CN105226131A - 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
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- CN105226131A CN105226131A CN201510521601.1A CN201510521601A CN105226131A CN 105226131 A CN105226131 A CN 105226131A CN 201510521601 A CN201510521601 A CN 201510521601A CN 105226131 A CN105226131 A CN 105226131A
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 49
- 239000010408 film Substances 0.000 claims abstract description 47
- 239000010409 thin film Substances 0.000 claims abstract description 32
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000000746 purification 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
- 238000013036 cure process Methods 0.000 claims abstract description 8
- 238000009766 low-temperature sintering Methods 0.000 claims abstract description 6
- 238000007650 screen-printing Methods 0.000 claims abstract description 6
- 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 14
- 239000000758 substrate Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 11
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 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
- 229910052718 tin 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000004886 process control Methods 0.000 abstract description 4
- 238000012827 research and development Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 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
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 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
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- 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, comprising: (S10) Jiang Tongyuan, zinc source, Xi Yuan and sulphur source adopt hydro thermal method to prepare Cu
2znSnS
4nanocrystalline; (S20) to the Cu of preparation
2znSnS
4nanocrystallinely carry out centrifugal purification processes; (S30) by the Cu after purification
2znSnS
4nanocrystallinely be dispersed in organic solvent, low-temperature sintering after silk screen printing film forming, obtained performed thin film; (S40) after cure process is carried out to the performed thin film that step (S30) obtains, obtain Cu
2znSnS
4absorbed layer film.Cu prepared by the present invention
2znSnS
4absorbed layer thin film composition is even, and impurity is less, is applicable to thin-film solar cells, as Cu
2znSnS
4the absorbed layer of thin-film solar cells, effectively can improve the electro-optical properties of battery, and the method is simple to operate, device simple, process control, is applicable to Cu
2znSnS
4the 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, what relate to is a kind of chemical synthesis process of copper zinc tin sulfur absorption layer film.
Background technology
Copper Indium Gallium Selenide (CuIn
xga
1-xse
2) thin-film solar cells has that conversion efficiency is high, long-time stability good, capability of resistance to radiation is strong, laboratory photoelectric conversion efficiency more than 20% etc. advantage, be considered to one of thin film solar cell most with prospects.But, CuIn
xga
1-xse
2in, Ga, Se in absorbed layer are rare element and have certain toxicity, seriously constrain CuIn
xga
1-xse
2the industrialized development of hull cell.Be all the semiconducting compound copper-zinc-tin-sulfur (Cu of yellow copper structure
2znSnS
4) be considered to most possibly become replacement CuIn
xga
1-xse
2the material of absorbed layer.Cu
2znSnS
4be p-type semiconductor, optical band gap 1.5eV, the absorption coefficient of light is up to 10
4cm
-1, be suitable as the absorbed layer of thin-film solar cells.Compare with In, Ga, Se, the rich reserves of Zn, Sn and S, cheap, toxicity is low and environmental protection.
Typical Cu
2znSnS
4the structure of thin-film solar cells and CuIn
xga
1-xse
2similar, be followed successively by the multi-layer film structure of substrate/back electrode/absorbed layer/resilient coating/Window layer/top electrode from bottom to up.Wherein Cu
2znSnS
4the performance of absorbed layer is directly connected to the performance of thin film solar cell, and the composition proportion of absorbed layer and filming performance are the key factors of the photoelectric conversion efficiency affecting battery.
At present, Cu
2znSnS
4the preparation method of absorbed layer mainly divides two large classes: the first kind is Physical, based on sputtering method and evaporation, and this class methods film forming compact structure, crystal property is excellent, but carries out under a high vacuum due to plated film whole process, and coating cost is high, Composition Control is not accurate, film forming lack of homogeneity.Equations of The Second Kind is chemical method, mainly comprises electrochemical process, sol-gal process, hydro thermal method etc., respectively has its pluses and minuses.The film growth direction of electrochemical production is controlled, but its film forming speed efficiency is low, and Composition Control is poor, and the waste liquid environmental pollution produced in film forming procedure; Sol-gal process is easy to implement and composition is controlled, 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 preparation
2znSnS
4absorbed layer battery efficiency is high, but reaction need under high pressure be carried out, and thin film composition is uncontrollable.
Summary of the invention
For overcoming the problems referred to above that prior art exists, the invention provides a kind of simple to operate, device simple and the chemical synthesis process of the copper zinc tin sulfur absorption layer film of process control.
To achieve these goals, the technical solution used in the present invention is as follows:
A chemical synthesis process for copper zinc tin sulfur absorption layer film, comprises the following steps:
(S10) Jiang Tongyuan, zinc source, Xi Yuan and sulphur source adopt hydro thermal method to prepare Cu
2znSnS
4nanocrystalline;
(S20) to the Cu of preparation
2znSnS
4nanocrystallinely carry out centrifugal purification processes;
(S30) by the Cu after purification
2znSnS
4nanocrystallinely be dispersed in organic solvent, low-temperature sintering after silk screen printing film forming, obtained performed thin film;
(S40) after cure process is carried out to the performed thin film that step (S30) obtains, obtain Cu
2znSnS
4absorbed layer film.
Particularly, in described step (S10), hydro thermal method prepares Cu
2znSnS
4nanocrystallinely to comprise the steps:
(S11) select the sulfate of copper, zinc, tin, nitrate or chloride as copper source, zinc source and Xi Yuan, thiocarbamide is as sulphur source, example is chosen after copper source, zinc source, Xi Yuan and sulphur source mix for 2:1:1:4 in molar ratio, be dissolved in specific solvent as solute by mixture and be mixed with mixed solution, wherein the mass ratio of specific solvent and solute is 10 ± 0.5:1;
(S12) ultrasonic disperse and ultrasonication are carried out to above-mentioned obtained mixed solution, until solute is dissolved completely in solvent;
(S13) solution obtained for step (S12) is transferred in water heating kettle carries out hydro-thermal reaction, obtained Cu
2znSnS
4nanocrystalline.
Wherein, in described step (S11), specific solvent is one or both in ethanol, ethylene glycol, oleyl amine, acetonitrile, thioacetamide, lauryl mercaptan.
Further, in described step (S13), the filling rate of hydro-thermal reaction is 50 ~ 90%, and heating-up temperature is 374 ~ 628 DEG C, and the reaction time is 1 ~ 42h.
Further, in described step (S30), organic solvent is the one in ethanol, ethylene glycol, the tert-butyl alcohol, oleyl amine, acetonitrile, thioacetamide, lauryl mercaptan.
As preferably, in described step (S30), the substrate of silk screen printing is the one in glass, pi film, stainless steel.
Further, the temperature of described step (S30) low temperature sintering is 100 ~ 250 DEG C, and sintering time is 2 ~ 10min, repeats 1 ~ 10 time.
Further, obtained in described step (S30) performed thin film thickness is 0.1 ~ 50 μm.
More specifically, in described step (S40), the step of after cure process is as follows:
(S41) substrate of performed thin film will be deposited at H
2be heated to 450 ~ 600 DEG C under S atmosphere, and be incubated 0.5 ~ 3h;
(S42) be cooled to substrate 200 ~ 300 DEG C with the speed of 10 ~ 30 DEG C/min, stop passing into H
2s gas;
(S43) stop heating, be cooled to after room temperature until substrate and take out, namely obtain Cu
2znSnS
4absorbed layer film.
Compared with prior art, the present invention has following beneficial effect:
The present invention is based on existing absorbed layer method for manufacturing thin film and carry out improvement integration, adopt hydro thermal method to prepare Cu
2znSnS
4nanocrystallinely rear centrifugal purification is carried out to it, obtain highly purified Cu
2znSnS
4, and then be dissolved in organic solvent, utilize spin-coating method to deposit Cu
2znSnS
4performed thin film, so incorporate advantage, improve shortcoming, significantly reduce the impurity content in performed thin film, eliminate part to be mingled with the larger secondary phase of film performance impact, improve the clean quality of performed thin film, the organic substance in performed thin film is removed finally by after cure process, sulfuration simultaneously promotes crystal grain recrystallization, decrease film internal flaw, thus reach the object improving performed thin film performance, obtain uniform composition and the absorbed layer film of excellent performance, and the present invention is skillfully constructed, simple to operate, device simple, with low cost, process control, be applicable to Cu
2znSnS
4the research and development of thin-film solar cells and middle-size and small-size production, be with a wide range of applications, and is applicable to applying.
Embodiment
Below in conjunction with embodiment, the invention will be further described, and embodiments of the present invention include but not limited to the following example.
Embodiment
The chemical synthesis process of this copper zinc tin sulfur absorption layer film, comprises the following steps:
(S10) Jiang Tongyuan, zinc source, Xi Yuan and sulphur source adopt hydro thermal method to prepare Cu
2znSnS
4nanocrystalline:
(S11) 0.2molCuCl is got respectively
22H
2o, 0.1molZnCl
2, 0.1molSnCl
22H
2o and 0.4molCS (NH
2)
2, after Homogeneous phase mixing, be dissolved in 50mL ethylene glycol solvent;
(S12) ultrasonic disperse and ultrasonication are carried out to above-mentioned mixed solution, until solute is dissolved completely in solvent;
(S13) get the above-mentioned obtained mixed solution of 40mL, be transferred in the water heating kettle of 50mL, 570 DEG C of hydro-thermal reaction 12h, obtained Cu
2znSnS
4nanocrystalline;
(S20) to the Cu of preparation
2znSnS
4nanocrystallinely carry out centrifugal purification processes: in above-mentioned hydro-thermal reaction product, add deionized water and ethanol respectively, by the centrifugal organic impurities removed in product of purifying;
(S30) by the high-purity C u after purification
2znSnS
4nanocrystallinely be dissolved in 10mL lauryl mercaptan organic solvent, ultrasonic disperse makes its particle dissolve completely; Then by solution silk screen printing film forming on a glass substrate, 150 DEG C of low-temperature sintering 3min, lay equal stress on multifilament reticulated printing and sintering process 2 times, obtained thickness is the Cu of 1 μm
2znSnS
4performed thin film;
(S40) after cure process is carried out to the performed thin film that step (S30) obtains, obtain Cu
2znSnS
4absorbed layer film:
(S41) substrate of performed thin film will be deposited at H
2be heated to 520 DEG C under S atmosphere, and be incubated 1h;
(S42) be cooled to substrate 200 DEG C with the speed of 10 ~ 15 DEG C/min, stop passing into H
2s gas;
(S43) stop heating, be cooled to after room temperature until substrate and take out, obtained Cu
2znSnS
4film, is copper zinc tin sulfur absorption layer film of the present invention.
By above-mentioned setting, the present invention combines the advantage that hydro thermal method and sol-gal process prepare copper-zinc-tin-sulfur film, prepares Cu in employing hydro thermal method
2znSnS
4nanocrystallinely rear centrifugal purification is carried out to it, obtain highly purified Cu
2znSnS
4nanocrystalline, and then be dissolved in organic solvent, utilize spin-coating method to deposit Cu
2znSnS
4performed thin film, finally by after cure process, obtains Cu
2znSnS
4absorbed layer film.The method effectively reduces the impurity content in absorbed layer film, reduces film internal flaw, improves film performance, and its simple to operate, device simple, process control, be applicable to Cu
2znSnS
4the research and development of thin-film solar cells and middle-size and small-size production.
In addition, it should be noted that, through verification experimental verification, one or both also in available ethanol, ethylene glycol, oleyl amine, acetonitrile, thioacetamide, lauryl mercaptan of the ethylene glycol solvent adopted in described step (S11) replace; In described step (S13) hydro-thermal reaction condition in, filling rate is 50 ~ 90%, heating-up temperature is 374 ~ 628 DEG C, the reaction time is that 1 ~ 42h all can meet and prepares requirement; The organic solvent lauryl mercaptan adopted in described step (S30) also available ethanol, ethylene glycol, the tert-butyl alcohol, oleyl amine, acetonitrile, thioacetamide replaces, the glass substrate adopted also available pi film or stainless steel material replaces, in sintering condition, sintering temperature is 100 ~ 250 DEG C, sintering time is 2 ~ 10min, repeat 1 ~ 10 time and all can meet preparation requirement, its obtained Cu
2znSnS
4film thickness, between 0.1 ~ 50 μm, also can meet instructions for use; The middle heating target temperature of described step (S41) is 450 ~ 600 DEG C, temperature retention time 0.5 ~ 3h, cooling rate are 10 ~ 30 DEG C/min, cooling target temperature is 200 ~ 300 DEG C and can meets preparation requirement.Because its preparation method is identical, be only that corresponding conditions changes, just the preparation process of each condition do not repeated in the present invention, in this unified explanation.
Above-described embodiment is only the preferred embodiments of the present invention, not limiting the scope of the invention, as long as adopt design principle of the present invention, and the change carried out non-creativeness work on this basis and make, all should belong within protection scope of the present invention.
Claims (9)
1. a chemical synthesis process for copper zinc tin sulfur absorption layer film, is characterized in that, comprises the following steps:
(S10) Jiang Tongyuan, zinc source, Xi Yuan and sulphur source adopt hydro thermal method to prepare Cu
2znSnS
4nanocrystalline;
(S20) to the Cu of preparation
2znSnS
4nanocrystallinely carry out centrifugal purification processes;
(S30) by the Cu after purification
2znSnS
4nanocrystallinely be dispersed in organic solvent, low-temperature sintering after silk screen printing film forming, obtained performed thin film;
(S40) after cure process is carried out to the performed thin film that step (S30) obtains, obtain Cu
2znSnS
4absorbed layer film.
2. the chemical synthesis process of a kind of copper zinc tin sulfur absorption layer film according to claim 1, is characterized in that, in described step (S10), hydro thermal method prepares Cu
2znSnS
4nanocrystallinely to comprise the steps:
(S11) select the sulfate of copper, zinc, tin, nitrate or chloride as copper source, zinc source and Xi Yuan, thiocarbamide is as sulphur source, example is chosen after copper source, zinc source, Xi Yuan and sulphur source mix for 2:1:1:4 in molar ratio, be dissolved in specific solvent as solute by mixture and be mixed with mixed solution, wherein the mass ratio of specific solvent and solute is 10 ± 0.5:1;
(S12) ultrasonic disperse and ultrasonication are carried out to above-mentioned obtained mixed solution, until solute is dissolved completely in solvent;
(S13) solution obtained for step (S12) is transferred in water heating kettle carries out hydro-thermal reaction, obtained Cu
2znSnS
4nanocrystalline.
3. the chemical synthesis process of a kind of copper zinc tin sulfur absorption layer film according to claim 2, it is characterized in that, in described step (S11), specific solvent is one or both in ethanol, ethylene glycol, oleyl amine, acetonitrile, thioacetamide, lauryl mercaptan.
4. the chemical synthesis process of a kind of copper zinc tin sulfur absorption layer film according to claim 2, is characterized in that, in described step (S13), the filling rate of hydro-thermal reaction is 50 ~ 90%, and heating-up temperature is 374 ~ 628 DEG C, and the reaction time is 1 ~ 42h.
5. the chemical synthesis process of a kind of copper zinc tin sulfur absorption layer film according to claim 1, it is characterized in that, in described step (S30), organic solvent is the one in ethanol, ethylene glycol, the tert-butyl alcohol, oleyl amine, acetonitrile, thioacetamide, lauryl mercaptan.
6. the chemical synthesis process of a kind of copper zinc tin sulfur absorption layer film according to claim 5, is characterized in that, in described step (S30), the substrate of silk screen printing is the one in glass, pi film, stainless steel.
7. the chemical synthesis process of a kind of copper zinc tin sulfur absorption layer film according to claim 6, is characterized in that, the temperature of described step (S30) low temperature sintering is 100 ~ 250 DEG C, and sintering time is 2 ~ 10min, repeats 1 ~ 10 time.
8. the chemical synthesis process of a kind of copper zinc tin sulfur absorption layer film according to claim 7, is characterized in that, performed thin film thickness obtained in described step (S30) is 0.1 ~ 50 μm.
9. the chemical synthesis process of a kind of copper zinc tin sulfur absorption layer film according to any one of claim 1 ~ 8, is characterized in that, in described step (S40), the step of after cure process is as follows:
(S41) substrate of performed thin film will be deposited at H
2be heated to 450 ~ 600 DEG C under S atmosphere, and be incubated 0.5 ~ 3h;
(S42) be cooled to substrate 200 ~ 300 DEG C with the speed of 10 ~ 30 DEG C/min, stop passing into H
2s gas;
(S43) stop heating, be cooled to after room temperature until substrate and take out, namely obtain Cu
2znSnS
4absorbed layer film.
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