Wu Hao, Wang Hua, Li Guanghai
Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, P. R. China.
Analyst. 2017 Jan 16;142(2):326-335. doi: 10.1039/c6an01959e.
A general route to transform metal oxide semiconductors from non-SERS active to SERS-active substrates based on defect engineering is reported. The SERS enhancement factor (EF) of metal oxide semiconductors like α-MoO and VO can be greatly enhanced and the SERS performance can be optimized according to the detecting analyte and activating laser wavelength by introducing oxygen vacancy defects. The EF of R6G on α-MoO nanobelts can be as high as 1.8 × 10 with a detection limit of 10 M, which is the best among metal oxide semiconductors and comparable to noble metals without a "hot spot". A model, named "effective electric current model", was proposed to describe the photo-induced charge transfer process between the absorbed molecules and semiconductor substrates. The EF of 4-MBA, R6G and MB on α-MoO nanobelts with different oxygen vacancy concentrations calculated based on the model matches very well with experimental results. As an extension, some potential metal oxide semiconductor SERS-active substrates were predicted based on the model. Our results clearly demonstrate that, through defect engineering, the metal oxide semiconductors can be made SERS-active substrates with high stability and high biocompatibility.
报道了一种基于缺陷工程将金属氧化物半导体从非表面增强拉曼散射(SERS)活性衬底转变为SERS活性衬底的通用方法。通过引入氧空位缺陷,诸如α-MoO和VO等金属氧化物半导体的SERS增强因子(EF)能够得到极大提高,并且可以根据检测的分析物和激活激光波长来优化SERS性能。在α-MoO纳米带上,罗丹明6G(R6G)的EF高达1.8×10,检测限为10 M,这在金属氧化物半导体中是最佳的,并且与没有“热点”的贵金属相当。提出了一个名为“有效电流模型”的模型来描述吸附分子与半导体衬底之间的光致电荷转移过程。基于该模型计算的不同氧空位浓度的α-MoO纳米带上4-巯基苯甲酸(4-MBA)、R6G和亚甲基蓝(MB)的EF与实验结果非常吻合。作为扩展,基于该模型预测了一些潜在的金属氧化物半导体SERS活性衬底。我们的结果清楚地表明,通过缺陷工程,金属氧化物半导体可以制成具有高稳定性和高生物相容性的SERS活性衬底。