CN103346194A - Copper indium gallium selenium solar battery device and preparing method thereof - Google Patents

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

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CN103346194A
CN103346194A CN2013102412730A CN201310241273A CN103346194A CN 103346194 A CN103346194 A CN 103346194A CN 2013102412730 A CN2013102412730 A CN 2013102412730A CN 201310241273 A CN201310241273 A CN 201310241273A CN 103346194 A CN103346194 A CN 103346194A
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film
indium gallium
preparation
copper indium
soda glass
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CN103346194B (en
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薛玉明
张嘉伟
赵彦民
乔在祥
李微
许楠
冯少君
刘浩
尹富红
朱亚东
潘宏刚
宋殿友
李鹏海
刘君
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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
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

A copper indium gallium selenium solar battery device is a copper indium gallium selenium solar battery based on a polyimide film-soda glass recombination substrate. The copper indium gallium selenium solar battery device is composed of glass, polyimide, a molybdenum back contacting layer, a copper indium gallium selenium absorbing layer, a cadmium sulfide buffering layer, a transparent window layer high resistance eigen zinc oxide thin film, a transparent window low resistance zinc oxide aluminum thin film and an aluminum top electrode, and a lamination structure is formed. A preparing method comprises the first step of coating the surface of the glass by polyimide gum, wherein the polyimide film-soda glass recombination substrate is formed in a solidifying mode, the second step of preparing all thin films on the surface of the polyimide film-soda glass recombination substrate sequentially, and the third step of separating the complete copper indium gallium selenium solar battery and the soda glass substrate after the complete copper indium gallium selenium solar battery is prepared. The soft copper indium gallium selenium solar battery with the polyimide film as the substrate is obtained. The copper indium gallium selenium solar battery device has the advantages that a copper indium gallium selenium thin film crystal based on the polyimide film-soda glass recombination substrate is large in grain; according to the preparing method of the copper indium gallium selenium solar battery device, the soft battery is prepared through the rigidity substrate, the method is easy to implement, and large-scale popularization and application are facilitated.

Description

A kind of Copper Indium Gallium Selenide 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 Copper Indium Gallium Selenide 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 occurring the seventies in 20th century, 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 the absorption coefficient of visible light up to 10 5Cm -1, CuInGaSe absorbed layer thickness only needs 1.5-2.5 μ m, and the thickness of entire cell is 3-4 μ m; 3) anti-irradiation ability is strong, relatively is suitable as space power system; 4) conversion efficiency height, the small size Copper Indium Gallium Selenide 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 Copper Indium Gallium Selenide polycrystal film solar cell is expected to one of main product that becomes by solar cell of future generation.
Aerospace field needs solar cell that the higher quality specific power is arranged, and 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 stronger relatively 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 bigger deformation, caused CIGS thin-film comparatively loose, came off easily.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 influenced battery performance.
Summary of the invention
The objective of the invention is at above-mentioned existing problems, a kind of Copper Indium Gallium Selenide solar cell device and preparation method thereof is provided, this solar cell device is the Copper Indium Gallium Selenide solar cell based on polyimide film-soda glass compound substrate, it is with rigidity substrate preparation flexible battery, CIGS thin-film crystalline quality based on polyimide film-soda glass compound substrate is good, crystal grain is big, and defective is few.
Technical scheme of the present invention:
A kind of Copper Indium Gallium Selenide solar cell device, be the Copper Indium Gallium Selenide 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 intrinsic zinc-oxide 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 constitute, 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 the n type, thickness is 45-50nm; Transparent window layer comprises high resistant intrinsic zinc-oxide film and low-resistance zinc oxide aluminum film, and conduction type is the n type, and the thickness of intrinsic zinc-oxide 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 described Copper Indium Gallium Selenide solar cell preparation of devices method, at first polyimides glue is applied to the soda glass surface, be solidified into polyimide film-soda glass compound substrate, secondly prepare molybdenum back contact, CuInGaSe absorbed layer, cadmium sulfide resilient coating, transparent window layer and top electrode successively on its surface, after complete Copper Indium Gallium Selenide solar cell preparation is finished, with itself and soda glass substrate separation, obtaining with the polyimide film is the flexible copper indium gallium selenide solar cell of 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 even adhesive process 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 ℃, slowly is cooled to 18-25 ℃ then, can obtain polyimide film-soda glass compound substrate.
The preparation method of described molybdenum back contact film, the preparation of employing DC magnetron sputtering system, sample to be prepared is placed the settling chamber of magnetically controlled DC sputtering depositing system, be that 99.99% molybdenum is target with purity, adopt rf magnetron sputtering technology to deposit high resistant molybdenum film and low-resistance molybdenum film successively respectively 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.
The preparation method of described CuInGaSe absorbed layer film adopts selenizing stove film preparing system and coevaporation one-step preparation process, 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 550-580 ℃, coevaporation Cu, In, Ga, Se, and wherein Cu evaporation source temperature is 1120-1160 ℃, In evaporation source temperature is 850-900 ℃, Ga evaporation source temperature is 880-920 ℃, and Se evaporation source temperature is 240-280 ℃, and evaporation time is 25-30min;
2) substrate being cooled to 18-25 ℃ gets final product.
The preparation method of described cadmium sulfide resilient coating adopts chemical bath method preparation technology, 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 -3Mol/L mixes 4 of thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirits then 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 preparation method of the high resistant intrinsic zinc-oxide film of described transparent window layer and low-resistance zinc oxide aluminum film adopts the preparation of rf magnetron sputtering system and DC magnetron sputtering system respectively, and step is as follows:
1) preparation of high resistant intrinsic zinc-oxide film
Sample to be prepared is placed the settling chamber of rf magnetron sputtering depositing system, is that 99.99% i-ZnO is target with purity, adopts rf magnetron sputtering technology at substrate surface deposition intrinsic zinc-oxide film, and 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) preparation of low-resistance zinc oxide aluminum film
Sample to be prepared being placed in the settling chamber of magnetically controlled DC sputtering depositing system, is that 99.99% ZnO:Al is target with purity, adopts magnetically controlled DC sputtering technology at substrate surface deposition ZnO:Al film, and 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 coevaporation systems produce, 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 heater strip 20A electric current successively, 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 is covered fully by the aluminium film, stop heating, slowly reduce giving the heater strip electric current, cooling gets final product then.
Know-why analysis of the present invention:
For satisfy the preparation crystalline quality better, the requirement of crystal grain is big, defective is less Copper Indium Gallium Selenide flexible thin-film solar cell, the substrate that must select for use substrate softness, light, thermal coefficient of expansion and CIGS thin-film comparatively to mate.The characteristics that polyimide film-soda glass compound substrate can rely on soda glass and CuInGaSe absorbed layer film thermal coefficient of expansion comparatively to approach prepare CIGS thin-film solar cell in compound substrate.With thin film solar cell with the polyimides be again afterwards substrate from the soda glass surface isolation, obtain flexible CIGS thin-film solar cell, realize the design with rigidity substrate preparation flexible solar cell.
The technical advantage of described Copper Indium Gallium Selenide 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 bigger, can not itself mate with the Copper Indium Gallium Selenide material well, easy deformation 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 taking place than large deformation, mate more with the Copper Indium Gallium Selenide material;
3) because and glass contact, deformation be difficult for to take place, 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 big, defective is few;
5) after complete Copper Indium Gallium Selenide solar cell preparation is finished, it from separation on glass, just can be prepared the flexible copper indium gallium selenide solar cell with big columnar grain.
Advantage of the present invention is: this kind is good based on the Copper Indium Gallium Selenide solar cell absorbed layer thin film crystallization quality of polyimide film-soda glass compound substrate, crystal grain is big, defective is few, utilizes rigidity substrate preparation 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 Copper Indium Gallium Selenide solar cell.
Embodiment
In order to make those skilled in the art person understand the present invention program better, the present invention is described in further detail below in conjunction with drawings and embodiments.
Embodiment 1:
A kind of Copper Indium Gallium Selenide solar cell device, be the Copper Indium Gallium Selenide 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 intrinsic zinc-oxide 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 constitute, 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 the n type, thickness is 45nm; Transparent window layer comprises high resistant intrinsic zinc-oxide film and low-resistance zinc oxide aluminum film, and conduction type is the n type, and the thickness of intrinsic zinc-oxide 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.
Described Copper Indium Gallium Selenide solar cell preparation of devices method, at first polyimides glue is applied to the soda glass surface, be solidified into polyimide film-soda glass compound substrate, secondly prepare molybdenum back contact, CuInGaSe absorbed layer, cadmium sulfide resilient coating, transparent window layer and top electrode successively on its surface, after complete Copper Indium Gallium Selenide solar cell preparation is finished, with itself and soda glass substrate separation, obtaining with the polyimide film is the flexible copper indium gallium selenide solar cell of 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 even adhesive process 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 ℃, slowly is cooled to 22 ℃ then, can obtain polyimide film-soda glass compound substrate.
The preparation method of described molybdenum back contact film, the preparation of employing DC magnetron sputtering system, sample to be prepared is placed the settling chamber of magnetically controlled DC sputtering depositing system, be that 99.99% molybdenum is target with purity, adopt rf magnetron sputtering technology to deposit high resistant molybdenum film and low-resistance molybdenum film successively respectively 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.
The preparation method of described CuInGaSe absorbed layer film adopts selenizing stove film preparing system and coevaporation one-step preparation process, 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 560 ℃, coevaporation Cu, In, Ga, Se, and wherein Cu evaporation source temperature is 1140 ℃, and In evaporation source temperature is 860 ℃, and Ga evaporation source temperature is 900 ℃, and Se evaporation source temperature is 260 ℃, evaporation time is 28min;
2) substrate being cooled to 18-25 ℃ gets final product.
The preparation method of described cadmium sulfide resilient coating adopts chemical bath method preparation technology, 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 -3Mol/L mixes 4 of thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirits then 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 preparation method of the high resistant intrinsic zinc-oxide film of described transparent window layer and low-resistance zinc oxide aluminum film adopts the preparation of rf magnetron sputtering system and DC magnetron sputtering system respectively, and step is as follows:
1) preparation of high resistant intrinsic zinc-oxide film
Sample to be prepared is placed the settling chamber of rf magnetron sputtering depositing system, is that 99.99% i-ZnO is target with purity, adopts rf magnetron sputtering technology at substrate surface deposition intrinsic zinc-oxide film, and 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) preparation of low-resistance zinc oxide aluminum film
Sample to be prepared being placed in the settling chamber of magnetically controlled DC sputtering depositing system, is that 99.99% ZnO:Al is target with purity, adopts magnetically controlled DC sputtering technology at substrate surface deposition ZnO:Al film, and 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 coevaporation systems produce, 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 heater strip 20A electric current successively, 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 is covered fully by the aluminium film, stop heating, slowly reduce giving the heater strip electric current, cooling gets final product then.
Pass through test shows: prepared Copper Indium Gallium Selenide solar cell device can form good PN junction, produces photovoltaic effect, can produce electric energy under solar light irradiation.
Embodiment 2:
A kind of Copper Indium Gallium Selenide solar cell device, be the Copper Indium Gallium Selenide 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 intrinsic zinc-oxide 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 constitute, 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 the n type, thickness is 50nm; Transparent window layer comprises high resistant intrinsic zinc-oxide film and low-resistance zinc oxide aluminum film, and conduction type is the n type, and the thickness of intrinsic zinc-oxide 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.
Described Copper Indium Gallium Selenide solar cell preparation of devices method 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 even adhesive process 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 ℃, slowly is cooled to 22 ℃ then, can obtain polyimide film-soda glass compound substrate.
The preparation method of described molybdenum back contact film, the preparation of employing DC magnetron sputtering system, sample to be prepared is placed the settling chamber of magnetically controlled DC sputtering depositing system, be that 99.99% molybdenum is target with purity, adopt rf magnetron sputtering technology to deposit high resistant molybdenum film and low-resistance molybdenum film successively respectively 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.
The preparation method of described CuInGaSe absorbed layer film adopts selenizing stove film preparing system and coevaporation one-step preparation process, 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 580 ℃, coevaporation Cu, In, Ga, Se, and wherein Cu evaporation source temperature is 1140 ℃, and In evaporation source temperature is 890 ℃, and Ga evaporation source temperature is 920 ℃, and Se evaporation source temperature is 260 ℃, evaporation time is 25min;
2) substrate being cooled to 18-25 ℃ gets final product.
The preparation method of described cadmium sulfide resilient coating adopts chemical bath method preparation technology, 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 -3Mol/L mixes 4 of thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirits then 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 preparation method of the high resistant intrinsic zinc-oxide film of described transparent window layer and low-resistance zinc oxide aluminum film adopts the preparation of rf magnetron sputtering system and DC magnetron sputtering system respectively, and step is as follows:
1) preparation of high resistant intrinsic zinc-oxide film
Sample to be prepared is placed the settling chamber of rf magnetron sputtering depositing system, is that 99.99% i-ZnO is target with purity, adopts rf magnetron sputtering technology at substrate surface deposition intrinsic zinc-oxide film, and 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) preparation of low-resistance zinc oxide aluminum film
Sample to be prepared being placed in the settling chamber of magnetically controlled DC sputtering depositing system, is that 99.99% ZnO:Al is target with purity, adopts magnetically controlled DC sputtering technology at substrate surface deposition ZnO:Al film, and 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 coevaporation systems produce, 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 heater strip 20A electric current successively, 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 is covered fully by the aluminium film, stop heating, slowly reduce giving the heater strip electric current, cooling gets final product then.
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 Copper Indium Gallium Selenide solar cell preparation of devices method 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 Copper Indium Gallium Selenide solar cell, after complete Copper Indium Gallium Selenide solar cell preparation is finished, it is separated with soda glass, formation is the flexible copper indium gallium selenide solar cell of substrate with the polyimide film, realizes with rigidity substrate preparation flexible battery.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. Copper Indium Gallium Selenide solar cell device, it is characterized in that: be the Copper Indium Gallium Selenide 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 intrinsic zinc-oxide 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 constitute, 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 the n type, thickness is 45-50nm; Transparent window layer comprises high resistant intrinsic zinc-oxide film and low-resistance zinc oxide aluminum film, and conduction type is the n type, and the thickness of intrinsic zinc-oxide 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. Copper Indium Gallium Selenide solar cell preparation of devices method according to 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 molybdenum back contact, CuInGaSe absorbed layer, cadmium sulfide resilient coating, transparent window layer and top electrode successively on its surface, after complete Copper Indium Gallium Selenide solar cell preparation is finished, with itself and soda glass substrate separation, obtaining with the polyimide film is the flexible copper indium gallium selenide solar cell of substrate.
3. according to the described Copper Indium Gallium Selenide solar cell of claim 2 preparation of devices method, it is characterized in that: 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 even adhesive process 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 ℃, slowly is cooled to 18-25 ℃ then, can obtain polyimide film-soda glass compound substrate.
4. according to the described Copper Indium Gallium Selenide solar cell of claim 2 preparation of devices method, it is characterized in that: the preparation method of described molybdenum back contact film, the preparation of employing DC magnetron sputtering system, sample to be prepared is placed the settling chamber of magnetically controlled DC sputtering depositing system, be that 99.99% molybdenum is target with purity, adopt rf magnetron sputtering technology to deposit high resistant molybdenum film and low-resistance molybdenum film successively respectively 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. according to the described Copper Indium Gallium Selenide solar cell of claim 2 preparation of devices method, it is characterized in that: the preparation method of described CuInGaSe absorbed layer film, adopt selenizing stove film preparing system and coevaporation three-step approach coevaporation one-step preparation process, 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 550-580 ℃, coevaporation Cu, In, Ga, Se, and wherein Cu evaporation source temperature is 1120-1160 ℃, In evaporation source temperature is 850-900 ℃, Ga evaporation source temperature is 880-920 ℃, and Se evaporation source temperature is 240-280 ℃, and evaporation time is 25-30min;
2) substrate being cooled to 18-25 ℃ gets final product.
6. according to the described Copper Indium Gallium Selenide solar cell of claim 2 preparation of devices method, it is characterized in that: the preparation method of described cadmium sulfide resilient coating, adopt chemical bath method preparation technology, 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 -3Mol/L mixes 4 of thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirits then 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. according to the described Copper Indium Gallium Selenide solar cell of claim 2 preparation of devices method, it is characterized in that: the preparation method of the high resistant intrinsic zinc-oxide film of described transparent window layer and low-resistance zinc oxide aluminum film, adopt the preparation of rf magnetron sputtering system and DC magnetron sputtering system respectively, step is as follows:
1) preparation of high resistant intrinsic zinc-oxide film
Sample to be prepared is placed the settling chamber of rf magnetron sputtering depositing system, is that 99.99% i-ZnO is target with purity, adopts rf magnetron sputtering technology at substrate surface deposition intrinsic zinc-oxide film, and 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) preparation of low-resistance zinc oxide aluminum film
Sample to be prepared being placed in the settling chamber of magnetically controlled DC sputtering depositing system, is that 99.99% ZnO:Al is target with purity, adopts magnetically controlled DC sputtering technology at substrate surface deposition ZnO:Al film, and 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. according to the described Copper Indium Gallium Selenide solar cell of claim 2 preparation of devices method, it is characterized in that: the preparation method of described aluminium top electrode, adopt the coevaporation systems produce, step is as follows:
1) sample to be prepared is placed the coevaporation system, at base vacuum 3.0 * 10 -4Under the Pa, give heater strip 20A electric current successively, 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 is covered fully by the aluminium film, stop heating, slowly reduce giving the heater strip electric current, cooling gets final product then.
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CN108010989A (en) * 2017-11-10 2018-05-08 深圳先进技术研究院 Flexible solar battery and preparation method thereof
CN108010985A (en) * 2017-11-10 2018-05-08 深圳先进技术研究院 Flexible thin-film solar cell and preparation method thereof
CN112786723A (en) * 2021-01-27 2021-05-11 重庆神华薄膜太阳能科技有限公司 Flexible thin-film solar cell module and preparation method thereof
CN116397200A (en) * 2023-06-08 2023-07-07 合肥工业大学 Single-source thermal evaporation preparation method of molybdenum-copper laminated substrate of copper-antimony-selenium light absorption layer

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CN101673777B (en) * 2009-10-13 2011-04-27 华东师范大学 Solar battery with soft copper, indium, gallium and selenium film
CN102509737A (en) * 2011-11-02 2012-06-20 南开大学 Flexible stainless steel substrate copper-indium-gallium-selenium film battery and preparation method thereof

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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
CN101673777B (en) * 2009-10-13 2011-04-27 华东师范大学 Solar battery with soft copper, indium, gallium and selenium film
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CN108010989A (en) * 2017-11-10 2018-05-08 深圳先进技术研究院 Flexible solar battery and preparation method thereof
CN108010985A (en) * 2017-11-10 2018-05-08 深圳先进技术研究院 Flexible thin-film solar cell and preparation method thereof
CN112786723A (en) * 2021-01-27 2021-05-11 重庆神华薄膜太阳能科技有限公司 Flexible thin-film solar cell module and preparation method thereof
CN116397200A (en) * 2023-06-08 2023-07-07 合肥工业大学 Single-source thermal evaporation preparation method of molybdenum-copper laminated substrate of copper-antimony-selenium light absorption layer
CN116397200B (en) * 2023-06-08 2023-08-08 合肥工业大学 Single-source thermal evaporation preparation method of molybdenum-copper laminated substrate of copper-antimony-selenium light absorption layer

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