CN106517314A - Preparing method of CZTS particulates - Google Patents
Preparing method of CZTS particulates Download PDFInfo
- Publication number
- CN106517314A CN106517314A CN201611108193.8A CN201611108193A CN106517314A CN 106517314 A CN106517314 A CN 106517314A CN 201611108193 A CN201611108193 A CN 201611108193A CN 106517314 A CN106517314 A CN 106517314A
- Authority
- CN
- China
- Prior art keywords
- zinc
- tin
- copper
- czts
- salt
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 26
- 238000005119 centrifugation Methods 0.000 claims abstract description 15
- 239000002159 nanocrystal Substances 0.000 claims abstract description 15
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims abstract description 14
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 8
- 239000012498 ultrapure water Substances 0.000 claims abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 16
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000000047 product Substances 0.000 description 15
- 229910052984 zinc sulfide Inorganic materials 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000005693 optoelectronics Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- 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 tin, with or without oxygen or hydrogen, and containing two or more other elements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明公开了一种铜锌锡硫纳米晶的制备方法，属光电材料制备领域。包括以下步骤：将铜盐、锌盐、锡盐、硫源和十六烷基三甲基溴化铵加入容器中，向容器中加入乙二醇和三乙烯四胺混合溶液并超声至溶解得到前驱体溶液；对前驱体溶液进行两步加热反应，反应完成后自然冷却至室温；向冷却后的反应液中分别加入无水乙醇和超纯水洗涤、经离心分离得到CZTS纳米晶沉淀物；将得到的CZTS纳米晶沉淀物干燥，即得到晶相可控的CZTS纳米晶粉末。该方法简单、成本低，适合批量合成。The invention discloses a method for preparing copper-zinc-tin-sulfur nanocrystals, belonging to the field of photoelectric material preparation. The method comprises the following steps: adding copper salt, zinc salt, tin salt, sulfur source and cetyltrimethylammonium bromide into a container, adding a mixed solution of ethylene glycol and triethylenetetramine into the container and ultrasonicating until dissolved to obtain a precursor The precursor solution is subjected to two-step heating reaction, and after the reaction is completed, it is naturally cooled to room temperature; absolute ethanol and ultrapure water are added to the cooled reaction solution to wash, and the CZTS nanocrystal precipitate is obtained by centrifugation; The obtained CZTS nanocrystal precipitate is dried to obtain CZTS nanocrystal powder with controllable crystal phase. The method is simple, low-cost, and suitable for batch synthesis.
Description
技术领域technical field
本发明涉及一种铜锌锡硫（Cu2ZnSnS4, CZTS）微粒的制备方法，属于属光电材料制备领域。The invention relates to a method for preparing copper-zinc-tin-sulfur (Cu 2 ZnSnS 4 , CZTS) particles, which belongs to the field of photoelectric material preparation.
背景技术Background technique
新型四元化合物半导体铜锌锡硫（Cu2ZnSnS4, CZTS）具有较高的光吸收系数(>104cm-1)，禁带宽度约1.5eV（与太阳能电池所需要的最佳禁带宽度相匹配），组成元素在在地壳中含量丰富、价格低廉，且成分无毒而适于非真空制备技术条件，因此CZTS是一种绿色、廉价、安全、适合大规模生产与应用的光伏材料。The new quaternary compound semiconductor copper zinc tin sulfur (Cu 2 ZnSnS 4 , CZTS) has a high light absorption coefficient (>10 4 cm -1 ), and a band gap of about 1.5eV (which is the best band gap required by solar cells. Width matches), the composition elements are abundant in the earth's crust, low in price, and the composition is non-toxic and suitable for non-vacuum preparation technology conditions, so CZTS is a green, cheap, safe, suitable for large-scale production and application of photovoltaic materials .
CZTS主要有黄锡矿、黄锡矿和纤锌矿三种晶型结构，其中锌黄锡矿和黄锡矿相具有四方晶系结构的，它们是热力学稳定相，纤锌矿相属于六方晶系结构，是热力学亚稳相。据报道，以锌黄锡矿结构CZTS为吸收层材料的CZTS薄膜太阳能电池的光电转换效率已达12.6%，以纤锌矿结构CZTS为吸收层材料的薄膜太阳能电池的光电转换效率为4.3%；而以纤锌矿CZTS和锌黄锡矿CZTS作为染料敏化太阳能电池的对电极时，电池的转换效率分别为6.89%和4.89%。这些结果表明，光电材料的晶体结构对光伏器件的光电性能具有重要影响。因此，可控合成晶体结构不同的CZTS对提高光电器件性能具有重要意义。CZTS mainly has three crystal structures of kesterite, kesterite and wurtzite, among which kesterite and kesterite phases have tetragonal crystal structure, which are thermodynamically stable phases, and wurtzite phase belongs to hexagonal crystal structure The system structure is a thermodynamically metastable phase. According to reports, the photoelectric conversion efficiency of CZTS thin-film solar cells with kesterite structure CZTS as the absorption layer material has reached 12.6%, and the photoelectric conversion efficiency of thin-film solar cells with wurtzite structure CZTS as the absorption layer material is 4.3%; When wurtzite CZTS and kesterite CZTS were used as the counter electrodes of dye-sensitized solar cells, the conversion efficiencies of the cells were 6.89% and 4.89%, respectively. These results indicate that the crystal structure of optoelectronic materials has an important influence on the optoelectronic performance of photovoltaic devices. Therefore, the controllable synthesis of CZTS with different crystal structures is of great significance for improving the performance of optoelectronic devices.
经文献检索发现，现有多种关于晶相可控CZTS的制备方法。但这些工艺反应所需应时间长（24h），不利于实现高效、快速的制备。专利CN201510456207.4使用单质硫和十二硫醇作为混合硫源，通过调控单质硫与十二硫醇的比例实现控制CZTS纳米材料中锌黄锡矿和纤锌矿的比例，但整个反应过程需要氩气保护，且反应温度较高，不利于低成本、大规模制备CZTS。Through literature search, it is found that there are many preparation methods for CZTS with controllable crystal phase. However, these processes require a long reaction time (24h), which is not conducive to the realization of efficient and rapid preparation. Patent CN201510456207.4 uses elemental sulfur and dodecanethiol as a mixed sulfur source, and controls the ratio of kesterite and wurtzite in CZTS nanomaterials by adjusting the ratio of elemental sulfur to dodecanethiol, but the entire reaction process requires Argon protection and high reaction temperature are not conducive to low-cost and large-scale preparation of CZTS.
发明内容Contents of the invention
本发明的目的在于针对上述现有技术的提供一种铜锌锡硫纳米晶的制备方法，采用两步加热法在空气中合成铜锌锡硫微粒，通过简单调节溶剂比例得到晶相可控的CZTS纳米晶，具体包括以下步骤：The purpose of the present invention is to provide a method for preparing copper-zinc-tin-sulfur nanocrystals in view of the above-mentioned prior art, using a two-step heating method to synthesize copper-zinc-tin-sulfur particles in the air, and obtaining crystal phase-controllable particles by simply adjusting the solvent ratio. CZTS nanocrystals specifically include the following steps:
（1）将铜盐、锌盐、锡盐、硫源和表面活性剂加入反应容器中，向反应容器中加入乙二醇和三乙烯四胺的混合溶液并超声溶解，其中，乙二醇的体积占混合溶液总体积的百分比为≥1.25%，三乙烯四胺的体积占混合溶液总体积的百分比为≥1.25%。(1) Add copper salt, zinc salt, tin salt, sulfur source and surfactant into the reaction vessel, add a mixed solution of ethylene glycol and triethylenetetramine into the reaction vessel and dissolve it ultrasonically. Among them, the volume of ethylene glycol The percentage of the total volume of the mixed solution is ≥ 1.25%, and the percentage of the volume of triethylenetetramine to the total volume of the mixed solution is ≥ 1.25%.
（2）对步骤1所得溶液进行两步加热反应。(2) Perform two-step heating reaction on the solution obtained in step 1.
（3）完成两步加热反应的反应液自然冷却至室温，向冷却后的反应液中分别加入无水乙醇和超纯水进行洗涤、然后经离心分离得到CZTS纳米晶沉淀物，将得到的CZTS纳米晶沉淀物干燥，即得到CZTS纳米晶。(3) The reaction solution that completed the two-step heating reaction was naturally cooled to room temperature, absolute ethanol and ultrapure water were added to the cooled reaction solution for washing, and then CZTS nanocrystalline precipitate was obtained by centrifugation, and the obtained CZTS The nanocrystal precipitate is dried to obtain CZTS nanocrystal.
优选的，本发明所述铜盐为二水合氯化铜、一水合醋酸铜、五水合硫酸铜中的一种。Preferably, the copper salt described in the present invention is one of copper chloride dihydrate, copper acetate monohydrate, and copper sulfate pentahydrate.
优选的，本发明所述锌盐为氯化锌、二水合醋酸锌、七水合硫酸锌中的一种。Preferably, the zinc salt of the present invention is one of zinc chloride, zinc acetate dihydrate, and zinc sulfate heptahydrate.
优选的，本发明所述锡盐为二水合氯化亚锡、四氯化锡中的一种。Preferably, the tin salt described in the present invention is one of stannous chloride dihydrate and tin tetrachloride.
优选的，本发明所述硫源为硫脲、硫粉、硫代乙酰胺中的一种。Preferably, the sulfur source in the present invention is one of thiourea, sulfur powder, and thioacetamide.
优选的，本发明所述铜盐、锌盐、锡盐和硫源的摩尔比为2:(1-1. 5):(1-1.25):(4-6)。Preferably, the molar ratio of the copper salt, zinc salt, tin salt and sulfur source of the present invention is 2:(1-1.5):(1-1.25):(4-6).
优选的，本发明所述表面活性剂为十六烷基三甲基溴化铵，其加入量为0-12.5mg/mL。Preferably, the surfactant described in the present invention is cetyltrimethylammonium bromide, and its addition amount is 0-12.5 mg/mL.
优选的，本发明步骤（2）中两步加热反应的温度和时间分别为120-150℃，20min-1h和180-220℃，1-4h，加热过程中通过磁力搅拌器对反应液进行搅拌，搅拌速度为300-900rpm。Preferably, the temperature and time of the two-step heating reaction in step (2) of the present invention are 120-150°C, 20min-1h and 180-220°C, 1-4h, and the reaction solution is stirred by a magnetic stirrer during the heating process , the stirring speed is 300-900rpm.
优选的，本发明步骤（3）中分别加入无水乙醇和超纯水进行洗涤、然后离心分离，“洗涤、离心分离”的次数为3-5次，离心时离心机转速为8000-12000rpm，离心时间为3-5min；干燥的条件为60-100℃下干燥6-12h。Preferably, in the step (3) of the present invention, absolute ethanol and ultrapure water are respectively added for washing, and then centrifuged. The number of "washing and centrifuging" is 3-5 times, and the centrifuge speed is 8000-12000rpm during centrifugation. The centrifugation time is 3-5min; the drying condition is 6-12h at 60-100°C.
本发明所有操作均在空气中进行。All operations of the present invention are carried out in air.
本发明的有益效果：Beneficial effects of the present invention:
（1）本发明所述方法所用到的原料易得、无毒、成本低；整个工艺操作均在空气条件下进行，不需要惰性气体保护环境，制备过程简单、直观可控；设备要求低，易于实现大规模生产。(1) The raw materials used in the method of the present invention are easy to obtain, non-toxic, and low in cost; the entire process operation is carried out under air conditions, no inert gas is required to protect the environment, and the preparation process is simple, intuitive and controllable; the equipment requirements are low, Easy to achieve mass production.
（2）本发明以低毒的乙二醇和三乙烯四胺混合液作为溶剂，可以通过简单调控乙二醇和三乙烯四胺的比例得到纯相锌黄锡矿结构的CZTS、纯相纤锌矿结构的CZTS以及两相混合的CZTS，实现CZTS的物相可控；同时，可以控制CZTS微粒的形貌从颗粒状、花簇状，以及具有微纳复合结构的变化，有利于提高光电器件的转换效率。(2) The present invention uses low-toxic ethylene glycol and triethylenetetramine mixture as a solvent, and can obtain pure-phase kesterite structure CZTS and pure-phase wurtzite by simply adjusting the ratio of ethylene glycol and triethylenetetramine Structured CZTS and two-phase mixed CZTS realize the controllable phase of CZTS; at the same time, the morphology of CZTS particles can be controlled from granular, flower-like, and micro-nano composite structures, which is conducive to improving the performance of optoelectronic devices. conversion efficiency.
（3）本发明所述方法制备得到的CZTS粉体结晶性好、尺寸均匀，可见光区域具有良好的吸收，所得CZTS粉体禁带宽度为1.42-1.48eV，非常接近薄膜太阳能电池吸收层材料所需最佳禁带宽度（1.5eV），适用于太阳能电池领域。(3) The CZTS powder prepared by the method of the present invention has good crystallinity, uniform size, and good absorption in the visible light region. The band gap of the obtained CZTS powder is 1.42-1.48eV, which is very close to that of the thin film solar cell absorbing layer material. The optimum band gap (1.5eV) is required, which is suitable for the field of solar cells.
附图说明Description of drawings
图1为发明流程示意图；Fig. 1 is a schematic diagram of the invention process;
图2为实施例1制备的样品的XRD图；Fig. 2 is the XRD figure of the sample prepared in embodiment 1;
图3为实施例2制备的样品的XRD图；Fig. 3 is the XRD pattern of the sample prepared in embodiment 2;
图4为实施例3制备的样品的XRD图；Fig. 4 is the XRD pattern of the sample prepared in embodiment 3;
图5为实施例4制备的样品的XRD图；Fig. 5 is the XRD figure of the sample prepared in embodiment 4;
图6为实施例4中a的样品的SEM图；Fig. 6 is the SEM picture of the sample of a in embodiment 4;
图7为实施例4中b的样品的SEM图；Fig. 7 is the SEM figure of the sample of b in embodiment 4;
图8为实施例4中c的样品的SEM图；Fig. 8 is the SEM picture of the sample of c in embodiment 4;
图9为实施例4中d的样品的SEM图；Fig. 9 is the SEM picture of the sample of d in embodiment 4;
图10为实施例4中a样品的UV-vis吸收光谱图和(αhν)2~hν图谱；Fig. 10 is the UV-vis absorption spectrogram and (αhν) 2 ～hν collection of spectra of sample a in embodiment 4;
图11为实施例4中c样品的UV-vis吸收光谱图和(αhν)2~hν图谱。Figure 11 is the UV-vis absorption spectrum and (αhν) 2 ~hν spectrum of sample c in Example 4.
具体实施方式detailed description
下面结合附图和具体实施例对本发明作进一步详细说明，但本发明的保护范围并不限于所述内容。The present invention will be described in further detail below in conjunction with the accompanying drawings and specific embodiments, but the protection scope of the present invention is not limited to the content described.
实施例1Example 1
（1）将2mmol二水合氯化铜、1mmol二水合醋酸锌、1mmol二水合氯化亚锡、4mmol硫粉和0.1g十六烷基三甲基溴化铵加入三口烧瓶中，向三口烧瓶中加入36mL乙二醇和4mL三乙烯四胺混合液，频率为28KHz的超声波清洗机超声15min。(1) Add 2mmol copper chloride dihydrate, 1mmol zinc acetate dihydrate, 1mmol stannous chloride dihydrate, 4mmol sulfur powder and 0.1g hexadecyltrimethylammonium bromide into a three-necked flask, and add Add 36mL of ethylene glycol and 4mL of triethylenetetramine mixed solution, and ultrasonic cleaner with a frequency of 28KHz for 15min.
（2）对步骤1所得溶液进行两步加热反应。两步加热反应的温度、时间分别为：120℃，20min和180℃，4h；加热过程中，通过磁力搅拌器对反应液进行搅拌，搅拌速度为360rpm。(2) Perform two-step heating reaction on the solution obtained in step 1. The temperature and time of the two-step heating reaction are respectively: 120° C., 20 minutes and 180° C., 4 hours; during the heating process, the reaction solution is stirred by a magnetic stirrer at a stirring speed of 360 rpm.
（3）使两步加热反应得到的反应液自然冷却至室温，向冷却后的反应液中分别3次加入无水乙醇和超纯水进行离心分离（离心机转速：8000rpm，每次离心时间：3min）得到CZTS纳米晶沉淀物，对得到的CZTS纳米晶胶体在60℃干燥8h，即得到纯相锌黄锡矿结构的CZTS纳米晶粉末。(3) Cool the reaction solution obtained by the two-step heating reaction to room temperature naturally, add absolute ethanol and ultrapure water to the cooled reaction solution three times for centrifugation (centrifuge speed: 8000rpm, each centrifugation time: 3min) to obtain a CZTS nanocrystalline precipitate, and dry the obtained CZTS nanocrystalline colloid at 60° C. for 8 hours to obtain a CZTS nanocrystalline powder with a pure phase kesterite structure.
对本实施例制备所得产物进行XRD测试，如图2所示，2θ=28.41°, 32.92°,47.30°, 56.15°, 76.46°处的衍射峰分别与锌黄锡矿CZTS的 (112), (200), (220),(312), (332)晶面相对应，表明所得产物为锌黄锡矿相CZTS晶体。The resulting product prepared in this embodiment is tested by XRD, as shown in Figure 2, the diffraction peaks at 2θ=28.41°, 32.92°, 47.30°, 56.15°, and 76.46° are respectively corresponding to (112), (200°) of kesterite CZTS ), (220), (312), (332) crystal planes correspond to each other, indicating that the obtained product is a kesterite phase CZTS crystal.
实施例2Example 2
（1）将2mmol一水合醋酸铜、1.2mmol氯化锌、1mmol四氯化锡和5mmol硫代乙酰胺加入三口烧瓶中，向三口烧瓶中加入8mL乙二醇和32mL三乙烯四胺混合液，频率为28KHz的超声波清洗机超声45min。(1) Add 2mmol copper acetate monohydrate, 1.2mmol zinc chloride, 1mmol tin tetrachloride and 5mmol thioacetamide into a three-necked flask, add 8mL ethylene glycol and 32mL triethylenetetramine mixed solution into the three-necked flask, frequency Ultrasonic for 45min with a 28KHz ultrasonic cleaner.
（2）对步骤1所得溶液进行两步加热反应。两步加热反应的温度、时间分别为：120℃，30min和190℃，3h；加热过程中，通过磁力搅拌器对反应液进行搅拌，搅拌速度为400rpm。(2) Perform two-step heating reaction on the solution obtained in step 1. The temperature and time of the two-step heating reaction are respectively: 120° C., 30 minutes and 190° C., 3 hours; during the heating process, the reaction solution is stirred by a magnetic stirrer at a stirring speed of 400 rpm.
（3）使两步加热反应得到的反应液自然冷却至室温，向冷却后的反应液中分别3次加入无水乙醇和超纯水进行离心分离（离心机转速：8600rpm，每次离心时间：3min）得到CZTS纳米晶沉淀物，对得到的CZTS纳米晶胶体在80℃干燥8h，即得到锌黄锡矿和纤锌矿两相混合的CZTS纳米晶粉末。(3) Cool the reaction solution obtained from the two-step heating reaction to room temperature naturally, add absolute ethanol and ultrapure water to the cooled reaction solution three times for centrifugation (centrifuge speed: 8600rpm, each centrifugation time: 3min) to obtain a CZTS nanocrystalline precipitate, and dry the obtained CZTS nanocrystalline colloid at 80° C. for 8 hours to obtain a CZTS nanocrystalline powder mixed with kesterite and wurtzite.
对本实施例制备所得产物进行XRD测试，如图3所示，2θ=28.41°、32.92°、47.30°、56.15°处的衍射峰分别与锌黄锡矿CZTS的 (112)、(200)、(220)、(312)晶面相对应，而2θ=26.91°、28.50°、30.53°、39.61°、47.56°、51.78°、56.39°处的衍射峰分别与纤锌矿CZTS的(100)、(002)、(101)、(102)、(110)、(103)、(112)晶面相对应，表明所得产物的为锌黄锡矿相CZTS和纤锌矿相CZTS的混合晶体。Carry out XRD test to the product prepared in this embodiment, as shown in Figure 3, the diffraction peaks at 2θ=28.41°, 32.92°, 47.30°, and 56.15° are respectively corresponding to (112), (200), ( 220), (312) corresponding to the crystal planes, and the diffraction peaks at 2θ=26.91°, 28.50°, 30.53°, 39.61°, 47.56°, 51.78°, 56.39° are corresponding to the (100), (002 ), (101), (102), (110), (103), and (112) crystal planes correspond to each other, indicating that the obtained product is a mixed crystal of kesterite phase CZTS and wurtzite phase CZTS.
实施例3Example 3
（1）将2mmol五水合硫酸铜、1.2mmol七水合硫酸锌、1.2mmol二水合氯化亚锡和5mmol硫脲加入三口烧瓶中，向三口烧瓶中加入20mL乙二醇和20mL三乙烯四胺混合液，频率为28KHz的超声波清洗机超声1.5h。(1) Add 2mmol of copper sulfate pentahydrate, 1.2mmol of zinc sulfate heptahydrate, 1.2mmol of stannous chloride dihydrate and 5mmol of thiourea into a three-necked flask, and add 20mL of ethylene glycol and 20mL of triethylenetetramine mixture into the three-necked flask , Ultrasonic cleaner with a frequency of 28KHz for 1.5h.
（2）对步骤1所得溶液进行两步加热反应。两步加热反应的温度、时间分别为：140℃，30min和190℃，2h；加热过程中，通过磁力搅拌器对反应液进行搅拌，搅拌速度为600rpm。(2) Perform two-step heating reaction on the solution obtained in step 1. The temperature and time of the two-step heating reaction are respectively: 140° C., 30 minutes and 190° C., 2 hours; during the heating process, the reaction solution is stirred by a magnetic stirrer at a stirring speed of 600 rpm.
（3）使两步加热反应得到的反应液自然冷却至室温，向冷却后的反应液中分别4次加入无水乙醇和超纯水进行离心分离（离心机转速：9000rpm，每次离心时间：5min）得到CZTS纳米晶沉淀物，对得到的CZTS纳米晶胶体在60℃干燥12h，即得到锌黄锡矿和纤锌矿两相混合的CZTS纳米晶粉末。(3) Cool the reaction solution obtained by the two-step heating reaction to room temperature naturally, add absolute ethanol and ultrapure water to the cooled reaction solution for 4 times for centrifugation (centrifuge speed: 9000rpm, each centrifugation time: 5 minutes) to obtain a CZTS nanocrystal precipitate, and dry the obtained CZTS nanocrystal colloid at 60° C. for 12 hours to obtain a CZTS nanocrystal powder in which kesterite and wurtzite are mixed.
对本实施例制备所得产物进行XRD测试，如图4所示，2θ=26.91°、28.50°、30.53°、39.61°、47.56°、51.78°、56.39°处的衍射峰分别与纤锌矿CZTS的 (100)、(002)、(101)、(102)、(110)、(103)、(112)晶面相对应，表明所得产物的为纤锌矿相CZTS晶体。Carry out XRD test to the product prepared in this embodiment, as shown in Figure 4, the diffraction peaks at 2θ=26.91°, 28.50°, 30.53°, 39.61°, 47.56°, 51.78°, and 56.39° are respectively corresponding to those of wurtzite CZTS ( 100), (002), (101), (102), (110), (103), and (112) correspond to crystal planes, indicating that the obtained product is a wurtzite phase CZTS crystal.
实施例4Example 4
（1）将2mmol二水合氯化铜、1.25mmol二水合醋酸锌、1mmol二水合氯化亚锡、6mmol硫脲加入三口烧瓶中，向三口烧瓶中加入40mL乙二醇和三乙烯四胺混合液（乙二醇和三乙烯四胺的体积及相应产物的物相、形貌如表1所示），频率为28KHz的超声波清洗机超声2h。(1) Add 2mmol copper chloride dihydrate, 1.25mmol zinc acetate dihydrate, 1mmol stannous chloride dihydrate, and 6mmol thiourea into a three-necked flask, and add 40mL of a mixture of ethylene glycol and triethylenetetramine to the three-necked flask ( The volumes of ethylene glycol and triethylenetetramine and the phases and shapes of the corresponding products are shown in Table 1), and the ultrasonic cleaning machine with a frequency of 28KHz was ultrasonicated for 2h.
（2）对步骤1所得溶液进行两步加热反应。两步加热反应的温度、时间分别为：130℃，30min和200℃，2h；加热过程中，通过磁力搅拌器对反应液进行搅拌，搅拌速度为800rpm。(2) Perform two-step heating reaction on the solution obtained in step 1. The temperature and time of the two-step heating reaction are respectively: 130° C., 30 minutes and 200° C., 2 hours; during the heating process, the reaction solution is stirred by a magnetic stirrer at a stirring speed of 800 rpm.
（3）使两步加热反应得到的反应液自然冷却至室温，向冷却后的反应液中分别3次加入无水乙醇和超纯水进行离心分离（离心机转速：12000rpm，每次离心时间：4min）得到CZTS纳米晶沉淀物，对得到的CZTS纳米晶胶体在80℃干燥8h，即得到物相结构可控的CZTS粉末。(3) Cool the reaction solution obtained by the two-step heating reaction to room temperature naturally, add absolute ethanol and ultrapure water to the cooled reaction solution three times for centrifugation (centrifuge speed: 12000rpm, each centrifugation time: 4min) to obtain a CZTS nanocrystal precipitate, and dry the obtained CZTS nanocrystal colloid at 80°C for 8h to obtain a CZTS powder with a controllable phase structure.
对本实施例制备所得产物进行XRD、SEM和紫外-可见光吸收光谱测试。如图5所示，类似实施例1、2、3所得产物的分析，表明该实施例中所得产物a为锌黄锡矿相CZTS晶体、b为锌黄锡矿相CZTS和纤锌矿相CZTS的混合晶体、c和d均为纤锌矿相CZTS晶体。XRD, SEM and ultraviolet-visible light absorption spectrum tests were performed on the product prepared in this embodiment. As shown in Figure 5, similar to the analysis of the products obtained in Examples 1, 2, and 3, it is shown that the product a obtained in this example is a kesterite phase CZTS crystal, b is kesterite phase CZTS and wurtzite phase CZTS The mixed crystals of c and d are all wurtzite phase CZTS crystals.
如图6的SEM照片表明该实施例中产物a为直径在300-700nm的CZTS颗粒；图7的SEM照片表明该实施例中产物b为直径在300-500nm的花簇状CZTS；图8的SEM照片表明该实施例中产物c为直径在100-400nm的不规则块状CZTS；图9的SEM照片表明该实施例中产物d为具有微纳复合结构的CZTS，此结构由直径为200-800nm，厚度为20-70nm的块状颗粒和在这种颗粒表面长着的长40-120nm、宽6-15nm的蠕虫状纳米线组成。The SEM photo of Figure 6 shows that product a is a CZTS particle with a diameter of 300-700nm in this embodiment; the SEM photo of Figure 7 shows that product b is a flower cluster CZTS with a diameter of 300-500nm in this embodiment; The SEM photo shows that the product c in this example is an irregular block CZTS with a diameter of 100-400 nm; the SEM photo of Figure 9 shows that the product d in this example is a CZTS with a micro-nano composite structure, which consists of a diameter of 200-400 nm. 800nm, blocky particles with a thickness of 20-70nm and worm-like nanowires with a length of 40-120nm and a width of 6-15nm growing on the surface of the particles.
图10、11为该实施例中样品a、d的紫外-可见光吸收光谱图和相应的(αhν)2~hν图谱，紫外-可见光吸收光谱图是测得的原始数据图，(αhν)2~hν图谱由紫外-可见光吸收光谱推出，结合两图可知，样品a、d在可见光区域均具有很强的吸收且一直延伸至近红外区，其禁带宽度分别为1.43 eV、1.48eV，接近薄膜太阳能电池吸收层材料所需最佳禁带宽度（1.5eV），对制备得到的太阳能薄膜电池的性能提高是有利的。Figures 10 and 11 are the UV-visible light absorption spectra and the corresponding (αhν) 2 ~hν spectra of samples a and d in this example, the UV-visible light absorption spectra are the original data graphs measured, (αhν) 2 ~ The hν spectrum is deduced from the ultraviolet-visible light absorption spectrum. Combining the two figures, it can be seen that both samples a and d have strong absorption in the visible light region and extend to the near-infrared region. The optimal band gap (1.5eV) required for the battery absorbing layer material is beneficial to the performance improvement of the prepared solar thin film battery.
表1. 实施例4的溶剂中乙二醇和三乙烯四胺体积及相应产物的物相、形貌The phase, appearance of ethylene glycol and triethylenetetramine volume and corresponding product in the solvent of table 1. embodiment 4
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611108193.8A CN106517314A (en) | 2016-12-06 | 2016-12-06 | Preparing method of CZTS particulates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611108193.8A CN106517314A (en) | 2016-12-06 | 2016-12-06 | Preparing method of CZTS particulates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106517314A true CN106517314A (en) | 2017-03-22 |
Family
ID=58342647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611108193.8A Pending CN106517314A (en) | 2016-12-06 | 2016-12-06 | Preparing method of CZTS particulates |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106517314A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110465309A (en) * | 2019-07-22 | 2019-11-19 | 昆明理工大学 | ZnS nano-particles reinforcement porous C u3SnS4The preparation method of the P-N bulk heterojunction photochemical catalyst of particle |
| CN112279306A (en) * | 2020-10-21 | 2021-01-29 | 南京晓庄学院 | Optimization method of sulfide nanocrystal, Sn-S-Co nanocrystal and optimized product thereof |
| CN113979468A (en) * | 2021-12-09 | 2022-01-28 | 山东中鸿新能源科技有限公司 | Preparation method of CZTS (Se) nano powder for solar cell module |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102254985A (en) * | 2011-04-14 | 2011-11-23 | 山东大学 | Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material |
| CN103359777A (en) * | 2012-03-29 | 2013-10-23 | 上海交通大学 | A kind of hydrothermal preparation method of Cu2ZnSnS4 and its Cu2ZnSnS4 material and application |
| CN103420411A (en) * | 2013-07-11 | 2013-12-04 | 南京航空航天大学 | A method of ultrasonic-assisted microwave controllable preparation of Cu2ZnSnS4 nanoparticles |
| CN105669045A (en) * | 2016-01-11 | 2016-06-15 | 广东工业大学 | A kind of preparation method and application of Cu2ZnSnS4/graphene composite semiconductor film |
-
2016
- 2016-12-06 CN CN201611108193.8A patent/CN106517314A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102254985A (en) * | 2011-04-14 | 2011-11-23 | 山东大学 | Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material |
| CN103359777A (en) * | 2012-03-29 | 2013-10-23 | 上海交通大学 | A kind of hydrothermal preparation method of Cu2ZnSnS4 and its Cu2ZnSnS4 material and application |
| CN103420411A (en) * | 2013-07-11 | 2013-12-04 | 南京航空航天大学 | A method of ultrasonic-assisted microwave controllable preparation of Cu2ZnSnS4 nanoparticles |
| CN105669045A (en) * | 2016-01-11 | 2016-06-15 | 广东工业大学 | A kind of preparation method and application of Cu2ZnSnS4/graphene composite semiconductor film |
Non-Patent Citations (1)
| Title |
|---|
| HONGMEI QING ET AL.: "A facile two-step-heating route to synthesize hierarchical metastable wurtzite Cu2ZnSnS4 microcrystals under the open-aircondition", 《MATERICALS LETTERS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110465309A (en) * | 2019-07-22 | 2019-11-19 | 昆明理工大学 | ZnS nano-particles reinforcement porous C u3SnS4The preparation method of the P-N bulk heterojunction photochemical catalyst of particle |
| CN110465309B (en) * | 2019-07-22 | 2021-07-13 | 昆明理工大学 | Preparation method of P-N bulk heterojunction photocatalyst based on ZnS nanoparticles composite porous Cu3SnS4 particles |
| CN112279306A (en) * | 2020-10-21 | 2021-01-29 | 南京晓庄学院 | Optimization method of sulfide nanocrystal, Sn-S-Co nanocrystal and optimized product thereof |
| CN112279306B (en) * | 2020-10-21 | 2021-07-06 | 南京晓庄学院 | Optimization method of sulfide nanocrystal, Sn-S-Co nanocrystal and optimized product thereof |
| CN113979468A (en) * | 2021-12-09 | 2022-01-28 | 山东中鸿新能源科技有限公司 | Preparation method of CZTS (Se) nano powder for solar cell module |
| CN113979468B (en) * | 2021-12-09 | 2023-05-09 | 山东中鸿新能源科技有限公司 | A kind of preparation method of CZTS (Se) series nanopowder for solar cell module |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103872186B (en) | FeS2The preparation method of film | |
| CN104016313B (en) | A kind of preparation method of six side's copper selenide nanometer sheet | |
| CN102502791B (en) | Method for preparing flower-cluster-shaped tin sulfide (SnS) nanometer particles by microwave hydrothermal method | |
| CN108409157A (en) | A kind of ZnIn2S4 nanometer wafer arrays structure and preparation method thereof | |
| CN101177296A (en) | Preparation method of ZnO nanopowder with sheet-like porous structure | |
| CN102502793B (en) | A kind of preparation method of rod-shaped SnS nanocrystal | |
| CN113087016A (en) | Preparation method of rod-shaped bismuth sulfide/reduced graphene oxide composite material | |
| CN103824902B (en) | A kind of FeS2Film and preparation method thereof | |
| CN106395886B (en) | A kind of buergerite Cu2ZnSnS4Nanocrystalline large-scale producing method | |
| CN106517314A (en) | Preparing method of CZTS particulates | |
| CN103274443A (en) | A kind of Cu2O-ZnO composite nano-structure semiconductor material of tetragonal leaf shape and preparation method thereof | |
| CN102951686A (en) | Preparation method for granular manganese tungstate nanocrystals | |
| CN107601441B (en) | Method for synthesizing tin selenide microcrystalline powder by hydrothermal method | |
| CN107083532A (en) | A kind of preparation method of CuI nanostructure | |
| CN105524617A (en) | Preparation method of molybdenum selenide quantum dots | |
| CN106277038B (en) | A kind of preparation method of micro-nano compound structure buergerite copper-zinc-tin-sulfur particulate | |
| CN102897722B (en) | A kind of solvothermal synthesis method of α-In2Se3 nano curd | |
| CN105060338A (en) | Preparation method of phase-selective copper-zinc-tin-sulfur nano crystal | |
| CN109437298B (en) | A kind of preparation method of sodium thioantimonite nanomaterial | |
| CN106379931A (en) | Method for rapidly preparing copper-zinc-tin-sulfur nanoparticles | |
| CN103887501A (en) | Method for preparing copper selenide lithium ion battery electrode material | |
| CN105253909A (en) | Preparation method of copper zinc tin sulfide nanocrystal with custerite structure | |
| CN102689920A (en) | Method for producing copper-tin-zinc-sulfur (CTZS) materials through solvent-thermal synthesis | |
| CN103613115A (en) | Method for synthesizing ZnO/ZnSe (zinc oxide/zinc selenide) coaxial nano structure through gas-phase anion exchange | |
| CN108117052B (en) | Two-dimensional mesoporous (GaN)1-x(ZnO)x solid solution nanomaterial and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170322 |
|
| RJ01 | Rejection of invention patent application after publication |