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At least 1,657 records · Page 92

Extensively Microtwinned Diamond with Nanolaminates of Lonsdaleite Formed by Flash Laser Heating of Glassy Carbon

Diamond’s unique properties on the nanoscale make it one of the most important materials for use in biosensors and quantum computing and for components that can withstand the harsh environments of space. We synthesize oriented, faceted diamond particles by flash laser heating of glassy carbon at 16 GPa and 2300 K. Detailed transmission electron microscopy shows them to consist of a mosaic of diamond nanocrystals frequently joined at twin boundaries forming microtwins. Striking 3-fold translational periodicity was observed in both imaging and diffraction. This periodicity was shown to originate from nanodimensional wedge-shaped overlapping regions of twinned diamond and not from a possible 9R polytype, which has also been reported in other group IVa elements and water ice. Extended bilayers of hexagonal layer stacking were observed, forming lonsdaleite nanolaminates. In conclusion, the particles exhibited optical fluorescence with a rapid quench time (<1 ns) attributed to their unique twinned microstructure.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Experimental results of a high Q quasioptical reflection cavity

A quasi-optical reflection cavity intended to be used as the resonant load of a submillimeter wavelength oscillator has been designed, constructed, and tested. The resonator consists of three elements in cascade: a high Q, high finesse folded Fabry-Perot resonator, a lower Q, low finesse Fabry-Perot resonator, and a Littrow mounted diffraction grating. The resonator exhibits a Q of 6600 and 2.5 dB of loss at 63 GHz. The design can be scaled to 1 THz, where waveguide structures become impractical, to serve as the resonator for high frequency quantum well resonant tunneling device oscillators.

Lee, Karen A.↗

Systems Issues Pertaining to Holographic Optical Data Storage in Thick Bacteriorhodopsin Films

The optical data storage capacity and raw bit-error-rate achievable with thick photochromic bacteriorhodopsin (BR) films are investigated for sequential recording and read- out of angularly- and shift-multiplexed digital holograms inside a thick blue-membrane D85N BR film. We address the determination of an exposure schedule that produces equal diffraction efficiencies among each of the multiplexed holograms. This exposure schedule is determined by numerical simulations of the holographic recording process within the BR material, and maximizes the total grating strength. We also experimentally measure the shift selectivity and compare the results to theoretical predictions. Finally, we evaluate the bit-error-rate of a single hologram, and of multiple holograms stored within the film.

Downie, John D.↗

Influence of Annealing and Composition on the Crystal Structure of Mixed-Halide, Ruddlesden–Popper Perovskites

Mixed-halide two-dimensional (2D) hybrid organic–inorganic perovskites offer an important opportunity to control the band gap for applications in optoelectronic devices. In this study, we focus on phenethylammonium lead halide [(PEA) 2 Pb(I 1– x Br x ) 4 ] films, the pure iodide form of which is one of the most widely studied optically active 2D perovskite systems. Resonant infrared, matrix-assisted pulsed laser evaporation is used to grow films to explore the effects of post-growth annealing and mixed-halide composition. The composition, crystal structure, and optical properties are studied for as-grown and annealed films of (PEA) 2 Pb(I 1– x Br x ) 4 for x = 0, 0.25, 0.5, 0.75, and 1. First-principles calculations are used in conjunction with the experimental data to explain the mixed-halide behavior that does not trend monotonically with the bromide content. Important results of this work are as follows: (i) X-ray diffraction reveals evidence for halide phase separation around x = 0.25, consistent with first-principles calculations, whereas no phase separation is observed for x = 0.5 and above and (ii) a unique photoluminescence (PL) peak splitting is observed for x = 0.75, a composition for which no compositional phase separation is observed. The PL splitting is tentatively explained by the coexistence of two distinct types of halide short-range ordering at x = 0.75. Overall, this study demonstrates that mixed-halide n = 1 Ruddlesden–Popper perovskites are not simple random alloys but that instead, they display distinct sites and ordering preferences of the different halide anions. These preferences are critical to understand and rationally tune the properties of the materials.

36 MATERIALS SCIENCE↗

Structural, Vibrational, and Electronic Properties of 1D-TlInTe 2 under High Pressure: A Combined Experimental and Theoretical Study

Analogous to 2D layered transition-metal dichalcogenides, the TlSe family of quasi-one dimensional chain materials with the Zintl-type structure exhibits novel phenomena under high pressure. In the present work, we have systematically investigated the high-pressure behavior of TlInTe 2 using Raman spectroscopy, synchrotron X-ray diffraction (XRD), and transport measurements, in combination with first principles crystal structure prediction (CSP) based on evolutionary approach. We found that TlInTe2 undergoes a pressure-induced semiconductor-to-semimetal transition at 4 GPa, followed by a superconducting transition at 5.7 GPa (with T c = 3.8 K). An unusual giant phonon mode (A g ) softening appears at ~10–12 GPa as a result of the interaction of optical phonons with the conduction electrons. The high-pressure XRD and Raman spectroscopy studies reveal that there is no structural phase transitions observed up to the maximum pressure achieved (33.5 GPa), which is in agreement with our CSP calculations. In addition, our calculations predict two high-pressure phases above 35 GPa following the phase transition sequence as I4/mcm (B37) → Pbcm → Pm$\bar{3}$m (B2). Electronic structure calculations suggest Lifshitz (L1 & L2-type) transitions near the superconducting transition pressure. Furthermore, our findings on TlInTe 2 open up a new avenue to study unexplored high-pressure novel phenomena in TlSe family induced by Lifshitz transition (electronic driven), giant phonon softening, and electron–phonon coupling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A systematic exploration of the hydrolysis products of the uranium trioxide polymorphs and their optical vibrational spectra

Study of the uranium trioxide (UO 3 )-water system is complex with inconclusive results and limited details in the literature. The UO 3 system is home to at least seven structural polymorphs and an amorphous phase. The proposed hydrolysis products of UO 3 are just as numerous, yet investigations of these alteration products are sporadic and generally antiquated, thus requiring systematic investigations. Recent developments in the understanding of UO 3 phase space, aided by improvements in analytical and computational techniques, necessitate more modern investigations into the uranyl hydroxide family and their naturally occurring mineral counterparts. We present findings from a systematic investigation of the products formed via hydrothermal reactions of common UO 3 polymorphs and discuss how the equatorial coordination of the uranyl/uranyl-like ions within the UO 3 precursors leads to differences in the optical vibrational spectra of the resulting hydrolysis products. The hypo-stochiometric nature of α-UO 2 (OH) 2 allows for the formation of multiple unique uranyl sites and a distortion of the unit cell to a lower symmetry. This study provides, for the first time, an analysis of β-UO 2 (OH) 2 using modern techniques and instrumentation (Raman/infrared spectroscopy and powder x-ray diffraction) and lays a foundation for future time-dependent investigations into the structural dependence of the hydrolysis kinetics of the UO 3 phases. In conclusion, given the prevalence of UO 3 at both ends of the nuclear fuel cycle, an understanding of its behavior with water has applications ranging from nuclear forensics to waste management and environmental transport.

Uranium trioxide↗

Optical design of a stigmatic spectroheliometer for photometric studies of dynamic phenomena at extreme-ultraviolet wavelengths

The design of a stigmatic spectroheliometer for photometric studies of dynamic phenomena in the solar atmosphere at extreme ultraviolet (EUV) wavelengths is described. The normal-incidence spectrometer requires only one reflective surface, and is equipped with a series of exit slits and associated one-dimensional detector arrays that are mounted at the secondary (vertical) foci of the concave diffraction grating. It is shown that such a spectrometer mounted at the focus of an off-axis paraboloid telescope mirror of the size employed in the EUV spectroheliometer flown on Skylab could record monochromatic images of a 2 x 2 (arcmin) sq field-of-view with a spatial resolution element of 1 x 1 (arcsec) sq in a time of 4 s, 24 s, or 4 min, depending on whether the region studied is flaring, active, or quiet. The resulting spectroheliograms would have an average photometric precision of 10% and a spectral purity of 0.1 A.

Huber, M. C. E.↗

High-power diode-pumped solid-state lasers for optical space communications

The design and performance of a large diode-pumped multi-stage Nd:YAG laser system for space and airborne applications will be described. The laser operates at a repetition rate of 40 Hz and produces an output either at 1.064 micron or 532 nm with an average power in the Q-switched mode of 30 W at the fundamental and 20 W at the second harmonic wavelength. The output beam is diffraction limited (TEM 00 mode) and can optionally also be operated in a single longitudinal mode. The output energy ranges from 1.25 Joule/pulse in the free lasing mode, 0.75 Joule in a 17 nsec Q-switched pulse, to 0.5 Joules/pulse at 532 nm. The overall electrical efficiency for the Q-switched second harmonic output is 4.

Koechner, Walter↗

Nature's crucible: Manufacturing optical nonlinearities for high resolution, high sensitivity encoding in the compound eye of the fly, Musca domestica

The number of pixels per unit area sampling an image determines Nyquist resolution. Therefore, the highest pixel density is the goal. Unfortunately, as reduction in pixel size approaches the wavelength of light, sensitivity is lost and noise increases. Animals face the same problems and have achieved novel solutions. Emulating these solutions offers potentially unlimited sensitivity with detector size approaching the diffraction limit. Once an image is 'captured', cellular preprocessing of information allows extraction of high resolution information from the scene. Computer simulation of this system promises hyperacuity for machine vision.

Wilcox, Mike↗

High Pressure Synthesis of Ultrasmall Nanodiamonds with Nitrogen Vacancy Centers

C–H terminated nanometer scale diamonds ( d = 1 to 15 nm) are synthesized from 1-fluoroadamantane at high pressure (6–8 GPa) and high temperature (500–1500 °C) in a multianvil press. High resolution transmission electron microscopy, X-ray diffraction, Raman, diffuse reflectance Fourier transform infrared, and X-ray absorption spectroscopies demonstrate the excellent crystallinity and atomically flat C–H terminated surfaces of nanodiamonds with (111) and (110) facets. The importance of hydrogen to the synthesis of nanodiamond and its faceting is discussed. Following vacancy generation, annealing and oxidation of the nanodiamonds, optically detected magnetic resonance and electron spin resonance coherence times ( T 2 = 0.9 and 2.1 μs) of nitrogen vacancy (NV) centers are measured. Finally, the obtained T 2 values are equivalent to the shallow NV centers (depth <10 nm) in bulk diamond crystals and larger nanocrystals prepared by mechanical milling.

36 MATERIALS SCIENCE↗

Multi-beam X-ray ptychography using coded probes for rapid non-destructive high resolution imaging of extended samples

Imaging large areas of a sample non-destructively and with high resolution is of great interest for both science and industry. For scanning coherent X-ray diffraction microscopy, i. e., ptychography, the achievable scan area at a given spatial resolution is limited by the coherent photon flux of modern X-ray sources. Multibeam X-ray ptychography can improve the scanning speed by scanning the sample with several parallel mutually incoherent beams, e. g., generated by illuminating multiple focusing optics in parallel by a partially coherent beam. The main difficulty with this scheme is the robust separation of the superimposed signals from the different beams, especially when the beams and the illuminated sample areas are quite similar. We overcome this difficulty by encoding each of the probing beams with its own X-ray phase plate. This helps the algorithm to robustly reconstruct the multibeam data. We compare the coded multibeam scans to uncoded multibeam and single beam scans, demonstrating the enhanced performance on a microchip sample with regular and repeating structures.

47 OTHER INSTRUMENTATION↗

Imaging plasma formation in isolated nanoparticles with ultrafast resonant scattering

We have recorded the diffraction patterns from individual xenon clusters irradiated with intense extreme ultraviolet pulses to investigate the influence of light-induced electronic changes on the scattering response. The clusters were irradiated with short wavelength pulses in the wavelength regime of different 4d inner-shell resonances of neutral and ionic xenon, resulting in distinctly different optical properties from areas in the clusters with lower or higher charge states. The data show the emergence of a transient structure with a spatial extension of tens of nanometers within the otherwise homogeneous sample. Simulations indicate that ionization and nanoplasma formation result in a light-induced outer shell in the cluster with a strongly altered refractive index. The presented resonant scattering approach enables imaging of ultrafast electron dynamics on their natural timescale.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Telescope-optical system performance analysis for the Cryogenic Limb Array Etalon Spectrometer (CLAES) on the Upper Atmospheric Research Satellite

A first-order performance analysis of the CLAES telescope-optical system is presented. The experiment involves the passive measurement of earth-limb radiance over a 10-60 km tangent altitude range, and is based on a solid Fabry-Perot spectrometer which provides spectral resolution of 0.25/cm for atmospheric emission spectroscopy over the 3.5-12 micron IR range. The optical system is required to provide a high degree of off-axis rejection and stray-light control, primarily to suppress intense emission from the earth surface. The astigmatism and other geometric aberrations are corrected by a secondary mirror which produces an excellent image of the primary one, allowing for location of a diffraction control or Lyot stop. The off-axis scattering performance of the telescope is examined in terms of the mirror scatter coefficient and point source rejection ratio. A mirror bidirectional reflectance distribution function of 0.0001 at 1 deg with a 1/theta-squared roll-off between 1 and 0.2 deg is realizable based on recent measurements. This results in an off-axis radiance term that is generally small in comparison with the system-limiting NER.

Roche, A. E.↗

The output beam quality of a Q-switched Nd:glass slab laser

The authors have constructed and tested a flashlamp pumped, Q-switched, Nd:glass zigzag slab laser. The thermally induced optical distortion through the slab is minimized by uniform pumping and cooling and the use of corrective pump shields at the slab ends. The laser spatial output for Q-switched resonators has been measured and modeled. It is shown that a larger aperture planar oscillator has an output divergence many times above the diffraction limit. Operation as a one-dimensional unstable resonator in the wide direction of the slab allows the efficient extraction of energy in a high-quality beam. Near-diffraction-limited laser output of 5 J at 4 Hz is achieved with a resonator that includes an intracavity telescope to correct for residual defocusing in the thin direction of the slab.

Reed, Murray K.↗

Beam Shape Effects on Grating Spectrometer Resolution

The collimated optical beam in a grating spectrometer may be circular or elliptical in cross section, so that different parts of the beam illuminate different numbers of grooves on the grating. Here we estimate the consequent loss in spectral resolution relative to that obtained with a beam which illuminates a fixed number of grooves. For representative diffraction resolution functions, the effect is to reduce the intrinsic resolving power of the spectrometer by about 13%, exclusive of other contributions such as finite entrance slit width.

Erickson, Edwin F.↗

Impact of Arsenic- and Indium-Terminated InGaAs Stressors on Carrier Confinement, Strain, Defects, and Transport Properties of Tensile-Strained Ge

Device-quality tensile-strained Ge (ε-Ge) grown on a large bandgap semiconductor with superior electrical and optical carrier confinement is essential for group-IV-based optoelectronics. Properties of ε-Ge active layers synthesized on In 0.24 Ga 0.76 As buffers with two different surface terminations─arsenic-rich and indium-rich─were experimentally demonstrated, highlighting the factors not considered in theoretical calculations. High-resolution X-ray diffraction and Raman spectroscopy analyses of these ε-Ge/In 0.24 Ga 0.76 As heterostructures confirmed the fully strained (1.6%) and partially relaxed (0.82%) nature of the ε-Ge bonded with arsenic-terminated (Ge As-terminated ) and indium-terminated (Ge In-terminated ) In 0.24 Ga 0.76 As stressors, respectively. High-resolution cross-sectional transmission electron microscopy showed a coherent, sharp, and fully strained ε-Ge/In 0.24 Ga 0.76 As heterointerface in the Ge As-terminated heterostructure, whereas microtwin defects were present in the Ge In-terminated heterostructure. These heterostructures were further characterized by evaluating the minority carrier lifetimes, high for Ge As-terminated (525 ns) and low for Ge In-terminated (69 ns), using the photoconductive decay technique. Moreover, band alignment was constructed using X-ray photoelectron spectroscopy, where the Ge As-terminated heterostructure revealed that both holes and electrons were confined within the ε-Ge active layer as a type-I band alignment with ΔE V, As-terminated = 0.22 eV and ΔE C,As-terminated = 0.38 eV. On the other hand, the Ge In-terminated heterostructure exhibited a type-II band alignment with ΔE V,In-terminated = – 0.02 eV and ΔE C,In-terminated = 0.53 eV. Furthermore, the magnetotransport properties revealed high mobility (321 cm 2 /(V s)) with single-electron transport in Ge As-terminated heterostructure and low mobility (3.34 cm 2 /(V s)) with multihole transport in the Ge In-terminated heterostructure. Therefore, preferring the ε-Ge on the arsenic-rich surface of In 0.24 Ga 0.76 As stressor over the indium-rich surface during material synthesis offers device-quality materials with high carrier lifetime and superior carrier confinement, which can provide an opportunity to fabricate efficient group-IV-based optoelectronic devices.

36 MATERIALS SCIENCE↗

ZnGa 2 Te 4 thin-film absorbers for photoelectrochemical CO 2 reduction

Photoelectrochemical (PEC) carbon dioxide reduction reaction (CO 2 RR) has been considered as a promising route to convert and store solar energy into chemical fuels. It is crucial to find suitable photoelectrode materials that are photo-catalytically active and exhibit excellent photochemical stability. One of the promising contenders is ZnTe with the ∼2.26 eV band gap and prolonged stability under CO 2 RR PEC conditions. Herein, a new telluride based thin-film ZnGa 2 Te 4 photocathode with lower band gap and stronger visible light absorption compared to ZnTe is synthesized and characterized using a combinatorial sputtering technique. A two-step annealing method with excess Te supply is implemented to synthesize nearly stoichiometric ZnGa 2 Te 4 absorber material with a zincblende-derived tetragonal crystal structure confirmed by synchrotron X-ray and electron diffraction. Theoretical calculations show that ZnGa 2 Te 4 has suitable direct bandgap (∼1.86 eV) and high absorption coefficient ∼10 5 cm −1 , in agreement with experimentally prepared films. Transient absorption spectroscopy reveals the biexponential decay dynamics, with time constants, τ 1 ∼ 0.04, and τ 2 ∼ 0.65 μs in microsecond time scales and provides the optical transition pathways for this semiconductor thin film. PEC measurements show that the ZnGa 2 Te 4 photocurrent densities are comparable to the widely investigated ZnTe photocathodes or even surpass it under simulated sunlight condition. ZnGa 2 Te 4 samples demonstrate promising photoelectrochemical stability, maintaining consistent performance under illumination. The inclusion of diaryliodonium additive substantially increases its CO 2 RR selectivity to ∼60%. These findings open a new avenue for the synthesis of telluride-based thin-film photocathodes for further exploration and will motivate future research to integrate this potential photocathode material into PEC devices.

36 MATERIALS SCIENCE↗