形貌可控ZnS材料的水热/溶剂热法制备
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摘要
近年来,无机材料的形貌控制制备受到了极大的关注,因为材料的结构决定材料的性能。不同形貌、大小及结构的材料具有不同的性能。许多研究者研究发现通过改变材料的不同形貌和尺寸可以使材料表现出一些普通材料所不具备的性能。ZnS作为重要的Ⅱ-Ⅵ族半导体材料,对其形貌控制制备研究有很多报道。现在已有很多方法,如固相法、液相法和气相法,都已制备出许多不同微观形貌的ZnS材料,例如微球、纳米粒子、空心微球、纳米线、纳米棒和纳米片等等。这些方法中,水热/溶剂热法具有很多优点,诸如液相环境、高温、高压等,其中最重要的是水热/溶剂热法有很多因素影响形貌的形成,通过这些因素的控制,诸如温度、时间、溶剂和表面活性剂等,可以得到很多新的奇特形貌。
本论文利用溶剂热法制备具有层状微观形貌的ZnS粉体材料,反应以乙酸锌Zn(CH3COO)2·2H2O为锌源,硫脲SC(NH2)2为硫源,利用水与乙二胺的混合溶液为反应溶剂,以十二烷基磺酸钠C12H25SO3Na形成的胶束为模板,在溶剂热下得到具有层状结构的ZnS粉体材料。测试表明所得ZnS材料结晶良好,层状形貌明显。并探讨了各因素,特别是溶剂和表面活性剂对形成形貌的影响。并由此探讨了层状ZnS材料的形成机制及形貌控制制备条件。
本论文对ZnS另一个研究的热点ZnS薄膜制备也有研究,ZnS薄膜因其在激光二极管、电致发光器件、电光调制器、光学镀膜材料、光电导体及光伏器件等方面的广泛应用而成为人们关注的热点。特别是在薄膜太阳电池方面,作为无镉太阳能电池过渡层,已经取得了较高的转换效率。本论文利用乙酸锌Zn(CH3COO)2·2H2O为锌源,硫脲SC(NH2)2为硫源,氨水和水合肼为络合剂,利用水热法在玻璃基板上制备出大面积、均匀的纳米结构网络状ZnS薄膜。测试表明所得薄膜均匀平整,且有纳米网络状结构。论文还对络合剂对薄膜的影响做了研究,提出了络合剂在水热制膜中的作用机理。
Recently, there has been growing interest in fabrication of nanometer to micrometer scale inorganic materials with special morphologies owing to the expectation of novel properties. Zinc sulfide, as an important semiconductor compound of theⅡ-Ⅵgroups, has been successfully synthesized some particular structures like quantum dots, nanowires, hollow spheres, nanosheets, and so on. Some methods have been developed to prepare the ZnS with different phases and morphologies, among which the hydrothermal or solvothermal route show many advantages such as mild reaction conditions, less energy consumption, simple equipment required, and the most important advantage is large number of variable factors to control the sample morphology, because the reaction path is very sensitive to the experimental conditions such as source species, surfactant molecules, reaction temperature, time and solvent.
So far, to our knowledge, laminated ZnS was not synthesized by solvothermal route before. Herein, a solvothermal approach was developed to prepare laminated ZnS at 160℃for 12h starting from Zn(CH3COO)2·2H2O with SC(NH2)2 in mixed solvents of ethylenediamine and water, using C12H25SO3Na as the surfactant. The effect of ethylenediamine and C12H25SO3Na on the morphology of products was studied too. This reaction route can further be applied to prepare other metal sulfides.
Zinc sulphide (ZnS) thin film is an important photoelectric semiconductor material, especially used in solar cell, has received a wide publicity, and the research has yielded substantial results.
A hydrothermal approach was developed to prepare ZnS nano thin film at 160℃for 12h starting from Zn(CH3COO)2·2H2O with SC(NH2)2, using NH3 and N2H4 as complexing agent, and the thin film was deposited on glass. the ZnS thin film was net-like, which was not got by hydrothermal route before. We also discuss the influence of the complexing agents upon hydrothermal approach depositing ZnS thin films.
本论文利用溶剂热法制备具有层状微观形貌的ZnS粉体材料,反应以乙酸锌Zn(CH3COO)2·2H2O为锌源,硫脲SC(NH2)2为硫源,利用水与乙二胺的混合溶液为反应溶剂,以十二烷基磺酸钠C12H25SO3Na形成的胶束为模板,在溶剂热下得到具有层状结构的ZnS粉体材料。测试表明所得ZnS材料结晶良好,层状形貌明显。并探讨了各因素,特别是溶剂和表面活性剂对形成形貌的影响。并由此探讨了层状ZnS材料的形成机制及形貌控制制备条件。
本论文对ZnS另一个研究的热点ZnS薄膜制备也有研究,ZnS薄膜因其在激光二极管、电致发光器件、电光调制器、光学镀膜材料、光电导体及光伏器件等方面的广泛应用而成为人们关注的热点。特别是在薄膜太阳电池方面,作为无镉太阳能电池过渡层,已经取得了较高的转换效率。本论文利用乙酸锌Zn(CH3COO)2·2H2O为锌源,硫脲SC(NH2)2为硫源,氨水和水合肼为络合剂,利用水热法在玻璃基板上制备出大面积、均匀的纳米结构网络状ZnS薄膜。测试表明所得薄膜均匀平整,且有纳米网络状结构。论文还对络合剂对薄膜的影响做了研究,提出了络合剂在水热制膜中的作用机理。
Recently, there has been growing interest in fabrication of nanometer to micrometer scale inorganic materials with special morphologies owing to the expectation of novel properties. Zinc sulfide, as an important semiconductor compound of theⅡ-Ⅵgroups, has been successfully synthesized some particular structures like quantum dots, nanowires, hollow spheres, nanosheets, and so on. Some methods have been developed to prepare the ZnS with different phases and morphologies, among which the hydrothermal or solvothermal route show many advantages such as mild reaction conditions, less energy consumption, simple equipment required, and the most important advantage is large number of variable factors to control the sample morphology, because the reaction path is very sensitive to the experimental conditions such as source species, surfactant molecules, reaction temperature, time and solvent.
So far, to our knowledge, laminated ZnS was not synthesized by solvothermal route before. Herein, a solvothermal approach was developed to prepare laminated ZnS at 160℃for 12h starting from Zn(CH3COO)2·2H2O with SC(NH2)2 in mixed solvents of ethylenediamine and water, using C12H25SO3Na as the surfactant. The effect of ethylenediamine and C12H25SO3Na on the morphology of products was studied too. This reaction route can further be applied to prepare other metal sulfides.
Zinc sulphide (ZnS) thin film is an important photoelectric semiconductor material, especially used in solar cell, has received a wide publicity, and the research has yielded substantial results.
A hydrothermal approach was developed to prepare ZnS nano thin film at 160℃for 12h starting from Zn(CH3COO)2·2H2O with SC(NH2)2, using NH3 and N2H4 as complexing agent, and the thin film was deposited on glass. the ZnS thin film was net-like, which was not got by hydrothermal route before. We also discuss the influence of the complexing agents upon hydrothermal approach depositing ZnS thin films.
引文
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[3]结晶化学导论,钱逸泰,中国科学技术大学出版社,1999,合肥
[4]赵福潭,李多禄,苏锡安,王淑梅,范希武,发光学报,1996,17,17
[5]刘新征,硫化物纳米和微晶材料的溶剂热合成及其机理研究,中国科学技术大学博士论文2006
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[9]马国峰,邵中宝,姜涛；室温固相合成纳米硫化锌及其性能研究J。有色矿冶,2004,20(6)：31-36
[10]徐甲强,刘艳丽,牛新书；纳米的合成及其气敏性能研究,J功能材料,2002,33(4)：425-427
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[12]江元汝,崔延青,杨琴,等.乳液法制备纳米硫化锌及表征[J].西安建筑科技大学学报,2005,37(2)：287-290.
[13]刘红华.反胶束法制备纳米硫化锌微粒及其润滑性能[J].润滑与密封,2006,(8)：122-124.
[14]邓玉荣,丁晓夏,甘仲惟,等.化学气相沉积法合成ZnS纳米球[J].华中师范大学学报,2002,36(3)：305-307.
[15]沈宗华,王安杰,解建国,等.二维硫化锌材料的制备及其研究[J].化工进展,2006,25(4)：392-39
[16]翁晴,程树英.ZnS薄膜的电沉积与表征[J].福州大学学报,2008,36(1)：73-76
[17]ZhangR G, Wang B Y, Wan D Y,et al.Effects of the sulfidation temperature on the structure, composition and optical properties of ZnS films prepared by sulfurizing ZnO fiIms[J]. Optical Materials,2004(27):419-423.
[18]GiardiniA, AmbricoM, Smaldone D,et al.Structural and optical properties of Ⅱ-Ⅵ thin films and Ⅱ-Ⅵ multilayered structures grown on silion by laser ablation[J]. Materials Science and Engineering,1997(43):102-10
[19]Kundu S, Olsen L C. Chemical bath deposited zinc sulfide buffer layers for copper indium gallium sulfur-selenide solar cells and device analysis[J]. Thin Solid Films,2005(471):298-303
[20]Oladeji IO, Chow L. A study of the effects ofammonium salts on chemicalbath deposited zinc sulfide thin films[J]. Thin Solid Films,1999(339):148-153.
[21]SubbaiahY PV, Prathap P, ReddyR K T. Structural electrical and opticalproperties of ZnS films deposited by close-spaced evaporation[J]. Applied Surface Science,2006 (253):2409-2415.
[22]Ximello-Quiebras JN, Contreras-PuenteG, Rueda-MoralesG,etal.Properties ofCdS thin films grown by CBD as a function of thiourea concentration[J]. Solar Energy Materials& Solar Cells,2006(90):727-732
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