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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Some optical and electron microscope comparative studies of excimer laser-assisted and nonassisted molecular-beam epitaxically grown thin GaAs films on Si

The quality of GaAs thin films grown via MBE under pulsed excimer laser irradiation on Si substrates is examined in both laser-irradiated and nonirradiated areas using Raman scattering, Rayleigh scattering, and by photoluminescence (PL), as a function of temperature, and by TEM. The temperature dependence of the PL and Raman peak positions indicates the presence of compressive stress in the thin GaAs films in both laser-irradiated and nonirradiated areas. This indicates incomplete homogeneous strain relaxation by dislocations at the growth temperature. The residual compressive strain at the growth temperature is large enough such that even with the introduction of tensile strain arising from the difference in thermal expansion coefficients of GaAs and Si, a compressive strain is still present at room temperature for these thin GaAs/Si films.

Lao, Pudong↗

Development of a Technique for Separating Raman Scattering Signals from Background Emission with Single-Shot Measurement Potential

A novel technique for extracting Q-branch Raman signals scattered by a diatomic species from the emission spectrum resulting from the irradiation of combustion products using a broadband excimer laser has been developed. This technique is based on the polarization characteristics of vibrational Raman scattering and can be used for both single-shot Raman extraction and time-averaged data collection. The Q-branch Raman signal has a unique set of polarization characteristics which depend on the direction of the scattering while fluorescence signals are unpolarized. For the present work, a calcite crystal is used to separate the horizonal component of a collected signal from the vertical component. The two components are then sent through a UV spectrometer and imaged onto an intensified CCD camera separately. The vertical component contains both the Raman signal and the interfering fluorescence signal. The horizontal component contains the fluorescence signal and a very weak component of the Raman signal; hence, the Raman scatter can be extracted by taking the difference between the two signals. The separation of the Raman scatter from interfering fluorescence signals is critically important to the interpretation of the Raman for cases in which a broadband ultraviolet (UV) laser is used as an excitation source in a hydrogen-oxygen flame and in all hydrocarbon flames. The present work provides a demonstration of the separation of the Raman scatter from the fluorescence background in real time.

Hartfield, Roy J., Jr.↗

Stimulated Raman-scattering threshold behavior of binary mixture micrometer-sized droplets

Stimulated Raman scattering (SRS) from binary liquid mixture micrometer-sized droplets irradiated by nanosecond laser pulses exhibits previously unreported features. SRS emission at wavelength shifts corresponding to combination frequencies of the individual component Stokes shifts are observed in droplets but not in bulk mixtures. Furthermore, droplet SRS thresholds are determined by component refractive indices and concentrations, in contrast to bulk thresholds, for which self-focusing likely plays a dominant role.

Biswas, Abhijit↗

Laser-induced stimulated Raman scattering in the forward direction of a droplet - Comparison of Mie theory with geometrical optics

This paper uses Mie theory to treat electromagnetic scattering and to evaluate field enhancement in the forward direction of a small droplet irradiated by a high-energy beam and compares the results of calculations with the field-enhancement evaluation obtained via geometrical optics treatment. Results of this comparison suggest that the field enhancement located at the critical ring region encircling the axis in the forward direction of the droplet can support laser-induced Raman scattering. The results are supported by experimental observations of the interaction of a 120-micron-diam water droplet with a high-energy Nd:YAG laser beam.

Srivastava, Vandana↗

Observations of stimulated Raman scattering and laser-induced breakdown in millimeter-sized droplets

We report the first observations, to our knowledge, of nonlinear optical effects in large (millimeter-sized) droplets. Stimulated Raman scattering (SRS) and laser-induced breakdown (LIB) are simultaneously observed in acoustically levitated millimeter-sized glycerol droplets irradiated by either a frequency-doubled (532-nm) or a frequency-tripled (355-nm) Nd:YAG laser. The two processes, which occur above a nearby coincident irradiation threshold, are conjectured to arise from a common initiation mechanism: self-focusing. LIB generates vapor bubbles within the droplet, resulting in the quenching of SRS emission.

Biswas, A.↗

Airborne oceanographic lidar participation in the US Joint Global Ocean Flux Study (JGOFS)

The U.S. JGOFS is part of a major international field experiment which the National Science Foundation (NSF) is conducting during the decade. It will combine ship and aircraft data collected in both the Atlantic and Pacific oceans. The primary data collected by the Airborne Oceanographic Lidar (AOL) is laser-induced chlorophyll fluorescence together with the concurrent laser-induced water Raman backscatter and phycoerythrin fluorescence. Passive solar-induced up-welling radiances and down-welling solar irradiance are also acquired. Results from the 1989 Atlantic mission as well as plans for use of the new long-range Wallops P-3 during the upcoming Equatorial Pacific mission are presented.

Hoge, Frank E.↗

Thermodynamic measurements in a high pressure hydrogen-oxygen flame using Raman scattering from a broadband excimer laser

Raman scattering is an inelastic molecular scattering process in which incident radiation is reemitted at a fixed change in frequency. Raman spectroscopy can be used to measure the number density and temperature of the irradiated species. The strength of the Raman signal is inversely proportional to the wavelength raised to the fourth power. Consequently, high signal to noise ratios are obtained by using ultraviolet (UV) excitation sources. Using UV sources for Raman Spectroscopy in flames is complicated by the fact that some of the primary constituents in hydrogen-oxygen combustion absorb and reemit light in the UV and these fluorescence processes interfere with the Raman signals. This problem has been handled in atmospheric pressure flames in some instances by using a narrowband tunable excimer laser as a source. This allows for detuning from absorption transitions and the elimination of interfering fluorescence signals at the Raman wavelengths. This approach works well in the atmospheric pressure flame; however, it has two important disadvantages. First, injection-locked narrowband tunable excimer lasers are very expensive. More importantly, however, is the fact that at the high pressures characteristic of rocket engine combustion chambers, the absorption transitions are broadened making it difficult to tune to a spectral location at which substantial absorption would not occur. The approach taken in this work is to separate the Raman signal from the fluorescence background by taking advantage of the fact that Raman signal has nonisotropic polarization characteristics while the fluorescence signals are unpolarized. Specifically, for scattering at right angles to the excitation beam path, the Raman signal is completely polarized. The Raman signal is separated from the fluorescence background by collecting both horizontally and vertically polarized signals separately. One of the polarizations has both the Raman signal and the fluorescence background while the other has only the fluorescence signal. The Raman scatter is the difference between the signals. By choosing an appropriate optical setup, both signals can be obtained simultaneously with the same monochromator; hence, time resolved measurements are possible using this approach.

Hartfield, Roy, Jr.↗

Organic Products of Fatty Acid and Magnesium Sulfate Mixtures after Gamma Radiolysis: Implications for Missions to Europa

If ocean-derived materials are present at Europa’s surface, they would represent accessible records of ocean chemistry and habitability, but such materials would be further processed by the moon’s harsh radiation environment. In this study, saturated fatty acids were precipitated onto a Europa-relevant hydrated magnesium sulfate and exposed to gamma radiation doses up to 2 MGy at -196° C. Alkane chains, with carbon numbers one less than those of the starting fatty acids, were the most abundant radiolysis products in solvent and thermal extracts analyzed by gas chromatography mass spectrometry. Detections of monounsaturated fatty acids and combined radiolysis products were attributed to the experiment’s Europa-like parameters. Additionally, elevated concentrations of shorter-chain saturated fatty acids suggest that gamma radiation induced charge remote fragmentation of the alkyl chains of some starting fatty acids under these experimental conditions. Quantitation of fatty acid concentrations in the irradiated samples enabled the calculation of a radiolysis constant that indicated exposure to a 5 MGy dose of gamma radiation would have resulted in a ~90% loss of the initial fatty acid population. The samples were further studied by Raman spectroscopy and laser desorption and ionization mass spectrometry, which characterized the distribution of fatty acids and their radiolysis products on sulfate surfaces. The substantial loss of starting fatty acids typically seen with increasing radiation dose, along with the remarkable diversity of radiolysis products identified, suggest that the detection of fatty acids in irradiated sulfate deposits on Europa will be challenged by rapid destruction of any initial fatty acid populations and scrambling of their residual signals by a myriad of organic radiolysis products. If missions to Europa encounter sulfate deposits, targeting minimally irradiated units may still enable the detection of surviving fatty acid signatures that could inform about Europa’s subsurface chemistry and habitability.

James M T Lewis↗

Microbial Pigments and Their Degradation Products as Biosignatures

Carotenoids are a class of vibrant biological pigments that have a characteristic chemical structure centered around a polyene core (Lu et al. 2018). Carotenoids and their derivatives are candidate biosignatures because they can persist in the terrestrial geologic record for up to 1.73 billion years (Vinnichenko et al. 2020), have specific structures that are likely the result of complex pathways, mediate the survival of many microorganisms in Mars and Ocean Worlds analog environments, and are detectable with multiple techniques, including Raman spectroscopy. In this project, we aim to investigate the detectability of carotenoid pigments with different spectroscopic methods to inform future instrument selection. We compare the spectra of five unaltered carotenoids, two model compounds, and carotenoid-forming archaeon with visible and deep UV Raman spectroscopy and UVVis absorption spectrophotometry. We then use one model pigment, beta-carotene, to evaluate the likelihood that unique spectral properties of carotenoids, or their refractory byproducts, would be preserved and detectable on a remote planetary surface by exposing it to simulated conditions for Mars. Sample Acquisition. Pigments betacarotene, lutein, zeaxanthin, astaxanthin, and lycopene were purchased from Sigma Aldrich. Halobacterium salinarum NRC-1 was acquired from Carlina Biological and grown in Halobacterium media. Mineral salts including sodium sulfate, sodium carbonate, and halite were used to form matrices in which the beta-carotene was embedded before exposure. Pigment-mineral mixes were at a 1:10 ratio in water. Analytical Techniques. Deep UV Raman data were collected on a custom laboratory mapping spectrometer called MOBIUS (Mineral and Organic Based Investigations using Ultraviolet Spectroscopy), which is an analog to the SHERLOC instrument on the Mars 2020 Perseverance rover (Bhartia et al. 2021). It features a 248.56 nm NeCu pulsed laser, liquid nitrogen-cooled detector, and tunable optical setup. Visible Raman data were collected using a Horiba Jobin Yvon LabRam HR spectrometer with a frequencydoubled Nd:YAG laser (532 nm) and a HeNe laser (633 nm). A VWR 6300 PC UV/Visible Spectrophotometer was used to collect absorption data for carotenoid solutions, model compounds, and solvents in UVpermissible capped cuvettes. Data were collected from 190-1100 nm at 1 nm increments. All spectral data were analyzed using Igor Pro 9 (Wavemetrics). Irradiation. We used a vacuum chamber equipped with a cryostat and a flood electron gun to simulate Martian surface temperatures, low pressures, and ionizing radiation (10keV, 10μA for 6h at 200K for our initial tests). The samples were prepared by drying the pigment-mineral mix onto polished metal tabs, then mounted on the cryostat for processing. Samples were then analyzed directly on the tabs after exposure. Results: In comparing the visible and deep UV Raman spectra of unaltered pigments, we found that they differed drastically. Carotenoids are often studied with visible Raman and typically have peaks at 1525 cm-1 and 1157 cm-1, due to the stretching of the C=C and C-C bonds in the polyene structure. However, in deep UV, the strongest feature is at ~1630 cm-1 and is broad, possibly indicating that multiple peaks are forming this feature. This stark difference is likely due to different preresonant enhancement effects. The UV-Vis results show that there is an absorption band in the deep UV <300 nm, which supports the hypothesis that the 248.6 nm excitation is interrogating another aspect of carotenoids than visible Raman. Our preliminary exposure tests indicated that pigments – even without minerals present - were largely unaltered in the applied conditions, with only a slight broadening in the primary polyene peaks apparent in the visible Raman data. Figure 1. A) Visible vs. deep UV Raman spectra of unaltered beta carotene. B) Schematic of exposure. Conclusions: Our results to date indicate that deep UV and visible Raman spectroscopy, both techniques with planetary mission heritage from Mars 2020 (Wiens et al. 2021, Bhartia et al. 2021), may be used in a complementary manner to observe carotenoids. In addition, we find that beta-carotene is largely resistant to our current exposure conditions, though there may be some amount of amorphization of the material which could cause the broadening of the peaks at 1525 and 1157 cm-1. As a next step, we aim to increase the dosage and duration of exposure to observe degradation of the parent pigment, possibly add UV as a factor via an Ar mini-arc UV lamp and use GC-MS to characterize possible degradation products.

pigments↗

Material for surface-enhanced Raman spectroscopy, and SER sensors and method for preparing same

Metal-doped sol-gel materials, suitable for use as sensors for surface-enhanced Raman spectroscopic analysis for trace chemical detection, are produced by effecting gelation and solvent removal of a doped sol-gel under mild temperature conditions. At least in certain instances reaction and drying will desirably be effected in an oxygen-starved environment. The metal of the sol-gel material functions, when irradiated, to produce a plasmon field for interaction with molecules of an analyte in contact therewith, increasing by orders of magnitude Raman photons that are generate by excitation radiation, and the method allows matching of the metal and metal particle size to a wavelength of light (or incident radiation, e.g., laser radiation) to generate surface plasmons. The porosity of the sol-gel material dramatically increases the surface area, and thereby the amount of metal exposed for analyte interaction. The sensors provided may be in the form of glass vials, fiber optics, multi-well micro-sample plates, etc., having surface coatings of the doped sol-gel material, to provide sampling systems for use in a Raman instrument.

Farquharson, Stuart↗

Spectroscopic Chemical Analysis Methods and Apparatus

This invention relates to non-contact spectroscopic methods and apparatus for performing chemical analysis and the ideal wavelengths and sources needed for this analysis. It employs deep ultraviolet (200- to 300-nm spectral range) electron-beam-pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor lightemitting devices, and hollow cathode metal ion lasers. Three achieved goals for this innovation are to reduce the size (under 20 L), reduce the weight [under 100 lb (.45 kg)], and reduce the power consumption (under 100 W). This method can be used in microscope or macroscope to provide measurement of Raman and/or native fluorescence emission spectra either by point-by-point measurement, or by global imaging of emissions within specific ultraviolet spectral bands. In other embodiments, the method can be used in analytical instruments such as capillary electrophoresis, capillary electro-chromatography, high-performance liquid chromatography, flow cytometry, and related instruments for detection and identification of unknown analytes using a combination of native fluorescence and/or Raman spectroscopic methods. This design provides an electron-beampumped semiconductor radiation-producing method, or source, that can emit at a wavelength (or wavelengths) below 300 nm, e.g. in the deep ultraviolet between about 200 and 300 nm, and more preferably less than 260 nm. In some variations, the method is to produce incoherent radiation, while in other implementations it produces laser radiation. In some variations, this object is achieved by using an AlGaN emission medium, while in other implementations a diamond emission medium may be used. This instrument irradiates a sample with deep UV radiation, and then uses an improved filter for separating wavelengths to be detected. This provides a multi-stage analysis of the sample. To avoid the difficulties related to producing deep UV semiconductor sources, a pumping approach has been developed that uses ballistic electron beam injection directly into the active region of a wide bandgap semiconductor material.

Hug, William F.↗

Ramdb: The NASA Raman Spectral Database (version 1.00).

Given that, in most instances, minimal sample preparation is required and due to its contactless instrument design, Raman spectroscopy is one of the most versatile vibrational spectroscopic techniques for the chemical analysis of environmental and biological specimens. The diversity of applications of Raman spectroscopy ranges anywhere from art [1] to planetary science missions [2]. The advancement in the use of Raman spectroscopy in Solar System missions, notably in post-mission sample return analysis, requires a spectral library holding the broad range of specimens that could be found in Solar System sources. For this purpose, we have initiated the development of a Raman spectral database (Ramdb) at NASA Ames Research Center. Currently, the database includes experimental and theoretical Raman spectra of PAHs [3, 4], as well as laboratory Raman spectra of amino acids, carbon allotropes, minerals, and analogs relevance to Earth Sciences [5], Exobiology [6], Planetary [7], and Astrochemistry [8] to name just a few examples. Ramdb can be found on the web at www.astrochemistry.org/ramdb, where raw and processed Raman spectra can be downloaded in CSV format. The laboratory Raman spectra are measured using a laser Raman spectrometer (JASCO NRS-5500-532QRI). The Raman instrument is equipped with three excitation lasers, with wavelengths of 405, 532, and 785 nm. A clean silicon substrate is used as the internal standard for wavenumber calibration. Powdered samples were prepared (microscopic >10 um, grounded microscopic < 10 um) on glass slides. Some raw data exhibited a background signal arising as a combination of laser-induced fluorescence from the sample. To correct this background, we developed a Python pipeline that uses open-source Python libraries. Ramdb provides both raw and processed (using Python pipeline) data, which includes tabulated Raman shift transitions and other measurement details. The theoretical Raman band positions of PAHs (pyrene monomers and tetramer clusters) were computed using density functional theory (DFT) with the help of the Gaussian 16 suite of programs [9]. In the near future, Ramdb will serve as a repository of Raman spectral data from Laboratory Astrophysics and Planetary Science experiments involving the irradiation of organic compounds under simulated space and planetary conditions. In addition, online and offline tools will be developed for utilising the database for comparison to the user’s sample.

N Punnakayathil↗