The high optical losses of metal-based plasmonic materials have driven an extensive search for alternative lower-loss materials that can support plasmonic-like effects, such as sub-diffraction confinement of optical fields. One such alternative employs phonon-mediated collective-charge oscillations (surface phonon polaritons, SPhPs) that can be optically excited in nanostructured polar dielectric materials. Similar to plasmonics, tailoring the geometry of polar-dielectric resonators results in resonances that can be spectrally tuned throughout the spectral range between the LO and TO phonons. However, generally, the spectral position and amplitude of these resonances remain fixed after sample fabrication. In this presentation, we discuss recent advancements made by our group in achieving actively tunable localized SPhP resonances in the long-wave- and far-infrared spectral regimes. In particular, we focus on three experiments that demonstrate active modulation of resonances. The first and second experiments focus on tuning the spectral position of localized SPhP resonances in cylindrical nanopillars that are etched into indium phosphide and silicon carbide substrates. In both of these cases we are able to induce resonance shifts as large as 15 cm-1 by optically injecting free-carriers into the pillars. The optical injection introduces a reversible, free-carrier perturbation to the dielectric permittivity that results in a spectral shift of the resonances. While the effects investigated for both the InP and SiC systems are similar, each material allows us to explore a different aspect of the phenomena. For InP we investigate the effects in the far-infrared (303-344 cm-1) with steady-state carrier photoinjection, while for SiC we investigate the dynamics of frequency modulated resonances in the long-wave infrared (797-972 cm-1) via transient reflection spectroscopy. Lastly, in the third experiment we demonstrate the ability to modulate the amplitude of resonances by coating SiC nanopillars with vanadium dioxide, a well-known phase change material that undergoes a metal-to-insulator transition near a temperature of 70 C. As such, we show that by exploiting this phase change we are able to modulate the reflectance and thermal emission of nanopillar arrays. The results described in this work may open the door to tunable, narrow-band thermal sources that operate in the long-wave to far-infrared spectral regimes.
Localized surface phonon-polariton (SPhP) resonances in polar semiconductor nanostructures can provide highly sub-diffractional electromagnetic fields. Furthermore, SPhP resonances offer enhanced resonant quality factors when compared to plasmon-polariton based systems. The various material platforms and nanostructure geometries achievable in polar semiconductors suggest they would be ideal platforms for tunable, long-wavelength photonics applications. Moreover, the constituent atomic basis defines the operating frequency regime for SPhP resonances; tunable from the mid-infrared to THz. Here, we investigate Raman active aspects of SPhP modes in GaN nanowire arrays that are grown via selective area molecular beam epitaxy. We detect strong Raman peaks within the Reststrahlen band of GaN that are not found in the bulk GaN Raman spectrum. These SPhP modes occur around 700 cm^-1 (~ 14.3 microns), offering a spectral region for device applications which is currently not accessible by plasmonic based systems or other SPhP enabled materials. Utilizing selective area epitaxy, we created GaN nanowire arrays with various diameters and pitches, from which the Raman spectra showed tuning of the apparent SPhP resonances. Infrared reflectance measurements were also performed with an FTIR microscope to further establish the physical properties of the resonances. Finally, computational studies of the structures’ reflectance were used to solidify our understanding of the geometry/SPhP-resonance-tuning relationship.
GaN nanowire LEDs with radial p-i-n junctions were grown by molecular beam epitaxy using N-polar selective area growth on Si(111) substrates. The N-polar selective area growth process facilitated the growth of isolated and highaspect-ratio n-type NW cores that were not subject to self-shadowing effects during the subsequent growth of a conformal low-temperature Mg:GaN shell. LED devices were fabricated from single-NW and multiple-NW arrays in their as-grown configuration by contacting the n-type core through an underlying conductive GaN layer and the p-type NW shell via a metallization layer. The NW LEDs exhibited rectifying I-V characteristics with a sharp turn-on voltage near the GaN bandgap and low reverse bias leakage current. Under forward bias, the NW LEDs produced electroluminescence with a peak emission wavelength near 380 nm and exhibited a small spectral blueshift with increasing current injection, both of which are consistent with electron recombination in the p-type shell layer through donor-acceptor-pair recombination. These core-shell NW devices demonstrate N-polar selective area growth as an effective technique for producing on-chip nanoscale light sources.
Coherent coupling between an optical transition and confined optical mode have been investigated for electronic-state transitions, however, only very recently have vibrational transitions been considered. Here, we demonstrate both static and dynamic results for vibrational bands strongly coupled to optical cavities. We experimentally and numerically describe strong coupling between a Fabry-Pérot cavity and carbonyl stretch (~1730 cm 1) in poly-methylmethacrylate and provide evidence that the mixed-states are immune to inhomogeneous broadening. We investigate strong and weak coupling regimes through examination of cavities loaded with varying concentrations of a urethane monomer. Rabi splittings are in excellent agreement with an analytical description using no fitting parameters.
Ultrafast pump-probe measurements reveal transient absorption signals over a frequency range well-separated from the vibrational band, as well as drastically modified relaxation rates. We speculate these modified kinetics are a consequence of the energy proximity between the vibration-cavity polariton modes and excited state transitions and that polaritons offer an alternative relaxation path for vibrational excitations. Varying the polariton energies by angle-tuning yields transient results consistent with this hypothesis. Furthermore, Rabi oscillations, or quantum beats, are observed at early times and we see evidence that these coherent vibration-cavity polariton excitations impact excited state population through cavity losses.
Together, these results indicate that cavity coupling may be used to influence both excitation and relaxation rates of vibrations. Opening the field of polaritonic coupling to vibrational species promises to be a rich arena amenable to a wide variety of infrared-active bonds that can be studied in steady state and dynamically.
One potential way to increase photovoltaic efficiency is to take advantage of hot-carriers. Nanocrystal based solar cells aim to take advantage of hot-carrier capture to boost device performance. The crucial parameter for gauging a given nanocrystal material for this application is the electron-phonon coupling. The electron-phonon coupling will dictate the thermalization time of hot-carriers. In this study we demonstrate a method of quantifying the electron-phonon coupling in semiconductor nanocrystals. By employing ultrafast transient absorption spectroscopy with temporal pulse shaping, we manipulate coherent phonons in CdTe_{1-x}Se_{x} nanocrystals to quantify the efficiency of the electron-phonon coupling. The Raman active longitudinal optical phonon (LO) modes were excited and probed as a function of time. Using a temporal pulse shaper, we were able to control pump pulse pairs to coherently excite and cancel coherent phonons in the CdTe_{1-x}Se_{x} nanocrystals, and estimate the relative amount of optical energy that is coupled to the coherent CdSe LO mode which is the dominant thermalization pathway for the hot-electrons in this system.
Coherent coupling between an optical-transition and confined optical mode, when sufficiently strong, gives rise to new modes separated by the vacuum Rabi splitting. Such systems have been investigated for electronic-state transitions, however, only very recently have vibrational transitions been considered. Here, we bring strong polaritonic-coupling in cavities from the visible into the infrared where a new range of static and dynamic vibrational processes await investigation.
First, we experimentally and numerically describe coupling between a Fabry-Perot cavity and carbonyl stretch (~1730 cm 1) in poly-methylmethacrylate. As is requisite for “strong coupling”, the measured vacuum Rabi splitting of 132 cm 1 is much larger than the full width of the cavity (34 cm-1) and the inhomogeneously broadened carbonyl-stretch (24 cm-1). Agreement with classical theories providea evidence that the mixed-states are relatively immune to inhomogeneous broadening. Next, we investigate strong and weak coupling regimes through examination of cavities loaded with varying concentrations of urethane. Rabi splittings increases from 0 to ~104 cm-1 with concentrations from 0-20 vol% and are in excellent agreement to an analytical description using no fitting parameters. Ultra-fast pump-probe measurements reveal transient absorption signals over a frequency range well-separated from the vibrational band as well as modifications of energy relaxation times. Finally, we demonstrate coupling to liquids using the C-O stretching band (~1985 cm-1) of Mo(CO)6 in an aqueous solution.
Opening the field of polaritonic coupling to vibrational species promises to be a rich arena amenable to a wide variety of infrared-active bonds that can be studied statically and dynamically.
Sub-diffractional confinement of light has led to advancements in imaging, metamaterials, nano-manufacturing, plasmonics, and other fields. One potential route to sub-diffractional confinement is via stimulated surface phonon polaritons (SPhPs). SPhPs couple infrared photons with optical phonons and consequently their lifetimes can be longer than surface plasmon polaritons (SPPs), whose lifetimes are dominated by electron scattering events. Thus, materials capable of generating SPhPs are of general interest to study. SPhPs are activated by photons with energies near the Reststrahlen band of semiconductors such as SiC. In this work we examine aspects of carrier dynamics by photo-injecting electrons into the SiC conduction band using a pulsed 355 nm laser and probe the resulting dynamics near the Reststrahlen band using a tunable CO2 laser. The fluence of the pump laser was varied to provide photo-injection levels ranging from ~1x10^17 to 1x10^19 free carriers. Probing the excited-state dynamics near the blue-edge of the Reststrahlen band resulted in complex transient behavior, showing both positive and negative changes in transient reflectance depending on the level of photo-injected carriers and probe energy. Numerical calculations of the SiC reflectance spectra with different doping levels were done to simulate the initial photo-injection level provided by the transient experiment. The computed spectra and the experimentally measured excited spectra for different photo-injection levels were compared and resulted in qualitative agreement.
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