Liu Shu-man, Xu Zheng, Wageh H, Xu Xu-rong
Institute of Optoelectronic Technology, Laboratory of Information Storage, Display and Materials, Northern Jiaotong University, Beijing 100044, China.
Guang Pu Xue Yu Guang Pu Fen Xi. 2002 Dec;22(6):908-11.
Semiconductor nanocrystals appear different optical properties from their bulk analogous due to quantum confinement effects. It is well known that optical absorption of nanocrystals shift to higher energy as the sizes decrease, while the emission at the absorption band edge is always too weak to be investigated in details due to much nonradiative recombination at nanoparticle surface. To eliminate the surface defects, some kinds of materials such as organic molecules, polymers and inorganic compounds are used to overcoat the nanoparticles. It has been found that nanocrystals overcoated with high band gap inorganic materials maned core/shell type nanocrystals exhibit high photoluminescence intensity at band edge due to effective elimination of surface nonradiative recombination. In this article we report the characteristics of CdSe/CdS core/shell nanocrystals synthesized with mercapto acid as stabilizer. The effect of CdS shell on the electronic characteristics and the luminescence of CdSe core were investigated by using optical absorption, photoluminescence and photoluminescence excitation spectra. Large band edge luminescence enhancement was found in CdSe nanoparticles overcoated with the CdS shell with a thickness of 0.3 nm due to passivation of nonradiative recombination sites on CdSe surfaces. Such bandadge emission also appeared redshift from the absorption maximum. This Stokes shift of the emission peak from the absorption edge was explained by a model of formation of excimer among the small nanoparticles based on the optical experimental results and the theoretical calculation on fine structures of bandadge excitons.
由于量子限制效应,半导体纳米晶体呈现出与其块状类似物不同的光学性质。众所周知,随着尺寸减小,纳米晶体的光吸收向更高能量移动,而由于纳米颗粒表面大量的非辐射复合,吸收带边缘的发射总是太弱而无法详细研究。为了消除表面缺陷,一些材料如有机分子、聚合物和无机化合物被用于包覆纳米颗粒。已经发现,用宽带隙无机材料包覆的纳米晶体,即核壳型纳米晶体,由于有效地消除了表面非辐射复合,在带边缘表现出高光致发光强度。在本文中,我们报道了以巯基酸为稳定剂合成的CdSe/CdS核壳纳米晶体的特性。通过光吸收、光致发光和光致发光激发光谱研究了CdS壳对CdSe核的电子特性和发光的影响。由于CdSe表面非辐射复合位点的钝化,在包覆有厚度为0.3nm的CdS壳的CdSe纳米颗粒中发现了大的带边缘发光增强。这种带边发射也出现了相对于吸收最大值的红移。基于光学实验结果和带边激子精细结构的理论计算,用小纳米颗粒之间形成激基缔合物的模型解释了发射峰相对于吸收边缘的这种斯托克斯位移。