Quantum plasmon resonances of individual metallic nanoparticles

摘要

The plasmon resonances of metallic nanoparticles have received considerable attention for their applications in nanophotonics, biology, sensing, spectroscopy and solar energy harvesting. Although thoroughly characterized for spheres larger than ten nanometres in diameter, the plasmonic properties of particles in the quantum size regime have been historically difficult to describe owing to weak optical scattering, metal-ligand interactions, and inhomogeneity in ensemble measurements. Such difficulties have precluded probing and controlling the plasmonic properties of quantum-sized particles in many natural and engineered processes, notably catalysis. Here we investigate the plasmon resonances of individual ligand-free silver nanoparticles using aberration-corrected transmission electron microscope (TEM) imaging and monochromated scanning TEM electron energy-loss spectroscopy (EELS). This technique allows direct correlation between a particle's geometry and its plasmon resonance. As the nanoparticle diameter decreases from 20 nanometres to less than two nanometres, the plasmon resonance shifts to higher energy by 0.5 electronvolts, a substantial deviation from classical predictions. We present an analytical quantum mechanical model that describes this shift due to a change in particle permittivity. Our results highlight the quantum plasmonic properties of small metallic nanospheres, with direct application to understanding and exploiting catalytically active and biologically relevant nanoparticles.%本期封面所示为“Through the Looking Glass”的一个细节内容，它是由Kate Njchols(TED Fellow 计划的一个资助对象)制作的 个大型玻璃艺术品，是用银纳米颗粒作为“颜料”创作出来的。作品的颜色来自金属颗粒中电子的振荡(局部化的表面“等离子体激元”的共振)。这些颗粒的“等离子体激元”性质，使它们对于各种成像、传感和可再生能源技术来说很有吸引力。