CN103205154B - Method for preparing copper-zinc-tin-selenium ink - Google Patents
Method for preparing copper-zinc-tin-selenium ink Download PDFInfo
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- CN103205154B CN103205154B CN201310119083.1A CN201310119083A CN103205154B CN 103205154 B CN103205154 B CN 103205154B CN 201310119083 A CN201310119083 A CN 201310119083A CN 103205154 B CN103205154 B CN 103205154B
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- tin
- copper
- selenium
- ink
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- PCRGAMCZHDYVOL-UHFFFAOYSA-N copper selanylidenetin zinc Chemical compound [Cu].[Zn].[Sn]=[Se] PCRGAMCZHDYVOL-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000005096 rolling process Methods 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000001856 Ethyl cellulose Substances 0.000 claims description 15
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920001249 ethyl cellulose Polymers 0.000 claims description 15
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 229910052711 selenium Inorganic materials 0.000 claims description 11
- 239000011669 selenium Substances 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 claims description 8
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 claims description 8
- KBPGBEFNGHFRQN-UHFFFAOYSA-N bis(selanylidene)tin Chemical compound [Se]=[Sn]=[Se] KBPGBEFNGHFRQN-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 8
- 238000003801 milling Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007858 starting material Substances 0.000 claims description 8
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 6
- 238000000498 ball milling Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 25
- 238000010521 absorption reaction Methods 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 12
- 238000000151 deposition Methods 0.000 description 8
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 229920002689 polyvinyl acetate Polymers 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a method for preparing a copper-zinc-tin-selenium ink. The method comprises steps of: taking raw materials, rolling a wet ball mill in a planetary manner and centrifuging to obtain particles of 5-15 nanometers and 200-400 nanometers; adding 10% of the particles of 5-15 nanometers by weight into 90% of powder of 200-400 nanometers by weight so as to produce copper-zinc-tin-selenium particles; mixing all the components of an ink solvent according to weight contents; and mixing the copper-zinc-tin-selenium particles with the ink solvent, and carrying out ultrasound treatment on a mixture in an ultrasound basin for 5 minutes-1 hour so as to obtain the ink, wherein the weight percent of the copper-zinc-tin-selenium particles and the solvent is 40-80%. The large size nano particles are prepared through a top-down method, and the copper-zinc-tin-selenium ink is also prepared and used for producing copper-zinc-tin-selenium solar cells through a non-vacuum method; various mixtures can directly, mechanical and chemically react at low temperature through adopting a convention ball milling method, and chemical solvents are not needed; the method is green and environment-friendly; and the method adopts no chemical solutions, does not produce wastes, does not need expensive vacuum experiment and is economic and practical.
Description
Technical field
The present invention relates to technical field of solar batteries, relate in particular to a kind of method of preparing copper-zinc-tin-selenium ink.
Background technology
Copper-zinc-tin-selenium solar cell comprises glass film plates or the flexible stainless steel of one deck rigidity conventionally, contain molybdenum layer simultaneously, p-type copper-zinc-tin-selenium absorption layer, Cadmium Sulfide or zinc sulphide buffer layer, native oxide zinc, transparent conductive oxide Window layer (TCO) and Surface Contact layer.Copper-zinc-tin-selenium ink is the core of CZTS battery production.The manufacture method of copper-zinc-tin-selenium solar cell can be divided into vacuum method and antivacuum method substantially at present.Vacuum method mainly comprises that common vapour deposition method and sputter add rear selenization method.
Be total to vapour deposition method: in laboratory and commercial applications, be all a kind of common deposition method.Vapour deposition method is manufactured copper-zinc-tin-sulfur absorption layer with a plurality of evaporation sources altogether.Vapour deposition method can well be controlled processing parameter and regulate film to form structure and band gap altogether.Yet the uniformity coefficient of vapour deposition method still faces some problems when scale operation altogether.Meanwhile, how accurately controlling each evaporation source is also a great problem that common vapour deposition method need to solve.With respect to CIGS, in CZTS research, coevaporation is used seldom, and reason may be when temperature is spent higher than 400, easily forms SnS, causes tin loss.Because SnS when 550 spend evaporates again, cause CZTS to decompose.However, coevaporation can be produced high efficiency CIGS battery, remains the ideal chose of CZTS research.
Sputter and rear sulphur (selenium) are changed facture: be the technology that the research of current copper-zinc-tin-sulfur (selenium) absorption layer is in daily use.It comprises the technological processs such as sputter and sulphur (selenium) change.It is raw material that the method be take cupric sulfide or copper/zinc/tin target, the method for using cosputtering or sputter continuously by alloy deposition to amorphous thin film; Again film is carried out to sulphur (selenium) in the environment of sulphur (selenium) change hydrogen or sulphur (selenium) afterwards and change, finally form p-type absorption layer.Last sulphur (selenium) is changed step certain environment hidden danger, because sulphur (selenium) is changed hydrogen, has toxicity, and the method needs high temperature simultaneously, and this has also increased process costs.
Antivacuum method: comprise electrochemical filming method, method of spin coating etc.In vacuum and antivacuum all methods, the CZTS battery efficiency that American I BM company obtains by antivacuum rotating coating is the highest, reaches 11.1% at present.But owing to having adopted hypertoxic diamine, human body and environment are had to very large hazardness.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of this invention is to provide a kind of method of preparing copper-zinc-tin-selenium ink, make it have simple environmental protection, the advantages such as economic actual effect.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is as follows:
A method of preparing copper-zinc-tin-selenium ink, comprises the following steps:
(1) stoichiometric ratio Cu0.98Zn0.5Sn0.5Se2.5 gets starting material, comprises copper powder, zinc powder, glass putty, selenium powder, copper selenide, zinc selenide and Tin diselenide, is 325 powder materials;
(2) adopt planet rolling wet ball mill, ratio of grinding media to material is 3 ~ 8/1; Alcohol and powder ratio: 1 ~ 5/10; Milling time 10 ~ 30h; Rotational velocity 150 ~ 4500rpm; Revolution speed 400 ~ 750rpm, grinding pot and ball are zirconia ceramic ball;
(3) 2000 ~ 8000rpm centrifugation 30s ~ 10min, the particle of acquisition 5-15 nanometer and 200-400 nanometer; The particle of getting the 5-15 nanometer of 10% weight joins the powder of the 200-400 nanometer of 90% weight, makes copper-zinc-tin-selenium particle;
(4) get ink solvent weight content component: 50-65% toluene, 20-35% ethanol, 5-15% polyvinyl alcohol (PVA), 4-9% ethyl cellulose (EC), 3-10% Vinyl Acetate Copolymer (PVAc), 3-8% ethylene glycol (EG), mix;
(5) mixed copper zinc-tin granules of selenium and ink solvent, in ultrasonic wave basin, ultrasonic 5min ~ 1h, makes ink; The weight percent of copper-zinc-tin-selenium particle and solvent is 40 ~ 80%.
All in being full of the glove box of nitrogen, carry out in steps, to prevent powder oxidation.
The present invention adopts from the top down legal system for copper-zinc-tin-selenium ink, completely different from conventional method from bottom to top.Method in conventional chemosynthesis is prepared nano particle, and size, is dispersed in solvent with synthetic particle to 15 nanometers in 5 nanometers, makes copper-zinc-tin-selenium ink, with rotary coating or injection printing technique, obtains copper-zinc-tin-selenium absorption layer film.Because copper-zinc-tin-selenium nano-scale is too little, when sintering, be difficult to form macrobead size crystal boundary, therefore, the efficiency of prepared solar cell is very low, cannot realize the commercialization of copper-zinc-tin-selenium solar cell with the little nanometer particle ink of method from bottom to top.The efficiency of copper-zinc-tin-selenium solar cell industry is minimum at 12-14%.Because the structure of copper-zinc-tin-selenium is equal to the structure of copper-indium-galliun-selenium completely, the best approach that therefore will improve solar battery efficiency is to keep grain boundary size to be greater than 1 micron.On the other hand, the thickness of the absorption layer of copper-zinc-tin-selenium battery key is 1-1.5 micron, so, obtain the ink that 200-400 nano particle is prepared into, after sintering, be easy to obtain the absorption layer film of large size crystal boundary.Current technology is difficult to obtain large-sized nano particle like this by synthetic method.
Beneficial effect: compared with prior art, the present invention prepares macro nanometer particle with top-down methods, and prepare copper-zinc-tin-selenium ink, for the production of antivacuum method copper-zinc-tin-selenium solar cell.Tool has the following advantages:
(1) adopt traditional ball milling method can realize various mixtures direct mechanical chemistry chemical reaction at low temperatures, without chemical solvents.
(2) environmental protection.Do not need chemical solution, do not produce refuse, do not need expensive vacuum apparatus, economical and practical.
(3) and by the mechanical energy in rotation and revolution process, pulverizing, friction with a step such as should press to obtain copper-zinc-tin-selenium nano particle.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described.
Embodiment 1
By stoichiometric ratio, Cu0.98Zn0.5Sn0.5Se2.5 gets starting material: copper powder, zinc powder, glass putty, selenium powder, copper selenide, zinc selenide and Tin diselenide, be 325 powder materials.Adopt planet rolling wet ball mill, ratio of grinding media to material is 3:1; Alcohol and powder ratio: 1:10; Milling time 30h; Rotational velocity 4500rpm; Revolution speed 750rpm, grinding pot and ball are zirconia ceramic ball.2000rpm centrifugation 10min, the particle of acquisition 5 ~ 15 nanometers and 200 ~ 400 nanometers.Get ink solvent component (weight content): 50% toluene, 20% ethanol, 15% polyvinyl alcohol (PVA), 9% ethyl cellulose (EC), 3% Vinyl Acetate Copolymer (PVAc), 3% ethylene glycol (EG), mix; The particle of getting the 5-15 nanometer of 10% weight joins the powder of the 200-400 nanometer of 90% weight, makes copper-zinc-tin-selenium particle; Mixed copper zinc-tin granules of selenium and ink solvent, in ultrasonic wave basin, ultrasonic 5min, makes ink, and the weight percent of copper-zinc-tin-selenium particle and solvent is 40%.Above nano particle and ink preparation are all carried out in being full of the glove box of nitrogen, to prevent powder oxidation.
With the ink of preparation, prepare absorption layer film, in the absorption layer film of formation, impurity level is few, and film quality is good, and the efficiency of solar cell is high, environmentally friendly, does not form the pressure too large to environment.
Embodiment 2
By stoichiometric ratio, Cu0.98Zn0.5Sn0.5Se2.5 gets starting material: copper powder, zinc powder, glass putty, selenium powder, copper selenide, zinc selenide and Tin diselenide, be 325 powder materials.Adopt planet rolling wet ball mill, ratio of grinding media to material is 8:1; Alcohol is 1:2 with powder ratio; Milling time 10h; Rotational velocity 150rpm; Revolution speed 400rpm, grinding pot and ball are zirconia ceramic ball.8000rpm centrifugation 30s, the particle of acquisition 5-15 nanometer and 200-400 nanometer.Get ink solvent component (weight content): 65% toluene, 20% ethanol, 5% polyvinyl alcohol (PVA), 4% ethyl cellulose (EC), 3% Vinyl Acetate Copolymer (PVAc), 3% ethylene glycol (EG), mix; The particle of getting the 5-15 nanometer of 10% weight joins the powder of the 200-400 nanometer of 90% weight, makes copper-zinc-tin-selenium particle; Mixed copper zinc-tin granules of selenium and ink solvent, in ultrasonic wave basin, ultrasonic 1h, makes ink, and the weight percent of copper-zinc-tin-selenium particle and solvent is 80%.Above nano particle and ink preparation are all carried out in being full of the glove box of nitrogen, to prevent powder oxidation.
With the ink of preparation, prepare absorption layer film, in the absorption layer film of formation, impurity level is few, and film quality is good, and the efficiency of solar cell is high, environmentally friendly, does not form the pressure too large to environment.
Embodiment 3
By stoichiometric ratio, Cu0.98Zn0.5Sn0.5Se2.5 gets starting material: copper powder, zinc powder, glass putty, selenium powder, copper selenide, zinc selenide and Tin diselenide, be 325 powder materials.Adopt planet rolling wet ball mill, ratio of grinding media to material is 5:1; Alcohol is 3:10 with powder ratio; Milling time 20h; Rotational velocity 3000rpm; Revolution speed 600rpm, grinding pot and ball are zirconia ceramic ball.6000rpm centrifugation 5min, the particle of acquisition 5-15 nanometer and 200-400 nanometer.Get ink solvent component (weight content): 50% toluene, 35% ethanol, 5% polyvinyl alcohol (PVA), 4% ethyl cellulose (EC), 3% Vinyl Acetate Copolymer (PVAc), 3% ethylene glycol (EG), mix; The particle of getting the 5-15 nanometer of 10% weight joins the powder of the 200-400 nanometer of 90% weight, makes copper-zinc-tin-selenium particle; Mixed copper zinc-tin granules of selenium and ink solvent, in ultrasonic wave basin, ultrasonic 20min, makes ink, and the weight percent of copper-zinc-tin-selenium particle and solvent is 60%.Above nano particle and ink preparation are all carried out in being full of the glove box of nitrogen, to prevent powder oxidation.
With the ink of preparation, prepare absorption layer film, in the absorption layer film of formation, impurity level is few, and film quality is good, and the efficiency of solar cell is high, environmentally friendly, does not form the pressure too large to environment.
Embodiment 4
By stoichiometric ratio, Cu0.98Zn0.5Sn0.5Se2.5 gets starting material: copper powder, zinc powder, glass putty, selenium powder, copper selenide, zinc selenide and Tin diselenide, be 325 powder materials.Adopt planet rolling wet ball mill, ratio of grinding media to material is 6:1; Alcohol is 2:10 with powder ratio; Milling time 15h; Rotational velocity 2000rpm; Revolution speed 500rpm, grinding pot and ball are zirconia ceramic ball.4000rpm centrifugation 8min, the particle of acquisition 5-15 nanometer and 200-400 nanometer.Get ink solvent component (weight content): 52% toluene, 23% ethanol, 10% polyvinyl alcohol (PVA), 6% ethyl cellulose (EC), 5% Vinyl Acetate Copolymer (PVAc), 4% ethylene glycol (EG), mix; The particle of getting the 5-15 nanometer of 10% weight joins the powder of the 200-400 nanometer of 90% weight, makes copper-zinc-tin-selenium particle; Mixed copper zinc-tin granules of selenium and ink solvent, in ultrasonic wave basin, ultrasonic 30min, makes ink, and the weight percent of copper-zinc-tin-selenium particle and solvent is 70%.Above nano particle and ink preparation are all carried out in being full of the glove box of nitrogen, to prevent powder oxidation.
With the ink of preparation, prepare absorption layer film, in the absorption layer film of formation, impurity level is few, and film quality is good, and the efficiency of solar cell is high, environmentally friendly, does not form the pressure too large to environment.
Embodiment 5
By stoichiometric ratio, Cu0.98Zn0.5Sn0.5Se2.5 gets starting material: copper powder, zinc powder, glass putty, selenium powder, copper selenide, zinc selenide and Tin diselenide, be 325 powder materials.Adopt planet rolling wet ball mill, ratio of grinding media to material is 6:1; Alcohol is 2:10 with powder ratio; Milling time 15h; Rotational velocity 2000rpm; Revolution speed 500rpm, grinding pot and ball are zirconia ceramic ball.4000rpm centrifugation 8min, the particle of acquisition 5-15 nanometer and 200-400 nanometer.Get ink solvent component (weight content): 51% toluene, 22% ethanol, 8% polyvinyl alcohol (PVA), 5% ethyl cellulose (EC), 6% Vinyl Acetate Copolymer (PVAc), 8% ethylene glycol (EG), mix; The particle of getting the 5-15 nanometer of 10% weight joins the powder of the 200-400 nanometer of 90% weight, makes copper-zinc-tin-selenium particle; Mixed copper zinc-tin granules of selenium and ink solvent, in ultrasonic wave basin, ultrasonic 30min, makes ink, and the weight percent of copper-zinc-tin-selenium particle and solvent is 70%.Above nano particle and ink preparation are all carried out in being full of the glove box of nitrogen, to prevent powder oxidation.
With the ink of preparation, prepare absorption layer film, in the absorption layer film of formation, impurity level is few, and film quality is good, and the efficiency of solar cell is high, environmentally friendly, does not form the pressure too large to environment.
Embodiment 6
By stoichiometric ratio, Cu0.98Zn0.5Sn0.5Se2.5 gets starting material: copper powder, zinc powder, glass putty, selenium powder, copper selenide, zinc selenide and Tin diselenide, be 325 powder materials.Adopt planet rolling wet ball mill, ratio of grinding media to material is 6:1; Alcohol is 2:10 with powder ratio; Milling time 15h; Rotational velocity 2000rpm; Revolution speed 500rpm, grinding pot and ball are zirconia ceramic ball.4000rpm centrifugation 8min, the particle of acquisition 5-15 nanometer and 200-400 nanometer.Get ink solvent component (weight content): 53% toluene, 21% ethanol, 6% polyvinyl alcohol (PVA), 5% ethyl cellulose (EC), 10% Vinyl Acetate Copolymer (PVAc), 5% ethylene glycol (EG), mix; The particle of getting the 5-15 nanometer of 10% weight joins the powder of the 200-400 nanometer of 90% weight, makes copper-zinc-tin-selenium particle; Mixed copper zinc-tin granules of selenium and ink solvent, in ultrasonic wave basin, ultrasonic 30min, makes ink, and the weight percent of copper-zinc-tin-selenium particle and solvent is 70%.Above nano particle and ink preparation are all carried out in being full of the glove box of nitrogen, to prevent powder oxidation.
With the ink of preparation, prepare absorption layer film, in the absorption layer film of formation, impurity level is few, and film quality is good, and the efficiency of solar cell is high, environmentally friendly, does not form the pressure too large to environment.
The present invention adopts from the top down legal system for copper-zinc-tin-selenium ink, completely different from conventional method from bottom to top.Method in conventional chemosynthesis is prepared nano particle, and size, is dispersed in solvent with synthetic particle to 15 nanometers in 5 nanometers, makes copper-zinc-tin-selenium ink, with rotary coating or injection printing technique, obtains copper-zinc-tin-selenium absorption layer film.Because copper-zinc-tin-selenium nano-scale is too little, when sintering, be difficult to form macrobead size crystal boundary, therefore, the efficiency of prepared solar cell is very low, cannot realize the commercialization of copper-zinc-tin-selenium solar cell with the little nanometer particle ink of method from bottom to top.The efficiency of copper-zinc-tin-selenium solar cell industry is minimum at 12-14%.Because the structure of copper-zinc-tin-selenium is equal to the structure of copper-indium-galliun-selenium completely, the best approach that therefore will improve solar battery efficiency is to keep grain boundary size to be greater than 1 micron.On the other hand, the thickness of the absorption layer of copper-zinc-tin-selenium battery key is 1-1.5 micron, so, obtain the ink that 200-400 nano particle is prepared into, after sintering, be easy to obtain the absorption layer film of large size crystal boundary.Current technology is difficult to obtain large-sized nano particle like this by synthetic method.Just because of this, the present invention prepares macro nanometer particle with top-down methods, and prepares copper-zinc-tin-selenium ink, for the production of antivacuum method copper-zinc-tin-selenium solar cell.A novel point of the present invention is to adopt traditional ball milling method can realize various mixtures direct mechanical chemistry chemical reaction at low temperatures, without chemical solvents.Another novel point is, environmental protection.Do not need chemical solution, do not produce refuse, do not need expensive vacuum apparatus, economical and practical.And by the mechanical energy in rotation and revolution process, pulverizing, friction with a step such as should press to obtain copper-zinc-tin-selenium nano particle.
Claims (2)
1. a method of preparing copper-zinc-tin-selenium ink, is characterized in that, comprises the following steps:
(1) stoichiometric ratio Cu0.98Zn0.5Sn0.5Se2.5 gets starting material, comprises copper powder, zinc powder, glass putty, selenium powder, copper selenide, zinc selenide and Tin diselenide, is 325 powder materials;
(2) adopt planet rolling wet ball mill, ratio of grinding media to material is 3～8/1; Alcohol and powder ratio: 1～5/10; Milling time 10～30h; Rotational velocity 150～4500rpm; Revolution speed 400～750rpm, grinding pot and ball are zirconia ceramic material;
(3) 2000～8000rpm centrifugation 30s～10min, the particle of acquisition 5-15 nanometer and 200-400 nanometer; The particle of getting the 5-15 nanometer of 10% weight joins the powder of the 200-400 nanometer of 90% weight, makes copper-zinc-tin-selenium particle;
(4) get ink solvent weight content component: 50-65% toluene, 20-35% ethanol, 5-15% polyvinyl alcohol, 4-9% ethyl cellulose, 3-10% Vinyl Acetate Copolymer, 3-8% ethylene glycol, mix;
(5) mixed copper zinc-tin granules of selenium and ink solvent, in ultrasonic wave basin, ultrasonic 5min～1h, makes ink; The weight percent of copper-zinc-tin-selenium particle and solvent is 40～80%.
2. the method for preparing copper-zinc-tin-selenium ink according to claim 1, is characterized in that: all in being full of the glove box of nitrogen, carry out in steps, preventing powder oxidation.
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| CN102642818A (en) * | 2012-05-03 | 2012-08-22 | 桂林理工大学 | Method for preparing CZTS (Copper Zinc Tin Sulfide) (Se) series nanometer powder by low-temperature mechanical alloying |
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| CN102642818A (en) * | 2012-05-03 | 2012-08-22 | 桂林理工大学 | Method for preparing CZTS (Copper Zinc Tin Sulfide) (Se) series nanometer powder by low-temperature mechanical alloying |
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