Jones Andrew C, Olmon Robert L, Skrabalak Sara E, Wiley Benjamin J, Xia Younan N, Raschke Markus B
Department of Physics, University of Washington, Seattle, Washington 98195, USA.
Nano Lett. 2009 Jul;9(7):2553-8. doi: 10.1021/nl900638p.
Chemically synthesized metallic nanostructures can exhibit a strong local optical field enhancement associated with their high degree of crystallinity and well-defined geometry-dependent surface plasmon resonances. The extension of the plasmon modes into the mid-IR spectral range (3-30 microm) is shown for micrometer-sized nanowires with high aspect ratios available in the form of pentagonally twinned Ag crystallites as grown by polyol synthesis. Using scattering-scanning near-field optical microscopy, the associated IR plasmon modes are identified, and their underlying spatial distribution and enhancement of the optical polarization density is measured via phase, amplitude, and polarization resolved optical vector-field mapping. The transition from dipolar to multipolar resonances is observed and described by modeling the Ag wires using a modified cylindrical waveguide theory. For 10.6 microm excitation, dipole antenna resonances are observed at a resonant length of L = lambda(eff)/2 with lambda(eff) approximately 10.6 microm/(1.8 +/- 0.5) approximately 6 +/- 2 microm. This effective wavelength scaling is the result of electronic damping, despite the high aspect ratios of the wires of order 1:10 to 1:200. With the optical cycle period tau(IR) being comparable to the Drude relaxation time of tau approximately 40 fs the mid-IR defines the low-energy limit of the coherent plasmon regime (tau(IR) less, similar tau) at the transition to purely geometric antenna resonances (tau(IR) > tau).
化学合成的金属纳米结构由于其高度的结晶性和明确的几何形状相关的表面等离子体共振,可表现出强烈的局部光场增强。对于通过多元醇合成生长的具有高纵横比的微米级纳米线,其等离子体模式扩展到中红外光谱范围(3 - 30微米),这些纳米线以五角孪晶银微晶的形式存在。使用散射扫描近场光学显微镜,识别出相关的红外等离子体模式,并通过相位、幅度和偏振分辨光学矢量场映射测量其潜在的空间分布和光偏振密度的增强。通过使用改进的圆柱波导理论对银线进行建模,观察并描述了从偶极共振到多极共振的转变。对于10.6微米的激发,在共振长度L = λeff/2处观察到偶极天线共振,其中λeff约为10.6微米/(1.8 ± 0.5)≈ 6 ± 2微米。尽管线的纵横比高达1:10至1:200,但这种有效波长缩放是电子阻尼的结果。由于光学周期τ(IR)与约40飞秒的德鲁德弛豫时间τ相当,中红外定义了在向纯几何天线共振(τ(IR) > τ)转变时相干等离子体区域(τ(IR) < τ)的低能量极限。