CN103325868A - Copper indium gallium selenium solar battery device and manufacturing method thereof - Google Patents

Copper indium gallium selenium solar battery device and manufacturing method thereof Download PDF

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CN103325868A
CN103325868A CN2013102412586A CN201310241258A CN103325868A CN 103325868 A CN103325868 A CN 103325868A CN 2013102412586 A CN2013102412586 A CN 2013102412586A CN 201310241258 A CN201310241258 A CN 201310241258A CN 103325868 A CN103325868 A CN 103325868A
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film
time
preparation
soda glass
substrate
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薛玉明
张嘉伟
乔在祥
李微
赵彦民
许楠
刘浩
尹富红
冯少君
潘宏刚
宋殿友
朱亚东
刘君
李鹏海
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Tianjin University of Technology
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Tianjin University of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • 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
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    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a copper indium gallium selenium solar battery device which is a copper indium gallium selenium solar battery based on a polyimide-film-soda-glass composite substrate. The copper indium gallium selenium solar battery device is composed of glass, polyimide, a molybdenum back contact layer, a copper indium gallium selenium absorbing layer, a cadmium sulfide buffering layer, a transparent window layer high-resistance intrinsic zinc oxide film, a transparent window layer low-resistance zinc oxide aluminum film and an upper aluminum electrode, and is of a laminated structure. The manufacturing method of the copper indium gallium selenium solar battery device includes the steps of, firstly, coating the surface of the glass through polyimide glue, solidifying to form the polyimide-film-soda-glass composite substrate, then sequentially manufacturing the various films on the surface of the polyimide-film-soda-glass composite substrate, separating the copper indium gallium selenium solar battery from the polyimide-film-soda-glass composite substrate after the complete copper indium gallium selenium solar battery is manufactured, and obtaining the flexible copper indium gallium selenium solar battery with the polyimide film as the substrate. The copper indium gallium selenium solar battery device and the manufacturing method of the copper indium gallium selenium solar battery device have the advantages that the copper indium gallium selenium film based on the polyimide-film-soda-glass composite substrate is large in crystal grain of crystals, the flexible battery is manufactured by the manufacturing method through the rigid substrate, and therefore the manufacturing method is easy to implement and benefit to large-scale popularization and application.

Description

A kind of CIGS solar cell device and preparation method thereof
Technical field
The present invention relates to the thin film solar cell technical field, particularly a kind of CIGS solar cell device based on polyimide film-soda glass compound substrate and preparation method thereof.
Background technology
Copper Indium Gallium Selenide material (CIGS) belongs to I-III-VI family quaternary compound semiconductor, has the crystal structure of chalcopyrite.CIGS thin-film too can battery since 20 century 70s occur, obtain very fast development, and will progressively realize industrialization.This battery has following characteristics: 1) energy gap of Copper Indium Gallium Selenide can be adjusted in the 1.04eV-1.67eV scope; 2) Copper Indium Gallium Selenide is a kind of direct gap semiconductor, to visible optical absorption coefficient up to 10 5Cm -1, CuInGaSe absorbed layer thickness only needs 1.5-2.5 μ m, and the thickness of whole battery is 3-4 μ m; 3) Radiation hardness is strong, relatively is suitable as space power system; 4) conversion efficiency is high, and the small size CIGS solar cell conversion efficiency of German solar energy in 2010 and Hydrogen Energy research center (ZSW) development is up to 20.3%; 5) low light level characteristic is good.Therefore the Copper Indium Gallium Selenide polycrystalline thin-film solar cell is expected to one of main product that becomes by solar cell of future generation.
Aerospace field needs solar cell higher quality to be arranged than power, wishes that namely the solar cell of unit mass can send more electric weight.Require solar cell to have flexibility, foldability and be not afraid of to fall for the surface modeling of ground photovoltaic building and portable photovoltaic plant etc. and bump, this has just promoted the development of flexible solar cell.Because relatively strong heat-resisting ability and the coefficient of expansion that comparatively is fit to, polyimides (PI) is shown one's talent therein.
Yet the thermal coefficient of expansion of polyimides still can't well mate with Copper Indium Gallium Selenide material itself.When temperature was higher, polyimides can produce larger deformation, caused CIGS thin-film comparatively loose, easily came off.So underlayer temperature was lower when present Copper Indium Gallium Selenide based on polyimide substrate prepared.Thereby cause that the thin film crystallization that grows is second-rate, crystal grain is tiny, defective is more, has increased the compound of charge carrier, has shortened the life-span of few son, and then affected battery performance.
Summary of the invention
The objective of the invention is for above-mentioned existing problems, a kind of CIGS solar cell device and preparation method thereof is provided, this solar cell device is the CIGS solar cell based on polyimide film-soda glass compound substrate, it prepares flexible battery with the rigidity substrate, CIGS thin-film crystalline quality based on polyimide film-soda glass compound substrate is good, crystal grain is large, and defective is few.
Technical scheme of the present invention:
A kind of CIGS solar cell device, be the CIGS solar cell based on polyimide film-soda glass compound substrate, form and form laminated construction by glass, polyimides, molybdenum back contact, CuInGaSe absorbed layer, cadmium sulfide resilient coating, transparent window layer high resistant native oxide zinc film, transparent window layer low-resistance zinc oxide aluminum film and aluminium top electrode, wherein substrate is by soda glass and grow in its surperficial polyimide film and consist of, the thickness of soda glass is 1.5-2mm, and the polyimides film thickness is 25-30 μ m; The molybdenum back contact comprises resistive formation film and low resistivity layer film, and wherein the thickness of resistive formation film is 80-120nm, and the thickness of low resistivity layer film is 600-700nm; The chemical molecular formula of CuInGaSe absorbed layer is CuIn 1-xGa xSe 2, x is 0.25-0.35 in the formula, and conduction type is p-type, and film thickness is 1.5-2 μ m; The cadmium sulfide resilient coating conduction type be N-shaped, thickness is 45-50nm; Transparent window layer comprises high resistant native oxide zinc film and low-resistance zinc oxide aluminum film, and conduction type is N-shaped, and the thickness of native oxide zinc film is 50-100nm, and the thickness of zinc oxide aluminum film is 0.4-0.6 μ m; The thickness of aluminium upper electrode film is 0.8-1.5 μ m.
A kind of preparation method of described CIGS solar cell device, at first polyimides glue is applied to the soda glass surface, be solidified into polyimide film-soda glass compound substrate, secondly prepare successively molybdenum back contact, CuInGaSe absorbed layer, cadmium sulfide resilient coating, transparent window layer and top electrode on its surface, after complete CIGS solar cell preparation is finished, with itself and soda glass substrate separation, obtain the flexible copper indium gallium selenide solar cell take polyimide film as substrate.
The preparation method of described polyimide film-soda glass compound substrate, step is as follows:
1) soda glass is carried out surface clean, cleaning method is:
At first the soda glass of 10cm * 10cm is put into potassium bichromate solution and soak 2h, potassium bichromate solution is by 300 grammes per square metre potassium chromates, 3 liters of concentrated sulfuric acids and the configuration of 300 ml deionized water form, the soda glass taking-up is placed in the acetone soln that concentration is 99.5w% with deionized water rinsing, putting into supersonic wave cleaning machine cleans, ultrasonic frequency is 20-30kHz, time is 20-25min, then soda glass is taken out from acetone soln, be placed in the alcohol that concentration is 99.7w% with deionized water rinsing, putting into supersonic wave cleaning machine cleaning ultrasonic frequency is 20-30kHz, time is 20-25min, at last soda glass is taken out from alcohol, put into the beaker that fills deionized water, put into supersonic wave cleaning machine and clean 3 times, ultrasonic frequency is 20-30kHz, and the time is 20-25min;
2) polyimides glue is coated on the soda glass surface, adopts spin processes to spare glue, technological parameter is: rotating speed is 1300-1500r/min, and the time is 35-45s;
3) will spare sample behind the glue puts into baking oven and is cured, can obtain polyimide film-soda glass compound substrate, the heating and heat preservation program of described curing process is: oven temperature is warming up to 125-135 ℃, and the heating-up time is 10-15min, and keeps 25-30min under 125-135 ℃; Oven temperature is warming up to 150-160 ℃, and the heating-up time is 5-10min, and keeps 10-15min under 150-160 ℃; Oven temperature is warming up to 200-210 ℃, and the heating-up time is 5-10min, and keeps 15-20min under 200-210 ℃; Oven temperature is warming up to 250-260 ℃, and the heating-up time is 5-10min, and keeps 15-20min under 250-260 ℃; Oven temperature is warming up to 340-350 ℃, and the heating-up time is 5-10min, and keeps 10-15min under 340-350 ℃, and then slow cooling can obtain polyimide film-soda glass compound substrate to 18-25 ℃.
Described molybdenum back contact thin film technology method, the preparation of employing DC magnetron sputtering system, sample to be prepared is placed the settling chamber of Deposited By Dc Magnetron Sputtering system, take the molybdenum of purity as 99.99% as target, adopt rf magnetron sputtering technique to deposit respectively successively high resistant molybdenum film and low-resistance molybdenum film at substrate surface, wherein:
1) deposition high resistant molybdenum film technological parameter is: base vacuum 3.0 * 10 -4Pa, operating air pressure 1-2Pa, underlayer temperature 25-50 ℃, radio-frequency power 500-700W, Ar throughput 30-50sccm, basic target speed of travel 4-6mm/s, sedimentation time is counted 2-4 time with the reciprocal time of basic target;
2) technological parameter of deposition low-resistance film is: base vacuum 3.0 * 10 -4Pa, operating air pressure are 0-0.5Pa, and underlayer temperature is room temperature 25-50 ℃, and radio-frequency power is 1500-2000W, and the Ar throughput is 15-20sccm, and the basic target speed of travel is 4-6mm/s, and sedimentation time is counted 4-6 time with the reciprocal time of basic target.
Described CuInGaSe absorbed layer thin film technology method adopts selenizing stove film preparing system and coevaporation three-step approach preparation technology, and step is as follows:
1) sample to be prepared being placed the coevaporation system, is 3.0 * 10 at base vacuum -4Pa, underlayer temperature are under 350-400 ℃, coevaporation In, Ga, Se initialization layer, wherein In evaporation source temperature is 850-900 ℃, Ga evaporation source temperature is 880-920 ℃, Se evaporation source temperature is 240-280 ℃, evaporation time is 15-20min, and the atomic ratio of control In/Ga is 0.7:0.3, (In+Ga)/and the atomic ratio of Se is 2:3;
2) be under 550-580 ℃ at underlayer temperature, coevaporation Cu, Se, wherein Cu evaporation source temperature is 1120-1160 ℃, and Se evaporation source temperature is 240-280 ℃, and evaporation time is 15-20min;
3) keep step 2 at underlayer temperature) temperature-resistant condition under, coevaporation In, Ga, Se, wherein In evaporation source temperature is 850-900 ℃, Ga evaporation source temperature is 880-920 ℃, Se evaporation source temperature is 240-280 ℃, evaporation time is 2-4min, obtains the Copper Indium Gallium Selenide p-type yellow copper structure of poor a little Cu, and the atomic ratio of control Cu/ (In+Ga) is 0.88-0.92;
4) with substrate cooling, during underlayer temperature when in the time of evaporation Se, substrate being cooled to the first step, close the Se evaporation source, substrate is cooled to 18-25 ℃ again and gets final product.
The preparation method of described cadmium sulfide resilient coating adopts the standby technique of chemical bath legal system, and step is as follows:
1) preparation feedback liquid: at first configuration concentration is 0.01mol/L thiourea solution 1L, configuration cadmium acetate and Ammonium Acetate mixed solution 1L, and wherein the cadmium acetate solution concentration is 0.001mol/L, and liquor ammonii acetatis concentration is 0.003mol/L, and ammonia spirit concentration is 1.3 * 10 -3Then mol/L mixes 4 of thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirits and stirs, and makes reactant liquor;
2) reactant liquor is added in the beaker be placed with sample and with beaker put into water-bath, bath temperature is set to 78-80 ℃, and the reaction time is 50-60min;
3) after reaction was finished, the cadmium sulfide particle of rinsing the unreacted film forming that residues in sample cadmium sulfide buffer-layer surface with deionized water well got final product.
The high resistant native oxide zinc film of described transparent window layer and low-resistance zinc oxide aluminum thin film technology method adopt respectively the preparation of rf magnetron sputtering system and DC magnetron sputtering system, and step is as follows:
1) high resistant native oxide zinc thin film technology
Sample to be prepared is placed the settling chamber of r. f. magnetron sputtering system, take the i-ZnO of purity as 99.99% as target, adopt rf magnetron sputtering technique at substrate surface deposition intrinsic zinc-oxide film, technological parameter is: base vacuum 3.0 * 10 -4Pa, underlayer temperature 25-50 ℃, radio-frequency power 800-1000W, Ar throughput 10-20sccm, O 2Throughput 2-6sccm, the basic target speed of travel is 2-6mm/s, sedimentation time is counted 6-10 time with the reciprocal time of basic target;
2) low-resistance zinc oxide aluminum thin film technology
Sample to be prepared is placed in the settling chamber of Deposited By Dc Magnetron Sputtering system, take the ZnO:Al of purity as 99.99% as target, adopts magnetically controlled DC sputtering technique at substrate surface deposition ZnO:Al film, technological parameter is: base vacuum 3.0 * 10 -4Pa, underlayer temperature 25-50 ℃, direct current power 1000-1200W, Ar throughput 12-18sccm, basic target speed of travel 2-6mm/s, sedimentation time is counted 10-15 time with the reciprocal time of basic target.
The preparation method of described aluminium top electrode adopts the preparation of coevaporation system, and step is as follows:
1) sample to be prepared is placed the coevaporation system, at base vacuum 3.0 * 10 -4Under the Pa, give successively heater strip 20A electric current, continue 1-2min, give heater strip 50A electric current, continue 1-2min, give heater strip 80A electric current, continue 1-2min; Give heater strip 120A electric current, continue 5-8min;
2) after glass pane to be seen was covered fully by the aluminium film, stopped heating slowly reduced giving the heater strip electric current, and then cooling gets final product.
Know-why analysis of the present invention:
For satisfy the preparation crystalline quality better, the requirement of crystal grain is large, defective is less Copper Indium Gallium Selenide flexible thin-film solar cell, the substrate that must select that substrate is soft, light, thermal coefficient of expansion and CIGS thin-film is mated comparatively.The characteristics that polyimide film-soda glass compound substrate can rely on soda glass and the CuInGaSe absorbed layer film thermal coefficient of expansion comparatively to approach prepare CIGS thin-film solar cell in compound substrate.Again thin film solar cell is separated from the soda glass surface take polyimides as substrate afterwards, obtain flexible CIGS thin-film solar cell, realize the design for preparing flexible solar cell with the rigidity substrate.
The technical advantage of described CIGS solar cell based on polyimide film-soda glass compound substrate:
1) polyimides glue is applied to glass surface, can better improves the roughness of substrate;
2) thermal coefficient of expansion of polyimides itself is larger, can not itself mate with the Copper Indium Gallium Selenide material well, easily distortion under higher temperature, cause film loose, very easily come off, and grow in the polyimides of glass surface, rely on and glass between adhesive force, make it be difficult for occuring than large deformation, more mate with the Copper Indium Gallium Selenide material;
3) because and glass contact, deformation be difficult for to occur, can give polyimides comparatively near the temperature of its heatproof upper limit, help CIGS thin-film better to grow;
4) its epontic CIGS thin-film crystalline quality is good, crystal grain is large, defective is few;
5) after complete CIGS solar cell preparation is finished, it from separation on glass, just can be prepared the flexible copper indium gallium selenide solar cell with larger columnar grain.
Advantage of the present invention is: this kind is good based on the CIGS solar cell absorbed layer thin film crystallization quality of polyimide film-soda glass compound substrate, crystal grain is large, defective is few, utilizes the rigidity substrate to prepare flexible solar cell; Its preparation method is simple, easy to implement, is conducive to apply on a large scale, especially has extremely important application prospect in space and special occasions.
Description of drawings
Accompanying drawing is the structural representation of this CIGS solar cell.
Embodiment
In order to make those skilled in the art person understand better the present invention program, the present invention is described in further detail below in conjunction with drawings and embodiments.
Embodiment 1:
A kind of CIGS solar cell device, be the CIGS solar cell based on polyimide film-soda glass compound substrate, as shown in Figure 1, form and form laminated construction by glass, polyimides, molybdenum back contact, CuInGaSe absorbed layer, cadmium sulfide resilient coating, transparent window layer high resistant native oxide zinc film, transparent window layer low-resistance zinc oxide aluminum film and aluminium top electrode, wherein substrate is by soda glass and grow in its surperficial polyimide film and consist of, the thickness of soda glass is 2mm, and the polyimides film thickness is 25 μ m; The molybdenum back contact comprises resistive formation film and low resistivity layer film, and wherein the thickness of resistive formation film is 100nm, and the thickness of low resistivity layer film is 600nm; The chemical molecular formula of CuInGaSe absorbed layer is CuIn 1-xGa xSe 2, x is 0.3 in the formula, and conduction type is p-type, and film thickness is 1.5 μ m; The cadmium sulfide resilient coating conduction type be N-shaped, thickness is 45nm; Transparent window layer comprises high resistant native oxide zinc film and low-resistance zinc oxide aluminum film, and conduction type is N-shaped, and the thickness of native oxide zinc film is 70nm, and the thickness of zinc oxide aluminum film is 0.6 μ m; The thickness of aluminium upper electrode film is 1 μ m.
The preparation method of described CIGS solar cell device, at first polyimides glue is applied to the soda glass surface, be solidified into polyimide film-soda glass compound substrate, secondly prepare successively molybdenum back contact, CuInGaSe absorbed layer, cadmium sulfide resilient coating, transparent window layer and top electrode on its surface, after complete CIGS solar cell preparation is finished, with itself and soda glass substrate separation, obtain the flexible copper indium gallium selenide solar cell take polyimide film as substrate.
The preparation method of described polyimide film-soda glass compound substrate, step is as follows:
1) soda glass is carried out surface clean, cleaning method is:
At first the soda glass of 10cm * 10cm is put into potassium bichromate solution and soak 2h, potassium bichromate solution is by 300 grammes per square metre potassium chromates, 3 liters of concentrated sulfuric acids and the configuration of 300 ml deionized water form, the soda glass taking-up is placed in the acetone soln that concentration is 99.5w% with deionized water rinsing, putting into supersonic wave cleaning machine cleans, ultrasonic frequency is 20kHz, time is 25min, then soda glass is taken out from acetone soln, be placed in the alcohol that concentration is 99.7w% with deionized water rinsing, putting into supersonic wave cleaning machine cleaning ultrasonic frequency is 20kHz, time is 25min, at last soda glass is taken out from alcohol, put into the beaker that fills deionized water, put into supersonic wave cleaning machine and clean 3 times, ultrasonic frequency is 20kHz, and the time is 25min;
2) polyimides glue is coated on the soda glass surface, adopts spin processes to spare glue, technological parameter is: rotating speed is 1300r/min, and the time is 45s;
3) will spare sample behind the glue puts into baking oven and is cured, can obtain polyimide film-soda glass compound substrate, the heating and heat preservation program of described curing process is: oven temperature is warming up to 125 ℃, and the heating-up time is 15min, and keeps 30min under 125 ℃; Oven temperature is warming up to 150 ℃, and the heating-up time is 5min, and keeps 15min under 150 ℃; Oven temperature is warming up to 200 ℃, and the heating-up time is 5min, and keeps 20min under 200 ℃; Oven temperature is warming up to 250 ℃, and the heating-up time is 5min, and keeps 20min under 250 ℃; Oven temperature is warming up to 350 ℃, and the heating-up time is 10min, and keeps 10min under 350 ℃, and then slow cooling to 22 ℃ can obtain polyimide film-soda glass compound substrate.
Described molybdenum back contact thin film technology method, the preparation of employing DC magnetron sputtering system, sample to be prepared is placed the settling chamber of Deposited By Dc Magnetron Sputtering system, take the molybdenum of purity as 99.99% as target, adopt rf magnetron sputtering technique to deposit respectively successively high resistant molybdenum film and low-resistance molybdenum film at substrate surface, wherein:
1) deposition high resistant molybdenum film technological parameter is: base vacuum 3.0 * 10 -4Pa, operating air pressure 1Pa, 25 ℃ of underlayer temperatures, radio-frequency power 600W, Ar throughput 40sccm, basic target speed of travel 4mm/s, sedimentation time is counted 2 times with the reciprocal time of basic target;
2) technological parameter of deposition low-resistance film is: base vacuum 3.0 * 10 -4Pa, operating air pressure are 0.1Pa, and underlayer temperature is 25 ℃, and radio-frequency power is 1500W, and the Ar throughput is 15sccm, and the basic target speed of travel is 4mm/s, and sedimentation time is counted 6 times with the reciprocal time of basic target.
Described CuInGaSe absorbed layer thin film technology method adopts selenizing stove film preparing system and coevaporation three-step approach preparation technology, and step is as follows:
1) sample to be prepared being placed the coevaporation system, is 3.0 * 10 at base vacuum -4Pa, underlayer temperature are under 380 ℃, coevaporation In, Ga, Se initialization layer, wherein In evaporation source temperature is 850 ℃, Ga evaporation source temperature is 880 ℃, Se evaporation source temperature is 250 ℃, evaporation time is 17min, and the atomic ratio of control In/Ga is 0.7:0.3, (In+Ga)/and the atomic ratio of Se is 2:3;
2) be under 550 ℃ at underlayer temperature, coevaporation Cu, Se, wherein Cu evaporation source temperature is 1140 ℃, and Se evaporation source temperature is 250 ℃, and evaporation time is 15min;
3) keep step 2 at underlayer temperature) temperature-resistant condition under, coevaporation In, Ga, Se, wherein In evaporation source temperature is 850 ℃, Ga evaporation source temperature is 880 ℃, Se evaporation source temperature is 250 ℃, evaporation time is 3min, obtains the Copper Indium Gallium Selenide p-type yellow copper structure of poor a little Cu, and the atomic ratio of control Cu/ (In+Ga) is 0.9;
4) with substrate cooling, when in the time of evaporation Se, substrate being cooled to 380 ℃, close the Se evaporation source, substrate is cooled to 18-25 ℃ again and gets final product.
The preparation method of described cadmium sulfide resilient coating adopts the standby technique of chemical bath legal system, and step is as follows:
1) preparation feedback liquid: at first configuration concentration is 0.01mol/L thiourea solution 1L, configuration cadmium acetate and Ammonium Acetate mixed solution 1L, and wherein the cadmium acetate solution concentration is 0.001mol/L, and liquor ammonii acetatis concentration is 0.003mol/L, and ammonia spirit concentration is 1.3 * 10 -3Then mol/L mixes 4 of thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirits and stirs, and makes reactant liquor;
2) reactant liquor is put into beaker and beaker put into water-bath, bath temperature is set to 78 ℃, and the reaction time is 60min;
3) after reaction was finished, the cadmium sulfide particle of rinsing the unreacted film forming that residues in sample cadmium sulfide buffer-layer surface with deionized water well got final product.
The high resistant native oxide zinc film of described transparent window layer and low-resistance zinc oxide aluminum thin film technology method adopt respectively the preparation of rf magnetron sputtering system and DC magnetron sputtering system, and step is as follows:
1) high resistant native oxide zinc thin film technology
Sample to be prepared is placed the settling chamber of r. f. magnetron sputtering system, take the i-ZnO of purity as 99.99% as target, adopt rf magnetron sputtering technique at substrate surface deposition intrinsic zinc-oxide film, technological parameter is: base vacuum 3.0 * 10 -4Pa, 35 ℃ of underlayer temperatures, radio-frequency power 800W, Ar throughput 10sccm, O 2Throughput 3sccm, the basic target speed of travel is 4mm/s, sedimentation time is counted 8 times with the reciprocal time of basic target;
2) low-resistance zinc oxide aluminum thin film technology
Sample to be prepared is placed in the settling chamber of Deposited By Dc Magnetron Sputtering system, take the ZnO:Al of purity as 99.99% as target, adopts magnetically controlled DC sputtering technique at substrate surface deposition ZnO:Al film, technological parameter is: base vacuum 3.0 * 10 -4Pa, 25 ℃ of underlayer temperatures, direct current power 1000W, Ar throughput 15sccm, basic target speed of travel 6mm/s, sedimentation time is counted 10 times with the reciprocal time of basic target.
The preparation method of described aluminium top electrode adopts the preparation of coevaporation system, and step is as follows:
1) sample to be prepared is placed the coevaporation system, at base vacuum 3.0 * 10 -4Under the Pa, give successively heater strip 20A electric current, continue 2min, give heater strip 50A electric current, continue 2min, give heater strip 80A electric current, continue 2min; Give heater strip 120A electric current, continue 6min;
2) after glass pane to be seen was covered fully by the aluminium film, stopped heating slowly reduced giving the heater strip electric current, and then cooling gets final product.
Show by test: prepared CIGS solar cell device can form good PN junction, produces photovoltaic effect, can produce electric energy under solar light irradiation.
Embodiment 2:
A kind of CIGS solar cell device, be the CIGS solar cell based on polyimide film-soda glass compound substrate, as shown in Figure 1, form and form laminated construction by glass, polyimides, molybdenum back contact, CuInGaSe absorbed layer, cadmium sulfide resilient coating, transparent window layer high resistant native oxide zinc film, transparent window layer low-resistance zinc oxide aluminum film and aluminium top electrode, wherein substrate is by soda glass and grow in its surperficial polyimide film and consist of, the thickness of soda glass is 2mm, and the polyimides film thickness is 30 μ m; The molybdenum back contact comprises resistive formation film and low resistivity layer film, and wherein the thickness of resistive formation film is 100nm, and the thickness of low resistivity layer film is 700nm; The chemical molecular formula of CuInGaSe absorbed layer is CuIn 1-xGa xSe 2, x is 0.28 in the formula, and conduction type is p-type, and film thickness is 1.8 μ m; The cadmium sulfide resilient coating conduction type be N-shaped, thickness is 50nm; Transparent window layer comprises high resistant native oxide zinc film and low-resistance zinc oxide aluminum film, and conduction type is N-shaped, and the thickness of native oxide zinc film is 80nm, and the thickness of zinc oxide aluminum film is 0.5 μ m; The thickness of aluminium upper electrode film is 1.2 μ m.
The preparation method of described CIGS solar cell device is identical with embodiment 1.
The preparation method of described polyimide film-soda glass compound substrate, step is as follows:
1) soda glass is carried out surface clean, cleaning method is:
At first the soda glass of 10cm * 10cm is put into potassium bichromate solution and soak 2h, potassium bichromate solution is by 300 grammes per square metre potassium chromates, 3 liters of concentrated sulfuric acids and the configuration of 300 ml deionized water form, the soda glass taking-up is placed in the acetone soln that concentration is 99.5w% with deionized water rinsing, putting into supersonic wave cleaning machine cleans, ultrasonic frequency is 30kHz, time is 20min, then soda glass is taken out from acetone soln, be placed in the alcohol that concentration is 99.7w% with deionized water rinsing, putting into supersonic wave cleaning machine cleaning ultrasonic frequency is 30kHz, time is 20min, at last soda glass is taken out from alcohol, put into the beaker that fills deionized water, put into supersonic wave cleaning machine and clean 3 times, ultrasonic frequency is 30kHz, and the time is 20min;
2) polyimides glue is coated on the soda glass surface, adopts spin processes to spare glue, technological parameter is: rotating speed is 1400r/min, and the time is 40s;
3) will spare sample behind the glue puts into baking oven and is cured, can obtain polyimide film-soda glass compound substrate, the heating and heat preservation program of described curing process is: oven temperature is warming up to 130 ℃, and the heating-up time is 20min, and keeps 25min under 130 ℃; Oven temperature is warming up to 160 ℃, and the heating-up time is 10min, and keeps 10min under 160 ℃; Oven temperature is warming up to 210 ℃, and the heating-up time is 10min, and keeps 20min under 210 ℃; Oven temperature is warming up to 260 ℃, and the heating-up time is 10min, and keeps 20min under 260 ℃; Oven temperature is warming up to 345 ℃, and the heating-up time is 10min, and keeps 15min under 345 ℃, and then slow cooling to 22 ℃ can obtain polyimide film-soda glass compound substrate.
Described molybdenum back contact thin film technology method, the preparation of employing DC magnetron sputtering system, sample to be prepared is placed the settling chamber of Deposited By Dc Magnetron Sputtering system, take the molybdenum of purity as 99.99% as target, adopt rf magnetron sputtering technique to deposit respectively successively high resistant molybdenum film and low-resistance molybdenum film at substrate surface, wherein:
1) deposition high resistant molybdenum film technological parameter is: base vacuum 3.0 * 10 -4Pa, operating air pressure 1.5Pa, 25 ℃ of underlayer temperatures, radio-frequency power 700W, Ar throughput 50sccm, basic target speed of travel 5mm/s, sedimentation time is counted 4 times with the reciprocal time of basic target;
2) technological parameter of deposition low-resistance film is: base vacuum 3.0 * 10 -4Pa, operating air pressure are 0.5Pa, and underlayer temperature is 25 ℃, and radio-frequency power is 1800W, and the Ar throughput is 20sccm, and the basic target speed of travel is 6mm/s, and sedimentation time is counted 6 times with the reciprocal time of basic target.
Described CuInGaSe absorbed layer thin film technology method adopts selenizing stove film preparing system and coevaporation three-step approach preparation technology, and step is as follows:
1) sample to be prepared being placed the coevaporation system, is 3.0 * 10 at base vacuum -4Pa, underlayer temperature are under 400 ℃, coevaporation In, Ga, Se initialization layer, wherein In evaporation source temperature is 870 ℃, Ga evaporation source temperature is 915 ℃, Se evaporation source temperature is 260 ℃, evaporation time is 15min, and the atomic ratio of control In/Ga is 0.7:0.3, (In+Ga)/and the atomic ratio of Se is 2:3;
2) be under 580 ℃ at underlayer temperature, coevaporation Cu, Se, wherein Cu evaporation source temperature is 1140 ℃, and Se evaporation source temperature is 260 ℃, and evaporation time is 18min;
3) keep step 2 at underlayer temperature) temperature-resistant condition under, coevaporation In, Ga, Se, wherein In evaporation source temperature is 870 ℃, Ga evaporation source temperature is 915 ℃, Se evaporation source temperature is 260 ℃, evaporation time is 4min, obtains the Copper Indium Gallium Selenide p-type yellow copper structure of poor a little Cu, and the atomic ratio of control Cu/ (In+Ga) is 0.88;
4) with substrate cooling, when in the time of evaporation Se, substrate being cooled to 380 ℃, close the Se evaporation source, substrate is cooled to 18-25 ℃ again and gets final product.
The preparation method of described cadmium sulfide resilient coating adopts the standby technique of chemical bath legal system, and step is as follows:
1) preparation feedback liquid: at first configuration concentration is 0.01mol/L thiourea solution 1L, configuration cadmium acetate and Ammonium Acetate mixed solution 1L, and wherein the cadmium acetate solution concentration is 0.001mol/L, and liquor ammonii acetatis concentration is 0.003mol/L, and ammonia spirit concentration is 1.3 * 10 -3Then mol/L mixes 4 of thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirits and stirs, and makes reactant liquor;
2) reactant liquor is put into beaker and beaker put into water-bath, bath temperature is set to 80 ℃, and the reaction time is 50min;
3) after reaction is finished, rinse the cadmium sulfide particle that sample residues in the unreacted film forming of cadmium sulfide buffer-layer surface well with deionized water and get final product.
The high resistant native oxide zinc film of described transparent window layer and low-resistance zinc oxide aluminum thin film technology method adopt respectively the preparation of rf magnetron sputtering system and DC magnetron sputtering system, and step is as follows:
1) high resistant native oxide zinc thin film technology
Sample to be prepared is placed the settling chamber of r. f. magnetron sputtering system, take the i-ZnO of purity as 99.99% as target, adopt rf magnetron sputtering technique at substrate surface deposition intrinsic zinc-oxide film, technological parameter is: base vacuum 3.0 * 10 -4Pa, 50 ℃ of underlayer temperatures, radio-frequency power 1000W, Ar throughput 15sccm, O 2Throughput 4sccm, the basic target speed of travel is 6mm/s, sedimentation time is counted 8 times with the reciprocal time of basic target;
2) low-resistance zinc oxide aluminum thin film technology
Sample to be prepared is placed in the settling chamber of Deposited By Dc Magnetron Sputtering system, take the ZnO:Al of purity as 99.99% as target, adopts magnetically controlled DC sputtering technique at substrate surface deposition ZnO:Al film, technological parameter is: base vacuum 3.0 * 10 -4Pa, 25 ℃ of underlayer temperatures, direct current power 1200W, Ar throughput 17sccm, basic target speed of travel 4mm/s, sedimentation time is counted 12 times with the reciprocal time of basic target.
The preparation method of described aluminium top electrode adopts the preparation of coevaporation system, and step is as follows:
1) sample to be prepared is placed the coevaporation system, at base vacuum 3.0 * 10 -4Under the Pa, give successively heater strip 20A electric current, continue 21min, give heater strip 50A electric current, continue 1min, give heater strip 80A electric current, continue 2min; Give heater strip 120A electric current, continue 5min;
2) after glass pane to be seen was covered fully by the aluminium film, stopped heating slowly reduced giving the heater strip electric current, and then cooling gets final product.
Testing result is identical with embodiment 1.
In sum, flexible copper indium gallium selenide battery for the preparation high conversion efficiency, the invention provides a kind of preparation method of the CIGS solar cell device based on polyimide film-soda glass compound substrate, polyimides glue is applied to the soda glass surface, be solidified into polyimide film-soda glass compound substrate, and at its surface preparation CIGS solar cell, after complete CIGS solar cell preparation is finished, it is separated with soda glass, the flexible copper indium gallium selenide solar cell of formation take polyimide film as substrate realized preparing flexible battery with the rigidity substrate.These preparation method's process conditions are convenient and easy, are conducive to apply on a large scale, especially have extremely important application prospect in space and special occasions.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (8)

1. CIGS solar cell device, it is characterized in that: be the CIGS solar cell based on polyimide film-soda glass compound substrate, form and form laminated construction by glass, polyimides, molybdenum back contact, CuInGaSe absorbed layer, cadmium sulfide resilient coating, transparent window layer high resistant native oxide zinc film, transparent window layer low-resistance zinc oxide aluminum film and aluminium top electrode, wherein substrate is by soda glass and grow in its surperficial polyimide film and consist of, the thickness of soda glass is 1.5-2mm, and the polyimides film thickness is 25-30 μ m; The molybdenum back contact comprises resistive formation film and low resistivity layer film, and wherein the thickness of resistive formation film is 80-120nm, and the thickness of low resistivity layer film is 600-700nm; The chemical molecular formula of CuInGaSe absorbed layer is CuIn 1-xGa xSe 2, x is 0.25-0.35 in the formula, and conduction type is p-type, and film thickness is 1.5-2 μ m; The cadmium sulfide resilient coating conduction type be N-shaped, thickness is 45-50nm; Transparent window layer comprises high resistant native oxide zinc film and low-resistance zinc oxide aluminum film, and conduction type is N-shaped, and the thickness of native oxide zinc film is 50-100nm, and the thickness of zinc oxide aluminum film is 0.4-0.6 μ m; The thickness of aluminium upper electrode film is 0.8-1.5 μ m.
2. preparation method of CIGS solar cell device as claimed in claim 1, it is characterized in that: at first polyimides glue is applied to the soda glass surface, be solidified into polyimide film-soda glass compound substrate, secondly prepare successively molybdenum back contact, CuInGaSe absorbed layer, cadmium sulfide resilient coating, transparent window layer and top electrode on its surface, after complete CIGS solar cell preparation is finished, with itself and soda glass substrate separation, obtain the flexible copper indium gallium selenide solar cell take polyimide film as substrate.
3. the preparation method of described CIGS solar cell device according to claim 2 is characterized in that: the preparation method of described polyimide film-soda glass compound substrate, and step is as follows:
1) soda glass is carried out surface clean, cleaning method is:
At first the soda glass of 10cm * 10cm is put into potassium bichromate solution and soak 2h, potassium bichromate solution is by 300 grammes per square metre potassium chromates, 3 liters of concentrated sulfuric acids and the configuration of 300 ml deionized water form, the soda glass taking-up is placed in the acetone soln that concentration is 99.5w% with deionized water rinsing, putting into supersonic wave cleaning machine cleans, ultrasonic frequency is 20-30kHz, time is 20-25min, then soda glass is taken out from acetone soln, be placed in the alcohol that concentration is 99.7w% with deionized water rinsing, putting into supersonic wave cleaning machine cleaning ultrasonic frequency is 20-30kHz, time is 20-25min, at last soda glass is taken out from alcohol, put into the beaker that fills deionized water, put into supersonic wave cleaning machine and clean 3 times, ultrasonic frequency is 20-30kHz, and the time is 20-25min;
2) polyimides glue is coated on the soda glass surface, adopts spin processes to spare glue, technological parameter is: rotating speed is 1300-1500r/min, and the time is 35-45s;
3) will spare sample behind the glue puts into baking oven and is cured, can obtain polyimide film-soda glass compound substrate, the heating and heat preservation program of described curing process is: oven temperature is warming up to 125-135 ℃, and the heating-up time is 10-15min, and keeps 25-30min under 125-135 ℃; Oven temperature is warming up to 150-160 ℃, and the heating-up time is 5-10min, and keeps 10-15min under 150-160 ℃; Oven temperature is warming up to 200-210 ℃, and the heating-up time is 5-10min, and keeps 15-20min under 200-210 ℃; Oven temperature is warming up to 250-260 ℃, and the heating-up time is 5-10min, and keeps 15-20min under 250-260 ℃; Oven temperature is warming up to 340-350 ℃, and the heating-up time is 5-10min, and keeps 10-15min under 340-350 ℃, and then slow cooling can obtain polyimide film-soda glass compound substrate to 18-25 ℃.
4. the preparation method of described CIGS solar cell device according to claim 2, it is characterized in that: described molybdenum back contact thin film technology method, the preparation of employing DC magnetron sputtering system, sample to be prepared is placed the settling chamber of Deposited By Dc Magnetron Sputtering system, take the molybdenum of purity as 99.99% as target, adopt rf magnetron sputtering technique to deposit respectively successively high resistant molybdenum film and low-resistance molybdenum film at substrate surface, wherein:
1) deposition high resistant molybdenum film technological parameter is: base vacuum 3.0 * 10 -4Pa, operating air pressure 1-2Pa, underlayer temperature 25-50 ℃, radio-frequency power 500-700W, Ar throughput 30-50sccm, basic target speed of travel 4-6mm/s, sedimentation time is counted 2-4 time with the reciprocal time of basic target;
2) technological parameter of deposition low-resistance film is: base vacuum 3.0 * 10 -4Pa, operating air pressure are 0-0.5Pa, and underlayer temperature is room temperature 25-50 ℃, and radio-frequency power is 1500-2000W, and the Ar throughput is 15-20sccm, and the basic target speed of travel is 4-6mm/s, and sedimentation time is counted 4-6 time with the reciprocal time of basic target.
5. the preparation method of described CIGS solar cell device according to claim 2 is characterized in that: described CuInGaSe absorbed layer thin film technology method, adopt selenizing stove film preparing system and coevaporation three-step approach preparation technology, and step is as follows:
1) sample to be prepared being placed the coevaporation system, is 3.0 * 10 at base vacuum -4Pa, underlayer temperature are under 350-400 ℃, coevaporation In, Ga, Se initialization layer, wherein In evaporation source temperature is 850-900 ℃, Ga evaporation source temperature is 880-920 ℃, Se evaporation source temperature is 240-280 ℃, evaporation time is 15-20min, and the atomic ratio of control In/Ga is 0.7:0.3, (In+Ga)/and the atomic ratio of Se is 2:3;
2) be under 550-580 ℃ at underlayer temperature, coevaporation Cu, Se, wherein Cu evaporation source temperature is 1120-1160 ℃, and Se evaporation source temperature is 240-280 ℃, and evaporation time is 15-20min;
3) keep step 2 at underlayer temperature) temperature-resistant condition under, coevaporation In, Ga, Se, wherein In evaporation source temperature is 850-900 ℃, Ga evaporation source temperature is 880-920 ℃, Se evaporation source temperature is 240-280 ℃, evaporation time is 2-4min, obtains the Copper Indium Gallium Selenide p-type yellow copper structure of poor a little Cu, and the atomic ratio of control Cu/ (In+Ga) is 0.88-0.92;
4) with substrate cooling, during underlayer temperature when in the time of evaporation Se, substrate being cooled to the first step, close the Se evaporation source, substrate is cooled to 18-25 ℃ again and gets final product.
6. the preparation method of described CIGS solar cell device according to claim 2 is characterized in that: the preparation method of described cadmium sulfide resilient coating, adopt the standby technique of chemical bath legal system, and step is as follows:
1) preparation feedback liquid: at first configuration concentration is 0.01mol/L thiourea solution 1L, configuration cadmium acetate and Ammonium Acetate mixed solution 1L, and wherein the cadmium acetate solution concentration is 0.001mol/L, and liquor ammonii acetatis concentration is 0.003mol/L, and ammonia spirit concentration is 1.3 * 10 -3Then mol/L mixes 4 of thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirits and stirs, and makes reactant liquor;
2) reactant liquor is added in the beaker be placed with sample and with beaker put into water-bath, bath temperature is set to 78-80 ℃, and the reaction time is 50-60min;
3) after reaction was finished, the cadmium sulfide particle of rinsing the unreacted film forming that residues in sample cadmium sulfide buffer-layer surface with deionized water well got final product.
7. the preparation method of described CIGS solar cell device according to claim 2, it is characterized in that: the high resistant native oxide zinc film of described transparent window layer and low-resistance zinc oxide aluminum thin film technology method, adopt respectively the preparation of rf magnetron sputtering system and DC magnetron sputtering system, step is as follows:
1) high resistant native oxide zinc thin film technology
Sample to be prepared is placed the settling chamber of r. f. magnetron sputtering system, take the i-ZnO of purity as 99.99% as target, adopt rf magnetron sputtering technique at substrate surface deposition intrinsic zinc-oxide film, technological parameter is: base vacuum 3.0 * 10 -4Pa, underlayer temperature 25-50 ℃, radio-frequency power 800-1000W, Ar throughput 10-20sccm, O 2Throughput 2-6sccm, the basic target speed of travel is 2-6mm/s, sedimentation time is counted 6-10 time with the reciprocal time of basic target;
2) low-resistance zinc oxide aluminum thin film technology
Sample to be prepared is placed in the settling chamber of Deposited By Dc Magnetron Sputtering system, take the ZnO:Al of purity as 99.99% as target, adopts magnetically controlled DC sputtering technique at substrate surface deposition ZnO:Al film, technological parameter is: base vacuum 3.0 * 10 -4Pa, underlayer temperature 25-50 ℃, direct current power 1000-1200W, Ar throughput 12-18sccm, basic target speed of travel 2-6mm/s, sedimentation time is counted 10-15 time with the reciprocal time of basic target.
8. the preparation method of described CIGS solar cell device according to claim 2 is characterized in that: the preparation method of described aluminium top electrode, adopt the preparation of coevaporation system, and step is as follows:
1) sample to be prepared is placed the coevaporation system, at base vacuum 3.0 * 10 -4Under the Pa, give successively heater strip 20A electric current, continue 1-2min, give heater strip 50A electric current, continue 1-2min, give heater strip 80A electric current, continue 1-2min; Give heater strip 120A electric current, continue 5-8min;
2) after glass pane to be seen was covered fully by the aluminium film, stopped heating slowly reduced giving the heater strip electric current, and then cooling gets final product.
CN2013102412586A 2013-06-18 2013-06-18 Copper indium gallium selenium solar battery device and manufacturing method thereof Pending CN103325868A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5436204A (en) * 1993-04-12 1995-07-25 Midwest Research Institute Recrystallization method to selenization of thin-film Cu(In,Ga)Se2 for semiconductor device applications
CN101510575A (en) * 2009-03-27 2009-08-19 南开大学 Method for producing medlin plastic substrate flexible silicon-based film solar battery integrated component
CN101673777A (en) * 2009-10-13 2010-03-17 华东师范大学 Solar battery with soft copper, indium, gallium and selenium film
CN102534491A (en) * 2011-10-19 2012-07-04 深圳市三海光电技术有限公司 Preparation device and preparation method for absorbing layer of high conversion efficiency CIGS (Copper Indium Gallium Selenium) thin film solar cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5436204A (en) * 1993-04-12 1995-07-25 Midwest Research Institute Recrystallization method to selenization of thin-film Cu(In,Ga)Se2 for semiconductor device applications
CN101510575A (en) * 2009-03-27 2009-08-19 南开大学 Method for producing medlin plastic substrate flexible silicon-based film solar battery integrated component
CN101673777A (en) * 2009-10-13 2010-03-17 华东师范大学 Solar battery with soft copper, indium, gallium and selenium film
CN102534491A (en) * 2011-10-19 2012-07-04 深圳市三海光电技术有限公司 Preparation device and preparation method for absorbing layer of high conversion efficiency CIGS (Copper Indium Gallium Selenium) thin film solar cell

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Application publication date: 20130925