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At least 343 records · Page 19

Vertically Resolved Retrievals of Aerosol Concentrations and Effective Radii from the DOE Combined HSRL and Raman lidar Measurement Study (CHARMS) Merged High-Spectral-Resolution Lidar-Raman Lidar Data Set

The Department of Energy’s (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility is a key component of DOE’s research strategy to address global climate change. The objective of the ARM Facility is to provide an experimental testbed for studying important atmospheric effects, particularly cloud and aerosol processes, and testing parameterizations of these processes for use in climate change models. ARM observational sites include a broad array of instruments to characterize cloud and aerosol properties, atmospheric state variables, and incoming and outgoing radiation. Advanced lidar systems provide valuable and unique information about the atmospheric column. We examine the potential for providing vertically resolved information about aerosol size and concentration with a combination of two such lidar systems, the Raman lidar and the High-Spectral-Resolution Lidar (HSRL). Currently ARM has a limited ability to remotely measure profiles of aerosol optical and microphysical properties on an operational basis. Although the Southern Great Plains (SGP), Eastern North Atlantic (ENA), and North Slope of Alaska (NSA, Oliktok Point location only) Raman lidars provide profiles of aerosol backscatter and extinction at 355 nm, additional information is required to better characterize the impacts of aerosols on radiation and clouds. Recent advances in lidar retrieval theory and algorithm development (Müller et al. 1999, 2014; Chemyakin et al. 2014) demonstrate that multi-wavelength lidar retrieval algorithms that use measurements of aerosol extinction at both 355 and 532 nm and backscatter at 355, 532, and 1064 nm have the potential to constrain both the aerosol optical (e.g., complex index of refraction, scattering, etc.) and microphysical properties (e.g., effective radius, concentration). This advancement greatly increases the utility of the remote-sensed aerosol observations. Based on this work, the HSRL group at the National Aeronautics and Space Administration (NASA)’s Langley Research Center (LaRC) developed automated algorithms for retrieving aerosol optical and microphysical properties, demonstrated these retrievals using data from the unique NASA/LaRC airborne multi-wavelength HSRL-2 system, and validated these retrievals using coincident airborne in situ data (Müller et al. 2014; Sawamura et al. 2017). We report here on the use of ARM instrumentation to gather a multi-wavelength ground-based lidar data set to test such retrievals. Continuous (24/7) operation of the co-located SGP Raman lidar and University of Wisconsin (UW) HSRL during the 10-week Combined HSRL and Raman lidar Measurement Study (CHARMS) (mid-July through September 2015) allowed the acquisition of a unique, multi-wavelength ground-based lidar data set. The ARM SGP Raman lidar (RLID) measured profiles of aerosol backscatter, extinction, and depolarization at 355 nm and profiles of water vapor mixing ratio and temperature. The UW HSRL simultaneously measured profiles of aerosol backscatter, extinction and depolarization at 532 nm and aerosol backscatter at 1064 nm. This RLID+HSRL combination provided a test data set to investigate these more advanced aerosol retrieval techniques with the potential to greatly improve aerosol characterization in the lower atmosphere.

54 ENVIRONMENTAL SCIENCES↗

An Optothermal Raman Model Accounting for Convection, Radiation, and Substrate Effects for Evaluation of the Thermal Conductivity of Two‐Dimensional Coatings

Thermal conductivity of two‐dimensional (2D) materials is important to characterize as this will govern thermal transport physics in the various thermal and energy applications benefitting from the unique properties of these materials. Here, analytical and numerical techniques are presented to determine the thermal conductivity and interfacial conductance of a 2D material coating using confocal micro‐Raman spectroscopy as a noncontact diagnostic. While several methods have been proposed for calculating the values of thermal conductivity, interfacial conductance, and spatial temperature profile, these models often do not consider effects of radiation, convection, and substrate resistance on the temperature and heat flux profiles. We present a model to calculate the thermal conductivity and interfacial conductance which accounts for convection, radiation, and substrate effects to characterize a variety of 2D material coatings, which is demonstrated using large area graphene transferred onto copper and nickel substrates. Convection and radiation effects are found to have a negligible effect on the temperature profile of supported coatings, while the substrate effects have a considerable effect and therefore impact the quantification of thermal conductivity and interfacial conductance in addition to limiting the spatial resolution of the technique. These findings will allow for more accurate and reproducible extraction of the thermal conductivity of graphene and other 2D material coatings when employing noncontact optothermal Raman spectroscopy methods.

2D coatings↗

Raman spectroscopy of neutron irradiated silicon carbide

The effects of neutron irradiation on microstructural evolution and the resultant changes in physical and mechanical properties are of critical importance for the development of silicon carbide (SiC) materials for nuclear applications. This study neutron-irradiated βSiC under a wide range of conditions at temperatures between 235 and 750°C and neutron doses of 0.01–11.8 displacements per atom, and then evaluated the effects on the SiC structure using Raman spectroscopy. The SiC optical phonon lines were shifted to lower wavenumbers by irradiation. Correlations were found among the wavenumber of the longitudinal optical phonon line, irradiation-induced swelling, and irradiation temperature. The peak shift also correlated indirectly with decreasing thermal conductivity of irradiated SiC. The irradiation-induced peak shift is explained by combinations of lattice strain, reduction of the elastic modulus, and other factors including decreasing coherent domain size. These findings bridge irradiation-induced microstructural changes and property changes and illustrate how Raman spectroscopy is a useful tool for nondestructively assessing irradiated SiC materials for nuclear applications.

Koyanagi, T.↗

Raman Scattering of Light by Molecules of Methyl Orange Dye on the Surface of Silicon Containing Ion-Synthesized Silver Nanoparticles

The possibility of using a new composite material based on porous silicon containing silver nanoparticles and synthesized by means of a unique implantation nanotechnology as an optically sensitive material in biological and chemical sensors is tested experimentally. It is demonstrated that detection of small amounts of the studied organic substance (methyl orange dye) is possible due to the effect of surface-enhanced Raman scattering (SERS) from the molecules affected by the local electromagnetic field of the silver nanoparticles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Nano-immunoassay with improved performance for detection of cancer biomarkers

Nano-immunoassay utilizing surface-enhanced Raman scattering (SERS) effect is a promising analytical technique for the early detection of cancer. In its current standing the assay is capable of discriminating samples of healthy individuals from samples of pancreatic cancer patients. Further improvements in sensitivity and reproducibility will extend practical applications of the SERS-based detection platforms to wider range of problems. In this report, we discuss several strategies designed to improve performance of the SERS-based detection system. We demonstrate that reproducibility of the platform is enhanced by using atomically smooth mica surface as a template for preparation of capture surface in SERS sandwich immunoassay. Furthermore, the assay's stability and sensitivity can be further improved by using either polymer or graphene monolayer as a thin protective layer applied on top of the assay addresses. The protective layer renders the signal to be more stable against photo-induced damage and carbonaceous contamination.

59 BASIC BIOLOGICAL SCIENCES↗

An operando surface enhanced Raman spectroscopy (SERS) study of carbon deposition on SOFC anodes

Thermally robust and chemically inert Ag@SiO 2 nanoprobes are employed to provide the surface enhanced Raman scattering (SERS) effect for an in situ/operando study of the early stage of carbon deposition on nickel-based solid oxide fuel cell (SOFC) anodes. The enhanced sensitivity to carbon enables the detection of different stages of coking, offering insights into intrinsic coking tolerance of material surfaces. Application of a thin coating of gadolinium doped ceria (GDC) enhances the resistance to coking of nickel surfaces. The electrochemically active Ni–YSZ interface appears to be more active for hydrocarbon reforming, resulting in the accumulation of different hydrocarbon molecules, which can be readily removed upon the application of an anodic current. Operando SERS is a powerful tool for the mechanistic study of coking in SOFC systems. It is also applicable to the study of other catalytic and electrochemical processes in a wide range of conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparative study of plant responses to carbon-based nanomaterials with different morphologies

The relationship between the morphology of carbon-based nanomaterials (CBNs) and the specific response of plants exposed to CBNs has not been studied systematically. Here, we prove that CBNs with different morphologies can activate cell growth, germination, and plant growth. A tobacco cell culture growth was found to increase by 22%–46% when CBNs such as helical multi-wall carbon nanotubes (MWCNTs), few-layered graphene, long MWCNTs, and short MWCNTs were added to the growth medium at a concentration of 50 μg ml –1 . The germination of exposed tomato seeds, as well as the growth of exposed tomato seedlings, were significantly enhanced by the addition of all tested CBNs. The presence of CBNs inside exposed seeds was confirmed by transmission electron microscopy and Raman spectroscopy. The effects of helical MWCNTs on gene expression in tomato seeds and seedlings were investigated by microarray technology and real time-PCR. Helical MWCNTs affected a number of genes involved in cellular and metabolic processes and response to stress factors. It was shown that the expression of the tomato water channel gene in tomato seeds exposed to helical MWCNTs was upregulated. Furthermore, these established findings demonstrate that CBNs with different morphologies can cause the same biological effects and share similar mechanisms in planta .

36 MATERIALS SCIENCE↗

Atomic Coherence of 2 Minutes and Instability of 1.5 × 10 −18 at 1 s in a Wannier-Stark Lattice Clock

We explore the limits of atomic coherence and measurement precision in a 87 Sr optical lattice clock. We perform a detailed characterization of key effects, including lattice Raman scattering and atomic collisions in a shallow lattice configuration, determining a 174(28) s 3 𝑃 0 clock state lifetime. Investigation of atomic coherence across a range of lattice depths and atomic densities reveals decoherence mechanisms related to photon scattering and atomic interaction. At a reduced density, we observe a coherence time of 118(9) s, approaching the fundamental limit set by spontaneous emission. Guided by this coherence understanding, we demonstrate a clock instability for an atomic ensemble of 1.5 × 10 −18 at 1 s in fractional frequency units. Our results are important for further advancing the state of the art of an optical lattice clock for fundamental physics applications.

atomic, optical, & lattice clocks↗

Laser Crystallization and Dopant Activation of a-Si:H Carrier-Selective Layer in TOPCon Si Solar Cells

Herein, we present a pulsed-laser processing method for crystallization and dopant activation of a highly n-doped amorphous silicon (a-Si:H) carrier-selective layer in a tunnel oxide passivated contact (TOPCon) Si solar cell structure. Here, the laser method provides enhanced conductivity and implied open circuit voltage while reducing emitter saturation current density and surface heating, as opposed to conventional high-temperature furnace annealing of the bulk Si wafer with a TOPCon structure. We identify an appropriate laser wavelength, fluence, and layer thickness using modeling and simulations. Raman and Hall effect measurements demonstrate increased crystallinity and dopant activation, whereas photoconductive decay shows enhanced surface and interface passivation quality. Additionally, we examine the role of subsequent SiNx deposition on further improving the passivation of laser-processed TOPCon layers to achieve a 5.9 kΩ/sq film sheet resistance, 2 ms effective carrier lifetime, 718 mV implied open-circuit voltage (iVOC), and 8.6 fA/cm 2 one-side recombination current density (J0) with the potential for further passivation improvement via laser process and a-Si layer thickness optimization.

14 SOLAR ENERGY↗

Water Raman normalization of airborne laser fluorosensor measurements - A computer model study

The technique for normalizing airborne lidar measurements of chlorophyll fluoresence by the water Raman scattering signal is investigated for laser-excitation wavelengths of 480 and 532 nm using a semianalytic Monte Carlo methodology (SALMON). The signal-integration depth for chlorophyll fluorescence Z(90,F), is found to be insensitive to excitation wavelength and ranges from a maximum of 4.5 m in clearest waters to less than 1 m at a chlorophyll concentration of 20 microgram/liter. For excitation at 532 nm, the signal-integration depth for Raman scattering, Z(90,R), is comparable to Z(90,F). For excitation at 480 nm, Z(90,R) is four times as large as Z(90,F) in clearest waters but nearly equivalent at chlorophyll concentrations greater than 2-3 microgram/liter. Absolute signal levels are stronger with excitation at 480 nm than with excitation at 532 nm, but this advantage must be weighed against potential ambiguities resulting from different integration depths for the fluorescence and Raman scattering signals in clearer waters. To the precision of the simulations, Raman normalization produces effectively linear response to chlorophyll concentration for both excitation wavelengths.

Poole, L. R.↗

Subsurface Sampling and Sensing Using Burrowing Moles

Finding evidence for life on Mars will likely require accessing the subsurface since the Martian surface is both hostile to life and to preservation of biosignatures due to the cold dry conditions, the strong W environment, and the presence of strong oxidants. Systems are needed to probe beneath the sun and oxidant baked surface of Mars and return samples to the surface for analysis or to bring the instrument sensing underground. Recognizing this need, the European Space Agency incorporated a small subsurface penetrometer or Mole onto the Beagle 2 Mars lander. Had the 2003 landing been successful, the Mole would have collected samples from 1-1.5 m depth and delivered them to an organic analysis instrument on the surface. The de- vice called the Planetary Underground Tool (PLUTO), also measured soil mechanical and thermophysical properties. Constrained by the small mass and volume allowance of the Beagle lander, the PLUTO mole was a slender cylinder only 2 cm diameter and 28 cm long equipped with a small sampling device designed to collect samples and bring them to the surface for analysis by other instrument. The mass of the entire system including deployment mechanism and tether was 1/2 kg. sensor package underground to make in situ measurements. The Mars Underground Mole (MUM) is a larger Mole based on the PLUTO design but incorporating light collection optics that interface to a fiber optic cable in the tether that transmits light to a combined stimulated emission Raman Spectrometer and Short Wave Infrared (SWIR) reflectance Spectrometer with sensitivity from 0.7 to 2.5 micrometers. This instrument is called the Dual Spectral Sensor and uses a Digital Array Scanning Interferometer as the sensor technology, a type of fourier transform interferometer that uses fixed element prisms and thus is highly rugged compared to a Michaelson interferometer. Due to the size limitations of an on-Mole instrument compartment, and the availability of a tether, the sensor head, light sources, and control electronics for the instrument are on the surface. The DSS sensor is capable of sensing a wide range of minerals relevant to Mars Astrobiology objectives including hydrated minerals, clays, carbonates, sulfates, and ice. Additionally, Raman spectroscopy is effective for detecting organics. The MUM is designed to achieve a maximum depth of penetration of 5 m in Mars regolith and can be repeatedly deployed and retrieved. The ability to perform repeated sampling, combined with the low mass and power requirements, means that Moles could be incorporated into a rover mission as well as used on a stationary platform. The Mole mechanism is a pointed slender cylinder that advances into soil by way of an internal sliding hammer mechanism. Part of the energy released by the spring-loaded hammer with each shock is transferred to the Mole casing and from there to the soil, resulting in penetration by displacing and compressing the surrounding soil. A backwards-directed impulse as a re- action to each forward shock is transferred via a suppressor mass against a second weaker spring allowing forward motion without requiring reactive forces provided by the lander. The Mole tip can be opened to collect soil samples. The Mole casing is tethered to a supporting mechanism that supplies power. Components supporting the Mole on the surface include a launch tube, tether reel and winch for pulling in tether, in addition to the tether itself.

Stoker, C. R.↗

Observations over Hurricanes from the Ozone Monitoring Instrument

There is an apparent inconsistency between the total column ozone derived from the total ozone mapping spectrometer (TOMS) and aircraft observations within the eye region of tropical cyclones. The higher spectral resolution, coverage, and sampling of the ozone monitoring instrument (OMI) on NASA s Aura satellite as compared with TOMS allows for improved ozone retrievals by including estimates of cloud pressure derived simultaneously using the effects of rotational Raman scattering. The retrieved cloud pressures from OM1 are more appropriate than the climatological cloud-top pressures based on infrared measurements used in the TOMS and initial OM1 algorithms. We find that total ozone within the eye of hurricane Katrina is significantly overestimated when we use climatological cloud pressures. Using OMI-retrieved cloud pressures, total ozone in the eye is similar to that in the surrounding area. The corrected total ozone is in better agreement with aircraft measurements that imply relatively small or negligible amounts of stratospheric intrusion into the eye region of tropical cyclones.

Joiner, J.↗

Incorporation of metal nanoparticles into wood substrate and methods

Metal nanoparticles were incorporated into wood. Ionic liquids were used to expand the wood cell wall structure for nanoparticle incorporation into the cell wall structure. Nanoparticles of elemental gold or silver were found to be effective surface enhanced Raman spectroscopy (SERS) imaging contrast or sensing agents. Nanoparticles of elemental iron were found to be efficient microwave absorbers and caused localized heating for disrupting the integrity of the lignocellulosic matrix. Controls suggest that the localized heating around the iron nanoparticles reduces losses of cellulose in the form of water, volatiles and CO.sub.2. The ionic liquid is needed during the incorporation process at room temperature. The use of small amounts of ionic liquid combined with the absence of an ionic liquid purification step and a lower energy and water use are expected to reduce costs in an up-scaled pretreatment process.

59 BASIC BIOLOGICAL SCIENCES↗

Sensitive Phonon-Based Probe for Structure Identification of 1T' MoTe 2

In this work, by combining transmission electron microscopy and polarized Raman spectroscopy for the 1T' MoTe 2 flakes with different thicknesses, we found that the polarization dependence of Raman intensity is given as a function of excitation laser wavelength, phonon symmetry, and phonon frequency, but has weak dependence on the flake thickness from few-layer to multilayer. Additionally, the frequency of Raman peaks and the relative Raman intensity are sensitive to flake thickness, which manifests Raman spectroscopy as an effective probe for thickness of 1T' MoTe 2 . This work demonstrates that polarized Raman spectroscopy is a powerful and nondestructive method to quickly identify the crystal structure and thickness of 1T' MoTe 2 simultaneously, which opens up opportunities for the in situ probe of anisotropic properties and broad applications of this novel material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DFT study of Raman scattering spectra of complexes of spiropyrans with the silver cluster

The computational simulation of structure, energy and spectral characteristics of spiropyrans and their complexes with the cluster containing ten silver atoms was carried out using the density functional theory method (B3LYP/6-31G(d,p)/SDD). A competitive coordination of oxygen-containing substituents in the indoline and benzopyran moieties in spirocyclic molecules to the metal atoms was studied and an effect of position of donor groups on the activity of CO vibrational bands was established in the calculated Raman spectra. We revealed compounds, whose trans-trans-trans isomers upon a complexation with the silver cluster are characterized by the more than 100 times enhanced activity of band associated with the valence vibrations of CO bond in the Raman spectrum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coherent scattering of an atom in the field of a standing wave under conditions of initial quantum correlation of subsystems

Coherent scattering of a two-level atom in the field of a quantized standing wave of a micromaser is considered under conditions of initial quantum correlation between the atom and the field. Such a correlation can be produced by a broadband parametric source. The interaction leading to scattering of the atom from the nonuniform field occurs in the dispersion limit or in the wing of the absorption line of the atom. Apart from the quantized field, the atom simultaneously interacts with two classical counterpropagating waves with different frequencies, which are acting in the plane perpendicular to the atom’s propagation velocity and to the wavevector of the standing wave. Joint action of the quantized field and two classical waves induces effective two-photon and Raman resonance interaction on the working transition. The effective Hamiltonian of the interaction is derived using the unitary transformation method developed for a moving atom. A strong effect is detected, which makes it possible to distinguish the correlated initial state of the atom and the field in the scattering of atom from the state of independent systems. For all three waves, scattering is not observed when systems with quantum correlation are prepared using a high-intensity parametric source. Conversely, when the atom interacts only with the nonuniform field of the standing wave, scattering is not observed in the case of the initial factorized state.

74 ATOMIC AND MOLECULAR PHYSICS↗

Tunable zinc interstitial related defects in ZnMgO and ZnCdO films

We report tunable band gap of ZnO thin films grown on quartz substrates by radio frequency magnetron sputtering. The zinc interstitial (Zn{sub i}) defects in ZnO films were investigated by X-ray diffraction, Raman scattering, Auger spectra, first-principle calculations, and Hall measurement. Undoped ZnO film exhibits an anomalous Raman mode at 275 cm{sup −1}. We first report that 275 cm{sup −1} mode also can be observed in ZnO films alloyed with Mg and Cd, whose Raman intensities, interestingly, decrease and increase with increasing Mg and Cd alloying content, respectively. Combined with the previous investigations, it is deduced that 275 cm{sup −1} mode is attributed to Zn{sub i} related defects, which is demonstrated by our further experiment and theoretical calculation. Consequently, the concentration of Zn{sub i} related defects in ZnO can be tuned by alloying Mg and Cd impurity, which gives rise to different conductivity in ZnO films. These investigations help to further understand the controversial origin of the additional Raman mode at 275 cm{sup −1} and also the natural n-type conductivity in ZnO.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗