DOE OSTI2018
The scientific theme of this award stated in its title is “Linear and Nonlinear Optical Properties of Metal Nanoparticle Composites.” The motivation for the proposal was based on prior work that highlighted unusual third-order nonlinear optical response of metal-nanoparticle composites created by Vanderbilt researchers at the Oak Ridge National Laboratory (ORNL) by implanting metal ions into fused-silica and sapphire substrates and annealing them under appropriate conditions to produce a solid solution comprising noble-metal nanoparticles embedded in an insulating matrix. For example, the well-known localized surface plasmon resonance (LSPR) of gold and silver nanoclusters and nanoparticles was known to yield enhanced effects on the nonlinear absorption and nonlinear refractive index of these materials. The project soon expanded to embrace a wider range of materials and nanostructures, including particularly vanadium dioxide with its insulator-to-metal transition, a wide variety of substrate hosts, and zinc oxide with its multi-faceted band-edge exciton that can be coupled to plasmonic degrees of freedom in silver and aluminum. We employed second- and third-order nonlinear optical spectroscopies and confocal microscopy to quantify the coupling between nanoparticles and adsorbates across interfaces. Because ORNL closed the ion-beam surface-modification facility in 2004, we then developed a nanofabrication technique combining focused ion-beam lithography and pulsed laser deposition to create ordered arrays of metal and oxide nanoparticles in various planar geometries and heterostructures. By 2008, aided by finite-difference time-domain and finite-element calculations, we began to design and fabricate plasmonic “workbenches” on which we could excite quasiparticles (e.g., excitons, phonons, plasmons) using optical signals and electrical impulses, and map the material response down to femtosecond time and nanometer length scales. We developed additional nanofabrication capabilities (e.g., dual-layer electron-beam lithography, quantum-well fabrication and multilayer magnetron sputtering and electron-beam deposition) to create a variety of novel heterostructures as model nanocomposite systems. This led to several new opportunities to study the optical properties of these composites informed by views of potential device configurations. Among the scientific themes that emerged in published papers based on new materials and nanostructures were the following: ultrafast electron dynamics in metamaterials, including ultrafast THz microscopy of the insulator-to-metal transition in VO 2 nanoparticles; plasmon-driven electron injection to promote phase transitions in VO 2 ; and second-harmonic generation in nanostructures without inversion symmetry, in particular, the Archimedean spiral with overall sub-wavelength dimensions. We also explored dimensional and structural effects in plasmonic coupling, including exciton-plasmon coupling in ZnO nanowires; exciton-plasmon coupling in structures incorporating two-dimensional dichalcogenides; and tunable plasmon-induced transparency in plasmonic heterostructures incorporating phase-changing VO 2 . Finally, it should be noted that the work on Archimedean nanospirals and plasmon-exciton coupling led directly into a current quantum-optics research project on photon correlations in diamond nanoparticles, exemplified by the first publication from that effort [Ref. [47] in the bibliography]. A more detailed account setting in the appropriate scientific context all forty-eight papers supported by this award follows.