SEARCH · Engineering Papers
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
The most common methods to prepare semiconductors are based on use of melts or vapor phase. A tendency to use thin film structures in modern semiconducting devices brought a variety of technologies based on vapor phase deposition. The preparation of chemical compounds and solid solutions from a melt begins with melting the elemental constituents together. Melt technology and techniques are discussed.
Quasi-two-dimensional semiconductor nanoplatelets (NPLs) are intriguing systems for studying the influence of Auger recombination processes on the multiexciton emission efficiencies in the weak in-plane confinement regime. We investigate CdSe/CdS core/shell NPLs using cryogenic temperature single particle spectroscopy and observe bright biexciton emission at high excitation powers. The average binding energy of the biexcitons is determined to be 16.5 meV. The observed switching between the biexciton and trion states indicates charging-decharging dynamics of the NPLs mediated by the Auger ionization process. These findings are highly relevant for harvesting efficient biexciton emission for energy, lighting, and quantum applications.
Synthesis, crystal structure, thermal stability, and electronic band structure of four new metal antimonides AMSb (A = Rb, Cs; M = Zn, Cd) are reported. CsZnSb and RbZnSb crystallize in the hexagonal ZrBeSi structure type, in a P6 3 /mmc space group (no. 194, Z = 2) and unit cell dimensions of a = 4.5588(2)/4.5466(4) Å and c = 11.9246(6)/11.0999(10) Å. CsCdSb and RbCdSb crystallize in the tetragonal PbFCl structure type in a P4/nmm space group (no. 129; Z = 2) and unit cell parameters of a = 4.8884(5)/4.8227(3) Å and c = 8.8897(9)/8.5492(7) Å. All four compounds are air- and water-sensitive and are shown through DSC measurements to decompose between 975 K and 1060 K. Analysis of the calculated electronic band structure shows that the Zn-containing antimonides are topologically trivial narrow bandgap semiconductors, whereas Cd-containing compounds exhibit a band inversion along Γ-Z direction.
The well-known classification of glass-forming melts into fragile and strong liquids has several notable exceptions, including water, silica, and certain phase-change materials (PCMs). These exceptional fluid systems exhibit a fragile-to-strong transition (FST) upon cooling: a transformation from a high-temperature liquid with fast atomic dynamics, low viscosity, and low flow activation energy, to a viscous supercooled melt with high energy barriers near the glass transition temperature T g . This behavior is critically important for non-volatile memories, photonic tensor cores, reconfigurable metamaterials, and other devices, that use PCMs, enabling nanosecond-scale crystallization in the fragile regime and long data retention in the strong regime near or below T g . A significant structural transformation is expected between these two viscosity regimes, along with a semiconductor-metal (SC-M) transition upon heating, driven by high internal pressure and associated density increase. By applying high external pressure to the canonical low-conducting chalcogenide melt As 2 S 3 , we observed both the FST and the SC-M transition, occurring simultaneously within the same domain of the P, T−phase space. These findings suggest that the FST is not limited to a few exceptional liquids but is a common phenomenon, at least in systems that exhibit melt metallization within specific regions of their P, T−phase diagrams.
In this work, modifying the energy alignment between the frontier levels of a chromophore and the band edges of a semiconductor substrate using a “blanket layer” of molecular dipoles is explored. The electronic structure, measured with ultraviolet and x-ray photoemission spectroscopy, of C 60 deposited directly onto the TiO 2 (110) surface is compared with that of C 60 deposited onto the surface covered by a blanket layer of the custom-designed helical peptide Z-(Aib) 6 -Ipa, which has a large dipole moment of 18.6 D oriented along its molecular axis and pointing toward the substrate. The C 60 HOMO level is shifted 600 meV to deeper binding energy in the presence of the blanket layer, in good agreement with what is expected from a simple parallel plate capacitor model. These results demonstrate a simple and versatile strategy for controlling energy level alignment at organic/inorganic interfaces.
We have carried out diffusion Monte Carlo calculations for an A 1 B -1 -stacked bilayer blue phosphorene to find that it undergoes a semiconductor-metal transition as the interlayer distance decreases. While the most stable bilayer structure is a semiconducting one with two monolayers coupled through weak van der Waals interaction, the metallic bilayer at a shorter interlayer distance is found to be only metastable. This is in contrast to a recent theoretical prediction based on random phase approximation that the metallic phase would be the most stable bilayer configuration of blue phosphorene. Our analysis of charge density distributions reveals that the metastable metallic phase is induced by interlayer chemical bonding and intralayer charge redistributions. This study enriches our understanding of interlayer binding of a blue phosphorene and contributes to establishment of correct energetic order between its different phases, which will be essential in devising an experimental pathway for a metallic phosphorene.
The goal of this work is to determine the kinetic factors that govern isovalent cation exchange in III–V colloidal quantum dots using molten salts as the solvent and cation source. We focus on the reactions of InP + GaI 3 → In 1 – x Ga x P and InAs + GaI 3 → In 1–x Ga x As to create technologically important ternary III–V phases. We find that the molten salt reaction medium causes the transformation of nearly spherical InP nanocrystals to tetrahedron-shaped In 1–x Ga x P nanocrystals. Furthermore, we determine that the activation energy for the cation exchange reaction is 0.9 eV for incorporation of Ga into InP and 1.2 eV for incorporation of Ga into InAs, both much lower than the measured values in bulk semiconductors. Next, we use powder XRD simulations to constrain our understanding of the structure of the In 1–x Ga x P nanocrystals. Together our results reveal several important features of molten salt-mediated cation exchange and provide guidance for future development of these materials.
The cluster regime of colloidal semiconductor quantum dots (QDs) occupies an interesting space on the continuum from molecule to bulk material and allow the study of QD properties at extreme quantum confinement limits. For typical QDs, several size-dependent property trends are well established including intraband relaxation rates and universal scaling of Auger recombination with particle volume. Advances in synthesis now allow isolation of atomically precise semiconductor magic-size clusters (MCs), which offer experimental insight regarding how electronic structure changes with particle size in the ultrasmall limit. Here, we report intraband cooling and Auger recombination for several stable CdSe MCs as a function of particle size and observe deviation from QD response in the cluster regime. We additionally show optical signatures ascribed to transient disordering 2 that appear in the single exciton regime for MCs, which point to complexities regarding their implementation.
Scintillators are materials that convert ionizing radiation in the form of particles or photons into low-energy photons in the ultraviolet to near-infrared spectral range. Here, this work reviews efforts to use colloidal nanocrystals as scintillator materials. To date, research on colloidal nanocrystals as scintillators has focused on doped phosphor systems, quantum dots and related structures, and perovskite-based nanocrystals. Among various material classes and forms, colloidal semiconductor nanocrystals stand out thanks to their appealing fluorescence properties, yet understanding of their radioluminescence and cathodoluminescence is incomplete. This review discusses fundamental limits and material design challenges toward achieving high brightness, fast speed, and durable scintillator performance with nanocrystal scintillators. First, this review describes the basic principles and efficiency limitations of scintillation, particularly the large influence of multiple exciton generation in many nanocrystal species, as well as performance metrics. Second, methods for measurement are described. Third, we review the results of the main classes of nanocrystal scintillators, including quantum dots and related particles, perovskites, and doped-phosphor particles. Fourth, scintillation imaging is discussed in terms of the relevant performance metrics and results obtained using nanocrystal materials. Finally, we note the strengths and weaknesses of nanocrystal scintillators and discuss potential areas of further development.
Abstract Time-resolved super-resolution microscopy was used in conjunction with scanning electron microscopy to image individual colloidal CdSe/CdS semiconductor quantum dots (QD) and QD dimers. The photoluminescence (PL) lifetimes, intensities, and structural parameters were acquired with nanometer scale spatial resolution and sub-nanosecond time resolution. The combination of these two techniques was more powerful than either alone, enabling us to resolve the PL properties of individual QDs within QD dimers as they blinked on and off, measure interparticle distances, and identify QDs that may be participating in energy transfer. The localization precision of our optical imaging technique was ∼3 nm, low enough that the emission from individual QDs within the dimers could be spatially resolved. While the majority of QDs within dimers acted as independent emitters, at least one pair of QDs in our study exhibited lifetime and intensity behaviors consistent with resonance energy transfer from a shorter lifetime and lower intensity donor QD to a longer lifetime and higher intensity acceptor QD. For this case, we demonstrate how the combined super-resolution optical imaging and scanning electron microscopy data can be used to characterize the energy transfer rate.
Pressure-induced superconductivity has been widely explored and observed in Bi 2 Se 3 -based topological materials to hunt for topological superconductors. Although their triggered superconductivity has a close connection to their pressure-induced structural phase transitions, the quest for the electron pairing mechanism of these superconducting semiconductors in both their initial rhombohedral and high-pressure phases remains unknown. In this work, we present a systematic study of the pressure effect on superconducting properties and lattice dynamics using a combination of electrical transport, Raman-scattering, and synchrotron x-ray diffraction measurements using diamond anvil cells. One key finding is our observation of a cooperative connection between the strength of the electron–phonon interaction (EPI) generated by optical branches and the pressure-tunable superconductivity in rhombohedral Sr x Bi 2 Se 3 crystal. The underlying suppression mechanism of the T c by pressure is ascribed to the weakening of the electrons' interaction with the optical phonon modes in the rhombohedral phase. In the intermediate monoclinic phase, the T c value underwent a sharp increase with carrier density accumulation accompanying the concurrent enhanced EPI. This is intuitively unusual since it is expected that the EPI shall be weakened by inducing more conducting carriers in a normal metal. In the tetragonal phase, the superconductivity is interpreted within BCS theory, since it is fully metallized and obeys the adiabatic Born–Oppenheimer approximation well. Our findings are important to fully understand unconventional superconductivity and the unusual pairing mechanism in the layered rhombohedral Bi 2 Se 3 -based superconductors.
The electronic, magnetic, thermoelectric, and topological properties of Heusler compounds (composition XYZ or X 2 YZ) are highly sensitive to stoichiometry and defects. Here we establish the existence and experimentally map the bounds of a semi-adsorption-controlled growth window for semiconducting half-Heusler FeVSb films, grown by molecular beam epitaxy (MBE). We show that due to the high volatility of Sb, the Sb stoichiometry is self-limiting for a finite range of growth temperatures and Sb fluxes, similar to the growth of III-V semiconductors such as GaSb and GaAs. Films grown within this window are nearly structurally indistinguishable by x-ray diffraction (XRD) and reflection high energy electron diffraction (RHEED). Here, the highest electron mobility and lowest background carrier density are obtained towards the Sb-rich bound of the window, suggesting that Sb vacancies may be a common defect. Similar semi-adsorption-controlled bounds are expected for other ternary intermetallics that contain a volatile species Z = {Sb, As, Bi}, e.g., CoTiSb, LuPtSb, GdPtBi, and NiMnSb. However, outstanding challenges remain in controlling the remaining Fe/V (X/Y) transition metal stoichiometry.
Grazing-incidence (GI) scattering techniques are widely used to characterize thin films, offering high surface sensitivity and insight into morphology and structure. However, these approaches typically provide statistical averaged information due to elongated footprint or limited spatial resolution due to beam size. Here we introduce a method that combines structured illumination with GI X-ray scattering and leverages our computational imaging approach to resolve local structural details. We demonstrate that our method captures local features of an organic semiconductor thin film without the need for sample rotation as in tomography. The method expands GI techniques from statistical averaging to high-resolution imaging, thereby providing the capability for detailed analysis of local material properties, such as domain shape, orientation and polymorphism, which are critical for advancing material design towards more efficient and tailored materials.
Topics covered include: Multi-Segment Radius Measurement Using an Absolute Distance Meter Through a Null Assembly; Fiber-Optic Magnetic-Field-Strength Measurement System for Lightning Detection; Photocatalytic Active Radiation Measurements and Use; Computer Generated Hologram System for Wavefront Measurement System Calibration; Non-Contact Thermal Properties Measurement with Low-Power Laser and IR Camera System; SpaceCube 2.0: An Advanced Hybrid Onboard Data Processor; CMOS Imager Has Better Cross-Talk and Full-Well Performance; High-Performance Wireless Telemetry; Telemetry-Based Ranging; JWST Wavefront Control Toolbox; Java Image I/O for VICAR, PDS, and ISIS; X-Band Acquisition Aid Software; Antimicrobial-Coated Granules for Disinfecting Water; Range 7 Scanner Integration with PaR Robot Scanning System; Methods of Antimicrobial Coating of Diverse Materials; High-Operating-Temperature Barrier Infrared Detector with Tailorable Cutoff Wavelength; A Model of Reduced Kinetics for Alkane Oxidation Using Constituents and Species for N-Heptane; Thermally Conductive Tape Based on Carbon Nanotube Arrays; Two Catalysts for Selective Oxidation of Contaminant Gases; Nanoscale Metal Oxide Semiconductors for Gas Sensing; Lightweight, Ultra-High-Temperature, CMC-Lined Carbon/Carbon Structures; Sample Acquisition and Handling System from a Remote Platform; Improved Rare-Earth Emitter Hollow Cathode; High-Temperature Smart Structures for Engine Noise Reduction and Performance Enhancement; Cryogenic Scan Mechanism for Fourier Transform Spectrometer; Piezoelectric Rotary Tube Motor; Thermoelectric Energy Conversion Technology for High-Altitude Airships; Combustor Computations for CO2-Neutral Aviation; Use of Dynamic Distortion to Predict and Alleviate Loss of Control; Cycle Time Reduction in Trapped Mercury Ion Atomic Frequency Standards; and A (201)Hg+ Comagnetometer for (199)Hg+ Trapped Ion Space Atomic Clocks.
Hematite (Fe 2 O 3 ) is a well-known oxide semiconductor suitable for photoelectrochemical (PEC) water splitting and industry gas sensing. It is widely known that Sn doping of Fe 2 O 3 can enhance the device performance, yet the underlying mechanism remains elusive. In this work, we determine the relationship between electronic structure, optical properties and PEC activity of Sn doped Fe 2 O 3 by studying highly crystalline, well-controlled thin films prepared by pulsed laser deposition (PLD). We show that Sn doping substantially increases the n-type conductivity of Fe 2 O 3 , and the conduction mechanism is better described by small-polaron hoping (SPH) model. Only 0.2% Sn doping significantly reduce the activation energy barrier for SPH conduction from at least 0.5 eV for undoped Fe 2 O 3 to 0.14 eV for doped ones. A combination of X-ray photoemission, X-ray absorption spectroscopy and DFT calculations reveals the Fermi level gradually shifts toward the conduction band minimum with Sn doping. A localized Fe 2+ like gap state is observed at the top of valence band, accounting for the SPH conduction. Interestingly, in contrast to the literature, we find that only 0.2% Sn doping in Fe 2 O 3 significantly improves the PEC activity, while more Sn decreases it. The improved PEC activity is partially attributed to an increased band bending potential which facilitates the charge separation at space charge region. The reduced activation energy barrier for SPH will facilitate the transport of photo-excited carriers for the enhanced PEC, which is of interest for further carrier dynamics study.
Traditional methods for fabricating nanoscale arrays are usually based on lithographic techniques. Alternative new approaches rely on the use of nanoscale templates made of synthetic or biological materials. Some proteins, for example, have been used to form ordered two-dimensional arrays. Here, we fabricated nanoscale ordered arrays of metal and semiconductor quantum dots by binding preformed nanoparticles onto crystalline protein templates made from genetically engineered hollow double-ring structures called chaperonins. Using structural information as a guide, a thermostable recombinant chaperonin subunit was modified to assemble into chaperonins with either 3 nm or 9 nm apical pores surrounded by chemically reactive thiols. These engineered chaperonins were crystallized into two-dimensional templates up to 20 microm in diameter. The periodic solvent-exposed thiols within these crystalline templates were used to size-selectively bind and organize either gold (1.4, 5 or 10nm) or CdSe-ZnS semiconductor (4.5 nm) quantum dots into arrays. The order within the arrays was defined by the lattice of the underlying protein crystal. By combining the self-assembling properties of chaperonins with mutations guided by structural modelling, we demonstrate that quantum dots can be manipulated using modified chaperonins and organized into arrays for use in next-generation electronic and photonic devices.
The working electrode of a dye-sensitized solar cell (DSSC) consists of dye molecules adsorbed onto nanoparticles of a semiconductor such as TiO 2 . A reliable prediction of the DSSC photovoltaic performance of a given dye requires in-depth knowledge about the precise structure of the dye···TiO 2 interface. In this work, X-ray reflectometry (XRR) and grazing-incidence small-angle X-ray scattering (GISAXS) are employed to determine the dye···TiO 2 interfacial structure and associated dye aggregation behavior of three high-performance DSSC dyes, i.e., a metal-free organic dye, MK-2, and the two archetypal ruthenium-based organometallic dyes, N3 and N749 (Black Dye). Results show that all three dyes form nanoaggregates in dye···TiO 2 interfaces. We determine the dye nanoaggregate separations, sizes, distribution densities, and the extent of short-range order within each dye self-assembly in the longitudinal and lateral directions. Dye···TiO 2 composites fabricated using dye solutions of varying concentrations are analyzed. We find that nanoaggregates of the three dyes are separated by several hundred nanometers (158-203 nm) in dye···TiO 2 interfaces that have been fabricated using concentrated dye solutions (0.5 mM or 1.0 mM). MK-2 and N749 dyes also display smaller interparticle separations. Dye nanoparticle diameters are of the order of 156-198 nm, sizes that are comparable to the largest interparticle separations. Thus, no extraneous dye particles can be fitted into gaps between particles, so the dye self-assembly is saturated. Self-assemblies of all three dyes exhibit both lateral and longitudinal short-range order; N3 displays a particularly short coherence length along the TiO 2 surface, with extensive structured disorder along the longitudinal direction. The operation of DSSC working electrodes would therefore seem to be dependent on a dye self-assembly that may exhibit several levels of structural granularity and dye aggregation effects.
Development of efficient energy materials is critical in order to ease the energy demand and reduce our dependence of fossil fuel. Thermoelectric materials are promising due to their capability of generating electrical power by recovering waste heat. The performance of thermoelectric materials is quantified by a dimensionless figure of merit zT, which depends on their properties such as electrical conductivity, Seebeck coefficient and thermal conductivity. Tetrahedrites, a copper antimony sulfosalt mineral, typified by Cu 12-x MxSb 4 S 13 , where M is a transition metal element such as Ni, Zn, Fe or Mn, have great potential for thermoelectric application due to their relatively high zT (close to 1 at 700 K), earth-abundance, environmental friendliness, favorable electrical properties, and most importantly intrinsic low lattice thermal conductivity (less than 1 W m -1 K -1 ) in wide temperature. In addition to energy recovery, reliable energy storage devices are also emerging to relieve the energy demand and improve the efficiency of consuming energy resources. Lithium-ion batteries are known to be reliable and successful electrochemical energy storage devices and appliable in various aspects, including laptops, smartphones and electrical vehicles. Lithium phosphorous oxynitride (LiPON) are widely used as thin-film solid-state electrolytes in Li-ion battery, which is the only demonstrated solid-state electrolyte that is quite stable in direct contact with Li metal at potentials from 0-5 V. However, the structure of LiPON, the effects of N doping, and the origin of its good electrochemical stability remains inconclusive. In this thesis, reliable modeling techniques accompanied with experimental tools, are applied to study the thermoelectric material tetrahedrite and the ionic conductor LiPON, in order to study their structural and dynamical properties. Accurate and efficient density-functional theory (DFT) and density-functional tight-binding (DFTB) methods, combined with molecular dynamics (MD) simulations are utilized in order to investigate the structures and properties of these energy materials. The incoherent and coherent atomic dynamics study of tetrahedrite Cu 10.5 NiZn 0.5 Sb 4 S 13 provides the origin of softening upon cooling by investigate the motion of Cu12e at different temperatures. The dynamic structure factors in the longitudinal and transverse direction will also be discussed. The Cu movement of Cu-rich tetrahedrite Cu 14 Sb 4 S 13 is revealed by Cu self-diffusivity, nuclear density map and “nudged elastic band” (NEB). Moreover, we investigate the effect of simulation cell size and basis sets on the DFT-based MD simulation results using tetrahedrite Cu1 0 Zn 2 Sb 4 S 13 thermoelectric as a model material, showing the advantage of larger cell by accessing smaller Q range. In addition, the low-temperature structural properties of Cu 12 Sb 4 S 13 is measured by neutron diffraction, which indicates that no cubic to tetragonal transition occurs at metal-semiconductor transition (MST) temperature. Thermoelectric properties such as Seebeck coefficient, electrical resistivity and electrical thermal conductivity will also be investigated. DFTB method is implemented to study the structure and transport properties of Li 3 PO 4 and LiPON, while the exploration of N doping effect is included. Lastly, the LiPON/Li interphase will be revealed in order to study the origin of electrochemical stability.