Fluorescence-Detected Mid-Infrared Photothermal Microscopy.

We demonstrate instrumentation and methods to enable fluorescence-detected photothermal infrared (F-PTIR) microscopy and then demonstrate the utility of F-PTIR to characterize the composition within phase-separated domains of model amorphous solid dispersions (ASDs) induced by water sorption. In F-PTIR, temperature-dependent changes in fluorescence quantum efficiency are shown to sensitively report on highly localized absorption of mid-infrared radiation. The spatial resolution with which infrared spectroscopy can be performed is dictated by fluorescence microscopy, rather than the infrared wavelength. Intrinsic ultraviolet autofluorescence of tryptophan and protein microparticles enabled label-free F-PTIR microscopy. Following proof of concept F-PTIR demonstration on model systems of polyethylene glycol (PEG) and silica gel, F-PTIR enabled the characterization of chemical composition within inhomogeneous ritonavir/polyvinylpyrrolidone-vinyl acetate (PVPVA) amorphous dispersions. Phase separation is implicated in the observation of critical behaviors in ASD dissolution kinetics, with the results of F-PTIR supporting the formation of phase-separated drug-rich domains upon water sorption in spin-cast films.

Portable broadband photoacoustic spectroscopy for trace gas detection by quantum cascade laser arrays.

We report a portable broadband photoacoustic spectroscopic system for trace gas detection using distributed feedback quantum cascade laser arrays. By sequentially firing 128 lasers, our system acquires a photoacoustic spectrum covering 565cm-1 (935-1500cm-1) with a normalized-noise-equivalent-absorption coefficient of 2.5×10-9cm-1WHz-1/2. The firing sequence that determines when and which laser to activate is programmable, which enables frequency-multiplexing excitation. For demonstration, 12 lasers are modulated simultaneously at distinct frequencies, and a photoacoustic spectrum is acquired within 13 ms. The compactness (28cm×17cm×13cm, 3.5 kg) and low power consumption enable convenient installation for on-site monitoring.

Broadband detection of methane and nitrous oxide using a distributed-feedback quantum cascade laser array and quartz-enhanced photoacoustic sensing.

Here we report on the broadband detection of nitrous oxide (N2O) and methane (CH4) mixtures in dry nitrogen by using a quartz-enhanced photoacoustic (QEPAS) sensor exploiting an array of 32 distributed-feedback quantum cascade lasers, within a spectral emission range of 1190-1340 cm-1 as the excitation source. Methane detection down to a minimum detection limit of 200 ppb at 10 s lock-in integration time was achieved. The sensor demonstrated a linear response in the range of 200-1000 ppm. Three different mixtures of N2O and CH4 in nitrogen at atmospheric pressure have been analyzed. The capability of the developed QEPAS sensor to selectively determine the N2O and CH4 concentrations was demonstrated, in spite of significant overlap in their respective absorption spectra in the investigated spectral range.

Portable standoff spectrometer for hazard identification using integrated quantum cascade laser arrays from 6.5 to 11 µm.

This article presents new spectroscopic results in standoff chemical detection that are enabled by monolithic arrays of Distributed Feedback (DFB) Quantum Cascade Lasers (QCLs), with each array element at a slightly different wavelength than its neighbor. The standoff analysis of analyte/substrate pairs requires a laser source with characteristics offered uniquely by a QCL Array. This is particularly true for time-evolving liquid chemical warfare agent (CWA) analysis. In addition to describing the QCL array source developed for long wave infrared coverage, a description of an integrated prototype standoff detection system is provided. Experimental standoff detection results using the man-portable system for droplet examination from 1.3 meters are presented using the CWAs VX and T-mustard as test cases. Finally, we consider three significant challenges to working with droplets and liquid films in standoff spectroscopy: substrate uptake of the analyte, time-dependent droplet spread of the analyte, and variable substrate contributions to retrieved signals.

Open-path spectroscopic methane detection using a broadband monolithic distributed feedback-quantum cascade laser array.

Methane is a powerful greenhouse gas that has both natural and anthropogenic sources. The ability to measure methane using an integrated path length approach such as an open/long-path length sensor would be beneficial in several environments for examining anthropogenic and natural sources, including tundra landscapes, rivers, lakes, landfills, estuaries, fracking sites, pipelines, and agricultural sites. Here a broadband monolithic distributed feedback-quantum cascade laser array was utilized as the source for an open-path methane sensor. Two telescopes were utilized for the launch (laser source) and receiver (detector) in a bistatic configuration for methane sensing across a 50 m path length. Direct-absorption spectroscopy was utilized with intrapulse tuning. Ambient methane levels were detectable, and an instrument precision of 70 ppb with 100 s averaging and 90 ppb with 10 s averaging was achieved. The sensor system was designed to work "off the grid" and utilizes batteries that are rechargeable with solar panels and wind turbines.

Low-dissipation 7.4-µm single-mode quantum cascade lasers without epitaxial regrowth.

We report continuous-wave operation of single-mode quantum cascade (QC) lasers emitting near 7.4 µm with threshold power consumption below 1 W at temperatures up to 40 °C. The lasers were fabricated with narrow, plasma-etched waveguides and distributed-feedback sidewall gratings clad with sputtered aluminum nitride. In contrast to conventional buried-heterostructure (BH) devices with epitaxial sidewall cladding and in-plane gratings, the devices described here were fabricated without any epitaxial regrowth processes, yet they exhibit power consumption comparable to the lowest-dissipation BH QC lasers reported to date. These low-dissipation devices are designed primarily as light sources for infrared spectroscopy instruments with limited volume, mass, and power budgets.

Controlled steering of Cherenkov surface plasmon wakes with a one-dimensional metamaterial.

In the Cherenkov effect a charged particle moving with a velocity faster than the phase velocity of light in the medium radiates light that forms a cone with a half angle determined by the ratio of the two speeds. Here, we show that by creating a running wave of polarization along a one-dimensional metallic nanostructure consisting of subwavelength-spaced rotated apertures that propagates faster than the surface plasmon polariton phase velocity, we can generate surface plasmon wakes, a two-dimensional analogue of Cherenkov radiation. The running wave of polarization travels with a speed determined by the angle of incidence and the photon spin angular momentum of the incident radiation. By changing either one of these properties we demonstrate controlled steering of the Cherenkov surface plasmon wakes.

High tuning stability of sampled grating quantum cascade lasers.

Predictable tuning behavior and stable laser operation are both crucial for laser spectroscopy measurements. We report a sampled grating quantum cascade laser (QCL) with high spectral tuning stability over the entire tuning range. We have determined the minimum loss margin required to suppress undesired lasing modes in order to ensure predictable tuning behavior. We have quantified power fluctuations and drift of our devices by measuring the Allan deviation. To demonstrate the feasibility of sampled grating QCLs for high-precision molecular spectroscopy, we have built a simple transmission spectroscopy setup. Our results prove that sampled grating QCLs are suitable light sources for highly sensitive spectroscopy measurements.

Harvesting renewable energy from Earth's mid-infrared emissions.

It is possible to harvest energy from Earth's thermal infrared emission into outer space. We calculate the thermodynamic limit for the amount of power available, and as a case study, we plot how this limit varies daily and seasonally in a location in Oklahoma. We discuss two possible ways to make such an emissive energy harvester (EEH): A thermal EEH (analogous to solar thermal power generation) and an optoelectronic EEH (analogous to photovoltaic power generation). For the latter, we propose using an infrared-frequency rectifying antenna, and we discuss its operating principles, efficiency limits, system design considerations, and possible technological implementations.

Generation of two-dimensional plasmonic bottle beams.

By analogy to the three dimensional optical bottle beam, we introduce the plasmonic bottle beam: a two dimensional surface wave which features a lattice of plasmonic bottles, i.e. alternating regions of bright focii surrounded by low intensities. The two-dimensional bottle beam is created by the interference of a non-diffracting beam, a cosine-Gaussian beam, and a plane wave, thus giving rise to a non-diffracting complex intensity distribution. By controlling the propagation constant of the cosine-Gauss beam, the size and number of plasmonic bottles can be engineered. The two dimensional lattice of hot spots formed by this new plasmonic wave could have applications in plasmonic trapping.

Thermal tuning of mid-infrared plasmonic antenna arrays using a phase change material.

We demonstrate that the resonances of infrared plasmonic antennas can be tuned or switched on/off by taking advantage of the thermally driven insulator-to-metal phase transition in vanadium dioxide (VO(2)). Y-shaped antennas were fabricated on a 180 nm film of VO(2) deposited on a sapphire substrate, and their resonances were shown to depend on the temperature of the VO(2) film in proximity of its phase transition, in good agreement with full-wave simulations. We achieved tunability of the resonance wavelength of approximately 10% (>1 µm at λ~10 µm).

Nanometre optical coatings based on strong interference effects in highly absorbing media.

Optical coatings, which consist of one or more films of dielectric or metallic materials, are widely used in applications ranging from mirrors to eyeglasses and photography lenses. Many conventional dielectric coatings rely on Fabry-Perot-type interference, involving multiple optical passes through transparent layers with thicknesses of the order of the wavelength to achieve functionalities such as anti-reflection, high-reflection and dichroism. Highly absorbing dielectrics are typically not used because it is generally accepted that light propagation through such media destroys interference effects. We show that under appropriate conditions interference can instead persist in ultrathin, highly absorbing films of a few to tens of nanometres in thickness, and demonstrate a new type of optical coating comprising such a film on a metallic substrate, which selectively absorbs various frequency ranges of the incident light. These coatings have a low sensitivity to the angle of incidence and require minimal amounts of absorbing material that can be as thin as 5-20 nm for visible light. This technology has the potential for a variety of applications from ultrathin photodetectors and solar cells to optical filters, to labelling, and even the visual arts and jewellery.

Widely tunable mid-infrared quantum cascade lasers using sampled grating reflectors.

We demonstrate a three-section, electrically pulsed quantum cascade laser which consists of a Fabry-Pérot section placed between two sampled grating distributed Bragg reflectors. The device is current-tuned between ten single modes spanning a range of 0.46 µm (63 cm(-1)), from 8.32 to 8.78 µm. The peak optical output power exceeds 280 mW for nine of the modes.

Aberration-free ultrathin flat lenses and axicons at telecom wavelengths based on plasmonic metasurfaces.

The concept of optical phase discontinuities is applied to the design and demonstration of aberration-free planar lenses and axicons, comprising a phased array of ultrathin subwavelength-spaced optical antennas. The lenses and axicons consist of V-shaped nanoantennas that introduce a radial distribution of phase discontinuities, thereby generating respectively spherical wavefronts and nondiffracting Bessel beams at telecom wavelengths. Simulations are also presented to show that our aberration-free designs are applicable to high-numerical aperture lenses such as flat microscope objectives.

Enhancement of optical processes in coupled plasmonic nanocavities [Invited].

We present detailed experimental and numerical investigations of resonances in deep nanogroove gratings in metallic substrates. These plasmonic nanocavity gratings feature enhanced fields within the grooves that enable a large enhancement of linear and nonlinear optical processes. This enhancement relies on both localized and propagating surface plasmons on the nanopatterned surface. We show that the efficiency of optical processes such as Raman scattering and four-wave mixing is dramatically enhanced by plasmonic nanocavity gratings.

Multi-wavelength mid-infrared plasmonic antennas with single nanoscale focal point.

We propose and demonstrate a novel photonic-plasmonic antenna capable of confining electromagnetic radiation at several mid-infrared wavelengths to a single sub-wavelength spot. The structure relies on the coupling between the localized surface plasmon resonance of a bow-tie nanoantenna with the photonic modes of surrounding multi-periodic particle arrays. Far-field measurements of the transmission through the central bow-tie demonstrate the presence of Fano-like interference effects resulting from the interaction of the bow-tie antenna with the surrounding nanoparticle arrays. The near-field of the multi-wavelength antenna is imaged using an aperture-less near-field scanning optical microscope. This antenna is relevant for the development of near-field probes for nanoimaging, spectroscopy and biosensing.

Spoof plasmon analogue of metal-insulator-metal waveguides.

We describe the properties of guided modes in metallic parallel plate structures with subwavelength corrugation on the surfaces of both conductors, which we refer to as spoof-insulator-spoof (SIS) waveguides, in close analogy to metal-insulator-metal (MIM) waveguides in plasmonics. A dispersion relation for SIS waveguides is derived, and the modes are shown to arise from the coupling of conventional waveguide modes with the localized modes of the grooves in the SIS structure. SIS waveguides have numerous design parameters and can be engineered to guide modes with very low group velocities and adiabatically convert light between conventional photonic modes and plasmonic ones.

Large enhancement of nonlinear optical phenomena by plasmonic nanocavity gratings.

Enhancing nonlinear processes at the nanoscale is a crucial step toward the development of nanophotonics and new spectroscopy techniques. Here we demonstrate a novel plasmonic structure, called plasmonic nanocavity grating, which is shown to dramatically enhance surface nonlinear optical processes. It consists of resonant cavities that are periodically arranged to combine local and grating resonances. The four-wave mixing signal generated in our gold nanocavity grating is enhanced by a factor up to ≈2000, 2 orders of magnitude higher than that previously reported.

Quantum cascade lasers with integrated plasmonic antenna-array collimators.

We demonstrated in simulations and experiments that by defining a properly designed two-dimensional metallic aperture-grating structure on the facet of quantum cascade lasers, a small beam divergence angle can be achieved in directions both perpendicular and parallel to the laser waveguide layers (denoted as theta perpendicular and theta parallel, respectively). Beam divergence angles as small as theta perpendicular=2.7 degrees and theta parallel=3.7 degrees have been demonstrated. This is a reduction by a factor of approximately 30 and approximately 10, respectively, compared to those of the original lasers emitting at a wavelength of 8.06 microm. The devices preserve good room temperature performance with output power as high as approximately 55% of that of the original unpatterned lasers. We studied in detail the trade-off between beam divergence and power throughput for the fabricated devices. We demonstrated plasmonic collimation for buried heterostructure lasers and ridge lasers; devices with different waveguide structures but with the same plasmonic collimator design showed similar performance. We also studied a device patterned with a "spider's web" pattern, which gives us insight into the distribution of surface plasmons on the laser facet.