碱式硫酸锌转化法制备ZnO多孔片及其光致发光性能

采用化学浴沉积法制备了碱式硫酸锌(ZSH)纳米片, 并经1000 ℃煅烧处理得到了ZnO多孔片. 详细研究了ZSH在Zn²⁺-六亚甲基四胺前驱体溶液体系中的形成机理、ZSH 的热解过程、ZnO的结晶性、微结构以及光致发光性能. 结果表明, 所得ZnO多孔片呈规则六角形状, 其尺寸为10-50 μm, 厚度为200-500 nm, 由于高温固相反应中传质等因素的限制, 构成薄片的ZnO晶粒呈多边形或不规则形貌, 晶粒间的孔为亚微米孔, 尺寸在100-500 nm范围. ZnO多孔薄片结晶性良好, 在388 nm处表现出较强紫外发光, 无可见光区的缺陷发光. 机理分析表明, SO₄^2- 与Zn²⁺的高亲和力是Zn²⁺-六亚甲基四胺体系中ZSH生成的根本原因, 而ZSH的热分解过程对ZnO多孔片的形貌和微结构影响显著. 本研究提出了一种制备高结晶质量ZnO多孔材料的新方法, 所得ZnO多孔片可望在催化、染料敏化太阳能电池、紫外光电器件等领域得到应用.

Porous ZnO Sheets Transformed from Zinc Sulfate Hydroxide Hydrate and Their Photoluminescence Performance

Highly crystalline, porous ZnO sheets were prepared from chemically-deposited zinc sulfate hydroxide hydrate (ZSH) sheets by sintering at 1000 ℃. The formation mechanism of ZSH in Zn²⁺- hexamethyltetramine (HMT) precursor system, the transformation process of ZSH to ZnO, and the crystalline, microstructural and optical properties of the ZnO sheets were investigated. The porous ZnO sheets possessed a well-defined hexagonal shape with controllable size (10-50 μm) and thickness (200-500 nm), high crystallinity, and strong ultraviolet photoluminescence without detectable defectrelated visible emission. Submicron-sized pores (100-500 nm) and polygonal or irregular ZnO particles resulting from the limited mass transport during high temperature sintering were observed in the ZnO sheets. Analysis of the formation mechanism indicated that the high affinity of SO₄^2- for Zn²⁺ was responsible for the formation of ZSH in the Zn²⁺-HMT precursor system, and the thermolysis of ZSH affected the morphology and microstructure of the ZnO sheets. This work reveals a facile route to porous ZnO nanostructures with good crystallinity and optical properties, which make them suitable for application in catalysis, and photo and/or electrical devices.