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At least 307 records · Page 17

Exotic silicon phases synthesized through ultrashort laser-induced microexplosion: Characterization with Raman microspectroscopy

Exotic metastable phases of silicon formed under high pressure are expected to have attractive semiconducting properties including narrow band gaps that open up novel technological applications. Confined microexplosions induced by powerful ultrashort laser pulses have been demonstrated as an advanced tool for the creation of new high-pressure phases that cannot be synthesized by other means. Tightly focused laser pulses are used to generate localized modifications inside the material structure, providing the possibility for precise controlled band-gap engineering. In this study, noninvasive Raman spectroscopy was used for analysis of laser-modified zones in silicon and to determine the metastable high-pressure phases contained. Low laser energies induced the formation of amorphous-only silicon, while higher energies led to crystalline silicon polymorphs within the modifications, albeit under considerable residual stress up to 4.5 GPa. The presence of the structurally similar r8-Si, bc8-Si, and bt8-Si phases is revealed, as well as other yet to be identified phases, and the stacking-related 9R Si polytype is evidenced, presumably stress-induced by the highly compressed laser-modified zone. The ab initio random structure searching approach is used to calculate the Raman signatures and to help identify different Si polymorphs. The findings of this study by Raman spectroscopy from ultrashort laser-induced microexplosion sites may yield insights into the local structure and properties of new silicon metastable phases and the prospect of utilizing exotic phases for extending current applications.

36 MATERIALS SCIENCE↗

Electronic Raman scattering in the 2D antiferromagnet NiPS 3

Correlated-electron systems have long been an important platform for various interesting phenomena and fundamental questions in condensed matter physics. As a pivotal process in these systems, d-d transitions have been suggested as a key factor toward realizing optical spin control in two-dimensional (2D) magnets. However, it remains unclear how d-d excitations behave in quasi-2D systems with strong electronic correlation and spin-charge coupling. Here, we present a systematic electronic Raman spectroscopy investigation on d-d transitions in a 2D antiferromagnet—NiPS 3 , from bulk to atomically thin samples. Two electronic Raman modes originating from the scattering of incident photons with d electrons in Ni 2+ ions are observed at ~1.0 eV. This electronic process persists down to trilayer flakes and exhibits insensitivity to the spin ordering of NiPS 3 . Our study demonstrates the utility of electronic Raman scattering in investigating the unique electronic structure and its coupling to magnetism in correlated 2D magnets.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Photoluminescence and Raman spectroscopy of wide bandgap semiconductors damaged by deep-UV laser irradiation

The effects of a pulsed, focused, deep-UV (4.66 eV) laser on wide and ultra-wide bandgap semiconductors were investigated with photoluminescence (PL) and Raman spectroscopy. Three semiconductor single crystals were studied: silicon carbide (6H-SiC), gallium nitride (GaN), and gallium oxide (β-Ga 2 O 3 ). Atomic emission lines from neutral Ga or Si were observed during the laser-damage process. For all three semiconductors, PL mapping (3.49 eV laser excitation) of the damaged material revealed visible emission bands in the 2.6–2.8 eV range, attributed to point defects. Raman spectra (2.33 eV excitation) showed a reduction in the Raman peak intensities in the damaged region, along with weak PL bands around 1.9–2.1 eV.

36 MATERIALS SCIENCE↗

Simultaneous measurements of forward Thomson scattering and rotational Raman scattering in a weakly ionized plasma

This paper demonstrates a simultaneous Thomson scattering and rotational Raman scattering spectroscopy in a weakly ionized plasma in air. Thomson scattering was collected in the forward scattering direction, in order to compress the relative spectra width of Thomson scattering from the plasma. Simultaneous measurements of rotational Raman scattering were obtained in the same direction, which was not affected by the collection angles. The measurements thus yielded electron temperature (T e ) and electron number density (n e ) as well as gas temperature in a weakly ionized atmospheric pressure plasma. The separation of rotational Raman scattering and Thomson scattering occurred when the scattering angle decreased to 20 degrees in the plasma, where the air temperature was found to be 150 ± 25 °C, and electron temperature of the plasma was 0.587 ± 0.087 eV, and electron number density was (1.608 ± 0.416) × 1021 m-3. The technique could be used for various plasma and combustion diagnostics in realistic engineering environments.

He, Zichen (ORCID:0000000183159882)↗

Monolithic Spatial Heterodyne Raman Spectrometers (mSHRS): Toward highly miniature chemical sensors for deployment on moving platforms (Final Report, Phase I)

This report covers phase 1 (year 1) of the mSHRS project. Our ultimate long-term goal is to develop highly miniature Raman analyzers, known as spatial heterodyne Raman spectrometers (SHRS), that are deployable as in-situ chemical sensors on moving platforms. During Phase I (FY19/20) funding, our team focused our efforts solely on the key innovation needed toward realizing that goal: the development of the monolithic interferometer comprising the beam splitter and gratings with the appropriate design parameters and tolerances to enable Raman interferometry. We successfully developed and characterized the performance of the first monolithic SHRS devices including a monolithic version that incorporates field-widened optics. Our solid-state design approach integrated all optical components as a single monolithic unit for maintaining precise optical alignment during sensor operation, a requirement for operating in a vibration prone environment. This project has two principle activities: (1) Design and fabricate monolithic SHRS devices (i.e. monolithic device task) and (2) characterize the mSHRS devices in terms of performance (i.e. the Monolithic SHRS characterization task).

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Leveraging design of experiments to build chemometric models for the quantification of uranium (VI) and HNO3 by Raman spectroscopy

Partial least squares regression (PLSR) and support vector regression (SVR) models were optimized for the quantification of U(VI) (10–320 g L −1 ) and HNO 3 (0.6–6 M) by Raman spectroscopy with optimized calibration sets chosen by optimal design of experiments. The designed approach effectively minimized the number of samples in the calibration set for PLSR and SVR by selecting sample concentrations with a quadratic process model, despite complex confounding and covarying spectral features in the spectra. The top PLS2 model resulted in percent root mean square errors of prediction for U(VI), HNO 3 , and NO 3 − of 3.7%, 3.6%, and 2.9%, respectively. PLS1 models performed similarly despite modeling an analyte with a majority linear response (i.e., uranyl symmetric stretch) and another with more covarying vibrational modes (i.e., HNO 3 ). Partial least squares (PLS) model loadings and regression coefficients were evaluated to better understand the relationship between weaker Raman bands and covarying spectral features. Support vector machine models outperformed PLS1 models, resulting in percent root mean square error of prediction values for U(VI) and HNO 3 of 1.5% and 3.1%, respectively. The optimal nonlinear SVR model was trained using a similar number of samples (11) compared with the PLSR model, even though PLS is a linear modeling approach. The generic D-optimal design presented in this work provides a robust statistical framework for selecting training set samples in disparate two-factor systems. This approach reinforces Raman spectroscopy for the quantification of species relevant to the nuclear fuel cycle and provides a robust chemometric modeling approach to bolster online monitoring in challenging process environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Raman scattering cross section for N2O4.

Measurement of the Raman scattering cross section for N2O4 at a Raman shift of 7.3 micron, using a Q-switched ruby laser as an excitation source. The cross section for N2 at a Raman shift of 4.3 micron was also measured and compared with the value given by Leonard (1970).

Chen, C. J.↗

Experimental investigation of transient stimulated Raman scattering in a linearly dispersionless medium.

The results of numerical calculations of the transient stimulated Raman scattering reported previously have been verified experimentally under conditions where both linear dispersion and self-focusing effects were negligible. The existence of a delay between maxima of the laser and Stokes pulses is experimentally demonstrated for the first time, while the pulse shortening in time via Raman scattering is established more firmly than in previous work. The incident-laser-pulse duration, generated-Stokes-pulse duration, and delay between intensity maxima for the laser and Stokes pulses were measured with the two-photon absorption-fluorescence technique. The effective phonon-dephasing time is determined via spontaneous Raman scattering. By using these measured quantities, inferences are made as to the magnitude of the transient gain and the shape of the exciting picosecond laser pulse.

Carman, R. L.↗

Remote measurements of the atmosphere using Raman scattering.

Raman optical radar measurements of the atmosphere demonstrate that the technique may be used to obtain quantitative measurements of the spatial distribution of individual atmospheric molecular trace constituents (in particular water vapor) and of the major constituents. It is shown that monitoring Raman signals from atmospheric nitrogen aids in interpreting elastic scattering measurements by eliminating attenuation effects. In general, the experimental results show good agreement with independent meteorological measurements. Finally, experimental data are utilized to estimate the Raman backscatter cross section for water vapor excited at 3471.5 A.

Melfi, S. H.↗

Remote monitoring of the atmosphere with Raman LIDAR

Some of the Raman LIDAR applications for monitoring the atmosphere are reviewed. Following a definition of Raman scattering, the basic design of a Raman LIDAR system is described and the atmosphere-monitoring potentialities and limitations of the system are discussed, along with the possibilities of further progress.

Melfi, S. H.↗

Simultaneous Raman and laser velocimeter measurements

The feasibility of performing Raman and laser velocimeter measurements simultaneously is demonstrated, and it is shown that the background radiation associated with the Mie scattering and large particulate concentrations does not saturate or distort the relatively weak rotational Raman signals. Under stringent conditions of low static gas densities and large particulate concentrations, Raman density and temperature measurements agree to within plus or minus 5% of the calculated values.

Hillard, M. E., Jr.↗

Raman backscatter measurement research on water vapor systems

Raman backscatter techniques proved to be a useful remote sensing tool, whose full potential has not been realized. The types of information available from laser probes in atmospheric studies are reviewed. Detection levels for known Raman cross sections are calculated using the laser radar equation. Laboratory experiments performed for H2O, N2, SO2, O2 and HCL indicate that accurate wavelength cross sections need to be obtained, as well as more emphasis on obtaining accurate Raman cross sections of molecular species at wavelengths in the ultraviolet spectra.

Workman, G. L.↗

Remote measurement of ocean temperature from depolarization in Raman scattering

Ocean temperatures may be mapped in three dimensions from an aircraft down to depths of 2 to 4 attenuation lengths by monitoring Raman radiation backscattered from a laser beam. This paper describes laboratory experiments on the temperature dependence of Raman spectra of saline solutions and calculations of the expected performance of a field system. The Raman technique is of greatest potential utility in coastal and estuarine waters where gradients are relatively high. It is estimated that seawater temperature may be measured to a statistical precision of 0.5 C at depths to four attenuation lengths in two meter water, using one Joule of transmitted laser energy.

Chang, C. H.↗

Raman spectra of gaseous and solid N2F4

The Raman spectrum of gaseous N2F4 at a pressure of 760 Torr was recorded with a spectral slit width of 3 kaysers. Ten of the expected eleven fundamentals of the symmetric motions of both the gauche and trans isomers give rise to strongly polarized Raman lines. These new data require a reassignment of some of the fundamentals for both the C2 and C2h conformers. The Raman of the solid at 18 K was also recorded. Both conformers were found in the solid even after annealing the sample for 9 hr at a temperature of 101.6 K and 3 hr at a temperature of 106.8 K. Bands attributable to the gauche isomer became more intense relative to those for the trans isomer after several hours of annealing.

Durig, J. R.↗

Stimulated Raman scattering and the extreme high-velocity H2O maser features in W49

Stimulated Raman scattering of the intense 22.2-GHz water-vapor maser radiation within W49 is examined as a possible explanation of the extremely broad spectrum of W49 extending to + or - 200 km/sec apparent Doppler velocity. Under the most favorable conditions, Raman scattering from ammonia molecules is calculated to be observable. It is unlikely that the Raman process contributes appreciably in the case of W49, as it fails to predict the observed spatial and spectral distribution of the radiation.

Boyd, R. W.↗

Third-order nonlinearities in molecular hydrogen - Two-photon resonance enhanced third-harmonic generation and Raman scattering

Effects of quantum mechanical interferences on third-order susceptibilities in molecules are studied. First principle calculations for molecular hydrogen are presented and shown to agree with results derived from experimental stimulated Raman gain and spontaneous Raman cross-section data. 10 percent third-harmonic conversion efficiency in H2 at 1 atm without phase matching should require a 150 MW per sq cm at 4.81 microns. As little as 5.9-MW power is sufficient when the beam is properly focused. Resonance Raman scattering (RRS) is proposed for experimentally investigating the interference effects, which tend to reduce the strength of third-order nonlinear susceptibilities.

Pan, C.-L.↗

Coherent anti-Stokes Raman spectroscopy - Spectra of water vapor in flames

The results of experimental measurements of the coherent anti-Stokes Raman spectra of water vapor in flames are reported. A pulsed, frequency-doubled neodymium laser was used to supply the pump beam and to pump a dye laser to provide a broadband Stokes beam at 6600 A. Spectra were obtained in the postflame region of a premixed methane-air flame in the Raman frequency shift region of the symmetric stretch mode (3651.7 kaysers) at an approximate temperature of 1675 K. A theoretical calculation of the coherent anti-Stokes Raman spectrum of water vapor at this temperature was made, taking into account only isotropic Q-branch transitions, and using the energy level data of Floud et al. (1976). The theoretical prediction is shown essentially to reproduce all qualitative features of the experimental spectrum, and to exhibit a strong temperature dependence.

Hall, R. J.↗

Application of Raman diagnostics to combustion

The use of laser Raman diagnostic techniques to measure the specie concentrations and their temperatures in combustion flow fields is discussed. The system designed to measure the specie concentrations, which included a ruby laser and a photodiode to trip the laser at the maximum light and heat output of the combustion process, is described and problems encountered in developing the system are reported. Photographs of the combustion process are presented and analyzed detailing the evolution of the combustion in terms of the photodiode and the lack of a noticeable Raman-Stokes signal. The absence of the Raman-Stokes signal is discussed.

Lederman, S.↗