Lee Kyeong-Seok, El-Sayed Mostafa A
Laser Dynamics Laboratory, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, 30332-0400, USA.
J Phys Chem B. 2006 Oct 5;110(39):19220-5. doi: 10.1021/jp062536y.
Plasmonic metal nanoparticles have great potential for chemical and biological sensor applications, due to their sensitive spectral response to the local environment of the nanoparticle surface and ease of monitoring the light signal due to their strong scattering or absorption. In this work, we investigated the dependence of the sensitivity of the surface plasmon resonance (frequency and bandwidth) response to changes in their surrounding environment and the relative contribution of optical scattering to the total extinction, on the size and shape of nanorods and the type of metal, that is, Au vs Ag. Theoretical consideration on the surface plasmon resonance condition revealed that the spectral sensitivity, defined as the relative shift in resonance wavelength with respect to the refractive index change of surrounding materials, has two controlling factors: first the bulk plasma wavelength, a property dependent on the metal type, and second on the aspect ratio of the nanorods which is a geometrical parameter. It is found that the sensitivity is linearly proportional to both these factors. To quantitatively examine the dependence of the spectral sensitivity on the nanorod metal composition and the aspect ratio, the discrete dipole approximation method was used for the calculation of optical spectra of Ag-Au alloy metal nanorods as a function of Ag concentration. It is observed that the sensitivity does not depend on the type of the metal but depends largely on the aspect ratio of nanorods. The direct dependence of the sensitivity on the aspect ratio becomes more prominent as the size of nanorods becomes larger. However, the use of larger nanoparticles may induce an excessive broadening of the resonance spectrum due to an increase in the contribution of multipolar excitations. This restricts the sensing resolution. The insensitivity of the plasmon response to the metal composition is attributable to the fact that the bulk plasma frequency of the metal, which determines the spectral dispersion of the real dielectric function of metals and the surface plasmon resonance condition, has a similar value for the noble metals. On the other hand, nanorods with higher Ag concentration show a great enhancement in magnitude and sharpness of the plasmon resonance band, which gives better sensing resolution despite similar plasmon response. Furthermore, Ag nanorods have an additional advantage as better scatterers compared with Au nanorods of the same size.
等离子体金属纳米颗粒在化学和生物传感器应用方面具有巨大潜力,这归因于它们对纳米颗粒表面局部环境的敏感光谱响应,以及由于其强烈的散射或吸收而易于监测光信号。在这项工作中,我们研究了表面等离子体共振(频率和带宽)响应的灵敏度对其周围环境变化的依赖性以及光散射对总消光的相对贡献,这取决于纳米棒的尺寸和形状以及金属类型,即金与银。对表面等离子体共振条件的理论考虑表明,光谱灵敏度定义为共振波长相对于周围材料折射率变化的相对偏移,有两个控制因素:首先是体等离子体波长,这是一个取决于金属类型的属性,其次是纳米棒的纵横比,这是一个几何参数。发现灵敏度与这两个因素都成线性比例。为了定量研究光谱灵敏度对纳米棒金属成分和纵横比的依赖性,使用离散偶极近似方法计算了作为银浓度函数的银 - 金合金金属纳米棒的光谱。观察到灵敏度不取决于金属类型,而是在很大程度上取决于纳米棒的纵横比。随着纳米棒尺寸变大,灵敏度对纵横比的直接依赖性变得更加突出。然而,使用较大的纳米颗粒可能会由于多极激发贡献的增加而导致共振光谱过度展宽。这限制了传感分辨率。等离子体响应对金属成分的不敏感性归因于这样一个事实,即决定金属实介电函数的光谱色散和表面等离子体共振条件的金属体等离子体频率,对于贵金属具有相似的值。另一方面,具有较高银浓度的纳米棒在等离子体共振带大小和锐度方面有很大增强,尽管等离子体响应相似,但能提供更好的传感分辨率。此外,与相同尺寸的金纳米棒相比,银纳米棒作为更好的散射体还有一个额外优势。