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金属氧化物半导体纳米材料的制备和性能研究

Preparation and Characterization of Metal-Oxide Semicomductor Nanomaterials

【作者】 杨静

【导师】 白守礼;

【作者基本信息】 北京化工大学 , 化学工程与技术, 2010, 硕士

【摘要】 氧化锌和二氧化锡是两种用途广泛的半导体材料,由于纳米材料具有一些特殊的性能,更加扩展了它们的应用范围,使其制备研究成为当前材料研究的热点之一。本论文分别采用电化学沉积和水辅助气相沉积方法制备了氧化锌和二氧化锡纳晶薄膜、二氧化锡纳米带,并探索了所制备材料在染料敏化太阳能电池,电催化方面的应用。主要研究工作包括以下三方面。1.通过在沉积液中添加具有吸附基团的曙红染料,采用电化学沉积的方法制备了多孔ZnO/EY复合纳晶薄膜,ZnO为六方晶型纤锌矿,单晶ZnO在垂直于FTO导电玻璃基底上沿c轴方向有较好的择优生长取向。在较负电位下可以沉积出较厚的薄膜。通过ZnO/EY复合纳晶薄膜上曙红的脱附和再吸附过程,可以得到曙红敏化的氧化锌纳晶薄膜。将其应用于染料敏化太阳能电池中,表现出良好的光电转换性能。2.采用电化学沉积的方法,在70℃下,在添加不同浓度的丁基罗丹明(BRhB)的氧气饱和的氯化亚锡的酸溶液中,制备了多孔二氧化锡纳晶薄膜。溶液中加入盐酸为了抑制SnCl2的水解,BRhB含有氨基取代基能溶于酸性的沉积溶液中,同时BRhB含有羧基能吸附在二氧化锡表面,所以采用BRhB作结构导向剂控制SnO2晶体生长,从而控制晶体的结构和薄膜的表面形貌。由于BRhB的加入,沉积的薄膜具有多孔结构形貌和四方金红石晶体结构。BRhB的添加促进了多孔结构的形成,多孔结构提高了二氧化锡薄膜降解苯酚的电催化性能。3.采用水辅助气相沉积法,以高纯锡粒为原料合成高纯度的二氧化锡纳米带,二氧化锡纳米带为四方金红石结构,表面光滑。同时研究了由合成的二氧化锡制备的薄膜的电催化氧化苯酚的性能。

【Abstract】 ZnO and SnO2, as a semiconductor material, are widely applied in many fields. Recently, their application is extended further due to some special characteristics as the size of the prepared material is decreased to nanoscale. Much attention has been paid to this area in the world. In this thesis, nanoporous ZnO crystalline thin films, nanoporous SnO2 thin films and crystalline SnO2 nanobelts were prepared by electrochemical deposition and water assisted vapor deposition technique. Their applications on dye sensitized solar cell, electrocatalytic oxidation were studied. The major research work and results for this dissertation are as follows:1. The electrochemical deposition was employed to prepare nanocrystalline ZnO/EY hybrid porous thin films from solution containing dye with adsorption group. ZnO is hexagonal wurtzite crystal. Single crystal ZnO has preferred growth direction perpendicular to the FTO conductive glass substrate along the c-axis. In the more negative potential, we can deposit a thicker film. Through desorption and re-adsorption process, eosinY sensitized nanocrystalline ZnO films can be prepared. This kind of film was applied to dye-sensitized solar cells presenting good photoelectric properties2. Porous crystalline SnO2 thin films were successfully electrodeposited from an oxygen-saturated acid aqueous solution of SnCl2 containing different concentrations of butyl rhodamine B (BRhB) at 70℃. HCl was added to suppress hydrolysis of SnCl2, BRhB can be dissolved in the acid deposition solution due to its substitutes of amidocyanogen, and can adsorb on the surface of SnO2 due to its carbonate group. Therefore, it was used as a structure-directing agent to control the crystal growth of SnO2 and thus affects the crystalline structure and surface morphology of the deposited film. The electrodeposited thin films show porous morphology and rutile-type SnO2 crystalline structure due to addition of BRhB, and these structure features were controlled by the added amount of BRhB. The SnO2 thin film electrodeposited with addition of BRhB exhibits electrocatalytic characteristic enhancement on oxidation of phenol due to its porous structure.3. SnO2 nanobelts were synthesized by the water-assisted vapor deposition method using high pure Sn particles as the source materials. The SnO2 nanobelts synthesized by this method have rutile structure and smooth surface. The SnO2 thin film prepared by SnO2 nanobelts has good electrocatalytic activity to degrade phenol.

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