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At least 19 records

The role of volume scattering in reducing spectral contrast of reststrahlen bands in spectra of powdered minerals

The first high-resolution quantitative directional hemispherical reflectance spectra of minerals were obtained for different particle sizes, and were used to develop an accurate prediction of the particles' spectral emissivity, using Kirchhoff's law (Nicodemus, 1965) and to interpret the nature and causes of changes in the spectral contrast of reststrahlen bands. It was found that the reststrahlen bands change in shape as well as intensity; this is explained by the occurrence of substantial volume scattering at fine particle sizes. The implication of this finding for remote sensing of the earth, moon, Mercury, Mars, and the asteroids is discussed.

Salisbury, John W.↗

Observations of silicate reststrahlen bands in lunar infrared spectra

Thermal emission spectra of three lunar sites (Apollo 11, Descartes Formation, and Tycho central peak) are measured in the 8-14 micron spectral range. Transmission and instrument effects are accounted for by forming ratios of the Descartes and Tycho spectra to the Apollo 11 spectrum. The ratio spectra are compared with ratios of published laboratory spectra of returned lunar samples and also with ratio spectra calculated using the Aronson-Emslie (1975) model. The comparisons show pyroxene bands in the Descartes ratio spectrum and plagioclase bands in the Tycho ratio spectrum. The Tycho spectrum is found to be consistent with the existence of fine plagioclase dust (approximately 1 micron) at the rock surface and a higher-than-usual sodium content of the plagioclase.

Potter, A. E., Jr.↗

Enhancing Graphene Plasmonic Device Performance via its Dielectric Environment

Graphene plasmons provide a compelling avenue toward chip-scale dynamic tuning of infrared light. Dynamic tunability emerges through controlled alterations in the optical properties of the system defining graphene’s plasmonic dispersion. Typically, electrostatic induced alterations of the carrier concentration in graphene working in conjunction with mobility have been considered the primary factors dictating plasmonic tunability. We find here that the surrounding dielectric environment also plays a primary role, dictating not just the energy of the graphene plasmon but so too the magnitude of its tuning and spectral width. To arrive at this conclusion, poles in the imaginary component of the reflection coefficient are used to efficiently survey the effect of the surrounding dielectric on the tuning of the graphene plasmon. By investigating several common polar materials, optical phonons (i.e., the Reststrahlen band) of the dielectric substrate are shown to appreciably affect not only the plasmon’s spectral location but its tunability, and its resonance shape as well. In particular, tunability is maximized when the resonances are spectrally distant from the Reststrahlen band, whereas sharp resonances (i.e., high-Q) are achievable at the band’s edge. Overall, these observations both underscore the necessity of viewing the dielectric environment in aggregate when considering the plasmonic response derived from two-dimensional materials and provide heuristics to design dynamically tunable graphene-based infrared devices.

36 MATERIALS SCIENCE↗

Mid- to Far-Infrared Anisotropic Dielectric Function of HfS 2 and HfSe 2

The far-infrared (far-IR) remains a relatively underexplored region of the electromagnetic spectrum extending roughly from 20 to 100 µm in free-space wavelength. Research within this range has been restricted due to a lack of optical materials that can be optimized to reduce losses and increase sensitivity, as well as by the long free-space wavelengths associated with this spectral region. Here the exceptionally broad Reststrahlen bands of two Hf-based transition metal dichalcogenides (TMDs) that can support surface phonon polaritons (SPhPs) within the mid-infrared (mid-IR) into the terahertz (THz) are reported. In this vein, the IR transmission and reflectance spectra of hafnium disulfide (HfS 2 ) and hafnium diselenide (HfSe 2 ) flakes are measured and their corresponding dielectric functions are extracted. These exceptionally broad Reststrahlen bands (HfS 2 : 165 cm -1 ; HfSe 2 : 95 cm -1 ) dramatically exceed that of the more commonly explored molybdenum- (Mo) and tungsten- (W) based TMDs (≈5–10 cm -1 ), which results from the over sevenfold increase in the Born effective charge of the Hf-containing compounds. Further, this work therefore identifies a class of materials for nanophotonic and sensing applications in the mid- to far-IR, such as deeply sub-diffractional hyperbolic and polaritonic optical antennas, as is predicted via electromagnetic simulations using the extracted dielectric function.

36 MATERIALS SCIENCE↗

Continuous-wave GaAs/AlGaAs quantum cascade laser at 5.7 THz

Design strategies for improving terahertz (THz) quantum cascade lasers (QCLs) in the 5–6 THz range are investigated numerically and experimentally, with the goal of overcoming the degradation in performance that occurs as the laser frequency approaches the Reststrahlen band. Two designs aimed at 5.4 THz were selected: one optimized for lower power dissipation and one optimized for better temperature performance. The active regions exhibited broadband gain, with the strongest modes lasing in the 5.3–5.6 THz range, but with other various modes observed ranging from 4.76 to 6.03 THz. Pulsed and continuous-wave (cw) operation is observed up to temperatures of 117 K and 68 K, respectively. In cw mode, the ridge laser has modes up to 5.71 THz – the highest reported frequency for a THz QCL in cw mode. The waveguide loss associated with the doped contact layers and metallization is identified as a critical limitation to performance above 5 THz.

47 OTHER INSTRUMENTATION↗

Mineralogy and Thermal Properties of V-Type Asteroid 956 Elisa: Evidence for Diogenitic Material from the Spitzer IRS (5-35 Micrometers) Spectrum

We present the thermal infrared (5-35 micrometer) spectrum of 956 Elisa as measured by the Spitzer Infrared Spectrograph ("IRS"; Houck,1.R. et .11. [20041. Astrophys, 1. SuppL 154, 18-24) together with new ground-based lightcurve data and near-IR spectra. From the visible lightcurve photometry, we determine a rotation period of 16.494 +/- 0.001 h, identify the rotational phase of the Spitzer observations, and estimate the visible absolute magnitude (Hv) at that rotational phase to be 12.58 +/- 0.04. From radiometric analysis of the thermal flux spectrum, we find that at the time of observation 956 Elisa had a projected radius of 5.3 +/- 0.4 km with a visible albedo pv = 0.142+/- 0.022, significantly lower than that of the prototype V-type asteroid, 4 Vesta. (This corresponds to a radius of 5.2 +/- 0.4 km at lightcurve mean.) Analysis with the standard thermal model (STM) results in a sub-solar temperature of 292.3 +/- 2.8 K and beaming parameter eta = 1.16 +/- 0.05. Thermophysical modeling places a lower limit of 20 J m(exp -2)K(exp -1)s(exp -1/2) on the thermal inertia of the asteroid's surface layer (if the surface is very smooth) but more likely values fall between 30 and 150 J m(exp -2)K(exp -1)s(exp -1/2) depending on the sense of rotation. The emissivity spectrum, calculated by dividing the measured thermal flux spectrum by the modeled thermal continuum, exhibits mineralogically interpretable spectral features within the 9-12 micrometer reststrahlen band, the 15-16.5 micrometer Si-O-Si stretching region, and the 16-25 micrometer reststrahlen region that are consistent with pyroxene of diogenitic composition: extant diogenitic pyroxenes fall within the narrow compositional range W0(sub 2+/-1)En(sub 74+/-2)Fs(sub 24+/-1). Spectral deconvolution of the 9-12 micrometer reststrahlen features indicates that up to approximately 20% olivine may also be present, suggesting an olivine-diogenite-like mineralogy. The mid-IR spectrum is inconsistent with non-cumulate eucrite as the major component on the surface of 956 Elisa, although cumulate eucrite material may be present at abundances lower than that of the diogenite component. Analysis of new near-IR spectra of 956 Elisa with the Modified Gaussian Model (MGM; Sunshine, J,M., Pieters, C.M., Pratt, S.F.[1990]. J. Geophys. Res, 95 (May), 6955-6966) results in two pyroxene compositions: 75% magnesian low-Ca pyroxene and 25% high-Ca pyroxene. High-Ca pyroxene is not evident in the mid-IR data, but may belong to a component that is underrepresented in the mid-IR spectrum either because of its spatial distribution on the asteroid or because of its particle size. High-Ca pyroxenes that occur as exsolution lamellae may also be more evident spectrally in the NIR than in the mid-IR. In any case, we find that the mid-IR spectrum of 956 Elisa is dominated by emission from material of diogenite- like composition, which has very rarely been observed among asteroids.

Lim, Lucy F.↗

Infrared (2.08-14 micron) spectra of powered stony meteorites

Infrared biconical reflectance spectra of 60 powdered meteorite samples, representing 50 different stony meteorites, were measured as analogues of asteroidal regolith. Representative samples were measured in directional hemispherical reflectance to assure that Kirchhoff's Law can be used to predict relative emissivity from the reflectance spectra. These spectral data confirm that the O-H fundamental absorption band near 2.9 microns is an extremely sensitive indicator of incipient alteration, which often has taken place in powdered meteorite samples exposed only to water vapor in the air. Such non-carbonaceous samples typically contain less than 1 percent water by weight. Likewise, the C-H fundamental absorption bands near 3.4 and 3.5 microns are equally sensitive indicators of contamination with volatile hydrocarbons, which can also be absorbed from the air. The heavy, macromolecular hydrocarbons native to chondrites do not display such heavy bands, making detection of these bands in remote sensing of asteroids unlikely. Despite the spectral artifacts introduced by alteration and hydrocarbon contamination, powdered stony meteorites display a wide variety of real spectral features that can be used for their identification, including residual reststrahlen bands, absorption bands, and the Christiansen feature. Researchers found that the wavelengths of the peaks or troughs of each of these spectral features can be used independently to infer meteorite composition, but the best results are obtained when the entire spectral curve is used, or at least the portion of it encompassed by the 8 to 14 micron atmospheric window, in a digital search library.

Salisbury, J. W.↗

Elimination of cloud effects in sensing ozone from 9.6 micron band.

Description of an objective method for extracting the spectral information from the 9.6 micron region pertaining to atmospheric ozone. This method has been developed by examining a large number of Nimbus 4 infrared interferometer-spectrometer spectra. The method is capable of eliminating, not only the effects of clouds, but also those of interference from the reststrahlen bands of desert sands.

Prabhakara, C.↗

The Mid-IR Spectral Effects of Darkening Agents and Porosity on the Silicate Surface Features of Airless Bodies

We systematically measured the mid-IR spectra of different mixtures of three silicates (antigorite, lizardite, and pure silica) with varying effective porosities and amounts of darkening agent (iron oxide and carbon). These spectra have broad implications for interpretation of current and future mission data for airless bodies, as well as for testing the capabilities of new instruments. Serpentines, such as antigorite and lizardite, are common to airless surfaces, and their mid-IR spectra in the presence of darkening agents and different surface porosities would be typical for those measured by spacecraft. Silica has only been measured in the plumes of Enceladus and presents exciting possibilities for other Saturn-system surfaces due to long range transport of E-ring material. Results show that the addition of the IR-transparent salt, KBr, to simulate surface porosity affected silicate spectra in ways that were not predictable from linear mixing models. The strengthening of silicate bands with increasing pore space, even when only trace amounts of KBr were added, indicates that spectral features of porous surfaces are more detectable in the mid-IR. Combining iron oxide with the pure silicates seemed to flatten most of the silicate features, but strengthened the reststrahlen band of the silica. Incorporating carbon with the silicates weakened all silicate features, but the silica bands were more resistant to being diminished, indicating silica may be more detectable in the mid-IR than the serpentines. We show how incorporating darkening agents and porosity provides a more complete explanation of the mid-IR spectral features previously reported on worlds such as Iapetus.

Young, Cindy L.↗

Spectral analysis of ALH 84001, a meteorite from Mars

ALH 84001 has recently been reclassified as a meteorite from Mars (SNC) and contains more than 90% orthopyroxene with minor chromite and accessory phases of augite, maskelynite, and carbonate. This meteorite represents a new class of igneous material from Mars. We have measured reflectance spectra of ALH 84001 as a chip as a powder, dry sieved to less than 125 microns to compare with previous spectral analyses of SNCs and remote observations of Mars. Spectra of the chip and powder in the visible-to-near-infrared region are shown. These spectra are composites of data measured with the RELAB bidirectional spectrometer from 0.3 to 2.55 microns and a Nicolet FTIR for longer wavelengths. As expected, the spectra of the chip have negative slopes and are significantly darker than the spectrum of the particulate sample, which has a positive slope. The strong absorptions near 1 micron and 2 microns are characteristic of low-Ca pyroxene and have band rninima of 0.925 microns and 1.930 microns. The strong absorption near 3 microns is characteristic of water. There is a distinct flattening in the spectrum between 1.0 and 1.5 microns indicating the presence of an additional absorption. This is interpreted to be the result of Fe(2+) in the M1 site of low-Ca pyroxene. Mid-infrared spectra showing the Christiansen feature and the reststrahlen bands are shown for spectra of the powder and of three different locations on the chip. These spectra exhibit several features in this range, some of which are associated with a specific region on the chip. Each of the spectra includes a doublet reststrahlen peak near 1100/cm, and peaks near 880 and 500/cm, which are typical for low-Ca pyroxenes. Weaker features at 940-1000/cm, 600-750/cm, and 530-560/cm are present in spectra from some locations on the chip, but not others, implying compositional and textural variation.

Bishop, J.↗

Wavelength Scaling of Widely-Tunable Terahertz Quantum-Cascade Metasurface Lasers

Terahertz (THz) external-cavity lasers based on quantum-cascade (QC) metasurfaces are emerging as widely-tunable, single-mode sources with the potential to cover the 1--6 THz range in discrete bands with milliwatt-level output power. By operating on an ultra-short cavity with a length on the order of the wavelength, the QC vertical-external-cavity surface-emitting-laser (VECSEL) architecture enables continuous, broadband tuning while producing high quality beam patterns and scalable power output. The methods and challenges for designing the metasurface at different frequencies are discussed. As the QC-VECSEL is scaled below 2 THz, the primary challenges are reduced gain from the QC active region, increased metasurface quality factor and its effect on tunable bandwidth, and larger power consumption due to a correspondingly scaled metasurface area. At frequencies above 4.5 THz, challenges arise from a reduced metasurface quality factor and the excess absorption that occurs from proximity to the Reststrahlen band. The results of four different devices — with center frequencies 1.8 THz, 2.8 THz, 3.5 THz, and 4.5 THz — are reported. Each device demonstrated at least 200 GHz of continuous single-mode tuning, with the largest being 650 GHz around 3.5 THz. The limitations of the tuning range are well modeled by a Fabry-Pérot cavity which accounts for the reflection phase of the metasurface and the effect of the metasurface quality factor on laser threshold. Lastly, the effect of different output couplers on device performance is studied, demonstrating a significant trade-off between the slope efficiency and tuning bandwidth.

47 OTHER INSTRUMENTATION↗

Modeling Wavelength Dependent Mid-infrared (5.5–25 μm) Optical Constants of Silicate Glasses: A Genetic Algorithm Approach

Wavelength-dependent mid-infrared (400–1,800 cm -1 ; 5.56–25 μm) optical constants (real and imaginary indices of refraction; n and k) are determined using reflectance spectra at a spectral sampling of 4 cm -1 for several silicate glasses of varying SiO 2 wt% which include (a) basaltic volcanic glass from Kilauea, Hawaii, (b) synthetic andesite, (c) two synthetic dacites, (d) obsidian volcanic glass from Mount Lassen, California, (e) synthetic rhyodacite, and (f) rhyolitic volcanic glass from Mexico. Because glasses are optically isotropic, no specific orientation was required for spectral measurements, and polished glass samples were measured at random orientations using micro-FTIR spectrometer. Lorentz-Lorenz dispersion theory and Fresnel reflectance model for high symmetry materials were used to model the optical constants by optimizing oscillator parameters in modeled spectra to match laboratory spectra. A genetic algorithm (GA) approach automatically finds the natural oscillators and their parameters for each spectrum, and then uses these parameters in a non-linear least squares optimization routine. The study compared spectral parameters such as Christiansen feature, reststrahlen bands (RBs), and the peaks centered around 860–1,100 (peak 1) and 400–480 cm -1 (peak 2) of n and k to their respective SiO 2 wt% of the glasses. CF, RBs, peak 1 of n and k, and peak 2 of n shift to higher wavenumbers with increased SiO 2 wt%, whereas peak 2 of k shifts to lower wavenumbers with increased SiO 2 wt%. Derived optical constants of these glasses will improve quantitative abundance mapping of volcanic materials on the surfaces of silicate targets in the Solar System.

58 GEOSCIENCES↗

Infrared-active phonon modes in single-crystal thorium dioxide and uranium dioxide

The infrared-active phonon modes, in single-crystal samples of thorium dioxide (ThO 2 ) and uranium dioxide (UO 2 ), were investigated using spectroscopic ellipsometry and compared with density functional theory. Both ThO 2 and UO 2 are found to have one infrared-active phonon mode pair [consisting of one transverse optic (TO) and one associated longitudinal optic (LO) mode], which is responsible for the dominant features in the ellipsometric data. Furthermore, at room temperature, our results for the mode pair’s resonant frequencies and broadening parameters are comparable with previous reflectance spectroscopy characterizations and density functional theory predictions. For ThO 2 , our ellipsometry and density function theory results both show that the LO mode broadening parameter is larger than the TO mode broadening. This signifies mode anharmonicity, which can be attributed to the intrinsic phonon–phonon interaction. In addition to the main mode pair, a broad low-amplitude impurity-like vibrational mode pair is detected within the reststrahlen band for both ThO 2 and UO 2 . Elevated temperature measurements were performed for ThO 2 in order to study the mechanisms by which the phonon parameters evolve with increased heat. The observed change in the TO resonant frequency is in excellent agreement with previous density functional calculations, which only consider volume expansion of the crystal lattice. This suggests that the temperature-dependent change in the TO frequency is primarily due to volume expansion. The change in the main mode pair’s broadening parameters is nearly linear within the temperature range of this study, which indicates the intrinsic anharmonic scattering (via cubic anharmonicities) as the main decay mechanism.

36 MATERIALS SCIENCE↗

Insights into hyperbolic phonon polaritons in h – BN using Raman scattering from encapsulated transition metal dichalcogenide layers

Alternative techniques for probing hyperbolic phonon polaritons (HPPs) in two-dimensional materials will support the development of the emerging technologies in this field. Previous reports have shown that it is possible for W Se 2 monolayers in contact with the hexagonal boron nitride (h– BN) to generate HPPs in the h– BN via Raman scattering. In this paper, we set out our results on HPP Raman scattering induced in h– BN by W Se 2 and Mo Se 2 monolayers including multiple resonances at which the Raman scattering is enhanced. Analysis of the observed Raman line shapes demonstrates that Raman scattering allows HPPs with wave vectors with magnitudes significantly in excess of 15 000 cm –1 to be probed. Finally, we present evidence that the Raman scattering can probe HPPs with frequencies less than the expected lower bound on the reststrahlen band, suggesting new HPP physics still waits to be discovered.

2-dimensional systems↗

Comparison of thermal emission spectroscopic measurements of the lunar surface - 1968-1990

Four sets of spectra of resolved locations on the lunar surface obtained by Earth-based telescopes since 1968 are compared. The results obtained show that there is good consistency among the datasets within limits of signal-to-noise, and that ranges of overlap in wavelength and major spectral differences due to both the Christiansen emission peak and reststrahlen bands can be detected in remote measurements of the moon in the thermal infrared wavelength region. The conclusion of Goetz (1968) that only minor differences exist on the lunar surface in the region of thermal emission is found to be incorrect. Direct comparison of the four highest quality spectroscopic experiments in the region of thermal emission from 7 to 14 microns, which collected spectra of spatially resolved locations on the lunar surface, shows that this wavelength region reveals major spectral differences among lunar locations.

Lucey, P. G.↗

Infrared (8-14 microns) remote sensing of soil particle size

Particle size of soils plays a significant role in erosion potential and other mechanical properties. Most soils are dominated by the residual mineral quartz, which displays prominent reststrahlen bands in the 8-14 microns atmospheric window. The Earth Observing System will likely provide world-wide multispectral imagery in the 8-14 microns region via the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) instrument. The ratio of ASTER bands 10/14 can be used to estimate particle size in soils, if other ASTER bands are used to minimize the confusion factors provided by soil moisture, vegetation cover, soil organic content, and the presence of abundant minerals other than quartz. Use of band ratios minimizes the effects of poor surface temperature estimates, but maximizes the need for high signal-to-noise data.

Salisbury, John W.↗

Mapping variations in weight percent silica measured from multispectral thermal infrared imagery - Examples from the Hiller Mountains, Nevada, USA and Tres Virgenes-La Reforma, Baja California Sur, Mexico

Remotely sensed multispectral thermal infrared (8-13 mu m) images are increasingly being used to map variations in surface silicate mineralogy. These studies utilize the shift to longer wavelengths in the main spectral feature in minerals in this wavelength region (reststrahlen band) as the mineralogy changes from felsic to mafic. An approach is described for determining the amount of this shift and then using the shift with a reference curve, derived from laboratory data, to remotely determine the weight percent SiO2 of the surface. The approach has broad applicability to many study areas and can also be fine-tuned to give greater accuracy in a particular study area if field samples are available. The approach was assessed using airborne multispectral thermal infrared images from the Hiller Mountains, Nevada, USA and the Tres Virgenes-La Reforma, Baja California Sur, Mexico. Results indicate the general approach slightly overestimates the weight percent SiO2 of low silica rocks (e.g. basalt) and underestimates the weight percent SiO2 of high silica rocks (e.g. granite). Fine tuning the general approach with measurements from field samples provided good results for both areas with errors in the recovered weight percent SiO2 of a few percent. The map units identified by these techniques and traditional mapping at the Hiller Mountains demonstrate the continuity of the crystalline rocks from the Hiller Mountains southward to the White Hills supporting the idea that these ranges represent an essentially continuous footwall block

Stock, Joann M.↗