Below the surface: Unraveling the intricacies of the nonlinear optical properties of aluminum through bound electrons

By uncovering novel aspects of second harmonic generation in aluminum, we show that there are unusual and remarkable consequences of resonant absorption, namely an unexpectedly critical role that bound electrons play for light-matter interactions across the optical spectrum, suggesting that a different basic approach is required to fully explain the physics of surfaces. We tackle an issue that is never under consideration given the generic hostile conditions to the propagation of light under resonant absorption. Unlike most noble metals, aluminum displays Lorentz-like behavior and interband transitions centered near 810 nm, thus splitting the plasmonic range in an atypical manner and setting its linear and nonlinear optical properties apart. Studies of aluminum nanostructures having complex topologies abound, as do reported inconsistencies in the linear spectral response of surface plasmons and harmonic generation. Our experimental observations of second harmonic generation from aluminum nanolayers show that bound electrons are responsible for a unique signature neither predicted nor observed previously: a hole in the second harmonic spectrum. A hydrodynamic-Maxwell theory explains these findings exceptionally well and becomes the basis for renewed studies of surface physics.