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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Shinkolobweite, from the Shinkolobwe Mine, Democratic Republic of Congo: A New Mineral Containing Uranium in the Rare Pentavalent Oxidation State

ABSTRACT Shinkolobweite, Pb1.333[U5+O(OH)(UO2)5O4.67(OH)5.33](H2O)5, is a new lead uranyl oxide-hydroxide hydrate mineral containing hexavalent and pentavalent uranium from the Shinkolobwe mine, Democratic Republic of Congo. Crystals of shinkolobweite are dark reddish-brown prisms up to 0.5 mm in length, occurring on a matrix of massive uraninite associated with fourmarierite, rutherfordine, soddyite, and sklodowskite. Crystals are translucent with subadamantine luster and light bronze-yellow streak, are flattened on {010}, are elongated on [001], and exhibit the forms {100}, {010}, {101}, and . The mineral is non-fluorescent under both longwave and shortwave ultraviolet illumination. It has a Mohs hardness of ∼2 and exhibits brittle tenacity with perfect cleavage on {010}, imperfect cleavage on {100}, and even fracture. The calculated density is 5.853 g/cm3 based on the empirical formula. Electron probe microanalysis provided the empirical formula Pb1.290U6+4.876U5+1.166O27H16.633 based on 27 O apfu and U5+:U6+ determined by X-ray photoelectron spectroscopy. Shinkolobweite is orthorhombic, superspace group Pnnm(0b0)000, a = 14.4808(4), b = 7.0681(8), c = 11.9423(3) Å, V = 1222.32(15) Å3, modulation wave vector [0 1/3 0], and Z = 2. The structure was refined from 8959 reflections to a final R1 = 0.0736 for all reflections. Uranyl oxide-hydroxide sheets in shinkolobweite adopt the β-U3O8 topology and possess (3 + 1) commensurately modulated ordering that results from the long-range ordering of U5+ and U6+ in the sheet, as well as the position and occupancy of interlayer Pb2+ cations. Observations of a topological transition between α-U3O8 and β-U3O8 type sheets in shinkolobweite supplements our understanding of U5+ mineral oxidation and stability.

Mineralogy↗
DOE OSTI2024

Trebiskyite, the First Titanium-Decavanadate Mineral

Abstract Trebiskyite, Na3Mg2[TiV9O28]·22H2O, from the Pickett Corral mine, Bull Canyon, Montrose County, Colorado, USA, is the first mineral containing essential Ti as a component of a decavanadate polyanion. Crystals are thin prisms or needles up to ∼0.3 mm in length, occurring as individuals and in divergent sprays. Trebiskyite crystals are translucent yellow with vitreous luster and pale-yellow streak and are non-fluorescent under both longwave and shortwave ultraviolet illumination. The crystals exhibit elongation on [001] and are modified by several 0kl prism forms, possibly corresponding to {010}, {011}, and {012}. The Mohs hardness is ca. 2 based on scratch tests. Crystals have brittle tenacity with irregular fracture. No apparent cleavage, nor twinning, was evident, and the mineral is readily soluble in H2O. The density measured by flotation in methylene iodide-toluene mixture is 2.38(2) g/cm3. The calculated density is 2.352 g/cm3 for the empirical formula and 2.343 g/cm3 for the ideal formula. Electron microprobe analyses provided the empirical formula Na3.39Mg1.87V8.75Ti1.25O50H44.00, based on Ti + V = 10 apfu, O = 50 apfu, with the Na content having been determined from the refined crystal structure. Trebiskyite is monoclinic, space group P21/c, a = 9.478(4), b = 21.426(11), c = 11.267(5) Å, β = 114.572(7)°, V = 2080.8(13) Å3, Z = 2. The structure was refined from 6642 reflections to a final R1 = 0.0517 for reflections I > 2σ(I). The structural unit of trebiskyite, (TiV9O28)7−, is built from a Ti-substituted decavanadate polyanion, (V10O28)6−, found in other members of the pascoite family. Chemically, trebiskyite is closely related to lasalite, Na2Mg2[V10O28]·20H2O, and huemulite, Na4Mg[V10O28]·24H2O; however, trebiskyite contains a novel structural arrangement that is unique among the decavanadate minerals. The interstitial complex in trebiskyite has the ideal formula {[Na3Mg2(H2O)19](H2O)3} and consists of chains of distorted octahedrally coordinated Na+ and regular Mg[O(H2O)5] octahedra. The observed low incident bond valence to the V1 site (4.45 vu) and marked deviation in vanadyl and V–Oeq bond lengths indicate that this site is host to the essential Ti4+ identified during chemical analyses.

Mineralogy↗
DOE OSTI2022

Spectroscopic investigation of the electronic and excited state properties of para-substituted tetraphenyl porphyrins and their electrochemically generated ions

Porphyrins play pivotal roles in many crucial biological processes including photosynthesis. However, there is still a knowledge gap in understanding electronic and excited state implications associated with functionalization of the porphyrin ring system. These effects can have electrochemical and spectroscopic signatures that reveal the complex nature of these somewhat minor substitutions, beyond simple inductive or electronic effect correlations. To obtain a deeper insight into the influences of porphyrin functionalization, four free-base, meso-substituted porphyrins: tetraphenyl porphyrin (TPP), tetra(4-hydroxyphenyl) porphyrin (THPP), tetra(4-carboxyphenyl) porphyrin (TCPP), and tetra(4-nitrophenyl) porphyrin (TNPP), were synthesized, characterized, and investigated. The influence of various substituents, (-hydroxy,-carboxy, and -nitro) in the para position of the meso-substituted phenyl moieties were evaluated by spectroelectrochemical techniques (absorption and fluorescence), femtosecond transient absorption spectroscopy, cyclic and differential pulse voltammetry, ultraviolet photoelectron spectroscopy (UPS), and time-dependent density functional theory (TD-DFT). Spectral features were evaluated for the neutral porphyrins and differences observed among the various porphyrins were further explained using rendered frontier molecular orbitals pertaining to the relevant transitions. Electrochemically generated anionic and cationic porphyrin species indicate similar absorbance spectroscopic signatures attributed to a red-shift in the Soret band. Emissive behavior reveals the emergence of one new fluorescence decay pathway for the ionic porphyrin, distinct from the neutral macrocycle. Femtosecond transient absorption spectroscopy analysis provided further analysis of the implications on the excited-state as a function of the para substituent of the free-base meso-substituted tetraphenyl porphyrins. Herein, we provide an in-depth and comprehensive analysis of the electronic and excited state effects associated with systematically varying the induced dipole at the methine bridge of the free-base porphyrin macrocycle and the spectroscopic signatures related to the neutral, anionic, and cationic species of these porphyrins.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Fluorescent air leakage detection system for enclosures

Provided is a Fluorescent Air Leakage Detection (FALD) system and method for locating a defect in an enclosure that uses a nontoxic fluorescent solution as a marker. The solution is aerosolized with an atomizing device and guided to defects by a gas pressure modifying device. Defects are visually located by surveying the enclosure with an ultraviolet or visible light source and identifying a location where accumulated solution fluoresces.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2024

Ultraviolet Superradiance from Mega-Networks of Tryptophan in Biological Architectures

Networks of tryptophan (Trp)–an aromatic amino acid with strong fluorescence response–are ubiquitous in biological systems, forming diverse architectures in transmembrane proteins, cytoskeletal filaments, subneuronal elements, photoreceptor complexes, virion capsids, and other cellular structures. We analyze the cooperative effects induced by ultraviolet (UV) excitation of several biologically relevant Trp mega-networks, thus giving insights into novel mechanisms for cellular signaling and control. Our theoretical analysis in the single-excitation manifold predicts the formation of strongly superradiant states due to collective interactions among organized arrangements of up to >10 5 Trp UV-excited transition dipoles in microtubule architectures, which leads to an enhancement of the fluorescence quantum yield (QY) that is confirmed by our experiments. We demonstrate the observed consequences of this superradiant behavior in the fluorescence QY for hierarchically organized tubulin structures, which increases in different geometric regimes at thermal equilibrium before saturation, highlighting the effect’s persistence in the presence of disorder. Our work thus showcases the many orders of magnitude across which the brightest (hundreds of femtoseconds) and darkest (tens of seconds) states can coexist in these Trp lattices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Methods for ultraviolet excitation microscopy of biological surfaces

Microscopy with Ultraviolet Surface Excitation (MUSE) for use in the classroom to enhance life sciences education and curricula, or for other applications, including without limtiation the operating room, other medical environments, research environments, and low resource environments. MUSE's suitability is based on multiple key factors including its simplicity of use, the incorporation of inexpensive hardware including LED illumination, and very basic tissue preparation. The ultraviolet excitation acts as passive optical sectioning confining the generated fluorescence signal to only a few micrometers below the tissue surface thus eliminating the out of focus signals. This facilitates image capture of tissue microstructure and organization from specimens at the intact or sliced surface arising from varying fluorophore concentration within the different cellular compartments. Although just the tissue auto fluorescence maybe used, image quality is enhanced with brief application of nontoxic fluorescent dyes to selectively highlight cellular compartments. Sample preparation is safe, efficient and familiar to students with basic chemistry or biology lab experience. Mixed-dye powders may be used to simplify translation of this method for educational, medical, research, low resource, and other settings.

Demos, Stavros G.↗
DOE OSTI2022

Observation of Long-Lived UV-Induced Fluorescence from Environmental Materials Using the HVeV Detector as Developed for SuperCDMS

Here, we describe recent experiments using a SuperCDMS HVeV single-charge sensitive detector illuminated with an ultraviolet LED (275 nm) and a monochromatic laser(650 nm) using a dual fiber optic system installed in a small dilution refrigerator at Stanford University. We observed a population of fluorescence background events after UV exposure but not after exposure to the laser source. The fluorescence was likely due to scattered UV photons absorbed outside the detector. We discuss the possibility of fluorescence being a contributor to the low energy excess background observed in above-ground Dark Matter experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Analysis of Coronado State Historic Site artifacts using X‐rays

Abstract Two historic‐period metal artifacts were provided by the New Mexico Historic Sites to Los Alamos National Laboratory for non‐destructive analysis. The artifacts were a crossbow quarrel (or bolthead) and a reliquary pendant recovered from Kuaua Pueblo (also known as the Coronado Historic Site) in Bernalillo, NM. The quarrel is a heavily patinated metal that had been flattened due to compressive forces. The pendant consisted of a metal casing that had previously surrounded two center gemstones on the front and rear face of the pendant. The gemstone in the rear setting had fractured and was displaced from the setting, leaving only a small, loose fragment within the pendant for study. The front gem appeared to be very dark, near‐black in color, and the fragment of the rear gem was a bright red color. The artifacts were analyzed to ascertain their composition and glean insight into their provenance using the following X‐ray techniques: X‐ray computed tomography, confocal micro X‐ray fluorescence, and X‐ray diffraction. Infrared spectroscopy and electron microscopy were used on selected areas. Ultraviolet Raman spectra were collected on the two gems and the pendant. The metal material of the artifacts was found to be primarily composed of copper. The gems in the pendant were composed of manganese (front gem) and calcium (side gem).

36 MATERIALS SCIENCE↗
DOE OSTI2023

Development of a Low-Cost, Sensitivity-Optimized Fluorescence Sensor for Visible Spectrum Analysis

This paper presents an economically viable, sensitivity-optimized fluorescence sensor for detecting low concentrations of fluorophores in the visible spectrum range. The sensor employs a deep ultraviolet (DUV) 275-nm LED and a dichroic mirror to establish a co-axial optical path for excitation and emission. Instead of utilizing a general-purposed spectrometer optimized for high spectral resolution, the sensor strikes a balance between resolution and sensitivity by using an appropriate aperture size and optimized optical design tailored for the spectral characteristics of fluorophores. Here, the manuscript demonstrates measurements of ppb-level rare earth element (REE) samples containing terbium (Tb), europium (Eu), dysprosium (Dy), and samarium (Sm) in aqueous solutions. Through balanced design that optimizes collection of fluorescence emission without losing spectral information, this work shows the feasibility of developing a low-cost, compact, and highly sensitive fluorescence sensors with improved detection sensitivity when compared to bench-top commercial spectrofluorometers at far higher costs.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

Extended Accelerated Stress Testing (EAST) of Glass/Glass, Glass/Backsheet and Glass/Transparent Backsheet PV Modules: Influence of EVA and POE Encapsulants: Preprint

This paper presents the indoor extended accelerated stress testing (EAST) results of glass/glass (GG), glass/backsheet (GB) and glass/transparent backsheet (GT) modules having identical cells and two different encapsulant types, ethyl-vinyl-acetate (EVA) and polyolefin-elastomer (POE). Six 4-cell modules having the above-mentioned construction combinations were subjected to extended ultraviolet (UV; 600 kWh/m2), damp-heat (DH; 2000 hours) and thermal-cycling (TC; 600 cycles) tests. The post-stress UV fluorescent imaging, electroluminescent imaging, reflectance spectrophotometry and colorimetry results indicated that the grid finger degradation and encapsulant browning are slightly higher in the GG modules compared to the GB modules. The post-stress IV test results indicated, in general, that the GG/EVA modules tend to perform inferior to the GG/POE modules with the EAST evaluation.

EVA↗
DOE OSTI2023

Analysis of Coronado State Historic Site artifacts using X-rays

Two historic-period metal artifacts were provided by the New Mexico Historic Sites to Los Alamos National Laboratory for non-destructive analysis. The artifacts were a crossbow quarrel (or bolthead) and a reliquary pendant recovered from Kuaua Pueblo (also known as the Coronado Historic Site) in Bernalillo, NM. The quarrel is a heavily patinated metal that had been flattened due to compressive forces. The pendant consisted of a metal casing that had previously surrounded two center gemstones on the front and rear face of the pendant. The gemstone in the rear setting had fractured and was displaced from the setting, leaving only a small, loose fragment within the pendant for study. The front gem appeared to be very dark, near-black in color, and the fragment of the rear gem was a bright red color. The artifacts were analyzed to ascertain their composition and glean insight into their provenance using the following X-ray techniques: X-ray computed tomography, confocal micro X-ray fluorescence, and X-ray diffraction. Infrared spectroscopy and electron microscopy were used on selected areas. Ultraviolet Raman spectra were collected on the two gems and the pendant. The metal material of the artifacts was found to be primarily composed of copper. The gems in the pendant were composed of manganese (front gem) and calcium (side gem).

36 MATERIALS SCIENCE↗
DOE OSTI2024

Quantum-enhanced photoprotection in neuroprotein architectures emerges from collective light-matter interactions

Background Superradiance is the phenomenon of many identical quantum systems absorbing and/or emitting photons collectively at a higher rate than any one system can individually. This phenomenon has been studied analytically in idealized distributions of electronic two-level systems (TLSs), each with a ground and excited state, as well as numerically in realistic photosynthetic nanotubes and cytoskeletal architectures. Methods Superradiant effects are studied here in idealized toy model systems and realistic biological mega-networks of tryptophan (Trp) molecules, which are strongly fluorescent amino acids found in many proteins. Each Trp molecule acts as a chromophore absorbing in the ultraviolet spectrum and can be treated approximately as a TLS, with its 1 L a excited singlet state; thus, organized Trp networks can exhibit superradiance. Such networks are found, for example, in microtubules, actin filaments, and amyloid fibrils. Microtubules and actin filaments are spiral-cylindrical protein polymers that play significant biological roles as primary constituents of the eukaryotic cytoskeleton, while amyloid fibrils have been targeted in a variety of neurodegenerative diseases. We treat these proteinaceous Trp networks as open quantum systems, using a non-Hermitian Hamiltonian to describe interactions of the chromophore network with the electromagnetic field. We numerically diagonalize the Hamiltonian to obtain its complex eigenvalues, where the real part is the energy and the imaginary part is its associated enhancement rate. We also consider multiple realizations of increasing static disorder in either the site energies or the decay rates. Results We obtained the energies and enhancement rates for realistic microtubules, actin filament bundles, and amyloid fibrils of differing lengths, and we use these values to calculate the quantum yield, which is the ratio of the number of photons emitted to the number of photons absorbed. We find that all three of these structures exhibit highly superradiant states near the low-energy portion of the spectrum, which enhances the magnitude and robustness of the quantum yield to static disorder and thermal noise. Conclusion The high quantum yield and stable superradiant states in these biological architectures may play a photoprotective rolein vivo, downconverting energetic ultraviolet photons—absorbed from those emitted by reactive free radical species—to longer, safer wavelengths and thereby mitigating biochemical stress and photophysical damage. Contrary to conventional assumptions that quantum effects cannot survive in large biosystems at high temperatures, our results suggest that macropolymeric collectives of TLSs in microtubules, actin filaments, and amyloid fibrils exhibit increasingly observable and robust effects with increasing length, up to the micron scale, due to quantum coherent interactions in the single-photon limit. Superradiant enhancement and high quantum yield exhibited in neuroprotein polymers could thus play a crucial role in information processing in the brain, the development of neurodegenerative diseases such as Alzheimer’s and related dementias, and a wide array of other pathologies characterized by anomalous protein aggregates.

Physics↗
DOE OSTI2021

Nanomechanical and Fluorescence Characterizations of Weathered PV Module Encapsulation

Nanoindentation and fluorescence spectroscopy provide spatially resolved mechanical and chemical characterization for degradation of poly (ethylene-co-vinyl acetate) (EVA) encapsulants aged under accelerated weathering and in field deployed photovoltaic (PV) modules. For the accelerated weathering tests, two different EVA formulations in the glass/EVA/glass-laminated coupons were exposed to ultraviolet (UV) light for 180 days at three different temperatures (40, 60, and 80 °C) and UV intensities (0.4, 2.2, and 2.9 W/m2/nm at 340 nm). The fluorescence spectra and moduli were uniform through the cross section of both EVA formulations at the lowest temperature and UV intensity; however, under the highest temperature and UV intensity, the UV irradiated sides showed lower moduli and higher fluorescence compared to the opposite sides. For EVA obtained from PV modules deployed 27 years in Sacramento, CA, USA, changes in fluorescence intensity across the thickness were relatively greater than changes in modulus. On the other hand, for EVA obtained from the same type of module stored in the shed for 27 years, no fluorescence was observed, and a uniform modulus was seen through the EVA layer, but with substantially higher values than those obtained from the field-deployed modules. The different extent of changes between laboratory and field exposures suggests the importance of considering effects of temperature and UV intensity for designing a reliable accelerated testing. This study uniquely demonstrates the capability of microscale characterization using nanoindentation and fluorescence microscopy to monitor mechanical and chemical degradation of EVA encapsulants in PV modules.

14 SOLAR ENERGY↗
DOE OSTI2020

Amplified spontaneous emission in the extreme ultraviolet by expanding xenon clusters

Focused short-wavelength free-electron laser (FEL) pulses interacting with gas phase samples can induce by inner-shell ionization a short-lived population inversion, followed by coherent collective emission of directed, short, and strong radiation bursts. We extend our studies into the warm-dense matter (WDM) regime by investigating the nanoplasmas produced in an ensemble of nanometer-sized clusters by FEL irradiation. Here, additional pathways can also lead to strong, laserlike emission: Electron-ion collisions can yield a long-lived population inversion, and subsequent amplified spontaneous emission. We observe amplified spontaneous emission (ASE) in the extreme ultraviolet in xenon clusters excited by soft x-ray FEL pulses, we diagnose the generated nanoplasmas by fluorescence spectroscopy, and we study under various cluster and FEL parameters the directed ASE from the Xe 2+ 65 nm line. We show its exponential increase as a function of FEL irradiation power, and an accompanying collisional broadening of the emission spectra. These findings are corroborated by extensive numerical simulations based on theory, combining detailed hydrodynamic and kinetic simulations with time-dependent calculations of radiation transport, amplification, and collective emission in the WDM nanoplasma. Furthermore, our theoretical findings underline that population inversion is due to electron-ion collisions and that the observed decoherence processes can be empirically characterized by a phenomenological decoherence time in the range of 100–200 fs.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Temperature-dependent x-ray fluorescent response from thermographic phosphors under x-ray excitation

Phosphor thermometry has been successfully applied within several challenging environments. Typically, the thermographic phosphors are excited by an ultraviolet light source, and the temperature-dependent spectral or temporal response is measured. However, this is challenging or impossible in optically thick environments. In addition, emission from other sources (e.g., a flame) may interfere with the optical phosphor emission. Furthermore, a temperature dependent x-ray excitation/emission could alleviate these issues as x-rays could penetrate obscurants with no interference from flame luminosity. In addition, x-ray emission could allow for thermometry within solids while simultaneously x-ray imaging the structural evolution. In this study, select thermographic phosphors were excited via x-ray radiation, and their x-ray emission characteristics were measured at various temperatures. Several of the phosphors showed varying levels of temperature dependence with the strongest sensitivity occurring for YAG:Dy and ZnGa 2 O 4 :Mn. This approach opens a path for less intrusive temperature measurements, particularly in optically opaque multiphase and solid phase combustion environments.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Multiplexed structured imaging of laser induced fluorescence at 10 GHz rate

The frame rate of conventional high-speed imaging devices is limited by exposure time and signal read-out time. Structured imaging is able to push the frame rate beyond the limit of the imaging device. This work demonstrates the feasibility of potential TeraHz rate structured imaging with a multiplexed structured imaging setup. In this work, a multiplexed structured image capture system was employed to image UV laser induced krypton-II emission lines at 10 GHz. The measured emission intensity of the 764 nm line over time suggests a temporal resolution of 97 ps. The temporal resolution is adjustable, and the frame rate can be further increased to the TeraHz level.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Development of a cosmic ray oriented trigger for the fluorescence telescope on EUSO-SPB2

The Extreme Universe Space Observatory on a Super Pressure Balloon 2 (EUSO-SPB2), in preparation, aims to make the first observations of Ultra-High Energy Cosmic Rays (UHECRs) from near space using optical techniques. EUSO-SPB2 will prototype instrumentation for future satellite-based missions, including the Probe of Extreme Multi-Messenger Astrophysics (POEMMA) and K-EUSO. The payload will consist of two telescopes. The first is a Cherenkov telescope (CT) being developed to quantify the background for future below-the-limb very high energy (E 10 PeV) astrophysical neutrino observations, and the second is a fluorescence telescope (FT) being developed for detection of UHECRs. The FT will consist of a Schmidt telescope, and a 6192 pixel ultraviolet camera with an integration time of 1.05 s. The first step in the data acquisition process for the FT is a hardware level trigger in order to decide which data to record. In order to maximize the number of UHECR induced extensive air showers (EASs) which can be detected, a novel trigger algorithm has been developed based on the intricacies and limitations of the detector. Finally, the expected performance of the trigger has been characterized by simulations and, pending hardware verification, shows that EUSO-SPB2 is well positioned to attempt the first near-space observation of UHECRs via optical techniques.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Growth and Characterization of Epitaxial FeWO 4 Thin Films with Controlled Oxygen Stoichiometry

Here, we report the growth of single-phase epitaxial FeWO 4 thin films, using plasma-assisted molecular beam epitaxy, and investigate structural, optical, and electronic properties. The FeWO 4 films grow in (100) orientation on c-plane sapphire (0001) substrates and exhibit 3 rotational twin variants where FeWO 4 [001] is aligned to sapphire [100] equivalent in-plane directions. X-ray diffraction measurements indicate that the epitaxial FeWO 4 (100) structure is optimized when 80-100 W of rf power is applied to an atomic oxygen source during growth, yielding films with minimal strain and impurity phases or other orientations. In films grown with 120 W of rf power, FeWO 4 crystallites develop inhomogeneous and homogeneous strains and are potentially contaminated with Fe 3+ oxide phase impurities. In films grown with 60 W of rf power, FeWO 4 crystallites do not form fully epitaxial layers. X-ray photoelectron spectroscopy indicates that the structural changes are correlated with the Fe 3+ /Fe 2+ oxidation state ratio increasing from 0.6-1.4 with rf power from 60-120 W. X-ray fluorescence spectroscopy indicates that the Fe/W composition ratio is also increasing from 1.1-1.8 with rf power from 60-120 W. Ultraviolet and visible optical absorption spectra indicate a 1.8 ± 0.1 eV band gap with an additional interband absorption feature at 3.1 ± 0.1 eV in the 80-100 W films, with similar onsets observed in the 60 W films. In the 120 W films, the higher lying transition is shifted to 2.7 ± 0.1 eV due to the Fe 3+ enrichment. Electrical resistivity decreases over 2 orders of magnitude with oxidation from 10 4 -10 5 Ω cm in 60 W films to 120 ± 10 Ω cm in 120 W films. Thermopower measurements show p-type to n-type conductivity conversion when oxidation states shift from Fe 2+ majority in the 100 W films to Fe 3+ majority in the 120 W films. We conclude that electron polaron hopping driven by Fe 3+ is a dominant transport mechanism and a source of n-type conductivity in overoxidized FeWO 4 films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗