CN105977318A - Sodium-doped CIGS (copper indium gallium selenide) film based on composite substrate and preparation method thereof - Google Patents

Sodium-doped CIGS (copper indium gallium selenide) film based on composite substrate and preparation method thereof Download PDF

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CN105977318A
CN105977318A CN201610333959.6A CN201610333959A CN105977318A CN 105977318 A CN105977318 A CN 105977318A CN 201610333959 A CN201610333959 A CN 201610333959A CN 105977318 A CN105977318 A CN 105977318A
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soda glass
film
temperature
cigs
substrate
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薛玉明
王玉昆
孙海涛
宋殿友
夏丹
冯少君
俞兵兵
张奥
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Tianjin University of Technology
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    • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035272—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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Abstract

The invention provides a sodium-doped CIGS (copper indium gallium selenide) film based on a composite substrate and a preparation method thereof. The substrate is composed of soda glass and a polyimide film grown on the surface of the soda glass, the thickness of the soda glass is in the range of 1.5-2mm, the thickness of the polyimide film is in the range of 25-30[mu]m, the chemical formula of a CIGS film grown on the surface of the composite substrate is CuIn<1-x>Ga<x>Se<2>, x represents 0.25-0.35, and the conduction is in a p type, the CIGS film CuIn<1-x>Ga<x>Se<2> is arranged on the surface of the polyimide film-soda glass composite substrate by means of thin-film deposition, and the thickness is in the range of 1.5-2[mu]m. The CIGS film based on the polyimide film-soda glass composite substrate is good in quality, large in crystal grain, and has fewer defects, a flexible solar cell is made by a rigid substrate, and the preparation method is simple and easy to implement, and is favorable for large-scale popularization and application.

Description

A kind of based on compound substrate mix sodium CIGS thin-film and preparation method thereof
Technical field
The present invention relates to thin film solar cell technical field, particularly a kind of based on polyimide film-soda glass The CIGS thin-film of compound substrate.
Background technology
CIGS material belongs to I-III-VI race quaternary compound semiconductor, has the crystal structure of Chalkopyrite. CIGS thin-film too can battery since 20 century 70s occur, obtain very fast development, and will be by Step realizes industrialization.This battery has following characteristics: 1) energy gap of CIGS can be at 1.04ev-1.67ev In the range of adjust；2) CIGS is a kind of direct band-gap semicondictor, is up to the absorptance of visible ray 105cm-1, CuInGaSe absorbed layer thickness only needs 1.52.5 μm, the thickness of whole battery to be 3-4 μm；3) anti- Irradiation ability is strong, compares and is suitable as space power system；4) conversion efficiency is high, German solar energys in 2014 and hydrogen The little area CIGS solar cell conversion efficiency that energy research center (ZSW) is developed up to 21.7%；5) Low light level characteristic is good.Therefore CIGS polycrystalline thin-film solar cell is expected to become the main flow product of solar cell of future generation One of product.
The Na mixing 0.1% in CIGS thin film can make CIGS solar cell performance improve 30～50%, In tradition Na-Ca glass (SLG) substrate CIGS solar cell preparation, Na can be absorbed to CIGS by substrate Layer spontaneous diffusion and realize the incorporation of Na.But, owing to PI substrate is without Na, therefore must add in preparation Enter Na and mix technique, improve the performance of CIGS thin film, improve flexible Pl substrate CIGS thin film further The photoelectric transformation efficiency of solar cell.Therefore, to copper and indium based on polyimide film-soda glass compound substrate Gallium selenium absorbed layer thin film mixes sodium and just becomes particularly important.
At present, during preparing CIGS thin-film solar cell, the method mixing Na has a variety of, including: On substrate, the initialization layer of one layer of NaF was first deposited before preparing Mo back electrode；On Mo back electrode surface Deposition initialization layer Han Na；Na element is co-deposited (for the most general during preparing CuInGaSe absorbed layer All over use three-step approach prepare CIGS, the first step can be divided into again to mix, second be co-doped with, the 3rd step is co-doped with) Etc. method.Although using these methods doping Na element can improve the electric property of thin film solar cell, But finding by observing its absorbed layer crystal structure, absorbed layer thin film crystallite dimension compares the sample not mixing Na Having reduced, crystal boundary increases, and this most again can be to the performance band of CIGS thin-film solar cell Carry out negative impact.
Summary of the invention
It is an object of the invention to for above-mentioned existing problems, it is provided that a kind of based on compound substrate mix sodium copper and indium Gallium selenium thin film and preparation method thereof, this mixes sodium CIGS thin-film for being combined based on polyimide film-soda glass Substrate mix sodium CIGS thin-film, it prepares flexible battery with rigidity substrate, and the CIGS thin-film of preparation is attached The property is outstanding, crystalline quality good, crystal grain is big, defect is few；And after mixing sodium element, can be greatly Improve the electrology characteristic of CIGS thin-film, improve open-circuit voltage and the fill factor, curve factor of battery, and then promote assembly The performance of battery.
Technical scheme:
A kind of CIGS thin-film based on polyimide film-soda glass compound substrate, chemical molecular formula is Culn1-xGaxSe2, in formula, x is 0.25-0.35, and conduction type is p-type；This CIGS thin-film Culn1-xGaxSe2 Thin film deposition is 1.5-2 μm in polyimide film-soda glass compound substrate surface, thickness.
A kind of described preparation method mixing sodium CIGS thin-film based on compound substrate, first by polyimides Glue is coated on soda glass surface, is solidified into polyimide film-soda glass compound substrate, then on its surface Make one layer of very thin sodium fluoride initialization layer thin film, prepare CIGS thin-film the most thereon.
Described acid imide film-soda glass compound substrate, by soda glass and the polyimides that is grown on its surface Film is constituted, and wherein the thickness of soda glass is 1.5-2mm, and polyimides film thickness is 25-30 μm；Use even Prepared by glue, solidification preparation technology, step is as follows:
1) by clean for soda glass removing surface；
2) preparation of polyimides prefabricated membrane: polyimides glue is coated on soda glass surface, uses spin coating Technique carries out spin coating, and the technological parameter of spin processes is: rotating speed is 1300-1500r/min, and the time is 35-45s；
3) solidification of polyimides prefabricated membrane: the soda glass after spin coating is put into baking oven and controls ginseng by temperature Number solidifies, and i.e. can get polyimide film-soda glass compound substrate.
The cleaning method on described soda glass surface is: the soda glass of 10cm × 10cm 1) is put into weight chromium Acid potassium-concentrated sulfuric acid solution, it is by 300 grammes per square metre Neutral potassium chromates, 3 liters of concentrated sulphuric acids and the configuration of 300 ml deionized water Become, soak 2h；2) by soda glass taking-up deionized water rinsing 2-3 time；3) clean soda will be rinsed Glass is placed in the acetone soln that mass percent concentration is 99.5%, puts in ultrasonic washing unit and cleans, super Frequency of sound wave is 20-30kHz, and scavenging period is 20-25min；4) soda glass is taken out from acetone soln, With deionized water rinsing 2-3 time；5) then soda glass is placed in the second that mass percent concentration is 99.7% In alcohol, putting in ultrasonic washing unit and clean, ultrasonic frequency is 20-30kHz, and scavenging period is 20-25min； 6) finally soda glass is taken out from ethanol, put in the beaker filling deionized water, be placed in ultrasound wave clear Cleaning in washing machine, ultrasonic frequency is 20-30kHz, and scavenging period is 20-25min.
The temperature control parameter of described solidification is: 1) oven temperature is warming up to 125-135 DEG C in 25 DEG C, heats up Time is 10-15min；2) oven temperature maintains 25-30min in 125-135 DEG C, then heats to 150-160 DEG C, the heating-up time is 5-10min；3) oven temperature maintains 10-15min in 150-160 DEG C, so After be warming up to 200-210 DEG C, the heating-up time is 5-10min；4) oven temperature is in 200-210 DEG C of maintenance 15-20min, then heats to 250-260 DEG C, and the heating-up time is 5-10min；5) oven temperature is in 250-260 DEG C Maintaining 15-20min, then heat to 340-350 DEG C, the heating-up time is 5-10min；6) oven temperature in 340-350 DEG C maintains 10-15min, is finally naturally cooling to 25 DEG C.
The preparation method of described sodium fluoride initialization layer thin film, sodium fluoride initialization layer thin film deposition in polyimide film- Soda glass compound substrate surface, thickness is 20-30nm, uses selenizing stove film preparing system and coevaporation system Standby technique, preparation method is: base vacuum be 3.0 × 10-4Pa, at underlayer temperature is 200-300 DEG C, altogether Evaporation NaF initialization layer, wherein the temperature of NaF evaporation source is 770-820 DEG C, and evaporation time is 3-7min.
A kind of preparation method of described CIGS thin-film based on polyimide film-soda glass compound substrate, Using selenizing stove film preparing system, apply coevaporation three-step approach preparation technology, preparation process is as follows:
1) sample to be prepared is placed in coevaporation system, is 3.0 × 10 at base vacuum-4Pa, underlayer temperature are At 350-400 DEG C, coevaporation In, Ga, Se height Ga content initialization layer, wherein In source temperature is 820-850 DEG C, Ga source temperature is 920-950 DEG C, and Se source temperature is 240-280 DEG C, during evaporation Between be 2-3min, control In/Ga atomic ratio be 0.3: 0.7, the atomic ratio of (In+Ga)/Se is 2: 3；
2) at underlayer temperature is 350-400 DEG C, coevaporation In, Ga, Se initialization layer, wherein In evaporation source Temperature is 850-900 DEG C, and Ga source temperature is 880-920 DEG C, and Se source temperature is 240-280 DEG C, Evaporation time is 15-20min, controls atomic ratio In: Ga=0.7: 0.3, (In+Ga)/Se2: 3:
3) at underlayer temperature is 550-580 DEG C, coevaporation Cu, Se, wherein Cu source temperature is 1120-1160 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 15-20min；
4) underlayer temperature keep step 2) temperature-resistant under the conditions of, coevaporation In, Ga, Se, wherein In source temperature is 850-900 DEG C, and Ga source temperature is 880-920 DEG C, and Se source temperature is 240-280 DEG C, evaporation time is 2-4min, obtains the CIGS p-type yellow copper structure of the leanest Cu, The atomic ratio controlling Cu/ (In+Ga) is 0.88-0.92；
5) substrate is cooled down, when evaporating underlayer temperature when substrate is cooled to while Se the first step, close Close Se evaporation source, then substrate is cooled to 18-25 DEG C.
The principle analysis of the present invention:
Preparing crystalline quality preferably to meet, crystal grain is relatively big, the defect less CIGS fexible film sun The requirement of battery, it is necessary to selecting substrate soft, light, thermal coefficient of expansion more mates with CIGS thin-film Substrate.Polyimide film-soda glass compound substrate can rely on soda glass and CuInGaSe absorbed layer thin film The feature that thermal coefficient of expansion is closer to, prepares CIGS thin-film solar cell in compound substrate.The most again Thin film solar cell is separated from soda glass surface for substrate with polyimides, obtains flexible copper indium gallium selenide thin-film Solar cell, to realize preparing flexible solar cell with rigidity substrate.Wherein CIGS thin-film uses coevaporation Prepared by one-step technology, obtain crystalline quality preferable, and crystal grain is relatively big, the less CIGS thin-film of defect, this Preparation method is convenient, fast, energy-conservation, is suitable for large-scale industrialization and produces.
The benefit analysis of CIGS thin-film based on polyimide film-soda glass compound substrate:
1) polyimides glue is applied to glass surface, can preferably improve the roughness of substrate.
2) thermal coefficient of expansion of polyimides itself is bigger, it is impossible to well carry out with CIGS material itself Coupling.It is easily deformed at relatively high temperatures, causes thin film to loosen, easily come off.And it is grown on glass surface Polyimides, relies on the adhesive force between glass so that it is be not susceptible to relatively large deformation, with CIGS material More mate.
3) due to glass contact, be not susceptible to deformation, polyimides can be given and be closer in its heatproof The temperature of limit, contributes to CIGS thin-film and preferably grows.
4) its epontic CIGS thin-film crystalline quality is preferable, and crystal grain is relatively big, and defect is less, afterwards Again it is separated from glass, it is possible to prepare the flexible copper indium gallium selenide sun electricity with bigger columnar grain Pond, and convenient, fast, energy-conservation, it is suitable for large-scale industrialization and produces.
The invention have the advantage that this kind CIGS thin-film based on polyimide film-soda glass compound substrate Crystalline quality is good, crystal grain is big, defect is few, utilizes rigidity substrate to prepare flexible solar cell；Its preparation method letter Single, easy to implement, the most large-scale popularization and application, especially have the heaviest in space and special occasions The application prospect wanted.
Accompanying drawing explanation
Figure is polyimide film-soda glass composite substrate structure schematic diagram.
Detailed description of the invention
In order to make those skilled in the art be more fully understood that the present invention program, below in conjunction with the accompanying drawings and embodiment The present invention is described in further detail.
Embodiment 1:
A kind of CIGS thin-film based on polyimide film-soda glass compound substrate, as it is shown in figure 1, change Credit minor is Culn1-xGaxSe2, in formula, x is 0.25, and conduction type is p-type, this CIGS thin-film Culn1-xGaxSe2Thin film deposition is 1.5 μm in polyimide film-soda glass compound substrate surface, thickness；Its Preparation method, uses spin coating, curing process to prepare polyimide film-soda glass substrate, and use selenizing stove Film preparing system, application coevaporation one-step preparation process is prepared the CIGS thin-film in compound substrate, is made Standby step is as follows:
(1) cleaning of soda glass
1) soda glass of 10cm × 10cm being put into potassium dichromate-concentrated sulfuric acid solution, it is by 300 grams Potassium dichromate, 3 liters of concentrated sulphuric acids and the configuration of 300 ml deionized water form, and soak 2h；2) by soda glass Take out and use deionized water rinsing 2 times；3) soda glass rinsing cleaning being placed in mass percent concentration is In the acetone soln of 99.5%, putting in ultrasonic washing unit and clean, ultrasonic frequency is 20kHz, during cleaning Between be 25min；4) soda glass is taken out from acetone soln, with deionized water rinsing 2 times；5) then Soda glass is placed in the ethanol that mass percent concentration is 99.7%, puts in ultrasonic washing unit and clean, Ultrasonic frequency is 20kHz, and scavenging period is 25min；6) finally soda glass is taken out from ethanol, Putting in the beaker filling deionized water, be placed in ultrasonic washing unit cleaning, ultrasonic frequency is 20kHz, Scavenging period is 25min.
(2) preparation of polyimides prefabricated membrane
Soda glass nitrogen after cleaned is dried up, is placed on the rotating disk of sol evenning machine, polyimides glue is coated with It is overlying on soda glass surface, with the rotating speed at the uniform velocity spin coating 45s of 1300r/min, i.e. can get polyimides prefabricated Film.
(3) solidification of polyimides prefabricated membrane
Soda glass after spin coating being put into baking oven solidify, temperature control parameter is: 1) oven temperature Being warming up to 125 DEG C in 25 DEG C, the heating-up time is 15min；2) oven temperature maintains 30min in 125 DEG C, so After be warming up to 150 DEG C, the heating-up time is 5min；3) oven temperature maintains 15min in 150 DEG C, then heats up To 200 DEG C, the heating-up time is 5min；4) oven temperature maintains 20min in 200 DEG C, then heats to 250 DEG C, Heating-up time is 5min；5) oven temperature maintains 20min in 250 DEG C, then heats to 350 DEG C, during intensification Between be 10min；6) oven temperature maintains 10min in 350 DEG C, is finally naturally cooling to 25 DEG C, the most available Polyimide film-soda glass compound substrate.
(4) preparation method of described sodium fluoride initialization layer thin film, sodium fluoride initialization layer thin film deposition is sub-in polyamides Amine film-soda glass compound substrate surface, uses selenizing stove film preparing system and coevaporation preparation technology, system Preparation Method is: base vacuum be 3.0 × 10-4Pa, underlayer temperature be at 200 DEG C, coevaporation NaF is preset Layer, wherein the temperature of NaF evaporation source is 770 DEG C, and evaporation time is 7min.
(5) preparation of CIGS thin-film based on polyimide film-soda glass compound substrate
1) sample to be prepared is placed in coevaporation system, is 3.0 × 10 at base vacuum-4Pa, underlayer temperature are At 350 DEG C, coevaporation In, Ga, Se height Ga content initialization layer, wherein In source temperature is 820 DEG C, Ga source temperature is 920 DEG C, and Se source temperature is 240 DEG C, and evaporation time is 3min, controls In/Ga Atomic ratio be 0.3: 0.7, the atomic ratio of (In+Ga)/Se is 2: 3；
2) at underlayer temperature is 350 DEG C, coevaporation In, Ga, Se initialization layer, wherein In source temperature Being 850 DEG C, Ga source temperature is 880 DEG C, and Se source temperature is 240 DEG C, and evaporation time is 15min, Control atomic ratio In: Ga=0.7: 0.3, (In+Ga)/Se=2: 3；
3) at underlayer temperature is 550 DEG C, coevaporation Cu, Se, wherein Cu source temperature is 1160 DEG C, Se source temperature is 240 DEG C, and evaporation time is 15min；
4) underlayer temperature keep step 2) temperature-resistant under the conditions of, coevaporation In, Ga, Se, wherein In source temperature is 850 DEG C, and Ga source temperature is 880 DEG C, and Se source temperature is 240 DEG C, evaporation Time is 4min, obtains the CIGS p-type yellow copper structure of the leanest Cu, controls the former of Cu/ (In+Ga) Sub-ratio is 0.88-0.92；
5) substrate is cooled down, when evaporating underlayer temperature when substrate is cooled to while Se the first step, Close Se evaporation source, then substrate is cooled to 25 DEG C.
Embodiment 2:
A kind of CIGS thin-film based on polyimide film-soda glass compound substrate, as it is shown in figure 1, change Credit minor is Culn1-xGaxSe2, in formula, x is 0.35, and conduction type is p-type；This CIGS thin-film CuIn1-xGaxSe2Thin film deposition is 2 μm in polyimide film-soda glass compound substrate surface, thickness；Its Preparation method uses spin coating, curing process to prepare polyimide film-soda glass substrate, and use selenizing stove thin Film preparation system, application coevaporation one-step preparation process is prepared the CIGS thin-film in compound substrate, is prepared Step is as follows:
(1) cleaning of soda glass
1) soda glass of 10cm × 10cm being put into potassium dichromate-concentrated sulfuric acid solution, it is by 300 Grammes per square metre Neutral potassium chromate, 3 liters of concentrated sulphuric acids and the configuration of 300 ml deionized water form, and soak 2h；2) by soda glass Glass takes out uses deionized water rinsing 3 times；3) soda glass rinsing cleaning being placed in mass percent concentration is In the acetone soln of 99.5%, putting in ultrasonic washing unit and clean, ultrasonic frequency is 30kHz, during cleaning Between be 20min；4) soda glass is taken out from acetone soln, with deionized water rinsing 3 times；5) then Soda glass is placed in the ethanol that mass percent concentration is 99.7%, puts in ultrasonic washing unit and clean, Ultrasonic frequency is 30kHz, and scavenging period is 20min；6) finally soda glass is taken out from ethanol, Putting in the beaker filling deionized water, be placed in ultrasonic washing unit cleaning, ultrasonic frequency is 30kHz, Scavenging period is 20min.
(2) preparation of polyimides prefabricated membrane
Soda glass nitrogen after cleaned is dried up, is placed on the rotating disk of sol evenning machine, polyimides glue is coated with It is overlying on soda glass surface, with the rotating speed at the uniform velocity spin coating 40s of 1400r/min, i.e. can get polyimides prefabricated Film.
(3) solidification of polyimides prefabricated membrane
Soda glass after spin coating being put into baking oven solidify, temperature control parameter is: 1) oven temperature Being warming up to 130 DEG C in 25 DEG C, the heating-up time is 20min；2) oven temperature maintains 25min in 130 DEG C, so After be warming up to 160 DEG C, the heating-up time is 10min；3) oven temperature maintains 10min in 160 DEG C, then rises Temperature is to 210 DEG C, and the heating-up time is 10min；1) oven temperature maintains 20min in 210 DEG C, then heats to 260 DEG C, the heating-up time is 10min；5) oven temperature maintains 20min in 260 DEG C, then heats to 345 DEG C, Heating-up time is 10min；6) oven temperature maintains 15min in 345 DEG C, is finally naturally cooling to 25 DEG C, i.e. Available polyimide film-soda glass compound substrate.
(4) preparation method of described sodium fluoride initialization layer thin film, sodium fluoride initialization layer thin film deposition is sub-in polyamides Amine film-soda glass compound substrate surface, uses selenizing stove film preparing system and coevaporation preparation technology, system Preparation Method is: base vacuum be 3.0 × 10-4Pa, underlayer temperature be at 300 DEG C, coevaporation NaF is preset Layer, wherein the temperature of NaF evaporation source is 820 DEG C, and evaporation time is 3min.
(5) preparation of CIGS thin-film based on polyimide film-soda glass compound substrate
1) sample to be prepared is placed in coevaporation system, is 3.0 × 10 at base vacuum-4Pa, underlayer temperature are At 400 DEG C, coevaporation In, Ga, Se height Ga content initialization layer, wherein In source temperature is 850 DEG C, Ga source temperature is 950 DEG C, and Se source temperature is 280 DEG C, and evaporation time is 2min, controls In/Ga Atomic ratio be 0.3: 0.7, the atomic ratio of (In+Ga)/Se is 2: 3；
2) at underlayer temperature is 400 DEG C, coevaporation In, Ga, Se initialization layer, wherein In source temperature Being 900 DEG C, Ga source temperature is 920 DEG C, and Se source temperature is 280 DEG C, and evaporation time is 18min, Control atomic ratio In: Ga=0.7: 0.3, (In+Ga)/Se=2: 3；
3) at underlayer temperature is 580 DEG C, coevaporation Cu, Se, wherein Cu source temperature is 1160 DEG C, Se source temperature is 280 DEG C, and evaporation time is 18min；
4) underlayer temperature keep step 2) temperature-resistant under the conditions of, coevaporation In, Ga, Se, wherein In source temperature is 900 DEG C, and Ga source temperature is 920 DEG C, and Se source temperature is 280 DEG C, evaporation Time is 4min, obtains the CIGS p-type yellow copper structure of the leanest Cu, controls the former of Cu/ (In+Ga) Sub-ratio is 0.88-0.92；
5) substrate is cooled down, when evaporating underlayer temperature when substrate is cooled to while Se the first step, close Close Se evaporation source, then substrate is cooled to 25 DEG C.
In sum, for preparing the flexible copper indium gallium selenide battery of high conversion efficiency, the invention provides a kind of base In the preparation scheme of the CIGS thin-film of polyimide film-soda glass compound substrate, polyimides glue is coated with In soda glass surface, it is solidified into polyimide film-soda glass compound substrate, and steams altogether in its surface applications Send out three-steps process and prepare CIGS thin-film, prepare flexible battery with rigidity substrate.This kind is based on polyimides The CIGS thin-film crystalline quality of film-soda glass compound substrate is preferable, and crystal grain is relatively big, and defect is less.Should Preparation method process conditions are convenient and easy, the most large-scale popularization and application, especially at space and special occasions In there is extremely important application prospect.
The above is only the preferred embodiment of the present invention, it is noted that common for the art For technical staff, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, this A little improvements and modifications also should be regarded as protection scope of the present invention.

Claims (5)

1. a CIGS thin-film based on polyimide film-soda glass compound substrate, it is characterised in that: change Credit minor is CuIn1-xGaxSe2, in formula, x is 0.25-0.35, and conduction type is p-type；This CIGS is thin Film CuIn1-xGaxSe2Thin film deposition is in polyimide film-soda glass compound substrate surface, and thickness is 1.5-2μm。
2. the preparation method mixing sodium CIGS thin-film based on compound substrate as claimed in claim 1, its It is characterised by: first polyimides glue is coated on soda glass surface, is solidified into polyimide film-soda glass Glass compound substrate, then prepares one layer of very thin sodium fluoride initialization layer thin film, prepares the most thereon on its surface CIGS thin-film.
CIGS thin-film based on polyimide film-soda glass compound substrate the most according to claim 2, It is characterized in that: the cleaning method on described soda glass surface is: 1) by the soda glass of 10cm × 10cm Putting into potassium dichromate-concentrated sulfuric acid solution, it is gone by 300 grammes per square metre Neutral potassium chromates, 3 liters of concentrated sulphuric acids and 300 milliliters Ionized water configuration forms, and soaks 2h；2) by soda glass taking-up deionized water rinsing 2-3 time；3) will punching The soda glass of detergent is placed in the acetone soln that mass percent concentration is 99.5%, puts into ultrasonic waves for cleaning Cleaning in machine, ultrasonic frequency is 20-30kHz, and scavenging period is 20-25min；4) by soda glass from third Ketone solution takes out, with deionized water rinsing 2-3 time；5) then soda glass is placed in mass percent dense Degree is in the ethanol of 99.7%, puts in ultrasonic washing unit and cleans, and ultrasonic frequency is 20-30kHz, cleans Time is 20-25min；6) finally soda glass is taken out from ethanol, put into the beaker filling deionized water In, it being placed in ultrasonic washing unit cleaning, ultrasonic frequency is 20-30kHz, and scavenging period is 20-25min.
CIGS thin-film based on polyimide film-soda glass compound substrate the most according to claim 2, It is characterized in that: the temperature control parameter of described solidification is: 1) oven temperature is warming up to 125-135 DEG C in 25 DEG C, Heating-up time is 10-15min；2) oven temperature maintains 25-30min in 125-135 DEG C, then heats to 150-160 DEG C, the heating-up time is 5-10min；3) oven temperature maintains 10-15min in 150-160 DEG C, so After be warming up to 200-210 DEG C, the heating-up time is 5-10min；4) oven temperature is in 200-210 DEG C of maintenance 15-20min, then heats to 250-260 DEG C, and the heating-up time is 5-10min；5) oven temperature is in 250-260 DEG C Maintaining 15-20min, then heat to 340-350 DEG C, the heating-up time is 5-10min；6) oven temperature in 340-350 DEG C maintains 10-15min, is finally naturally cooling to 25 DEG C.
5. a CIGS based on polyimide film-soda glass compound substrate as claimed in claim 1 is thin The preparation method of film, it is characterised in that: use selenizing stove film preparing system, application coevaporation three-step approach to prepare Technique, preparation process is as follows:
1) sample to be prepared is placed in coevaporation system, is 3.0 × 10 at base vacuum-4Pa, underlayer temperature are At 350-400 DEG C, coevaporation In, Ga, Se height Ga content initialization layer, wherein In source temperature is 820-850 DEG C, Ga source temperature is 920-950 DEG C, and Se source temperature is 240-280 DEG C, during evaporation Between be 2-3min, control In/Ga atomic ratio be 0.3: 0.7, the atomic ratio of (In+Ga)/Se is 2: 3；
2) at underlayer temperature is 350-400 DEG C, coevaporation In, Ga, Se initialization layer, wherein In evaporation source Temperature is 850-900 DEG C, and Ga source temperature is 880-920 DEG C, and Se source temperature is 240-280 DEG C, Evaporation time is 15-20min, controls atomic ratio In: Ga=0.7: 0.3, (In+Ga)/Se=2: 3；
3) at underlayer temperature is 550-580 DEG C, coevaporation Cu, Se, wherein Cu source temperature is 1120-1160 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 15-20min；
4) underlayer temperature keep step 2) temperature-resistant under the conditions of, coevaporation In, Ga, Se, wherein In source temperature is 850-900 DEG C, and Ga source temperature is 880-920 DEG C, and Se source temperature is 240-280 DEG C, evaporation time is 2-4min, obtains the CIGS p-type yellow copper structure of the leanest Cu, The atomic ratio controlling Cu/ (In+Ga) is 0.88-0.92；
5) substrate is cooled down, when evaporating underlayer temperature when substrate is cooled to while Se the first step, Close Se evaporation source, then substrate is cooled to 18-25 DEG C.
CN201610333959.6A 2016-07-07 2016-07-07 Sodium-doped CIGS (copper indium gallium selenide) film based on composite substrate and preparation method thereof Pending CN105977318A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109841702A (en) * 2017-11-27 2019-06-04 中国电子科技集团公司第十八研究所 Preparation method of alkali metal doped copper indium gallium selenide thin film solar cell absorption layer
CN110061075A (en) * 2019-04-26 2019-07-26 圣晖莱南京能源科技有限公司 A kind of CIGS solar battery and preparation method thereof of metal Na doping
CN113314629A (en) * 2021-05-26 2021-08-27 深圳市泰晶太阳能科技有限公司 CIGS flexible amorphous silicon solar module

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109841702A (en) * 2017-11-27 2019-06-04 中国电子科技集团公司第十八研究所 Preparation method of alkali metal doped copper indium gallium selenide thin film solar cell absorption layer
CN110061075A (en) * 2019-04-26 2019-07-26 圣晖莱南京能源科技有限公司 A kind of CIGS solar battery and preparation method thereof of metal Na doping
CN110061075B (en) * 2019-04-26 2020-06-26 圣晖莱南京能源科技有限公司 CIGS solar cell doped with metal Na and preparation method thereof
CN113314629A (en) * 2021-05-26 2021-08-27 深圳市泰晶太阳能科技有限公司 CIGS flexible amorphous silicon solar module

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