Wang Xiao-Fang, Xie Ping-Bo, Zhao Fu-Li, Wang He-Zhou
College of Materials Science and Engineering, South China University of Technology, Guangzhou 510641, China.
Guang Pu Xue Yu Guang Pu Fen Xi. 2009 Nov;29(11):2881-4.
The size-dependence of photoluminescence (PL) of ZnO nanoparticles with diameter from 17 to 300 nm was demonstrated by time resolved laser spectroscopy. Broad PL spectra were obtained and found to consist of three Gaussian components. The authors found that the PL peak position and relative amplitude depend on the size of nanoparticles for the Gaussian PL band inside the energy band-gap. The Gaussian band Xc3 is believed to be associated with the transitions between surface states. It is well known that as the dimensions of a semiconductor are reduced to the nanometer scale, one of the key features is the large surface-to-volume ratio. The larger surface-to-volume ratio in nanostructures means the larger bulk density of dangling bonds. The existence of dangling bond in a crystal surface is likely to change a state localized by splitting the state out of the border of the energy gap. The Gaussian peak Xc3 lying inside the band gap of ZnO indicates the existence of such initial states in the forbidden bulk band gap. Furthermore, we found that with the decrease in particle size, the Gaussian curve Xc3 shifts to the lower energy. With the particle size increaseing, the comparative amplitude of PL band Xc3 descends rapidly and so does the corresponding relative PL intensity. The sensitive correlation between the particle size and the optical properties of the below gap broadband shows a key role of the surface states recombination in PL of nanosized particles. Furthermore, our exploration indicates that the surface states recombination plays a dominant role in PL of nanostructures with particle sizes down to a certain degree.
通过时间分辨激光光谱法证明了直径为17至300nm的ZnO纳米颗粒的光致发光(PL)的尺寸依赖性。获得了宽的PL光谱,发现其由三个高斯分量组成。作者发现,对于能带隙内的高斯PL带,PL峰位置和相对幅度取决于纳米颗粒的尺寸。高斯带Xc3被认为与表面态之间的跃迁有关。众所周知,随着半导体尺寸减小到纳米尺度,关键特征之一是大的表面体积比。纳米结构中较大的表面体积比意味着悬空键的体密度较大。晶体表面悬空键的存在可能会通过将状态从能隙边界分裂出来而改变一个局域态。位于ZnO带隙内的高斯峰Xc3表明在禁带体带隙中存在这样的初始态。此外,我们发现随着粒径减小,高斯曲线Xc3向较低能量移动。随着粒径增大,PL带Xc3的相对幅度迅速下降,相应的相对PL强度也迅速下降。粒径与带隙以下宽带光学性质之间的敏感相关性表明表面态复合在纳米颗粒PL中起关键作用。此外,我们的研究表明,表面态复合在粒径降至一定程度的纳米结构PL中起主导作用。