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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 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Fabricating Graphene Oxide/h-BN Metal Insulator Semiconductor Diodes by Nanosecond Laser Irradiation

To employ graphene’s rapid conduction in 2D devices, a heterostructure with a broad bandgap dielectric that is free of traps is required. Within this paradigm, h-BN is a good candidate because of its graphene-like structure and ultrawide bandgap. We show how to make such a heterostructure by irradiating alternating layers of a-C and a-BN film with a nanosecond excimer laser, melting and zone-refining constituent layers in the process. With Raman spectroscopy and ToF-SIMS analyses, we demonstrate this localized zone-refining into phase-pure h-BN and rGO films with distinct Raman vibrational modes and SIMS profile flattening after laser irradiation. Furthermore, in comparing laser-irradiated rGO-Si MS and rGO/h-BN/Si MIS diodes, the MIS diodes exhibit an increased turn-on voltage (4.4 V) and low leakage current. The MIS diode I-V characteristics reveal direct tunneling conduction under low bias and Fowler-Nordheim tunneling in the high-voltage regime, turning the MIS diode ON with improved rectification and current flow. This study sheds light on the nonequilibrium approaches to engineering h-BN and graphene heterostructures for ultrathin field effect transistor device development.

2D materials↗
DOE OSTI2025

A-Cation-Dependent Structure–Optical Property Relationships of Halide Perovskite Heterostructures with Complex Interfaces

Halide perovskite heterostructures offer promising interfacial interactions for energy conversion, yet challenges in synthesizing structurally well-defined systems limit detailed investigations into structure–property relationships. In this article, we report the synthesis of compositionally controlled 3D/3D and 3D/2D halide perovskite heterostructures using evaporation crystallization-polymer pen lithography (EC-PPL) and a single-particle analysis of their properties. By systematically varying A-site cation combinations and crystal dimensions, we show that heterointerfaces induce local lattice distortions that modulate vibrational dynamics and electron-phonon coupling. These interfacial effects result in significantly extended carrier lifetimes compared to compositionally similar pure phases. Raman spectroscopy, temperature-dependent photoluminescence, and power-dependent emission analysis reveal that localized structural modulations at the interface govern exciton-phonon interactions. These effects are magnified in smaller crystals due to increased interfacial contributions. Our findings highlight the critical role of interface-driven lattice control in tuning the optoelectronic properties of halide perovskites and provide design principles for engineering heterostructures in next-generation optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Binding and stability of MgO monomers on anatase TiO 2 (101)

In catalysis, MgO is often used to modify the acid-base properties of support oxides and to stabilize supported metal atoms and particles on oxides. In this study, we show how the sublimation of MgO powder can be used to deposit MgO monomers, hither on anatase TiO 2 (101). A combination of X-ray electron spectroscopy, high-resolution scanning tunneling microscopy, and density functional theory is employed to gain insight into the MgO monomer binding, electronic and vibrational properties, and thermal stability. In the most stable configuration, the Mg and O of the MgO monomer bind to two surface oxygens and one undercoordinated surface titanium, respectively. The additional binding weakens the Mg-O monomer bond and makes the Mg more ionic. The monomers are thermally stable up to 650 K, where the onset of diffusion into the TiO 2 bulk is observed. Finally, the monomeric MgO species on TiO 2 (101) represent an ideal, atomically precise system with modified acid-base properties and will be employed in our future catalytic studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Spin–Phonon Coupling in Ferromagnetic Monolayer Chromium Tribromide

Novel 2D magnets exhibit intrinsic electrically tunable magnetism down to the monolayer limit, which has significant value for nonvolatile memory and emerging computing device applications. In these compounds, spin–phonon coupling (SPC) typically plays a crucial role in magnetic fluctuations, magnon dissipation, and ultimately establishing long-range ferromagnetic order. However, a systematic understanding of SPC in 2D magnets that combines theory and experiment is still lacking. Here in this work, monolayer chromium tribromide is studied to investigate SPC in 2D magnets via Raman spectroscopy and first principle calculations. The experimental Curie temperature and phonon shifts are found to be in good agreement with the numerical simulations. Specifically, it is demonstrated how magnetic exchange interactions affect phonon vibrations, which helps establish design fundamentals for 2D magnetic materials and other related devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Spectroscopic Investigation of Catalyst Inks and Thin Films Toward the Development of Ionomer Quality Control

As the production of polymer electrolyte fuel cells expands, novel quality control methods must be invented or adapted in order to support expected rates of production. Ensuring the quality of deposited catalyst layers is an essential step in the fuel cell manufacturing process, as the efficiency of a fuel cell is reliant on the catalyst layer being uniform at both the target platinum loading and the target ionomer content. Implementing a quality control method that is sensitive to these aspects is imperative, as wasting precious metals and other catalyst materials is expensive, and represents a potential barrier to entry into the field for manufacturers experimenting with novel deposition processes. In this work, we analyzed catalyst inks to determine if their ionomer content could be quantized spectroscopically. Attenuated total reflection (ATR) Fourier transform infrared spectroscopic technique was investigated producing a signal proportional to the ionomer content. ATR spectroscopy was able to quantitatively differentiate samples in which the ionomer to carbon mass ratio (I/C) varied between 0.9 and 3.0. The I/C ratio was correlated to the measured ATR signal near the CF 2 vibrational bands located between 1100 cm −1 and 1400 cm −1 . The experimental results obtained constitute a step toward the development of novel quality control methodologies for catalyst inks utilized by the fuel cell industry.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Coupled nuclear–electronic decay dynamics of O2 inner valence excited states revealed by attosecond XUV wave-mixing spectroscopy

Multiple Rydberg series converging to the $O_2^+$ c $^{4}Σ^{-}_{u}$ state, accessed by 20-25 eV extreme ultraviolet (XUV) light, serve as important model systems for the competition between nuclear dissociation and electronic autoionization. The dynamics of the lowest member of these series, the $3sσ_g $ state around 21 eV, has been challenging to study owing to its ultra-short lifetime (<10 fs). Here, we apply transient wave-mixing spectroscopy with an attosecond XUV pulse to investigate the decay dynamics of this electronic state. Lifetimes of 5.8 ± 0.5 fs and 4.5 ± 0.7 fs at 95% confidence intervals are obtained for v = 0 and v = 1 vibrational levels of the 3s Rydberg state, respectively. A theoretical treatment of predissociation and electronic autoionization finds that these lifetimes are dominated by electronic autoionization. The strong dependence of the electronic autoionization rate on the internuclear distance because of two ionic decay channels that cross the 3s Rydberg state results in the different lifetimes of the two vibrational levels. The calculated lifetimes are highly sensitive to the location of the 3s potential with respect to the decay channels; by slight adjustment of the location, values of 6.2 and 5.0 fs are obtained computationally for the v = 0 and v = 1 levels, respectively, in good agreement with experiment. Overall, an intriguing picture of the coupled nuclear-electronic dynamics is revealed by attosecond XUV wave-mixing spectroscopy, indicating that the decay dynamics are not a simple competition between isolated autoionization and predissociation processes.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Utilizing Quantum Cascade Lasers for Ultranarrow Velocity Resolution and Quantum-State Selectivity in Molecular Beam Scattering and Spectroscopy

Here, we demonstrate the capability of a narrow linewidth quantum cascade laser (QCL) to selectively excite a very narrow velocity range of nitric oxide (σ ≤ 7(3) m/s) with a pure ro-vibrational quantum state. By implementing a counter-propagating geometry, the molecules are selectively excited according to the Doppler shift of the ro-vibrational transition frequency such that the velocity width associated with the excited molecules depends only on the QCL linewidth. We demonstrate a velocity distribution limited by the effective linewidth of our free-running QCL (Γ = 3.2 MHz). Our development provides a cost-effective, flexible approach to resolve quantum-state selective chemical dynamics with excellent velocity resolution in a wide variety of molecules with infrared-active transitions. This technique has been formulated to provide ultrahigh collisional energy resolution in molecular beams to delineate final quantum-state product pairs in studies of molecular collisions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Infrared spectroscopy data- and physics-driven machine learning for characterizing surface microstructure of complex materials

There is a need to characterize complex materials and their dynamics under reaction conditions to accelerate materials design. Adsorbate vibrational excitations are selective to adsorbate/surface interactions and infrared (IR) spectra associated with activating adsorbate vibrational modes are accurate, capture details of most modes, and can be obtained operando. Current interpretation depends on heuristic peak assignments for simple spectra, precluding the possibility of obtaining detailed structural information. Here, we combine data-based approaches with chemistry-dependent problem formulation to develop physics-driven surrogate models that generate synthetic IR spectra from first-principles calculations. Using synthetic IR spectra of carbon monoxide on platinum, we implement multinomial regression via neural network ensembles to learn probability distributions functions (pdfs) that describe adsorption sites and quantify uncertainty. We use these pdfs to infer detailed surface microstructure from experimental spectra and extend this methodology to other systems as a first step towards characterizing complex interfaces and closing the materials gap.

Science & Technology - Other Topics↗
NASA NTRS1989

Fourier-transform spectroscopy of O3 in the 3-micron region

Fourier transform spectra of ozone have been recorded in the 2-5-micron region at a resolution of 0.01/cm. Absorption lines belonging to numerous vibration-rotation transitions have been observed in these spectra, and a detailed analysis of the band system centered at 3.6 microns has been completed.

Smith, M. A. H.↗
DOE OSTI2021

Vibronic Excitons and Conical Intersections in Semiconductor Quantum Dots

Surface defects and organic surface-capping ligands affect the photoluminescence properties of semiconductor quantum dots (QDs) by altering the rates of competing nonradiative relaxation processes. In this study, broadband two-dimensional electronic spectroscopy reveals that absorption of light by QDs prepares vibronic excitons, excited states derived from quantum coherent mixing of the core electronic and ligand vibrational states. Rapidly damped coherent wavepacket motions of the ligands are observed during hot-carrier cooling, with vibronic coherence transferred to the photoluminescent state. Furthermore, these findings suggest a many-electron, molecular theory for the electronic structure of QDs, which is supported by calculations of the structures of conical intersections between the exciton potential surfaces of a small ammonia-passivated model CdSe nanoparticle.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Real-Time Diagnostics of 2D Crystal Transformations by Pulsed Laser Deposition: Controlled Synthesis of Janus WSSe Monolayers and Alloys

Energetic processing methods such as hyperthermal implantation hold special promise to achieve the precision synthesis of metastable two-dimensional (2D) materials such as Janus monolayers; however, they require precise control. Here, we report a feedback approach to reveal and control the transformation pathways in materials synthesis by pulsed laser deposition (PLD) and apply it to investigate the transformation kinetics of monolayer WS 2 crystals into Janus WSSe and WSe 2 by implantation of Se clusters with different maximum kinetic energies (<42 eV/Se-atom) generated by laser ablation of a Se target. Real-time Raman spectroscopy and photoluminescence are used to assess the structure, composition, and optoelectronic quality of the monolayer crystal as it is implanted with well-controlled fluxes of selenium for different kinetic energies that are regulated with in situ ICCD imaging, ion probe, and spectroscopy diagnostics. First-principles calculations, XPS, and atomic-resolution HAADF STEM imaging are used to understand the intermediate alloy compositions and their vibrational modes to identify transformation pathways. The real-time kinetics measurements reveal highly selective top-layer conversion as WS 2 transforms through WS 2(1–x) Se 2x alloys to WSe 2 and provide the means to adjust processing conditions to achieve fractional and complete Janus WSSe monolayers as metastable transition states. The general approach demonstrates a real-time feedback method to achieve Janus layers or other metastable alloys of the desired composition, and a general means to adjust the structure and quality of materials grown by PLD, addressing priority research directions for precision synthesis with real-time adaptive control.

2D materials↗
DOE OSTI2020

Coupling of fully symmetric As phonon to magnetism in Ba(Fe 1-x Au x ) 2 As 2

In this work, we study the coupling of the fully symmetric vibration mode of arsenic atoms to magnetism in a Ba ( Fe 1 - x Au x ) 2 As 2 system by polarization-resolved Raman spectroscopy and neutron diffraction. In this system, there are two phase transitions: a tetragonal-to-orthorhombic structural phase transition at temperature T S and a magnetic phase transition into collinear spin-density wave (SDW) state at temperature T N ( ≤ T S ). T S and T N almost coincide in the pristine compound, whereas they differ by as much as 8 K for compounds with dilute gold substitution for iron. Raman coupling to the A g (As) phonon is forbidden for the X Y scattering geometry in the tetragonal phase above T S , whereas it becomes allowed in the orthorhombic phase below T S : The emerging mode's intensity indicates the lattice orthorhombicity. Furthermore, we find that upon cooling below T S , first, weak A g (As) phonon mode intensity appears in the X Y scattering geometry spectra; however, the mode's intensity is significantly enhanced in the magnetic phase below T N . The A g (As) phonon also shows an asymmetric line shape below T N and an anomalous linewidth broadening upon Au doping. We describe the anomalous behavior of the A g (As) mode in the X Y scattering geometry using a Fano model involving the A g (As) phonon interacting with the B 2 g ( D 4 h )-symmetry-like electron-hole continuum. We conclude that the temperature dependence of light coupling amplitude to the A g (As) phonon follows the evolution of the magnetic order parameter M ( T ) . We propose that the intensity enhancement of the A g (As) phonon in the X Y scattering geometry below T N is due to electronic anisotropy induced by the collinear SDW order parameter.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1989

The dissociation energy of He2(+)

Ab initio potential energy curves for He2(+) are computed using full CI wavefunctions in conjuction with large Gaussian and Slater basis sets. The computed curves yield rotational-vibrational transitions with errors of less than 1/cm. They also yield quasi-bound levels with energies and lifetimes in reasonable agreement with translational spectroscopy measurements. The best D(e) is estimated to be 2.470 eV. Green's function Monte Carlo calculations yield a very similar value, 2.466 + or - 0.005.

Bauschlicher, Charles W., Jr.↗
NASA NTRS2001

The AstroBiology Explorer (ABE) MIDEX Mission Concept: Exploring the Links Between the Interstellar Medium and Meteorites

Infrared spectroscopy in the 2.5-16 micron range is a principle means by which organic compounds can be detected and identified in space via their vibrational transitions. Ground-based, airborne, and spaceborne IR spectral studies have already demonstrated that a significant fraction of the carbon in the interstellar medium (ISM) resides in the form of complex organic molecular species. Furthermore, the presence of D-enriched organics in meteorites suggests that a portion of these materials survives incorporation into protosolar nebulae. Unfortunately, neither the distribution of these materials nor their genetic and evolutionary relationships with each other or their environments are well understood. The Astrobiology Explorer (ABE) is a MIDEX mission concept currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corporation. ABE will conduct IR spectroscopic observations to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. The core observational program would make fundamental scientific progress in understanding (1) the evolution of ices and organic matter in dense molecular clouds and young forming stellar systems, (2) the chemical evolution of organic molecules in the ISM as they transition from AGB outflows to planetary nebulae to the general diffuse ISM to HII regions and dense clouds, (3) the distribution of organics in the diffuse ISM, (4) the nature of organics in the Solar System (in comets, asteroids, satellites), and (5) the nature and distribution of organics in local galaxies. In addition, ABE will attempt to detect and quantify deuterium enrichments in a select set of these materials and environments. This should assist both with understanding the chemical processes that occur in these environments and with establishing any links that exist between interstellar and meteoritic organics.

Sandford, Scott A.↗
NASA NTRS2004

The AstroBiology Explorer (ABE) Mission Concept

Infrared spectroscopy in the 2.5-16 micron range is a principle means by which organic compounds can be detected and identified in space via their vibrational transitions. Ground-based, airborne, and spaceborne IR spectral studies have already demonstrated that a significant fraction of the carbon in the interstellar medium (ISM) resides in the form of complex organic molecular species. Unfortunately, neither the distribution of these materials nor their genetic and evolutionary relationships with each other or their environments are well understood. The Astrobiology Explorer (ABE) is a MIDEX mission concept currently under study by a team of partners: NASA's Ames Research Center, Ball Aerospace and Technologies Corporation, and the Jet Propulsion Laboratory. ABE will conduct IR spectroscopic observations to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. The core observational program would make fundamental scientific progress in understanding (1) The evolution of ices and organic matter in dense molecular clouds and young forming stellar systems, (2) The chemical evolution of organic molecules in the ISM as they transition from AGB outflows to planetary nebulae to the general diffuse ISM to HII regions and dense clouds, (3) The distribution of organics in the diffuse ISM, (4) The nature of organics in the Solar System (in comets, asteroids, satellites), and (5) The nature and distribution of organics in local galaxies. The technical considerations of achieving these science objectives in a MIDEX-sized mission will be presented.

Sandford, Scott A.↗
NASA NTRS1994

Electronic spectroscopy of diatomic molecules

This article provides an overview of the principal computational approaches and their accuracy for the study of electronic spectroscopy of diatomic molecules. We include a number of examples from our work that illustrate the range of application. We show how full configuration interaction benchmark calculations were instrumental in improving the understanding of the computational requirements for obtaining accurate results for diatomic spectroscopy. With this understanding it is now possible to compute radiative lifetimes accurate to within 10% for systems involving first- and second-row atoms. We consider the determination of the infrared vibrational transition probabilities for the ground states of SiO and NO, based on a globally accurate dipole moment function. We show how we were able to assign the a(sup "5)II state of CO as the upper state in the recently observed emission bands of CO in an Ar matrix. We next discuss the assignment of the photoelectron detachment spectra of NO and the alkali oxide negative ions. We then present several examples illustrating the state-of-the-art in determining radiative lifetimes for valence-valence and valence-Rydberg transitions. We next compare the molecular spectroscopy of the valence isoelectronic B2, Al2, and AlB molecules. The final examples consider systems involving transition metal atoms, which illustrate the difficulty in describing states with different numbers of d electrons.

Partridge, Harry↗
NASA NTRS2021

Design and Commissioning of an In-Air Coronagraph Testbed in the HCIT facility at NASA’s Jet Propulsion Laboratory

After completing its duty in the vacuum chamber at the High Contrast Imaging Testbed (HCIT) facility at NASA’s Jet Propulsion Laboratory, the General Purpose Coronagraph Testbed (GPCT) has been retrofitted as the In-Air Coronagraph Testbed (IACT), with the purpose of verification of Boston Micromachines (BMC) 50x50 MEMS deformable mirrors (MEMS DM) performance by contrast comparison before and after random vibration testing. The testbed is configured as a vortex coronagraph, with one MEMS DM in the pupil plane to create a half dark hole in monochromatic light. High wavefront stability is achieved using an environmentally isolating enclosure, based on the enclosure design previously used on Caltech’s High Contrast Spectroscopy Testbed (HCST). Further, a smaller enclosure has been designed which will enforce humidity conditions necessary for the MEMS DM to operate. We expect this testbed to achieve 1e-8 contrast, and will use this contrast level as a baseline to assess survival or failure of MEMS DMs during vibration testing. In this presentation, we will present an overview of the design of the IACT, commissioning results, and plans for upcoming DM tests in preparation for launch on future space telescopes with coronagraph instruments.

Mejia-Prada, Camilo↗