at deep sub-wavelengths, [2] leading to a variety of applications including nanolasers, [3] sensors, [4] bioimaging, [5] surfaceenhanced Raman spectroscopy, [6,7] color displays, [8] and others. [9][10][11][12] To improve the performance of today's photonic systems, researchers have extensively investigated the fundamental relation between the wave vector and energy of an SPP wave-named dispersion relation. This quantity describes the propagation of light within a material (i.e., medium), extremely relevant for the abovementioned optical devices. Therefore, understanding the dispersion relation can allow the design of optical materials with superior response, ranging from 2D van der Waals to oxides and metals. Concerning 2D materials, it can uncover the origin of tunable polaritons in hyperbolic metamaterials based on graphene and hexagonal boron nitride (h-BN), which is due to the hybridization of SPP and surface phonon polaritons. [13] As another example, by utilizing the band-edge mode of the dispersion relation in metallic nanocavities, [3] lasing with a 200 times enhancement of the spontaneous emission rate of the dye has been reached. [14] As a class of emerging photonic materials, noble metal alloys with permittivity and localized surface plasmon resonances not achievable by pure metals [9,15,16] have been proposed as alternative candidates for plasmonics [12,[17][18][19][20] because of their tunable dielectric functions, which make it possible to engineer the alloy composition to attain optical properties that will meet desired resonances. In turn, this tunability could be used to Surface plasmon polaritons (SPPs) enable the deep subwavelength confinement of an electromagnetic field, which can be used in optical devices ranging from sensors to nanoscale lasers. However, the limited number of metals that satisfy the required boundary conditions for SPP propagation in a metal/dielectric interface severely limits its occurrence in the visible range of the electromagnetic spectrum. We introduce the strategy of engineering the band structure of metallic materials by alloying. We experimentally and theoretically establish the control of the dispersion relation in Ag-Au alloys by varying the film chemical composition. Through X-ray photoelectron spectroscopy (XPS) measurements and partial density-of-states calculations we deconvolute the d band contribution of the density-of-states from the valence band spectrum, showing that the shift in energy of the d band follows the surface plasmon resonance change of the alloy. Our density functional theory calculations of the alloys band structure predict the same variation of the threshold of the interband transition, which is in very good agreement with our optical and XPS experiments. By elucidating the correlation between the optical behavior and band structure of alloys, we anticipate the fine control of the optical properties of metallic materials beyond pure metals.
Band Structure EngineeringThe ORCID identification number(s) for the author(s) of this article can b...