拉曼应用举例
成像分析:拉曼成像是表征化学信息的有力手段。它对样品的不同位置逐点扫描并获取拉曼光谱,基于这些光谱生成伪彩图像,从而显示出材料的结构信息和分布: 拉曼峰强度成像——材料浓度分布
拉曼峰位成像——分子结构、物相和材料应力/张力分布 拉曼峰半高宽成像——结晶度和相分布
将原本单一的数据做成各种拉曼图像,为研究者提供更多深入、有价值的信息
Figure 1: (a) Raman hyperspectral data set from a polysilicon test structure with (d) whitereflected light image in lower right corner; (b) a Raman image generated from the spatiallyvarying signal strengths between the color coded brackets in the spectral traces; (c) the singlespectrum corresponding to the cross hairs in the Raman and white reflected light images. September 2019 Spectroscopy 34(9) 1
Figure 2: Optical micrograph (top left), Raman image of graphene bi-layer (in green), multi-layergraphene (in red), edges (in pink) and SiO2/Si substrate (in blue) (top right) based on themodelling algorithm using “pure” spectra of the different regions (bottom).
1、结晶度分析
一般而言晶体材料的拉曼光谱拥有尖锐、高强度的拉曼峰,而非晶材料的拉曼峰大多很宽,强度较低。不同的中间态的差别可能是比较精细的,高光谱分辨率能够清晰地确认这些精细的变化,对于区分这些中间态非常必要。通过软件对拉曼峰进行拟合,可以较为准确地计算出峰的半高宽和强度,再和其它技术方法比较和校正,可以用来作为定量测量结晶度的方法。
Figure 3: Raman spectra of Si amorphized through ion implantation and single-crystal Si
2、原位拉曼(变温、电化学等)
温度相关性研究有助于了解材料的精细结构和属性,通过探测声子和其他粒子的相互作用,可以了解电子器件和热电器件的性能变温拉曼测量能够清楚展示材料随温度的相变、峰位移动、峰位半高宽的变化,通过无损测量获得样品特性随温度的变化。
Figure 4. Raman spectra of single-layer WS2 with (a) E12g and (b) A1g mode measured in a temperature range from 77 to 623 K Appl. Mater. Interfaces 2014, 6, 1158?1163
Figure 5. 锂电池嵌锂/脱锂过程中石墨G峰变化,左列:电压从2.53V降到0.45V,嵌锂过程。右列:电压从0.38V升到2.89V,脱锂过程
3、 二维材料的研究
晶格振动(声子)是材料的基本属性。二维材料具有独特的声子结构,这些声子会随着层数的变化而显著地发生改变。这些变化难以通过SEM和XRD等方法进行表征拉曼光谱作为探测晶格振动特性和声子物理的最常用工具,在研究二维材料中起到了重要作用,可以分析: 层数或厚度,掺杂、缺陷,应力/应变,晶界,化学修饰,异质结的层间耦合等。
Figure 6. Raman spectrum of an optically trapped graphene flake with 633-nm trapping and excitation wavelength,Ferrari, Nature Nanotechnology, 2013
Figure 7.a , High-resolution TEM image. b, c, Enlarged high-resolution TEM images. d, e, The related schematic atomic models, clearly showing distinct atomic configuration corresponding to hexagonal Co and cubic Co3O4. f–h, Elemental mapping. i, Micro-Raman spectra for the products obtained at 220°C for 3h (red line) and 48h (black line). Nature volume 529, pages 68–71