Wang Xiao-fang, Xie Ping-boz, Zhao Fu-li, Wang He-zhou
State Key Laboratory of Optoelectonic Materials and Technologies, School of Physics and Engineering, Sun Yat-sen University, Guangzhou 510275, China.
Guang Pu Xue Yu Guang Pu Fen Xi. 2009 May;29(5):1160-3.
Time-resolved photoluminescence (TRPL) and time-integrated photoluminescence (TIPL)measurements were performed at ZnO nanoparticles with grain size from 17 nm to 110 nm prepared by homogenous precipitation method (HPM). With a quasi-continuous picoseconds laser excitation at a low photon energy of 2. 33 eV (wavelength 532 nm)from a Vanguard 2000-HM532 laser, ultrafast emission with the wavelength ranging from 550 to 1000 nm was detected. It was observed that the wavelength position of all the peaks of the samples regularly redshifted with the increase in the particle sizes. The PL spectra were fitted with Gaussian curves, in which a good fitting consisting of four Gaussian peaks was obtained. The Gaussian analysis indicates that the redshift in PL is due to the increased relative magnitude of the Gaussian combination in the low energy region. The analysis of the experiment suggests the existence of surface states in the bad gap near Fermi level of ZnO. At the same time, a strong dependence of the PL lifetime on grain size was found. Upon the increase in particle size, the decay of the emission shortened much, in which the PL intensity reveals bi-exponential decay for samples with small diameters while no identified decay of emission was observed within 2 nanoseconds for large particles. The dependence of the decay time on the grain size of nanoparticles can be suitably attributed to the surface related mechanism. Combined analysis of the lifetime dependence on particle size validates the model of surface states recombination in nanostructures due to large surface-to-volume ratio.
采用均相沉淀法(HPM)制备了粒径从17 nm到110 nm的ZnO纳米颗粒,并对其进行了时间分辨光致发光(TRPL)和时间积分光致发光(TIPL)测量。使用Vanguard 2000-HM532激光器在2.33 eV(波长532 nm)的低光子能量下进行准连续皮秒激光激发,检测到波长范围为550至1000 nm的超快发射。观察到样品所有峰的波长位置随粒径增加而有规律地红移。PL光谱用高斯曲线拟合,得到了由四个高斯峰组成的良好拟合。高斯分析表明,PL中的红移是由于低能量区域高斯组合的相对幅度增加。实验分析表明,在ZnO费米能级附近的禁带中存在表面态。同时,发现PL寿命对晶粒尺寸有很强的依赖性。随着粒径的增加,发射的衰减大大缩短,其中对于小直径样品,PL强度呈现双指数衰减,而对于大颗粒,在2纳秒内未观察到发射的明显衰减。衰减时间对纳米颗粒粒径的依赖性可适当地归因于表面相关机制。对寿命与粒径依赖性的综合分析验证了由于大的表面体积比导致的纳米结构中表面态复合模型。