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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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At least 775 records · Page 43

Lead-Halide Perovskites for Photocatalytic α-Alkylation of Aldehydes

Here, cost-effective and efficient photocatalysis are highly desirable in chemical synthesis. Here we demonstrate that readily prepared suspensions of APbBr 3 (A = Cs or methylammonium (MA)) type perovskite colloids (ca. 2-100 nm) can selectively photocatalyze carbon-carbon bond formation reactions, i.e., ..alpha..-alkylations. Specifically, we demonstrate ..alpha..-alkylation of aldehydes with a turnover number (TON) of over 52,000 under visible light illumination. Hybrid organic/inorganic perovskites are revolutionizing photovoltaic research and are now impacting other research fields, but their exploration in organic synthesis is rare. Our low-cost, easy-to-process, highly efficient and bandedge-tunable perovskite photocatalyst is expected to bring new insights in chemical synthesis.

14 SOLAR ENERGY↗

𝐴𝑏 initio density-matrix approach to exciton coherence: Phonon scattering, Coulomb interactions, and radiative recombination

Relaxation processes following light excitation in semiconductors are key in materials-based quantum technology applications. These processes are broadly studied in atomically thin transition-metal dichalcogenides, quasi-two-dimensional excitonic semiconductors in which atomistic design allows for tunable excited-state properties, such as relaxation lifetimes and photoinduced coherence. In this work, we present a density-matrix-based approach to compute exciton relaxation within a many-body ab initio perspective. We expand our previously developed Lindblad density-matrix formalism to capture multichannel electron-hole pair relaxation processes, including phonon and Coulomb scattering as well as radiative recombination, and we study their effect on the time-resolved excited-state propagation. Using monolayer MoSe 2 as a prototypical example, we examine many-body effects on the time-dependent dynamics of photoactive excitations, exploring how the electron-hole pair interactions are reflected in variations of the excitation energy, spectral signature, and state coherence. In conclusion, our method supplies a detailed understanding of exciton relaxation mechanisms in realistic materials, offering a previously unexplored pathway to study excited-state dynamics in semiconductors from first principles.

Band structure methods↗

Bulk photovoltaic effect in hexagonal LuMnO 3 single crystals

Hexagonal manganites, such as h-LuMnO 3 , are ferroelectric and have a narrow electronic band gap of ≈1.5eV. Here we report on the photoresponse of h-LuMnO 3 single crystals. It is found that the short circuit photocurrent density (J sc ) and the open circuit voltage (V oc ) are dependent on the direction of the polarization plane of a linearly polarized impinging light. Its angular dependence indicates the contribution of bulk photovoltaic effect to the short circuit photocurrent (J BPE ). It is also observed that a switchable drift photocurrent, originating from the depoling field of the ferroelectric and thus tunable(<10%) by its polarization direction, also contributes to J sc . Although its presence precludes accurate determination of the bulk photovoltaic tensor elements and Glass coefficients, some bounds can be established. The Glass coefficients are found to be significantly larger than those obtained in BiFeO 3 . We argue that the smaller band gap of h-LuMnO 3 , its distinctive bipyramidal crystal field, and electronic configuration (3d 4 vs 3d 5 ), account for the difference and suggest a path towards ferroelectrics of higher photoconversion efficiency.

14 SOLAR ENERGY↗

Display system employing acousto-optic tunable filter

An acousto-optic tunable filter (AOTF) is employed to generate a display by driving the AOTF with a RF electrical signal comprising modulated red, green, and blue video scan line signals and scanning the AOTF with a linearly polarized, pulsed light beam, resulting in encoding of color video columns (scan lines) of an input video image into vertical columns of the AOTF output beam. The AOTF is illuminated periodically as each acoustically-encoded scan line fills the cell aperture of the AOTF. A polarizing beam splitter removes the unused first order beam component of the AOTF output and, if desired, overlays a real world scene on the output plane. Resolutions as high as 30,000 lines are possible, providing holographic display capability.

Lambert, James L.↗

Non-invasive optical detection of glucose in cell culture nutrient medium

The objective of the proposed research was to begin the development of a non-invasive optical sensor for measuring glucose concentration in the output medium of cell cultures grown in a unique NASA bioreactor referred to as an integrated rotating-wall vessel (IRWV). The input, a bovine serum based nutrient media, has a known glucose concentration. The cells within the bioreactor digest a portion of the glucose. Thus, the non-invasive optical sensor is needed to monitor the decrease in glucose due to cellular consumption since the critical parameters for sustained cellular productivity are glucose and pH. Previous glucose sensing techniques have used chemical reactions to quantify the glucose concentration. Chemical reactions, however, cannot provide for continuous, real time, non-invasive measurement as is required in this application. Our effort while in the fellowship program was focused on the design, optical setup, and testing of one bench top prototype non-invasive optical sensor using a mid-infrared absorption spectroscopy technique. Glucose has a fundamental vibrational absorption peak in the mid-infrared wavelength range at 9.6 micron. Preliminary absorption data using a CO2 laser were collected at this wavelength for water based glucose solutions at different concentrations and one bovine serum based nutrient medium (GTSF) with added glucose. The results showed near linear absorption responses for the glucose-in-water data with resolutions as high at 108 mg/dl and as low as 10 mg/dl. The nutrient medium had a resolution of 291 mg/dl. The variability of the results was due mainly to thermal and polarization drifts of the laser while the decrease in sensitivity to glucose in the nutrient medium was expected due to the increase in the number of confounders present in the nutrient medium. A multispectral approach needs to be used to compensate for these confounders. The CO2 laser used for these studies was wavelength tunable (9.2 to 10.8 micrometers), however, it was to unstable across wavelengths to test the multispectral approach. From this research, further NASA support was obtained to continue the work throughout the year in which a more stable light source will be used at smaller, near-infrared, wavelengths. It is anticipated that a more compact, non-invasive, optical glucose sensor will be realized which can be used with a bioreactor on future space shuttle missions. It is also anticipated that a multispectral optical sensor may be used to determine the concentration of other molecules needed within the NASA bioreactor, such as fructose and galactose.

Cote, Gerald L.↗

Display system employing acousto-optic tunable filter

An acousto-optic tunable filter (AOTF) is employed to generate a display by driving the AOTF with a RF electrical signal comprising modulated red, green, and blue video scan line signals and scanning the AOTF with a linearly polarized, pulsed light beam, resulting in encoding of color video columns (scan lines) of an input video image into vertical columns of the AOTF output beam. The AOTF is illuminated periodically as each acoustically-encoded scan line fills the cell aperture of the AOTF. A polarizing beam splitter removes the unused first order beam component of the AOTF output and, if desired, overlays a real world scene on the output plane. Resolutions as high as 30,000 lines are possible, providing holographic display capability.

Lambert, James L.↗

Microcavity-Modified Emission from Rare-Earth Ion-Based Molecular Complexes

Despite the remarkable optical properties of rare-earth ion materials, their applications as light sources and in quantum technologies are often hindered by their long lifetimes and weak emission. Leveraging the natural compatibility of rare-earth ion molecular complexes with photonic structures, here we modify their photoluminescence properties by coupling them to a flexible open Fabry-Perot cavity. The full in situ tunability of the Fabry-Perot cavity allows fine control over its cavity modes and the achievement of resonant coupling between the rare-earth ion emission and the cavity modes. This configuration allows us to achieve a maximum photoluminescence enhancement factor of 30 and accelerate the decay rate up to two orders of magnitude. Our pump-power-dependent spectroscopic studies of the emitter-cavity system suggest that the cavity-modified emission is primarily caused by amplified spontaneous emission. These results suggest that integrating rare-earth ion molecular complexes with photonic structures could be a viable approach for the effective tuning of their optical properties. This natural compatibility, together with their versatile molecular structures and the resultant electronic states, renders rare-earth ion molecular complexes a potential alternative material platform for lighting and quantum applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transparency and color tunable electro-optical device using colloidal core/shell nanoparticles

According to one embodiment, a product is a mixture including a solvent and generally spherical colloidal nanoparticles, the colloidal nanoparticles each having a core and a shell surrounding the core, and an electrode. In addition, the mixture is characterized as having a transparency to light in a predetermined wavelength range, where the transparency increases as a voltage of the electrode increases.

42 ENGINEERING↗

Hybrid Metasurface-Based Mid-Infrared Biosensor for Simultaneous Quantification and Identification of Monolayer Protein

Metasurfaces emerge as a promising photonic platform for biosensing because they offer strong optical confinement and tunable optical resonances. Here, we show that metasurface-based biosensors consisting of gold nanoantenna arrays loaded with graphene and working in the mid-infrared (mid-IR) spectral range can achieve simultaneous high-sensitivity and high-specificity detection of biomolecules. Strong light–molecule interactions in deeply subwavelength optical spots created by the biosensors allow us to determine the concentration of protein molecules via spectral shifts of the metasurface resonance. A combination of passive and active tuning of the metasurface sensors allows us to spectrally overlap the metasurface resonance and the protein vibrational modes, so that protein molecules can be identified via their characteristic mid-IR “fingerprints”. As a result, the high sensitivity and specificity of the metasurface sensors enable us to determine the secondary structure of protein immunoglobulin (IgG) molecules 4 orders of magnitude more sensitive than attenuated total reflection Fourier transform infrared spectroscopy.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Wide range yellow emission Sr8MgLa(PO4)7: Eu2+, Mn2+, Tb3+ phosphors for near ultraviolet white LEDs

Highlights: • The wide range of the emission spectra of Sr{sub 8}MgLa(PO{sub 4}){sub 7}: Eu{sup 2+}{sub 0.03} were clarified by Van Uitert equation and the crystal field strength equation. • The Mn{sup 2+} and Tb{sup 3+} had enhanced the total PL intensity up to 30% comparing to only Eu{sup 2+} doped phosphor. • W-LEDs using Sr{sub 8}MgLa(PO{sub 4}){sub 7}: Eu{sup 2+}{sub 0.03}, Mn{sup 2+}{sub 0.06}, Tb{sup 3+}{sub 0.06} and BAM: Eu{sup 2+} resulted in an excellent CRI of 89 and CIE coordinates of (0.3463, 0.3898). - Abstract: A series of single phased phosphors Sr{sub 8}MgLa(PO{sub 4}){sub 7}: Eu{sup 2+}, Mn{sup 2+}, Tb{sup 3+} were synthesized by solid state reaction methods for applications of white light emitting diodes(w-LEDs). The broad absorption band at the near ultraviolet (NUV) region of 250–450 nm was obtained, which is ascribed to the 4f{sup 7}→ 4f{sup 6}5d{sup 1} electronic transition of the Eu{sup 2+} ions. Under NUV excitation, the broad yellow emission was obtained from tri-activated Sr{sub 8}MgLa(PO{sub 4}){sub 7} phosphors via combining three emission bands centered at 500, 550, and 600 nm contributed by Eu{sup 2+}, Tb{sup 3+} and Mn{sup 2+}, respectively. The optimized concentrations of Mn{sup 2+} and Tb{sup 3+} were 6 mol%, respectively, which enhanced the total PL intensity up to 30% comparing to only Eu{sup 2+} doped phosphor. Moreover, the quantum efficiency of Sr{sub 8}MgLa(PO{sub 4}){sub 7}: Eu{sup 2+}, Mn{sup 2+}, Tb{sup 3+} phosphor had achieved up to 52%. The combination of a NUV chip with compound of Sr{sub 8}MgLa(PO{sub 4}){sub 7}: Eu{sup 2+}, Mn{sup 2+}, Tb{sup 3+} and BaMgAl{sub 10}O{sub 17}:Eu{sup 2+} achieved tunable w-LEDs with high CRI. The results suggest that this single phased Sr{sub 8}MgLa(PO{sub 4}){sub 7}: Eu{sup 2+}, Mn{sup 2+}, Tb{sup 3+} phosphor can be a key for the phosphor converted w-LEDs for warm white light emission.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Catalytic Light Alkanes Conversion through Anaerobic Ammodehydrogenation

Catalytic transformation of light alkanes could have considerable practical value, yet remains one of the most challenging areas in catalysis research due to the inertness of the C–H bond. Here, we proposed an efficient ammodehydrogenation (ADeH) catalytic system for the direct C–N linkage between light alkanes and ammonia for CH 3 CN and H 2 (CO x free) production. This breakthrough is achieved over bifunctional metal-modified HZSM-5 catalysts, through the tandem dehydrogenation–amination–dehydrogenation mechanism. We show that ethane ADeH over the Pt/HZSM-5 catalyst can be realized under atmospheric pressure at temperatures as low as 350 °C. The specific rate of CH 3 CN is ~60 μmol/(g min), and the selectivity is up to 99% under such mild conditions. The yield of CH 3 CN increases with increasing temperature; however, the selectivity decreases due to the formation of HCN, C 2 H 4 , and CH 4 . Additionally, the Pt/HZSM-5 catalyst is coke-resistant during the ADeH owing to the strong interaction between NH 3 and the acid sites of the catalyst. So, we anticipate that the proposed ADeH could be extended for the transformation of various n/iso-alkanes with tunable selectivity to alkene and nitriles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer Stabilized Paraboloid Liquid Crystal Microlenses with Integrated Pancharatnam–Berry Phase

Aspheric lenses reduce aberration and provide sharper images with improved spot size compared to spherical lenses. Here this paper demonstrates that applying shear flow can produce plano-concave liquid crystal (LC) lens arrays with paraboloid aspheric profiles. The focal length of individual lenses, with a 0.2 mm aperture, decreases from 0.67 to 0.45 mm as the chiral dopant increases from 0 to 6 wt%. The focal length is also sensitive to the polarization state of the incoming light. The lenses are stabilized by photopolymerizing with 6 wt% of reactive monomer added to the LC. A qualitative explanation for the flow-induced lens formation and the optical properties of the lenses is provided. The potential tunability of the lenses in various fields and their use as paraboloid reflectors are discussed.

36 MATERIALS SCIENCE↗

Direct Experimental Observation of the Tetrabromine Cluster Br 4 by Synchrotron Photoionization Mass Spectrometry

We present a first spectroscopic characterization of the homoatomic polyhalogen tetrabromine, Br 4 , in the gas phase. Photolysis of CHBr 3 at 248 nm is used to generate atomic bromine radicals in a flow tube reactor. Resulting combination products are detected by photoionization mass spectrometry at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Interpretation of the experimental mass spectra is informed by calculated adiabatic ionization energies carried out at the CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ//cam-B3LYP/6-311++g** levels of theory. Tunable VUV synchrotron radiation enables the collection of the mass-selected photoionization spectra by which Br 4 is assigned using Franck-Condon simulations of a Br 2 dimer with a stretched tetrahedral geometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stretchable Nanolasing from Hybrid Quadrupole Plasmons

This paper reports a robust and stretchable nanolaser platform that can preserve its high mode quality by exploiting hybrid quadrupole plasmons as an optical feedback mechanism. Increasing the size of metal nanoparticles in an array can introduce ultra-sharp lattice plasmon resonances with out-of-plane charge oscillations that are tolerant to lateral strain. By patterning these nanoparticles onto an elastomeric slab surrounded by liquid gain, we realized reversible, tunable nanolasing with high strain sensitivity and no hysteresis. Furthermore, our semi-quantum modeling demonstrates that lasing build-up occurs at the hybrid quadrupole electromagnetic hot spots, which provides a route towards mechanical modulation of light-matter interactions on the nanoscale.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Lateral Heterostructures of Multilayer GeS and SnS van der Waals Crystals

Engineered heterostructures derive distinct properties from materials integration and interface formation. Two-dimensional crystals have been combined to form vertical stacks and lateral heterostuctures with covalent line interfaces. While thicker vertical stacks have been realized, lateral heterostructures from multilayer van der Waals crystals, which could bring the benefits of high-quality interfaces to bulk-like layered materials, have remained much less explored. In this work, we demonstrate the integration of anisotropic layered Sn and Ge monosulfides into complex heterostructures with seamless lateral interfaces and tunable vertical design using a two-step growth process. The anisotropic lattice mismatch at the lateral interfaces between GeS and SnS is relaxed via dislocations and interfacial alloying. Nanoscale optoelectronic measurements by cathodoluminescence spectroscopy show the characteristic light emission of joined high-quality van der Waals crystals. Spectroscopy across the lateral interface indicates valley-selective luminescence in the bulk SnS component that arises due to anisotropic electron transfer across the interface. The results demonstrate the ability to realize high-quality lateral heterostructures of multilayer van der Waals crystals for diverse applications, e.g., in optoelectronics or valleytronics.

36 MATERIALS SCIENCE↗

Low threshold lasing of bubble-containing glass microspheres by non-whispering gallery mode excitation over a wide wavelength range

Bubble-containing Nd{sup 3+}-doped tellurite glass microspheres were fabricated by localized laser heating technique to investigate their optical properties for use as microresonators. Fluorescence and excitation spectra measurements were performed by pumping with a tunable CW-Ti:Sapphire laser. The excitation spectra manifested several sharp peaks due to the conventional whispering gallery mode (WGM) when the pumping laser was irradiated to the edge part of the microsphere. However, when the excitation light was irradiated on the bubble position inside the microsphere, “non-WGM excitation” was induced, giving rise to numerous peaks at a broad wavelength range in the excitation spectra. Thus, efficient excitation was achieved over a wide wavelength range. Lasing threshold excited at the bubble position was much lower than that for the excitation at the edges of the microsphere. The lowest value of the laser threshold was 34 μW for a 4 μm sphere containing a 0.5 μm bubble. Efficiency of the excitation at the bubble position with broadband light was calculated to be 5 times higher than that for the edge of the microsphere. The bubble-containing microsphere enables efficient utilization of broadband light excitation from light-emitting diodes and solar light.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Interface-induced heavy-hole/light-hole splitting of acceptors in silicon

The energy spectrum of spin-orbit coupled states of individual sub-surface boron acceptor dopants in silicon have been investigated using scanning tunneling spectroscopy at cryogenic temperatures. The spatially resolved tunnel spectra show two resonances, which we ascribe to the heavy- and light-hole Kramers doublets. This type of broken degeneracy has recently been argued to be advantageous for the lifetime of acceptor-based qubits [R. Ruskov and C. Tahan, Phys. Rev. B 88, 064308 (2013)]. The depth dependent energy splitting between the heavy- and light-hole Kramers doublets is consistent with tight binding calculations, and is in excess of 1 meV for all acceptors within the experimentally accessible depth range (<2 nm from the surface). These results will aid the development of tunable acceptor-based qubits in silicon with long coherence times and the possibility for electrical manipulation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Ultrafast extreme ultraviolet photoemission without space charge

Time- and Angle-resolved photoelectron spectroscopy from surfaces can be used to record the dynamics of electrons and holes in condensed matter on ultrafast time scales. However, ultrafast photoemission experiments using extreme-ultraviolet (XUV) light have previously been limited by either space-charge effects, low photon flux, or limited tuning range. In this article, we describe XUV photoelectron spectroscopy experiments with up to 5 nA of average sample current using a tunable cavity-enhanced high-harmonic source operating at 88 MHz repetition rate. The source delivers >1011 photons/s in isolated harmonics to the sample over a broad photon energy range from 18 to 37 eV with a spot size of 58 × 100 μm2. From photoelectron spectroscopy data, we place conservative upper limits on the XUV pulse duration and photon energy bandwidth of 93 fs and 65 meV, respectively. The high photocurrent, lack of strong space charge distortions of the photoelectron spectra, and excellent isolation of individual harmonic orders allow us to observe laser-induced modifications of the photoelectron spectra at the 10−4 level, enabling time-resolved XUV photoemission experiments in a qualitatively new regime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗