CN105097965A - Preparation method of copper-indium-gallium-selenium light absorption layer of thin-film solar cell - Google Patents
Preparation method of copper-indium-gallium-selenium light absorption layer of thin-film solar cell Download PDFInfo
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- CN105097965A CN105097965A CN201510446282.2A CN201510446282A CN105097965A CN 105097965 A CN105097965 A CN 105097965A CN 201510446282 A CN201510446282 A CN 201510446282A CN 105097965 A CN105097965 A CN 105097965A
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- indium gallium
- copper indium
- absorption layer
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- gallium selenide
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- 239000010409 thin film Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000031700 light absorption Effects 0.000 title abstract description 4
- 239000011669 selenium Substances 0.000 claims abstract description 40
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 230000004913 activation Effects 0.000 claims abstract description 17
- 239000012159 carrier gas Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims description 46
- 239000010949 copper Substances 0.000 claims description 21
- 238000010521 absorption reaction Methods 0.000 claims description 19
- 230000003287 optical effect Effects 0.000 claims description 19
- ALCDAWARCQFJBA-UHFFFAOYSA-N ethylselanylethane Chemical compound CC[Se]CC ALCDAWARCQFJBA-UHFFFAOYSA-N 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 11
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- RVIXKDRPFPUUOO-UHFFFAOYSA-N dimethylselenide Chemical compound C[Se]C RVIXKDRPFPUUOO-UHFFFAOYSA-N 0.000 claims description 8
- 238000009834 vaporization Methods 0.000 claims description 6
- 230000008016 vaporization Effects 0.000 claims description 6
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 3
- 238000007086 side reaction Methods 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 8
- 239000003595 mist Substances 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000011430 maximum method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01L31/0248—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
- H01L31/0256—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 the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a preparation method of a copper-indium-gallium-selenium light absorption layer of a thin-film solar cell. The method comprises the following selenylation processes: (1) heating an organic selenium source, evaporating the organic selenium source into steam and volatilizing the steam; (2) introducing the organic selenium source steam into a reaction chamber with a carrier gas through a high-temperature activation pipeline; and (3) by a metal preformed layer, finishing a selenylation process according to the predetermined heating procedure, so as to form the copper-indium-gallium-selenium light absorption layer with good crystal. With the low-toxic and cheap organic selenium source as a selenylation material, the operation is relatively safe; the production cost can be effectively reduced; and formation of good copper-indium-gallium-selenium crystal can be prompted by the organic selenium source activated at high temperature. The preparation method is simple in process, high in repeatability and suitable for large-scale industrial production.
Description
Technical field
The present invention relates to thin film solar cell technologies, specifically the preparation method of thin-film solar cells copper indium gallium selenide optical absorption layer.
Background technology
Due to the development of society, the fossil energy such as coal, oil is close to exhausted, and the exploitation of following clean energy resource is imperative.Solar cell, owing to directly solar energy can be converted into electric energy, is one of first-selection of following clean energy resource.0003 Copper Indium Gallium Selenide (CIGS) solar cell is considered to the second generation solar cell that can replace crystal silicon solar batteries, is one of thin-film solar cells that photoelectric conversion efficiency is the highest.Copper Indium Gallium Selenide (CIGS) thin-film solar cells has that low light level effect is good, cost is low, without light-induced degradation, stability is good, capability of resistance to radiation is strong, be applicable to the advantages such as volume to volume technique large-scale production.This battery typical structure is from top to bottom: gate electrode/antireflective coating/transparency conducting layer/high resistant intrinsic zno layer/CdS resilient coating/CIGS light absorbing zone/Mo layer back electrode/substrate is formed.Wherein the preparation of CIGS light absorbing zone is the most crucial technology of CIGS solar cell.
Current CIGS thin film solar cell light absorption layer preparation method mainly contains the method such as selenizing method, antivacuum coating process, electroplating process after coevaporation method, metal preformed layer.The most high conversion efficiency in the current world is obtained by coevaporation method, but its apparatus expensive, complicated operation, the shortcomings such as large area production uniformity is not good, and raw material utilization ratio is not high, and repeatability is bad.
Selenizing method after metal preformed layer produces the maximum method of upper use at present.Main employing H
2se gas and the selenizing of solid-state Se steam.H
2se belongs to hypertoxicity gas, and operational hazards is current domestic without manufacturer, and the prices of raw and semifnished materials are expensive.The method of solid-state selenium steam selenizing, there is selenium not active, the selenium atmosphere maintaining higher concentration is needed in course of reaction, therefore need to pass into a large amount of selenium steams or put into a large amount of solid-state selenium, but the selenium of the overwhelming majority has neither part nor lot in reaction, final cooling is condensed in cavity cold junction, pipe interior, even can discharges with gas and be deposited on vacuum pump inside and cannot clear up, and exists and reclaims difficulty, waste raw material selenium, permanent accumulation can damage the problems such as equipment.The selenizing method of the open thin film solar cell cigs layer of China Patent No. CN102965641A, it adopts the solid-state selenium steam of radio frequency ionization, improve the method for selenium steam activity, but this method increase equipment cost, charged ion may produce injury to face, and cannot solve the problem of solid-state selenium steam-condensation.
The method of antivacuum coating process and electroplating process, existing defects is more, the not high drawback of product yield.China Patent No. CN103334081A discloses a kind of method that CIGS thin film is prepared in low temperature selenizing, what it adopted is that CIGS is nanocrystalline coats on substrate, and then induce selenizing with the alcoholic solution of Organic Selenium, the method is owing to adopting antivacuum coating CIGS, easy introducing impurities left, follow-up selenization process is caused to occur defect, the Organic Selenium induction selenizing adopted in addition, Organic Selenium is dissolved in alcoholic solution, introduce other nonreactive gas, although the alcoholic solution introduced can help to dissolve the alkylamine in CIGS precursor film, but the whether thoroughly invalidated of dissolving, the alcoholic solution introduced, CIGS may be made at high-temperature oxydation, be unfavorable for crystallization.
Summary of the invention
The present invention aims to provide the preparation method of thin-film solar cells copper indium gallium selenide optical absorption layer, replaces traditional H by adopting organic selenium source of high-temperature activation
2se or solid-state selenium, complete selenizing, not only economic security but also can realize good CIGS crystallization, is applicable to large-scale industrial production.
The present invention is achieved through the following technical solutions:
The preparation method of thin-film solar cells copper indium gallium selenide optical absorption layer, is characterized in that: comprise following selenidation process:
(1) by having deposited in metal back electrode and forerunner's metal alloy layer copper ingaas substrate loading selenizing stove reaction chamber, being evacuated to certain vacuum degree, carrying out several with high-purity N 2 pairs of reaction chambers and purge, discharge air, be then evacuated to 10
-2pa;
(2) heat organic selenium source, make it vaporize, with carrier gas, organic selenium source is sent into high-temperature activation pipeline and carry out high-temperature activation, described high-temperature activation heating-up temperature is 250 DEG C ~ 550 DEG C;
(3) the organic selenium source after high-temperature activation is passed in reaction chamber, carry out selenizing heat treatment and obtain Copper Indium Gallium Selenide CuIn
(1 -x)ga
xse
2crystallization
(4) cooling discharge side reaction gases, terminates selenizing;
Described organic selenium source is diethyl selenide (C
4h
10se), dimethyl-selenide (C
2h
6se), dimethyl selenide (C
2h
6se) one or several in.
The heating-up temperature of described organic selenium source is 40 DEG C ~ 200 DEG C;
Described carrier gas is inert gas, is preferably argon gas.
Described selenizing heat treatment comprises intensification, pyroreaction, cooling step formation Copper Indium Gallium Selenide CuIn
(1-x)ga
xse
2light absorbing zone;
Described Copper Indium Gallium Selenide CuIn
(1-x)ga
xse
2, the scope of X is 0<X<1; The atomic ratio of component meets: 0.8≤Cu/ (In+Ga)≤1.1,0.25≤Ga/ (In+Ga)≤0.45, thicknesses of layers 1.0um ~ 3.0um.
Described intensification, heating rate is 30 DEG C/min ~ 200 DEG C/min, the mode of heating that can adopt is that Halogen lamp LED is according to the one in heating, infrared heating, Resistant heating;
Described pyroreaction, reaction temperature is 450 DEG C ~ 650 DEG C, continues to pass into organic selenium source in reaction, and keep constant pressure, pressure limit 10kPa ~ 101kPa, the reaction time is 1min ~ 60min;
Described discharge side reaction gases need be carried out more than 200 DEG C;
The preparation method of described thin-film solar cells copper indium gallium selenide optical absorption layer, does high temperature vulcanized process after also comprising selenizing, forms Cu-In-Ga-Se-S CuIn
(1-x)ga
x(Se
(1-y)s
y)
2light absorbing zone;
Part selenium atom in described high temperature vulcanized process in Copper Indium Gallium Selenide is substituted by sulphur atom, and the atomic ratio in constituent shared by element sulphur meets 0.05≤S/ (S+Se)≤0.2;
The present invention compared with prior art, by controlling the flow of organic selenium source heating-up temperature and carrier gas, can control reacting gas concentration in real time; Participate in selenylation reaction by organic selenium source of high-temperature activation, contribute to forming good CIGS crystallization; Simultaneously the present invention uses the highly active organic selenium source of low toxicity to participate in selenizing, greatly reduces production cost and technique is simple, and manufacturing process repeatability is high, is applicable to following large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the structural representation of copper-indium-galliun-selenium film solar cell of the present invention, wherein 110-substrate, 120-back electrode, 130-Copper Indium Gallium Selenide, 140-resilient coating, 150-native oxide zinc, 160-transparency conducting layer, 170-anti-reflection rete, 180-gate-shaped electrode;
Fig. 2 is the Copper Indium Gallium Selenide scanning electron microscopy sectional view after the embodiment of the present invention 1 selenizing;
Embodiment
Below in conjunction with Fig. 1, the present invention will be further described, but institute of the present invention protection range is not limited thereto.
Embodiment 1
Sputter Mo layer back electrode 120 on cleaned soda-lime glass substrate 110;
On back electrode, magnetron sputtering copper indium gallium alloy target list target is adopted to prepare precursor layer, make made forerunner's copper indium gallium preformed layer constituent atoms than meeting: 0.8≤Cu/ (In+Ga)≤1.1,0.25≤Ga/ (In+Ga)≤0.45, the present embodiment adopts Cu/ (In+Ga)=0.9, Ga/ (In+Ga)=0.35;
The substrate having plated Mo back electrode and CIG precursor layer is put in selenizing stove, is loaded into reaction chamber, close chamber door;
Be evacuated to 10
-1pa, purges cavity with high pure nitrogen, discharges chamber air, then is evacuated to 10
-2below Pa;
Heating diethyl selenide (C
4h
10se) to 110 DEG C, make it seethe with excitement and vaporize, by high-purity Ar the diethyl selenide (C after vaporization
4h
10se) Steam dilution be loaded into the high-temperature activation pipeline of 450 DEG C, by regulating the heating-up temperature of high-purity Ar flow and diethyl selenide, can control the concentration of diethyl selenide steam, but preferred mode is the flow regulating high temperature Ar;
Adopt Fast Heating reaction cavity, heating rate is about 100 DEG C/min, the diethyl selenide (C pass into activation below 100 DEG C after
4h
10se) mist of steam and high-purity Ar, to pressure 66kPa, regulates flow and the speed of exhaust of mist, makes pressure maintain 66kPa;
Reaction chamber is warming up to 540 DEG C, regulates heater power to export, makes reaction temperature maintain 540 DEG C, constant temperature and pressure reaction 30min;
Close heater, take reacting gas away, cooling down forms copper indium gallium selenide optical absorption layer 130;
Fig. 2 is the Copper Indium Gallium Selenide scanning electron microscopy sectional view after selenizing, and can know and see Copper Indium Gallium Selenide well-crystallized, crystallite dimension is about about 1um, and Copper Indium Gallium Selenide is combined well with selenizing molybdenum cross section.
Its photoelectric conversion efficiency 10.39% of solar cell test is made, battery open circuit voltage 580mV, current density 31.83mA/cm by this light absorbing zone
2
Embodiment 2
Sputter Mo layer back electrode 120 on cleaned soda-lime glass substrate 110;
On back electrode, adopt the copper indium gallium alloy target combination preparation precursor layer of magnetron sputtering different component, after high temperature selenizing Elements Diffusion, in copper indium gallium selenide optical absorption layer, the component distribution of gallium forms the high gallium in bottom, middle low gallium, top height gallium, contributes to the open circuit voltage improving battery like this.
Preferred combination execution mode is 0.9≤Cu/ (In+Ga)≤1.1 for first sputtering its elemental constituent atomic ratio of the low gallium alloy layer of the rich copper of one deck, 0.1≤Ga/ (In+Ga)≤0.3, Cu/ (In+Ga)=0.95, Ga/ (In+Ga)=0.2 that the present embodiment adopts; Then the low gallium alloy layer of one deck is sputtered, its elemental constituent atomic ratio is 0.8≤Cu/ (In+Ga)≤1.1,0.1≤Ga/ (In+Ga)≤0.3, the present embodiment adopts Cu/ (In+Ga)=0.9, Ga/ (In+Ga)=0.2, finally sputtering its elemental constituent atomic ratio of one deck poor copper height gallium alloy layer is 0.8≤Cu/ (In+Ga)≤0.9,0.4≤Ga/ (In+Ga)≤0.5, the Cu/ (In+Ga)=0.85 that the present embodiment adopts, Ga/ (In+Ga)=0.45, forms forerunner's alloy-layer of the poor copper of the rich gallium in top layer thus.
The substrate having plated Mo back electrode and CIG precursor layer is put in selenizing stove, is loaded into reaction chamber, close chamber door;
Be evacuated to 10
-1pa, purges cavity with high pure nitrogen, discharges chamber air, then is evacuated to 10
-2below Pa;
Heating diethyl selenide (C
4h
10se) to 110 DEG C, its vaporization of seething with excitement is made, by high-purity Ar the diethyl selenide (C after vaporization
4h
10se) Steam dilution be loaded into the high-temperature activation pipeline of 500 DEG C, by regulating the heating-up temperature of high-purity Ar flow and diethyl selenide, can control the concentration of diethyl selenide steam, but preferred mode is the flow regulating high temperature Ar;
Adopt Fast Heating reaction cavity, heating rate is about 100 DEG C/min, the diethyl selenide (C pass into activation below 100 DEG C after
4h
10se) mist of steam and high-purity Ar, to pressure 66kPa, regulates flow and the speed of exhaust of mist, makes pressure maintain 66kPa;
Reaction chamber is warming up to 550 DEG C, regulates heater power to export, makes reaction temperature maintain 540 DEG C, constant temperature and pressure reaction 15min;
Close heater, take reacting gas away, cooling down forms copper indium gallium selenide optical absorption layer 130;
Because the method for selenizing after the present embodiment employing combination sputtering preformed layer prepares copper indium gallium selenide optical absorption layer, optimize the distribution of each element in copper indium gallium selenide optical absorption layer compared with single target, particularly contribute to forming gallium element component in copper indium gallium selenide optical absorption layer and form middle low V-shaped higher bottom face and rete distribution.Make its photoelectric conversion efficiency 11.4% of solar cell test, battery open circuit voltage 660mV has obvious lifting, current density 30.5mA/cm
2
Embodiment 3
Sputter Mo layer back electrode 120 on cleaned soda-lime glass substrate 110;
Preferred combination execution mode is first sputter the rich copper low gallium alloy layer Cu/ (In+Ga)=0.95, Ga/ (In+Ga)=0.2 of one deck; Then one deck low gallium alloy layer its elemental constituent atomic ratio Cu/ (In+Ga)=0.9 is sputtered, Ga/ (In+Ga)=0.2, finally sputtering its elemental constituent atomic ratio of one deck poor copper height gallium alloy layer is Cu/ (In+Ga)=0.85, Ga/ (In+Ga)=0.45, forms forerunner's alloy-layer of the poor copper of the rich gallium in top layer thus.
The substrate having plated Mo back electrode and CIG precursor layer is put in selenizing stove, is loaded into reaction chamber, close chamber door;
Be evacuated to 10
-1pa, purges cavity with high pure nitrogen, discharges chamber air, then is evacuated to 10
-2below Pa;
Heating diethyl selenide (C
4h
10se) to 110 DEG C, its vaporization of seething with excitement is made, by high-purity Ar the diethyl selenide (C after vaporization
4h
10se) Steam dilution be loaded into the high-temperature activation pipeline of 500 DEG C, by regulating the heating-up temperature of high-purity Ar flow and diethyl selenide, can control the concentration of diethyl selenide steam, but preferred mode is the flow regulating high temperature Ar;
Adopt Fast Heating reaction cavity, heating rate is about 100 DEG C/min, the diethyl selenide (C pass into activation below 100 DEG C after
4h
10se) mist of steam and high-purity Ar, to pressure 66kPa, regulates flow and the speed of exhaust of mist, makes pressure maintain 66kPa;
Reaction chamber is warming up to 550 DEG C, regulates heater power to export, makes reaction temperature maintain 540 DEG C, constant temperature and pressure reaction 15min;
Close heater, take reacting gas away, cooling down forms copper indium gallium selenide optical absorption layer 130;
The Copper Indium Gallium Selenide after selenizing, be again loaded into high temperature furnace, pass into Ar and H2S mist (wherein volume ratio shared by H2S is 5%), be rapidly heated, to 550 DEG C of vulcanization reaction 5min, vacuumize cooling and form Cu-In-Ga-Se-S light absorbing zone..
The present embodiment 3 is on embodiment 2 basis, increase sulfuration link, contribute to regulating copper indium gallium to wash light absorbing zone and can be with distribution, improve solar cell open circuit voltage, its photoelectric conversion efficiency 12% of solar cell test is made by this light absorbing zone, battery open circuit voltage 680mV, current density 30.1mA/cm
2.
Claims (10)
1. the preparation method of thin-film solar cells copper indium gallium selenide optical absorption layer, is characterized in that: comprise following selenidation process:
(1) by having deposited in metal back electrode and forerunner's metal alloy layer copper ingaas substrate loading selenizing stove reaction chamber, being evacuated to certain vacuum degree, carrying out several with high-purity N 2 pairs of reaction chambers and purge, discharge air, be then evacuated to 10
-2below Pa;
(2) heat organic selenium source, make it vaporize, with carrier gas, the organic selenium source after vaporization is sent into high-temperature activation pipeline and carry out high-temperature activation; Described high-temperature activation heating-up temperature is 250 DEG C ~ 550 DEG C;
(3) the organic selenium source after high-temperature activation is passed in reaction chamber, selenizing heat treatment is carried out to forerunner's metal alloy layer copper indium gallium and obtains Copper Indium Gallium Selenide CuIn
(1-x)ga
xse
2crystallization;
(4) reaction chamber reaction gases is discharged in cooling, terminates selenizing.
2. the preparation method of thin-film solar cells copper indium gallium selenide optical absorption layer as claimed in claim 1, is characterized in that, described organic selenium source is one or several in diethyl selenide, dimethyl-selenide, dimethyl selenide.
3. the preparation method of thin-film solar cells copper indium gallium selenide optical absorption layer as claimed in claim 1, is characterized in that, step 2) the heat vaporized temperature of organic selenium source is 40 DEG C ~ 200 DEG C.
4. the preparation method of thin-film solar cells copper indium gallium selenide optical absorption layer as claimed in claim 1, is characterized in that, step 3) described in selenizing heat treatment comprise intensifications, pyroreaction, cooling step formation Copper Indium Gallium Selenide CuIn
(1-x)ga
xse
2light absorbing zone.
5. copper indium gallium selenide optical absorption layer as claimed in claim 4, is characterized in that, described Copper Indium Gallium Selenide CuIn
(1-x)ga
xse
2the atomic ratio of component meets: 0.8≤Cu/ (In+Ga)≤1.1,0.25≤Ga/ (In+Ga)≤0.45, thicknesses of layers 1.0um ~ 3.0um.
6. selenizing heat treatment as claimed in claim 4, is characterized in that, described intensification, heating rate is 30 DEG C/and min ~ 200 DEG C/min, the mode of heating of employing is that Halogen lamp LED is according to the one in heating, infrared heating, Resistant heating.
7. selenizing heat treatment as claimed in claim 4, is characterized in that, described pyroreaction, reaction temperature is 450 DEG C ~ 650 DEG C, continues to pass into organic selenium source in reaction, keeps constant pressure, pressure limit 10kPa ~ 101kPa, the reaction time is 1min ~ 60min.
8. the preparation method of thin-film solar cells copper indium gallium selenide optical absorption layer as claimed in claim 1, it is characterized in that, the discharge side reaction gases described in step (4) is carried out more than 200 DEG C.
9. the preparation method of thin-film solar cells copper indium gallium selenide optical absorption layer as claimed in claim 1, its feature does the process of sulfuration after also comprising selenizing, form Cu-In-Ga-Se-S CuIn
(1-x)ga
x(Se
(1-y)s
y)
2light absorbing zone.
10. high temperature vulcanized process as claimed in claim 9, is characterized in that, described Copper Indium Gallium Selenide part selenium atom is substituted by sulphur atom, and the atomic ratio wherein in constituent shared by element sulphur meets 0.05≤y≤0.2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109817734A (en) * | 2018-12-26 | 2019-05-28 | 北京铂阳顶荣光伏科技有限公司 | A kind of preparation method of copper-indium-galliun-selenium film solar cell absorbed layer |
| CN110565060A (en) * | 2019-09-12 | 2019-12-13 | 深圳先进技术研究院 | Preparation method of light absorption layer of thin-film solar cell |
-
2015
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109817734A (en) * | 2018-12-26 | 2019-05-28 | 北京铂阳顶荣光伏科技有限公司 | A kind of preparation method of copper-indium-galliun-selenium film solar cell absorbed layer |
| CN110565060A (en) * | 2019-09-12 | 2019-12-13 | 深圳先进技术研究院 | Preparation method of light absorption layer of thin-film solar cell |
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