Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Photoexcitations”

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.

At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Spontaneous exciton dissociation in transition metal dichalcogenide monolayers

Since the seminal work on MoS 2 , photoexcitation in atomically thin transition metal dichalcogenides (TMDCs) has been assumed to result in excitons, with binding energies order of magnitude larger than thermal energy at room temperature. Here, we reexamine this foundational assumption and show that photoexcitation of TMDC monolayers can result in a substantial population of free charges. Performing ultrafast terahertz spectroscopy on large-area, single-crystal TMDC monolayers, we find that up to ~10% of excitons spontaneously dissociate into charge carriers with lifetimes exceeding 0.2 ns. Scanning tunneling microscopy reveals that photocarrier generation is intimately related to mid-gap defects, likely via trap-mediated Auger scattering. Only in state-of-the-art quality monolayers, with mid-gap trap densities as low as 10 9 cm –2 , does intrinsic exciton physics start to dominate the terahertz response. Our findings reveal the necessity of knowing the defect density in understanding photophysics of TMDCs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Electron Transfer from Semiconductor Nanocrystals to Redox Enzymes

This review summarizes progress in understanding electron transfer from photoexcited nanocrystals to redox enzymes. The combination of the light-harvesting properties of nanocrystals and the catalytic properties of redox enzymes has emerged as a versatile platform to drive a variety of enzyme-catalyzed reactions with light. Transfer of a photoexcited charge from a nanocrystal to an enzyme is a critical first step for these reactions. This process has been studied in depth in systems that combine Cd-chalcogenide nanocrystals with hydrogenases. The two components can be assembled in close proximity to enable direct interfacial electron transfer or integrated with redox mediators to transport charges. Time-resolved spectroscopy and kinetic modeling have been used to measure the rates and efficiencies of the electron transfer. Electron transfer has been described within the framework of Marcus theory, providing insights into the factors that can be used to control the photochemical activity of these biohybrid systems. The range of potential applications and reactions that can be achieved using nanocrystal–enzyme systems is expanding, and numerous fundamental and practical questions remain to be addressed.

Chemistry↗
DOE OSTI2024

Plasmon assisted synthesis of TiN-supported single-atom nickel catalysts

We report the deposition of single atom nickel catalyst on refractory plasmonic titanium nitride (TiN) nanomaterials supports using the wet synthesis method under visible light irradiation. TiN nanoparticles efficiently absorb visible light to generate photoexcited electrons and holes. Photoexcited electrons reduce nickel precursor to deposit Ni atoms on TiN nanoparticles’ surface. The generated hot holes are scavenged by the methanol. We studied the Ni deposition on TiN nanoparticles by varying light intensity, light exposure time, and metal precursor concentration. These studies confirmed the photodeposition method is driven by hot electrons and helped us to find optimum synthesis conditions for single atoms deposition. We characterized the nanocatalysts using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), energy dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). We used density functional theory (DFT) calculations to predict favorable deposition sites and aggregation energy of Ni atoms on TiN. Surface defect sites of TiN are most favorable for single nickel atoms depositions. Interestingly, the oxygen sites on native surface oxide layer of TiN also exhibit strong binding with the single Ni atoms. Plasmon enhanced synthesis method can facilitate photodeposition of single atom catalysts on a wide class of metallic supports with plasmonic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Imaging Nanoscale Energy Transport and Conversion with Ultrafast Electron Microscopy (Final Technical Report)

Light-matter interactions are ubiquitous in nature and reside at the heart of innumerable technologies. The cascade of processes that occur when a material absorbs a photon of light are exceedingly complex and are interwoven in both space and time, rendering precise determination of the atomic-scale and ultrafast mechanisms immensely challenging. The advent of methods for generating short pulses of light several decades ago led to major advances in understanding the initial moments of light absorption and the resultant effects, though directly interrogating the response of the atoms within the material continued to prove challenging. More recently, methods for generating ultrashort pulses of X-rays and fast electrons have opened the way to probing photoinduced structural dynamics of a wide range of matter in multiple phases. An especially promising laboratory-scale method is ultrafast electron microscopy (UEM), wherein the modalities of conventional transmission electron microscopes (imaging, diffraction, spectroscopy) are extended into the femtosecond temporal regime. Here, the ultrafast imaging and diffraction modalities of UEM were used to study the transient structural aspects of photoexcitation of semiconducting materials (e.g., spatially-resolved electron-phonon coupling, excitation and emission of acoustic phonons, and discrete nanoscale scattering processes). The project had three main objectives: (1) determination of the excitation mechanisms of dense, hypersonic charge-carrier waves and the spatially mediated means by which they couple to the lattice via coherent phonon emission, especially with UEM imaging, wherein effects of nanoscale structural and morphological features on the coupling and relaxation dynamics are expected to dictate nucleation sites and preferred wave vectors, (2) elucidation of photoinduced acoustic-phonon seeding, emergence, propagation, and decay over nanoscale crystal regions and especially with respect to local strain fields and atomic-scale disruptions in lattice order, and (3) interwoven with the first two were efforts aimed at realizing combined angstrom-femtosecond spatiotemporal imaging with UEM. The outcomes and impacts of this project were the generation of new knowledge with respect to fundamental light-matter interactions and, especially, the spatially-mediated excitation and evolution of the structural response of materials following coherent photoexcitation. Importantly, the spatial and temporal resolutions of the UEM imaging modalities used are well-suited for such studies and enable spatially-resolved mechanisms to be determined as a function of atomic order, structural features, and morphology. In addition, ultrafast crystallographic measurements were used to correlate real- and reciprocal-space dynamics in order to determine atomic-scale preferential wave vectors and ultrafast scattering mechanisms, especially as dictated by specimen boundary conditions. The obtained results, as detailed in peer-reviewed publications and presentations, illustrate the importance of ultrafast, angstrom-scale real-space imaging for developing a comprehensive understanding of energy transport and conversion in materials.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Using Ultrafast Entangled Photon Correlations to Measure the Temporal Evolution of Optically Excited Molecular Entanglement (Final Technical Report)

The goal of this project is to build an ultrafast entangled photon spectrometer and use it to measure theoretical predictions that photoexcited states are enhanced by spin-photon interactions. Entanglement of two states describes a specific type of quantum superposition in which measuring one state gives information about a second state. While entanglement is well explored for quantum information and computing systems, its effects on photoexcited states are less understood, especially in the ultrafast domains of molecular vibronic coupling. The grant designs a frequency and temporally resolved entangled photon spectrometer and uses it to test theoretical predictions like enhanced two photon absorption, non-reciprocal Fourier relations, and coupling of photons to spin systems. The end goal of the project is an understanding of how, when, and where entanglement is useful for spectroscopy.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Topological phase transition to a hidden charge density wave liquid

Charge density waves (CDWs), electronic crystals that form within a host solid, have long been speculated to melt into a spatially textured electronic liquid. Though they have not been previously detected, liquid CDWs may nonetheless be fundamental to the phase diagrams of many correlated electron systems, including high temperature superconductors and quantum Hall states. In one of the most promising candidate materials capable of hosting a liquid CDW, 1T-TaS2, a structural phase transition impedes its observation. Here, by irradiating the material with a femtosecond light pulse, we circumvent the structural phase transition to reveal how topological defect dynamics govern the otherwise invisible CDW correlations. Upon photoexcitation, the CDW diffraction peaks broaden azimuthally, initially revealing a hexatic state. At higher temperatures, photoexcitation completely destroys translational and orientational order and only a ring of diffuse scattering is observed, a key signature of a liquid CDW. Our work provides compelling evidence for a defect-unbinding transition to a CDW liquid and presents a protocol for uncovering states that are hidden by other transitions in thermal equilibrium.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1974

Thermally-restorable optical degradation and the mechanism of current transport in Cu2S-CdS photovoltaic cells

The photovoltaic properties of single-crystal Cu2S-CdS heterojunctions have been investigated as a function of heat treatment by detailed measurements of the dependence of short-circuit current on photon energy, temperature, and the state of optical degradation or enhancement. A coherent picture is formulated for the relationship between enhancement and optical degradation, and their effect on the transport of short-circuit photoexcited current and dark, forward-bias current in the cell. Optical degradation in the Cu2S-CdS cell is shown to be closely identical to optical degradation of lifetime in a homogeneous CdS:Cd:Cu crystal, indicating that the CdS:Cu layer near the junction interface controls carrier transport in the cell. It is proposed that both the photoexcited short-circuit current and the dark, forward-bias current are controlled by a tunneling-recombination process through interface states.

Fahrenbruch, A. L.↗
NASA NTRS1975

G2.4 + 1.4, a supernova remnant or ring nebula around a peculiar star

G2.4 + 1.4 is a probable nonthermal radio source and an optical nebula which appears to be a supernova remnant (SNR). It also contains an O VI sequence star of great excitation. We present new radiofrequency-continuum and (nil) H 92 alpha observations, optical spectroscopy, and Fabry-Perot scanner observations of the nebula. The object distance (possibly 5 kpc), origin of gas kinematics (possibly SNR expansion), and mode of excitation of the gas (possibly photoexcitation and/or shock wave) remain uncertain. We discuss the possible roles of the O VI star as 'runaway' in an SNR, as a source of photoexcitation, and as an ejector of a 'counterfeit' SNR.

Johnson, H. M.↗
NASA NTRS1980

Solar-pumped gas laser development

A survey of gas properties through detailed kinetic models led to the identification of critical gas parameters for use in choosing appropriate gas combinations for solar pumped lasers. Broadband photoabsorption in the visible or near UV range is required to excite large volumes of gas and to insure good solar absorption efficiency. The photoexcitation density is independent of the absorption bandwidth. The state excited must be a metastable state which is not quenched by the parent gas. The emission bandwidth must be less than 10 A to insure lasing threshold over reasonable gain lengths. The system should show a high degree of chemical reversibility and an insensitivity to increasing temperature. Other properties such as good quantum efficiency and kinetic efficiency are also implied. Although photoexcitation of electronic vibrational transitions is considered as a possible system if the emission bands sufficiently narrow, it appears that photodissociation into atomic metastables is more likely to result in a successful solar pumped laser system.

Wilson, J. W.↗
NASA NTRS1983

The solar O III spectrum. II - Longer wavelengths, line widths, and the He II Lyman alpha radiation field

The solar O III spectrum above 900 A is analyzed, including several visible and infrared lines which are important in nebular studies. The dependence of the line intensities on the rate of photoexcitation by He Ly-alpha is determined, and the observability of these lines in the solar spectrum is studied. The impact approximation is employed to calculate the expected line widths of the stronger solar O III lines. The photoexciting field at 304 A calculated from the observed intensities of the O III lines below 900 A (Bhatia et al., 1982) is compared with the field predicted by a recent model (Avrett et al., 1976). It is shown that additional radiation trapping must be present beyond that given by this model.

Kastner, S. O.↗
NASA NTRS1984

On Bowen enhancement of the N III spectrum under solar and nebular conditions

Expected enhancement of the N III emission-line spectrum by the Bowen He II to O III to N III resonant photoexcitation process is computed using a six-configuration model. Preliminary comparisons with available solar and nebular observations indicate that the process may play only a small role, although photoexcitation quenching of the N III and O III far-infrared fine-structure lines is noted as a possibly important mechanism. Some features are discussed in connection with the nebular emission at 1750 A, which is suggested as an indicator of excitation class for planetary nebulae.

Kastner, S. O.↗
NASA NTRS1985

Measurements of HO2 chemical kinetics with a new detection method

In this research program, HO2 was detected by the OH(A-X) photofragment from dissociative excitation of HO2 at 147 nm. This detection method was applied to measure the reaction rate constant of HO2 + O3. This reaction rate constant is needed for the understanding of stratospheric chemistry. Since C12 was used in the flow system, photoexcitation of C12 may produce fluorescence to interfere with the measurements. Thus, the photoexcitation process of C12 in the vacuum ultraviolet region was also examined in this research period using synchrotron radiation as a light source. The research results are summarized.

Lee, L. C.↗
NASA NTRS1987

Polarized fluorescence spectroscopy of O2(+)

Polarized fluorescence measurements involving the A 2Pi(u) - X 2Pi(g) and b 4Sigma(g)(-) - a 4Pi(u) transitions in O2(+) following narrow-band photoexcitation of O2/X 3Sigma(g)(-)/ are reported. The analysis, based on the conventional high-J limit, involves deducing the quadrupole alignment factor from which the relative strengths of degenerate photoexcitation channels responsible for the population distribution in the A 2Pi(u) and b 4Sigma(g)(-) states of O2(+) can be estimated. The measured A-channel polarization exhibits pronounced structure which correlates well with the known positions of Rydberg states, whereas the polarization signal in the b channel has broad and less prominent features. Discrepancies between theoretical and measured results can largely be accounted for by additional configuration mixing and autoionization considerations.

Keller, J. W.↗
NASA NTRS1988

Fluorescence yields from photodissociative excitation of HCOOH, HCOOCH3, and CH3COOH in the vacuum-ultraviolet region

The photoexcitation processes of HCOOH, HCOOCH3, and CH3COOH were studied in the vacuum-ultraviolet region by using synchroton radiation and a pulsed discharge lamp as light sources. The absorption and fluorescence cross sections of these molecules were measured in the 106-250-nm region. Fluorescences were detected from photoexcitation of HCOOH and HCOOCH3, but not from CH3COOH. Fluorescence produced at 123.9 nm was dispersed and identified as the excited OH and HCOO radicals. Fluorescence quantum yields of HCOOH and HCOOCH3 increase with decreasing excitation wavelengths with maxima of 5 and 0.3 percent at 106 nm, respectively.

Suto, Masako↗
NASA NTRS1990

The Fe XI-excited fluorescent cascade in Ne IV

A theoretical spectroscopic investigation of the fluorescent cascade to be expected in nitrogen-like Ne IV, when it is resonantly photoexcited by Fe XI in the solar atmosphere, symbiotic stars, or novae, is described. Primary and secondary cascade intensities are obtained as functions of photoexcitation rate, and expected absolute intensities in the solar atmosphere are derived on the basis of observed Fe XI and Ne EUV emission. Comparisons between the spatially resolved solar situation and spatially unresolved stellar cases of cataclysmic variables, in which these ions have been found to coexist, are made. An interesting possibility of periodic time-dependent fluorescence exists for the binary cataclysmics.

Bhatia, A. K.↗
NASA NTRS1991

3.3 micron emission from ultraviolet excitation of some aromatic molecules

Infrared emissions are observed from photoexcitation of benzene, naphthalene, phenanthrene, anthracene, pyrene, and their methyl derivatives in the gas phase at 193 nm using an ArF laser as a light source. An emission band with peak at 3.3 microns is observed from all the molecules studied. This band is attributed to the aromatic C-H stretching vibrational modes. In addition to the 3.3-microns band, an emission band at 3.4-3.6 microns is observed from photoexcitation of the methyl derivatives, which is attributed to the C-H stretching vibrational modes of the CH3 group. The observed spectra are compared with the IR emission bands observed in many astronomical objects. The current laboratory data lend support to a model in which PAH molecules are responsible for the 'unidentified' interstellar IR emissions. IR emissions from the 193-nm excitation of several interstellar molecules other than PAHs are also observed, but they are quite different from the interstellar IR bands.

Shan, Jun↗
NASA NTRS1992

Laser power transmission

An overview of previous studies related to laser power transmission is presented. Particular attention is given to the use of solar pumped lasers for space power applications. Three general laser mechanisms are addressed: photodissociation lasing driven by sunlight, photoexcitation lasing driven directly by sunlight, and photoexcitation lasing driven by thermal radiation.

Conway, Edmund J.↗
NASA NTRS1984

Photochemistry of porphyrins: a model for the origin of photosynthesis

A series of porphyrins and catalysts has been prepared as a model for the origin of photosynthesis on the primordial earth. These compounds have been used to test the hypotheses that (1) the biosynthetic pathway to chlorophyll recapitulates the evolutionary history of photosynthesis, and (2) the proto-photosythetic function of biogenetic porphyrins (biosynthetic chlorophyll precursors) was the oxidation of organic molecules by photoexcited porphyrins with the attendant emission of molecular hydrogen. This paper describes experiments in which photoexcited biogenetic porphyrins oxidize ethylenediamine tetraacetic acid (EDTA). The concomitant reduction of protons to hydrogen gas occurs in the presence of a colloidal platinum catalyst. The addition of methyl viologen, a one-electron shuttle, increases the amount of molecular hydrogen generated during long irradiations and the quantum yield of hydrogen production. When the porphyrin and catalyst are held in association by molecular complexes, the increased efficiency of electron transfer produces higher yields of hydrogen gas.

Hydrogen/chemistry↗