CN115872439B - Method for preparing film for promoting growth of copper zinc tin sulfide particles by nanocrystalline - Google Patents
Method for preparing film for promoting growth of copper zinc tin sulfide particles by nanocrystalline Download PDFInfo
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- CN115872439B CN115872439B CN202211577708.4A CN202211577708A CN115872439B CN 115872439 B CN115872439 B CN 115872439B CN 202211577708 A CN202211577708 A CN 202211577708A CN 115872439 B CN115872439 B CN 115872439B
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- 239000002245 particle Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000001737 promoting effect Effects 0.000 title claims abstract description 10
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 238000004528 spin coating Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000002105 nanoparticle Substances 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 16
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 claims description 3
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 claims description 2
- WVDYBOADDMMFIY-UHFFFAOYSA-N Cyclopentanethiol Chemical compound SC1CCCC1 WVDYBOADDMMFIY-UHFFFAOYSA-N 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- 239000002159 nanocrystal Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000003921 particle size analysis Methods 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000242 pagocytic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- 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
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- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Abstract
The invention discloses a method for preparing a film for promoting growth of copper zinc tin sulfide particles by nanocrystalline. The method comprises the following steps: firstly, dissolving nano crystals in an organic solution A to prepare stable emulsion B; secondly, slowly dripping the emulsion B into the precursor solution C of CZTS to prepare a precursor solution D; and (3) spin-coating the precursor solution D to prepare a CZTS prefabricated layer film, and annealing the CZTS prefabricated layer film to prepare the CZTS film. The nano-crystal serving as an additive of the precursor solution C can serve as a seed crystal in the annealing process of the CZTS prefabricated layer film, so that the growth of CZTS particles in the film is promoted.
Description
Technical Field
The invention relates to the field of film preparation, in particular to a film preparation method for promoting growth of copper zinc tin sulfide particles by nanocrystalline.
Background
As a green nontoxic light absorbing material, copper zinc tin sulfide (Cu 2 ZnSnS 4 CZTS) is widely studied and applied in the field of thin film solar cells. Although CZTS thin film solar cell device efficiency has broken through 10%, its device efficiency is still at a lower level compared to single crystal silicon and perovskite solar cells. One important reason for limiting the improvement of the device efficiency is that the polycrystalline CZTS film has excessive grain boundaries and cannot form an excellent carrier transportation channel, so that the carrier life of the polycrystalline CZTS film is only tens of ns, and the performance of the CZTS film solar cell device is greatly limited. Thus, the first and second substrates are bonded together,how to prepare large particles, polycrystal with few grain boundaries and even monocrystal CZTS films are key to improving the performance of solar cell devices. According to the invention, the growth of CZTS nano particles is improved by adding nano crystals into the precursor solution to serve as seed crystals for subsequent film formation.
Disclosure of Invention
The invention aims at overcoming the technical defects of a CZTS film preparation process, and provides a film preparation method for promoting growth of CZTS particles by nanocrystalline so as to improve the performance of a CZTS film solar cell device.
In order to achieve the above purpose, the technical scheme of the invention is as follows, and the method comprises the following steps:
s1: cu is added with 2 SnS 3 Dispersing the nano particles in the organic solution A to prepare stable emulsion B;
s2: slowly dripping the emulsion B into the precursor solution C of CZTS to prepare a precursor solution D;
s3: spin coating is carried out on the precursor solution D to prepare a CZTS prefabricated layer film;
s4: and (3) annealing the prepared CZTS prefabricated layer film to finish the preparation of the CZTS film.
Preferably, in the step S1, cu 2 SnS 3 The size of the nano particles is selected to be 2-10nm, and the nano particles are favorable for phagocytic fusion between high-temperature condition bodies; in step S1, cu is dispersed 2 SnS 3 The organic solvent of the nano particles is any one of propanethiol, pentanethiol, 2-propanethiol, cyclopentanethiol or n-dodecyl mercaptan; in step S1, cu is dispersed 2 SnS 3 The solubility of the emulsion B of the nanoparticles is 10-1000mmol/L.
Further, in the step S2, the emulsion B is slowly dropped into a CZTS precursor solution of 1-10mol/L, and dispersed Cu 2 SnS 3 The ratio of the nano particles to the substances in the original CZTS precursor is 1/1000 to 5/100.
Further, in the step S3, the spin coating speed of the prepared precursor solution D is 5-15S low rotation speed of 200-1500rpm, and 20-60S high rotation speed of 3000-6000rpm.
Further, in the step S4, the annealing atmosphere is S vapor, the heating speed is 10-30min, the temperature is increased to 450 ℃, the temperature is increased to 600 ℃ for 30-120min, and the temperature is kept for 30-60min.
The technical principle of the invention is as follows:
in the preparation method provided by the invention, the dispersion ratio of the nano particles in the precursor solution and the prefabricated layer directly influences the uniform dispersion degree of the nano particles in the prefabricated layer, thereby influencing the film forming quality of the CZTS film in the annealing process. The nanoparticle is an important intermediate product in the CZTS film forming process, and is highly dispersed Cu with a certain size 2 SnS 3 A large number of polymerization centers are provided for the nucleation of the CZTS, the mutual fusion of small-size CZTS particles is promoted, and the further growth of the CZTS particles is facilitated, so that the preparation of the CZTS film with small grain boundary and large particle size is realized.
Compared with the prior art, the invention has the following advantages:
the invention introduces important intermediate product Cu in the process of forming CZTS film 2 SnS 3 Nanocrystalline, the nanocrystalline has two roles: first, as an intermediate of CZTS, cu can be promoted 2 SnS 3 The reaction with ZnS reduces the generation of ZnS secondary phase; second, nano-scale Cu 2 SnS 3 The particles are favorable for forming nano-scale CZTS particles, and the particles are easy to fuse or phagocytize with other CZTS particles in the film forming process of the CZTS film, so that the generation of large-particle CZTS particles is promoted, and the film forming quality is improved.
Detailed Description
The technical scheme of the present invention is further described in detail below with reference to specific examples, but is not limited thereto.
Example 1
Step S1: to 2nm Cu 2 SnS 3 Dispersing the nano particles in propanethiol to prepare emulsion A with the concentration of 10 mmol/L;
step S2: slowly dripping emulsion A into CZTS precursor solution of 10mol/L, and controlling Cu 2 SnS 3 The molar ratio of the catalyst to CZTS is 1/1000, and the preparation of the CZTS precursor solution D is completed;
step S3: spin-coating the precursor solution D onto a substrate by 1500rpm 5s+3000rpm 20s to finish the preparation of the CZTS prefabricated layer film;
step S4: and (3) annealing the CZTS prefabricated layer film in an S steaming atmosphere, heating to 450 ℃ for 10min, heating to 600 ℃ for 30min, and preserving heat for 30min.
Example 2
Step S1: to 5nm Cu 2 SnS 3 Dispersing the nano particles in propanethiol to prepare emulsion A with the concentration of 500 mmol/L;
step S2: slowly dripping emulsion A into 5mol/L CZTS precursor solution, and controlling Cu 2 SnS 3 The molar ratio of the catalyst to CZTS is 1/100, and the preparation of the CZTS precursor solution D is completed;
step S3: spin-coating the precursor solution D onto a substrate by 1000rpm 10s+4500rpm 40s to finish the preparation of the CZTS prefabricated layer film;
step S4: and (3) annealing the CZTS prefabricated layer film in an S steaming atmosphere, heating to 450 ℃ for 20min, heating to 600 ℃ for 60min, and preserving heat for 45min.
Example 3
Step S1: 10nm Cu 2 SnS 3 Dispersing the nano particles in propanethiol to prepare emulsion A with the concentration of 1 mol/L;
step S2: slowly dripping emulsion A into CZTS precursor solution of 1mol/L, and controlling Cu 2 SnS 3 The molar ratio of the catalyst to CZTS is 5/100, and the preparation of the CZTS precursor solution D is completed;
step S3: spin-coating the precursor solution D onto a substrate by 200rpm 15s+6000rpm 60s to finish the preparation of the CZTS prefabricated layer film;
step S4: and (3) annealing the CZTS prefabricated layer film in an S steaming atmosphere, heating to 450 ℃ for 30min, heating to 600 ℃ for 120min, and preserving heat for 60min.
Comparative example 1
The difference from example 1 is that the preparation process does not include the step of preparing and adding the nanocrystalline emulsion in step S1 and step S2 in example 1.
Comparative example 2
The difference from example 2 is that the preparation process does not include the step of preparing and adding the nanocrystalline emulsion in step S1 and step S2 in example 1.
Comparative example 3
The difference from example 3 is that the preparation process does not include the step of preparing and adding the nanocrystalline emulsion in step S1 and step S2 in example 1.
Application example
The CZTS film prepared in the examples 1-3 and the CZTS film prepared in the comparative examples 1-3 are subjected to grain size measurement, meanwhile, the preparation of the CZTS film solar cell device is further completed, the open circuit voltage, the short circuit current and the photoelectric conversion efficiency of the prepared solar cell device are respectively tested, and the related test results are shown in the following table:
TABLE 1
As can be seen from the above table, the data,
comparative examples 1 to 3 were free of Cu 2 SnS 3 CZTS film solar cell device prepared by spin coating of CZTS precursor sol of nanocrystalline, and has low short-circuit current (lower than 10 mA/cm) 2 ) The photoelectric conversion efficiency is about 3%; particle size analysis of CZTS thin films revealed that the particle size distribution was mainly distributed to less than 1 micron, and that small particle size was detrimental to collection of photogenerated carriers, affecting the short-circuit current of the battery device.
Examples 1 to 3 adopt Cu provided by the present invention 2 SnS 3 Preparation method for promoting growth of CZTS film particles by nanocrystalline, and short-circuit current of solar cell device prepared by using the method reaches 11mA/cm 2 The photoelectric conversion efficiency can reach about 4.0%, and is obviously improved compared with comparative examples 1-3. The particle size analysis of the CZTS film prepared by the method of the invention shows that Cu is added 2 SnS 3 The grain size of the CZTS layer prepared by the nanocrystalline is obviously increased, and the main distribution area of the grain size is larger than 1 micron. This demonstrates that the preparation method provided by the invention is beneficial to CZTS thinnessFilm growth improves the short circuit current of the device.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not intended to limit the embodiments and scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the teachings of the present invention, which are intended to be included within the scope of the present invention.
Claims (4)
1. A method for preparing a film for promoting growth of copper zinc tin sulfide particles by nanocrystalline is characterized by comprising the following steps: the method comprises the following steps:
s1: cu is added with 2 SnS 3 Dispersing the nano particles in the organic solution A to prepare stable emulsion B;
in the step S1, cu 2 SnS 3 The size of the nano particles is selected to be 2-10nm; the solvent of the organic solution A is any one of propanethiol, pentanethiol, 2-propyl mercaptan, cyclopentanethiol or n-dodecyl mercaptan; dispersing Cu 2 SnS 3 The solubility of the emulsion B of the nano particles is 10-1000 mmol/L;
s2: slowly dripping the emulsion B into the precursor solution C of CZTS to prepare a precursor solution D;
in the step S2, dispersed Cu 2 SnS 3 The ratio of the nano particles to the substances in the original CZTS precursor is 1/1000-5/100;
s3: spin coating is carried out on the precursor solution D to prepare a CZTS prefabricated layer film;
s4: and (3) annealing the prepared CZTS prefabricated layer film to finish the preparation of the CZTS film.
2. The method for preparing the film for promoting the growth of copper zinc tin sulfide particles by nanocrystalline according to claim 1, which is characterized in that:
in the step S2, the concentration of the CZTS precursor in the precursor solution of the CZTS is 1-10 mol/L.
3. The method for preparing the film for promoting the growth of copper zinc tin sulfide particles by nanocrystalline according to claim 2, which is characterized in that:
in the step S3, the spin coating speed of the prepared precursor solution D is 5-15S, the low rotation speed is 200-1500rpm, and the high rotation speed is 3000-6000rpm, wherein the rotation speed is 20-60S.
4. A method for preparing a film for promoting the growth of copper zinc tin sulfide particles by nanocrystalline according to any one of claims 1 to 3, characterized in that:
in the step S4, the annealing atmosphere is S vapor, the heating speed is 10-30min, and the temperature is increased to 450 o C, heating to 600 for 30-120min o C, preserving heat for 30-60min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211577708.4A CN115872439B (en) | 2022-12-09 | 2022-12-09 | Method for preparing film for promoting growth of copper zinc tin sulfide particles by nanocrystalline |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211577708.4A CN115872439B (en) | 2022-12-09 | 2022-12-09 | Method for preparing film for promoting growth of copper zinc tin sulfide particles by nanocrystalline |
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| Publication Number | Publication Date |
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| CN115872439A CN115872439A (en) | 2023-03-31 |
| CN115872439B true CN115872439B (en) | 2023-11-17 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103236466A (en) * | 2013-04-07 | 2013-08-07 | 上海大学 | Method for manufacturing window layers of copper, zinc, tin and sulfur solar cells |
| CN104060235A (en) * | 2014-07-10 | 2014-09-24 | 吉林化工学院 | Preparation method for increasing grain size of copper, cadmium, tin and sulphur thin film by doping selenium element |
| CN105518872A (en) * | 2013-09-12 | 2016-04-20 | 株式会社Lg化学 | Metal chalcogenide nanoparticles for manufacturing optical absorption layer for solar cell and method for preparing same |
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2022
- 2022-12-09 CN CN202211577708.4A patent/CN115872439B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103236466A (en) * | 2013-04-07 | 2013-08-07 | 上海大学 | Method for manufacturing window layers of copper, zinc, tin and sulfur solar cells |
| CN105518872A (en) * | 2013-09-12 | 2016-04-20 | 株式会社Lg化学 | Metal chalcogenide nanoparticles for manufacturing optical absorption layer for solar cell and method for preparing same |
| CN104060235A (en) * | 2014-07-10 | 2014-09-24 | 吉林化工学院 | Preparation method for increasing grain size of copper, cadmium, tin and sulphur thin film by doping selenium element |
Non-Patent Citations (4)
| Title |
|---|
| Fabrication of solar cells based on Cu2ZnSnS4 prepared from Cu2SnS3 synthesized using a novel chemical procedure;John M. Correa et al.;《EPJ Photovoltaics》;第1-9页 * |
| In situpreparedCu2ZnSnS4 ultrathin film counterelectrode in dye-sensitizedsolarcells;Zhengfu Tong et al.;《MaterialsLetters》;第241-243页 * |
| Synthesis and characterization of Cu2ZnSnS4 from Cu2SnS3 and ZnS compounds;LI Shi-na et al.;《OPTOELECTRONICS LETTERS》;第1-4页 * |
| Synthesis of Cu2ZnSnS4 thin film from mixed solution of Cu2SnS3 nanoparticles and Zn ions;Zheng-fu TONG et al.;《Trans. Nonferrous Met. Soc. China》;第2102−2108页 * |
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