CN109686817A - A kind of AgBiS2The preparation method of semiconductive thin film - Google Patents
A kind of AgBiS2The preparation method of semiconductive thin film Download PDFInfo
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- CN109686817A CN109686817A CN201811564344.XA CN201811564344A CN109686817A CN 109686817 A CN109686817 A CN 109686817A CN 201811564344 A CN201811564344 A CN 201811564344A CN 109686817 A CN109686817 A CN 109686817A
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- 239000010409 thin film Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 19
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 239000005864 Sulphur Substances 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 9
- 238000004528 spin coating Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 230000009977 dual effect Effects 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000001548 drop coating Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 229940031098 ethanolamine Drugs 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 229940012017 ethylenediamine Drugs 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 229960004592 isopropanol Drugs 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- 229940096017 silver fluoride Drugs 0.000 claims description 2
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 2
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229960001516 silver nitrate Drugs 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 48
- 239000000463 material Substances 0.000 abstract description 15
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 238000003756 stirring Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 60
- 239000013078 crystal Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- -1 moisture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 230000009466 transformation Effects 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
- C01G29/006—Compounds containing, besides bismuth, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- 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
Abstract
The invention discloses a kind of AgBiS2The preparation method of semiconductive thin film, this method is first to prepare the solution containing silver respectively and containing the solution of bismuth, then two kinds of solution are mixed again, heating stirring after addition thiocarbamide, it adds additive and is mixed to get stable, the suitable precursor solution of viscosity, then plated film, pre-burning obtain preformed layer, finally using annealing process, the crystallinity for promoting film, finally prepares AgBiS2Semiconductive thin film.This method has the advantages that easy to operate, reaction condition is mild, low for equipment requirements, low in cost, easy to industrialized production, the AgBiS of preparation2Semiconductive thin film quality of forming film is good, and particle is larger, and object is mutually pure, be conducive to improve the photovoltaic performance of thin-film material, and the absorption coefficient of light of film is high, forbidden bandwidth is suitable, electric property is good, and carrier mobility is high, is highly suitable as the battery obsorbing layer material of the film sun.
Description
Technical field
The present invention relates to solar cell photovoltaic absorbed layer material manufacture technical field more particularly to a kind of AgBiS2Partly lead
The preparation method of body thin film.
Background technique
Compound film solar cell be considered to be substitution silicon solar cell a kind of novel solar cell, including CdTe,
The thin film solar cells such as CIGSe, photoelectric conversion efficiency have respectively reached 22.1% and 22.3%, but its there are Cd,
The toxic elements such as Se limit the sustainable and extensive development of both hull cells.Researcher has been devoted to find
, there is the quaternary compound thin film solar cell such as CZTS in a kind of material that can substitute CdTe, CIGSe, but due to
The loss of open-circuit voltage caused by the material antistructure defect, so that the promotion of its photoelectric conversion efficiency is slower.The CZTS of current pure Sization is thin
The highest photoelectric conversion efficiency of film solar cell is 11%, is at least up to 20% commercialization requirement also apart from photoelectric conversion efficiency
Farther out；And due to quaternary compound complicated composition, prepare also relatively difficult.Therefore, researcher proposes IB-Bi-S2(IB=
Ag, Cu) the extinction layer material of this kind of ternary metal sulfide as thin film solar cell imagination.
AgBiS2Element composition it is nontoxic, chemical stability is preferable, the absorption coefficient of light height (105, nearly one is higher by compared with CZTS
The order of magnitude), forbidden bandwidth is suitble to (according to preparation method difference, between 1.0-1.3eV), and ternary compound is compared with CZTS and CIGS etc.
Quaternary compound preparation is simple, it is considered to be a kind of very promising photovoltaic absorption layer material.AgBiS2It is main at present
It can be prepared by hot injection method and hot solvent method, but what it was prepared is all nano-particle material.Report at present with
AgBiS2The solar cell peak efficiency of material preparation has reached 6.3%, but it uses the AgBiS of hot injection method preparation2It is nanocrystalline
Solar cell, using organic matter as hole transmission layer, it is difficult to after annealing processing is born, so that film particles are small, crystal boundary is excessive,
It will cause the loss of short circuit current to a certain extent, AgBiS could not be given full play to2The advantage of material, thickness is lower, may be not complete
Hypersorption photon energy；And hot injection method yield is lower, is unfavorable for large-scale production application.Pass through solvent in addition, having been reported that
Thermal method is prepared into AgBiS2Nanometer particle material, and the AgBiS of nanometer-size die size2It is difficult deposition and obtains adequate thickness, crystal grain
Big film limits its application in terms of photovoltaic conversion.
Summary of the invention
Based on preparing AgBiS in the prior art2The deficiency of semiconductor film film method, the purpose of the present invention is to provide one kind
It is low in cost, AgBiS is prepared under mild, non-vacuum condition2The method of absorption layer of thin film solar cell, this method can be prepared
Certain thickness film is obtained, it is made to fully absorb sunlight；The crystalline property being prepared is preferable, and crystal grain is big, prepares work
Skill is simple, is suitable for industrialized production.In addition, the method also extends to CuBiS2The preparation of film, only need to be by corresponding silver-colored source
It is substituted for copper source.
To achieve the goals above, AgBiS proposed by the present invention2The preparation method of semiconductive thin film, comprising the following steps:
1) silver-colored source is dissolved in solvent I, obtains solution A；Bismuth source is dissolved in solvent II, obtains solution B；
2) solution A and solution B are uniformly mixed, excessive thiocarbamide is added, heat and obtain presoma after being sufficiently stirred and is molten
Liquid；
3) additive is added to precursor solution and is stirred, then applied on substrate, pre-burning is repeated several times
After obtain preformed layer；
4) prefabricated be placed in the atmosphere of sulfur-bearing is made annealing treatment, and obtains AgBiS2Semiconductive thin film.
Preferably, the concentration in silver-colored source is 0.1~2.0mol/L in the solution A；Silver nitrate, fluorination are selected in the silver source
At least one of silver, silver acetate, silver carbonate, silver sulfate, silver orthophosphate.
Preferably, the solvent I is in pure water, ethyl alcohol, ethylene glycol monomethyl ether, dimethyl sulfoxide, acetic acid, ammonium hydroxide, nitric acid
It is at least one；It is described that obtain the temperature that solution A uses be room temperature to 60 DEG C.
Preferably, bismuth source concentration is 0.1~2.0mol/L in the solution B；The bismuth source using bismuth nitrate, bismuth chloride,
At least one of bismuth acetate.
Preferably, the solvent II is at least one in acetic acid, dust technology, ethyl alcohol, acetone, ethylene glycol monomethyl ether, benzene, pure water
Kind；It is described to obtain the temperature that solution B uses as 40~80 DEG C.
Preferably, in step 2), 1:0.3~1.5 is mixed by volume for the solution A and solution B；The thiocarbamide additional amount
It is 2~6 times of the amount of silver-colored source substance；The heating temperature is 40~60 DEG C.
Preferably, in step 3), the additive is ethylenediamine, ethanol amine, diethanol amine, triethanolamine, isopropanol, second
At least one of alcohol；The additive amount is the 1~5% of precursor solution total volume.
Preferably, in step 3), the substrate uses FTO electro-conductive glass substrate, ITO electro-conductive glass substrate, Mo conduction glass
Any one of glass substrate, stainless steel base；The coating and the duplicate number of pre-burning are 8~20 times；The coating method packet
Include spin coating, drop coating, spraying or blade coating；The temperature of the pre-burning is 200~300 DEG C.
Preferably, in step 4), the annealing stablizes ambient anneal using dual temperature area；Stablize ambient anneal in the dual temperature area
Process uses solid-state sulphur source, and atmosphere area holding temperature is 200~300 DEG C, and sample area holding temperature is 400~650 DEG C, heating speed
Rate is 5~15 DEG C/min, and annealing pressure is -0.1~0.101325MPa, and soaking time is 20~60min.
Preferably, the sulphur source includes sulphur powder and/or thioacetamide.
In technical solution proposed by the present invention, AgBiS is first deposited using sol-gal process on conductive substrates2Preformed layer is thin
Film, then made annealing treatment under sulphur atmosphere, obtain AgBiS2Semiconductive thin film.The relatively existing hot injection method preparation of this method
AgBiS2Nano-crystalline thin film solar cell and hot solvent method prepare AgBiS2Nano particle has absolute technical advantage: film object
Mutually pure, crystal grain is big, and thickness is controllable, can fully absorb photon energy, and film constituent controllable precise is low for equipment requirements,
Low energy consumption, raw material utilize high, particularly suitable industrialization large-scale production.Preparation AgBiS is realized by the method for the invention2Half
The key technology of conductor thin film is to prepare stable, the suitable precursor solution of viscosity and annealing process.In precursor solution
Suitable solvent is used in preparation process, dissolution process is carried out to silver-colored source, bismuth source etc., can obtain the good silver of dissolution dispersity
The solution such as source, bismuth source；Suitable additive is added, can be stablized, the precursor solution that viscosity is suitable, coating, pre- is conducive to
The preformed layer of burning process forms a film.In addition, the present invention makes annealing treatment preformed layer, make film growth densification, crystal grain
It is larger, pattern is preferable, be conducive to improve thin-film material photovoltaic performance.
Compared with the prior art, technical solution of the present invention bring the utility model has the advantages that
1, the present invention prepares AgBiS using sol-gal process for the first time2Film, process conditions are mild, easy to operate, energy consumption
It is low, it can be with large-scale serial production.
2, the present invention prepares AgBiS using sol-gal process2Film mixes raw material using solution form, and each group divides it
Between with molecular ion rank mixing, realize the accurate control of thin film composition.
3, AgBiS prepared by the present invention2Object is mutually pure, film is fine and close, crystal grain is larger, pattern is preferable, is conducive to mention
The photovoltaic performance of high solar battery obsorbing layer.
4, AgBiS prepared by the present invention2Film has the absorption coefficient of light high, and forbidden bandwidth is suitable, and electric property is good, very
It is suitble to absorption layer of thin film solar cell material.
5, the heating temperature that mixed solution A and when solution B use, can be to avoid too low or excessively high temperature for 40~60 DEG C
Cause precursor solution obtained unstable, directly affects subsequent thin film quality.
6, additive amount is the 1~5% of precursor solution total volume, is not had surely to avoid very few additive amount
Determine the effect of solution, optimization film forming, excessive additive amount causes solution to precipitate.
7, the temperature of pre-burning be 200~300 DEG C, can by precursor solution organic substance, moisture, nitrogen and its
He removes substance, preliminarily forms AgBiS2Prefabricated layer film.
8, the generation and film surface grain growth of ternary object phase can be promoted by stablizing ambient anneal using dual temperature area, be made
Film surface dense uniform.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
The structure shown according to these attached drawings obtains other attached drawings.
Fig. 1 is AgBiS obtained in embodiment 12The XRD diagram of film；
Fig. 2 is AgBiS obtained in embodiment 22The band gap diagram of film；
Fig. 3 is AgBiS obtained in embodiment 22The SEM of film schemes；
Fig. 4 is AgBiS obtained in embodiment 22The absorption coefficient figure of film；
Fig. 5 is AgBiS obtained in embodiment 32The AgBiS of prefabricated layer film (as) and 580 DEG C of after annealings2Film
XRD diagram.
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts it is all its
His embodiment, shall fall within the protection scope of the present invention.
Embodiment 1
Silver nitrate is dissolved in and obtains the silver nitrate solution of 0.25mol/L in 10ml pure water and (stirs 30 minutes and obtain under room temperature
Colorless cleared solution).Five water bismuth nitrates addition 10ml acetic acid solution is obtained in the solution of 0.25mol/L bismuth source that (50 DEG C are stirred simultaneously
It mixes 30 minutes, obtains colorless cleared solution).
Then silver nitrate solution and bismuth source solution are mixed, is heated to 60 DEG C, is rapidly added 1.903g thiocarbamide, and sufficiently stir
It mixes 30min and obtains yellow clear solution, which is not present deposited phenomenon.0.5ml diethanol is added dropwise after above-mentioned solution is cooling
Amine and 0.5ml triethanolamine stir five minutes under room temperature and obtain precursor solution, and when precursor solution more non-doping is viscous
Degree is obviously improved.
Again by prepared AgBiS2Precursor solution is spin-coated on Mo glass, pre- using 200 DEG C between every spin coating twice
It burns, repeats spin coating 12 times, complete AgBiS2The spin coating of preformed layer.
The AgBiS that spin coating is obtained2Prefabricated be placed in dual temperature tube furnace stablizes atmosphere after cure annealing, and sulphur source is sulphur
Powder, sulphur source atmosphere area's temperature be 200 DEG C, sample area temperature be 400 DEG C, heating rate be 5 DEG C/min, annealing pressure be-
0.1MPa, soaking time 20min, i.e. completion AgBiS2Absorb the preparation of layer film.
Prepared AgBiS2The X ray diffracting spectrum of film is as shown in Fig. 1, the AgBiS that we obtain2Film is vertical
Prismatic crystal architecture, object is mutually pure, and no secondary phase miscellaneous peak exists；Ag/Bi=1.0432 is obtained by XRF analysis, S/ (Ag+Bi)=
1.0963；AgBiS is obtained by film thickness gauge2Film thickness 1023nm.
Embodiment 2
Silver fluoride is dissolved in 30ml pure water and obtains the silver-colored source solution of 0.5mol/L.The dilute nitre of 30ml is added in bismuth chloride simultaneously
Acid solution obtains in the solution of 0.25mol/L bismuth source (50 DEG C are stirred 30 minutes, and colorless cleared solution is obtained).
Then silver-colored source solution and bismuth source solution are mixed, is heated to 50 DEG C, is rapidly added 4.5672g thiocarbamide, and sufficiently stir
It mixes 30min and obtains yellow clear solution, which is not present deposited phenomenon.
2ml ethanol amine is added dropwise after above-mentioned solution is cooling, is stirred five minutes under room temperature and obtains precursor solution, it is spare.Again
By prepared AgBiS2Precursor solution is scratched in FTO electro-conductive glass substrate and white glass (for carrying out UV test), often
270 DEG C of pre-burnings are used between blade coating twice, are repeated spin coating 10 times, AgBiS is completed2The spin coating of preformed layer, through detecting, AgBiS2In advance
The thickness of preparative layer is about 830nm.
The AgBiS that blade coating is obtained2Prefabricated be placed in dual temperature tube furnace stablizes atmosphere after cure annealing, and sulphur source is sulphur
Powder, sulphur source atmosphere area's temperature be 200 DEG C, sample area temperature be 650 DEG C, heating rate be 10 DEG C/min, annealing pressure be-
0.1MPa, soaking time 40min complete AgBiS2Absorb the preparation of layer film
Prepared AgBiS2The band gap diagram of film is as shown in Fig. 2, the AgBiS that we obtain2Film band gap is 1.09eV
Left and right, is suitable as the extinction layer material of thin film solar cell.Prepared AgBiS2The SEM spectrum of film is as shown in Fig. 3,
The AgBiS that we obtain2Film, film particles growth is larger, and crystallite dimension reaches 500nm or so, if annealed by improving
Journey can also further promote the quality of film.Prepared AgBiS2The absorption coefficient of light of film is as shown in Fig. 4, preparation
Obtained AgBiS2Film visible absorption coefficient is close to 105cm-1, photon energy can be fully absorbed, is a kind of very outstanding
Light absorbing material.
Embodiment 3
Silver nitrate is dissolved in obtained in 50ml pure water 2mol/L silver nitrate solution (stirred under room temperature obtain within 60 minutes it is colourless
Clear solution).Five water bismuth nitrates addition 70ml acetic acid solution is obtained into the solution of 2mol/L bismuth source (80 DEG C of 60 points of stirrings simultaneously
Clock obtains colorless cleared solution).
Then silver nitrate solution and bismuth source solution are mixed, is heated to 40 DEG C, is rapidly added 28g thiocarbamide, and be sufficiently stirred
30min obtains yellow clear solution, which is not present deposited phenomenon.2ml ethyl alcohol and 2ml tri- is added dropwise after above-mentioned solution is cooling
Ethanol amine stirs five minutes under room temperature, obtains precursor solution, and viscosity obviously mentions when the precursor solution more non-doping
It rises.
Again by prepared AgBiS2Precursor solution drop coating is in two panels Mo electro-conductive glass substrate, per between drop coating twice
It using 270 DEG C of pre-burnings, repeats spin coating 12 times, completes AgBiS2The drop coating of preformed layer.
The AgBiS that drop coating is obtained2One of preformed layer, which is placed in dual temperature tube furnace, stablizes atmosphere after cure annealing, and sulphur source is
Sulphur powder, sulphur source atmosphere area's temperature be 300 DEG C, sample area temperature be 580 DEG C, heating rate be 5 DEG C/min, annealing pressure be-
0.1MPa, soaking time 20min complete AgBiS2Absorb the preparation of layer film.
The AgBiS that drop coating is obtained2Preformed layer carries out XRD test, carries out with the film XRD diagram annealed through over cure pair
Than please referring to attached drawing 5, film its XRD peak intensity after annealing is obviously improved, and illustrates that crystallinity enhancing is significant.By suddenly
You test to obtain at effect: prepared AgBiS2For P-type semiconductor, doping concentration 3.814 × 1013cm-3, carrier mobility is
22.60cm2/ Vs has preferable electric property, meets the requirement of the absorption layer material as thin film solar cell.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all at this
Under the design of invention, using equivalent structure transformation made by description of the invention and accompanying drawing content, or directly/it is used in it indirectly
He is included in scope of patent protection of the invention relevant technical field.
Claims (10)
1. a kind of AgBiS2The preparation method of semiconductive thin film, it is characterised in that: the following steps are included:
1) silver-colored source is dissolved in solvent I, obtains solution A；Bismuth source is dissolved in solvent II, obtains solution B；
2) solution A and solution B are uniformly mixed, excessive thiocarbamide is added, heat and obtain precursor solution after being sufficiently stirred；
3) additive is added to precursor solution and is stirred, then applied on substrate, pre-burning, after being repeated several times
To preformed layer；
4) prefabricated be placed in the atmosphere of sulfur-bearing is made annealing treatment, and obtains AgBiS2Semiconductive thin film.
2. AgBiS according to claim 12The preparation method of semiconductive thin film, it is characterised in that:
The concentration in silver-colored source is 0.1~2.0mol/L in the solution A；Silver nitrate, silver fluoride, silver acetate, carbon are selected in the silver source
At least one of sour silver, silver sulfate, silver orthophosphate.
3. AgBiS according to claim 1 or 22The preparation method of semiconductive thin film, it is characterised in that:
The solvent I is selected from least one of pure water, ethyl alcohol, ethylene glycol monomethyl ether, dimethyl sulfoxide, acetic acid, ammonium hydroxide, nitric acid；Institute
It states to obtain the temperature that solution A uses to be room temperature to 60 DEG C.
4. AgBiS according to claim 12The preparation method of semiconductive thin film, it is characterised in that:
Bismuth source concentration is 0.1~2.0mol/L in the solution B；The bismuth source using bismuth nitrate, bismuth chloride, in bismuth acetate at least
It is a kind of.
5. AgBiS according to claim 1 or 42The preparation method of semiconductive thin film, it is characterised in that:
The solvent II is selected from least one of acetic acid, dust technology, ethyl alcohol, acetone, ethylene glycol monomethyl ether, benzene, pure water；It is described to obtain
The temperature that solution B uses is 40~80 DEG C.
6. AgBiS according to claim 12The preparation method of semiconductive thin film, it is characterised in that:
In step 2), 1:0.3~1.5 is mixed by volume for the solution A and solution B；The thiocarbamide additional amount is silver-colored source substance
2~6 times of amount；The heating temperature is 40~60 DEG C.
7. AgBiS according to claim 62The preparation method of semiconductive thin film, it is characterised in that:
In step 3), the additive be ethylenediamine, ethanol amine, diethanol amine, triethanolamine, isopropanol, in ethyl alcohol at least
It is a kind of；The additive amount is the 1~5% of precursor solution total volume.
8. AgBiS according to claim 12The preparation method of semiconductive thin film, it is characterised in that:
In step 3), the substrate is using FTO electro-conductive glass substrate, ITO electro-conductive glass substrate, Mo electro-conductive glass substrate, stainless
Any one of steel base；The coating and the duplicate number of pre-burning are 8~20 times；The coating method include spin coating, drop coating,
Spraying or blade coating；The temperature of the pre-burning is 200~300 DEG C.
9. AgBiS according to claim 12The preparation method of semiconductive thin film, it is characterised in that:
In step 4), the annealing stablizes ambient anneal using dual temperature area；Stablize ambient anneal process using solid in the dual temperature area
State sulphur source, atmosphere area holding temperature are 200~300 DEG C, and sample area holding temperature is 400~650 DEG C, and heating rate is 5~15
DEG C/min, annealing pressure is -0.1~0.101325MPa, and soaking time is 20~60min.
10. AgBiS according to claim 92The preparation method of semiconductive thin film, it is characterised in that:
The sulphur source includes sulphur powder and/or thioacetamide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110911568A (en) * | 2019-12-03 | 2020-03-24 | 武汉大学 | Silver bismuth sulfide thin film photoelectric detector and preparation method thereof |
| CN113620342A (en) * | 2021-08-30 | 2021-11-09 | 浙江理工大学 | Shuttle-shaped silver bismuth disulfide nano material and preparation method thereof |
| CN113913794A (en) * | 2021-09-30 | 2022-01-11 | 武汉大学 | AgBiS2Film, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107195697A (en) * | 2017-06-01 | 2017-09-22 | 中南大学 | A kind of preparation method of copper barium (strontium/calcium) tin sulphur (selenium) film |
-
2018
- 2018-12-20 CN CN201811564344.XA patent/CN109686817A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107195697A (en) * | 2017-06-01 | 2017-09-22 | 中南大学 | A kind of preparation method of copper barium (strontium/calcium) tin sulphur (selenium) film |
Non-Patent Citations (2)
| Title |
|---|
| DI CHEN: ""Microwave synthesis of AgBiS2 dendrites in aqueous solution"", 《INORGANIC CHEMISTRY COMMUNICATIONS》 * |
| ENING GU: ""Single molecular precursor ink for AgBiS2 thin films: synthesis and characterization"", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110911568A (en) * | 2019-12-03 | 2020-03-24 | 武汉大学 | Silver bismuth sulfide thin film photoelectric detector and preparation method thereof |
| CN113620342A (en) * | 2021-08-30 | 2021-11-09 | 浙江理工大学 | Shuttle-shaped silver bismuth disulfide nano material and preparation method thereof |
| CN113913794A (en) * | 2021-09-30 | 2022-01-11 | 武汉大学 | AgBiS2Film, preparation method and application thereof |
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