化学水浴法制备ZnS

1、Department of Materials Science and EngineeringApplying Materials Innovation to Energy and Environmental Problems. Group NO.6Reporter 孔令军孔令军 Group 程位任、邾强强程位任、邾强强members 张张 帆、党军杰帆、党军杰 Dec.22.2010Department of Materials Science and EngineeringUniversity of Science and Technology of China结论结论CBD方法简介方法简

2、介CBD制备制备ZnS过程过程1234ZnS简介简介Department of Materials Science and EngineeringUniversity of Science and Technology of China一、一、ZnS简介简介v1.1 ZnS 特点特点： 1、-族宽禁带直接带隙半导体 2、带隙宽度为3.2-3.6eV 3、ZnS晶体分为立方晶系和六角晶系。 4、良好的荧光性能 5、良好的透光性能v1.2 ZnS 薄膜应用：薄膜应用： 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；作为薄膜太阳能电池缓冲层也展示了其良好的应用前景。Dep

3、artment of Materials Science and EngineeringUniversity of Science and Technology of China 1.3 ZnS薄膜的制备方法薄膜的制备方法v 溅射法( Sputtering) v 原子层沉积法(Atomic layer deposition ,ALD ) v 热蒸发法( Thermal evaporation) v 分子束外延生长法(Molecular beam epitaxy ,MBE) v 电沉积法( Elect rodeposition ,ED) v 脉冲激光沉积法( Pulsed laser depos

4、ition , PLD ) v 化学水浴法( Chemical bath deposition CBD) Department of Materials Science and EngineeringUniversity of Science and Technology of China二、化学水浴法（二、化学水浴法（CBD）简介）简介加热磁力搅拌器水浴锅（大烧杯）反应容器（小烧杯）化学浴装置图基本构造2.1 CBD装置图示装置图示支架温度计搅拌子（磁子）Department of Materials Science and EngineeringUniversity of Science

5、and Technology of China2.2 CBD工艺流程图工艺流程图金属盐金属盐硫源硫源NH3衬底材料衬底材料混合溶液混合溶液均匀薄膜均匀薄膜清洗，垂直放入络合剂络合剂+PH值调节剂值调节剂替代氨水搅拌、恒温水浴Department of Materials Science and EngineeringUniversity of Science and Technology of China 生产成本低、容易操作、仪器设备简单、低温常压下反应 可用来制备各种-族半导体化合物能大面积成膜、所得膜较均匀连续 优势2.3、CBD制备方法的优点制备方法的优点Department of M

6、aterials Science and EngineeringUniversity of Science and Technology of China三、三、CBD制备制备ZnS过程过程The deposition process requires the release of cations Zn2+ and anions S2 in the solution: Zn(NH3)n 2+ Zn 2+ +nNH3 (1) SC(NH2)2 +2OH S 2 +CN2H2 +2H2O (2) and then Zn 2+ +S2 ZnS (3)3.1、CBD沉积沉积ZnS薄膜反应机理薄膜反应机

7、理沉积过程沉积过程homogeneous deposition （同质沉积）heterogeneous deposition （异质沉积）cluster-by-cluster(簇簇机制)ion-by-ion（离子离子机制），Department of Materials Science and EngineeringUniversity of Science and Technology of China化学浴装置图金属盐： 氯化锌、硝酸锌、硫酸锌、乙酸锌硫属离子源： 硫脲、硫代硫酸根(S2O32-)、硫代乙酞胺(CH3CSNH2);络合剂如： 氨(NH3)、水合肼（N2H4H2O）、 乙酸根

8、、三乙醇胺(N(CH2CH2OH)3)、柠檬酸根3.2 CBD制备制备ZnS的原料简介：的原料简介：Department of Materials Science and EngineeringUniversity of Science and Technology of ChinaZnSO40.025 MSC(NH2)20.2 M混合溶液Ammonia25%薄膜沉积洗涤干燥热处理结构与性能测试3.3、详细制备流程、详细制备流程CBD装置80 玻璃沉底清洗 垂直Applied Surface Science 254 (2008) 57115714Department of Materials

9、Science and EngineeringUniversity of Science and Technology of ChinaSEM micrographs of ZnS films deposited on various growth phases: (A) none-film phase; (B) quasi-linear phase; (C) in the saturation phaseDepartment of Materials Science and EngineeringUniversity of Science and Technology of China如：温

10、度对如：温度对CBDCBD制备制备ZnSZnS薄膜影响薄膜影响 温度对薄膜的生长机制有重要的影响cluster by clusterIon by ion晶体结构、薄膜成分、厚度、透光率、表面形貌、电学性质、分层现象以及成核机理在不同温度下沉积 以及沉积过程中改变温度3.4、制备过程中影响成膜的参数、制备过程中影响成膜的参数n CBD法合成ZnS薄膜的条件繁多且杂，主要：时间、温度、时间、温度、PH值、络合剂、源材料值、络合剂、源材料Department of Materials Science and EngineeringUniversity of Science and Technolog

11、y of China四、结论四、结论 尽管CBD制备ZnS薄膜有诸多优势，但仍存在诸多的问题：缺陷: 1、沉积过程ion-by-ion机制难以控制 2、原材料利用率很低 3、废液处理困难 4、存在Zn(OH)2或ZnO杂相展望： 1、进一步完善CBD工艺 2、对各参数对成膜影响还需深入研究Department of Materials Science and EngineeringUniversity of Science and Technology of China参考文献参考文献:v1.Chemical bath-deposited ZnS thin films: Preparation

12、 and characterization Applied Surface Science 254 (2008) 57115714v2.Developing an understanding of the processes controlling the chemical bath deposition of ZnS and CdS J. Mater. Chem (1998)v3. Effect of Zn/S ratios on the properties of chemical bath deposited zinc sulfide thin films Applied Surface Science 257 (2010) 122126v4.Effect of pH on the characteristics of nanocrystalline ZnS thin films pre