CN103346194B - A kind of CIGS solar cell device and preparation method thereof - Google Patents
A kind of CIGS solar cell device and preparation method thereof Download PDFInfo
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- CN103346194B CN103346194B CN201310241273.0A CN201310241273A CN103346194B CN 103346194 B CN103346194 B CN 103346194B CN 201310241273 A CN201310241273 A CN 201310241273A CN 103346194 B CN103346194 B CN 103346194B
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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
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Abstract
A kind of CIGS solar cell device, for the CIGS solar cell based on polyimide film-soda glass compound substrate, 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 form and form laminated construction, its preparation method is: first polyimides glue is applied to glass surface, be solidified into polyimide film-soda glass compound substrate, then each layer film is prepared successively on its surface successively, after prepared by complete CIGS solar cell, by itself and soda glass substrate separation, obtaining take polyimide film as the flexible copper indium gallium selenide solar cell of substrate.Advantage of the present invention is: this kind is large based on the CIGS thin-film crystal grain of polyimide film-soda glass compound substrate; Its preparation method prepares flexible battery with rigidity substrate, easy to implement, is conducive to applying on a large scale.
Description
Technical field
The present invention relates to 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 race's quaternary compound semiconductor, has the crystal structure of chalcopyrite.CIGS thin-film too can battery from 20 century 70s occur since, obtain very fast development, and progressively will realize industrialization.This battery has following characteristics: 1) energy gap of Copper Indium Gallium Selenide can adjust within the scope of 1.04eV-1.67eV; 2) Copper Indium Gallium Selenide is a kind of direct gap semiconductor, to the absorption coefficient of visible ray up to 10
5cm
-1, CuInGaSe absorbed layer thickness only needs 1.5-2.5 μm, and the thickness of whole battery is 3-4 μm; 3) Radiation hardness is strong, compares and is suitable as space power system; 4) conversion efficiency is high, and the small size CIGS solar cell conversion efficiency that German solar energy in 2010 and Hydrogen Energy research center (ZSW) develop is up to 20.3%; 5) low light level characteristic is good.Therefore Copper Indium Gallium Selenide polycrystalline thin-film solar cell is expected to one of main product becoming solar cell of future generation.
Aerospace field needs solar cell to have higher quality than power, namely wishes that the solar cell of unit mass can send more electricity.The surface modeling of ground photovoltaic building and the photovoltaic plant etc. of movable type are required that solar cell has flexibility, foldability and is not afraid of to fall touch, this promotes the development of flexible solar cell.Due to relatively strong heat-resisting ability and the comparatively applicable coefficient of expansion, polyimides (PI) is shown one's talent wherein.
But the thermal coefficient of expansion of polyimides still well cannot mate with Copper Indium Gallium Selenide material itself.When temperature is higher, polyimides can produce larger deformation, causes CIGS thin-film comparatively loose, easily comes off.So underlayer temperature is lower when preparing based on the Copper Indium Gallium Selenide of polyimide substrate at present.Thus cause that the thin film crystallization that grows is second-rate, crystal grain is tiny, defect is more, adds the compound of charge carrier, shorten the life-span of few son, and then have impact on battery performance.
Summary of the invention
The object of the invention is for above-mentioned existing problems, provide a kind of CIGS solar cell device and preparation method thereof, this solar cell device is the CIGS solar cell based on polyimide film-soda glass compound substrate, it prepares flexible battery with rigidity substrate, CIGS thin-film crystalline quality based on polyimide film-soda glass compound substrate is good, crystal grain is large, and defect is few.
Technical scheme of the present invention:
A kind of CIGS solar cell device, for the CIGS solar cell based on polyimide film-soda glass compound substrate, formed 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 and formed laminated construction, wherein substrate is made up of soda glass and the polyimide film that is grown on its surface, the thickness of soda glass is 1.5-2mm, and polyimides film thickness is 25-30 μm; 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, in formula, x is 0.25-0.35, and conduction type is p-type, and film thickness is 1.5-2 μm; 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 μm; The thickness of aluminium upper electrode film is 0.8-1.5 μm.
A kind of preparation method of described CIGS solar cell device, first polyimides glue is applied to soda glass surface, be solidified into polyimide film-soda glass compound substrate, secondly molybdenum back contact, CuInGaSe absorbed layer, cadmium sulfide resilient coating, transparent window layer and top electrode is prepared successively on its surface, after prepared by complete CIGS solar cell, by itself and soda glass substrate separation, obtaining take polyimide film as 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) carry out surface clean to soda glass, cleaning method is:
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, it is in the acetone soln of 99.5w% that soda glass taking-up deionized water rinsing is placed on concentration, put into supersonic wave cleaning machine to clean, ultrasonic frequency is 20-30kHz, time is 20-25min, then soda glass is taken out from acetone soln, being placed on concentration with deionized water rinsing is in the alcohol of 99.7w%, putting into supersonic wave cleaning machine, to clean ultrasonic frequency be 20-30kHz, time is 20-25min, finally soda glass is taken out from alcohol, put into the beaker filling deionized water, put into supersonic wave cleaning machine cleaning 3 times, ultrasonic frequency is 20-30kHz, time is 20-25min,
2) polyimides glue is coated on soda glass surface, adopt spin processes to carry out even glue, technological parameter is: rotating speed is 1300-1500r/min, and the time is 35-45s;
3) sample after even glue is put into baking oven to be cured, polyimide film-soda glass compound substrate can be obtained, the heating and heat preservation program of described curing process is: oven temperature is warming up to 125-135 DEG C, and the heating-up time is 10-15min, and maintains 25-30min at 125-135 DEG C; Oven temperature is warming up to 150-160 DEG C, and the heating-up time is 5-10min, and maintains 10-15min at 150-160 DEG C; Oven temperature is warming up to 200-210 DEG C, and the heating-up time is 5-10min, and maintains 15-20min at 200-210 DEG C; Oven temperature is warming up to 250-260 DEG C, and the heating-up time is 5-10min, and maintains 15-20min at 250-260 DEG C; Oven temperature is warming up to 340-350 DEG C, and the heating-up time is 5-10min, and maintains 10-15min at 340-350 DEG C, and then slow cooling is to 18-25 DEG C, can obtain polyimide film-soda glass compound substrate.。
The preparation method of described molybdenum back contact film, prepared by employing DC magnetron sputtering system, sample to be prepared is placed in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the molybdenum of 99.99% be target, rf magnetron sputtering technique is adopted to deposit high resistant molybdenum film and low-resistance molybdenum film respectively successively at substrate surface, wherein:
1) depositing high resistant molybdenum film technological parameter is: base vacuum 3.0 × 10
-4pa, operating air pressure 1-2Pa, underlayer temperature 25-50 DEG C, radio-frequency power 500-700W, Ar throughput 30-50sccm, base target speed of travel 4-6mm/s, sedimentation time is counted 2-4 time with the reciprocal time of base target;
2) technological parameter depositing low-resistance film is: base vacuum 3.0 × 10
-4pa, operating air pressure is 0-0.5Pa, and underlayer temperature is room temperature 25-50 DEG C, and radio-frequency power is 1500-2000W, Ar throughput is 15-20sccm, and the base target speed of travel is 4-6mm/s, and sedimentation time is counted 4-6 time with the reciprocal time of base target.
The preparation method of described CuInGaSe absorbed layer film, adopt selenizing stove film preparing system and coevaporation one-step preparation process, step is as follows:
1) sample to be prepared being placed in coevaporation system, is 3.0 × 10 at base vacuum
-4pa, underlayer temperature are at 550-580 DEG C, coevaporation Cu, In, Ga, Se, and wherein Cu source temperature is 1120-1160 DEG C, In source temperature is 850-900 DEG C, Ga source temperature is 880-920 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 25-30min;
2) substrate is cooled to 18-25 DEG C.
The preparation method of described cadmium sulfide resilient coating, adopt chemical bath method preparation technology, step is as follows:
1) preparation feedback liquid: first configuration concentration is 0.01mol/L thiourea solution 1L, configuration cadmium acetate and Ammonium Acetate mixed solution 1L, wherein 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, then mixes thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirit 4 and stirs, obtained reactant liquor;
2) being added by reactant liquor in the beaker being placed with sample and beaker is put into water-bath, bath temperature is set to 78-80 DEG C, and the reaction time is 50-60min;
3), after having reacted, the cadmium sulfide particle of the unreacted film forming of sample cadmium sulfide buffer-layer surface is totally residued in deionized water rinsing.
The high resistant native oxide zinc film of described transparent window layer and the preparation method of low-resistance zinc oxide aluminum film, adopt rf magnetron sputtering system and DC magnetron sputtering system preparation respectively, step is as follows:
1) preparation of high resistant native oxide zinc film
Sample to be prepared being placed in the settling chamber of r. f. magnetron sputtering system, take purity as the i-ZnO of 99.99% is target, and 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 DEG C, radio-frequency power 800-1000W, Ar throughput 10-20sccm, O
2throughput 2-6sccm, the base target speed of travel is 2-6mm/s, and sedimentation time is counted 6-10 time with the reciprocal time of base target;
2) preparation of low-resistance zinc oxide aluminum film
Being placed at by sample to be prepared in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the ZnO:Al of 99.99% is target, and adopt DC magnetron sputtering process at substrate surface deposition ZnO:Al film, technological parameter is: base vacuum 3.0 × 10
-4pa, underlayer temperature 25-50 DEG C, direct current power 1000-1200W, Ar throughput 12-18sccm, base target speed of travel 2-6mm/s, sedimentation time is counted 10-15 time with the reciprocal time of base target.
The preparation method of described aluminium top electrode, adopt the preparation of coevaporation system, step is as follows:
1) sample to be prepared is placed in coevaporation system, at base vacuum 3.0 × 10
-4under 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 completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, then cool.
Know-why analysis of the present invention:
In order to meet the requirement preparing the Copper Indium Gallium Selenide flexible thin-film solar cell that crystalline quality is better, crystal grain is comparatively large, defect is less, the substrate that substrate is soft, light, thermal coefficient of expansion comparatively mates with CIGS thin-film must be selected.Polyimide film-soda glass compound substrate can rely on soda glass and the comparatively close feature of the CuInGaSe absorbed layer film thermal coefficient of expansion, and compound substrate prepares CIGS thin-film solar cell.Be that substrate is separated from soda glass surface afterwards again with polyimides by thin film solar cell, obtain flexible CIGS thin-film solar cell, realize the design preparing flexible solar cell with rigidity substrate.
The technical advantage of the described CIGS solar cell based on polyimide film-soda glass compound substrate:
1) polyimides glue is applied to glass surface, better can improves the roughness of substrate;
2) thermal coefficient of expansion of polyimides itself is larger, can not itself mate with Copper Indium Gallium Selenide material well, easily be out of shape at relatively high temperatures, film is caused to loosen, very easily come off, and be grown on the polyimides of glass surface, rely on the adhesive force between glass, make it that comparatively large deformation not easily occur, more mate with Copper Indium Gallium Selenide material;
3) due to glass contact, not easily there is deformation, polyimides can be given comparatively close to the temperature of its heatproof upper limit, contribute to CIGS thin-film and better grow;
4) its epontic CIGS thin-film crystalline quality is good, crystal grain is large, defect is few; .
5) after prepared by complete CIGS solar cell, it is separated from glass, just can prepares 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, defect is few, utilizes rigidity substrate to prepare flexible solar cell; Its preparation method is simple, easy to implement, is conducive to applying on a large scale, especially in space and special occasions, has extremely important application prospect.
Accompanying drawing explanation
Accompanying drawing is the structural representation of this CIGS solar cell.
Embodiment
In order to make those skilled in the art person understand the present invention program better, below in conjunction with drawings and embodiments, the present invention is described in further detail.
Embodiment 1:
A kind of CIGS solar cell device, for the CIGS solar cell based on polyimide film-soda glass compound substrate, as shown in Figure 1, formed 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 and formed laminated construction, wherein substrate is made up of soda glass and the polyimide film that is grown on its surface, the thickness of soda glass is 2mm, and polyimides film thickness is 25 μm; 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, in formula, x is 0.3, and conduction type is p-type, and film thickness is 1.5 μm; 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 μm; The thickness of aluminium upper electrode film is 1 μm.
The preparation method of described CIGS solar cell device, first polyimides glue is applied to soda glass surface, be solidified into polyimide film-soda glass compound substrate, secondly molybdenum back contact, CuInGaSe absorbed layer, cadmium sulfide resilient coating, transparent window layer and top electrode is prepared successively on its surface, after prepared by complete CIGS solar cell, by itself and soda glass substrate separation, obtaining take polyimide film as 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) carry out surface clean to soda glass, cleaning method is:
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, it is in the acetone soln of 99.5w% that soda glass taking-up deionized water rinsing is placed on concentration, put into supersonic wave cleaning machine to clean, ultrasonic frequency is 20kHz, time is 25min, then soda glass is taken out from acetone soln, being placed on concentration with deionized water rinsing is in the alcohol of 99.7w%, putting into supersonic wave cleaning machine, to clean ultrasonic frequency be 20kHz, time is 25min, finally soda glass is taken out from alcohol, put into the beaker filling deionized water, put into supersonic wave cleaning machine cleaning 3 times, ultrasonic frequency is 20kHz, time is 25min,
2) polyimides glue is coated on soda glass surface, adopt spin processes to carry out even glue, technological parameter is: rotating speed is 1300r/min, and the time is 45s;
3) sample after even glue is put into baking oven to be cured, polyimide film-soda glass compound substrate can be obtained, the heating and heat preservation program of described curing process is: oven temperature is warming up to 125 DEG C, and the heating-up time is 15min, and maintains 30min at 125 DEG C; Oven temperature is warming up to 150 DEG C, the heating-up time is 5min, and maintains 15min at 150 DEG C; Oven temperature is warming up to 200 DEG C, the heating-up time is 5min, and maintains 20min at 200 DEG C; Oven temperature is warming up to 250 DEG C, the heating-up time is 5min, and maintains 20min at 250 DEG C; Oven temperature is warming up to 350 DEG C, the heating-up time is 10min, and maintains 10min at 350 DEG C, then slow cooling to 22 DEG C, can obtain polyimide film-soda glass compound substrate.
The preparation method of described molybdenum back contact film, prepared by employing DC magnetron sputtering system, sample to be prepared is placed in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the molybdenum of 99.99% be target, rf magnetron sputtering technique is adopted to deposit high resistant molybdenum film and low-resistance molybdenum film respectively successively at substrate surface, wherein:
1) depositing high resistant molybdenum film technological parameter is: base vacuum 3.0 × 10
-4pa, operating air pressure 1Pa, underlayer temperature 25 DEG C, radio-frequency power 600W, Ar throughput 40sccm, base target speed of travel 4mm/s, sedimentation time counts 2 times with the reciprocal time of base target;
2) technological parameter depositing low-resistance film is: base vacuum 3.0 × 10
-4pa, operating air pressure is 0.1Pa, and underlayer temperature is 25 DEG C, and radio-frequency power is 1500W, Ar throughput is 15sccm, and the base target speed of travel is 4mm/s, and sedimentation time counts 6 times with the reciprocal time of base target.
The preparation method of described CuInGaSe absorbed layer film, adopt selenizing stove film preparing system and coevaporation one-step preparation process, step is as follows:
1) sample to be prepared being placed in coevaporation system, is 3.0 × 10 at base vacuum
-4pa, underlayer temperature are at 560 DEG C, coevaporation Cu, In, Ga, Se, and wherein Cu source temperature is 1140 DEG C, and In source temperature is 860 DEG C, and Ga source temperature is 900 DEG C, and Se source temperature is 260 DEG C, and evaporation time is 28min;
2) substrate is cooled to 18-25 DEG C.
The preparation method of described cadmium sulfide resilient coating, adopt chemical bath method preparation technology, step is as follows:
1) preparation feedback liquid: first configuration concentration is 0.01mol/L thiourea solution 1L, configuration cadmium acetate and Ammonium Acetate mixed solution 1L, wherein 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, then mixes thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirit 4 and stirs, obtained reactant liquor;
2) reactant liquor is put into beaker and beaker is put into water-bath, bath temperature is set to 78 DEG C, and the reaction time is 60min;
3), after having reacted, the cadmium sulfide particle of the unreacted film forming of sample cadmium sulfide buffer-layer surface is totally residued in deionized water rinsing.
The high resistant native oxide zinc film of described transparent window layer and the preparation method of low-resistance zinc oxide aluminum film, adopt rf magnetron sputtering system and DC magnetron sputtering system preparation respectively, step is as follows:
1) preparation of high resistant native oxide zinc film
Sample to be prepared being placed in the settling chamber of r. f. magnetron sputtering system, take purity as the i-ZnO of 99.99% is target, and adopt rf magnetron sputtering technique at substrate surface deposition intrinsic zinc-oxide film, technological parameter is: base vacuum 3.0 × 10
-4pa, underlayer temperature 35 DEG C, radio-frequency power 800W, Ar throughput 10sccm, O
2throughput 3sccm, the base target speed of travel is 4mm/s, and sedimentation time counts 8 times with the reciprocal time of base target;
2) preparation of low-resistance zinc oxide aluminum film
Being placed at by sample to be prepared in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the ZnO:Al of 99.99% is target, and adopt DC magnetron sputtering process at substrate surface deposition ZnO:Al film, technological parameter is: base vacuum 3.0 × 10
-4pa, underlayer temperature 25 DEG C, direct current power 1000W, Ar throughput 15sccm, base target speed of travel 6mm/s, sedimentation time counts 10 times with the reciprocal time of base target.
The preparation method of described aluminium top electrode, adopt the preparation of coevaporation system, step is as follows:
1) sample to be prepared is placed in coevaporation system, at base vacuum 3.0 × 10
-4under 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 completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, then cool.
Shown by test: prepared CIGS solar cell device can form good PN junction, produce photovoltaic effect, can electric energy be produced under solar light irradiation.
Embodiment 2:
A kind of CIGS solar cell device, for the CIGS solar cell based on polyimide film-soda glass compound substrate, as shown in Figure 1, formed 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 and formed laminated construction, wherein substrate is made up of soda glass and the polyimide film that is grown on its surface, the thickness of soda glass is 2mm, and polyimides film thickness is 30 μm; 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, in formula, x is 0.28, and conduction type is p-type, and film thickness is 1.8 μm; 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 μm; The thickness of aluminium upper electrode film is 1.2 μm.
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) carry out surface clean to soda glass, cleaning method is:
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, it is in the acetone soln of 99.5w% that soda glass taking-up deionized water rinsing is placed on concentration, put into supersonic wave cleaning machine to clean, ultrasonic frequency is 30kHz, time is 20min, then soda glass is taken out from acetone soln, being placed on concentration with deionized water rinsing is in the alcohol of 99.7w%, putting into supersonic wave cleaning machine, to clean ultrasonic frequency be 30kHz, time is 20min, finally soda glass is taken out from alcohol, put into the beaker filling deionized water, put into supersonic wave cleaning machine cleaning 3 times, ultrasonic frequency is 30kHz, time is 20min,
2) polyimides glue is coated on soda glass surface, adopt spin processes to carry out even glue, technological parameter is: rotating speed is 1400r/min, and the time is 40s;
3) sample after even glue is put into baking oven to be cured, polyimide film-soda glass compound substrate can be obtained, the heating and heat preservation program of described curing process is: oven temperature is warming up to 130 DEG C, and the heating-up time is 20min, and maintains 25min at 130 DEG C; Oven temperature is warming up to 160 DEG C, the heating-up time is 10min, and maintains 10min at 160 DEG C; Oven temperature is warming up to 210 DEG C, the heating-up time is 10min, and maintains 20min at 210 DEG C; Oven temperature is warming up to 260 DEG C, the heating-up time is 10min, and maintains 20min at 260 DEG C; Oven temperature is warming up to 345 DEG C, the heating-up time is 10min, and maintains 15min at 345 DEG C, then slow cooling to 22 DEG C, can obtain polyimide film-soda glass compound substrate.
The preparation method of described molybdenum back contact film, prepared by employing DC magnetron sputtering system, sample to be prepared is placed in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the molybdenum of 99.99% be target, rf magnetron sputtering technique is adopted to deposit high resistant molybdenum film and low-resistance molybdenum film respectively successively at substrate surface, wherein:
1) depositing high resistant molybdenum film technological parameter is: base vacuum 3.0 × 10
-4pa, operating air pressure 1.5Pa, underlayer temperature 25 DEG C, radio-frequency power 700W, Ar throughput 50sccm, base target speed of travel 5mm/s, sedimentation time counts 4 times with the reciprocal time of base target;
2) technological parameter depositing low-resistance film is: base vacuum 3.0 × 10
-4pa, operating air pressure is 0.5Pa, and underlayer temperature is 25 DEG C, and radio-frequency power is 1800W, Ar throughput is 20sccm, and the base target speed of travel is 6mm/s, and sedimentation time counts 6 times with the reciprocal time of base target.
The preparation method of described CuInGaSe absorbed layer film, adopt selenizing stove film preparing system and coevaporation one-step preparation process, step is as follows:
1) sample to be prepared being placed in coevaporation system, is 3.0 × 10 at base vacuum
-4pa, underlayer temperature are at 580 DEG C, coevaporation Cu, In, Ga, Se, and wherein Cu source temperature is 1140 DEG C, and In source temperature is 890 DEG C, and Ga source temperature is 920 DEG C, and Se source temperature is 260 DEG C, and evaporation time is 25min;
2) substrate is cooled to 18-25 DEG C.
The preparation method of described cadmium sulfide resilient coating, adopt chemical bath method preparation technology, step is as follows:
1) preparation feedback liquid: first configuration concentration is 0.01mol/L thiourea solution 1L, configuration cadmium acetate and Ammonium Acetate mixed solution 1L, wherein 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, then mixes thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirit 4 and stirs, obtained reactant liquor;
2) reactant liquor is put into beaker and beaker is put into water-bath, bath temperature is set to 80 DEG C, and the reaction time is 50min;
3) after having reacted, with the cadmium sulfide particle of the clean sample carryover of deionized water rinsing in the unreacted film forming of cadmium sulfide buffer-layer surface.
The high resistant native oxide zinc film of described transparent window layer and the preparation method of low-resistance zinc oxide aluminum film, adopt rf magnetron sputtering system and DC magnetron sputtering system preparation respectively, step is as follows:
1) preparation of high resistant native oxide zinc film
Sample to be prepared being placed in the settling chamber of r. f. magnetron sputtering system, take purity as the i-ZnO of 99.99% is target, and adopt rf magnetron sputtering technique at substrate surface deposition intrinsic zinc-oxide film, technological parameter is: base vacuum 3.0 × 10
-4pa, underlayer temperature 50 DEG C, radio-frequency power 1000W, Ar throughput 15sccm, O
2throughput 4sccm, the base target speed of travel is 6mm/s, and sedimentation time counts 8 times with the reciprocal time of base target;
2) preparation of low-resistance zinc oxide aluminum film
Being placed at by sample to be prepared in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the ZnO:Al of 99.99% is target, and adopt DC magnetron sputtering process at substrate surface deposition ZnO:Al film, technological parameter is: base vacuum 3.0 × 10
-4pa, underlayer temperature 25 DEG C, direct current power 1200W, Ar throughput 17sccm, base target speed of travel 4mm/s, sedimentation time counts 12 times with the reciprocal time of base target.
The preparation method of described aluminium top electrode, adopt the preparation of coevaporation system, step is as follows:
1) sample to be prepared is placed in coevaporation system, at base vacuum 3.0 × 10
-4under 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 completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, then cool.
Testing result is identical with embodiment 1.
In sum, for preparing the flexible copper indium gallium selenide battery of 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 soda glass surface, be solidified into polyimide film-soda glass compound substrate, and prepare CIGS solar cell on its surface, after prepared by complete CIGS solar cell, it is separated with soda glass, formation take polyimide film as the flexible copper indium gallium selenide solar cell of substrate, realize preparing flexible battery with rigidity substrate.These preparation method's process conditions are convenient and easy, are conducive to applying on a large scale, especially in space and special occasions, have extremely important application prospect.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles 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 (1)
1. the preparation method of a CIGS solar cell device, described CIGS solar cell device is the CIGS solar cell based on polyimide film-soda glass compound substrate, 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 form and form laminated construction, wherein substrate is made up of soda glass and the polyimide film that is grown on its surface, the thickness of soda glass is 1.5-2mm, polyimides film thickness is 25-30 μm, 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, in formula, x is 0.25-0.35, and conduction type is p-type, and film thickness is 1.5-2 μm, 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 μm, the thickness of aluminium upper electrode film is 0.8-1.5 μm, its preparation method is: first polyimides glue is applied to soda glass surface, be solidified into polyimide film-soda glass compound substrate, secondly molybdenum back contact, CuInGaSe absorbed layer, cadmium sulfide resilient coating, transparent window layer and top electrode is prepared successively on its surface, after prepared by complete CIGS solar cell, by itself and soda glass substrate separation, obtaining take polyimide film as the flexible copper indium gallium selenide solar cell of substrate, it is characterized in that: the preparation method of described polyimide film-soda glass compound substrate, step is as follows:
1) carry out surface clean to soda glass, cleaning method is:
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, it is in the acetone soln of 99.5w% that soda glass taking-up deionized water rinsing is placed on concentration, put into supersonic wave cleaning machine to clean, ultrasonic frequency is 20-30kHz, time is 20-25min, then soda glass is taken out from acetone soln, being placed on concentration with deionized water rinsing is in the alcohol of 99.7w%, putting into supersonic wave cleaning machine, to clean ultrasonic frequency be 20-30kHz, time is 20-25min, finally soda glass is taken out from alcohol, put into the beaker filling deionized water, put into supersonic wave cleaning machine cleaning 3 times, ultrasonic frequency is 20-30kHz, time is 20-25min,
2) polyimides glue is coated on soda glass surface, adopt spin processes to carry out even glue, technological parameter is: rotating speed is 1300-1500r/min, and the time is 35-45s;
3) sample after even glue is put into baking oven to be cured, polyimide film-soda glass compound substrate can be obtained, the heating and heat preservation program of described curing process is: oven temperature is warming up to 125-135 DEG C, and the heating-up time is 10-15min, and maintains 25-30min at 125-135 DEG C; Oven temperature is warming up to 150-160 DEG C, and the heating-up time is 5-10min, and maintains 10-15min at 150-160 DEG C; Oven temperature is warming up to 200-210 DEG C, and the heating-up time is 5-10min, and maintains 15-20min at 200-210 DEG C; Oven temperature is warming up to 250-260 DEG C, and the heating-up time is 5-10min, and maintains 15-20min at 250-260 DEG C; Oven temperature is warming up to 340-350 DEG C, and the heating-up time is 5-10min, and maintains 10-15min at 340-350 DEG C, and then slow cooling is to 18-25 DEG C, can obtain polyimide film-soda glass compound substrate.
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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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| 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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