CN106098814A - A kind of oxide nano particles prepares the method for solar battery obsorbing layer CTSSe thin film - Google Patents
A kind of oxide nano particles prepares the method for solar battery obsorbing layer CTSSe thin film Download PDFInfo
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- CN106098814A CN106098814A CN201610516240.6A CN201610516240A CN106098814A CN 106098814 A CN106098814 A CN 106098814A CN 201610516240 A CN201610516240 A CN 201610516240A CN 106098814 A CN106098814 A CN 106098814A
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- thin film
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- 239000010409 thin film Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 42
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000010408 film Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000005987 sulfurization reaction Methods 0.000 claims abstract description 9
- 238000001238 wet grinding Methods 0.000 claims abstract description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 36
- 239000011669 selenium Substances 0.000 claims description 25
- 229910052711 selenium Inorganic materials 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 9
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000005361 soda-lime glass Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008267 milk Substances 0.000 claims description 4
- 210000004080 milk Anatomy 0.000 claims description 4
- 235000013336 milk Nutrition 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229910000058 selane Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 14
- 230000008021 deposition Effects 0.000 abstract description 4
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 229910020923 Sn-O Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229960004756 ethanol Drugs 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 150000003346 selenoethers Chemical class 0.000 description 4
- -1 tin sulphur compound Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 241000282693 Cercopithecidae Species 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229940126680 traditional chinese medicines Drugs 0.000 description 2
- 239000008946 yang xin Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101150023635 Ctse gene Proteins 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a kind of method that oxide nano particles prepares solar battery obsorbing layer CTSSe thin film.Its scheme is: by a step low-temperature solid phase reaction synthesis containing copper and the oxide nano particles powder body of stannum, and being scattered in organic solvent by granule, wet grinding forms precursor pulp；Substrate surface is carried out, precursor pulp is carried out on substrate formation of deposits precursor thin-film；By the precursor thin-film containing copper and tin-oxide, carrying out sulfuration annealing in being placed in tube furnace that is airtight or that circulate under sulfur atmosphere, be absorbed a layer CTS thin film；Selecting airtight intensification tube furnace to carry out selenizing heat treatment, be absorbed a layer CTSSe thin film.The present invention uses low-temperature solid phase reaction process, can complete in atmospheric environment, and process is simple, and the cycle is short；Thin film composition is realized by the ratio controlling reacting metal salt, accomplishes large-area deposition；It is absorbed layer film by sulfuration and selenizing, low cost, can large area preparation deposition.
Description
Technical field
The present invention relates to solar cell material and device arts, be specifically related to a kind of oxide nano particles and prepare
The method of solar battery obsorbing layer CTSSe thin film.
Background technology
Along with socioeconomic fast development, conventional fossil energy resource consumption is growing, the conventional fossil energy thus caused
Source crisis is increasingly serious.Meanwhile, a large amount of use of conventional fossil energy can welding.Therefore, ask to solve energy shortage
Topic and the relation of environmental harmony, searching one cleaning, the reproducible energy are extremely urgent.Solar energy is the height of a kind of rich reserves
Usefulness source.And utilizing solar energy can the most direct effective manner be photovoltaic generation, i.e. solaode.
In numerous solaodes, copper-zinc-tin-sulfur (CZTS) thin film solar has abundant raw materials, cheap etc.
Feature and advantage, so being counted as a class to be expected to replace the novel thin film of CIGS (CIGS), having and growing a lot most
Potentiality.But constituent element is too much in CZTS, easily generate ZnS dephasign.And Cu2SnS3(CTS) it is simple ternary compound, component
The single generation that can avoid other dephasigns is a kind of direct band-gap semicondictor and has the band gap more mated with solar spectrum
Width (1.0eV), absorptance (104cm-1) relatively big, therefore thin as a kind of novel solar battery substituting CZTS or CIGS
Membrane material has begun to cause the attention of researcher.Be currently based on magnetron sputtering preparing CTS thin film is absorbed layer, achieves
The solaode of 4.63% efficiency；Further by using the stannum in germanium part replacement CTS to have been achieved for the solar-electricity of 6%
Pond conversion efficiency；But similar with CZTS and CIGS system, bright sulfur CTS thin film also exists following problem, such as crystalline property
Differ from, crystal grain is little, defect is many, carrier collection efficiency is low.This kind of material character inherently will limit CTS solar-electricity
The raising of pond efficiency.And the Cu containing Se2Sn(S,Se)3(CTSSe) there is the Cu-Se chemical combination of low melting point in absorbed layer growth course
Thing cosolvent, this is conducive to thin film grain growth.Therefore, usual CTSSe thin film has that crystal grain is big, degree of crystallinity is high, defect state is few
Etc. advantage, cause the attention of numerous research work.So, this new CT SSe compound film solaode has
Huge application prospect and business opportunity.
The current method preparing CTSSe absorbed layer has a lot, can be divided into vacuum method and antivacuum method.Wherein vacuum method is main
Including the method such as evaporation, magnetron sputtering method, costly, production cost is higher for this kind of method equipment needed thereby；Rather than vacuum method
Electro-deposition can be divided into, based on solution and nano-particle method etc., this kind of method has that preparation process is simple, preparation cost cheap,
It is prone to the multiple advantages such as large-scale production, obtains more concern and research.Nano-particle is wherein used to prepare CTSSe thin film tool
There are the features such as stock utilization is high, easily operated.Through finding prior art literature patent retrieval, preparing, absorbed layer CTS is thin
In the method for film and absorbed layer CTSSe thin film, utilize metal sulfide, selenides and copper and tin sulphur compound nano-particle
The patent (application number CN201080052113.6) of absorbed layer CTS thin film or absorbed layer CTSSe thin film is prepared for presoma.But
It is that the synthesis of metal sulfide, selenides and copper and tin sulphur compound nano-particle typically requires and synthesizes under an inert atmosphere, preparation
Condition is the harshest.Therefore this patent is absorbed in this problem, uses good stability, to synthesize simple oxide nano particles be front
Driving, prepare oxide precursor thin film by simple film forming, in sulfur atmosphere, annealing forms CTS thin film subsequently, then passes through
Heat treatment in selenium atmosphere, it is thus achieved that uniform large-area, high-quality absorbed layer CTSSe thin film.
Summary of the invention
The purpose of the present invention is to propose to a kind of low cost oxide nano particles method and prepare solar battery obsorbing layer CTSSe
The method of thin film.Used in the present invention is that in air, synthesis oxide nano-particle is presoma, through over cure (S) and selenium (Se)
Heat-treating methods in atmosphere, have that synthesis technique is simple, Preparation equipment is uncomplicated, low raw-material cost, stock utilization are high,
Can large area uniformly prepare, thin film composition and the advantage such as thickness is easily-controllable, it is adaptable to large-scale commercial production.
Be the technical scheme is that by realizing the purpose of the present invention
Step one: by a step low-temperature solid phase reaction synthesis containing copper and the oxide nano particles powder body of stannum, and by oxide
Nano-particle is scattered in organic solvent, and wet grinding forms stable precursor pulp；
Step 2: be carried out substrate surface, carries out formation of deposits oxidation on substrate by precursor pulp described in step one
Thing precursor thin-film, preserves after drying；
Step 3: by obtain in step 2 containing copper and the precursor thin-film of tin-oxide, be placed in airtight under sulfur (S) atmosphere
Or carrying out sulfuration annealing in the tube furnace of circulation, be absorbed a layer CTS thin film.
Step 4: utilize step 3) the absorbed layer CTS thin film that obtains, select airtight intensification tube furnace, enter in selenium atmosphere
Row selenizing heat treatment, be absorbed a layer CTSSe thin film.
Low-temperature solid phase reaction synthesis oxide nano-particle method described in step one of the present invention refers to: inorganic by copper and stannum
After salt, with reactant ammonium hydrogen carbonate mixed grinding, sinter under middle low temperature, it is thus achieved that oxide nano particles.
The inorganic salt of copper of the present invention and the inorganic salt of stannum, copper and stannum mol ratio between the two are 1.6～2.4:
1。
Ammonium hydrogen carbonate of the present invention, its usage amount is 1.1～2.0 times of copper and Xi Moer total amount.
Grinding of the present invention, uses general milling machine, super ball mill, wet milk or mortar, milling time be 6～
15 min。
Wet grinding of the present invention, uses general milling machine, super ball mill, wet milk or mortar, and the wet grinding time is 36
～48 h, in wet grinding disposed slurry, solid content controls at 200～400 mg/ml.
In slurry, solid content controls at 200～400 mg/ml.
Under described middle low temperature sinter, its temperature range between 300～400 DEG C, sintering time 10min～180min.
Substrate described in step 2 of the present invention is in plating molybdenum film, soda-lime glass, quartz glass and metal forming
Kind.
The inorganic salt of copper of the present invention refers to the mixture of one or both arbitrary proportions in copper nitrate, copper acetate；
The inorganic salt of stannum of the present invention refers to the mixture of one or both arbitrary proportions in tin acetate, stannous oxalate；
Organic solvent of the present invention refers to one or several the mixing in ethanol, ethylene glycol or terpineol；
Deposition of the present invention, refer to cutter scrape, spin coating, one in silk screen printing；
Oxide precursor body thin film of the present invention, its THICKNESS CONTROL is between 1～3 μm.
Carry out sulfuration annealing under the atmosphere of sulfur (S) described in step 3 of the present invention, refer to precursor thin-film and solid-state sulfur source
Or hydrogen sulfide gas is placed in confined space annealing, or precursor thin-film is in sulfur steam or the hydrogen sulfide of flowing
Gas is annealed；
When the sulfuration in above-mentioned steps is annealed and is used solid-state sulfur source, holding solid-state sulfur source temperature 450～600 DEG C, cure time
20～60 min.
Selenizing heat treatment described in step 4 of the present invention, refers to absorbed layer CTS thin film and solid selenium source or selenizing hydrogen
Body is placed in confined space and carries out selenizing heat treatment, or precursor thin-film is in selenium steam or the hydrogen selenide gas of flowing
In carry out selenizing heat treatment.
When selenizing heat treatment in above-mentioned steps uses solid selenium source, selenium powder and absorbed layer CTS thin film are placed in airtight tube type
In stove, it is added on one end of tube furnace, takes out background vacuum to 10-2Pa, makes selenium powder with absorbed layer CTS thin film simultaneously from the beginning of room temperature
Heat up, heating rate 40oC/min, holding solid selenium source temperature 450～600 DEG C, selenizing time 20～60 min, the most slowly
It is cooled to room temperature
The chemical reagent such as copper involved in technique scheme and the inorganic salt of stannum, ammonium hydrogen carbonate, organic solvent are all purchased
All purchase in Aladdin Chemistry co.ltd, substrate in chemical reagents corporation of traditional Chinese medicines group, selenium powder and stannous oxalate
Involved plating molybdenum glass and soda-lime glass are purchased respectively in raw Yangxin material science and technology (Ningbo) company limited and the credit of Luoyang dragon
Glass Co., Ltd..
The principle of the present invention is:
1) on substrate, deposit the oxide of cupric and stannum after using low-temperature solid phase reaction synthesis oxide nano-particle again
Precursor thin-film.
2) above-mentioned oxide precursor body thin film is annealed under sulfur atmosphere after formation absorbed layer CTS thin film, and then at selenium
Annealing under atmosphere, be absorbed a layer CTSSe thin film.
The present invention has beneficial effect highlighted below: the present invention proposes one and utilizes low cost, preparation process simple
Low heat temperature solid state reaction prepares the oxide nano particles presoma of cupric and stannum, through ball milling, dispersed with stirring in alcoholic solvent,
Scraped by cutter, spin coating or silk screen printing film forming, and utilize subsequent annealing process to be absorbed layer film.According to above Patents
Report, the synthesis of other metal sulfides, selenides and copper and tin sulphur compound nano-particle typically requires closes under an inert atmosphere
Becoming, preparation condition is the harshest.Therefore this patent have employed generally acknowledged preparation method simple Low Temperature Solid-Phase method and successfully synthesizes
The oxide nano particles presoma of cupric and stannum.Concrete useful following some:
1) synthesis having patent report metal sulfide, selenides and copper and tin sulphur compound nano-particle is complex, this patent
Using low-temperature solid phase reaction synthesis oxide nano-particle, preparation process can complete in atmospheric environment, and process is simple, the cycle
Short, solve the problem that large-scale production cost is high.
2) patent retrieval finds, it is thin that this patent utilizes the oxide precursor of low cost to prepare absorbed layer CTSSe first
Film；
3) oxide nano particles method prepares cuprio (CIGS, copper-zinc-tin-sulfur) thin film has document report to have two big aspects
Benefit: one, be thin film composition can easily by control reacting metal salt ratio realize；Its two, be
Low heat temperature solid state reaction synthesis oxide nano-particle can accomplish large-area deposition, and applicable industrialization is prepared on a large scale will
Ask；
4) present invention utilizes the method for oxide nano particles to prepare precursor thin-film, and is absorbed layer by sulfuration and selenizing
Thin film, has equipment simple, and preparation cost is cheap, can large area preparation deposit, and manufacturing cycle is shorter, composition and film thickness
The advantage such as easily-controllable.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings, the invention will be further described.
Fig. 1 is of the present invention to prepare absorbed layer CTSSe thin-film technique flow chart.
Fig. 2 is the precursor thin-film SEM figure of embodiment 1 of the present invention preparation.
Fig. 3 is the absorbed layer CTSSe XRD figure of embodiment 1 of the present invention preparation.
Detailed description of the invention
In order to present invention may be better understood, existing the present invention is described further by way of example.Implement
Example 1
1, first soda-lime glass substrate is carried out: substrate is immersed successively detergent, deionized water, ethanol, acetone soln
In, then deionized water is ultrasonic and rinses well, and nitrogen dries up；
2, by copper nitrate (Cu (NO3)23H2O) with stannous oxalate (SnC2O4) raw material, according to copper, the mol ratio of tin element
Weigh 16.2 and 6.9 grams for 2:1 respectively, separately weigh the ammonium hydrogen carbonate (NH of 1.5 times that mole is Cu+Sn mole4HCO3)
11.9 grams.These three raw material is put into mortar, carries out mixed grinding 10min.Along with carbon dioxide, ammonia gas in course of reaction
Leaving of body, there is substantial amounts of bubble in whole reaction system.After griding reaction terminates, finally obtain blue solid mixture.
Subsequently gained mixture is put into the Muffle furnace 380 that monkey is placed in atmospheric environmentoC sintering 30min obtain mixing CuO and
SnO2Powder.
3, by CuO and SnO2Mixture of powders is scattered in ethanol, and after dispersion, the solid content of system is 400mg/ml, at ball
Grinding machine grinds 2 days, obtains uniform precursor pulp.Then gained precursor pulp is deposited on sodium calcium glass by knife scraping method
Film forming on glass, by the thin film after coating 100oAfter being dried 2 hours under the baking oven of C, obtain the Cu-Sn-O forerunner of 2.5 μ m thick
Body thin film.Its surface scan Electronic Speculum result is as shown in Figure 2.
4, Cu-Sn-O oxide precursor body thin film heat treatment in sulfur atmosphere that step 3) obtains is utilized.Select sealed tube
Formula stove, uses solid-state sulfur as sulfur source, 0.01g sulfur powder and oxide precursor body thin film is placed in airtight tube type stove, takes out background
Vacuum is to 10-2pa.Make sulfur powder start to warm up from room temperature with Cu-Sn-O oxide precursor body thin film, heating rate 40 simultaneouslyoC/
Min, is eventually held in 580 C, is incubated 30min, and after being slowly cooled to room temperature subsequently, be absorbed a layer CTS thin film.
5, absorbed layer CTS thin film heat treatment in selenium atmosphere that previous step obtains is utilized.Select airtight intensification tube furnace,
Use solid selenium powder as selenium source, 0.02g selenium powder and absorbed layer CTS thin film are placed in airtight tube type stove, are added on tube furnace
One end, take out background vacuum to 10-2Pa, makes selenium powder start to warm up from room temperature with absorbed layer CTS thin film, heating rate simultaneously
40oC/min, is eventually held in 580 C, is incubated 30min, and after being slowly cooled to room temperature subsequently, be absorbed a layer CTSSe thin film.
The CTSSe thin film utilizing X-ray diffraction to prepare the present embodiment is tested, and obtains CTSSe's as shown in Figure 3
X ray diffracting spectrum.From figure 3, it can be seen that the XRD diffraction maximum of prepared CTSSe thin film is between CTS and CTSe standard x RD
Between diffraction maximum, for compound phase CTSSe.
Embodiment 2
1, first plating molybdenum film substrate is carried out: substrate is immersed successively detergent, deionized water, ethanol, acetone soln
In, then deionized water is ultrasonic and rinses well, and nitrogen dries up；
2, by copper nitrate (Cu (NO3)2•3H2And stannous oxalate (SnC O)2O4) raw material, according to copper, the mol ratio of tin element
Weigh 12.9 grams and 6.9 grams for 1.6:1 respectively, separately weigh the ammonium hydrogen carbonate of 1.8 times that mole is Cu+Sn mole
(NH4HCO3) 10.3 grams, it is ensured that NH4HCO3Excess.Finally these three raw material is put into mortar, carry out mixed grinding 10min.Instead
Along with carbon dioxide, the leaving of ammonia gas during Ying, there is substantial amounts of bubble in whole reaction system.When griding reaction is tied
Shu Hou, finally obtains blue solid mixture.Subsequently gained mixture is put into the Muffle furnace that monkey is placed in atmospheric environment
380oC sintering 30min obtains CuO and SnO of mixing2Powder.
3, by CuO and SnO2Mixture of powders is scattered in ethylene glycol, and after dispersion, the solid content of system is 300mg/ml,
Grinding in ball grinder 36 h, obtains uniform precursor pulp.Then gained precursor pulp is deposited on plating by knife scraping method
Thin film is formed, by the thin film after coating 100 on molybdenum filmoAfter being dried 2 hours under the baking oven of C, obtain the Cu-Sn-of 3 μ m thick
O precursor thin-film.
4, Cu-Sn-O precursor thin-film heat treatment in sulfur atmosphere that step 3) obtains is utilized.Select airtight tube type stove, make
With sulfur powder as sulfur source, 0.02g sulfur powder and Cu-Sn-O precursor film are placed in airtight tube type stove, take out background vacuum to 10-2pa。
Make sulfur powder start to warm up from room temperature with Cu-Sn-O precursor thin-film, heating rate 40 simultaneouslyoC/min, is eventually held in 550 C,
Insulation 30min, after being slowly cooled to room temperature subsequently, be absorbed a layer CTS thin film.
5, absorbed layer CTS thin film heat treatment in selenium atmosphere that previous step obtains is utilized.Select airtight intensification tube furnace,
Use solid selenium powder as selenium source, 0.02g selenium powder and CTS thin film be placed in airtight tube type stove, be added on one end of tube furnace,
Take out background vacuum to 10-2Pa, makes selenium powder start to warm up from room temperature with absorbed layer CTS thin film, heating rate 40 simultaneouslyoC/min,
Being maintained at 600 C eventually, be incubated 20min, after being slowly cooled to room temperature subsequently, be absorbed a layer CTSSe thin film.
Embodiment 3
1, first quartz glass substrate is carried out: substrate is immersed successively detergent, deionized water, ethanol, acetone soln
In, then deionized water is ultrasonic and rinses well, and nitrogen dries up；
2, Cu (NO is weighed respectively3)2•3H2O, copper acetate, tin acetate and stannous oxalate raw material 5.784 grams, 4.766 grams, 2.36 grams
With 2.07 grams, more separately weigh the ammonium hydrogen carbonate NH that mole is 1.8 times of (Cu+Sn) mole4HCO319.67 grams.Finally by upper
State raw material and put into mortar, carry out mixed grinding 10min.Along with carbon dioxide, the leaving of ammonia gas in course of reaction, whole
There is substantial amounts of bubble in reaction system.After griding reaction terminates, finally obtain blue solid mixture.Subsequently gained is mixed
Thing puts into the Muffle furnace 400 that monkey is placed in atmospheric environmentoC sintering 30min obtains CuO and SnO of mixing2Powder.Above-mentioned former
In material, Cu (NO3)2•3H2O and copper acetate mole are than for 1:1；Tin acetate and stannous oxalate mole are than for 1:1；Copper and
The mol ratio of tin element is 2.4:1.
3, by CuO and SnO2Mixture of powders is scattered in ethylene glycol and the terpineol solvent of mixed in equal amounts, body after dispersion
The solid content of system is 300mg/ml, at grinding in ball grinder 36 h, obtains uniform precursor pulp.Then by gained presoma
Slurry is deposited on quartz glass formation thin film by knife scraping method, by the thin film after coating 100oIt is dried 2 hours under the baking oven of C
After, obtain the Cu-Sn-O precursor thin-film of 3 μ m thick.
4, Cu-Sn-O precursor thin-film heat treatment in sulfur atmosphere that step 3) obtains is utilized.Select airtight tube type stove, make
With sulfur powder as sulfur source, 0.15g sulfur powder and Cu-Sn-O precursor thin-film are placed in airtight tube type stove, take out background vacuum to 10- 2pa.Make sulfur powder start to warm up from room temperature with Cu-Sn-O precursor thin-film, heating rate 40 simultaneouslyoC/min, is eventually held in 500
C, is incubated 40min, and after being slowly cooled to room temperature subsequently, be absorbed a layer CTS thin film.
5, the absorbed layer CTS thin film utilizing previous step to obtain is in the selenium steam gas of flowing and carries out at selenizing heat
Reason.Selecting two ends with the intensification tube furnace of Valve controlling, use solid selenium powder is as selenium source, by 0.1g selenium powder and absorbed layer
CTS thin film is placed in tube furnace ,-take out background vacuum to 10-2Pa, is passed through the argon of high-purity 99.999% in one end of tube furnace, when
Overpressure is more than 105During Pa, open the tail gas valve of the other end, make argon be drained in tail gas filter, be ultimately discharged into
In air.Being started to warm up from room temperature with absorbed layer CTS thin film by selenium powder, the argon now flowed will drive selenium steam to inhaling simultaneously
Receive layer CTS film surface and carry out selenized annealing.Heating rate 40oC/min, is eventually held in 600 C, is incubated 20min.Delay subsequently
Slow cool down is to after room temperature, and be absorbed a layer CTSSe thin film.
In above-described embodiment, the chemical reagent copper nitrate involved by preparation, copper acetate, ammonium hydrogen carbonate, dehydrated alcohol, pine
Oleyl alcohol, ethylene glycol are all purchased in chemical reagents corporation of traditional Chinese medicines group, sulfur powder, selenium powder, tin acetate and stannous oxalate all purchase in
Aladdin Chemistry co.ltd, plating molybdenum glass and soda-lime glass involved by substrate are purchased respectively in raw Yangxin material
Science and technology (Ningbo) company limited and Luoyang Long Yao Glass Co., Ltd..
Embodiment described above only have expressed two detailed description of the invention of the present invention, has been the present invention furtherly
Bright, describe more in detail and concrete, but can not be therefore understands that be the restriction to patent of the present invention.It should be pointed out that, not
On the premise of departing from present inventive concept, making some deformation and improvement, these broadly fall into protection scope of the present invention.Therefore, originally
The protection domain of patent of invention should be as the criterion with claims.
Claims (11)
1. the method that oxide nano particles prepares solar battery obsorbing layer CTSSe thin film, is characterized in that:
Step one: by a step low-temperature solid phase reaction synthesis containing copper and the oxide nano particles powder body of stannum, and by oxide
Nano-particle is scattered in organic solvent, and wet grinding forms stable precursor pulp；
Step 2: substrate surface is carried out, precursor pulp described in step one uses on substrate cutter scrape, spin coating, silk
One in wire mark brush carries out formation of deposits oxide precursor body thin film, preserves after drying；
Step 3: by obtain in step 2 containing copper and the precursor thin film of tin-oxide, under sulfur atmosphere atmosphere airtight or
Making annealing treatment in the tube furnace of person's circulation, be absorbed a layer CTS thin film；
Step 4: utilize step 3) the absorbed layer CTS thin film that obtains, select airtight intensification tube furnace, carry out in selenium atmosphere
Selenizing heat treatment, be absorbed a layer CTSSe thin film.
A kind of oxide nano particles the most according to claim 1 prepares the side of solar battery obsorbing layer CTSSe thin film
Method, is characterized in that step one) described in a step low-temperature solid phase reaction synthesis oxide nano-particle method refer to: by copper and the nothing of stannum
Machine salt, is mixed to form solid content with reactant ammonium hydrogen carbonate and controls the slurry at 200～400 mg/ml, polished, in low
The lower sintering of temperature, it is thus achieved that oxide nano particles.
A kind of oxide nano particles the most according to claim 2 prepares the side of solar battery obsorbing layer CTSSe thin film
Method, is characterized in that the inorganic salt of described copper and the inorganic salt of stannum, copper and stannum mol ratio between the two are 1.6～2.4:1.
A kind of oxide nano particles the most according to claim 2 prepares the side of solar battery obsorbing layer CTSSe thin film
Method, is characterized in that ammonium hydrogen carbonate of the present invention, and its usage amount is 1.1～2.0 times of copper and Xi Moer total amount.
A kind of oxide nano particles the most according to claim 2 prepares the side of solar battery obsorbing layer CTSSe thin film
Method, is characterized in that grinding of the present invention, uses general milling machine, super ball mill, wet milk or mortar, and milling time is
6～15 min.
A kind of oxide nano particles the most according to claim 2 prepares the side of solar battery obsorbing layer CTSSe thin film
Method, it is characterized in that under described middle low temperature sinter, its temperature range between 300～400 DEG C, sintering time 10min～
180min。
A kind of oxide nano particles the most according to claim 2 prepares the side of solar battery obsorbing layer CTSSe thin film
Method, is characterized in that the inorganic salt of described copper refers to the mixture of one or both arbitrary proportions in copper nitrate, copper acetate；Described
The inorganic salt of stannum refers to the mixture of one or both arbitrary proportions in tin acetate, stannous oxalate；Described organic solvent is
Refer to one or several the mixing in ethanol, ethylene glycol or terpineol.
A kind of oxide nano particles the most according to claim 1 prepares the side of solar battery obsorbing layer CTSSe thin film
Method, is characterized in that described wet grinding, uses general milling machine, super ball mill, wet milk or mortar, and the wet grinding time is 36～48
h。
A kind of oxide nano particles the most according to claim 1 prepares the side of solar battery obsorbing layer CTSSe thin film
Method, is characterized in that described substrate is the one in plating molybdenum film, soda-lime glass, quartz glass and metal forming.
A kind of oxide nano particles the most according to claim 1 prepares the side of solar battery obsorbing layer CTSSe thin film
Method, is characterized in that carrying out sulfuration annealing under sulfur atmosphere described in step 3, refers to precursor thin-film and solid-state sulfur source or sulfuration
Hydrogen is placed in confined space annealing, or precursor thin-film is in sulfur steam or the hydrogen sulfide gas of flowing
Annealing；When sulfuration annealing annealing uses solid-state sulfur source, holding solid-state sulfur source temperature 450～600 DEG C, cure time 20～60
min。
11. a kind of oxide nano particles according to claim 1 prepare the side of solar battery obsorbing layer CTSSe thin film
Method, is characterized in that carrying out under selenium atmosphere described in step 4 selenized annealing, refers to precursor thin-film and solid selenium source or selenizing
Hydrogen is placed in confined space annealing, or precursor thin-film is in selenium steam or the hydrogen selenide gas of flowing
Annealing；When selenized annealing annealing uses solid selenium source, holding solid selenium source temperature 450～600 DEG C, cure time 20～60
min。
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| CN110255603A (en) * | 2019-05-17 | 2019-09-20 | 福建师范大学 | A kind of CuInS2The method that film uniformly mixes sodium |
| CN111689695A (en) * | 2019-03-15 | 2020-09-22 | 天津大学 | Method for preparing copper indium selenide film by dipping and drawing process with indium selenide and monovalent copper as intermediates |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107134507A (en) * | 2016-12-08 | 2017-09-05 | 福建师范大学 | Preparation method with gradient components solar battery obsorbing layer copper and indium sulfur-selenium thin film |
| CN107134507B (en) * | 2016-12-08 | 2021-04-09 | 福建师范大学 | Preparation method of copper indium sulfur selenium film with gradient component solar cell absorption layer |
| CN111689695A (en) * | 2019-03-15 | 2020-09-22 | 天津大学 | Method for preparing copper indium selenide film by dipping and drawing process with indium selenide and monovalent copper as intermediates |
| CN110255603A (en) * | 2019-05-17 | 2019-09-20 | 福建师范大学 | A kind of CuInS2The method that film uniformly mixes sodium |
| CN110255603B (en) * | 2019-05-17 | 2021-09-07 | 福建师范大学 | CuInS2Method for uniformly doping sodium into thin film |
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