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Plasmonic nanostructures have attracted increasing interest in the fields of photochemistry and photocatalysis for their ability to enhance reactivity and tune reaction selectivity, a benefit of their strong interactions with light and their multiple energy decay mechanisms. Here we introduce the use of earth-abundant plasmonic aluminum nanoparticles as a promising renewable detoxifier of the sulfur mustard simulant 2-chloroethylethylsulfide through gas phase photodecomposition. Analysis of the decomposition products indicates that C-S bond breaking is facilitated under illumination, while C-Cl breaking and HCl elimination are favored under thermocatalytic (dark) conditions. This difference in reaction pathways illuminates the potential of plasmonic nanoparticles to tailor reaction selectivity toward less hazardous products in the detoxification of chemical warfare agents. Moreover, the photocatalytic activity of the Al nanoparticles can be regenerated almost completely after the reaction concludes through a simple surface treatment.

Although gas phase rotational spectroscopy is a mature field for which millions of rotational spectral lines have been measured in hundreds of molecules with sub-MHz accuracy, it remains a challenge to measure these rotational spectra in excited vibrational modes with the same accuracy. Recently, it was demonstrated that virtually any rotational transition in excited vibrational modes of most molecules may be made to lase when pumped by a continuously tunable quantum cascade laser (QCL). Here, we demonstrate how an infrared QCL may be used to enhance absorption strength or induce lasing of terahertz rotational transitions in highly excited vibrational modes in order to measure their frequencies more accurately. To illustrate the concepts, we used a tunable QCL to excite v3 R-branch transitions in N2O and either enhanced absorption or induced lasing on 20 v3 rotational transitions, whose frequencies between 299 and 772 GHz were then measured using either heterodyne or modulation spectroscopy. The spectra were fitted to obtain the rotational constants B3 and D3, which reproduce the measured spectra to within the experimental uncertainty of ± 5 kHz. We then show how this technique may be generalized by estimating the threshold power to make any rotational transition lase in any N2O vibrational mode.

In a hybrid gas/liquid phase reactor, C1/C2 product selectivity is determined by externally controlled conditions: humidity, voltage, and temperature.

We present a general framework for inverse design of nanopatterned surfaces that maximize spatially averaged surface-enhanced Raman (SERS) spectra from molecules distributed randomly throughout a material or fluid, building upon a recently proposed trace formulation for optimizing incoherent emission. This leads to radically different designs than optimizing SERS emission at a single known location, as we illustrate using several 2D design problems addressing effects of hot-spot density, angular selectivity, and nonlinear damage. We obtain optimized structures that perform about 4 × better than coating with optimized spheres or bowtie structures and about 20 × better when the nonlinear damage effects are included.

Plasmonic photocatalysis represents the synergetic union of two active fields of research: plasmonic effects in illuminated metallic nanoparticles and catalytic effects in tailored metallic nanoparticles. Traditionally, metallic nanoparticles that excel for one application are limited for the other, but recent developments have shown that desirable catalytic behaviors, such as reduced activation barriers and improved product selectivity, derive from nonthermal behaviors uniquely produced by this synergy. After examining such findings, this review will address a specific debate that has recently surfaced: what is the relative degree of contributions of thermal and nonthermal effects in plasmonic photocatalysis? We demonstrate the importance of correctly accounting for thermal effects before characterizing nonthermal contributions. We show that another synergy occurs: these desirable nonthermal behaviors have a temperature dependence, and the resulting temperature-dependent reaction rates far exceed what can be explained from purely thermal effects alone. Thus, the synergy of plasmonic photocatalysis offers an exciting new contribution to the quest for efficient, selective, sustainable methods for chemical synthesis and energy conversion.

Localized surface plasmon resonances optically excited in metallic nanoparticles (NPs) produce beneficial thermal and nonthermal effects. Nonthermal effects, such as enhancing and localizing fields...

Plasmon-induced photocatalysis is a topic of rapidly increasing interest, due to its potential for substantially lowering reaction barriers and temperatures and for increasing the selectivity of chemical reactions. Of particular interest for plasmonic photocatalysis are antenna-reactor nanoparticles and nanostructures, which combine the strong light-coupling of plasmonic nanostructures with reactors that enhance chemical specificity. Here, we introduce Al@TiO

This is an introduction to the feature issue of Optical Materials Express on Non-Hermitian Optics and Photonics.

Ring laser gyroscopes (RLGs) based on non-Hermitian exceptional points (EPs) have garnered much recent interest due to their exceptional sensitivity. Such gyroscopes typically consist of two-ring laser resonators, one with loss and one with an equal amount of optical gain. The coupling strength between these ring resonators is a key parameter determining the sensitivity of EP-based RLGs. Here we explore how the exceptional sensitivity demonstrated in this coupled dimer may be further enhanced by adding more dimers in an array. Specifically, we propose two types of ring laser gyroscope lattice arrays, each composed of N coupled dimers arrayed serially or concentrically with periodic boundary conditions, that guide counter-propagating photons in a rotating frame. Using coupled mode theory, we show that these lattice gyroscopes exhibit an enhanced effective coupling rate between the gain and loss resonators at the EP, thereby producing greater sensitivity to the angular rotation rate than their constituent dimers. This work paves the way toward EP-based RLGs with the necessary sensitivity for GPS-free navigation.

Infrared/Terahertz double resonance spectroscopy is explored for remote identification of trace molecular gases at atmospheric pressures. Free induction decay of low pressure hyperfine-resolved transitions in CH335Cl inform a roadmap for future atmospheric pressure studies.

The synergy between topology and non-Hermiticity in photonics holds immense potential for next-generation optical devices that are robust against defects. However, most demonstrations of non-Hermitian and topological photonics have been limited to super-wavelength scales due to increased radiative losses at the deep-subwavelength scale. By carefully designing radiative losses at the nanoscale, we demonstrate a non-Hermitian plasmonic–dielectric metasurface in the visible with non-trivial topology. The metasurface is based on a fourth order passive parity-time symmetric system. The designed device exhibits an exceptional concentric ring in its momentum space and is described by a Hamiltonian with a non-Hermitian Z 3 ${\mathbb{Z}}_{3}$ topological invariant of V = −1. Fabricated devices are characterized using Fourier-space imaging for single-shot k-space measurements. Our results demonstrate a way to combine topology and non-Hermitian nanophotonics for designing robust devices with novel functionalities.

The quantum cascade laser pump molecular laser (QPML) is a tunable source of terahertz frequencies operating at room temperature that can easily scale beyond the milliwatt level. We present here new progress in QPML research.

The effect of Al doping on the nature of ultraviolet (UV) near band edge emission and broadband “green” visible emission from deep defects in ZnO nanowires is explored by temperature- and excitation intensity-dependent photoluminescence (PL) spectroscopy. Unlike comparably fabricated undoped ZnO nanowires, whose PL spectra is dominated by green emission from oxygen vacancies and whose UV emission broadens and redshifts with increasing excitation intensity, Al-doped ZnO nanowires grown by chemical vapor deposition are smaller and have PL spectra dominated by UV emission that neither broadens nor redshifts significantly with increasing excitation intensity. The excitation intensity-dependent manner in which Al doping enhances UV emission at the expense of green emission indicates that the doping process creates many new donor sites that prevent excitons localized there from activating these green emitting defects.

In some cases, illumination of traditional thermal catalysts and tailored plasmonic photocatalysts may synergistically combine thermal and nonthermal mechanisms to enhance reaction rates and improve product selectivity at reduced temperatures. To understand how these attributes are achieved in plasmon-driven catalysis, these intertwined thermal and nonthermal effects must be untangled. Here, we show how a novel indirect illumination technique, in conjunction with precisely monitored thermal profiles of the catalyst, can confirm and clarify the role of nonthermal effects in plasmon-enhanced carbon dioxide methanation on a Rh/TiO2 photocatalyst. We find that the extracted nonthermal methane production rate has a linear dependence on the top surface temperature, distinctly different from an exponential dependence for thermal catalysis. We also find that the apparent quantum efficiency from the nonthermal contribution has no dependence on light intensity but maintains a linear dependence on top surface temperatures between 200 and 350 °C. The clear exposition of nonthermal effects in the Rh/TiO2 plasmonic photocatalyst illustrates how this methodology may be applied for the quantitative evaluation of thermal and nonthermal light effects in other plasmon-enhanced catalytic reactions.

Synthetic ammonia has been the primary worldwide source of agricultural fertilizer over the last century and is a promising carbon-free energy carrier for sustainable transportation. Despite its gl...

By introducing methyl fluoride (CH$_3$F) as a new gain medium for a quantum cascade laser-pumped molecular laser (QPML), we demonstrate continuous-wave lasing from more than 120 discrete transitions spanning the frequency range 0.25 to 1.3 THz. The unprecedented degree of spectral tuning achieved with CH$_3$F also confirms the universality of the QPML concept: for all polar gas molecules, lasing can be induced on any dipole-allowed rotational transition by sufficient pumping of a related roto-vibrational transition using a continuously tunable quantum cascade laser., main text: 4 pages, 4 figures, supplement: 7 pages, 5 figures. APL Photonics (2021)

Gaseous ammonia has previously been demonstrated as a compelling gain medium for a quantum cascade laser pumped molecular laser (QPML), exhibiting good power efficiency but limited tunability. Here we explore the potential of the ammonia QPML to produce powerful, broadly tunable terahertz frequency lasing on rotational and pure inversion transitions. After theoretically predicting possible laser frequencies, pump thresholds, and efficiencies, we experimentally demonstrate unprecedented tunability -- from 0.762 to more than 4.5 THz -- by pumping Q- and R-branch infrared transitions with widely tunable quantum cascade lasers. We additionally demonstrate two types of multi-line lasing: simultaneous pure inversion and rotation-inversion transitions from the same pumped rotational state, and cascaded lasing involving transitions below the pumped rotational state. We report single frequency power levels as great as 0.33 mW from a low volume laser cavity., Comment: 6 pages, 4 figures, 1 tables. Supplement: 13 pages, 5 figures, 4 tables

We demonstrate and characterize a new quantum cascade laser-pumped molec- ular laser using methyl fluoride as its gain medium. We show that a laser using this gain medium can exhibit a low pump threshold while allowing emission over more than 100 lines spanning from 300 GHz up to 1.3 THz.

We demonstrate a quantum cascade laser-pumped terahertz laser using methyl fluoride gas. The large dipole moment of this molecule allows for a low threshold laser with frequency tunable emission spanning more than one terahertz.

In preparation for remote atmospheric detection, preliminary double resonance spectroscopic measurements were made of CH3Cl and CH3F using a LWIR pump to excite transient vibrational states and a THz source to probe the rotational levels.

Quantum-cascade-laser- (QCL) pumped molecular lasers (QPMLs) have recently been introduced as a source of powerful ($g\phantom{\rule{-2pt}{0ex}}1$ mW) tunable ($g\phantom{\rule{-2pt}{0ex}}1$ THz) narrow-band ($l\phantom{\rule{-2pt}{0ex}}10$ kHz) continuous-wave terahertz radiation. The performance of these lasers depends critically on molecular collision physics, pump saturation, and on the design of the laser cavity. Using a validated three-level model that captures the essential collision and saturation behaviors of the QPML gas nitrous oxide (${\mathrm{N}}_{2}\mathrm{O}$), we explore how the threshold pump power and output terahertz power depend on the pump power and gas pressure, as well as on the diameter, length, and output-coupler transmissivity of a cylindrical cavity. The analysis indicates that maximum power occurs as pump saturation is minimized in a manner that depends much more sensitively on pressure than on cell diameter, length, or transmissivity. A near-optimal compact laser cavity can produce tens of milliwatts of power tunable over frequencies above 1 THz when pumped by a multiwatt QCL.

Terahertz metamaterials with strain-sensitive junctions are introduced to identify structurally compromised regions of composite materials. Spatially mapping the local polarimetric metamaterial response visualizes and records regions of stress extrema experienced by visibly opaque materials.

Polydisperse rhodium nanoparticles have recently shown promise for ultraviolet (UV) plasmonics, but controlling the size and morphology of metal nanoparticles is essential for tuning surface plasmon resonances. Here we report the use of slow-injection polyol methods to synthesize monodisperse Rh nanocubes with unprecedentedly large sizes and slightly concave faces. The associated local surface plasmon resonances (LSPRs) red-shifted with increasing sizes in the UV region from deep UV to around 400 nm, consistent with numerical simulations. UV illumination of p-aminothiophenol attached to the Rh nanocubes generated surface-enhanced Raman spectra and accelerated photo-decomposition, and these enhancements were largest for nanocubes whose LSPR was resonant with the UV laser. The lack of a native oxide coating, the precise control of nanocube size and morphology demonstrated here, and the ability to tune the surface plasmon resonance from the deep UV to near UV spectral region, make rhodium a compelling choice for UV plasmonic applications.

In plasmon-enhanced heterogeneous catalysis, illumination accelerates reaction rates by generating hot carriers and hot surfaces in the constituent nanostructured metals. In order to understand how photogenerated carriers enhance the nonthermal reaction rate, the effects of photothermal heating and thermal gradients in the catalyst bed must be confidently and quantitatively characterized. This is a challenging task considering the conflating effects of light absorption, heat transport, and reaction energetics. Here, we introduce a methodology to distinguish the thermal and nonthermal contributions from plasmon-enhanced catalysts, demonstrated by illuminated rhodium nanoparticles on oxide supports to catalyze the CO2 methanation reaction. By simultaneously measuring the total reaction rate and the temperature gradient of the catalyst bed, the effective thermal reaction rate may be extracted. The residual nonthermal rate of the plasmon-enhanced reaction is found to grow with a superlinear dependence on illu...

A rail-mounted synthetic aperture radar has been constructed to operate at W-band (75 - 110 GHz) and a THz band (325 - 500 GHz) in order to ascertain its ability to locate isolated small, visually obscured metallic scatterers embedded in highly scattering dielectric hosts that are either semi-transparent or opaque. A top view 2D algorithm was used to reconstruct scenes from the acquired data, locating metallic scatterers at W-band with high range and cross-range resolution of 4.3 and 2 mm, respectively, and with improved range resolution of 0.86 mm at the THz band. Millimeter-sized metallic scatterers were easily located when embedded in semi-transparent, highly scattering target hosts of Styrofoam and waxy packing foam but were more difficult to locate when embedded in relatively opaque, highly scattering Celotex panels. Although the THz band provided the expected greater spatial resolution, it required the target to be moved closer to the rail and had a more limited field of view that prevented some targets from being identified. Techniques for improving the signal to noise ratio are discussed. This work establishes a path for developing techniques to render a complete 3D reconstruction of a scene., Comment: 23 pages, 9 figures, 2 tables

We demonstrate a new type of Terahertz Gas Laser pumped by a tunable solid-state laser. This laser has a wide tuning range and operates at room temperature with a high efficiency in a very compact design.

We demonstrate a new class of optically pumped far-infrared lasers using quantum cascade lasers as the pump. Following an initial demonstration using nitrous oxide, we show how we can generate light at THz frequencies using different gases.

Double resonant spectroscopy measurements are presented using a tunable 9-11 pm pump source with a sub-nanosecond pulse train output. This method is demonstrated at atmospheric pressure for methyl halides using a THz probe.

This work presents the design and performance of a 10 pm sub-picosecond laser source. Initial measurements of high-intensity atmospheric propagation are also presented, which represent the first kilometer-range studies of ultrashort pulses in this wavelength regime.

A photoelastic material will reveal its internal stresses when observed through polarizing filters. This eye-catching property has enlightened our understanding of granular materials for over half a century, whether in the service of art, education, or scientific research. In this review article in honor of Robert Behringer, we highlight both his pioneering use of the method in physics research, and its reach into the public sphere through museum exhibits and outreach programs. We aim to provide clear protocols for artists, exhibit-designers, educators, and scientists to use in their own endeavors. It is our hope that this will build awareness about the ubiquitous presence of granular matter in our lives, enlighten its puzzling behavior, and promote conversations about its importance in environmental and industrial contexts. To aid in this endeavor, this paper also serves as a front door to a detailed wiki containing open, community-curated guidance on putting these methods into practice., Comment: 13 pages

In order to exploit gallium’s (Ga) rich polymorphism in the design of phase-change plasmonic systems, accurate understanding of the dielectric function of the different Ga-phases is crucial. The dielectric dispersion profiles of those phases appearing at atmospheric pressure have been reported in the literature, but there is no information on the dielectric function of the high-pressure Ga-phases. Through first principles calculations we present a comprehensive analysis of the interdependence of the crystal structure, band structure, and dielectric function of two high-pressure Ga phases (Ga(II) and Ga(III)). The plasmonic behavior of these high-pressure Ga-phases is compared to those stable (liquid- and α-Ga) and metastable (β-, γ- and δ-Ga) at atmospherics pressure. This analysis can have important implications in the design of pressure-driven phase-change Ga plasmonic devices and high-pressure SERS substrates. European Commission (GA692034); Army Research Laboratory (W911NF-17-2-0023); Ministerio de Economía, Industria y Competitividad, Gobierno de España (PGC2018-096955-B-C41); Ramón y Cajal Grant (RyC-2013-12515); SODERCAN through the Research Vice-rectorate of the Universidad de Cantabria (4JU2864661). M.L. acknowledges the support of the European Commission under the H2020 grant TWINFUSYON (GA692034). Y.G. and F.M. acknowledges the support by the Army Research Laboratory under Cooperative Agreement Number W911NF-17-2-0023 and by SODERCAN (Sociedad para el Desarrollo de Cantabria) and the Research Vicerrectorate of the University of Cantabria through project 4JU2864661. Y.G. thanks the University of Cantabria for her FPU grant. P.G.-F. and J.J. acknowledge financial support from the Spanish Ministry of Economy and Competitiveness through grant number PGC2018-096955-B-C41, and P.G.-F. acknowledges support from Ramón y Cajal grant no. RyC-2013-12515.

Filling the terahertz gap Compared with other wavelengths, coherent sources of electromagnetic radiation in the terahertz regime are relatively scarce. Despite a number of applications in security imaging, spectroscopy, and chemical analysis, it has been experimentally challenging to produce such light. Chevalier et al. demonstrate an approach involving the excitation of a molecular gas with a quantum cascade laser. They show that they can tune into a broad range of desired wavelengths by carefully selecting the required molecular transition. A compact platform—the size of a shoe box—and widely tunable source of coherent terahertz radiation should find immediate application across a number of fields. Science , this issue p. 856

The mechanism for producing efficient white light phosphors from sulfidated zinc oxide (ZnO) powders is elucidated. ZnO powders prepared by vacuum annealing produce powders of oxygen-deficient ZnO:Zn, while ZnO powders annealed in a sulfur atmosphere produce a doped ZnO core with a radially-increasing sulfur concentration gradient capped by a shell of zinc sulfide (ZnS) domains, ZnO:S/ZnS. As compared to ZnO:Zn powders, the intensity and quantum efficiency of the broad, green-tinted white defect fluorescence more than doubled for the ZnO:S/ZnS powders. This fluorescence is mediated by certain neutral donor-bound excitons (DBEs), and it is found that the DBE lifetime and the rate of energy transfer to the defect emission band increases for the ZnO:S/ZnS powders. These DBEs are destroyed by photoexcited free holes, and the hypothesis that they are removed by the type-II band alignment of the ZnS cap with the ZnO:S core is confirmed when ZnO:Zn and ZnO:S/ZnS powders under vacuum are dosed with the hole scavenger methanol: defect emission increases as the free hole concentration decreases. The highest ZnO:S/ZnS quantum efficiency occurs when excited through an impurity band, also produced by sulfur doping, whose energy coincides with the light emitting diodes used for commercial solid state lighting.

Organic-inorganic hybrid materials formed by sequential vapor infiltration (SVI) of trimethylaluminum into polyester fibers are demonstrated, and the photoluminescence of the fibers is evaluated using a combined UV-vis and photoluminescence excitation (PLE) spectroscopy approach. The optical activity of the modified fibers depends on infiltration thermal processing conditions and is attributed to the reaction mechanisms taking place at different temperatures. At low temperatures a single excitation band and dual emission bands are observed, while, at high temperatures, two distinct absorption bands and one emission band are observed, suggesting that the physical and chemical structure of the resulting hybrid material depends on the SVI temperature. Along with enhancing the photoluminescence intensity of the PET fibers, the internal quantum efficiency also increased to 5-fold from ∼4-5% to ∼24%. SVI processing also improved the photocatalytic activity of the fibers, as demonstrated by photodeposition of Ag and Au metal particles out of an aqueous metal salt solution onto fiber surfaces via UVA light exposure. Toward applications in flexible electronics, well-defined patterning of the metallic materials is achieved by using light masking and focused laser rastering approaches.

The reflected microwave power from the photo-excited high mobility GaAs/AlGaAs 2D device has been measured over the wide frequency band spanning from 30 to 330 GHz simultaneously along with diagonal magnetoresistance as a function of the magnetic field. Easily distinguishable resonances in the reflected power signal are observed at the same magnetic fields as a reduced amplitude in the Shubnikov-de Haas (SdH) oscillations of the diagonal magnetoresistance. The reflection resonances with concurrent amplitude reduction in SdH oscillations are correlated with cyclotron resonance induced by microwave, mm-wave, and terahertz photoexcitation. The magnetoplasma effect was also investigated. The results suggest a finite frequency zero-magnetic-field intercept, providing an estimate for the plasma frequency. The experimentally measured plasma frequency appears to be somewhat lower than the estimated plasma frequency for these Hall bars. The results, in sum, are consistent with an effective mass ratio of m*/m = 0.067, the standard value, even in these high mobility GaAs/AlGaAs devices, at very large filling factors. Preliminary findings from this article have been published as conference proceedings, see Kriisa, A., et al., J. of Phys. Conf. Ser. 864, 012057 (2017).

Industrial scale catalytic chemical synthesis demands both high reaction rates and high product yields. In exothermic chemical reactions, these conflicting objectives require a complex balance of optimized catalysts, high temperatures, high pressures, and multiple recycling steps, as in the energy-intensive Haber-Bosch process for ammonia synthesis. Here we report that illumination of a conventional ruthenium-based catalyst produces ammonia with high reaction rates and high conversion yields. Indeed, using continuous wave light-emitting diodes that simulate concentrated solar illumination, ammonia is copiously produced without any external heating or elevated pressures. The possibility of nonthermal plasmonic effects are excluded by carefully comparing the catalytic activity under direct and indirect illumination. Instead, thermal gradients, created and controlled by photothermal heating of the illuminated catalyst surface, are shown to be responsible for the high reaction rates and conversion yields. This nonisothermal environment enhances both by balancing the conflicting requirements of kinetics and thermodynamics, heralding the use of optically controlled thermal gradients as a universal, scalable strategy for the catalysis of many exothermic chemical reactions.

Significance Optically pumped far-infrared (OPFIR) lasers are one of the most powerful continuous-wave terahertz sources. However, such lasers have long been thought to have intrinsically low efficiency and large sizes. Moreover, all previous theoretical models failed to predict even qualitatively the experimental performance at high pressures. Here, we have developed an innovative model that captures the full physics of the lasing process and correctly predicts the behavior in the high-pressure regime. Validated against experiments, our model shows that nearly all previous OPFIR lasers were operating in the wrong regime and that 10 × greater efficiency is possible by redesigning the terahertz cavity. Our results reintroduce the use of OPFIR lasers as a powerful and compact source of terahertz radiation.