CN111924874A - Preparation method of copper-zinc-tin-based powder - Google Patents
Preparation method of copper-zinc-tin-based powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 110
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 48
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 48
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 48
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 44
- 239000011812 mixed powder Substances 0.000 claims description 40
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 26
- 238000003746 solid phase reaction Methods 0.000 claims description 24
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 10
- 239000012071 phase Substances 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 102
- 238000000227 grinding Methods 0.000 description 66
- 239000010949 copper Substances 0.000 description 49
- 239000011135 tin Substances 0.000 description 28
- 239000011701 zinc Substances 0.000 description 24
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 238000005303 weighing Methods 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 13
- 229910052718 tin Inorganic materials 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 11
- 239000011669 selenium Substances 0.000 description 10
- 238000003801 milling Methods 0.000 description 9
- 229910052711 selenium Inorganic materials 0.000 description 9
- 239000011858 nanopowder Substances 0.000 description 8
- 230000031700 light absorption Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 229910018038 Cu2ZnSnSe4 Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910017987 Cu—Zn—Sn—S—Se Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- PCRGAMCZHDYVOL-UHFFFAOYSA-N copper selanylidenetin zinc Chemical compound [Cu].[Zn].[Sn]=[Se] PCRGAMCZHDYVOL-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
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
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Abstract
The invention provides a preparation method of copper-zinc-tin-based powder, belonging to the technical field of preparation of photovoltaic materials. The invention takes simple substances as raw materials to prepare the copper-zinc-tin-based powder, and adopts a one-step method of reaction raw materials to prepare the copper-zinc-tin-based powder through room temperature solid phase ball milling reaction, and the prepared powder has uniform components and no impurity phase; the preparation process is simple and easy to implement, easy to control, cost-saving, energy-saving and environment-friendly; meanwhile, the use of a surfactant, a template agent and a solvent is avoided, the product purity is improved, the requirement of green material synthesis is met, and the method is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of photovoltaic materials, in particular to a preparation method of copper-zinc-tin-based powder.
Background
The light absorption efficiency and the photoelectric conversion efficiency of the light absorption layer are important factors for energy conversion of the photovoltaic material. Quaternary compound copper zinc tin sulfur Cu2ZnSnS4(CZTS) has become a focus of research in recent years, and its energy gap is about 1.5eV, which is very close to the optimum energy gap (1.45 eV) of a semiconductor solar cell; is a direct band gap semiconductor with light absorption coefficient over 104cm-1The thickness of the CZTS film in the cell is thin, and most incident sunlight can be absorbed only by 1-2 mu m; Cu-Zn-Sn-S-Se Cu2ZnSn(SxSe1-x)4(abbreviated asCZTSSe of which 0<x<1) The crystal is a direct band gap semiconductor and has an adjustable forbidden band width of 1.0-1.5 eV; and the light absorption coefficient is up to 104cm-1(ii) a Both CZTS and CZTSSe are the most widely used Cu (In, Ga) Se2(CIGS) has a similar crystal structure, each element in CZTS is abundant and nontoxic in nature, and the CZTS is most hopeful to replace expensive CIGS materials, is considered to be one of materials for preparing an absorption layer of a high-efficiency thin-film solar cell, and has led to extensive research worldwide. In addition, copper zinc tin selenium (Cu)2ZnSnSe4The abbreviation CZTSe) not only has photoelectric properties similar to CIGS, but also more importantly contains non-toxic elements, has abundant reserves on the earth and high light absorption coefficient (>104cm-1) The forbidden band width (Eg ≈ 1eV) is matched with the solar spectrum, and the optical and electrical properties are excellent, so the material is considered to be one of ideal materials of the solar cell absorption layer.
The preparation methods of CZTS, CZTSSe and CZTSe are divided into vacuum process and non-vacuum process according to whether vacuum is required or not. The vacuum process mainly comprises an evaporation method, a sputtering method, a pulse laser deposition method and the like; non-vacuum processes include electrochemical deposition, spray pyrolysis, sol-gel processes, hydrothermal synthesis, and the like.
Although the existing preparation method can prepare CZTS, CZTSSe or CZTSe, the existing preparation method still has some defects, such as: in the preparation process, the evaporation method, the sputtering method, the pulse laser deposition method and the like all need expensive vacuum equipment, which is not favorable for improving the production efficiency and controlling the cost. In addition, in the liquid phase method, the product particles are easy to agglomerate, and in addition, CZTS and CZTSSe are easy to decompose, so that the powder is difficult to prepare. In addition, the methods have complex processes, the components of each element are difficult to accurately control, toxic hydrogen sulfide gas is often used in the preparation process, and the preparation cost is high. Therefore, it is necessary to develop a new preparation method of copper-zinc-tin-based powder material which can be produced in a large scale, has a simple process, is low in cost and is environment-friendly.
Disclosure of Invention
The invention aims to provide a preparation method of copper-zinc-tin-based powder, which is simple and feasible, saves cost, is energy-saving and environment-friendly and can be used for large-scale production.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of copper-zinc-tin-based powder, which comprises the following steps:
mixing raw materials corresponding to the copper-zinc-tin-based powder to obtain mixed powder;
carrying out mechanical ball milling on the mixed powder to initiate a solid-phase reaction, and drying in vacuum to obtain copper-zinc-tin-based powder;
the raw materials corresponding to the copper-zinc-tin-based powder comprise copper powder, zinc powder and tin powder, and also comprise sulfur powder and/or selenium powder;
or the raw materials corresponding to the copper-zinc-tin-based powder simultaneously comprise copper powder, zinc powder, tin powder, sulfur powder and germanium powder.
Preferably, when the raw materials corresponding to the copper-zinc-tin-based powder comprise copper powder, zinc powder and tin powder, and further comprise sulfur powder or selenium powder, the molar ratio of the copper powder to the zinc powder to the tin powder to the sulfur powder is 2: 1: 1: 4; the molar ratio of the copper powder to the zinc powder to the tin powder to the selenium powder is 2: 1: 1: 4.
preferably, when the raw materials corresponding to the copper-zinc-tin-based powder comprise copper powder, zinc powder, tin powder, sulfur powder and selenium powder, the molar ratio of the copper powder to the zinc powder to the tin powder to the sulfur powder to the selenium powder is 2: 1: 1: x: (4-x), wherein 0< x < 4.
Preferably, when the raw materials corresponding to the copper-zinc-tin-based powder simultaneously comprise copper powder, zinc powder, tin powder, sulfur powder and germanium powder, the molar ratio of the copper powder to the zinc powder to the tin powder to the germanium powder is 2: 1: (1-x): x: 4, wherein x is more than or equal to 0 and less than or equal to 1.
Preferably, the rotation speed of the mechanical ball mill is 500 rpm.
Preferably, the temperature of the solid-phase reaction is room temperature, and the time of the solid-phase reaction is 10-80 h.
Preferably, the temperature of the vacuum drying is 50-70 ℃, the pressure is 0-0.1 MPa, and the time is 1-2 h.
The invention provides a preparation method of copper-zinc-tin-based powder, which comprises the following steps: mixing raw materials corresponding to the copper-zinc-tin-based powder to obtain mixed powder; carrying out mechanical ball milling on the mixed powder to initiate a solid-phase reaction, and drying in vacuum to obtain copper-zinc-tin-based powder; the raw materials corresponding to the copper-zinc-tin-based powder comprise copper powder, zinc powder and tin powder, and also comprise sulfur powder and/or selenium powder; or the raw materials corresponding to the copper-zinc-tin-based powder simultaneously comprise copper powder, zinc powder, tin powder, sulfur powder and germanium powder. The invention takes simple substances as raw materials to prepare the copper-zinc-tin-based powder, and adopts a one-step method of reaction raw materials to prepare the copper-zinc-tin-based powder through room temperature solid phase ball milling reaction, and the prepared powder has uniform components and no impurity phase; the preparation process is simple and easy to implement, easy to control, cost-saving, energy-saving and environment-friendly; meanwhile, the use of a surfactant, a template agent and a solvent is avoided, the product purity is improved, the requirement of green material synthesis is met, and the method is suitable for large-scale production.
Drawings
FIG. 1 shows Cu obtained in example 22ZnSnS4An X-ray diffraction pattern of the powder;
FIG. 2 shows Cu obtained in example 32ZnSnS4An X-ray diffraction pattern of the powder;
FIG. 3 shows Cu obtained in example 22ZnSnS4SEM image of the powder;
FIG. 4 shows Cu obtained in example 42ZnSnSe4An X-ray diffraction pattern of the powder;
FIG. 5 shows Cu obtained in example 52ZnSnSe4An X-ray diffraction pattern of the powder;
FIG. 6 is an XRD pattern of CZTSSe powder prepared in example 7;
FIG. 7 is an XRD pattern of CZTSSe powder prepared in example 8;
FIG. 8 shows Cu obtained in examples 11 to 152Zn(Sn1-x，Gex)S4XRD pattern of the powder;
FIG. 9 shows Cu prepared in examples 11 to 142Zn(Sn1-x，Gex)S4Typical of powder (ahv)2Hv relation graph.
Detailed Description
The invention provides a preparation method of copper-zinc-tin-based powder, which comprises the following steps:
mixing raw materials corresponding to the copper-zinc-tin-based powder to obtain mixed powder;
carrying out mechanical ball milling on the mixed powder to initiate a solid-phase reaction, and drying in vacuum to obtain copper-zinc-tin-based powder;
the raw materials corresponding to the copper-zinc-tin-based powder comprise copper powder, zinc powder and tin powder, and also comprise sulfur powder and/or selenium powder;
or the raw materials corresponding to the copper-zinc-tin-based powder simultaneously comprise copper powder, zinc powder, tin powder, sulfur powder and germanium powder.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The invention mixes the raw materials corresponding to the copper-zinc-tin-based powder to obtain the mixed powder. In the invention, the raw materials corresponding to the copper-zinc-tin-based powder comprise copper powder, zinc powder and tin powder, and also comprise sulfur powder and/or selenium powder; or the raw materials corresponding to the copper-zinc-tin-based powder simultaneously comprise copper powder, zinc powder, tin powder, sulfur powder and germanium powder. In the invention, the particle size of the raw material corresponding to the copper-zinc-tin-based powder is preferably 20-40 μm.
In the present invention, when the raw materials corresponding to the copper-zinc-tin-based powder include copper powder, zinc powder, and tin powder, and further include sulfur powder or selenium powder, the molar ratio of the copper powder, the zinc powder, the tin powder, and the sulfur powder is preferably 2: 1: 1: 4; the mole ratio of the copper powder, the zinc powder, the tin powder and the selenium powder is preferably 2: 1: 1: 4.
in the invention, when the raw materials corresponding to the copper-zinc-tin-based powder comprise copper powder, zinc powder, tin powder, sulfur powder and selenium powder, the molar ratio of the copper powder, the zinc powder, the tin powder, the sulfur powder and the selenium powder is preferably 2: 1: 1: x: (4-x), wherein 0< x < 4.
In the invention, when the raw materials corresponding to the copper-zinc-tin-based powder simultaneously comprise copper powder, zinc powder, tin powder, sulfur powder and germanium powder, the molar ratio of the copper powder, the zinc powder, the tin powder, the germanium powder and the sulfur powder is preferably 2: 1: (1-x): x: 4, wherein x is more than or equal to 0 and less than or equal to 1.
In the present invention, it is preferable to mix the raw materials corresponding to the copper-zinc-tin-based powder in a glove box under an argon or nitrogen atmosphere, thereby preventing oxidation. The specific process of mixing is not particularly limited in the present invention, and the raw materials can be uniformly mixed by mixing according to a process known in the art.
After the mixed powder is obtained, the mixed powder is mechanically ball-milled to initiate a solid-phase reaction, and the copper-zinc-tin-based powder is obtained after vacuum drying.
In the present invention, the mechanical ball milling is preferably carried out in a ball mill, preferably a BM6 planetary ball mill; the grinding ball of the mechanical ball milling is preferably a zirconia grinding ball, an agate grinding ball, a corundum grinding ball or a tungsten carbide grinding ball. The source of the grinding balls is not particularly limited in the present invention, and commercially available products well known in the art may be selected. The present invention preferably performs the mechanical ball milling by controlling the mass ratio of the mixed powder and the grinding balls, or by limiting the diameter and number of the grinding balls. In the invention, the mass ratio of the mixed powder to the grinding balls is preferably 1 (2-5), and more preferably 1: 3; the diameter of the grinding balls preferably comprises 20mm, 15mm, 10mm and 5mm, and the number of the grinding balls is preferably adjusted according to actual requirements. In the embodiment of the invention, the zirconia grinding balls are prepared in a specific mode of 2 zirconia grinding balls with the diameter of 20mm, 5 zirconia grinding balls with the diameter of 15mm, 8 zirconia grinding balls with the diameter of 10mm and 10 zirconia grinding balls with the diameter of 5 mm.
In the present invention, the rotation speed of the mechanical ball mill is preferably 500 rpm; the temperature of the solid-phase reaction is preferably room temperature, and the time of the solid-phase reaction is preferably 10-80 h, more preferably 20-60 h, and further preferably 30-50 h; and in the process of the solid-phase reaction, the mechanical ball milling is continuously carried out. During the solid-phase reaction, the particles in the raw material powder are physically and chemically bonded under the action and induction of mechanical forces (impact, friction, shear, grinding and compression forces).
After the solid-phase reaction is finished, the obtained product is dried in vacuum; in the invention, the temperature of the vacuum drying is preferably 50-70 ℃, more preferably 60 ℃, the pressure is preferably 0-0.1 MPa, more preferably 0.05MPa, and the time is preferably 1-2 h, more preferably 1.5 h. The apparatus used in the vacuum drying of the present invention is not particularly limited, and any apparatus known in the art capable of achieving the above conditions may be used.
Compared with the method for preparing CZTS by taking sulfide or selenide as raw material, the method for preparing CZTS by taking simple substance as raw material can realize Cu by controlling the doping amount of germanium2Zn(Sn1-x,Gex)S4And (4) controllably adjusting the forbidden band width.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the particle size of the raw material corresponding to the copper-zinc-tin-based powder is 20 to 40 μm.
Example 1
This example prepares Cu as follows2ZnSnS4Nano powder:
according to the following steps: 1: 1: 4, weighing simple substance powder (total 20g) of copper, zinc, tin and sulfur according to the molar ratio, and uniformly mixing in a glove box under the nitrogen atmosphere to obtain mixed powder; adding the mixed powder into a 250mL ball milling tank equipped with 2 zirconia grinding balls with the diameter of 20mm, 5 zirconia grinding balls with the diameter of 15mm, 8 zirconia grinding balls with the diameter of 10mm and 10 zirconia grinding balls with the diameter of 5mm, continuously milling for 20 hours at 500rpm in a BM6 planetary ball mill, and carrying out solid-phase reaction; vacuum drying the obtained product at 60 deg.C under 0.1MPa for 2 hr to obtain Cu2ZnSnS4And (3) powder.
Example 2
This example prepares Cu as follows2ZnSnS4Nano powder：
According to the following steps: 1: 1: 4, weighing simple substance powder (total 20g) of copper, zinc, tin and sulfur according to the molar ratio, and uniformly mixing in a glove box under the nitrogen atmosphere to obtain mixed powder; adding the mixed powder into a 250mL ball milling tank equipped with 2 zirconia grinding balls with the diameter of 20mm, 5 zirconia grinding balls with the diameter of 15mm, 8 zirconia grinding balls with the diameter of 10mm and 10 zirconia grinding balls with the diameter of 5mm, continuously milling for 40 hours at 500rpm in a BM6 planetary ball mill, and carrying out solid-phase reaction; vacuum drying the obtained product at 60 deg.C under 0.1MPa for 2 hr to obtain Cu2ZnSnS4And (3) powder.
Example 3
This example prepares Cu as follows2ZnSnS4Powder:
according to the following steps: 1: 1: 4, weighing simple substance powder (total 20g) of copper, zinc, tin and sulfur according to the molar ratio, and uniformly mixing in a glove box under the nitrogen atmosphere to obtain mixed powder; adding the mixed powder into a 250mL ball milling tank equipped with 2 zirconia grinding balls with the diameter of 20mm, 5 zirconia grinding balls with the diameter of 15mm, 8 zirconia grinding balls with the diameter of 10mm and 10 zirconia grinding balls with the diameter of 5mm, continuously milling for 60 hours in a BM6 planetary ball mill at 500rpm, and carrying out solid-phase reaction; vacuum drying the obtained product at 60 deg.C under 0.1MPa for 2 hr to obtain Cu2ZnSnS4And (3) powder.
Performance testing
1) Cu obtained in example 2 to 32ZnSnS4XRD analysis of the powder was carried out, and the results are shown in FIGS. 1 and 2. The mole ratio of copper, zinc, tin and sulfur in the reaction raw materials is 2: 1: 4, the X-ray diffraction pattern obtained by continuously grinding for 40 hours and 60 hours at 500rpm is consistent with that of standard card JCPDS26-0575 and has three obvious strong peaks, which indicates that the sample is well crystallized. Shows that single-phase Cu is obtained by a simple mechanical ball milling method under the room temperature condition2ZnSnS4And (3) powder.
2) Cu obtained in example 22ZnSnS4SEM analysis of the powder showed that in FIG. 3; as can be seen from FIG. 3, Cu2ZnSnS4Size of nanoparticlesAbout 100 nm.
Example 4
This example prepares Cu as follows2ZnSnSe4Nano powder:
according to the following steps: 1: 1: 4, weighing simple substance powder (total 20g) of copper, zinc, tin and selenium according to the molar ratio, and uniformly mixing in a glove box under the nitrogen atmosphere to obtain mixed powder; adding the mixed powder into a 250mL ball milling tank equipped with 2 zirconia grinding balls with the diameter of 20mm, 5 zirconia grinding balls with the diameter of 15mm, 8 zirconia grinding balls with the diameter of 10mm and 10 zirconia grinding balls with the diameter of 5mm, continuously milling for 40 hours at 500rpm in a BM6 planetary ball mill, and carrying out solid-phase reaction; vacuum drying the obtained product at 60 deg.C under 0.1MPa for 2 hr to obtain Cu2ZnSnSe4And (3) powder.
Example 5
This example prepares Cu as follows2ZnSnSe4Powder:
according to the following steps: 1: 1: 4, weighing simple substance powder (total 20g) of copper, zinc, tin and selenium according to the molar ratio, and uniformly mixing in a glove box under the nitrogen atmosphere to obtain mixed powder; adding the mixed powder into a 250mL ball milling tank equipped with 2 zirconia grinding balls with the diameter of 20mm, 5 zirconia grinding balls with the diameter of 15mm, 8 zirconia grinding balls with the diameter of 10mm and 10 zirconia grinding balls with the diameter of 5mm, continuously milling for 60 hours in a BM6 planetary ball mill at 500rpm, and carrying out solid-phase reaction; vacuum drying the obtained product at 60 deg.C under 0.1MPa for 2 hr to obtain Cu2ZnSnSe4And (3) powder.
Example 6
This example prepares Cu as follows2ZnSnSe4Nano powder:
according to the following steps: 1: 1: 4, weighing simple substance powder (total 20g) of copper, zinc, tin and selenium according to the molar ratio, and uniformly mixing in a glove box under the nitrogen atmosphere to obtain mixed powder; the mixed powder was charged into a 250mL ball mill jar equipped with 2 zirconia grinding balls having a diameter of 20mm, 5 zirconia grinding balls having a diameter of 15mm, 8 zirconia grinding balls having a diameter of 10mm and 10 zirconia grinding balls having a diameter of 5mm, at BContinuously grinding for 20 hours at 500rpm in an M6 planetary ball mill to perform solid-phase reaction; vacuum drying the obtained product at 60 deg.C under 0.1MPa for 2 hr to obtain Cu2ZnSnSe4And (3) powder.
Performance testing
1) For Cu prepared in example 42ZnSnSe4The powder was subjected to XRD test, and the results are shown in FIG. 4. As can be seen from FIG. 4, the X-ray diffraction pattern has three distinct strong peaks and no hetero-peaks, which indicates that the sample has good crystallization and no hetero-phase, and shows that single-phase Cu is obtained by simple mechanical ball milling method at room temperature2ZnSnSe4And (3) powder.
2) For Cu prepared in example 52ZnSnSe4The powder was subjected to XRD test, and the results are shown in FIG. 5. As can be seen from FIG. 5, the X-ray diffraction pattern has three distinct strong peaks and no hetero-peaks, which indicates that the sample has good crystallization and no hetero-phase, and shows that single-phase Cu is obtained by simple mechanical ball milling method at room temperature2ZnSnSe4And (3) powder.
Example 7
In this example, CZTSSe nanopowder was prepared as follows:
according to the following steps: 1: 1: 2: 2, weighing simple substance powder (total 20g) of copper, zinc, tin, sulfur and selenium according to the molar ratio, and uniformly mixing in a glove box under the nitrogen atmosphere to obtain mixed powder; adding the mixed powder into a 250mL ball milling tank equipped with 2 zirconia grinding balls with the diameter of 20mm, 5 zirconia grinding balls with the diameter of 15mm, 8 zirconia grinding balls with the diameter of 10mm and 10 zirconia grinding balls with the diameter of 5mm, continuously milling for 60 hours at 500rpm in a BM6 planetary ball mill, and carrying out solid-phase reaction; vacuum drying the obtained product at 60 ℃ under the vacuum degree of 0.1MPa for 2 hours to obtain the CZTSSe powder.
Example 8
In this example, CZTSSe nanopowder was prepared as follows:
weighing simple substance powder (20 g in total) of copper, zinc, tin, sulfur and selenium according to the molar ratio of 2: 1: 3: 1, and uniformly mixing in a glove box under nitrogen atmosphere to obtain mixed powder; adding the mixed powder into a 250mL ball milling tank equipped with 2 zirconia grinding balls with the diameter of 20mm, 5 zirconia grinding balls with the diameter of 15mm, 8 zirconia grinding balls with the diameter of 10mm and 10 zirconia grinding balls with the diameter of 5mm, continuously milling for 60 hours in a BM6 planetary ball mill at 500rpm, and carrying out solid-phase reaction; vacuum drying the obtained product at 60 ℃ under the vacuum degree of 0.1MPa for 2 hours to obtain the CZTSSe powder.
Example 9
In this example, CZTSSe powder was prepared as follows:
weighing simple substance powder (total 20g) of copper, zinc, tin, sulfur and selenium according to the molar ratio of 2: 1:3, and uniformly mixing in a glove box under nitrogen atmosphere to obtain mixed powder; adding the mixed powder into a 250mL ball milling tank equipped with 2 zirconia grinding balls with the diameter of 20mm, 5 zirconia grinding balls with the diameter of 15mm, 8 zirconia grinding balls with the diameter of 10mm and 10 zirconia grinding balls with the diameter of 5mm, continuously milling for 60 hours in a BM6 planetary ball mill at 500rpm, and carrying out solid-phase reaction; vacuum drying the obtained product at 60 ℃ under the vacuum degree of 0.1MPa for 2 hours to obtain the CZTSSe powder.
Example 10
In this example, CZTSSe nanopowder was prepared as follows:
weighing simple substance powder (20 g in total) of copper, zinc, tin, sulfur and selenium according to the molar ratio of 2: 1:3, and uniformly mixing in a glove box under nitrogen atmosphere to obtain a mixed raw material; adding the mixed raw materials into a 250mL ball milling tank equipped with 2 zirconia grinding balls with the diameter of 20mm, 5 zirconia grinding balls with the diameter of 15mm, 8 zirconia grinding balls with the diameter of 10mm and 10 zirconia grinding balls with the diameter of 5mm, and continuously milling for 40 hours in a BM6 planetary ball mill at 500 rpm; and (3) carrying out vacuum drying on the product obtained by the ball-milling reaction for 2 hours at the temperature of 60 ℃ and under the vacuum degree of 0.1MPa to obtain the CZTSSe powder.
Performance testing
XRD analysis was performed on the CZTSSe powders obtained in examples 7 to 8, and the results are shown in FIGS. 6 to 7. The mole ratio of the copper, zinc, tin, sulfur and selenium in the reaction raw materials is respectively 2: 1: 2 and 2: 1: 3: 1, and the X-ray diffraction pattern obtained by continuously grinding for 60 hours at 500rpm has three obvious strong peaks and no impurity peak, which indicates that the sample has good crystallization and no impurity phase. In addition, as sulfur/(sulfur + selenium) increases, diffraction shifts to a high angle direction. The above results show that: single phase CZTSSe powder was obtained by simple mechanical ball milling at room temperature.
Example 11
This example prepares Cu as follows2Zn(Sn1-x，Gex)S4Nano powder:
weighing copper powder, zinc powder, tin powder, germanium powder and sulfur powder elementary substance powder (total 20g) according to a molar ratio of 2: 1: 0.9: 0.1: 4 (namely x is 0.1), and uniformly mixing in a glove box under a nitrogen atmosphere to obtain mixed powder; putting the mixed powder and zirconia grinding balls into a 250mL ball-milling tank according to the mass ratio of 1:3, and carrying out ball milling for 40 hours in a BM6 planetary ball mill at 500rpm to carry out solid-phase reaction; vacuum drying the obtained product at 60 deg.C under 0.1MPa for 2 hr to obtain Cu2ZnSn0.9Ge0.1S4And (3) powder.
Example 12
This example prepares Cu as follows2Zn(Sn1-x，Gex)S4Powder:
weighing copper powder, zinc powder, tin powder, germanium powder and sulfur powder elementary substance powder (total 20g) according to a molar ratio of 2: 1: 0.8: 0.2: 4 (namely x is 0.2), and uniformly mixing in a glove box under a nitrogen atmosphere to obtain mixed powder; putting the mixed powder and zirconia grinding balls into a 250mL ball-milling tank according to the mass ratio of 1:3, and carrying out ball milling for 40 hours in a BM6 planetary ball mill at 500 rpm; vacuum drying the product obtained by the ball milling reaction for 2 hours at the temperature of 60 ℃ and the vacuum degree of 0.1MPa to prepare Cu2ZnSn0.8Ge0.2S4And (3) powder.
Example 13
This example prepares Cu as follows2Zn(Sn1-x，Gex)S4Powder:
weighing copper powder, zinc powder, tin powder, germanium powder and sulfur powder elementary substance powder (total 20g) according to the molar ratio of 2: 1: 0.7: 0.3: 4 (namely x is 0.3), and uniformly mixing in a glove box under nitrogen atmosphere to obtain a mixed powderMixing the powder; putting the mixed powder and zirconia grinding balls into a 250mL ball-milling tank according to the mass ratio of 1:3, and carrying out ball milling for 20 hours in a BM6 planetary ball mill at 500 rpm; vacuum drying the product obtained by the ball milling reaction for 2 hours at the temperature of 60 ℃ and the vacuum degree of 0.1MPa to prepare Cu2ZnSn0.7Ge0.3S4And (3) powder.
Example 14
This example prepares Cu as follows2Zn(Sn1-x，Gex)S4Powder:
weighing copper powder, zinc powder, tin powder, germanium powder and sulfur powder elementary substance powder (total 20g) according to a molar ratio of 2: 1: 0.6: 0.4: 4 (namely x is 0.4), and uniformly mixing in a glove box under a nitrogen atmosphere to obtain mixed powder; putting the mixed powder and zirconia grinding balls into a 250mL ball-milling tank according to the mass ratio of 1:3, and carrying out ball milling for 20 hours in a BM6 planetary ball mill at 500 rpm; vacuum drying the product obtained by the ball milling reaction for 2 hours at the temperature of 60 ℃ and the vacuum degree of 0.1MPa to prepare Cu2ZnSn0.6Ge0.4S4And (3) powder.
Example 15
This example prepares Cu as follows2Zn(Sn1-x，Gex)S4Powder:
weighing copper powder, zinc powder, tin powder, germanium powder and sulfur powder elementary substance powder (total 20g) according to a molar ratio of 2: 1: 0.5: 4 (namely x is 0.5), and uniformly mixing in a glove box under a nitrogen atmosphere to obtain mixed powder; putting the mixed powder and zirconia grinding balls into a 250mL ball-milling tank according to the mass ratio of 1:3, and carrying out ball milling for 60 hours in a BM6 planetary ball mill at 500 rpm; vacuum drying the product obtained by the ball milling reaction for 2 hours at the temperature of 60 ℃ and the vacuum degree of 0.1MPa to prepare Cu2ZnSn0.5Ge0.5S4And (3) powder.
Performance testing
1) Cu obtained in examples 11 to 15 was used2Zn(Sn1-x，Gex)S4XRD analysis of the powder showed that FIG. 8; as can be seen from FIG. 8, the molar ratios of the simple substances of Cu, Zn, Sn and S in the reaction raw materials are respectively 2: 1: 0.9: 0.1: 4 and 2: 1: 0.8: 02: 4, 2: 1: 0.7: 0.3: 4, 2: 1: 0.6: 0.4: 4, 2: 1: 0.5: the X-ray diffraction patterns obtained after heat treatment after grinding for 40 hours, 20 hours and 60 hours at 500rpm of 0.5: 4 are consistent with that of standard card JCPDS26-0575 and have three obvious diffraction peaks, and the diffraction peaks are slightly shifted due to Ge doping, which shows that the method can obtain the single-phase Cu doped with germanium2Zn(Sn1-x,Gex)S4And (3) powder.
2) For Cu prepared in examples 11 to 142Zn(Sn1-x，Gex)S4The powder was subjected to optical property analysis (UV-Vis analysis), and the obtained powder was typical (ahv)2FIG. 9 shows the relationship between Ge/(Sn + Ge) ═ 0.1EgI.e. x is 0.1, Ge/(Sn + Ge) is 0.2EgNamely, x is 0.2; Ge/(Sn + Ge) ═ 0.3EgNamely, x is 0.3; Ge/(Sn + Ge) ═ 0.4EgNamely, x is 0.4; the abscissa is photon energy, the ordinate is the square of the product of light absorption coefficient multiplied by photon energy, the dotted line is the intersection point of the tangent of the linear part of the curve and the abscissa, the intersection point of the tangent of the linear part and the X axis is the band gap width, the Ge content is different, and the band gap width is different. As can be seen from fig. 9, the band gap can be controllably adjusted by controlling the germanium doping amount.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The preparation method of the copper-zinc-tin-based powder is characterized by comprising the following steps of:
mixing raw materials corresponding to the copper-zinc-tin-based powder to obtain mixed powder;
carrying out mechanical ball milling on the mixed powder to initiate a solid-phase reaction, and drying in vacuum to obtain copper-zinc-tin-based powder;
the raw materials corresponding to the copper-zinc-tin-based powder comprise copper powder, zinc powder and tin powder, and also comprise sulfur powder and/or selenium powder;
or the raw materials corresponding to the copper-zinc-tin-based powder simultaneously comprise copper powder, zinc powder, tin powder, sulfur powder and germanium powder.
2. The preparation method of claim 1, wherein when the raw materials corresponding to the copper-zinc-tin-based powder comprise copper powder, zinc powder, tin powder, and sulfur powder, and further comprise sulfur powder or selenium powder, the molar ratio of the copper powder, the zinc powder, the tin powder, and the sulfur powder is 2: 1: 1: 4; the molar ratio of the copper powder to the zinc powder to the tin powder to the selenium powder is 2: 1: 1: 4.
3. the preparation method of claim 1, wherein when the copper-zinc-tin-based powder comprises copper powder, zinc powder, tin powder, sulfur powder and selenium powder, the molar ratio of the copper powder, the zinc powder, the tin powder, the sulfur powder and the selenium powder is 2: 1: 1: x: (4-x), wherein 0< x < 4.
4. The preparation method of claim 1, wherein when the raw materials corresponding to the copper-zinc-tin-based powder simultaneously comprise copper powder, zinc powder, tin powder, sulfur powder and germanium powder, the molar ratio of the copper powder, the zinc powder, the tin powder, the germanium powder and the sulfur powder is 2: 1: (1-x): x: 4, wherein x is more than or equal to 0 and less than or equal to 1.
5. The method of claim 1, wherein the mechanical ball milling is performed at a speed of 500 rpm.
6. The method according to claim 1, wherein the temperature of the solid phase reaction is room temperature, and the time of the solid phase reaction is 10 to 80 hours.
7. The preparation method according to claim 1, wherein the temperature of the vacuum drying is 50-70 ℃, the pressure is 0-0.1 MPa, and the time is 1-2 h.
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