Tong-Ho Kim

Shape matters: plasmonic nanoparticle shape enhances interaction with dielectric substrate.

Numerical analyses of the ultraviolet and visible plasmonic spectra measured from hemispherical gallium nanostructures on dielectric substrates reveal that resonance frequencies are quite sensitive to illumination angle and polarization in a way that depends on nanostructure size, shape, and substrate. Large, polarization-dependent splittings arise from the broken symmetry of hemispherical gallium nanoparticles on sapphire substrates, inducing strong interactions with the substrate that depend sensitively on the angle of illumination and the nanoparticle diameter.

Ultraviolet Nanoplasmonics: A Demonstration of Surface-Enhanced Raman Spectroscopy, Fluorescence, and Photodegradation Using Gallium Nanoparticles

Self-assembled arrays of hemispherical gallium nanoparticles deposited by molecular beam epitaxy on a sapphire support are explored as a new type of substrate for ultraviolet plasmonics. Spin-casting a 5 nm film of crystal violet upon these nanoparticles permitted the demonstration of surface-enhanced Raman spectra, fluorescence, and degradation following excitation by a HeCd laser operating at 325 nm. Measured local Raman enhancement factors exceeding 10(7) demonstrate the potential of gallium nanoparticle arrays for plasmonically enhanced ultraviolet detection and remediation.

Real-time plasmon resonance tuning of liquid Ga nanoparticles by in situ spectroscopic ellipsometry

Liquid Ga nanoparticles have been deposited on sapphire substrates at room temperature. The optical evolution of Ga nanoparticle surface plasmon resonance during deposition has been characterized by in situ real-time spectroscopic ellipsometry to control and tune the plasmon resonance photon energy. The existence of both longitudinal and transverse modes for spheroidal Ga nanoparticles supported on a sapphire substrate is demonstrated and the dependence of the longitudinal and transverse plasmon energies on particle size is discussed. Stability of the Ga surface plasmon resonance to air exposure and high temperature is also demonstrated.

Demonstration of surface-enhanced Raman scattering by tunable, plasmonic gallium nanoparticles

Size-controlled gallium nanoparticles deposited on sapphire were explored as alternative substrates to enhance Raman spectral signatures. Galliums resilience following oxidation is inherently advantageous in comparison with silver for practical ex vacuo nonsolution applications. Ga nanoparticles were grown using a simple molecular beam epitaxy-based fabrication protocol, and monitoring their corresponding surface plasmon resonance energy through in situ spectroscopic ellipsometry allowed the nanoparticles to be easily controlled for size. The Raman spectra obtained from cresyl fast violet (CFV) deposited on substrates with differing mean nanoparticle sizes represent the first demonstration of enhanced Raman signals from reproducibly tunable self-assembled Ga nanoparticles. Nonoptimized aggregate enhancement factors of approximately 80 were observed from the substrate with the smallest Ga nanoparticles for CFV dye solutions down to a dilution of 10 ppm.

Surface oxide relationships to band bending in GaN

A trend of increased near-surface valence band maximum band bending with increasing O∕Ga relative fraction was observed, extrapolating to 2.7eV±0.1eV for pristine GaN surfaces (0% O 1s peak area). This trend of apparent oxide overlayer coverage affecting the band bending linearly could lead to better understanding and characterization of oxidized GaN surfaces to control band bending for sensors or other devices.

Plasmonic gallium nanoparticles on polar semiconductors: interplay between nanoparticle wetting, localized surface plasmon dynamics, and interface charge.

Ga nanoparticles supported on large band gap semiconductors like SiC, GaN, and ZnO are interesting for plasmon-enhanced UV-emitting solid-state devices. We investigate the influence of the polarity of the SiC, GaN, and ZnO wurtzite semiconductors on the wetting of Ga nanoparticles and on the resulting surface plasmon resonance (SPR) by exploiting real time plasmonic ellipsometry. The interface potential between polar semiconductors (SiC, GaN, and ZnO) and plasmonic nanoparticles (gallium) is shown to influence nanoparticle formation dynamics, geometry, and consequently the SPR wavelength. We invoke the Lippman electrowetting framework to elucidate the mechanisms controlling nanoparticle dynamics and experimentally demonstrate that the charge transfer at the Ga nanoparticle/polar semiconductor interface is an intrinsic method for tailoring the nanoparticle plasmon resonance. Therefore, the present data demonstrate that for supported nanoparticles, surface and interface piezoelectric charge of polar semiconductors also affects SPR along with the well-known effect of the media refractive index.

Evidence of Plasmonic Coupling in Gallium Nanoparticles/Graphene/SiC

Graphene is emerging as a promising material for plasmonics applications due to its strong light-matter interactions, most of which are theoretically predicted but not yet experimentally realized. Therefore, the integration of plasmonic nanoparticles to create metal nanoparticle/graphene composites enables numerous phenomena important for a range of applications from photonics to catalysis. For these applications it is important to articulate the coupling of photon-based excitations such as the interaction between plasmons in each of the material components, as well as their charge-based interactions dependent upon the energy alignment at the metal/graphene interface. These coupled phenomena underpin an active application area in graphene-based composites due to nanoparticle-dependent surface-enhanced Raman scattering (SERS) of graphene phonon modes. This study reveals the coupling of a graphene/SiC support with Ga-nanoparticle-localized surface plasmon resonance, which is of particular interest due to its ability to be tuned across the UV into the near-IR region. This work is the first demonstration of the evolving plasmon resonance on graphene during the synthesis of surface-supported metal nanoparticles, thus providing evidence for the theoretically predicted screening revealed by a damped resonance with little energy shift. Therefore, the role of the graphene/substrate heterojunction in tailoring the plasmon resonance for nanoplasmonic applications is shown. Additionally, the coupled phenomena between the graphene-Ga plasmon properties, charge transfer, and SERS of graphene vibrational modes are explored.

Demonstrating the capability of the high-performance plasmonic gallium-graphene couple

Metal nanoparticle (NP)-graphene multifunctional platforms are of great interest for exploring strong light-graphene interactions enhanced by plasmons and for improving performance of numerous applications, such as sensing and catalysis. These platforms can also be used to carry out fundamental studies on charge transfer, and the findings can lead to new strategies for doping graphene. There have been a large number of studies on noble metal Au-graphene and Ag-graphene platforms that have shown their potential for a number of applications. These studies have also highlighted some drawbacks that must be overcome to realize high performance. Here we demonstrate the promise of plasmonic gallium (Ga) nanoparticle (NP)-graphene hybrids as a means of modulating the graphene Fermi level, creating tunable localized surface plasmon resonances and, consequently, creating high-performance surface-enhanced Raman scattering (SERS) platforms. Four prominent peculiarities of Ga, differentiating it from the commonly used noble (gold and silver) metals are (1) the ability to create tunable (from the UV to the visible) plasmonic platforms, (2) its chemical stability leading to long-lifetime plasmonic platforms, (3) its ability to n-type dope graphene, and (4) its weak chemical interaction with graphene, which preserves the integrity of the graphene lattice. As a result of these factors, a Ga NP-enhanced graphene Raman intensity effect has been observed. To further elucidate the roles of the electromagnetic enhancement (or plasmonic) mechanism in relation to electron transfer, we compare graphene-on-Ga NP and Ga NP-on-graphene SERS platforms using the cationic dye rhodamine B, a drug model biomolecule, as the analyte.

In situ spectroscopic ellipsometry to monitor surface plasmon resonant group-III metals deposited by molecular beam epitaxy

The evolution of the surface plasmon resonance of Al, Ga, and In deposited by molecular beam epitaxy on GaN surfaces was monitored in real-time using spectroscopic ellipsometry. The correlation between the metal plasmon resonance modes, the particle size, and the growth mode is addressed. Ga and In deposited on GaN substrates form nanoparticles while the Al is shown to form a nearly coalesced thin film. The plasmon resonance of the Ga and In nanoparticles redshift with increasing average particle size while the pseudodielectric function of Al approaches that of a Drude metal.

GaMg alloy nanoparticles for broadly tunable plasmonics.

Manipulating the properties of well understood materials systems for novel technological applications can be achieved by creating nanoscale structures and mixed compounds. The design of novel nanomaterials that underpin plasmonic applications drives the rapid progress in advancing plasmonic materials over the last few years. [ 1 , 2 ] Control of metal nanoparticle shape, [ 3 , 4 ] density, and spacing [ 5 ] is continually improving with novel synthetic techniques. Nevertheless, to continue advancing plasmonics, new metallic nanostructure systems must be developed that offer unique properties and are superior to Ag, [ 6 ] Au, [ 3 , 7 ] and mixtures thereof—the most widely exploited metals [ 8–10 ] and bimetallic systems. [ 11 ]