Kurudirek Sinem V, Pradel Ken C, Summers Christopher J
Ataturk University, Faculty of Science, Department of Physics, 25240 Erzurum, Turkey.
School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0245, USA.
J Alloys Compd. 2017 Apr 25;702:700-709. doi: 10.1016/j.jallcom.2017.01.273. Epub 2017 Jan 27.
The hydrothermal synthesis of ZnO nanorods (NRs) has been investigated using ammonium hydroxide and polyethyleneimine as additives to the conventional nitrate based synthesis route, to obtain thin-films of well-aligned, ultradense and ultralong nanostructures. ZnO NRs longer than 60 μm were obtained in a one-cycle growth run and rod lengths ~ 100 μm by a two-cycle growth. The lengths of the rods were distributed uniformly across the substrate in all samples and highly dense NR arrays were observed. These conditions were obtained by a careful review of the nucleation and growth kinetics for this material system, such that the supersaturation of the solution was only relieved by precipitation on and in the presence of crystalline ZnO, and by the exploitation of a second growth phase due to the chelating behave of PEI and the products of HMTA. Also, the growth behavior was correlated to the solution pH values. The structural and optical data were found to be supportive of the growth conditions. The photoluminescence (PL) spectra from as-grown ultralong ZnO NRs exhibited a strong broad (580-625 nm) visible emission peak. However, annealing in a forming gas atmosphere at 623K (350°C) revealed a PL spectrum with a significantly decreased visible emission and an increased near band gap UV emission at 379 nm. Thus, the mechanisms associated with ammonium hydroxide and PEI addition provide a simple route for synthesizing ultralong and dense arrays of ZnO NRs at low temperature i.e. 368K (95°C).
以氢氧化铵和聚乙烯亚胺作为添加剂,采用水热法合成氧化锌纳米棒(NRs),并将其应用于传统的硝酸盐基合成路线,以获得排列良好、超致密且超长的纳米结构薄膜。在一个生长周期内可获得长度超过60μm的氧化锌纳米棒,通过两个生长周期可获得长度约为100μm的纳米棒。在所有样品中,纳米棒的长度在整个衬底上均匀分布,并且观察到了高密度的纳米棒阵列。通过仔细研究该材料体系的成核和生长动力学获得了这些条件,使得溶液的过饱和度仅通过在结晶氧化锌存在下的沉淀来缓解,并且由于聚乙烯亚胺的螯合行为和六亚甲基四胺的产物利用了第二个生长阶段。此外,生长行为与溶液的pH值相关。发现结构和光学数据支持生长条件。生长的超长氧化锌纳米棒的光致发光(PL)光谱显示出一个强烈的宽(580 - 625nm)可见发射峰。然而,在623K(350°C)的形成气体气氛中退火后,PL光谱显示可见光发射显著降低,379nm处的近带隙紫外发射增加。因此,与添加氢氧化铵和聚乙烯亚胺相关的机制为在低温即368K(95°C)下合成超长且致密的氧化锌纳米棒阵列提供了一条简单的途径。