Optical anticounterfeiting tags utilize the photoluminescent properties of materials to encode unique patterns, enabling identification and validation of important items and assets. These tags must combine optical complexity with ease of production and authentication to both prevent counterfeiting and to remain practical for widespread use. Metal-organic frameworks (MOFs) based on polynuclear, rare earth clusters are ideal materials platforms for this purpose, combining fine control over structure and composition, with tunable, complex energy transfer mechanisms via both linker and metal components. Here we report the design and synthesis of a set of heterometallic MOFs based on combinations of Eu, Nd, and Yb with the tetratopic linker 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene. The energetics of this linker facilitate the intentional concealment of the visible emissions from Eu while retaining the infrared emissions of Nd and Yb, creating an optical tag with multiple covert elements. Unique to the materials system reported herein, we document the occurrence of a previously not observed 11-metal cluster correlated with the presence of Yb in the MOFs, coexisting with a commonly encountered 9-metal cluster. We demonstrate the utility of these materials as intricate optical tags with both rapid and in-depth screening techniques, utilizing orthogonal identifiers across composition, emission spectra, and emission decay dynamics. This work highlights the important effect of linker selection in controlling the resulting photoluminescent properties in MOFs and opens an avenue for the targeted design of highly complex, multifunctional optical tags.
Understanding the fundamental mechanisms underpinning shock initiation is critical to predicting energetic material (EM) safety and performance. Currently, the timescales and pathways by which shock-excited lattice modes transfer energy into specific chemical bonds remains an open question. Towards understanding these mechanisms, our group has previously measured the vibrational energy transfer (VET) pathways in several energetic thin films using broadband, femtosecond transient absorption spectroscopy. However, new technologies are needed to move beyond these thin film surrogates and measure broadband VET pathways in realistic EM morphologies. Herein, we describe a new broadband, femtosecond, attenuated total reflectance spectroscopy apparatus. Performance of the system is benchmarked against published data and the first VET results from a pressed EM pellet are presented. This technology enables fundamental studies of VET dynamics across sample configurations and environments (pressure, temperature, etc .) and supports the potential use of VET studies in the non-destructive surveillance of EM components.
Despite their wide use in terahertz (THz) research and technology, the application spectra of photoconductive antenna (PCA) THz detectors are severely limited due to the relatively high optical gating power requirement. This originates from poor conversion efficiency of optical gate beam photons to photocurrent in materials with subpicosecond carrier lifetimes. Here we show that using an ultra-thin (160 nm), perfectly absorbing low-temperature grown GaAs metasurface as the photoconductive channel drastically improves the efficiency of THz PCA detectors. This is achieved through perfect absorption of the gate beam in a significantly reduced photoconductive volume, enabled by the metasurface. This Letter demonstrates that sensitive THz PCA detection is possible using optical gate powers as low as 5 μW-three orders of magnitude lower than gating powers used for conventionalPCAdetectors.We show that significantly higher optical gate powers are not necessary for optimal operation, as they do not improve the sensitivity to the THz field. This class of efficient PCA THz detectors opens doors for THz applications with low gate power requirements.
Optical tags provide a way to quickly and unambiguously identify valuable assets. Current tag fluorophore options lack the tunability to allow combined methods of encoding in a single material. Herein we report a design strategy to encode multilayer complexity in a family of heterometallic rare-earth metal–organic frameworks based on highly connected nonanuclear clusters. To impart both intricacy and security, a synergistic approach was implemented resulting in both overt (visible) and covert (near-infrared, NIR) properties, with concomitant multi-emissive spectra and tunable luminescence lifetimes. Tag authentication is validated with a variety of orthogonal detection methodologies. Importantly, the effect induced by subtle compositional changes on intermetallic energy transfer, and thus on the resulting photophysical properties, is demonstrated. This strategy can be widely implemented to create a large library of highly complex, difficult-to-counterfeit optical tags.
We report experimental and numerical developments extending the operating range of vanadium dioxide based optical limiters into the short-wavelength infrared. Pixelated sensor elements have been fabricated which show optically-triggered limiting of a 2.7 µm probe.
Hydrogen lithography has been used to template phosphine-based surface chemistry to fabricate atomic-scale devices, a process we abbreviate as atomic precision advanced manufacturing (APAM). Here, we use mid-infrared variable angle spectroscopic ellipsometry (IR-VASE) to characterize single-nanometer thickness phosphorus dopant layers (δ-layers) in silicon made using APAM compatible processes. A large Drude response is directly attributable to the δ-layer and can be used for nondestructive monitoring of the condition of the APAM layer when integrating additional processing steps. The carrier density and mobility extracted from our room temperature IR-VASE measurements are consistent with cryogenic magneto-transport measurements, showing that APAM δ-layers function at room temperature. Finally, the permittivity extracted from these measurements shows that the doping in the APAM δ-layers is so large that their low-frequency in-plane response is reminiscent of a silicide. However, there is no indication of a plasma resonance, likely due to reduced dimensionality and/or low scattering lifetime.
Composition dependence of second harmonic generation, refractive index, extinction coefficient, and optical bandgap in 20 nm thick crystalline Hf1-xZrxO2 (0 ≤ x ≤ 1) thin films is reported. The refractive index exhibits a general increase with increasing ZrO2 content with all values within the range of 1.98-2.14 from 880 nm to 400 nm wavelengths. A composition dependence of the indirect optical bandgap is observed, decreasing from 5.81 eV for HfO2 to 5.17 eV for Hf0.4Zr0.6O2. The bandgap increases for compositions with x > 0.6, reaching 5.31 eV for Hf0.1Zr0.9O2. Second harmonic signals are measured for 880 nm incident light. The magnitude of the second harmonic signal scales with the magnitude of the remanant polarization in the composition series. Film compositions that display near zero remanent polarizations exhibit minimal second harmonic generation while those with maximum remanent polarization also display the largest second harmonic signal. The results are discussed in the context of ferroelectric phase assemblage in the hafnium zirconium oxide films and demonstrate a path toward a silicon-compatible integrated nonlinear optical material.
Toroidal dielectric metasurface with a Q-factor of 728 in 1500 nm wavelength are reported. The resonance couples strongly to the environment, as demonstrated with a refractometric sensing experiment.
The Lorentz-like effective medium resonance (LEMR) exhibited by the longitudinal effective permittivity of semiconductor hyperbolic metamaterials (SHMs) has been known for some time. However, direct observation of this resonance proved to be difficult. Herein, we experimentally demonstrate its existence by strongly coupling SHMs to plasmonic metasurfaces. We consider four strong coupling implementations of SHMs that exhibit different LEMR absorption profiles (both in frequency and in strength) to validate our approach.
Transparent conducting oxides, such as doped indium oxide, zinc oxide, and cadmium oxide (CdO), have recently attracted attention as tailorable materials for applications in nanophotonic and plasmonic devices such as low-loss modulators and all-optical switches due to their tunable optical properties, fast optical response, and low losses. In this work, optically induced extraordinarily large reflection changes (up to 135%) are demonstrated in bulk CdO films in the mid-infrared wavelength range close to the epsilon near zero (ENZ) point. To develop a better understanding of how doping level affects the static and dynamic optical properties of CdO, the evolution of the optical properties with yttrium (Y) doping is investigated. An increase in the metallicity and a blueshift of the ENZ point with increasing Y-concentrations is observed. Broadband all-optical switching from near-infrared to mid-infrared wavelengths is demonstrated. The major photoexcited carrier relaxation mechanisms in CdO are identified and it is shown that the relaxation times can be significantly reduced by increasing the dopant concentration in the film. This work could pave the way to practical dynamic and passive optical and plasmonic devices with doped CdO spanning wavelengths from the ultraviolet to the mid-infrared region.
High-harmonic generation (HHG) is a signature optical phenomenon of strongly driven, nonlinear optical systems. Specifically, the understanding of the HHG process in rare gases has played a key role in the development of attosecond science1. Recently, HHG has also been reported in solids, providing novel opportunities such as controlling strong-field and attosecond processes in dense optical media down to the nanoscale2. Here, we report HHG from a low-loss, indium-doped cadmium oxide thin film by leveraging the epsilon-near-zero (ENZ) effect3–8, whereby the real part of the material’s permittivity in certain spectral ranges vanishes, as well as the associated large resonant enhancement of the driving laser field. We find that ENZ-assisted harmonics exhibit a pronounced spectral redshift as well as linewidth broadening, resulting from the photo induced electron heating and the consequent time-dependent ENZ wavelength of the material. Our results provide a new platform to study strong-field and ultrafast electron dynamics in ENZ materials, reveal new degrees of freedom for spectral and temporal control of HHG, and open up the possibilities of compact solid-state attosecond light sources.
Terahertz (THz) photoconductive devices are used for generation, detection, and modulation of THz waves, and they rely on the ability to switch electrical conductivity on a subpicosecond time scale using optical pulses. However, fast and efficient conductivity switching with high contrast has been a challenge, because the majority of photoexcited charge carriers in the switch do not contribute to the photocurrent due to fast recombination. Here, we improve efficiency of electrical conductivity switching using a network of electrically connected nanoscale GaAs resonators, which form a perfectly absorbing photoconductive metasurface. We achieve perfect absorption without incorporating metallic elements, by breaking the symmetry of cubic Mie resonators. As a result, the metasurface can be switched between conductive and resistive states with extremely high contrast using an unprecedentedly low level of optical excitation. We integrate this metasurface with a THz antenna to produce an efficient photoconductive THz detector. The perfectly absorbing photoconductive metasurface opens paths for developing a wide range of efficient optoelectronic devices, where required optical and electronic properties are achieved through nanostructuring the resonator network.
We numerically analyze the role of carrier mobility in transparent conducting oxides in epsilon-near-zero phase modulators. High-mobility materials such as cadmium oxide enable compact photonic phase modulators with a modulation figure of merit >29 º/dB.
De Ceglia, Domenico; Scalora, Michael; Vincenti, Maria A.; Campione, Salvatore; Kelley, Kyle; Runnerstrom, Evan L.; Maria, Jon P.; Keeler, Gordon A.; Luk, Ting S.
Optical nonlocalities are elusive and hardly observable in traditional plasmonic materials like noble and alkali metals. Here we report experimental observation of viscoelastic nonlocalities in the infrared optical response of epsilon-near-zero nanofilms made of low-loss doped cadmium-oxide. The nonlocality is detectable thanks to the low damping rate of conduction electrons and the virtual absence of interband transitions at infrared wavelengths. We describe the motion of conduction electrons using a hydrodynamic model for a viscoelastic fluid, and find excellent agreement with experimental results. The electrons' elasticity blue-shifts the infrared plasmonic resonance associated with the main epsilon-near-zero mode, and triggers the onset of higher-order resonances due to the excitation of electron-pressure modes above the bulk plasma frequency. We also provide evidence of the existence of nonlocal damping, i.e., viscosity, in the motion of optically-excited conduction electrons using a combination of spectroscopic ellipsometry data and predictions based on the viscoelastic hydrodynamic model.
We study semiconductor hyperbolic metamaterials (SHMs) at the quantum limit experimentally using spectroscopic ellipsometry as well as theoretically using a new microscopic theory. The theory is a combination of microscopic density matrix approach for the material response and Green’s function approach for the propagating electric field. Our approach predicts absorptivity of the full multilayer system and for the first time allows the prediction of in-plane and out-of-plane dielectric functions for every individual layer constructing the SHM as well as effective dielectric functions that can be used to describe a homogenized SHM.
In this paper, we analyze a compact silicon photonic phase modulator at 1.55 μm using epsilon-near-zero transparent conducting oxide (TCO) films. The operating principle of the non-resonant phase modulator is field-effect carrier density modulation in a thin TCO film deposited on top of a passive silicon waveguide with a CMOS-compatible fabrication process. We compare phase modulator performance using both indium oxide (In2O3) and cadmium oxide (CdO) TCO materials. Our findings show that practical phase modulation can be achieved only when using high-mobility (i.e. low-loss) epsilon-near-zero materials such as CdO. The CdO-based phase modulator has a figure of merit of 17.1°/dB in a compact 5 μm length. This figure of merit can be increased further through the proper selection of high-mobility TCOs, opening a path for device miniaturization and increased phase shifts.
Optical communication systems increasingly require electrooptical modulators that deliver high modulation speeds across a large optical bandwidth with a small device footprint and a CMOS-compatible fabrication process. Although silicon photonic modulators based on transparent conducting oxides (TCOs) have shown promise for delivering on these requirements, modulation speeds to date have been limited. Here, we describe the design, fabrication, and performance of a fast, compact electroabsorption modulator based on TCOs. The modulator works by using bias voltage to increase the carrier density in the conducting oxide, which changes the permittivity and hence optical attenuation by almost 10 dB. Under bias, light is tightly confined to the conducting oxide layer through nonresonant epsilon-near-zero (ENZ) effects, which enable modulation over a broad range of wavelengths in the telecommunications band. Our approach features simple integration with passive silicon waveguides, the use of stable inorganic materials, and the ability to modulate both transverse electric and magnetic polarizations with the same device design. Using a 4-μm-long modulator and a drive voltage of 2 Vpp, we demonstrate digital modulation at rates of 2.5 Gb/s. We report broadband operation with a 6.5 dB extinction ratio across the 1530–1590 nm band and a 10 dB insertion loss. This work verifies that high-speed ENZ devices can be created using conducting oxide materials and paves the way for additional technology development that could have a broad impact on future optical communications systems.
Epsilon-near-zero materials provide a new path for tailoring light-matter interactions at the nanoscale. In this paper, we analyze a compact electroabsorption modulator based on epsilon-near-zero confinement in transparent conducting oxide films. The nonresonant modulator operates through field-effect carrier density tuning. We compare the performance of modulators composed of two different conducting oxides, namely, indium oxide (In2O3) and cadmium oxide (CdO), and show that better modulation performance is achieved when using high-mobility (i.e., low loss) epsilon-near-zero materials such as CdO. In particular, we show that nonresonant electroabsorption modulators with submicron lengths and greater than 5 dB extinction ratios may be achieved through the proper selection of high-mobility transparent conducting oxides, opening a path for device miniaturization and increased modulation depth.
Herein, we describe a novel multifunctional metal–organic framework (MOF) materials platform that displays both porosity and tunable emission properties as a function of the metal identity (Eu, Nd, and tuned compositions of Nd/Yb). Their emission collectively spans the deep red to near-infrared (NIR) spectral region (~614–1350 nm), which is highly relevant for in vivo bioimaging. These new materials meet important prerequisites as relevant to biological processes: they are minimally toxic to living cells and retain structural integrity in water and phosphate-buffered saline. To assess their viability as optical bioimaging agents, we successfully synthesized the nanoscale Eu analog as a proof-of-concept system in this series. In vitro studies show that it is cell-permeable in individual RAW 264.7 mouse macrophage and HeLa human cervical cancer tissue culture cells. The efficient discrimination between the Eu emission and cell autofluorescence was achieved with hyperspectral confocal fluorescence microscopy, used here for the first time to characterize MOF materials. Importantly, this is the first report that documents the long-term conservation of the intrinsic emission in live cells of a fluorophore-based MOF to date (up to 48 h). As a result this finding, in conjunction with the materials’ very low toxicity, validates the biocompatibility in these systems and qualifies them as promising for use in long-term tracking and biodistribution studies.
Ultrafast control of the polarization state of light may enable a plethora of applications in optics, chemistry and biology. However, conventional polarizing elements, such as polarizers and waveplates, are either static or possess only gigahertz switching speeds. Here, with the aid of high-mobility indium-doped cadmium oxide (CdO) as the gateway plasmonic material, we realize a high-quality factor Berreman-type perfect absorber at a wavelength of 2.08 μm. On sub-bandgap optical pumping, the perfect absorption resonance strongly redshifts because of the transient increase of the ensemble-averaged effective electron mass of CdO, which leads to an absolute change in the p-polarized reflectance from 1.0 to 86.3%. By combining the exceedingly high modulation depth with the polarization selectivity of the perfect absorber, we experimentally demonstrate a reflective polarizer with a polarization extinction ratio of 91 that can be switched on and off within 800 fs.
We report lasing from nonpolar p-i-n InGaN/GaN multi-quantum well core-shell single-nanowire lasers by optical pumping at room temperature. The nanowire lasers were fabricated using a hybrid approach consisting of a top-down two-step etch process followed by a bottom-up regrowth process, enabling precise geometrical control and high material gain and optical confinement. The modal gain spectra and the gain curves of the core-shell nanowire lasers were measured using micro-photoluminescence and analyzed using the Hakki-Paoli method. Significantly lower lasing thresholds due to high optical gain were measured compared to previously reported semipolar InGaN/GaN core-shell nanowires, despite significantly shorter cavity lengths and reduced active region volume. Mode simulations show that due to the core-shell architecture, annular-shaped modes have higher optical confinement than solid transverse modes. The results show the viability of this p-i-n nonpolar core-shell nanowire architecture, previously investigated for next-generation light-emitting diodes, as low-threshold, coherent UV-visible nanoscale light emitters, and open a route toward monolithic, integrable, electrically injected single-nanowire lasers operating at room temperature.
The efficiency of photoconductive (PC) devices, including terahertz detectors, is constrained by the bulk optical constants of PC materials. Here, we show that optical absorption in a PC layer can be modified substantially within a hybrid cavity containing nanoantennas and a Distributed Bragg Reflector. We find that a hybrid cavity, consisting of a GaAs PC layer of just 50 nm, can be used to absorb >75% of incident photons by trapping the light within the cavity. We provide an intuitive model, which describes the dependence of the optimum operation wavelength on the cavity thickness. We also find that the nanoantenna size is a critical parameter, small variations of which lead to both wavelength shifting and reduced absorption in the cavity, suggesting that impedance matching is key for achieving efficient absorption in the optically thin hybrid cavities.
We study the role of carrier mobility in transparent conducting oxides integrated into epsilon-near-zero modulators. High-mobility materials including CdO enable sub-micron length electroabsorption modulators through >4dB/μm extinction ratios.
We present a new approach to dielectric metasurface design that relies on a single resonator per unit cell and produces robust, high quality factor Fano resonances. Our approach utilizes symmetry breaking of highly symmetric resonator geometries, such as cubes, to induce couplings between the otherwise orthogonal resonator modes. In particular, we design perturbations that couple "bright" dipole modes to "dark" dipole modes whose radiative decay is suppressed by local field effects in the array. Our approach is widely scalable from the near-infrared to radio frequencies. We first unravel the Fano resonance behavior through numerical simulations of a germanium resonator-based metasurface that achieves a quality factor of ∼1300 at ∼10.8 μm. Then, we present two experimental demonstrations operating in the near-infrared (∼1 μm): a silicon-based implementation that achieves a quality factor of ∼350; and a gallium arsenide-based structure that achieves a quality factor of ∼600, the highest near-infrared quality factor experimentally demonstrated to date with this kind of metasurface. Importantly, large electromagnetic field enhancements appear within the resonators at the Fano resonant frequencies. We envision that combining high quality factor, high field enhancement resonances with nonlinear and active/gain materials such as gallium arsenide will lead to new classes of active optical devices.
The development of novel thermal sources that control the emission spectrum and the angular emission pattern is of fundamental importance. In this paper, we investigate the thermal emission properties of semiconductor hyperbolic metamaterials (SHMs). Our structure does not require the use of any periodic corrugation to provide monochromatic and directional emission properties. We show that these properties arise because of epsilon-near-zero conditions in SHMs. The thermal emission is dominated by the epsilon-near-zero effect in the doped quantum wells composing the SHM. Furthermore, different properties are observed for s and p polarizations, following the characteristics of the strong anisotropy of hyperbolic metamaterials.
Metamaterial dielectric resonators represent a promising path toward low-loss metamaterials at optical frequencies. In this paper we utilize perturbations of high symmetry resonator geometries, such as cubes, either to overlap the electric and magnetic dipole resonances, thereby enabling directional scattering and Huygens' metasurfaces, or to induce couplings between the otherwise orthogonal resonator modes to achieve high-quality factor Fano resonances. Our results are fully scalable across any frequency bands where high-permittivity dielectric materials are available, including microwave, THz, and infrared frequencies.
We investigate optical polariton modes supported by subwavelength-thick degenerately doped semiconductor nanolayers (e.g. indium tin oxide) on glass in the epsilon-near-zero (ENZ) regime. The dispersions of the radiative (R, on the left of the light line) and non-radiative (NR, on the right of the light line) ENZ polariton modes are experimentally measured and theoretically analyzed through the transfer matrix method and the complex-frequency/real-wavenumber analysis, which are in remarkable agreement. We observe directional near-perfect absorption using the Kretschmann geometry for incidence conditions close to the NR-ENZ polariton mode dispersion. Along with field enhancement, this provides us with an unexplored pathway to enhance nonlinear optical processes and to open up directions for ultrafast, tunable thermal emission.
Amorphous titania thin films were examined for use as the active material in a polarimetry based HF sensor. The amorphous titania films were found to be sensitive to vapor phase HF and the reaction product was identified as a hydronium oxofluorotitanate phase, which has previously only been synthesized in aqueous solution. The extent of reaction varied both with vapor phase HF concentration, relative humidity, and the exposure time. HF concentrations as low as 1 ppm could be detected for exposure times of 120 h.
We demonstrate intrinsic, linearly polarized lasing from single GaN nanowires using cross-sectional shape control. A two-step top-down fabrication approach was employed to create straight nanowires with controllable rectangular cross-sections. A clear lasing threshold of 444 kW cm-2 and a narrow spectral line width of 0.16 nm were observed under optical pumping at room temperature, indicating the onset of lasing. The polarization was along the short dimension (y-direction) of the nanowire due to the higher transverse confinement factors for y-polarized transverse modes resulting from the rectangular nanowire cross-section. The results show that cross-sectioned shape control can enable inherent control over the polarization of nanowire lasers without additional environment requirements, such as placement onto lossy substrates.
Epsilon-near-zero (ENZ) modes provide a new path for tailoring light-matter interactions at the nanoscale. In this paper, we analyze a strongly coupled system at near-infrared frequencies comprising plasmonic metamaterial resonators and ENZ modes supported by degenerately doped semiconductor nanolayers. In strongly coupled systems that combine optical cavities and intersubband transitions, the polariton splitting (i.e., the ratio of Rabi frequency to bare cavity frequency) scales with the square root of the wavelength, thus favoring the long-wavelength regime. In contrast, we observe that the polariton splitting in ENZ/metamaterial resonator systems increases linearly with the thickness of the nanolayer supporting the ENZ modes. In this work, we employ an indium-tin-oxide nanolayer and observe a large experimental polariton splitting of approximately 30% in the near-infrared. This approach opens up many promising applications, including nonlinear optical components and tunable optical filters based on controlling the polariton splitting by adjusting the frequency of the ENZ mode.
Nanoscale structuring of optical materials leads to modification of their properties and can be used for improving efficiencies of photonic devices and for enabling new functionalities. In ultrafast optoelectronic switches for generation and detection of terahertz (THz) radiation, incorporation of nanostructures allows us to overcome inherent limitations of photoconductive materials. We propose and demonstrate a nanostructured photoconductive THz detector for sampling highly localized THz fields, down to the level of λ/150. The nanostructure that consists of an array of optical nanoantennas and a distributed Bragg reflector forms a hybrid cavity, which traps optical gate pulses within the photoconductive layer. The effect of photon trapping is observed as enhanced absorption at a designed wavelength. This optically thin photoconductive THz detector allows us to detect highly confined evanescent THz fields coupled through a deeply subwavelength aperture as small as 2 μm (λ/150 at 1 THz). By monolithically integrating the THz detector with apertures ranging from 2 to 5 μm we realize higher spatial resolution and higher sensitivity in aperture-type THz near-field microscopy and THz time-domain spectroscopy.
Establishing processing-structure-property relationships for monolayer materials is crucial for a range of applications spanning optics, catalysis, electronics and energy. Presently, for molybdenum disulfide, a promising catalyst for artificial photosynthesis, considerable debate surrounds the structure/property relationships of its various allotropes. Here we unambiguously solve the structure of molybdenum disulfide monolayers using high-resolution transmission electron microscopy supported by density functional theory and show lithium intercalation to direct a preferential transformation of the basal plane from 2H (trigonal prismatic) to 1T′ (clustered Mo). These changes alter the energetics of molybdenum disulfide interactions with hydrogen (ΔG H), and, with respect to catalysis, the 1T′ transformation renders the normally inert basal plane amenable towards hydrogen adsorption and hydrogen evolution. Indeed, we show basal plane activation of 1T′ molybdenum disulfide and a lowering of ΔG H from +1.6 eV for 2H to +0.18 eV for 1T′, comparable to 2H molybdenum disulfide edges on Au(111), one of the most active hydrogen evolution catalysts known.
QD-solids comprising self-assembled semiconductor nanocrystals such as CdSe are currently under investigation for use in a wide array of applications including light emitting diodes, solar cells, field effect transistors, photodetectors, and biosensors. The goal of this LDRD project was develop a fundamental understanding of the relationship between nanoparticle interactions and the different regimes of charge and energy transport in semiconductor quantum dot (QD) solids. Interparticle spacing was tuned through the application of hydrostatic pressure in a diamond anvil cell, and the impact on interparticle interactions was probed using x-ray scattering and a variety of static and transient optical spectroscopies. During the course of this LDRD, we discovered a new, previously unknown, route to synthesize semiconductor quantum wires using high pressure sintering of self-assembled quantum dot crystals. We believe that this new, pressure driven synthesis approach holds great potential as a new tool for nanomaterials synthesis and engineering.
There is strong interest in minimizing the volume of lasers to enable ultracompact, low-power, coherent light sources. Nanowires represent an ideal candidate for such nanolasers as stand-alone optical cavities and gain media, and optically pumped nanowire lasing has been demonstrated in several semiconductor systems. Electrically injected nanowire lasers are needed to realize actual working devices but have been elusive due to limitations of current methods to address the requirement for nanowire device heterostructures with high material quality, controlled doping and geometry, low optical loss, and efficient carrier injection. In this project we proposed to demonstrate electrically injected single nanowire lasers emitting in the important UV to visible wavelengths. Our approach to simultaneously address these challenges is based on high quality III-nitride nanowire device heterostructures with precisely controlled geometries and strong gain and mode confinement to minimize lasing thresholds, enabled by a unique top-down nanowire fabrication technique.
We experimentally demonstrate a functional silicon metadevice at telecom wavelengths that can efficiently control the wavefront of optical beams by imprinting a spatially varying transmittance phase independent of the polarization of the incident beam. Near-unity transmittance efficiency and close to 0-2 phase coverage are enabled by utilizing the localized electric and magnetic Mie-type resonances of low-loss silicon nanoparticles tailored to behave as electromagnetically dual-symmetric scatterers. We apply this concept to realize a metadevice that converts a Gaussian beam into a vortex beam. The required spatial distribution of transmittance phases is achieved by a variation of the lattice spacing as a single geometric control parameter.
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 (∼5μm): 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.
We experimentally demonstrate efficient third harmonic generation from an indium tin oxide nanofilm (λ/42 thick) on a glass substrate for a pump wavelength of 1.4 μm. A conversion efficiency of 3.3 × 10-6 is achieved by exploiting the field enhancement properties of the epsilon-near-zero mode with an enhancement factor of 200. This nanoscale frequency conversion method is applicable to other plasmonic materials and reststrahlen materials in proximity of the longitudinal optical phonon frequencies.
Infrared thermal emission from metals has important energy applications in thermophotovoltaics, radiative cooling, and lighting. Unfortunately, the emissivity of flat metal films is close to zero because the screening effect prevents metals' fluctuating currents from emitting to the far field. As a result, metal films are often used as reflecting mirrors instead of thermal emitters. Recently, nanostructured metals, such as metamaterials, have emerged as an interesting way to enhance and to spectrally control thermal emission based on plasmonic resonant effects. However, they require sophisticated lithography. Here, we proposed and experimentally demonstrated a completely different mechanism to achieve spectrally selective metallic emitters based on a tunneling effect. This effect allows a simple flat metal film to achieve a near-unity emissivity with controlled spectral selectivity for efficient heat-to-light energy conversion.
We employ both the effective medium approximation (EMA) and Bloch theory to compare the dispersion properties of semiconductor hyperbolic metamaterials (SHMs) at mid-infrared frequencies and metallic hyperbolic metamaterials (MHMs) at visible frequencies. This analysis reveals the conditions under which the EMA can be safely applied for both MHMs and SHMs. We find that the combination of precise nanoscale layering and the longer infrared operating wavelengths puts the SHMs well within the effective medium limit and, in contrast to MHMs, allows for the attainment of very high photon momentum states. In addition, SHMs allow for new phenomena such as ultrafast creation of the hyperbolic manifold through optical pumping. In particular, we examine the possibility of achieving ultrafast topological transitions through optical pumping which can photo-dope appropriately designed quantum wells on the femtosecond time scale.
Lasing is demonstrated from gallium nitride nanotubes fabricated using a two-step top-down technique. By optically pumping, we observed characteristics of lasing: a clear threshold, a narrow spectral, and guided emission from the nanotubes. In addition, annular lasing emission from the GaN nanotube is also observed, indicating that cross-sectional shape control can be employed to manipulate the properties of nanolasers. The nanotube lasers could be of interest for optical nanofluidic applications or application benefitting from a hollow beam shape.
Ultrafast optical excitation of photocarriers has the potential to transform undoped semiconductor superlattices into semiconductor hyperbolic metamaterials (SHMs). In this paper, we investigate the optical properties associated with such ultrafast topological transitions. We first show reflectance, transmittance, and absorption under TE and TM plane wave incidence. In the unpumped state, the superlattice exhibits a frequency region with high reflectance (>80%) and a region with low reflectance (<1%) for both TE and TM polarizations over a wide range of incidence angles. In contrast, in the photopumped state, the reflectance for both frequencies and polarizations is very low (<1%) for a similar range of angles. Interestingly, this system can function as an all-optical reflection switch on ultrafast timescales. Furthermore, for TM incidence and close to the epsilon-near-zero point of the longitudinal permittivity, directional perfect absorption on ultrafast timescales may also be achieved. Finally, we discuss the onset of negative refraction in the photopumped state.
We utilize the unique dispersion properties of leaky plasmon polaritons in epsilon-near-zero (ENZ) thin films to demonstrate thermal radiation control. Owing to its highly flat dispersion above the light line, a thermally excited leaky wave at the ENZ frequency out-couples into free space without any scattering structures, resulting in a narrowband, wide-angle, p-polarized thermal emission spectrum. We demonstrate this idea by measuring angle- and polarization-resolved thermal emission spectra from a single layer of unpatterned, doped semiconductors with deep-subwavelength film thickness (d / λ 0 ∼ 6 × 10 - 3, where d is the film thickness and λ 0 is the free space wavelength). We show that this semiconductor ENZ film effectively works as a leaky wave thermal radiation antenna, which generates far-field radiation from a thermally excited mode. The use of semiconductors makes the radiation frequency highly tunable by controlling doping densities and also facilitates device integration with other components. Therefore, this leaky plasmon polariton emission from semiconductor ENZ films provides an avenue for on-chip control of thermal radiation.
We have demonstrated single-mode lasing in a single gallium nitride nanowire using distributed feedback by external coupling to a dielectric grating. By adjusting the nanowire grating alignment we achieved a mode suppression ratio of 17dB.
A considerable amount research is being conducted on microalgae, since microalgae are becoming a promising source of renewable energy. Most of this research is centered on lipid production in microalgae because microalgae produce triacylglycerol which is ideal for biodiesel fuels. Although we are interested in research to increase lipid production in algae, we are also interested in research to sustain healthy algal cultures in large scale biomass production farms or facilities. The early detection of fluctuations in algal health, productivity, and invasive predators must be developed to ensure that algae are an efficient and cost-effective source of biofuel. Therefore we are developing technologies to monitor the health of algae using spectroscopic measurements in the field. To do this, we have proposed to spectroscopically monitor large algal cultivations using LIDAR (Light Detection And Ranging) remote sensing technology. Before we can deploy this type of technology, we must first characterize the spectral bio-signatures that are related to algal health. Recently, we have adapted our confocal hyperspectral imaging microscope at Sandia to have two-photon excitation capabilities using a chameleon tunable laser. We are using this microscope to understand the spectroscopic signatures necessary to characterize microalgae at the cellular level prior to using these signatures to classify the health of bulk samples, with the eventual goal of using of LIDAR to monitor large scale ponds and raceways. By imaging algal cultures using a tunable laser to excite at several different wavelengths we will be able to select the optimal excitation/emission wavelengths needed to characterize algal cultures. To analyze the hyperspectral images generated from this two-photon microscope, we are using Multivariate Curve Resolution (MCR) algorithms to extract the spectral signatures and their associated relative intensities from the data. For this presentation, I will show our two-photon hyperspectral imaging results on a variety of microalgae species and show how these results can be used to characterize algal ponds and raceways.
The fundamental spontaneous emission rate for a photon source can be modified by placing the emitter inside a periodic dielectric structure allowing the emission to be dramatically enhanced or suppressed depending on the intended application. We have investigated the relatively unexplored realm of interaction between semiconductor emitters and three dimensional photonic crystals in the visible spectrum. Although this interaction has been investigated at longer wavelengths, very little work has been done in the visible spectrum. During the course of this LDRD, we have fabricated TiO{sub 2} logpile photonic crystal structures with the shortest wavelength band gap ever demonstrated. A variety of different emitters with emission between 365 nm and 700 nm were incorporated into photonic crystal structures. Time-integrated and time-resolved photoluminescence measurements were performed to measure changes to the spontaneous emission rate. Both enhanced and suppressed emission were demonstrated and attributed to changes to the photonic density of states.
The key accomplishment of this project is to achieve a much more in-depth understanding of the thermal emission physics of metallic photonic crystal through theoretical modeling and experimental measurements. An improved transfer matrix technique was developed to enable incorporation of complex dielectric function. Together with microscopic theory describing emitter radiative and non-radiative relaxation dynamics, a non-equilibrium thermal emission model is developed. Finally, experimental methodology was developed to measure absolute emissivity of photonic crystal at high temperatures with accuracy of +/-2%. Accurate emissivity measurements allow us to validate the procedure to treat the effect of the photonic crystal substrate.
In this project we developed photonic crystal modeling capability and fabrication technology that is scaleable to large area. An intelligent optimization code was developed to find the optimal structure for the desired spectral response. In terms of fabrication, an exhaustive survey of fabrication techniques that would meet the large area requirement was reduced to Deep X-ray Lithography (DXRL) and nano-imprint. Using DXRL, we fabricated a gold logpile photonic crystal in the <100> plane. For the nano-imprint technique, we fabricated a cubic array of gold squares. These two examples also represent two classes of metallic photonic crystal topologies, the connected network and cermet arrangement.
A 100-GW optical parametric chirped-pulse amplifier system is used to study nonlinear effects in the 1.54 {micro}m regime. When focusing this beam in air, strong third-harmonic generation (THG) is observed, and both the spectra and efficiency are measured. Broadening is observed on only the blue side of the third-harmonic signal and an energy conversion efficiency of 0.2% is achieved. When propagated through a 10-cm block of fused silica, a collimated beam is seen to collapse and form multiple filaments. The measured spectral features span 400-2100 nm. The spectrum is dominated by previously unobserved Stokes emissions and broad emissions in the visible.
Terahertz radiation from optically-induced plasmas on metal, semiconductor, and dielectric surfaces is compared to electron-hole plasma radiation from GaAs and Ge. Electro-optic sampling and electric-field probes measure radiated field waveforms and distributions to 0.350 THz.
At Sandia National Laboratories, miniaturization dominates future hardware designs, and technologies that address the manufacture of micro-scale to nano-scale features are in demand. Currently, Sandia is developing technologies such as photolithography/etching (e.g. silicon MEMS), LIGA, micro-electro-discharge machining (micro-EDM), and focused ion beam (FIB) machining to fulfill some of the component design requirements. Some processes are more encompassing than others, but each process has its niche, where all performance characteristics cannot be met by one technology. For example, micro-EDM creates highly accurate micro-scale features but the choice of materials is limited to conductive materials. With silicon-based MEMS technology, highly accurate nano-scale integrated devices are fabricated but the mechanical performance may not meet the requirements. Femtosecond laser processing has the potential to fulfill a broad range of design demands, both in terms of feature resolution and material choices, thereby improving fabrication of micro-components. One of the unique features of femtosecond lasers is the ability to ablate nearly all materials with little heat transfer, and therefore melting or damage, to the surrounding material, resulting in highly accurate micro-scale features. Another unique aspect to femtosecond radiation is the ability to create localized structural changes thought nonlinear absorption processes. By scanning the focal point within transparent material, we can create three-dimensional waveguides for biological sensors and optical components. In this report, we utilized the special characteristics of femtosecond laser processing for microfabrication. Special emphasis was placed on the laser-material interactions to gain a science-based understanding of the process and to determine the process parameter space for laser processing of metals and glasses. Two areas were investigated, including laser ablation of ferrous alloys and direct-write optical waveguides and integrated optics in bulk glass. The effects of laser and environmental parameters on such aspects as removal rate, feature size, feature definition, and ablation angle during the ablation process of metals were studied. In addition, the manufacturing requirements for component fabrication including precision and reproducibility were investigated. The effect of laser processing conditions on the optical properties of direct-written waveguides and an unusual laser-induced birefringence in an optically isotropic glass are reported. Several integrated optical devices, including a Y coupler, directional coupler, and Mach-Zehnder interferometer, were made to demonstrate the simplicity and flexibility of this technique in comparison to the conventional waveguide fabrication processes.
The spatial, spectral and temporal properties of self-focusing 798-nm 100-fs pulses in air were experimentally measured. It was measured using high-resolution, single-shot techniques at a set propagation distance of 10.91 m. The data were taken over an extended energy range and can thus be used to test the validity of physical models. The experimental results show that significant spatial, spectral and temporal changes occur at intensities lower than than those required for strong ionization of air.
Journal of Physics B: Atomic, Molecular and Optical Physics
Borisov, A.B.; Cameron, Stewart M.; Luk, Ting S.; Nelson, T.R.; Van Tassle, A.J.; Santoro, J.; Schroeder, W.A.; Dai, Y.; Longworth, J.W.; Boyer, K.; Rhodes, C.K.
Stable self-channelling of ultra-powerful (P0 ∼ 1 TW-1 PW) laser pulses in dense plasmas is a key process for many applications requiring the controlled compression of power at high levels. Theoretical computations predict that the transition zone between the stable and highly unstable regimes of relativistic/charge-displacement self-channelling is well characterized by a form of weak instability that involves bifurcation of the propagating energy into two channels. Recent observations of unstable behaviour with femtosecond 248 nm pulses reveal a mode of bifurcation that corresponds well to these theoretical predictions. It is further experimentally shown that the use of a suitable longitudinal gradient in the plasma density can eliminate this unstable response and restore the efficient formation of single stable channels.
Summary form only given. It has been shown in 3 + 1 dimensional Kerr-nonlinearity self-focusing models, that group velocity dispersion is responsible for the temporal pulse-splitting of ultrashort pulses during propagation. Previous experiments have demonstrated pulse splitting due to the Kerr nonlinearity for short pulse propagation in bulks or gaseous media. However, studies in gaseous media are often in a focused geometry, or use pressurized gaseous media. This experiment elucidates the relationship between pulse splitting and spot-size change and does not use any optic to initiate self-focusing. We find pulse splitting occurs at a distance merely 0.7x the diffraction length and occurs before spatial collapse to a filament. In addition, multiple pulse splitting is also observed. Peak fluence information from the beam-profile is monitored, indicating nonlinear loss mechanisms. We believe this is the first data on multiple pulse-splitting events in air.
Summary form only given. Numerous groups have demonstrated that tabletop high peak power femtosecond lasers are capable of inducing nonlinear self-focused propagation in atmosphere at 800 nm. The phenomenon unfailingly exhibits (1) light concentration in long single or multiple filaments of the order of 150 μm diameter and tens of meters in length; (2) conical emission associated with these filaments has a considerably wider spectral content than the original laser pulse. Conical emission became apparent after the filaments were formed. While the divergence angle of these conical emissions has been studied, unfortunately there is no reasonable model proposed that can qualitatively describe (Brodeur et al, 1996; Nibbering et al, 1996) even the most basic features such as divergence angles of the different colors. Furthermore, the color ordering of these conical emissions can be changed upon changing the chirp of the launched pulse. In this paper, we present conical emission data to show its behavior as the pulse is chirped. In addition, we also present the spectral distribution of the conical emissions and how it depends on chirp. Finally, we compare our result with numerical result of Gaeta (Phys. Rev. Lett. vol. 84, pp. 3582-3585, 2000).
Efficient (1.2% yield) multikilovolt x-ray emission from Ba(L) (2.4--2.8{angstrom}) and Gd(L) (1.7--2.1{angstrom}) is produced by ultraviolet (248nm) laser-excited BaF{sub 2} and Gd solids. The high efficiency is attributed to an inner shell-selective collisional electron ejection. Much effort has been expended recently in attempts to develop an efficient coherent x-ray source suitable for high-resolution biological imaging. To this end, many experiments have been performed studying the x-ray emissions from high-Z materials under intense (>10{sup 18}W/cm{sup 2}) irradiation, with the most promising results coming from the irradiation of Xe clusters with a UV (248nm) laser at intensities of 10{sup 18}--10{sup 19}W/cm{sup 2}. In this paper the authors report the production of prompt x-rays with energies in excess of 5keV with efficiencies on the order of 1% as a result of intense irradiation of BaF{sub 2} and Gd targets with a terawatt 248nm laser. The efficiency is attributed to an inner shell-selective collisional electron ejection mechanism in which the previously photoionized electrons are ponderomotively driven into an ion while retaining a portion of their atomic phase and symmetry. This partial coherence of the laser-driven electrons has a pronounced effect on the collisional cross-section for the electron ion interaction.
UV filaments in air have been examined on the basis of the diameter and length of the filament, the generation of new spectral components, and the ionization by multiphoton processes. There have been numerous observations of filaments at 800 nm. The general perception is that, above a critical power, the beam focuses because nonlinear self-lensing overcomes diffraction. The self-focusing proceeds until an opposing higher order nonlinearity forms a stable balance.