CN101805136A - Chemical method for preparing nano mesh-like sulfur-indium-zinc ternary compound optoelectronic film on ITO conductive glass in situ - Google Patents
Chemical method for preparing nano mesh-like sulfur-indium-zinc ternary compound optoelectronic film on ITO conductive glass in situ Download PDFInfo
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- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 4
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
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- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
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- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种在ITO导电玻璃上原位制备纳米网状硫铟锌三元化合物光电薄膜的化学方法。该方法把具有纳米化铟锌合金表面的ITO导电玻璃基底材料、单质硫粉、以及无水乙醇溶剂共置于聚四氟乙烯反应釜中，单质硫粉的浓度为0.001～0.0015克硫/毫升无水乙醇溶剂，在160℃～180℃温度下反应12～24小时，反应结束后，自然冷却至室温，最后产物依次用去离子水和无水乙醇清洗，室温下自然晾干，即得到在ITO导电玻璃基底的铟锌合金表面原位制得由纳米薄片组成的网状ZnIn2S4三元化合物光电薄膜材料，其中纳米薄片厚度为20～30nm。本方法制得的薄膜透明，纳米网状结构形貌均一、完美，表面非常均匀平整。同时，本方法低温原位生长重复性好，操作简便，不需要进一步的后处理，环境友好，便于工业化生产。
A chemical method for in-situ preparation of nano-network sulfur-indium-zinc ternary compound photoelectric thin film on ITO conductive glass. In this method, the ITO conductive glass substrate material with a nano-sized indium-zinc alloy surface, elemental sulfur powder, and anhydrous ethanol solvent are placed in a polytetrafluoroethylene reactor, and the concentration of the elemental sulfur powder is 0.001-0.0015 grams of sulfur/ml Anhydrous ethanol solvent, react at a temperature of 160°C to 180°C for 12 to 24 hours, after the reaction is completed, naturally cool to room temperature, and the final product is washed with deionized water and absolute ethanol in turn, and dried naturally at room temperature to obtain the On the indium-zinc alloy surface of the ITO conductive glass substrate, a network-like ZnIn 2 S 4 ternary compound photoelectric thin film material composed of nano-flakes is prepared in situ, wherein the thickness of the nano-flakes is 20-30nm. The film prepared by the method is transparent, the nano-network structure is uniform and perfect in appearance, and the surface is very uniform and smooth. At the same time, the method has good repeatability of low-temperature in-situ growth, is easy to operate, does not require further post-processing, is environmentally friendly, and is convenient for industrial production.
Description
技术领域：Technical field:
本发明属于材料化学技术领域，尤其涉及一种在ITO导电玻璃基底上原位制备由纳米薄片组成的网状硫铟锌三元化合物光电薄膜材料的化学方法。The invention belongs to the technical field of material chemistry, and in particular relates to a chemical method for in-situ preparation of a net-shaped sulfur-indium-zinc ternary compound photoelectric thin film material composed of nano flakes on an ITO conductive glass substrate.
背景技术：Background technique:
ZnIn2S4(ZIS)作为II-III-VI族化合物半导体，属于AB2C4系列的三元硫化物。因其具有适中的带隙能、较高的转换效率以及较低的制造成本等被广泛的应用于太阳能电池、光催化、光致发光二极管、生物标记和光敏元件等方面。ZnIn 2 S 4 (ZIS), as a II-III-VI compound semiconductor, belongs to the AB 2 C 4 series of ternary sulfides. Because of its moderate bandgap energy, high conversion efficiency, and low manufacturing cost, it is widely used in solar cells, photocatalysis, photoluminescent diodes, biomarkers, and photosensitive elements.
目前，关于硫铟锌(ZnIn2S4)晶体的制备方法已有不少报道，南开大学苟兴龙等人[X.L.Gou，F.Y.Cheng，Y.H.Shi，L.Zhang，S.J.Peng，J.Chen，P.W.Shen.J.Am.Chem.Soc.2006，128，7222-7229.]以硫酸锌(ZnSO4)、氯化铟(InCl3)和硫代乙酰胺(TAA)为原料在表面活性剂存在的条件下溶剂热制备出了不同形貌的硫铟锌微纳米材料。福州大学陈志新等人[Z.X.Chen，D.Z.Li，W.J.Zhang，C.Chen，W.J.Li，M.Sun，Y.H.He，X.Z.Fu.Inorganic Chemistry 2008，42，9766-9772.]在没有任何表面活性剂和模板的前提下用水浴法制备出了硫铟锌微米球结构。这两类方法虽然可以简单方便的制备出硫铟锌微/纳米材料，但是他们得到的最终产物都是硫铟锌(ZnIn2S4)粉末材料，如果要将其作为光电材料应用到太阳能电池中，还需要进一步的制备成膜。近来，西安交大李明涛等人[M.T.Li，J.Z.Su，L.J.Guo.International Journal of HydrogenEnergy 2008，33，2891-2896.]利用喷雾热分解法在ITO导电玻璃基底上制备了ZnIn2S4薄膜材料，该方法以ZnCl2，InCl3和(NH2)2CS为前驱体溶液，在基底温度400℃的条件下在ITO导电玻璃上沉积ZnIn2S4薄膜。该方法虽然制备成本较低，但是需要依赖于复杂的反应设备和苛刻的反应条件，并且在较高的基底温度下有可能会破坏ITO玻璃的导电性。而且得到的ZnIn2S4纳米材料的形貌不均一，不易控制，很难形成三维结构，因此，寻找一种简单、快速、温和、廉价且环保的方法，在ITO导电玻璃基底上直接制备具有理想三维结构的ZnIn2S4三元化合物光电薄膜材料仍然是研究人员们需要解决的问题。At present, there have been many reports on the preparation methods of sulfur indium zinc (ZnIn 2 S 4 ) crystals. Nankai University Gou Xinglong et al. Chem.Soc.2006, 128, 7222-7229.] Using zinc sulfate (ZnSO 4 ), indium chloride (InCl 3 ) and thioacetamide (TAA) as raw materials, it was prepared solvothermally in the presence of surfactants Indium zinc sulfide micro-nanomaterials with different morphologies. Chen Zhixin of Fuzhou University et al. [ZXChen, DZLi, WJZhang, C.Chen, WJLi, M.Sun, YHHe, XZFu. Inorganic Chemistry 2008, 42, 9766-9772.] in water bath without any surfactant and template The sulfur indium zinc microsphere structure was prepared by this method. Although these two types of methods can easily and conveniently prepare sulfur indium zinc micro/nano materials, the final products they obtain are all sulfur indium zinc (ZnIn 2 S 4 ) powder materials. If it is to be used as a photoelectric material in solar cells However, further film formation is required. Recently, Li Mingtao et al [MTLi, JZSu, LJGuo. International Journal of HydrogenEnergy 2008, 33, 2891-2896.] of Xi’an Jiaotong University prepared ZnIn 2 S 4 film materials on ITO conductive glass substrates by spray pyrolysis method. ZnCl 2 , InCl 3 and (NH 2 ) 2 CS are precursor solutions, and a ZnIn 2 S 4 film is deposited on ITO conductive glass at a substrate temperature of 400°C. Although the preparation cost of this method is low, it needs to rely on complex reaction equipment and harsh reaction conditions, and may destroy the conductivity of ITO glass at a higher substrate temperature. Moreover, the obtained ZnIn 2 S 4 nanomaterials have inhomogeneous morphology, are difficult to control, and are difficult to form a three-dimensional structure. Therefore, it is necessary to find a simple, fast, gentle, cheap and environmentally friendly method to directly prepare on the ITO conductive glass substrate. The ideal three-dimensional structure of ZnIn 2 S 4 ternary compound photoelectric thin film materials is still a problem that researchers need to solve.
另外，需要特别指出的是由纳米薄片组成的网状薄膜结构，因具有较大的比表面积、易于与其他物质形成互穿网络结构等特点，将会具有一些独特的电子传输能力。以无机半导体-共轭聚合物杂化太阳能电池为例，这种类型的太阳能电池是将纳米尺度的无机半导体与共轭聚合物进行混合形成异质结，这种结构既利用了无机纳米晶载流子迁移率高、化学稳定性好的特点又保留了高分子材料良好的柔韧性和可加工性。在太阳光的照射下，自由电荷载体经光激发后在异质结内的无机(半导体)-有机(聚合物)界面处产生并分离，无机-有机两组分的混合效果及有效接触面积是决定太阳能电池的光电性能的重要因素之一。具有特殊网状结构的ZnIn2S4光电薄膜材料由于其较高的比表面积和复杂的三维结构，并且易于与有机聚合物材料形成接触良好的互穿网络结构，因此它们是作为无机半导体-共轭聚合物杂化太阳能电池的理想备选材料。In addition, it needs to be pointed out that the network film structure composed of nano-sheets will have some unique electron transport capabilities due to its large specific surface area and easy formation of interpenetrating network structures with other substances. Taking inorganic semiconductor-conjugated polymer hybrid solar cells as an example, this type of solar cell is a heterojunction formed by mixing nanoscale inorganic semiconductors with conjugated polymers. This structure uses both inorganic nanocrystals to carry current The characteristics of high molecular mobility and good chemical stability also retain the good flexibility and processability of polymer materials. Under the irradiation of sunlight, free charge carriers are generated and separated at the inorganic (semiconductor)-organic (polymer) interface in the heterojunction after photoexcitation. The mixing effect and effective contact area of the inorganic-organic two components are It is one of the important factors to determine the photovoltaic performance of solar cells. ZnIn 2 S 4 photoelectric thin film materials with a special network structure, due to their high specific surface area and complex three-dimensional structure, and easy to form an interpenetrating network structure with good contact with organic polymer materials, so they are used as inorganic semiconductor-co- Ideal candidates for conjugated polymer hybrid solar cells.
申请人使用了一种简单、快捷、温和、绿色的合成方法，把具有铟锌合金表面的ITO玻璃基底材料，单质硫粉(S)，以及无水乙醇溶剂共置于聚四氟乙烯反应釜中，在160℃～180℃温度下直接反应12～24小时，在ITO导电玻璃基底上成功地原位制备出了由纳米薄片(20～30nm厚)组成的网状ZnIn2S4三元化合物光电薄膜材料，网状薄膜材料的孔隙度在100～400nm之间。经扫描电子显微镜(SEM)和X-射线粉末衍射仪(XRD)表征手段表明，当反应温度在140℃时，铟锌合金表面与硫粉基本上没发生反应。当反应温度为160℃，铟锌合金表面与硫粉发生反应但不完全。只有当溶剂热反应温度超过160℃时才会生成完美的纳米网状硫铟锌三元化合物光电薄膜材料，生成网状硫铟锌三元化合物光电薄膜材料的最佳条件是在180℃反应24小时，降低反应温度或者缩短反应时间都得不到完美的网状硫铟锌三元化合物光电薄膜材料。The applicant used a simple, fast, mild and green synthesis method, and put the ITO glass substrate material with indium-zinc alloy surface, elemental sulfur powder (S), and absolute ethanol solvent in a polytetrafluoroethylene reactor In 2009, the network-shaped ZnIn 2 S 4 ternary compound composed of nanoflakes (20-30nm thick) was successfully prepared in situ on the ITO conductive glass substrate by direct reaction at 160°C-180°C for 12-24 hours. Photoelectric thin film material, the porosity of the mesh thin film material is between 100-400nm. The scanning electron microscope (SEM) and X-ray powder diffractometer (XRD) characterization means show that when the reaction temperature is 140°C, the surface of the indium-zinc alloy does not react with the sulfur powder substantially. When the reaction temperature was 160℃, the surface of indium-zinc alloy reacted with sulfur powder but not completely. Only when the solvothermal reaction temperature exceeds 160 °C can a perfect nano-network sulfur-indium-zinc ternary compound photoelectric thin film material be generated. The best condition for generating a net-like sulfur-indium-zinc ternary compound photoelectric film material is to react at 180 °C for 24 Hours, lowering the reaction temperature or shortening the reaction time cannot obtain a perfect network-shaped sulfur-indium-zinc ternary compound photoelectric thin film material.
发明内容：Invention content:
本发明针对目前制备出的ZnIn2S4纳米晶材料多是粉末状产物，无法作为光电材料直接用于太阳能电池器件中；现有的制备ZnIn2S4薄膜材料的方法中存在基底温度较高、工艺复杂、反应条件苛刻和形貌不理想等缺点。提供一种不需要任何模板，不需要添加任何表面活性剂，不必经过除杂等繁琐的后处理操作，在较低的温度下即可制得高纯度的纳米网状结构的ZnIn2S4三元化合物光电薄膜材料的方法。该方法通过一步化学反应直接在ITO玻璃基底上原位生长ZnIn2S4三元化合物光电薄膜材料，具有广泛的工业应用前景，The present invention aims at the ZnIn 2 S 4 nanocrystalline materials prepared at present are mostly powdery products, which cannot be directly used in solar cell devices as photoelectric materials; existing methods for preparing ZnIn 2 S 4 thin film materials have relatively high substrate temperature , complex process, harsh reaction conditions and unsatisfactory morphology. It provides a kind of ZnIn 2 S 4 tri with high purity nano-network structure that can be prepared at a lower temperature without any template, without adding any surfactant, and without going through cumbersome post-treatment operations such as impurity removal. The method of elemental compound photoelectric thin film material. This method directly grows ZnIn 2 S 4 ternary compound photoelectric thin film materials on the ITO glass substrate through a one-step chemical reaction, which has a wide range of industrial application prospects.
本发明所采取的技术方案是：The technical scheme that the present invention takes is:
一种硫铟锌(ZnIn2S4)三元化合物光电薄膜材料，其特征在于：该材料为在具有纳米化铟锌合金表面的ITO导电玻璃基底上原位制备的由纳米薄片组成的网状ZnIn2S4三元化合物光电薄膜材料，其中纳米薄片厚度为20～30nm。A sulfur indium zinc (ZnIn 2 S 4 ) ternary compound photoelectric thin film material, characterized in that the material is a network composed of nano flakes prepared in situ on an ITO conductive glass substrate with a nano-indium zinc alloy surface ZnIn 2 S 4 ternary compound photoelectric thin film material, wherein the thickness of the nano flakes is 20-30nm.
本发明所述的硫铟锌三元化合物光电薄膜材料的制备方法，其特征在于：该方法把具有纳米化铟锌合金表面的ITO导电玻璃基底材料、单质硫粉和无水乙醇溶剂共置于反应釜的聚四氟乙烯内胆中，单质硫粉的浓度为0.001～0.0015克硫/毫升无水乙醇溶剂，在160℃～180℃温度下反应12～24小时，反应结束后，自然冷却至室温，最后产物依次用去离子水和无水乙醇清洗，室温下自然晾干，即得到在ITO导电玻璃基底的铟锌合金表面原位制备的由纳米薄片组成的网状ZnIn2S4三元化合物光电薄膜材料，其中纳米薄片厚度为20～30nm。The preparation method of the sulfur-indium-zinc ternary compound photoelectric thin film material according to the present invention is characterized in that: the method puts the ITO conductive glass substrate material with the surface of nano-sized indium-zinc alloy, elemental sulfur powder and absolute ethanol solvent together In the polytetrafluoroethylene liner of the reaction kettle, the concentration of elemental sulfur powder is 0.001-0.0015 g sulfur/ml absolute ethanol solvent, react at 160°C-180°C for 12-24 hours, after the reaction, cool naturally to At room temperature, the final product was washed with deionized water and absolute ethanol in turn, and dried naturally at room temperature, that is, a network-shaped ZnIn 2 S 4 ternary composed of nanoflakes prepared in situ on the surface of the indium-zinc alloy of the ITO conductive glass substrate. Compound photoelectric thin film material, wherein the thickness of the nano flakes is 20-30nm.
所述的硫铟锌三元化合物光电薄膜材料的制备方法，优选反应温度为180℃，反应时间为18～24小时。更优反应温度为180℃，反应时间为24小时。In the preparation method of the sulfur-indium-zinc ternary compound photoelectric thin film material, the preferred reaction temperature is 180° C., and the reaction time is 18-24 hours. The more optimal reaction temperature is 180°C, and the reaction time is 24 hours.
所述的具有纳米化铟锌合金表面的ITO导电玻璃基底材料是指通过离子溅射在ITO导电玻璃表面镀了一层纳米铟锌合金的材料。The ITO conductive glass base material with a nano-indium-zinc alloy surface refers to a material coated with a layer of nano-indium-zinc alloy on the surface of the ITO conductive glass by ion sputtering.
本发明的优点：Advantages of the present invention:
1、低温原位生长重复性好，薄膜透明，纳米网状结构形貌均一、完美，表面非常均匀平整，解决了其他旋涂方法晶体薄膜不均匀的问题。1. The low-temperature in-situ growth has good repeatability, the film is transparent, the nano-network structure is uniform and perfect, and the surface is very uniform and flat, which solves the problem of uneven crystal film by other spin-coating methods.
2、操作简便，不需要进一步的后处理，还可以避免其它湿法化学反应制备所造成的产品不纯的现象。而且无需用到毒性较大的溶剂如三苯基膦、水合肼、乙二胺、以及甲苯等，属于环境友好型反应。便于工业化生产和技术推广。2. It is easy to operate, does not need further post-processing, and can also avoid the phenomenon of product impurity caused by other wet chemical reaction preparations. Moreover, it does not need to use toxic solvents such as triphenylphosphine, hydrazine hydrate, ethylenediamine, and toluene, and belongs to an environment-friendly reaction. It is convenient for industrialized production and technology promotion.
3、在ITO导电玻璃基底上低温原位制备纳米网状ZnIn2S4三元化合物光电薄膜材料，从而克服了物理气相沉淀法、喷涂裂解法等方法制备工艺复杂及基底温度较高的缺点。3. The nano-reticular ZnIn 2 S 4 ternary compound photoelectric thin film material is prepared in situ at low temperature on the ITO conductive glass substrate, thereby overcoming the disadvantages of complex preparation process and high substrate temperature of physical vapor deposition method, spray cracking method and other methods.
4、不需要进一步的旋涂成膜过程，便于组装太阳能电池器件。4. No further spin-coating film forming process is required, which is convenient for assembling solar cell devices.
本发明的方法对其他多元硫化合物薄膜材料的制备具有指导意义。The method of the invention has guiding significance for the preparation of other polysulfide compound film materials.
附图说明Description of drawings
图1、ITO导电玻璃上镀有一层厚度约为20nm的铟锌合金薄膜的原子力显微镜照片Figure 1. Atomic force microscope photo of ITO conductive glass coated with a layer of indium-zinc alloy film with a thickness of about 20nm
图2、实施例1制备的硫铟锌纳米晶薄膜材料的电子显微照片The electron micrograph of the sulfur indium zinc nanocrystalline film material prepared by Fig. 2, embodiment 1
图3、实施例2制备的硫铟锌纳米晶薄膜材料的电子显微照片The electron micrograph of the sulfur indium zinc nanocrystalline film material prepared by Fig. 3, embodiment 2
图4、实施例3制备的硫铟锌纳米晶薄膜材料的电子显微照片The electron micrograph of the sulfur indium zinc nanocrystalline film material prepared by Fig. 4, embodiment 3
图5、实施例4制备的硫铟锌纳米晶薄膜材料的电子显微照片The electron micrograph of the sulfur indium zinc nanocrystalline film material prepared by Fig. 5, embodiment 4
图6、实施例5制备的硫铟锌纳米晶薄膜材料的电子显微照片The electron micrograph of the sulfur indium zinc nanocrystalline film material prepared by Fig. 6, embodiment 5
图7、实施例4制备的硫铟锌纳米晶薄膜材料的X射线衍射图谱The X-ray diffraction pattern of the sulfur indium zinc nanocrystalline film material prepared in Fig. 7, embodiment 4
图8、实施例4制备的硫铟锌纳米晶薄膜材料的紫外-漫反射光谱图The ultraviolet-diffuse reflection spectrogram of the sulfur indium zinc nanocrystalline film material prepared in Fig. 8, embodiment 4
图9、实施例4在ITO导电玻璃基底上制备的亮黄色透明硫铟锌纳米晶薄膜材料实物图(A)及起始的铟锌合金薄膜材料的实物图(B)Figure 9, the physical figure (A) of the bright yellow transparent sulfur indium zinc nanocrystalline film material prepared on the ITO conductive glass substrate in embodiment 4 and the physical figure (B) of the initial indium zinc alloy film material
具体实施方式：Detailed ways:
本发明制备硫铟锌三元化合物光电薄膜材料的实施方法，首先将具有纳米铟锌合金表面的ITO导电玻璃基底材料，单质硫粉，以及无水乙醇溶剂在反应釜的聚四氟乙烯内胆中共混，密封后置于有程序升温功能的恒温鼓风干燥箱中，在160℃～180℃温度下直接反应12～24小时；反应结束后，待反应釜在恒温鼓风干燥箱中冷却至室温后，将反应釜取出；最后将产物取出依次用去离子水和无水乙醇清洗，室温下自然晾干。The implementation method of the present invention to prepare sulfur-indium-zinc ternary compound photoelectric thin film material, first put the ITO conductive glass substrate material with nano-indium-zinc alloy surface, elemental sulfur powder, and absolute ethanol solvent in the polytetrafluoroethylene liner of the reaction kettle Co-blended, sealed and placed in a constant temperature blast drying oven with temperature programming function, and directly reacted at a temperature of 160 ° C to 180 ° C for 12 to 24 hours; after the reaction, the reaction kettle was cooled in a constant temperature blast drying oven to After room temperature, the reactor was taken out; finally, the product was taken out and washed with deionized water and absolute ethanol in sequence, and dried naturally at room temperature.
实施例1Example 1
(1)准备工作：将镀有一层厚度约为20nm的铟锌合金薄膜的ITO导电玻璃依次用去离子水和无水乙醇在超声波清洗器中清洗5分钟，然后取出放在滤纸上自然晾干；将反应釜的聚四氟乙烯内胆依次用自来水、蒸馏水洗涤，干燥后待用；(1) Preparation: Clean the ITO conductive glass coated with an indium-zinc alloy film with a thickness of about 20nm in an ultrasonic cleaner for 5 minutes with deionized water and absolute ethanol in turn, then take it out and put it on filter paper to dry naturally ; Wash the polytetrafluoroethylene liner of the reaction kettle with tap water and distilled water successively, and dry it for later use;
(2)反应步骤：把处理过的具有纳米铟锌合金表面的ITO导电玻璃基底放入聚四氟乙烯内胆中，加入硫粉，然后加入无水乙醇溶剂至容器75％的高度，硫粉浓度为0.001克/毫升，将聚四氟乙烯内胆放入不锈钢外套并置于具有程序升温功能的恒温鼓风干燥箱中，升温到180℃反应24小时；(2) Reaction steps: put the treated ITO conductive glass substrate with nano-indium-zinc alloy surface into the polytetrafluoroethylene liner, add sulfur powder, then add absolute ethanol solvent to the height of 75% of the container, sulfur powder The concentration is 0.001 g/ml, the polytetrafluoroethylene liner is put into a stainless steel jacket and placed in a constant temperature blast drying oven with a temperature programming function, and the temperature is raised to 180 ° C for 24 hours;
(3)后处理：反应结束后，关闭恒温鼓风干燥箱并自然冷却至室温，依次用去离子水和无水乙醇清洗产物后，将样品置于室温下自然晾干。将得到的硫铟锌薄膜样品小心转入样品瓶中，在避光、干燥的环境中保存。产品颜色为亮黄色，在电子显微镜下的微观结构为网格状纳米晶。电子显微照片见图2。(3) Post-treatment: After the reaction, the constant temperature blast drying oven was closed and cooled to room temperature naturally, and the product was washed with deionized water and absolute ethanol in turn, and the sample was placed at room temperature to dry naturally. The obtained sulfur-indium-zinc film sample was carefully transferred into a sample bottle, and stored in a light-proof and dry environment. The color of the product is bright yellow, and the microstructure under the electron microscope is grid-like nanocrystals. The electron micrograph is shown in Figure 2.
实施例2Example 2
(1)准备工作：将镀有一层厚度约为80nm的铟锌合金薄膜的ITO导电玻璃依次用去离子水和无水乙醇在超声波清洗器中清洗5分钟，然后取出放在滤纸上自然晾干；将反应釜的聚四氟乙烯内胆依次用自来水、蒸馏水洗涤，干燥后待用；(1) Preparation: Clean the ITO conductive glass coated with an indium-zinc alloy film with a thickness of about 80nm in an ultrasonic cleaner for 5 minutes with deionized water and absolute ethanol in sequence, then take it out and put it on filter paper to dry naturally ; Wash the polytetrafluoroethylene liner of the reaction kettle with tap water and distilled water successively, and dry it for later use;
(2)反应步骤：把处理过的具有纳米铟锌合金表面的ITO导电玻璃基底放入聚四氟乙烯内胆中，加入硫粉，然后加入无水乙醇溶剂至容器75％的高度，硫粉浓度为0.0015克/毫升，将聚四氟乙烯内胆放入不锈钢外套并置于具有程序升温功能的恒温鼓风干燥箱中，升温到180℃反应12小时；(2) Reaction steps: put the treated ITO conductive glass substrate with nano-indium-zinc alloy surface into the polytetrafluoroethylene liner, add sulfur powder, then add absolute ethanol solvent to the height of 75% of the container, sulfur powder The concentration is 0.0015 g/ml, the polytetrafluoroethylene liner is put into a stainless steel jacket and placed in a constant temperature blast drying oven with a temperature programming function, and the temperature is raised to 180 ° C for 12 hours;
(3)后处理：反应结束后，关闭恒温鼓风干燥箱并自然冷却至室温，依次用去离子水和无水乙醇清洗产物后，将样品置于室温下自然晾干；将得到的硫铟锌薄膜样品小心转入样品瓶中，在避光、干燥的环境中保存。产品颜色为亮黄色略显金属光泽，在电子显微镜下的微观结构为网格状纳米晶，但有部分金属没有完全反应。电子显微照片见图3。(3) Post-treatment: After the reaction is over, close the constant temperature blast drying oven and cool to room temperature naturally. After cleaning the product with deionized water and absolute ethanol in turn, place the sample at room temperature to dry naturally; the obtained sulfur indium The zinc film sample was carefully transferred into a sample bottle and stored in a dark and dry environment. The color of the product is bright yellow with a slight metallic luster. The microstructure under the electron microscope is grid-like nanocrystals, but some metals have not completely reacted. The electron micrograph is shown in Figure 3.
实施例3Example 3
(1)准备工作：同实施例2；(1) preparatory work: with embodiment 2;
(2)反应步骤：把处理过的具有纳米铟锌合金表面的ITO导电玻璃基底放入聚四氟乙烯内胆中，加入硫粉，然后加入无水乙醇溶剂至容器75％的高度，硫粉浓度为0.0015克/毫升，将聚四氟乙烯内胆放入不锈钢外套并置于具有程序升温功能的恒温鼓风干燥箱中，升温到160℃反应24小时；(2) Reaction steps: put the treated ITO conductive glass substrate with nano-indium-zinc alloy surface into the polytetrafluoroethylene liner, add sulfur powder, then add absolute ethanol solvent to the height of 75% of the container, sulfur powder The concentration is 0.0015 g/ml, the polytetrafluoroethylene liner is put into a stainless steel jacket and placed in a constant temperature blast drying oven with a temperature programming function, and the temperature is raised to 160 ° C for 24 hours;
(3)后处理：反应结束后，关闭恒温鼓风干燥箱并自然冷却至室温，依次用去离子水和无水乙醇清洗产物后，将样品置于室温下自然晾干；将得到的硫铟锌薄膜样品小心转入样品瓶中，在避光、干燥的环境中保存。产品颜色为亮黄色略显金属光泽，在电子显微镜下的微观结构为网格状纳米晶但有部分金属没有完全反应。电子显微照片见图4。(3) Post-treatment: After the reaction is over, close the constant temperature blast drying oven and cool to room temperature naturally. After cleaning the product with deionized water and absolute ethanol in turn, place the sample at room temperature to dry naturally; the obtained sulfur indium The zinc film sample was carefully transferred into a sample bottle and stored in a dark and dry environment. The color of the product is bright yellow with a slight metallic luster, and the microstructure under the electron microscope is grid-like nanocrystals, but some metals have not completely reacted. An electron micrograph is shown in Figure 4.
实施例4Example 4
(1)准备工作：同实施例3；(1) preparatory work: with embodiment 3;
(2)反应步骤：把处理过的具有纳米铟锌合金表面的ITO导电玻璃基底放入聚四氟乙烯内胆中，加入硫粉，然后加入无水乙醇溶剂至容器75％的高度，硫粉浓度为0.0015克/毫升，将聚四氟乙烯内胆放入不锈钢外套并置于具有程序升温功能的恒温鼓风干燥箱中，升温到180℃反应24小时；(2) Reaction steps: put the treated ITO conductive glass substrate with nano-indium-zinc alloy surface into the polytetrafluoroethylene liner, add sulfur powder, then add absolute ethanol solvent to the height of 75% of the container, sulfur powder The concentration is 0.0015 g/ml, the polytetrafluoroethylene liner is put into a stainless steel jacket and placed in a constant temperature blast drying oven with a temperature programming function, and the temperature is raised to 180 ° C for 24 hours;
(3)后处理：反应结束后，关闭恒温鼓风干燥箱并自然冷却至室温，依次用去离子水和无水乙醇清洗产物后，将样品置于室温下自然晾干；将得到的硫铟锌薄膜样品小心转入样品瓶中，在避光、干燥的环境中保存。产品颜色为亮黄色，在电子显微镜下的微观结构为网格状纳米晶。电子显微照片见图5。(3) Post-treatment: After the reaction is over, close the constant temperature blast drying oven and cool to room temperature naturally. After cleaning the product with deionized water and absolute ethanol in turn, place the sample at room temperature to dry naturally; the obtained sulfur indium The zinc film sample was carefully transferred into a sample bottle and stored in a dark and dry environment. The color of the product is bright yellow, and the microstructure under the electron microscope is grid-like nanocrystals. The electron micrograph is shown in Figure 5.
实施例5Example 5
(1)准备工作：同实施例4；(1) preparatory work: with embodiment 4;
(2)反应步骤：把处理过的具有纳米铟锌合金表面的ITO导电玻璃基底放入聚四氟乙烯内胆中，加入硫粉，然后加入无水乙醇溶剂至容器75％的高度，硫粉浓度为0.001克/毫升，将聚四氟乙烯内胆放入不锈钢外套并置于具有程序升温功能的恒温鼓风干燥箱中，升温到180℃反应24小时；(2) Reaction steps: put the treated ITO conductive glass substrate with nano-indium-zinc alloy surface into the polytetrafluoroethylene liner, add sulfur powder, then add absolute ethanol solvent to the height of 75% of the container, sulfur powder The concentration is 0.001 g/ml, the polytetrafluoroethylene liner is put into a stainless steel jacket and placed in a constant temperature blast drying oven with a temperature programming function, and the temperature is raised to 180 ° C for 24 hours;
(3)后处理：反应结束后，关闭恒温鼓风干燥箱并自然冷却至室温，依次用去离子水和无水乙醇清洗产物后，将样品置于室温下自然晾干；将得到的硫铟锌薄膜样品小心转入样品瓶中，在避光、干燥的环境中保存。产品颜色为亮黄色，在电子显微镜下的微观结构为网格状纳米晶。电子显微照片见图6。(3) Post-treatment: After the reaction is over, close the constant temperature blast drying oven and cool to room temperature naturally. After cleaning the product with deionized water and absolute ethanol in turn, place the sample at room temperature to dry naturally; the obtained sulfur indium The zinc film sample was carefully transferred into a sample bottle and stored in a dark and dry environment. The color of the product is bright yellow, and the microstructure under the electron microscope is grid-like nanocrystals. An electron micrograph is shown in Figure 6.
本发明直接采用单质硫与镀有铟锌合金的ITO导电玻璃基底经过一步反应制备纳米网状硫铟锌三元化合物光电薄膜材料，并使用最简单的无水乙醇溶剂作为反应介质。属于环境友好型反应。低温原位生长重复性好，薄膜透明，纳米网状结构形貌均一、完美，表面非常均匀平整，解决了其他旋涂方法晶体薄膜不均匀的问题。没有用到任何添加剂及表面活性剂，不需要后续的热处理和提纯步骤。反应快捷，操作方便，便于工业化生产和技术推广。因其制备装置简单，无需进行后处理等优点大大降低了成本，在太阳能电池领域将有广泛的应用前景。The present invention directly adopts elemental sulfur and ITO conductive glass substrate plated with indium-zinc alloy to prepare nano-network sulfur-indium-zinc ternary compound photoelectric film material through one-step reaction, and uses the simplest anhydrous ethanol solvent as a reaction medium. It is an environment-friendly reaction. Low-temperature in-situ growth has good repeatability, the film is transparent, the nano-network structure is uniform and perfect, and the surface is very uniform and flat, which solves the problem of uneven crystal film of other spin-coating methods. No additives and surfactants are used, and subsequent heat treatment and purification steps are not required. The reaction is fast, the operation is convenient, and it is convenient for industrialized production and technology popularization. Because of the advantages of simple preparation device and no need for post-treatment, the cost is greatly reduced, and it will have a wide application prospect in the field of solar cells.
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| CN102225847A (en) * | 2011-05-09 | 2011-10-26 | 浙江大学宁波理工学院 | Preparation method for porous In2S3 film |
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