CN103915528A - Method for synthesizing copper-zinc-tin-sulfur-copper sulfide-copper-tin-sulfur thin film - Google Patents
Method for synthesizing copper-zinc-tin-sulfur-copper sulfide-copper-tin-sulfur thin film Download PDFInfo
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- CN103915528A CN103915528A CN201410124033.7A CN201410124033A CN103915528A CN 103915528 A CN103915528 A CN 103915528A CN 201410124033 A CN201410124033 A CN 201410124033A CN 103915528 A CN103915528 A CN 103915528A
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- -1 copper-zinc-tin-sulfur-copper sulfide-copper-tin-sulfur Chemical compound 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000010409 thin film Substances 0.000 title abstract description 4
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 239000000758 substrate Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001509 sodium citrate Substances 0.000 claims abstract description 19
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 19
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 19
- 239000011975 tartaric acid Substances 0.000 claims abstract description 19
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 19
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 19
- 235000019263 trisodium citrate Nutrition 0.000 claims abstract description 19
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 229910052786 argon Inorganic materials 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 15
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 14
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims abstract description 8
- 230000008021 deposition Effects 0.000 claims abstract description 8
- 238000004070 electrodeposition Methods 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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 3
- 238000010189 synthetic method Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 14
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 13
- 239000001119 stannous chloride Substances 0.000 claims description 13
- 235000011150 stannous chloride Nutrition 0.000 claims description 13
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 10
- 229960001763 zinc sulfate Drugs 0.000 claims description 10
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 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 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 abstract 2
- 150000001879 copper Chemical class 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 59
- 239000004332 silver Substances 0.000 description 14
- 229910052709 silver Inorganic materials 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 12
- 239000003518 caustics Substances 0.000 description 11
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- SEAVSGQBBULBCJ-UHFFFAOYSA-N [Sn]=S.[Cu] Chemical compound [Sn]=S.[Cu] SEAVSGQBBULBCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
- H01L31/1832—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising ternary compounds, e.g. Hg Cd Te
-
- 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
- H01L31/0324—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIVBVI or AIIBIVCVI chalcogenide compounds, e.g. Pb Sn Te
-
- 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 method for synthesizing a copper-zinc-tin-sulfur-copper sulfide-copper-tin-sulfur thin film. The method comprises the following steps that (1) an electrolyte is prepared, namely copper salt, zinc salt, tin salt, sodium thiosulfate, trisodium citrate and tartaric acid are respectively dissolved in water and then mixed, and after even mixture, a pH value is adjusted; (2) a substrate is cleaned, namely a metal Mo sheet serves as the substrate, the surface is wiped through a sodium hydroxide solution, rust on the surface is removed, ultrasonic cleaning is conducted in ethyl alcohol and deionized water in sequence, and oil stains on the surface are removed; (3) electrochemical deposition is conducted, namely the cleaned substrate is placed in the prepared electrolyte, the deposition voltage and time are set, deposition is started, the substrate is taken out after deposition is finished, the substrate is washed through a large amount of deionized water and ethyl alcohol and is dried; (4) a sample obtained through the step (3) is calcined in nitrogen or argon for an hour, so that the copper-zinc-tin-sulfur-copper sulfide-copper-tin-sulfur thin film is obtained. According to the method, cost is low, the process is simple, and the obtained sample is excellent in performance.
Description
Technical field
The present invention relates to a kind of synthetic method of film, relate in particular to the synthetic method of a kind of copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.
Background technology
The energy and environmental problem have caused people's concern in recent years, to efficiently, the research of solar absorptive material is cheaply also more and more.Copper-zinc-tin-sulfur material (CZTS is made in abbreviation) has lot of advantages, such as: the absorption coefficient of light exceedes 10
4cm
-1, band gap is approximately 1.5eV, copper, zinc, tin, element sulphur enrich at nature reserves, free from environmental pollution.The efficiency that at present it is applied to solar cell has reached 12%.For the preparation of copper-zinc-tin-sulfur film, conventionally use physical method, comprise coevaporation, magnetron sputtering etc., these method costs are too high, are not suitable for very much fairly large production.So, in recent decades, prepare copper-zinc-tin-sulfur film by chemical method and become the most important thing.Conventional chemical method has electrochemical process, continuous ionic layer absorption reaction, hydro thermal method etc.But the copper-zinc-tin-sulfur film that these methods are prepared all will be through over cure (having severe toxicity) in further crystallization.Wherein, electrochemical method is that cost is minimum comparatively speaking.For this quaternary sulfide of copper-zinc-tin-sulfur, prefabricated metal layer again vulcanization process is widely used.But this method not only needs sulfuration, also will carry out 2～3 times electrochemical deposition.
Consider for these, those skilled in the art wish to adopt that cost is low, process simple, the synthetic method of safety non-toxic.Meanwhile, explore the use field of an one-step electrochemistry legal system for polynary sulfide actively.
Summary of the invention
Because the above-mentioned defect of prior art, technical problem to be solved by this invention is to provide the synthetic copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film (Cu of an a kind of one-step electrochemistry
2znSnS
4-CuS-Cu
3snS
4) method.
For achieving the above object, the invention provides an one-step electrochemistry synthetic method of a kind of copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film, do not use surfactant in building-up process, synthesis step is as follows:
(1) preparation electrolyte: mantoquita, zinc salt, pink salt, sodium thiosulfate, trisodium citrate and tartaric acid are dissolved in water respectively, and then mix, mix rear adjusting pH value;
(2) clean substrate: metal M o sheet, as substrate, is used sodium hydroxide solution wipe surfaces, removes surperficial rusty stain, then in ethanol, deionized water, successively carries out ultrasonic cleaning, removes surperficial oil stain;
(3) electrochemical deposition: cleaned substrate is put into the electrolyte having prepared, set deposition voltage and time also to start, after deposition finishes, substrate is taken out, with a large amount of deionized waters and alcohol flushing and dry up;
(4) sample step (3) being obtained is calcined 1 hour in nitrogen or argon gas, obtains copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.
Preferably, in step (1), in mole, mantoquita: zinc salt: pink salt: sodium thiosulfate: trisodium citrate: tartaric acid=0.5～3:1:0.5～3:1～5:4～10:2～8; Wherein, when mantoquita: zinc salt: pink salt: sodium thiosulfate: trisodium citrate: when tartaric acid=2:3:2:3:20:10, the film performance of synthesized is better.
Preferably, the mantoquita in step (1) is copper sulphate, copper nitrate or copper chloride, and zinc salt is zinc sulfate, zinc nitrate or zinc chloride, and pink salt is stannous chloride or stannous sulfate.
Preferably, in step (1), regulating pH value scope is 2～7.
Preferably, in substrate cleaning process, being used for the naoh concentration of wiping substrate is 1～15 mol/L, and ultrasonic time is 5～30 minutes.The clean-up performance of substrate, has a great impact film forming.
Preferably, voltage used in electrochemical deposition process is-0.8V～-1.5V that sedimentation time is 15～60 minutes.Thickness and the quality of the voltage of deposition and time meeting appreciable impact film.
Preferably, calcination temperature range is 200～600 ℃.
The invention has the beneficial effects as follows:
(1) this preparation method is simple, and cost is very low, and safety non-toxic is applicable to suitability for industrialized production;
(2) use the method prepared copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film performance good;
(3) can be widely used in production and the photocatalysis field of semiconductive thin film.
Below with reference to accompanying drawing, the technique effect of design of the present invention, concrete structure and generation is described further, to understand fully object of the present invention, feature and effect.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film of making of embodiment 1;
Fig. 2 is 10000 times of electron scanning micrographs of the film that makes of embodiment 1;
Fig. 3 is 50000 times of electron scanning micrographs of the film that makes of embodiment 1;
Fig. 4 is 10000 times of electron scanning micrographs of the film that makes of embodiment 2;
Fig. 5 is 50000 times of electron scanning micrographs of the film that makes of embodiment 2;
Fig. 6 is the current-voltage curve of the film that makes of embodiment 1 and embodiment 2, and silver/silver chloride electrode is made reference electrode, platinized platinum (2x2cm
2) do electrode, the sodium sulphate of 0.2 mol/L does electrolyte, and test light intensity is 15mW cm
-2, sweep speed is 0.01V/s.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Under room temperature, prepare respectively 0.02 mol/L copper sulphate, 0.03 mol/L zinc sulfate, 0.02 mol/L stannous chloride, 0.02 mol/L sodium thiosulfate, 0.2 mol/L trisodium citrate and 0.1 mol/L aqueous tartaric acid solution, these solution equal-volumes are evenly mixed, and regulating pH is 5.With the strong caustic wiping Mo substrate of 15 mol/L, and in second alcohol and water, distinguish ultrasonic cleaning 30 minutes.Substrate is put in the electrolyte having stirred.Under constant voltage-1.05V (with respect to silver/silver chlorate) condition, deposit after 45 minutes, sample is taken out, with drying up after a large amount of deionized water rinsings.The film obtaining is 350 ℃ of calcining 1h in argon gas or nitrogen, and the sample obtaining is copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.By its called after film 1.
Embodiment 2
Under room temperature, prepare respectively 0.02 mol/L copper sulphate, 0.03 mol/L zinc sulfate, 0.02 mol/L stannous chloride, 0.03 mol/L sodium thiosulfate, 0.2 mol/L trisodium citrate and 0.1 mol/L aqueous tartaric acid solution, these solution equal-volumes are evenly mixed, and regulating pH is 5.With the strong caustic wiping Mo substrate of 15 mol/L, and in second alcohol and water, distinguish ultrasonic cleaning 30 minutes.Substrate is put in the electrolyte having stirred.Under constant voltage-1.05V (with respect to silver/silver chlorate) condition, deposit after 45 minutes, sample is taken out, with drying up after a large amount of deionized water rinsings.The film obtaining is 350 ℃ of calcining 1h in argon gas or nitrogen, and the sample obtaining is copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.By its called after film 2.
Fig. 1 is the X-ray diffractogram of the present embodiment synthetic copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.As can be seen from Figure 1: in this sample, have copper-zinc-tin-sulfur (CZTS), copper sulfide (CuS), copper tin sulphur (Cu simultaneously
3snS
4).In figure, the peak of substrate Mo is very strong, makes the peak of sulfide seem very weak.
Fig. 2, Fig. 3, Fig. 4, Fig. 5 are scanning electron microscopy (SEM) picture of copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film, respectively corresponding 10000x(film 1), 50000x(film 1), 10000x(film 2), 50000x(film 2).From Fig. 2, Fig. 3, Fig. 4, Fig. 5, can find out: copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film is to be formed by very little particle agglomeration, wherein the particle on film 1 surface tends to be gathered into larger spherical, and the particle on film 2 surfaces tends to be gathered into short chain shape.
Fig. 6 is the current-voltage curve of film 1 and film 2.Silver/silver chloride electrode is made reference electrode, platinized platinum (2x2cm
2) do electrode, the sodium sulphate of 0.2 mol/L does electrolyte, and test light intensity is 15mW cm
-2, sweep speed is 0.01V/s.As can be seen from the figure, the performance of film 2 is better than film 1, may be because this short chain structure has increased the specific area of film.
Embodiment 3
Under room temperature, prepare respectively 0.02 mol/L copper sulphate, 0.03 mol/L zinc sulfate, 0.02 mol/L stannous chloride, 0.03 mol/L sodium thiosulfate, 0.2 mol/L trisodium citrate and 0.1 mol/L aqueous tartaric acid solution, these solution equal-volumes are evenly mixed, and regulating pH is 7.With the strong caustic wiping Mo substrate of 15 mol/L, and in second alcohol and water, distinguish ultrasonic cleaning 20 minutes.Substrate is put in the electrolyte having stirred.Under constant voltage-1.5V (with respect to silver/silver chlorate) condition, deposit after 15 minutes, sample is taken out, with drying up after a large amount of deionized water rinsings.The film obtaining is 350 ℃ of calcining 1h in argon gas or nitrogen, and the sample obtaining is copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.
Embodiment 4
Under room temperature, prepare respectively 0.02 mol/L copper nitrate, 0.03 mol/L zinc nitrate, 0.02 mol/L stannous sulfate, 0.03 mol/L sodium thiosulfate, 0.2 mol/L trisodium citrate and 0.1 mol/L aqueous tartaric acid solution, these solution equal-volumes are evenly mixed, and regulating pH is 5.With the strong caustic wiping Mo substrate of 12 mol/L, and in second alcohol and water, distinguish ultrasonic cleaning 10 minutes.Substrate is put in the electrolyte having stirred.Under constant voltage-1.05V (with respect to silver/silver chlorate) condition, deposit after 25 minutes, sample is taken out, with drying up after a large amount of deionized water rinsings.The film obtaining is 350 ℃ of calcining 1h in argon gas or nitrogen, and the sample obtaining is copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.
Embodiment 5
Under room temperature, prepare respectively 0.02 mol/L copper chloride, 0.03 mol/L zinc chloride, 0.02 mol/L stannous chloride, 0.03 mol/L sodium thiosulfate, 0.2 mol/L trisodium citrate and 0.1 mol/L aqueous tartaric acid solution, these solution equal-volumes are evenly mixed, and regulating pH is 5.With the strong caustic wiping Mo substrate of 12 mol/L, and in second alcohol and water, distinguish ultrasonic cleaning 20 minutes.Substrate is put in the electrolyte having stirred.Under constant voltage-1.3V (with respect to silver/silver chlorate) condition, deposit after 45 minutes, sample is taken out, with drying up after a large amount of deionized water rinsings.The film obtaining is 350 ℃ of calcining 1h in argon gas or nitrogen, and the sample obtaining is copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.
Embodiment 6
Under room temperature, prepare respectively 0.02 mol/L copper sulphate, 0.03 mol/L zinc sulfate, 0.02 mol/L stannous chloride, 0.03 mol/L sodium thiosulfate, 0.2 mol/L trisodium citrate and 0.1 mol/L aqueous tartaric acid solution, these solution equal-volumes are evenly mixed, and regulating pH is 2.With the strong caustic wiping Mo substrate of 15 mol/L, and in second alcohol and water, distinguish ultrasonic cleaning 5 minutes.Substrate is put in the electrolyte having stirred.Under constant voltage-1.3V (with respect to silver/silver chlorate) condition, deposit after 35 minutes, sample is taken out, with drying up after a large amount of deionized water rinsings.The film obtaining is 350 ℃ of calcining 1h in argon gas or nitrogen, and the sample obtaining is copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.
Embodiment 7
Under room temperature, prepare respectively 0.02 mol/L copper nitrate, 0.03 mol/L zinc nitrate, 0.02 mol/L stannous chloride, 0.03 mol/L sodium thiosulfate, 0.2 mol/L trisodium citrate and 0.1 mol/L aqueous tartaric acid solution, these solution equal-volumes are evenly mixed, and regulating pH is 6.With the sodium hydroxide solution wiping Mo substrate of 8 mol/L, and in second alcohol and water, distinguish ultrasonic cleaning 30 minutes.Substrate is put in the electrolyte having stirred.Under constant voltage-1.5V (with respect to silver/silver chlorate) condition, deposit after 25 minutes, sample is taken out, with drying up after a large amount of deionized water rinsings.The film obtaining is 350 ℃ of calcining 1h in argon gas or nitrogen, and the sample obtaining is copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.
Embodiment 7
Under room temperature, prepare respectively 0.02 mol/L copper sulphate, 0.03 mol/L zinc sulfate, 0.02 mol/L stannous chloride, 0.03 mol/L sodium thiosulfate, 0.2 mol/L trisodium citrate and 0.1 mol/L aqueous tartaric acid solution, these solution equal-volumes are evenly mixed, and regulating pH is 5.With the strong caustic wiping Mo substrate of 12 mol/L, and in second alcohol and water, distinguish ultrasonic cleaning 30 minutes.Substrate is put in the electrolyte having stirred.Under constant voltage-0.8V (with respect to silver/silver chlorate) condition, deposit after 60 minutes, sample is taken out, with drying up after a large amount of deionized water rinsings.The film obtaining is 350 ℃ of calcining 1h in argon gas or nitrogen, and the sample obtaining is copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.
Embodiment 8
Under room temperature, prepare respectively 0.02 mol/L copper sulphate, 0.03 mol/L zinc sulfate, 0.02 mol/L stannous chloride, 0.03 mol/L sodium thiosulfate, 0.2 mol/L trisodium citrate and 0.1 mol/L aqueous tartaric acid solution, these solution equal-volumes are evenly mixed, and regulating pH is 5.With the strong caustic wiping Mo substrate of 15 mol/L, and in second alcohol and water, distinguish ultrasonic cleaning 30 minutes.Substrate is put in the electrolyte having stirred.Under constant voltage-0.8V (with respect to silver/silver chlorate) condition, deposit after 35 minutes, sample is taken out, with drying up after a large amount of deionized water rinsings.The film obtaining is 350 ℃ of calcining 1h in argon gas or nitrogen, and the sample obtaining is copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.
Embodiment 9
Under room temperature, prepare respectively 0.02 mol/L copper chloride, 0.03 mol/L zinc chloride, 0.02 mol/L stannous chloride, 0.03 mol/L sodium thiosulfate, 0.2 mol/L trisodium citrate and 0.1 mol/L aqueous tartaric acid solution, these solution equal-volumes are evenly mixed, and regulating pH is 5.With the strong caustic wiping Mo substrate of 15 mol/L, and in second alcohol and water, distinguish ultrasonic cleaning 20 minutes.Substrate is put in the electrolyte having stirred.Under constant voltage-1.3V (with respect to silver/silver chlorate) condition, deposit after 25 minutes, sample is taken out, with drying up after a large amount of deionized water rinsings.The film obtaining is 350 ℃ of calcining 1h in argon gas or nitrogen, and the sample obtaining is copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.
Embodiment 10
Under room temperature, prepare respectively 0.015 mol/L copper sulphate, 0.03 mol/L zinc sulfate, 0.015 mol/L stannous chloride, 0.03 mol/L sodium thiosulfate, 0.12 mol/L trisodium citrate and 0.06 mol/L aqueous tartaric acid solution, these solution equal-volumes are evenly mixed, and regulating pH is 5.With the strong caustic wiping Mo substrate of 15 mol/L, and in second alcohol and water, distinguish ultrasonic cleaning 30 minutes.Substrate is put in the electrolyte having stirred.Under constant voltage-1.05V (with respect to silver/silver chlorate) condition, deposit after 45 minutes, sample is taken out, with drying up after a large amount of deionized water rinsings.The film obtaining is 350 ℃ of calcining 1h in argon gas or nitrogen, and the sample obtaining is copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.
Embodiment 11
Under room temperature, prepare respectively 0.09 mol/L copper sulphate, 0.03 mol/L zinc sulfate, 0.09 mol/L stannous chloride, 0.15 mol/L sodium thiosulfate, 0.3 mol/L trisodium citrate and 0.24 mol/L aqueous tartaric acid solution, these solution equal-volumes are evenly mixed, and regulating pH is 6.With the strong caustic wiping Mo substrate of 12 mol/L, and in second alcohol and water, distinguish ultrasonic cleaning 30 minutes.Substrate is put in the electrolyte having stirred.Under constant voltage-1.05V (with respect to silver/silver chlorate) condition, deposit after 45 minutes, sample is taken out, with drying up after a large amount of deionized water rinsings.The film obtaining is 350 ℃ of calcining 1h in argon gas or nitrogen, and the sample obtaining is copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just can design according to the present invention make many modifications and variations without creative work.Therefore, all technical staff in the art, all should be in by the determined protection range of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. a synthetic method for copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film, is characterized in that, synthesis step is as follows:
(1) preparation electrolyte: mantoquita, zinc salt, pink salt, sodium thiosulfate, trisodium citrate and tartaric acid are dissolved in water respectively, and then mix, mix rear adjusting pH value;
(2) clean substrate: metal M o sheet, as substrate, is used sodium hydroxide solution wipe surfaces, removes surperficial rusty stain, then in ethanol, deionized water, successively carries out ultrasonic cleaning, removes surperficial oil stain;
(3) electrochemical deposition: cleaned substrate is put into the electrolyte having prepared, set deposition voltage and time also to start, after deposition finishes, substrate is taken out, with a large amount of deionized waters and alcohol flushing and dry up;
(4) sample step (3) being obtained is calcined 1 hour in nitrogen or argon gas, obtains copper-zinc-tin-sulfur-copper sulfide-copper tin sulphur film.
2. synthetic method as claimed in claim 1, is characterized in that, in described step (1), in mole, mantoquita: zinc salt: pink salt: sodium thiosulfate: trisodium citrate: tartaric acid=0.5～3:1:0.5～3:1～5:4～10:2～8.
3. synthetic method as claimed in claim 1, is characterized in that, in described step (1), in mole, mantoquita: zinc salt: pink salt: sodium thiosulfate: trisodium citrate: tartaric acid=2:3:2:3:20:10.
4. synthetic method as claimed in claim 1, is characterized in that, in described step (1), mantoquita is copper sulphate, copper nitrate or copper chloride.
5. synthetic method as claimed in claim 1, is characterized in that, in described step (1), zinc salt is zinc sulfate, zinc nitrate or zinc chloride.
6. synthetic method as claimed in claim 1, is characterized in that, in described step (1), pink salt is stannous chloride or stannous sulfate.
7. synthetic method as claimed in claim 1, is characterized in that, in described step (1), regulating pH value scope is 2～7.
8. the synthetic method as described in claim 1-6 any one, is characterized in that, the concentration of sodium hydroxide solution in described step (2) is 1～15 mol/L, and ultrasonic time is 5～30 minutes.
9. the synthetic method as described in claim 1-6 any one, is characterized in that, in the electrochemical deposition process in described step (3), voltage used is-0.8V～-1.5V, and sedimentation time is 15～60 minutes.
10. the synthetic method as described in claim 1-6 any one, is characterized in that, the calcination temperature range in described step (4) is 200～600 ℃.
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| Title |
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| B.S.PAWAR ET AL.: "《Effect of complexing agent on the properties of electrochemically deposited Cu2ZnSnS4 (CZTS) thin films》", 《APPLIED SURFACE SCIENCE》 * |
| S.M.PAWAR ET AL.: "《Fabrication of Cu2ZnSnS4 Thin Film Solar Cell Using Single Step Electrodeposition Method》", 《JAPANESE JOURNAL OF APPLIED PHYSICS》 * |
| S.M.PAWAR ET AL.: "《Single step electrosynthesis of Cu2ZnSnS4 (CZTS) thin films for solar cell application》", 《ELECTROCHIMICA ACTA》 * |
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| CN104409566A (en) * | 2014-11-06 | 2015-03-11 | 云南师范大学 | Two-electrode electrochemical preparation method of copper zinc tin sulfide thin film material |
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