【作者】 龚敏；

【导师】 朱启安；

【作者基本信息】 湘潭大学 ， 无机化学， 2009， 硕士

【摘要】 本文旨在探索半导体纳米材料硫化锑的制备方法,研究其微结构、生长机理和光学性质。Sb₂S₃是一类重要的高度各向异性的半导体热电材料,已在电视摄象机的光电导靶材、热电器件和电子装置,以及红外谱学等许多领域得到广泛的应用。本研究利用水热法合成了四棱柱状的Sb₂S₃纳米棒;采用表面活性剂辅助回流法合成了Sb₂S₃纳米棒、纳米花以及微波辐射热分解单源前驱体法合成了硫化锑纳米花,并对其微观结构、反应形成机理和光学性质进行了探讨。主要内容如下:以SbCl3和硫粉为反应物、硼氢化钠（NaBH4）作还原剂以及乙二醇（EG）为辅助溶剂,用水热法成功地合成了四棱柱状的Sb₂S₃纳米棒。用X-射线衍射（XRD）、能量分散光谱（EDS）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、选区电子衍射（SAED）和紫外可见光谱（UV-Vis）对样品的结构、成份、形貌和光学性质进行了表征。结果显示,经180℃水热反应12 h可得到结晶良好、形貌规整的四棱柱状的正交晶系Sb₂S₃单晶纳米棒,棒的横截面为矩形,其宽约75²15 nm、厚约50¹10 nm,长度达2⁵μm,并沿[001]方向生长。经计算,其晶胞参数为a=1.126 nm, b=1.128 nm,c=0.382 nm。UV-Vis分析表明,Sb₂S₃纳米棒为半导体材料,带隙能量为1.56 eV,该值与最佳光电转换能量相近,因而Sb₂S₃纳米棒可用于太阳能、光电转换等领域。本文还对纳米棒可能的生长机理进行了初步探讨。以SbCl3与硫脲为反应物,PEG400、OP-10为表面活性剂,用回流方法制得Sb₂S₃纳米棒、纳米花。X-射线衍射（XRD）表明,所得的产物为正交晶系结构,经计算,其晶胞参数为a=1.124 nm,b=1.134 nm,c=0.382 nm。扫描电子显微镜（SEM）与透射电子显微镜（TEM）研究显示Sb₂S₃纳米花直径约9¹0μm,它是由厚约0.05⁰.2μm,宽约0.8².2μm,长度达2.5³μm的纳米叶构成;棒状硫化锑的平均直径为45³60 nm,长约0.7⁴μm。UV-Vis分析表明,该Sb₂S₃纳米材料带隙能量为1.52 eV,适用于光电转换领域。另外探讨了纳米材料可能的生长机理,并且讨论了各种反应条件如反应时间、反应温度和表面活性剂对Sb₂S₃纳米棒形成以及形貌的影响。以Sb（S₂CNEt₂）₃为单源前驱体,乙二醇为溶剂,用微波辐射方法成功合成了三维的Sb₂S₃菜花状超结构。XRD研究表明,Sb₂S₃纳米超结构为正交晶系,经计算,其晶胞参数为a=1.141 nm, b=1.131 nm, c=0.3807 nm。SEM和TEM研究显示,花状的Sb₂S₃纳米结构的每个菜花都是由纳米棒由中心呈发射状组装而成,棒的直径约为20³50 nm,长约5¹2μm。相应的电子衍射（ED）表明组成菜花状纳米棒为单晶结构。进一步实验结果表明,微波辐射和表面活性剂PEG400对菜花状Sb₂S₃纳米花超结构的形成有很重要的作用。紫外可见（UV-Vis）分析表明,该Sb₂S₃纳米材料带隙能量为1.90 eV,大于之前的文献报道。另外我们还探讨了菜花状Sb₂S₃纳米花超结构可能的形成机理。更多还原

【Abstract】 The dissertation focus on exploring new synthetic methods for nanoscaled semiconducting materials Sb₂S₃, on characterzing microstructures and on studying its growth mechanism and optical properties. It well knows that Sb₂S₃ is a highly anisotropic semiconductor material and has many applications in elevision cameras with photoconducting targets, electronic and optoelectronic devices, thermoelectric devices, and IR spectroscopy. Tetra-prism-like antimony trisufide （Sb₂S₃） nanorods were successfully synthesized under hydrothermal conditions. Single-crystalline antimony sulfide （Sb₂S₃） nanomaterials with flower-like and rod-like morphologies were synthesized under refluxing conditions. Three-dimensional （3D） antimony sulfide （Sb₂S₃） cauliflower-like superstructures were prepared by the microwave irradiation method. Microstructure, growth mechanism and optical properties of all the synthesized nanostructures were studied and discussed.Tetra-prism-like antimony trisufide （Sb₂S₃） nanorods were successfully synthesized under hydrothermal conditions by the reaction of antimony trichloride （SbCl3） and sulfur powders （S） with ethylene glycol （EG） as the assistant. The products were characterized by XRD, EDS, SEM, TEM, HRTEM, SAED and UV-Vis techniques. The results show that the well-crystallized and regular- morphology tetra-prism-like Sb₂S₃ nanorods can be obtained at 180℃for 12 h under hydrothermal conditions. Typically, the as-prepared nanorods are usually 2⁵μm in length, 75²15 nm in width and 50¹10 nm in thickness, which exhibits a rectangle cross section, and grow along the [001] direction. The obtained sample is orthorhombic phase Sb₂S₃ with lattice parameters a=1.126 nm, b=1.128 nm, c=0.382 nm. UV-Vis analysis exhibits that Sb₂S₃ nanorods a semiconductors with bandwidth Eg =1.56 eV, suggesting that Sb₂S₃ nanorods could be used in solar energy and photoelectronic application. The possible growth mechanism was also discussed.Single-crystalline antimony sulfide （Sb₂S₃） nanomaterials with flower-like and rod-like morphologies were successfully synthesized under refluxing conditions by the reaction of antimony trichloride （SbCl3） and thiourea with PEG400 and OP-10 as the surfactant. X-ray diffraction （XRD） indicates that the obtained sample is orthorhombic-phase Sb₂S₃ with calculated lattice parameters a=1.124 nm, b=1.134 nm, c=0.382 nm. Scanning electron microscopy （SEM） and transmission electron microscopy （TEM） images show that the flower-like Sb₂S₃ is 9¹0μm in diameter, which is composed of thin nanoleaves with thickness of 0.05⁰.2μm, width of 0.8².2μm and length of 2.5³μm, and the rod-like Sb₂S₃ is 45³60 nm in diameter and 0.7⁴μm in length, respectively. UV-Vis analysis indicates that the band gap of Sb₂S₃ nanostructures is 1.52 eV, suitable for photovoltaic conversion. A possible mechanism of formation was proposed. The effects of reaction time and surfactants on the growth of nanomaterials with different morphologies were also investigated.Three-dimensional （3D） antimony sulfide （Sb₂S₃） cauliflower-like superstructures were prepared by the microwave irradiation method with single-source precursors Sb（S₂CNEt₂）₃ as raw materials and ethylene glycol as solvent. The powder X-ray diffraction （XRD） pattern shows the product belongs to the orthorhombic Sb₂S₃ phase with calculated lattice parameters a =1.141 nm, b=1.131 nm, and c=0.3807 nm. SEM and TEM images show that the cauliflower-like Sb₂S₃ superstructure consists of uniform Sb₂S₃ nanorod with a diameter of 20³50 nm and length about 5¹2μm extending radially from a nucleation site, the corresponding ED pattern shows its single crystal nature. The results of further experiments show that microwave radiation and surfactant PEG400 all played an important role on the formation of Sb₂S₃ cauliflower-like superstructures. UV-Vis analysis indicates that the band gap of Sb₂S₃ nanostructures is 1.90 eV, which is larger than the reported value. The possible growth mechanisms were proposed.更多还原