<strong>ZnO</strong>纳米棒阵列和薄膜的同步外延生长及其光电化学性能

doi:10.11901/1005.3093.2021.149

材料研究学报

2022, Vol. 36

Issue (7): 481-488 DOI: 10.11901/1005.3093.2021.149

研究论文

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ZnO纳米棒阵列和薄膜的同步外延生长及其光电化学性能

熊庭辉¹^,², 蔡文汉¹^,², 苗雨¹^,², 陈晨龙²(

)

^1.福州大学化学学院福州 350108
^2.中国科学院福建物质结构研究所中科院光电材料化学与物理重点实验室福州 350002

Simultaneous Epitaxy Growth and Photoelectrochemical Performance of ZnO Nanorod Arrays and Films

XIONG Tinghui¹^,², CAI Wenhan¹^,², MIAO Yu¹^,², CHEN Chenlong²(

)

^1.College of Chemistry, Fuzhou University, Fuzhou 350108, China
^2.Key Laboratory of Optoelectronic Materials Chemistry and Physics, Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou 350002, China

引用本文:

熊庭辉, 蔡文汉, 苗雨, 陈晨龙. ZnO纳米棒阵列和薄膜的同步外延生长及其光电化学性能[J]. 材料研究学报, 2022, 36(7): 481-488.
Tinghui XIONG, Wenhan CAI, Yu MIAO, Chenlong CHEN. Simultaneous Epitaxy Growth and Photoelectrochemical Performance of ZnO Nanorod Arrays and Films[J]. Chinese Journal of Materials Research, 2022, 36(7): 481-488.

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摘要:

使用化学气相沉积法在a面蓝宝石衬底上同步外延生长氧化锌(ZnO)竖直纳米棒阵列和薄膜,研究了阵列和薄膜的光电化学性能。结果表明,纳米结构中的竖直单晶纳米棒有六棱柱形和圆柱形,其底部ZnO薄膜使竖直纳米棒互相联通。与ZnO纳米薄膜的比较表明,这种纳米结构具有优异的光电化学性能,其入射光电流效率是ZnO纳米薄膜的2.4倍；光能转化效率是ZnO纳米薄膜的5倍。这种纳米结构优异的光电化学性能,可归因于其高表面积-体积比以及其底部薄膜提供的载流子传输通道。本文分析了这种纳米结构的生长过程,提出了协同生长机理：Au液化吸收气氛中的Zn原子生成合金,合金液滴过饱和后ZnO开始成核,随后在衬底表面生成了ZnO薄膜。同时,还发生了Zn自催化的气-固(VS)生长和Au催化的气-液-固(VLS)生长,分别生成六棱柱纳米棒和圆柱形纳米棒,制备出底部由薄膜连接的竖直纳米棒阵列。

关键词 ：无机非金属材料, ZnO纳米棒阵列, 同步外延, 光电化学

Abstract：

The simultaneous epitaxial growth of vertical nanorod arrays and thin films of zinc oxide (ZnO) was realized on a gold-plated plane sapphire substrate via a simple chemical vapor deposition method. In this nanostructure, the vertical single crystal nanorods are hexagonal prism or cylindrical in shape, and are all grown on a ZnO thin film, so that the vertical nanorods are connected to each other through the beneath thin oxide ZnO film. In comparison with ZnO nanofilms, the prepared nanostructure has excellent photoelectrochemistry (PEC) performance with an incident photocurrent efficiency of 2.4 times that of the simple ZnO nanofilms; while its light energy conversion efficiency is 5 times that of ZnO nanofilms. Its excellent PEC performance can be attributed to its high surface area-to-volume ratio and the carrier transport channel provided by the supporter ZnO film. The mechanism for cooperative growth of ZnO nanorod arrays and thin films was proposed as follows: during the processing, Au liquefies and absorbs Zn atoms in the atmosphere forming alloys. After the alloy droplets were supersaturated ZnO begins to nucleate, and then ZnO film formed on the surface of the substrate. At the same time, Zn autocatalyzed (vapor-solid)VS growth and Au catalyzed (vapor-liquid-solid)VLS growth occurred, respectively forming hexagonal prism nanorods and cylindrical nanorods, and finally a vertical nanorod array was connected through the underneath thin ZnO film.

Key words： inorganic non-metallic materials ZnO nanorod arrays simultaneous epitaxy PEC

收稿日期: 2021-02-24

ZTFLH:

O646

基金资助:福建省自然科学基金(2018J01110)

作者简介: 熊庭辉,男,1996年生,硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2021.149 或 https://www.cjmr.org/CN/Y2022/V36/I7/481

图1 实验用管式炉的示意图

图2 同步外延生长的ZnO纳米结构(ZnO纳米薄膜和纳米棒阵列)的俯视SEM照片和截面SEM照片

图3 同步外延生长的ZnO纳米结构的XRD谱

图4 生长时间不同的ZnO纳米结构的30°斜视照片

图5 ZnO纳米结构的生长机理

图6 生长时间分别为2 min和8 min样品的XPS全谱和Au 4f-Zn 3p轨道窄谱

图7 ZnO纳米薄膜和ZnO纳米结构的紫外-可见吸收光谱以及 ZnO纳米薄膜和ZnO纳米结构光阳极的入射光电流效率(IPCE)

图8 ZnO纳米薄膜和ZnO纳米结构光阳极的线性扫描伏安(LSV)曲线、光电流-时间(J-t)曲线、光能转化效率(η)曲线和Nyquist图,实线曲线为对应的拟合曲线

表1 其它类似结构的ZnO光电流密度

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