CN105226131B - A kind of chemical synthesis process of copper zinc tin sulfur absorption layer film - Google Patents
A kind of chemical synthesis process of copper zinc tin sulfur absorption layer film Download PDFInfo
- Publication number
- CN105226131B CN105226131B CN201510521601.1A CN201510521601A CN105226131B CN 105226131 B CN105226131 B CN 105226131B CN 201510521601 A CN201510521601 A CN 201510521601A CN 105226131 B CN105226131 B CN 105226131B
- Authority
- CN
- China
- Prior art keywords
- znsns
- source
- film
- copper
- nanocrystalline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 11
- 239000010408 film Substances 0.000 claims abstract description 42
- 239000010949 copper Substances 0.000 claims abstract description 32
- 239000010409 thin film Substances 0.000 claims abstract description 32
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 11
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005864 Sulphur Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000007650 screen-printing Methods 0.000 claims abstract description 7
- 238000005119 centrifugation Methods 0.000 claims abstract description 6
- 238000009766 low-temperature sintering Methods 0.000 claims abstract description 4
- 238000012545 processing Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 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 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 238000002525 ultrasonication Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000004886 process control Methods 0.000 abstract description 3
- 238000012827 research and development Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process 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
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- -1 hydrazine amine Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 239000002699 waste material 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials For Photolithography (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a kind of chemical synthesis process of copper zinc tin sulfur absorption layer film, including：（S10）Copper source, zinc source, tin source and sulphur source are prepared into Cu using hydro-thermal method2ZnSnS4It is nanocrystalline；（S20）To the Cu of preparation2ZnSnS4Nanocrystalline progress centrifugation purification processes；（S30）By the Cu after purification2ZnSnS4Nanocrystalline to be dispersed in organic solvent, performed thin film is made in low-temperature sintering after silk-screen printing film forming；（S40）To step（S30）The performed thin film of acquisition carries out after cure processing, obtains Cu2ZnSnS4Absorb layer film.Cu prepared by the present invention2ZnSnS4Absorbed layer thin film composition is uniform, and impurity is less, it is adaptable to thin-film solar cells, is used as Cu2ZnSnS4The absorbed layer of thin-film solar cells, can effectively improve the electro-optical properties of battery, and this method is simple to operate, device simple, process control, it is adaptable to Cu2ZnSnS4The research and development of thin-film solar cells and middle-size and small-size production.
Description
Technical field
The present invention relates to solar cell device preparing technical field, specifically, refer to a kind of copper-zinc-tin-sulfur and inhale
Receive the chemical synthesis process of layer film.
Background technology
CIGS（CuInxGa1-xSe2）Thin-film solar cells has that high conversion efficiency, long-time stability are good, radioresistance
Ability is strong, laboratory photoelectric transformation efficiency more than 20% the advantages of, it is considered to be thin film solar cell most with prospects it
One.However, CuInxGa1-xSe2In, Ga, Se in absorbed layer are rare element and have certain toxicity, are seriously constrained
CuInxGa1-xSe2The industrialized development of hull cell.It is all the semiconducting compound copper-zinc-tin-sulfur of yellow copper structure
（Cu2ZnSnS4）It is considered as that most possible turn into replaces CuInxGa1-xSe2The material of absorbed layer.Cu2ZnSnS4It is that p-type is partly led
Body, optical band gap 1.5eV, the absorption coefficient of light is up to 104cm-1, it is suitable as the absorbed layer of thin-film solar cells.With In, Ga,
Se is compared, and Zn, Sn and S rich reserves, cheap, toxicity is low and environmental protection.
Typical Cu2ZnSnS4The structure and CuIn of thin-film solar cellsxGa1-xSe2It is similar, sequentially consist of lining
The multi-layer film structure of bottom/back electrode/absorbed layer/cushion/Window layer/Top electrode.Wherein Cu2ZnSnS4The performance of absorbed layer is straight
The performance for being related to thin film solar cell is connect, the composition proportion and filming performance of absorbed layer are to influence the photoelectric transformation efficiency of battery
Key factor.
At present, Cu2ZnSnS4The preparation method of absorbed layer is mainly divided to two major classes：The first kind is Physical, with sputtering method and steaming
Based on hair method, such method film forming compact structure, crystal property is excellent, but is due to that plated film whole process is carried out under a high vacuum, plates
Film cost is high, and Composition Control is not accurate, film forming lack of homogeneity.Equations of The Second Kind is chemical method, mainly including electrochemical process, collosol and gel
Method, hydro-thermal method etc., respectively there is its advantage and disadvantage.The film direction of growth prepared by electrochemical process is controllable, but its film forming speed efficiency is low, into
Divide controlling poor, and the waste liquid environmental pollution produced in film forming procedure；Sol-gal process is easy to implement and composition is controllable, but its
Impurity is more, and film forming crystalline quality is poor, and efficiency is low；Hydro-thermal method, is also hydrazine amine method, the Cu of preparation2ZnSnS4Absorbed layer battery efficiency
Height, but react and need to carry out under high pressure, and thin film composition is uncontrollable.
The content of the invention
To overcome the above mentioned problem that prior art is present, the present invention provides a kind of simple to operate, device simple and process can
The chemical synthesis process of the copper zinc tin sulfur absorption layer film of control.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of chemical synthesis process of copper zinc tin sulfur absorption layer film, comprises the following steps：
（S10）Copper source, zinc source, tin source and sulphur source are prepared into Cu using hydro-thermal method2ZnSnS4It is nanocrystalline；
（S20）To the Cu of preparation2ZnSnS4Nanocrystalline progress centrifugation purification processes；
（S30）By the Cu after purification2ZnSnS4It is nanocrystalline to be dispersed in organic solvent, low temperature after silk-screen printing film forming
Sintering, is made performed thin film；
（S40）To step（S30）The performed thin film of acquisition carries out after cure processing, obtains Cu2ZnSnS4Absorb layer film.
Specifically, the step（S10）Middle hydro-thermal method prepares Cu2ZnSnS4It is nanocrystalline to comprise the following steps：
（S11）Selection copper, zinc, the sulfate of tin, nitrate or chloride are used as copper source, zinc source and tin source, thiocarbamide conduct
Sulphur source, example is 2 in molar ratio:1:1:It is molten using mixture as solute after 4 selection copper sources, zinc source, tin source and sulphur source are well mixed
Mixed solution is configured in specific solvent, the wherein mass ratio of specific solvent and solute is 10 ± 0.5:1；
（S12）Ultrasonic disperse and ultrasonication are carried out to mixed solution obtained above, until solute be dissolved completely in it is molten
In agent；
（S13）By step（S12）Obtained solution, which is transferred in water heating kettle, carries out hydro-thermal reaction, and Cu is made2ZnSnS4Nanometer
It is brilliant.
Wherein, the step（S11）Middle specific solvent is ethanol, ethylene glycol, oleyl amine, acetonitrile, thioacetamide, dodecane
One or both of base mercaptan.
Also, the step（S13）The filling rate of middle hydro-thermal reaction is 50 ~ 90%, and heating-up temperature is 374 ~ 628 DEG C, reaction
Time is 1 ~ 42h.
Further, the step（S30）Middle organic solvent is ethanol, ethylene glycol, the tert-butyl alcohol, oleyl amine, acetonitrile, thio second
One kind in acid amides, lauryl mercaptan.
Preferably, the step（S30）The substrate of middle silk-screen printing is in glass, pi film, stainless steel
It is a kind of.
Further, the step（S30）The temperature of low temperature sintering is 100 ~ 250 DEG C, and sintering time is 2 ~ 10min,
Repeat 1 ~ 10 time.
Further, the step（S30）In obtained performed thin film thickness be 0.1 ~ 50 μm.
More specifically, the step（S40）The step of middle after cure is handled is as follows：
（S41）The substrate of performed thin film will be deposited in H2450 ~ 600 DEG C are heated under S atmosphere, and is incubated 0.5 ~ 3h；
（S42）200 ~ 300 DEG C of substrate is cooled to 10 ~ 30 DEG C/min speed, stopping is passed through H2S gas；
（S43）Stop heating, taken out after substrate is cooled to room temperature, that is, obtain Cu2ZnSnS4Absorb layer film.
Compared with prior art, the invention has the advantages that：
The present invention is improved integration based on existing absorbed layer method for manufacturing thin film, and Cu is prepared using hydro-thermal method2ZnSnS4
Centrifugation purification is carried out after nanocrystalline to it, the Cu of high-purity is obtained2ZnSnS4, then it is dissolved in again in organic solvent, utilizes rotation
Coating deposits Cu2ZnSnS4Performed thin film, so incorporates advantage, improves shortcoming, significantly reduces miscellaneous in performed thin film
Matter content, eliminating part influences larger secondary phase to be mingled with film performance, improves the clean quality of performed thin film, finally
The organic matter removed in performed thin film is handled by after cure, crystal grain recrystallization is promoted while vulcanizing, reduces and lacks inside film
Fall into, so as to reach the purpose for improving performed thin film performance, obtain that composition is uniform and absorption layer film of excellent performance, and this hair
It is bright to be skillfully constructed, simple to operate, device simple, with low cost, process control, it is adaptable to Cu2ZnSnS4Thin-film solar cells
Research and development and middle-size and small-size production, are with a wide range of applications, and are adapted to popularization and application.
Embodiment
With reference to embodiment, the invention will be further described, and embodiments of the present invention include but is not limited to following reality
Apply example.
Embodiment
The chemical synthesis process of the copper zinc tin sulfur absorption layer film, comprises the following steps：
（S10）Copper source, zinc source, tin source and sulphur source are prepared into Cu using hydro-thermal method2ZnSnS4It is nanocrystalline：
（S11）0.2mol CuCl are taken respectively2•2H2O、0.1mol ZnCl2、0.1mol SnCl2•2H2O and 0.4mol CS
(NH2)2, after uniform mixing, it is dissolved in 50mL ethylene glycol solvents；
（S12）Ultrasonic disperse and ultrasonication are carried out to above-mentioned mixed solution, until solute is completely dissolved in a solvent；
（S13）40mL mixed solutions obtained above are taken, are transferred in 50mL water heating kettle, 570 DEG C of hydro-thermal reaction 12h,
Cu is made2ZnSnS4It is nanocrystalline；
（S20）To the Cu of preparation2ZnSnS4Nanocrystalline progress centrifugation purification processes：In to above-mentioned hydro-thermal reaction product respectively
Deionized water and ethanol are added, by centrifuging the organic impurities in purification removal product；
（S30）By the high-purity C u after purification2ZnSnS4It is nanocrystalline to be dissolved in 10mL lauryl mercaptan organic solvents,
Ultrasonic disperse is completely dissolved its particle；Then by solution silk-screen printing film forming on a glass substrate, 150 DEG C of low-temperature sinterings
3min, and silk-screen printing and sintering process 2 times are repeated, the Cu that thickness is 1 μm is made2ZnSnS4Performed thin film；
（S40）To step（S30）The performed thin film of acquisition carries out after cure processing, obtains Cu2ZnSnS4Absorb layer film：
（S41）The substrate of performed thin film will be deposited in H2520 DEG C are heated under S atmosphere, and is incubated 1h；
（S42）200 DEG C of substrate is cooled to 10 ~ 15 DEG C/min speed, stopping is passed through H2S gas；
（S43）Stop heating, taken out after substrate is cooled to room temperature, obtained Cu2ZnSnS4Film, is the present invention's
Copper zinc tin sulfur absorption layer film.
By above-mentioned setting, the present invention combines hydro-thermal method and sol-gal process prepares the advantage of copper-zinc-tin-sulfur film,
Cu is prepared using hydro-thermal method2ZnSnS4Centrifugation purification is carried out after nanocrystalline to it, the Cu of high-purity is obtained2ZnSnS4It is nanocrystalline, so
It is dissolved in again in organic solvent afterwards, Cu is deposited using spin-coating method2ZnSnS4Performed thin film, is handled finally by after cure, is obtained
Cu2ZnSnS4Absorb layer film.This method effectively reduces the impurity content absorbed in layer film, reduces film internal flaw, carries
High film performance, and its simple to operate, device simple, process control, it is adaptable to Cu2ZnSnS4Thin-film solar cells is ground
Hair and middle-size and small-size production.
In addition, it is necessary to explanation, experiment proves that, the step（S11）The ethylene glycol solvent of middle use also can use second
One or both of alcohol, ethylene glycol, oleyl amine, acetonitrile, thioacetamide, lauryl mercaptan are replaced；The step（S13）In
In the condition of hydro-thermal reaction, filling rate be 50 ~ 90%, heating-up temperature be 374 ~ 628 DEG C, the reaction time be that 1 ~ 42h can meet system
It is standby to require；The step（S30）The organic solvent lauryl mercaptan of middle use also can use ethanol, ethylene glycol, the tert-butyl alcohol, oil
Amine, acetonitrile, thioacetamide are replaced, and the glass substrate of use also can use pi film or stainless steel material to replace, sintering
Sintering temperature is 100 ~ 250 DEG C in condition, and sintering time is 2 ~ 10min, and preparation requirement can be met by repeating 1 ~ 10 time, and it is made
Cu2ZnSnS4Film thickness also disclosure satisfy that use requirement between 0.1 ~ 50 μm；The step（S41）Middle heating target
Temperature is 450 ~ 600 DEG C, 0.5 ~ 3h of soaking time, cooling rate are that 10 ~ 30 DEG C/min, cooling target temperature are 200 ~ 300 DEG C
It disclosure satisfy that preparation is required.Only it is that corresponding conditionses change, just not to each condition in the present invention because its preparation method is identical
Preparation process is repeated, and is described collectively herein.
Above-described embodiment is only the preferred embodiments of the present invention, not limiting the scope of the invention, as long as using
The design principle of the present invention, and the change for carrying out non-creativeness work on this basis and making, all should belong to the present invention's
Within protection domain.
Claims (4)
1. a kind of chemical synthesis process of copper zinc tin sulfur absorption layer film, it is characterised in that comprise the following steps：
（S10）Copper source, zinc source, tin source and sulphur source are prepared into Cu using hydro-thermal method2ZnSnS4It is nanocrystalline：
（S11）Copper, zinc, the sulfate of tin, nitrate or chloride are selected as copper source, zinc source and tin source, thiocarbamide as sulphur source,
Example is 2 in molar ratio:1:1:After 4 selection copper sources, zinc source, tin source and sulphur source are well mixed, spy is dissolved in using mixture as solute
Determine to be configured to mixed solution in solvent, wherein the mass ratio of specific solvent and solute is 10 ± 0.5:1；
（S12）Ultrasonic disperse and ultrasonication are carried out to mixed solution obtained above, until solute is completely dissolved in a solvent；
（S13）By step（S12）Obtained solution, which is transferred in water heating kettle, carries out hydro-thermal reaction, and its filling rate is 50 ~ 90%, plus
Hot temperature is 374 ~ 628 DEG C, and the reaction time is 1 ~ 42h, and Cu is made2ZnSnS4It is nanocrystalline；
（S20）To the Cu of preparation2ZnSnS4Nanocrystalline progress centrifugation purification processes；
（S30）By the Cu after purification2ZnSnS4It is nanocrystalline to be dispersed in organic solvent, low-temperature sintering after silk-screen printing film forming,
Performed thin film is made；Wherein, low sintering temperature is 100 ~ 250 DEG C, and sintering time is 2 ~ 10min, is repeated 1 ~ 10 time, is made
Performed thin film thickness be 0.1 ~ 50 μm；
（S40）To step（S30）The performed thin film of acquisition carries out after cure processing：
（S41）The substrate of performed thin film will be deposited in H2450 ~ 600 DEG C are heated under S atmosphere, and is incubated 0.5 ~ 3h；
（S42）200 ~ 300 DEG C of substrate is cooled to 10 ~ 30 DEG C/min speed, stopping is passed through H2S gas；
（S43）Stop heating, taken out after substrate is cooled to room temperature, obtain Cu2ZnSnS4Absorb layer film.
2. the chemical synthesis process of a kind of copper zinc tin sulfur absorption layer film according to claim 1, it is characterised in that described
Step（S11）Middle specific solvent be ethanol, ethylene glycol, oleyl amine, acetonitrile, thioacetamide, lauryl mercaptan in one kind or
Two kinds.
3. the chemical synthesis process of a kind of copper zinc tin sulfur absorption layer film according to claim 1, it is characterised in that described
Step（S30）Middle organic solvent is in ethanol, ethylene glycol, the tert-butyl alcohol, oleyl amine, acetonitrile, thioacetamide, lauryl mercaptan
It is a kind of.
4. the chemical synthesis process of a kind of copper zinc tin sulfur absorption layer film according to claim 3, it is characterised in that described
Step（S30）The substrate of middle silk-screen printing is one kind in glass, pi film, stainless steel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510521601.1A CN105226131B (en) | 2015-08-24 | 2015-08-24 | A kind of chemical synthesis process of copper zinc tin sulfur absorption layer film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510521601.1A CN105226131B (en) | 2015-08-24 | 2015-08-24 | A kind of chemical synthesis process of copper zinc tin sulfur absorption layer film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105226131A CN105226131A (en) | 2016-01-06 |
| CN105226131B true CN105226131B (en) | 2017-09-29 |
Family
ID=54994965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510521601.1A Expired - Fee Related CN105226131B (en) | 2015-08-24 | 2015-08-24 | A kind of chemical synthesis process of copper zinc tin sulfur absorption layer film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105226131B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181847A (en) * | 2011-04-14 | 2011-09-14 | 山东大学 | Method for depositing Cu-Zn-Tin-Sulfur film by ethanol heat |
| CN102201498A (en) * | 2011-05-18 | 2011-09-28 | 东华大学 | Method for preparing Cu2ZnSnS4 nanocrystalline thin-film solar cell |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792175B (en) * | 2010-03-11 | 2012-10-10 | 山东大学 | Cu-Sn-Zn-S semiconductor material with adjustable forbidden band width and preparation method thereof |
| CN101844797B (en) * | 2010-05-14 | 2011-12-14 | 东华大学 | Method for preparing solar energy absorbing layer material Cu2ZnSnS4 by hydrothermal synthesis |
| CN102107905B (en) * | 2011-01-12 | 2012-08-29 | 东华大学 | Method for preparing Cu2ZnSnS4 solar battery material |
| CN102254985B (en) * | 2011-04-14 | 2013-05-08 | 山东大学 | Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material |
| CN102583510A (en) * | 2012-03-05 | 2012-07-18 | 南京航空航天大学 | Microwave-synthesis method for preparation of copper-zinc-tin-sulphur (CZTS) nanoparticles |
| CN102689920A (en) * | 2012-06-20 | 2012-09-26 | 上海大学 | Method for producing copper-tin-zinc-sulfur (CTZS) materials through solvent-thermal synthesis |
| CN102931286B (en) * | 2012-11-11 | 2015-09-30 | 河南大学 | A kind of method preparing absorbing layer of copper-zinc-tin-sulfur film solar cell |
| KR101716367B1 (en) * | 2013-03-15 | 2017-03-14 | 나노코 테크놀로지스 리미티드 | Cu2ZnSnS4 Nanoparticles |
| CN103337551B (en) * | 2013-05-28 | 2015-12-23 | 湘潭大学 | A kind of antivacuum preparation method of not carbon-containing bed CZTS or CZTSe film |
| CN103408065B (en) * | 2013-05-28 | 2016-01-20 | 北京工业大学 | A kind of superfine nano-crystalline Cu 2znSnS 4preparation method |
| CN103482687B (en) * | 2013-09-27 | 2015-06-17 | 电子科技大学 | Preparation method for CZTS nano-particle material |
| CN103943721A (en) * | 2014-03-27 | 2014-07-23 | 上海交通大学 | Copper-zinc-tin-sulfur (CZTS) thin film and preparation method and purposes thereof |
| CN104264211B (en) * | 2014-08-27 | 2017-01-18 | 南京航空航天大学 | High temperature solvent thermal preparation method and applications of monocrystalline submicron Cu2ZnSnS4 particle |
-
2015
- 2015-08-24 CN CN201510521601.1A patent/CN105226131B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181847A (en) * | 2011-04-14 | 2011-09-14 | 山东大学 | Method for depositing Cu-Zn-Tin-Sulfur film by ethanol heat |
| CN102201498A (en) * | 2011-05-18 | 2011-09-28 | 东华大学 | Method for preparing Cu2ZnSnS4 nanocrystalline thin-film solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105226131A (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107195697B (en) | A kind of preparation method of copper barium (strontium/calcium) tin sulphur (selenium) film | |
| CN105932114A (en) | Method for preparing solar cell absorbing layer film based on water bath and post-selenization | |
| CN110194718B (en) | Preparation method of highly stable lead-based organic-inorganic hybrid perovskite nanosheet | |
| CN103426971A (en) | Sol-gel preparation method of copper-zinc-tin-sulfur solar cell film | |
| CN110010769B (en) | Preparation method of oriented growth organic-inorganic hybrid perovskite film | |
| CN104795456A (en) | Electro-deposition method for preparing three band gap Fe-doped with copper gallium sulfur solar cell materials | |
| CN108807145A (en) | A method of preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell | |
| CN101982567A (en) | Preparation method of copper indium selenium sulphur (CuInSe2-xSx) film for solar battery | |
| CN108190942A (en) | A kind of nanocrystalline preparation method of the controllable copper silver-colored zinc tin sulphur of crystalline phase | |
| CN106505114A (en) | A kind of preparation method of copper and tin sulfur light absorbing zone thin-film material | |
| CN103318851A (en) | Copper-indium-gallium-sulfur-selenium solar cell, film absorbing layer and preparation method thereof | |
| CN102181893A (en) | Method for preparing indium-enriched CuInSe2 membrane by adjusting pH value and electrodepositing | |
| CN106531845B (en) | Chemical bath prepares solar battery obsorbing layer CuInS2The method of film | |
| CN105428539A (en) | Preparation method for perovskite solar cell absorption layer capable of improving photoelectric properties through controlling annealing pressure intensity atmosphere | |
| CN110808335B (en) | Preparation method and application of tin-lead binary perovskite film with preferred orientation growth | |
| CN105226131B (en) | A kind of chemical synthesis process of copper zinc tin sulfur absorption layer film | |
| CN108550642A (en) | A kind of preparation method of copper-zinc-tin-sulfur film | |
| Tian et al. | Stabilizing black-phase CsPbI 3 under over 70% humidity | |
| CN107134507A (en) | Preparation method with gradient components solar battery obsorbing layer copper and indium sulfur-selenium thin film | |
| CN108231925B (en) | A kind of preparation method of efficient CIS/CIGS solar battery | |
| CN103390692B (en) | A kind of method preparing copper indium tellurium thin films | |
| CN103924272B (en) | A kind of preparation method of solar cell predecessor Mo/Cu/Sn/Zn multilayer film | |
| CN103400894A (en) | Method for preparing zinc sulfide optoelectronic film | |
| CN106340545B (en) | The application of the preparation and novel solvent of CIS and CIGS thin film solar cell light-absorption layer wherein | |
| CN109671787A (en) | A kind of CuInGaSe absorbed layer of no selenidation process antivacuum method preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 610000 Sichuan Province, Chengdu Shuangliu the Milky Way Road No. 596 Applicant after: Inst. of Materials, Chinese Academy of Engineering Physics Address before: 621700 Jiangyou, Sichuan Huafeng village, No. 9, No. Applicant before: Inst. of Materials, Chinese Academy of Engineering Physics |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170929 Termination date: 20190824 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |