning mode of the substrate is as follows: the substrate is cleaned by a roller brush and a cleaning agent for the first time, then washed by deionized water under ultrasonic waves, and finally dried by a hot air knife.
In the step a, the barrier layer is a simple substance film, a nitride/oxide film or a tungsten-titanium alloy film, the sputtering air pressure for preparing the barrier layer is 0.2-1pa, and the sputtering power is 0.1-8w/cm 2 。
In the step a, when the substrate is made of polyimide material, the barrier layer is a multilayer metal film of aluminum/titanium/tungsten alternately.
In the step b, the back electrode layer is a molybdenum film or a double-layer film of molybdenum sodium and molybdenum.
In the step c, the step of introducing hydrogen in the process of sputtering the CIGS absorbing layer means introducing hydrogen in the whole process of sputtering the CIGS absorbing layer, or introducing hydrogen in the end section process of sputtering the CIGS absorbing layer.
In the step c, when the CIGS absorbing layer is prepared, the sputtering process parameters are as follows: sputtering pressure is 0.1-1pa, total gas flow is 5-20sccm, sputtering power is 1-4w/cm 2 。
In the step d, the buffer layer is a cadmium sulfide film, a zinc sulfide film, an indium selenide film or a composite film of cadmium sulfide and zinc sulfide.
In the step d, when the sputtered target material is indium sulfide, the atomic molar ratio of In to S of the target material is 2: 3; when the sputtered target material is indium selenide, the atomic molar ratio of In to Se of the target material is 2: 3.
In the step d, after the preparation of the CIGS absorbing layer is finished and the temperature is reduced to the room temperature, the buffer layer is sputtered at the normal temperature, the sputtering gas is argon, the sputtering pressure is 0.3-0.8pa, the sputtering gas flow is 5-20sccm, and the sputtering power density is 0.3-1w/cm 2 。
According to the invention, hydrogen is introduced into a selenium-free sputtering process as active gas, so that the concentrations of Vcu vacancy defects and InCu substitutional defects in the absorption layer are reduced, the doping step of hydrogen and the optimization of hydrogen flow are controlled, the secondary phase on the surface of the absorption layer can be passivated, and the copper vacancy defects formed by selenium-deficient atmosphere can also be passivated. The hydrogen element diffuses into the surface of the CIGS absorption layer, so that the subsequent cadmium element and sulfur are promoted to diffuse into the surface of the CIGS absorption layer, and a surface inversion is formed on the surface, so that the high-efficiency device preparation is realized. In the sputtering process of the absorption layer, CIGS crystal grain growth with the grain size larger than 2 microns is obtained when the hydrogen flow is optimized, which cannot be realized in the sputtering process of the prior art without selenium atmosphere, the process is CIGS one-step sputtering forming, the process is simple and good in consistency, the defect density of the prepared absorption layer is small, the contact between the front and the back is excellent, a high-efficiency battery can be prepared, and the method has a wide application prospect.
Drawings
Fig. 1 is an SEM surface picture of the CIGS absorber prepared in example 1.
Fig. 2 is an SEM surface picture of the CIGS absorber prepared in comparative example 1.
Figure 3 is the sample XRD test (112) (220) full width at half maximum fit results for examples 1 to 5 and comparative example 1.
Detailed Description
The following examples are intended to illustrate the present invention in further detail, but the present invention is not limited thereto in any way. Reagents, gases, methods and apparatus used in the present invention are reagents, gases, methods and apparatus common in the art unless otherwise specified.
Example 1
The preparation method of the battery comprises the following steps:
step one, cleaning a substrate: selecting a 430 stainless steel sheet with the thickness of 150 mu m, firstly cleaning the sheet by a rolling brush and cleaning agent, then washing the sheet by deionized water under ultrasonic waves, and then drying the substrate by a hot air knife at 80 ℃;
step two, preparing a barrier layer: miningThe mode of magnetron sputtering tungsten-titanium alloy target material is adopted, and the sputtering power is 4w/cm 2 Preparing a 600nm barrier layer by using argon as sputtering gas, wherein the gas flow is 10sccm, and the gas pressure is preferably 0.15 pa;
step three, preparing a back electrode layer: preparing a 300nm molybdenum-sodium film by adopting a magnetron sputtering molybdenum-sodium target containing 5% sodium molybdate, wherein the argon flow is 10sccm, the sputtering pressure is 0.5pa, and the sputtering power is 2w/cm 2 Then preparing a 600nm molybdenum film on the molybdenum sodium film by adopting a magnetron sputtering mode;
step four, preparing a CIGS absorption layer: hydrogen is used as sputtering gas, hydrogen is introduced in the whole sputtering process, the sputtering pressure is 0.5pa, the gas flow is 10sccm, the ratio of hydrogen to argon is 5 percent, and the sputtering power is 2.3w/cm 2 Preparing an absorbing layer with the thickness of 1.5 mu m;
step five, preparing a buffer layer: firstly, 0.4g of cadmium acetate is dissolved in 50mL of deionized water, 0.882g of sodium citrate is dissolved in 20mL of deionized water, 1.9g of thiourea is dissolved in 40mL of deionized water, polytetrafluoroethylene magnetons are adopted to rotate and stir until powder is completely dissolved, the easily mixed gold is added into 10mL of ammonia water, the mixture is uniformly stirred and put into a reaction container, the container is placed into a 75 ℃ water bath kettle, the container is taken out after reaction for 10min, the thickness of a buffer layer is controlled by controlling the reaction time after the deionized water is used for cleaning and drying, the chemical water bath mode is adopted for 10min, and the thickness of the cadmium sulfide buffer layer prepared on the surface of a CIGS absorption layer is 60 nm;
step six, preparing a high-resistance layer: preparing a 100nm zinc oxide high-resistance layer on the surface of the buffer layer by adopting a magnetron sputtering intrinsic zinc oxide target, wherein the sputtering gas is argon, the gas flow is 15sccm, the sputtering pressure is 0.4pa, and the sputtering power is 100 w;
step seven, preparing a window layer: a magnetron sputtering mode of the aluminum-doped zinc oxide target is adopted, a front electrode window layer with the thickness of 400nm is prepared on the surface of the high-resistance layer, the sputtering gas is argon, the gas flow is 15sccm, the gas sputtering pressure is 0.4pa, and the sputtering power is 500 w. The samples obtained were characterized and the results are shown in fig. 1, fig. 3 and table 1.
Example 2
The preparation method of the battery comprises the following steps:
step one, cleaning a substrate: selecting a 430 stainless steel sheet with the thickness of 150 mu m, firstly cleaning the sheet by a rolling brush and cleaning agent, then washing the sheet by deionized water under ultrasonic waves, and then drying the substrate by a hot air knife at 80 ℃;
step two, preparing a barrier layer: preparing a 600nm barrier layer by adopting a magnetron sputtering mode of a tungsten-titanium alloy target material, wherein the sputtering power is 4w/cm2, the sputtering gas is argon, the gas flow is 10sccm, and the gas pressure is 0.15 pa;
step three, preparing a back electrode layer: preparing a 300nm molybdenum-sodium film by adopting magnetron sputtering of a molybdenum-sodium target containing 5% sodium molybdate, wherein the argon flow is 10sccm, the sputtering pressure is 0.5pa, and the sputtering power is 2w/cm 2 Then preparing a 600nm molybdenum film on the molybdenum sodium film by adopting a magnetron sputtering mode;
step four, preparing a CIGS absorption layer: adopting hydrogen as sputtering gas, introducing hydrogen in the whole sputtering process, wherein the sputtering gas pressure is 0.5pa, the gas flow is 10sccm, the ratio of hydrogen to argon is 1%, and the sputtering power is 2.3w/cm 2 Preparing an absorbing layer with the thickness of 1.5 mu m;
step five, preparing a buffer layer: firstly, 0.4g of cadmium acetate is dissolved in 50mL of deionized water, 0.882g of sodium citrate is dissolved in 20mL of deionized water, 1.9g of thiourea is dissolved in 40mL of deionized water, polytetrafluoroethylene magnetons are adopted to rotate and stir until powder is completely dissolved, the easily mixed gold is added into 10mL of ammonia water, the mixture is uniformly stirred and put into a reaction container, the container is placed into a 75 ℃ water bath kettle, the container is taken out after reaction for 10min, the thickness of a buffer layer is controlled by controlling the reaction time after the deionized water is used for cleaning and drying, the chemical water bath mode is adopted for 10min, and the thickness of the cadmium sulfide buffer layer prepared on the surface of a CIGS absorption layer is 60 nm;
step six, preparing a high-resistance layer: preparing a 100nm zinc oxide high-resistance layer on the surface of the buffer layer by adopting a magnetron sputtering intrinsic zinc oxide target, wherein the sputtering gas is argon, the gas flow is 15sccm, the sputtering pressure is 0.4pa, and the sputtering power is 100 w;
step seven, preparing a window layer: a400 nm front electrode window layer is prepared on the surface of the high-resistance layer by adopting a magnetron sputtering mode of an aluminum-doped zinc oxide target, the sputtering gas is argon, the gas flow is 15sccm, the gas sputtering pressure is 0.4pa, and the sputtering power is 500 w. The samples obtained were characterized and the results are shown in fig. 1, fig. 3 and table 1.
Example 3
The preparation method of the battery comprises the following steps:
step one, cleaning a substrate: selecting a 430 stainless steel sheet with the thickness of 150 mu m, firstly cleaning the sheet for the first time in a mode of rolling brush and cleaning agent, then washing the sheet with deionized water under ultrasonic waves, and then drying the substrate with a hot air knife at 80 ℃;
step two, preparing a barrier layer: preparing a 600nm barrier layer by adopting a magnetron sputtering mode of a tungsten-titanium alloy target material, wherein the sputtering power is 4w/cm2, the sputtering gas is argon, the gas flow is 10sccm, and the gas pressure is preferably 0.15 pa;
step three, preparing a back electrode layer: preparing a 300nm molybdenum-sodium film by adopting a magnetron sputtering molybdenum-sodium target containing 5% sodium molybdate, wherein the argon flow is 10sccm, the sputtering pressure is 0.5pa, and the sputtering power is 2w/cm 2 Then preparing a 600nm molybdenum film on the molybdenum sodium film by adopting a magnetron sputtering mode;
step four, preparing a CIGS absorption layer: hydrogen is used as sputtering gas, hydrogen is introduced in the whole sputtering process, the sputtering pressure is 0.5pa, the gas flow is 10sccm, the ratio of hydrogen to argon is 3 percent, and the sputtering power is 2.3w/cm 2 Preparing an absorbing layer with the thickness of 1.5 mu m;
step five, preparing a buffer layer: firstly, 0.4g of cadmium acetate is dissolved in 50mL of deionized water, 0.882g of sodium citrate is dissolved in 20mL of deionized water, 1.9g of thiourea is dissolved in 40mL of deionized water, polytetrafluoroethylene magnetons are adopted to rotate and stir until powder is completely dissolved, the easily mixed gold is added into 10mL of ammonia water, the mixture is uniformly stirred and put into a reaction container, the container is placed into a 75 ℃ water bath kettle, the container is taken out after reaction for 10min, the thickness of a buffer layer is controlled by controlling the reaction time after the deionized water is used for cleaning and drying, the chemical water bath mode is adopted for 10min, and the thickness of the cadmium sulfide buffer layer prepared on the surface of a CIGS absorption layer is 60 nm;
step six, preparing a high-resistance layer: preparing a 100nm zinc oxide high-resistance layer on the surface of the buffer layer by adopting a magnetron sputtering mode of an intrinsic zinc oxide target, wherein the sputtering gas is argon, the gas flow is 15sccm, the sputtering pressure is 0.4pa, and the sputtering power is 100 w;
step seven, preparing a window layer: a magnetron sputtering mode of the aluminum-doped zinc oxide target is adopted, a front electrode window layer with the thickness of 400nm is prepared on the surface of the high-resistance layer, the sputtering gas is argon, the gas flow is 15sccm, the gas sputtering pressure is 0.4pa, and the sputtering power is 500 w. The samples obtained were characterized and the results are shown in fig. 1, fig. 3 and table 1.
Example 4
The preparation method of the battery comprises the following steps:
step one, cleaning a substrate: selecting a 430 stainless steel sheet with the thickness of 150 mu m, firstly cleaning the sheet by a rolling brush and cleaning agent, then washing the sheet by deionized water under ultrasonic waves, and then drying the substrate by a hot air knife at 80 ℃;
step two, preparing a barrier layer: preparing a 600nm barrier layer by adopting a magnetron sputtering mode of a tungsten-titanium alloy target material, wherein the sputtering power is 4w/cm2, the sputtering gas is argon, the gas flow is 10sccm, and the gas pressure is preferably 0.15 pa;
step three, preparing a back electrode layer: preparing a 300nm molybdenum-sodium film by adopting a magnetron sputtering molybdenum-sodium target containing 5% sodium molybdate, wherein the argon flow is 10sccm, the sputtering pressure is 0.5pa, and the sputtering power is 2w/cm 2 Then preparing a 600nm molybdenum film on the molybdenum sodium film by adopting a magnetron sputtering mode;
step four, preparing a CIGS absorption layer: hydrogen is used as sputtering gas, hydrogen is introduced in the whole sputtering process, the sputtering pressure is 0.5pa, the gas flow is 10sccm, the ratio of hydrogen to argon is 7 percent, and the sputtering power is 2.3w/cm 2 Preparing an absorbing layer with the thickness of 1.5 mu m;
step five, preparing a buffer layer: firstly, 0.4g of cadmium acetate is dissolved in 50mL of deionized water, 0.882g of sodium citrate is dissolved in 20mL of deionized water, 1.9g of thiourea is dissolved in 40mL of deionized water, polytetrafluoroethylene magnetons are adopted to rotate and stir until powder is completely dissolved, the easily mixed gold is added into 10mL of ammonia water, the mixture is uniformly stirred and put into a reaction container, the container is placed into a 75 ℃ water bath kettle, the container is taken out after reaction for 10min, the thickness of a buffer layer is controlled by controlling the reaction time after the deionized water is used for cleaning and drying, the chemical water bath mode is adopted for 10min, and the thickness of the cadmium sulfide buffer layer prepared on the surface of a CIGS absorption layer is 60 nm;
step six, preparing a high-resistance layer: preparing a 100nm zinc oxide high-resistance layer on the surface of the buffer layer by adopting a magnetron sputtering intrinsic zinc oxide target, wherein the sputtering gas is argon, the gas flow is 15sccm, the sputtering pressure is 0.4pa, and the sputtering power is 100 w;
step seven, preparing a window layer: a magnetron sputtering mode of the aluminum-doped zinc oxide target is adopted, a front electrode window layer with the thickness of 400nm is prepared on the surface of the high-resistance layer, the sputtering gas is argon, the gas flow is 15sccm, the gas sputtering pressure is 0.4pa, and the sputtering power is 500 w. The samples obtained were characterized and the results are shown in fig. 1, fig. 3 and table 1.
Example 5
The preparation method of the battery comprises the following steps:
step one, cleaning a substrate: selecting a 430 stainless steel sheet with the thickness of 150 mu m, firstly cleaning the sheet by a rolling brush and cleaning agent, then washing the sheet by deionized water under ultrasonic waves, and then drying the substrate by a hot air knife at 80 ℃;
step two, preparing a barrier layer: preparing a 600nm barrier layer by adopting a magnetron sputtering mode of a tungsten-titanium alloy target material, wherein the sputtering power is 4W/cm2, the sputtering gas is argon, the gas flow is 10sccm, and the gas pressure is preferably 0.15 pa;
step three, preparing a back electrode layer: preparing a 300nm molybdenum-sodium film by adopting a magnetron sputtering molybdenum-sodium target containing 5% sodium molybdate, wherein the argon flow is 10sccm, the sputtering pressure is 0.5pa, and the sputtering power is 2w/cm 2 Then magnetron sputtering is adopted on the molybdenum sodium filmPreparing a 600nm molybdenum film;
step four, preparing a CIGS absorption layer: adopting hydrogen as sputtering gas, introducing hydrogen in the whole sputtering process, wherein the sputtering gas pressure is 0.5pa, the gas flow is 10sccm, the ratio of hydrogen to argon is 9 percent, and the sputtering power is 2.3w/cm 2 Preparing an absorbing layer with the thickness of 1.5 mu m;
step five, preparing a buffer layer: firstly, 0.4g of cadmium acetate is dissolved in 50mL of deionized water, 0.882g of sodium citrate is dissolved in 20mL of deionized water, 1.9g of thiourea is dissolved in 40mL of deionized water, polytetrafluoroethylene magnetons are adopted to rotate and stir until powder is completely dissolved, the easily mixed gold is added into 10mL of ammonia water, the mixture is uniformly stirred and put into a reaction container, the container is placed into a 75 ℃ water bath kettle, the container is taken out after reaction for 10min, the thickness of a buffer layer is controlled by controlling the reaction time after the deionized water is used for cleaning and drying, the chemical water bath mode is adopted for 10min, and the thickness of the cadmium sulfide buffer layer prepared on the surface of a CIGS absorption layer is 60 nm;
step six, preparing a high-resistance layer: preparing a 100nm zinc oxide high-resistance layer on the surface of the buffer layer by adopting a magnetron sputtering intrinsic zinc oxide target, wherein the sputtering gas is argon, the gas flow is 15sccm, the sputtering pressure is 0.4pa, and the sputtering power is 100 w;
step seven, preparing a window layer: a magnetron sputtering mode of the aluminum-doped zinc oxide target is adopted, a front electrode window layer with the thickness of 400nm is prepared on the surface of the high-resistance layer, the sputtering gas is argon, the gas flow is 15sccm, the gas sputtering pressure is 0.4pa, and the sputtering power is 500 w. The samples obtained were characterized and the results are shown in fig. 1, fig. 3 and table 1.
Comparative example 1
The preparation method of the battery comprises the following steps:
step one, cleaning a substrate: selecting a 430 stainless steel sheet with the thickness of 150 mu m, firstly cleaning the sheet by a rolling brush and cleaning agent, then washing the sheet by deionized water under ultrasonic waves, and then drying the substrate by a hot air knife at 80 ℃;
step two, preparing a barrier layer: preparing a 600nm barrier layer by adopting a magnetron sputtering mode of a tungsten-titanium alloy target material, wherein the sputtering power is 4w/cm2, the sputtering gas is argon, the gas flow is 10sccm, and the gas pressure is preferably 0.15 pa;
step three, preparing a back electrode layer: preparing a 300nm molybdenum-sodium film by adopting a magnetron sputtering molybdenum-sodium target containing 5% sodium molybdate, wherein the argon flow is 10sccm, the sputtering pressure is 0.5pa, and the sputtering power is 2w/cm 2 Then preparing a 600nm molybdenum film on the molybdenum sodium film by adopting a magnetron sputtering mode;
step four, preparing a CIGS absorption layer: only argon is introduced, the sputtering pressure is 0.5pa, the gas flow is 10sccm, and the sputtering power is 2.3w/cm 2 Preparing an absorbing layer with the thickness of 1.5 mu m;
step five, preparing a buffer layer: firstly, 0.4g of cadmium acetate is dissolved in 50mL of deionized water, 0.882g of sodium citrate is dissolved in 20mL of deionized water, 1.9g of thiourea is dissolved in 40mL of deionized water, polytetrafluoroethylene magnetons are adopted to rotate and stir until powder is completely dissolved, the easily mixed gold is added into 10mL of ammonia water, the mixture is uniformly stirred and put into a reaction container, the container is placed into a 75 ℃ water bath kettle, the container is taken out after reaction for 10min, the thickness of a buffer layer is controlled by controlling the reaction time after the deionized water is used for cleaning and drying, the chemical water bath mode is adopted for 10min, and the thickness of the cadmium sulfide buffer layer prepared on the surface of a CIGS absorption layer is 60 nm;
step six, preparing a high-resistance layer: preparing a 100nm zinc oxide high-resistance layer on the surface of the buffer layer by adopting a magnetron sputtering intrinsic zinc oxide target, wherein the sputtering gas is argon, the gas flow is 15sccm, the sputtering pressure is 0.4pa, and the sputtering power is 100 w;
step seven, preparing a window layer: a magnetron sputtering mode of the aluminum-doped zinc oxide target is adopted, a front electrode window layer with the thickness of 400nm is prepared on the surface of the high-resistance layer, the sputtering gas is argon, the gas flow is 15sccm, the gas sputtering pressure is 0.4pa, and the sputtering power is 500 w. The samples obtained were characterized and the results are shown in fig. 1, fig. 3 and table 1.
SEM surface picture of CIGS absorber prepared in example 1 as shown in fig. 1; fig. 2 is an SEM picture of the CIGS absorber prepared in comparative example 1, fig. 3 is a full width at half maximum fit result of XRD test (112) (220) of the samples of examples 1 to 5 and comparative example 1, and the comparison results of fig. 1 and 2 show that the grain size of the CIGS absorber obtained by adding hydrogen as a sputtering gas is significantly enlarged, and the full width at half maximum result of XRD test also confirms this conclusion. Table 1 shows cell efficiency parameters of examples 1 to 5 and comparative example 1, and the results show that the device efficiency is the highest and the cell efficiency reaches 16.43% when the hydrogen ratio of example 1 is 5%.
Table 1:
example 6
The preparation method of the battery comprises the following steps:
step one, cleaning a substrate: selecting a 430 stainless steel sheet with the thickness of 150 mu m, firstly cleaning the sheet by a rolling brush and cleaning agent, then washing the sheet by deionized water under ultrasonic waves, and then drying the substrate by a hot air knife at 80 ℃;
step two, preparing a barrier layer: adopts a mode of magnetron sputtering tungsten-titanium alloy target material with sputtering power of 4w/cm 2 Preparing a 600nm barrier layer by using argon as sputtering gas, wherein the gas flow is 10sccm, and the gas pressure is preferably 0.15 pa;
step three, preparing a back electrode layer: preparing a 300nm molybdenum sodium film by adopting magnetron sputtering of a molybdenum sodium target containing 5% sodium molybdate, wherein the sputtering gas is argon, the sputtering pressure is 10sccm, the sputtering pressure is 0.5pa, and the sputtering power is 2w/cm 2 Then preparing a 600nm molybdenum film on the molybdenum sodium film by adopting a magnetron sputtering mode;
step four, preparing a CIGS absorption layer: argon is used as sputtering gas, the sputtering pressure is 0.5pa, the gas flow is 10sccm, and the sputtering power is 2.3w/cm 2 Preparing an absorbing layer with the thickness of 1.5 mu m; after sputtering is finished, the heater maintains the temperature unchanged, the CIGS sputtering power is reduced, argon-hydrogen mixed gas with the hydrogen proportion of 3 percent is introduced, the gas flow is 10sccm, the sputtering pressure is 0.5Pa, and the sputtering power is 0.12W/cm 2 The sputtering time is2 minutes;
step five, preparing a buffer layer: firstly, 0.4g of cadmium acetate is dissolved in 50mL of deionized water, 0.882g of sodium citrate is dissolved in 20mL of deionized water, 1.9g of thiourea is dissolved in 40mL of deionized water, polytetrafluoroethylene magnetons are adopted to rotate and stir until powder is completely dissolved, the easily mixed gold is added into 10mL of ammonia water, the mixture is uniformly stirred and put into a reaction container, the container is placed into a 75 ℃ water bath kettle, the container is taken out after reaction for 10min, the thickness of a buffer layer is controlled by controlling the reaction time after the deionized water is used for cleaning and drying, the chemical water bath mode is adopted for 10min, and the thickness of the cadmium sulfide buffer layer prepared on the surface of a CIGS absorption layer is 60 nm;
step six, preparing a high-resistance layer: preparing a 100nm zinc oxide high-resistance layer on the surface of the buffer layer by adopting a magnetron sputtering intrinsic zinc oxide target, wherein the sputtering gas is argon, the flow rate of the sputtering gas is 15sccm, the sputtering pressure is 0.4pa, and the sputtering power is 100 w;
step seven, preparing a window layer: a magnetron sputtering mode of the aluminum-doped zinc oxide target is adopted, a front electrode window layer with the thickness of 400nm is prepared on the surface of the high-resistance layer, the sputtering gas is argon, the flow rate of the sputtering gas is 15sccm, the sputtering pressure is 0.4pa, and the sputtering power is 1200 w. The resulting sample was characterized and had similar properties as example 1.
Example 7
Step one, cleaning a substrate: selecting a polyimide PI substrate with the thickness of 25 mu m, firstly carrying out primary cleaning in a mode of rolling brush and cleaning agent, then washing with deionized water under ultrasonic waves, and then drying the substrate with a hot air knife at 80 ℃;
step two, preparing a barrier layer: preparing a 50nm barrier layer by magnetron sputtering of an aluminum target, preparing an 80nm titanium metal layer by magnetron sputtering of a titanium target, repeating and alternating the two targets for 4 times to prepare the 650nm aluminum-titanium multilayer barrier layer, wherein the sputtering gas is argon, the flow of the argon gas is 10sccm, the sputtering pressure is 0.15pa, and the sputtering power is 3w/cm 2 ；
Step three, preparing a back electrode layer: adopting magnetron sputtering to prepare sodium molybdate containing 5 percent of sodium molybdatePreparing a 300nm molybdenum sodium film by using a target material, wherein the sputtering gas is argon, the flow of the argon gas is 10sccm, the sputtering pressure is 0.5pa, and the sputtering power is 2w/cm 2 Then preparing a 600nm molybdenum film on the molybdenum sodium film by adopting a magnetron sputtering mode;
step four, preparing a CIGS absorption layer: hydrogen is used as sputtering gas, hydrogen is introduced in the whole sputtering process, the sputtering pressure is 0.5pa, the gas flow is 10sccm, the ratio of hydrogen to argon is 5 percent, and the sputtering power is 2.3w/cm 2 Preparing an absorbing layer with the thickness of 1.5 mu m;
step five, preparing a buffer layer: firstly, 0.4g of cadmium acetate is dissolved in 50mL of deionized water, 0.882g of sodium citrate is dissolved in 20mL of deionized water, 1.9g of thiourea is dissolved in 40mL of deionized water, polytetrafluoroethylene magnetons are adopted to rotate and stir until powder is completely dissolved, the easily mixed gold is added into 10mL of ammonia water, the mixture is uniformly stirred and put into a reaction container, the container is placed into a 75 ℃ water bath kettle, the container is taken out after reaction for 10min, the thickness of a buffer layer is controlled by controlling the reaction time after the deionized water is used for cleaning and drying, the chemical water bath mode is adopted for 10min, and the thickness of the cadmium sulfide buffer layer prepared on the surface of a CIGS absorption layer is 60 nm;
step six, preparing a high-resistance layer: preparing a 100nm zinc oxide high-resistance layer on the surface of the buffer layer by adopting a magnetron sputtering intrinsic zinc oxide target, wherein the sputtering gas is argon, the sputtering pressure is 0.4pa, and the sputtering power is 100 w;
step seven, preparing a window layer: preparing a 400nm front electrode window layer on the surface of the high-resistance layer by adopting a magnetron sputtering mode of an aluminum-doped zinc oxide target, wherein the sputtering gas is argon, the sputtering pressure is 0.4pa, and the sputtering power is 1200 w. The resulting sample was characterized and had similar properties as example 1.
Example 8
The preparation method of the battery comprises the following steps:
step one, cleaning a substrate: selecting a 430 stainless steel sheet with the thickness of 150 mu m, firstly cleaning the sheet by a rolling brush and cleaning agent, then washing the sheet by deionized water under ultrasonic waves, and then drying the substrate by a hot air knife at 80 ℃;
step two, preparing a barrier layer: preparing a 600nm barrier layer by adopting a magnetron sputtering mode of a tungsten-titanium alloy target material, wherein the sputtering gas is argon, the flow rate of the sputtering gas is 10sccm, the sputtering gas pressure is 0.15pa, and the sputtering power is 3w/cm 2 ；
Step three, preparing a back electrode layer: preparing a 300nm molybdenum sodium film by adopting a magnetron sputtering molybdenum sodium target containing 5% sodium molybdate, wherein the sputtering pressure is 0.5pa, and the sputtering power is 2w/cm 2 Then preparing a 600nm molybdenum film on the molybdenum sodium film by adopting a magnetron sputtering mode;
step four, preparing a CIGS absorption layer: hydrogen is used as sputtering gas, hydrogen is introduced in the whole sputtering process, the sputtering pressure is 0.5pa, the gas flow is 10sccm, the ratio of hydrogen to argon is 5 percent, and the sputtering power is 2.3w/cm 2 Preparing an absorbing layer with the thickness of 1.5 mu m;
step five, when the temperature in the step four is reduced to the room temperature, sputtering the indium selenide target material by adopting a magnetron sputtering mode to prepare the indium selenide thin film with the thickness of 80nm, introducing argon gas during sputtering, wherein the gas flow is 10sccm, the sputtering pressure is preferably 0.4pa, and the sputtering power is 0.6w/cm 2 。
Step six, preparing a high-resistance layer: preparing a 100nm zinc oxide high-resistance layer on the surface of the buffer layer by adopting a magnetron sputtering mode of an intrinsic zinc oxide target, wherein the sputtering gas is argon, the flow of the argon is 15sccm, the sputtering pressure is 0.4pa, and the sputtering power is 100 w;
step seven, preparing a window layer: a mode of magnetron sputtering of the aluminum-doped zinc oxide target is adopted, a front electrode window layer with the thickness of 400nm is prepared on the surface of the high-resistance layer, the sputtering gas is argon, the argon flow is 15sccm, the sputtering pressure is 0.4pa, and the sputtering power is 1200 w. The resulting sample was characterized and had similar properties to example 1.
Claims (7)
1. A method for preparing a copper indium gallium selenide thin-film solar cell in a selenium-free atmosphere is characterized by comprising the following steps:
a. preparation of a barrier layer: depositing a barrier layer with the thickness of 50nm-800nm on the pretreated substrate by adopting a magnetron sputtering or plasma enhanced chemical vapor deposition method;
b. preparing a back electrode layer: depositing a back electrode layer with the thickness of 600nm-1000nm on the barrier layer by adopting a magnetron sputtering method;
c. preparing a copper indium gallium selenide absorption layer: c, heating the substrate processed in the step b to 400-600 ℃ by adopting an annular graphite device, and preparing the copper indium gallium selenide absorption layer with the thickness of 1.3-1.7 mu m by adopting a magnetron sputtering method, wherein the sputtering process parameters are as follows: sputtering gas pressure is 0.1pa-1pa, gas flow is 5sccm-20sccm, sputtering power is 1w/cm 2 -4w/cm 2 (ii) a After the copper indium gallium selenide absorption layer is sputtered, the temperature of the substrate is kept unchanged, and the sputtering pressure is 0.5-2pa and the sputtering power is 0.1w/cm 2 -0.5w/cm 2 Sputtering the copper indium gallium selenide target material for 1-5min under the condition, and introducing hydrogen, wherein the introduced hydrogen is 0.1-100% of the argon flow;
d. preparing a buffer layer: preparing a buffer layer with the thickness of 40nm-100nm on the copper indium gallium selenide absorption layer by adopting a chemical water bath or magnetron sputtering method; the buffer layer is a cadmium sulfide film, a zinc sulfide film, an indium sulfide film or a composite film of cadmium sulfide and zinc sulfide;
e. preparing a high-resistance layer: preparing an intrinsic zinc oxide high-resistance layer with the thickness of 80nm-120nm on the buffer layer by adopting a magnetron sputtering method;
f. preparation of a window layer: and preparing an aluminum-doped zinc oxide window layer with the thickness of 200nm-500nm on the high-resistance layer by adopting a magnetron sputtering method.
2. The method for preparing the CIGS thin-film solar cell in the selenium-free atmosphere according to claim 1, wherein: in the step a, the substrate is one of a stainless steel sheet with the thickness of 50-300 μm, a soda-lime glass sheet with the thickness of 1-3.2mm and a polyimide substrate with the thickness of 25-200 μm; the cleaning mode of the substrate is as follows: the substrate is cleaned by a roller brush and a cleaning agent for the first time, then washed by deionized water under ultrasonic waves, and finally dried by a hot air knife.
3. The method for preparing a copper indium gallium selenide thin-film solar cell in a selenium-free atmosphere according to claim 1, wherein: in the step a, the barrier layer is a simple substance film, a nitride/oxide film or a tungsten-titanium alloy film, the sputtering air pressure for preparing the barrier layer is 0.2 pa-1pa, and the sputtering power is 0.1w/cm 2 -8w/cm 2 。
4. The method for preparing the CIGS thin-film solar cell in the selenium-free atmosphere according to claim 1, wherein: in step a, when the substrate is made of polyimide material, the barrier layer is a multilayer metal film of aluminum/titanium/tungsten alternately.
5. The method for preparing the CIGS thin-film solar cell in the selenium-free atmosphere according to claim 1, wherein: in the step b, the back electrode layer is a molybdenum film or a double-layer film of molybdenum sodium and molybdenum.
6. The method for preparing the CIGS thin-film solar cell in the selenium-free atmosphere according to claim 1, wherein: in step d, when the sputtered target material is indium sulfide, the atomic molar ratio of In to S of the target material is 2: 3.
7. The method for preparing the CIGS thin-film solar cell in the selenium-free atmosphere according to claim 1, wherein: in the step d, after the preparation of the CIGS absorbing layer is finished and the temperature is reduced to the room temperature, sputtering the buffer layer at the normal temperature, wherein the sputtering gas is argon, the sputtering pressure is 0.3-0.8pa, the sputtering gas flow is 5-20sccm, and the sputtering power density is 0.3w/cm 2 -1w/cm 2 。
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