Tetracyanoethylene oxide- functionalized graphene and graphite characterized by Raman and Auger spectroscopy.

The tetracyanoethylene oxide (TCNEO) functionalization of chemical vapor deposition grown large area graphene and graphite was performed using reaction of TCNEO with carbon surface in chlorobenzene. The successful functionalization has been confirmed by Raman and Auger spectroscopy, and by numerical modeling of the structure and vibrational modes of TCNEO-functionalized graphene. Raman spectra of TCNEO-functionalized graphene and graphite show several groups of lines corresponding to vibrations of attached carbonyl ylide. One of key signatures of TCNEO attachment is the high intensity Raman band at ~1450 cm-1, which represents the C-C=C in plane vibrations in functionalization-distorted graphene. Raman spectra indicate the existence of central (pristine) attachment of TCNEO to graphene surface.

Chemical Vapor Deposition of Phosphorous- and Boron-Doped Graphene Using Phenyl-Containing Molecules.

Simultaneous chemical vapor deposition (CVD) of graphene and "in-situ" phosphorous or boron doping of graphene was accomplished using Triphenylphosphine (TPP) and 4-Methoxyphenylboronic acid (4-MPBA). The TPP and 4-MPBA molecules were sublimated and supplied along with CH4 molecules during graphene growth at atmospheric pressure. The grown graphene samples were characterized using Raman spectroscopy. Phosphorous and boron presence in phosphorous and boron doped graphene was confirmed with Auger electron spectroscopy. The possibility of obtaining phosphorous and boron doped graphene using solid-source molecule precursors via CVD can lead to an easy and rapid production of modified large area graphene.

Interferometric measurement of far infrared plasmons via resonant homodyne mixing.

We present an electrically tunable terahertz two dimensional plasmonic interferometer with an integrated detection element that down converts the terahertz fields to a DC signal. The integrated detector utilizes a resonant plasmonic homodyne mixing mechanism that measures the component of the plasma waves in-phase with an excitation field functioning as the local oscillator. Plasmonic interferometers with two independently tuned paths are studied. These devices demonstrate a means for developing a spectrometer-on-a-chip where the tuning of electrical length plays a role analogous to that of physical path length in macroscopic spectroscopic tools such as Fourier transform interferometers.

Highly directional thermal emission from two-dimensional silicon structures.

We simulate, fabricate, and characterize near perfectly absorbing two-dimensional grating structures in the thermal infrared using heavily doped silicon (HdSi) that supports long wave infrared surface plasmon polaritons (LWIR SPP's). The devices were designed and optimized using both finite difference time domain (FDTD) and rigorous coupled wave analysis (RCWA) simulation techniques to satisfy stringent requirements for thermal management applications requiring high thermal radiation absorption over a narrow angular range and low visible radiation absorption over a broad angular range. After optimization and fabrication, characterization was performed using reflection spectroscopy and normal incidence emissivity measurements. Excellent agreement between simulation and experiment was obtained.

Benzyne-functionalized graphene and graphite characterized by Raman spectroscopy and energy dispersive X-ray analysis.

The benzyne functionalization of chemical vapor deposition grown large area graphene and graphite was performed using a mixture of o-trimethylsilylphenyl triflate and cesium fluoride that react with the carbon surface. The reaction requires at least 2 days of treatment before the appearance of Raman and energy-dispersive X-ray spectral signatures that verify modification. Raman spectra of modified graphene and graphite show a rich structure of lines corresponding to C=C-C, C-H, and low frequency modes of surface-attached benzyne rings.

Active tuning of mid-infrared metamaterials by electrical control of carrier densities.

We demonstrate electrically-controlled active tuning of mid-infrared metamaterial resonances using depletion-type devices. The depletion width in an n-doped GaAs epilayer changes with an electric bias, inducing a change of the permittivity of the substrate and leading to frequency tuning of the resonance. We first present our detailed theoretical analysis and then explain experimental data of bias-dependent metamaterial transmission spectra. This electrical tuning is generally applicable to a variety of infrared metamaterials and plasmonic structures, which can find novel applications in chip-scale active infrared devices.

Observation of Rabi splitting from surface plasmon coupled conduction state transitions in electrically excited InAs quantum dots.

We demonstrate strong coupling between a surface plasmon and intersublevel transitions in self-assembled InAs quantum dots. The surface plasmon mode exists at the interface between the semiconductor emitter structure and a periodic array of holes perforating a metallic Pd/Ge/Au film that also serves as the top electrical contact for the emitters. Spectrally narrowed quantum-dot electroluminescence was observed for devices with varying subwavelength hole spacing. Devices designed for 9, 10, and 11 µm wavelength emission also exhibit a significant spectral splitting. The association of the splitting with quantum-dot Rabi oscillation is consistent with results from a calculation of spontaneous emission from an interacting plasmonic field and quantum-dot ensemble. The fact that this Rabi oscillation can be observed in an incoherently excited, highly inhomogeneously broadened system demonstrates the utility of intersublevel transitions in quantum dots for investigations of coherent transient and quantum coherence phenomena.

Reduction in the thermal conductivity of single crystalline silicon by phononic crystal patterning.

Phononic crystals (PnCs) are the acoustic wave equivalent of photonic crystals, where a periodic array of scattering inclusions located in a homogeneous host material causes certain frequencies to be completely reflected by the structure. In conjunction with creating a phononic band gap, anomalous dispersion accompanied by a large reduction in phonon group velocities can lead to a massive reduction in silicon thermal conductivity. We measured the cross plane thermal conductivity of a series of single crystalline silicon PnCs using time domain thermoreflectance. The measured values are over an order of magnitude lower than those obtained for bulk Si (from 148 W m(-1) K(-1) to as low as 6.8 W m(-1) K(-1)). The measured thermal conductivity is much smaller than that predicted by only accounting for boundary scattering at the interfaces of the PnC lattice, indicating that coherent phononic effects are causing an additional reduction to the cross plane thermal conductivity.

Microwave and terahertz wave sensing with metamaterials.

We have designed, fabricated, and characterized metamaterial enhanced bimaterial cantilever pixels for far-infrared detection. Local heating due to absorption from split ring resonators (SRRs) incorporated directly onto the cantilever pixels leads to mechanical deflection which is readily detected with visible light. Highly responsive pixels have been fabricated for detection at 95 GHz and 693 GHz, demonstrating the frequency agility of our technique. We have obtained single pixel responsivities as high as 16,500 V/W and noise equivalent powers of 10(-8) W/Hz(1/2) with these first-generation devices.

Infrared rectification in a nanoantenna-coupled metal-oxide-semiconductor tunnel diode.

Direct rectification of electromagnetic radiation is a well-established method for wireless power conversion in the microwave region of the spectrum, for which conversion efficiencies in excess of 84% have been demonstrated. Scaling to the infrared or optical part of the spectrum requires ultrafast rectification that can only be obtained by direct tunnelling. Many research groups have looked to plasmonics to overcome antenna-scaling limits and to increase the confinement. Recently, surface plasmons on heavily doped Si surfaces were investigated as a way of extending surface-mode confinement to the thermal infrared region. Here we combine a nanostructured metallic surface with a heavily doped Si infrared-reflective ground plane designed to confine infrared radiation in an active electronic direct-conversion device. The interplay of strong infrared photon-phonon coupling and electromagnetic confinement in nanoscale devices is demonstrated to have a large impact on ultrafast electronic tunnelling in metal-oxide-semiconductor (MOS) structures. Infrared dispersion of SiO2 near a longitudinal optical (LO) phonon mode gives large transverse-field confinement in a nanometre-scale oxide-tunnel gap as the wavelength-dependent permittivity changes from 1 to 0, which leads to enhanced electromagnetic fields at material interfaces and a rectified displacement current that provides a direct conversion of infrared radiation into electric current. The spectral and electrical signatures of the nanoantenna-coupled tunnel diodes are examined under broadband blackbody and quantum-cascade laser (QCL) illumination. In the region near the LO phonon resonance, we obtained a measured photoresponsivity of 2.7 mA W(-1) cm(-2) at -0.1 V.

Phased-array sources based on nonlinear metamaterial nanocavities.

Coherent superposition of light from subwavelength sources is an attractive prospect for the manipulation of the direction, shape and polarization of optical beams. This phenomenon constitutes the basis of phased arrays, commonly used at microwave and radio frequencies. Here we propose a new concept for phased-array sources at infrared frequencies based on metamaterial nanocavities coupled to a highly nonlinear semiconductor heterostructure. Optical pumping of the nanocavity induces a localized, phase-locked, nonlinear resonant polarization that acts as a source feed for a higher-order resonance of the nanocavity. Varying the nanocavity design enables the production of beams with arbitrary shape and polarization. As an example, we demonstrate two second harmonic phased-array sources that perform two optical functions at the second harmonic wavelength (∼5 µm): a beam splitter and a polarizing beam splitter. Proper design of the nanocavity and nonlinear heterostructure will enable such phased arrays to span most of the infrared spectrum.

Few-layer graphene characterization by near-field scanning microwave microscopy.

Near-field scanning microwave microscopy is employed for quantitative imaging at 4 GHz of the local impedance for monolayer and few-layer graphene. The microwave response of graphene is found to be thickness dependent and determined by the local sheet resistance of the graphene flake. Calibration of the measurement system and knowledge of the probe geometry allows evaluation of the AC impedance for monolayer and few-layer graphene, which is found to be predominantly active. The use of localized evanescent electromagnetic field in our experiment provides a promising tool for investigations of plasma waves in graphene with wave numbers determined by the spatial spectrum of the near-field. By using near-field microwave microscopy one can perform simultaneous imaging of location, geometry, thickness, and distribution of electrical properties of graphene without a need for device fabrication.