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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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NASA NTRS1988

Scanning Tunneling Microscopy methods for spectroscopic imaging of subsurface interfaces

A new method for spatially-resolved, spectroscopic investigation of subsurface interface structure has been developed. The method, Ballistic Electron Emission Microscopy (BEEM), is based on Scanning Tunneling Microscopy (STM) techniques. BEEM combines STM vacuum tunneling with unique ballistic electron spectroscopy capabilities. BEEM enables, for the first time, direct imaging of subsurface interface electronic properties with nanometer spatial resolution. STM topographic images of surface structure and BEEM images of subsurface properties are obtained simultaneously. BEEM capabilities are demonstrated by investigation of important metal-semiconductor interfaces.

Bell, L. D.↗
NASA NTRS1990

Off-plane imaging for milli-arcsecond X-ray observatories

The development of milliarcsecond imaging in X-ray astronomy is discussed in terms of a concept in which off-plane imaging is utilized to significantly increase spectroscopic and imaging resolution. Grazing incidence optics permit practical improvements of a factor of 10 in X-ray spectrographs, and a similar technique is described for a milliarcsecond X-ray observatory (MAX). MAX requires a very smooth mirror surface, operates at a plate scale that existing detectors cannot support, requires a small collecting area, and has to be designed as a highly stable structure.

Cash, Webster↗
NASA NTRS1997

Observations of the orbital debris complex by the Midcourse Space Experiment (MSX) satellite

The midcourse space experiment (MSX) provides the opportunity to observe debris at multiple, simultaneous wavelengths, or in conjunction with other sensors and prior data sets. The instruments onboard MSX include an infrared telescope, an infrared interferometer, a visible telescope, an ultraviolet telescope and a spectroscopic imager. The spacecraft carries calibration spheres for instrument calibration and atmospheric drag studies. The experimental program, the implementation aspects, the data reduction techniques and the preliminary results are described.

Vilas, Faith↗
DOE OSTI2020

Spectroscopic and theoretical studies of UN and UN +

The low-energy electronic states of UN and UN+ have been examined using high-level electronic structure calculations and two-color photoionization techniques. The experimental measurements provided an accurate ionization energy for UN (IE = 50 802 +/- 5 cm -1 ). Spectra for UN+ yielded ro-vibrational constants and established that the ground state has the electronic angular momentum projection omega = 4. Ab initio calculations were carried out using the spin-orbit state interacting approach with the complete active space second-order perturbation theory method. A series of correlation consistent basis sets were used in conjunction with small-core relativistic pseudopotentials on U to extrapolate to the complete basis set limits. The results for UN correctly obtained an omega = 3.5 ground state and demonstrated a high density of configurationally related excited states with closely similar ro-vibrational constants. Similar results were obtained for UN + , with reduced complexity owing to the smaller number of outer-shell electrons. The calculated IE for UN was in excellent agreement with the measured value. Improved values for the dissociation energies of UN and UN + , as well as their heats of formation, were obtained using the Feller-Peterson-Dixon composite thermochemistry method, including corrections up through coupled cluster singles, doubles, triples and quadruples. An analysis of the ab initio results from the perspective of the ligand field theory shows that the patterns of electronic states for both UN and UN + can be understood in terms of the underlying energy level structure of the atomic metal ion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Biomass Electrochemical Reactor for Upgrading Biorefinery Waste to Industrial Chemicals and Hydrogen

The goal of this project was to develop an electrochemical process for depolymerization of biorefinery lignin to industrial chemicals, most notably as replacements in resins. The project team consisted of Ohio University (lead organization), Hexion, Inc. and Lakehead University. There were six distinct project tasks, consisting of Initial Validation, Development of TiO 2 Nanowire-supported Ni-Co Electrocatalysts, Electrochemical Characterization of TiO 2 Nanowire-supported Ni-Co Electrocatalysts, Development of Electrochemical Flow Reactor for Production of Industrial Chemicals and Hydrogen, Product Formulations and Integrated Biorefinery Analysis. The project was divided into two budget periods. After intermediate validation near the end of Budget Period 1, the project was discontinued. This final report is intended to highlight major project objectives and results. Technical metrics were developed between the project team and the DOE validation team during the initial validation period. Critical technical metrics included conversion of lignin to products and product selectivity. Desired products were low molecular weight aromatic compounds in the 150-300 MW range. We targeted this class of compounds because of their potential to replace petroleum derivatives in resin formulations. Electrochemical oxidation of biorefinery lignin can lead to significant lignin depolymerization and conversion, with >40% of the lignin reacted. However, product stream analysis is extremely difficult. We were not able to adequately quantify the concentration of the primary oxidation products, or to determine with any degree of certainty what the product selectivity was. The project team initially proposed analytical techniques such as GC-MS to identify product distributions. However, due to 1) difficulty in extracting products into an organic phase suitable for GC analysis and 2) the wide range of product compounds with similar structures, GC-MS analysis was difficult to perform. The project team did have some success with NMR spectroscopic analysis, but not enough so to adequately identify product selectivity. By UV-vis spectroscopy and statistical analysis, we were able to confirm achieving the technical milestone for lignin conversion, and achieved at least 40% conversion by the electrochemical oxidation technique. However, we were not able to confirm product selectivity using GC-MS analysis, as originally postulated. Despite these difficulties, we were able to incorporate the product stream into a resin, and observed better resin synthesis behavior using the oxidized lignin versus the unoxidized lignin. However, no resin synthesized with oxidized biorefinery lignin met the commercial standards for resin quality. One potential problem with electrochemical oxidation of biomass is the competing oxygen evolution reaction (OER) at the reactor anode. We observed that, especially at higher anode potentials, the OER can consume up to 50% of the energy input to the system, meaning that much of the energy goes toward generation of an essentially worthless product (O 2 ). However, we also observed that the OER can be avoided almost entirely at lower potentials. These uncertainties made assigning a value to the electrochemical reactor product stream difficult. Any product generated electrochemically would have to be valuable enough to offset the additional cost of electricity incurred, including electricity to run the electrochemical reactor and the additional electricity that must be purchased because some of the lignin (which is currently burned in biorefineries to recover energy) is diverted to the electrochemical reactor. It is not clear at this time whether the product stream has sufficient economic value to offset these additional electricity costs. The two most promising areas for this project in terms of demonstrating economic feasibility are product stream analysis and resin synthesis. In particular, product stream analysis has proven to be difficult. With additional time, we would refine analytical techniques to better understand key product stream characteristics, such as aromatic compound content. Evaluating the product streams in resin synthesis would likely provide more information on the economic value of the product stream. If we could determine that value, then we would be able to better evaluate whether the electrochemical conversion approach is feasible. The details of this work are presented in the following final report. The report is organized into individual tasks for clarity, although all tasks were integrated and many occurred simultaneously.

09 BIOMASS FUELS↗
DOE OSTI2016

The clustering of galaxies in the completed SDSS-III Baryon Oscillation Spectroscopic Survey: combining correlated Gaussian posterior distributions

The cosmological information contained in anisotropic galaxy clustering measurements can often be compressed into a small number of parameters whose posterior distribution is well described by a Gaussian. Here, we present a general methodology to combine these estimates into a single set of consensus constraints that encode the total information of the individual measurements, taking into account the full covariance between the different methods. We also illustrate this technique by applying it to combine the results obtained from different clustering analyses, including measurements of the signature of baryon acoustic oscillations and redshift-space distortions, based on a set of mock catalogues of the final SDSS-III Baryon Oscillation Spectroscopic Survey (BOSS). Our results show that the region of the parameter space allowed by the consensus constraints is smaller than that of the individual methods, highlighting the importance of performing multiple analyses on galaxy surveys even when the measurements are highly correlated. Our paper is part of a set that analyses the final galaxy clustering data set from BOSS. The methodology presented here is used in Alam et al. to produce the final cosmological constraints from BOSS.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Catalog-level blinding on the bispectrum for DESI-like galaxy surveys

We evaluate the performance of the catalog-level blind analysis technique (blinding) presented in Brieden et al. (2020) in the context of a fixed template power spectrum and bispectrum analysis. This blinding scheme, which is tailored for galaxy redshift surveys similar to the Dark Energy Spectroscopic Instrument (DESI), has two components: the so-called “AP blinding” (concerning the dilation parameters α$_{∥}$, α$_{⊥}$) and “RSD blinding” (redshift space distortions, affecting the growth rate parameter f). Through extensive testing, including checks for the RSD part in cubic boxes, the impact of AP blinding on mocks with realistic survey sky coverage, and the implementation of a full AP+RSD blinding pipeline, our analysis demonstrates the effectiveness of the technique in preserving the integrity of cosmological parameter estimation when the analysis includes the bispectrum statistic. We emphasize the critical role of sophisticated — and difficult to accidentally unblind — blinding methods in precision cosmology.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Carrier recombination dynamics and temperature dependent optical properties of InAs–GaSb heterostructures

Heterostructures with two dissimilar materials could offer unprecedented properties if one can carefully synthesize these heterostructures with atomically smooth interfaces and reduced number of recombination centers. InAs/GaSb-based heterostructures have technological importance for long wavelength infrared photodetectors if one can synthesize these materials with high-optical quality and high-carrier lifetime. In this work, the InAs/GaSb heterostructures with a different number of heterointerfaces and growth conditions were grown by solid source molecular beam epitaxy using valved cracker sources for both arsenic and antimony. Precise control of growth parameters and shutter sequences enabled abrupt InAs/GaSb heterointerfaces, as supported by a high-resolution transmission electron microscopic study. The temperature and power-dependent optical properties by photoluminescence (PL) spectroscopic analysis of InAs/GaSb heterostructures with 4 and 28 heterointerfaces displayed donor to the acceptor and the exciton bound to complex defects (V Ga Ga Sb ) 0 . Since the optical transition in PL measurements serves to determine the quality of the material, and the observed excitonic transitions from these InAs/GaSb heterostructures is an indication of high-quality materials. The high-carrier lifetimes of 139 ns to 185 ns from InAs/GaSb heterostructures were measured using microwave photoconductivity decay (μ-PCD) technique at room temperature. The observed increase in carrier lifetime is due to the decreasing number of Ga-related carrier recombination centers or defect complexes. This is further supported by the PL spectroscopic study. In addition, the carrier lifetime with different injection levels is supported by Shockley–Read–Hall recombination. We report these InAs/GaSb heterostructures with high-optical quality and high-carrier lifetimes would offer a path for the development of high-performance infrared photodetectors.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Trends in alkali metal hydrosulfides: A combined Fourier transform microwave/millimeter-wave spectroscopic study of KSH (X{sup ~1}A{sup ′})

The pure rotational spectrum of KSH (X{sup ~1}A{sup ′}) has been measured using millimeter-wave direct absorption and Fourier transform microwave (FTMW) techniques. This work is the first gas-phase experimental study of this molecule and includes spectroscopy of KSD as well. In the millimeter-wave system, KSH was synthesized in a DC discharge from a mixture of potassium vapor, H{sub 2}S, and argon; a discharge-assisted laser ablation source, coupled with a supersonic jet expansion, was used to create the species in the FTMW instrument. Five and three rotational transitions in the range 3–57 GHz were recorded with the FTMW experiment for KSH and KSD, respectively, in the K{sub a} = 0 component; in these data, potassium quadrupole hyperfine structure was observed. Five to six transitions with K{sub a} = 0–5 were measured in the mm-wave region (260–300 GHz) for the two species. The presence of multiple asymmetry components in the mm-wave spectra indicates that KSH has a bent geometry, in analogy to other alkali hydrosulfides. The data were analyzed with an S-reduced asymmetric top Hamiltonian, and rotational, centrifugal distortion, and potassium electric quadrupole coupling constants were determined for both isotopolgues. The r{sub 0} geometry for KSH was calculated to be r{sub S-H} = 1.357(1) Å, r{sub K-S} = 2.806(1) Å, and θ{sub M-S-H} (°) = 95.0 (1). FTMW measurements were also carried out on LiSH and NaSH; metal electric quadrupole coupling constants were determined for comparison with KSH. In addition, ab initio computations of the structures and vibrational frequencies at the CCSD(T)/6-311++G(3df,2pd) and CCSD(T)/aug-cc-pVTZ levels of theory were performed for LiSH, NaSH, and KSH. Overall, experimental and computational data suggest that the metal-ligand bonding in KSH is a combination of electrostatic and covalent forces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Reduced electron exposure for energy-dispersive spectroscopy using dynamic sampling

Analytical electron microscopy and spectroscopy of biological specimens, polymers, and other beam sensitive materials has been a challenging area due to irradiation damage. There is a pressing need to develop novel imaging and spectroscopic imaging methods that will minimize such sample damage as well as reduce the data acquisition time. The latter is useful for high-throughput analysis of materials structure and chemistry. Here, in this work, we present a novel machine learning based method for dynamic sparse sampling of EDS data using a scanning electron microscope. Our method, based on the supervised learning approach for dynamic sampling algorithm and neural networks based classification of EDS data, allows a dramatic reduction in the total sampling of up to 90%, while maintaining the fidelity of the reconstructed elemental maps and spectroscopic data. In conclusion, we believe this approach will enable imaging and elemental mapping of materials that would otherwise be inaccessible to these analysis techniques.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Nine lensed quasars and quasar pairs discovered through spatially extended variability in Pan-STARRS

We present the proof of concept of a method for finding strongly lensed quasars using their spatially extended photometric variability through difference imaging in cadenced imaging survey data. We applied the method to Pan-STARRS, starting with an initial selection of 14 107Gaiamultiplets with quasar-like infrared colours from WISE. We identified 229 candidates showing notable spatially extended variability during the Pan-STARRS survey period. These include 20 known lenses and an additional 12 promising candidates for which we obtained long-slit spectroscopy follow-up. This process resulted in the confirmation of four doubly lensed quasars, four unclassified quasar pairs, and one projected quasar pair. Only three are pairs of stars or quasar+star projections. The false-positive rate accordingly is 25%. The lens separations are between 0.81″ and 1.24″, and the source redshifts lie betweenz = 1.47 andz = 2.46. Three of the unclassified quasar pairs are promising dual-quasar candidates with separations ranging from 6.6 to 9.3 kpc. We expect that this technique is a particularly efficient way to select lensed variables in the upcomingRubin-LSST, which will be crucial given the expected limitations for spectroscopic follow-up.

Astronomy & Astrophysics↗
DOE OSTI2011

BERYLLIUM AND ALPHA-ELEMENT ABUNDANCES IN A LARGE SAMPLE OF METAL-POOR STARS

The light elements, Li, Be, and B, provide tracers for many aspects of astronomy including stellar structure, Galactic evolution, and cosmology. We have made observations of Be in 117 metal-poor stars ranging in metallicity from [Fe/H] = -0.5 to -3.5 with Keck I/HIRES. Our spectra are high resolution ({approx}42,000) and high signal to noise (the median is 106 per pixel). We have determined the stellar parameters spectroscopically from lines of Fe I, Fe II, Ti I, and Ti II. The abundances of Be and O were derived by spectrum synthesis techniques, while abundances of Fe, Ti, and Mg were found from many spectral line measurements. There is a linear relationship between [Fe/H] and A(Be) with a slope of +0.88 {+-} 0.03 over three orders of magnitude in [Fe/H]. We find that Be is enhanced relative to Fe; [Be/Fe] is +0.40 near [Fe/H] {approx}-3.3 and drops to 0.0 near [Fe/H] {approx}-1.7. For the relationship between A(Be) and [O/H], we find a gradual change in slope from 0.69 {+-} 0.13 for the Be-poor/O-poor stars to 1.13 {+-} 0.10 for the Be-rich/O-rich stars. Inasmuch as the relationship between [Fe/H] and [O/H] seems robustly linear (slope = +0.75 {+-} 0.03), we conclude that the slope change in Be versus O is due to the Be abundance. Much of the Be would have been formed in the vicinity of Type II supernova (SN II) in the early history of the Galaxy and by Galactic cosmic-ray (GCR) spallation in the later eras. Although Be is a by-product of CNO, we have used Ti and Mg abundances as alpha-element surrogates for O in part because O abundances are rather sensitive to both stellar temperature and surface gravity. We find that A(Be) tracks [Ti/H] very well with a slope of 1.00 {+-} 0.04. It also tracks [Mg/H] very well with a slope of 0.88 {+-} 0.03. We have kinematic information on 114 stars in our sample and they divide equally into dissipative and accretive stars. Almost the full range of [Fe/H] and [O/H] is covered in each group. There are distinct differences in the relationships of A(Be) and [Fe/H] and of A(Be) and [O/H] for the dissipative and the accretive stars. It is likely that the formation of Be in the accretive stars was primarily in the vicinity of SN II, while the Be in the dissipative stars was primarily formed by GCR spallation. We find that Be is not as good a cosmochronometer as Fe. We have found a spread in A(Be) that is valid at the 4{sigma} level between [O/H] = -0.5 and -1.0, which corresponds to -0.9 and -1.6 in [Fe/H].

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Studies of Heterogeneously Catalyzed Liquid-Phase Alcohol Oxidation on Platinum bySum-frequency Generation Vibrational Spectroscopy and Reaction Rate Measurements

Compared to many branches of chemistry, the molecular level study of catalytically active surfaces is young. Only with the invention of ultrahigh vacuum technology in the past half century has it been possible to carry out experiments that yield useful molecular information about the reactive occurrences at a surface. The reason is two-fold: low pressure is necessary to keep a surface clean for an amount of time long enough to perform an experiment, and most atomic scale techniques that are surface speci c (x-ray photoelectron spectroscopy, electron energy loss spectroscopy, Auger electron spectroscopy, etc.) cannot be used at ambient pressures, because electrons, which act as chemical probes in these techniques, are easily scattered by molecules. Sum-frequency generation (SFG) vibrational spectroscopy is one technique that can provide molecular level information from the surface without the necessity for high vacuum. Since the advent of SFG as a surface spectroscopic tool it has proved its worth in the studies of surface catalyzed reactions in the gas phase, with numerous reactions in the gas phase having been investigated on a multitude of surfaces. However, in situ SFG characterization of catalysis at the solid-liquid interface has yet to be thoroughly pursued despite the broad interest in the use of heterogeneous catalysts in the liquid phase as replacements for homogeneous counterparts. This work describes an attempt to move in that direction, applying SFG to study the solid-liquid interface under conditions of catalytic alcohol oxidation on platinum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Delayed Gamma-ray Assay for Nuclear Materials Safeguards. Comprehensive Technology Readiness Assessment

Spectroscopic analysis of beta-delayed gamma-rays emitted from fission products following active interrogation was investigated as a non-destructive assay technique for detection and characterization of nuclear materials in shielded and complex configurations. This measurement technique is expected to be applicable to a variety of applications within the nuclear material safeguards, arms control, and emergency response areas, where active neutron interrogation is acceptable. Potential applications of the delayed gamma-ray assay in the nuclear material safeguards area include characterization of U and Pu isotopic content in spent and unirradiated nuclear fuel, enrichment measurements, verification of bulk material in containers, and the characterization of nuclear wastes. In the arms control area, this method can be used as a part of warhead dismantlement measurements to confirm separation of components, and may be applicable in warhead confirmation. In the context of emergency response, it can be used for detailed diagnostics of an unknown item. At present, the delayed gamma-ray assay technology reliably qualifies for the Technical Readiness Level 3 (TRL 3). The R&D work completed under this project has successfully demonstrated the empirical proof-of-concept for this active interrogation technology for a variety of measurement configurations, neutron sources, and nuclear material samples. A robust first-principles analytical signature modeling methodology was developed, experimentally validated, and can be easily extrapolated to a range of realistic measurement scenarios. Several response analysis methodologies have been implemented and deemed reliable for a variety of active interrogation applications in the areas of nuclear material safeguards, arms control, and emergency response. The initial readiness level before the start of this project was assessed at TRL 0, since only fragmentary records of the signature observations and speculative statements of the relevant non-destructive assay applications existed at that time. The delayed gamma-ray technology readiness can be easily advanced to TRL 4 in a short period, if a certain measurement application is specified and set for a demonstration in a laboratory environment. The critical hardware components of the delayed gamma-ray measurement technology (neutron generators, gamma-ray spectrometers) are readily available as COTS and can be configured for a specific deployment configuration. The primary risk of the delayed gamma-ray assay methodology is defined by the applicationspecific uncertainties. Evaluation of the system performance can be effectively completed once the expected measurement purpose, nuclear material characteristics, dimensions, and radiation exposure constraints are specified. A minor risk can be associated with the delayed gamma-ray response analysis techniques. Several approaches were proposed and demonstrated primarily using the modeled signatures. The observed performance may not be easily transferrable to the conditions of a real measurement setup, and some additional R&D may be required. Overall, the delayed gamma-ray assay technology can be recommended for follow-up demonstrations addressing relevant measurement applications in the areas of nuclear material safeguards, arms control, and emergency response.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1989

Comments on containerless bulk crystal growth and epitaxy in space and on their implications regarding non-contact temperature measurements

Containerless methods are sought for bulk crystal growth and epitaxy which thus far are a less visible component of materials science in space efforts. In the opinion of the author, this is an anomaly which ought to be corrected, because container interactions are a major problem in earth bound materials processing, including crystal growth, and can be avoided or at least significantly reduced in space. The space environment is unique in solving some of these problems, e.g., memory effects in the integration of different classes of materials in high resolution multilayer heterostructures by molecular beam epitaxy or organometallic molecular beam epitaxy. Spectroscopic method of noncontact temperature measurements exist that could be developed in this context. The error in the absolute temperature measurement achieved by these techniques decreases with decreasing substrate temperature and supplements pyrometric measurements that are better suited for high temperature measurements.

Bachmann, Klaus J.↗
DOE OSTI2017

The Solar X-Ray Limb

We describe a new technique to measure the height of the X-ray limb with observations from occulted X-ray flare sources as observed by the RHESSI (the Reuven Ramaty High-Energy Spectroscopic Imager) satellite. This method has model dependencies different from those present in traditional observations at optical wavelengths, which depend upon detailed modeling involving radiative transfer in a medium with complicated geometry and flows. It thus provides an independent and more rigorous measurement of the “true” solar radius, which means that of the mass distribution. RHESSI’s measurement makes use of the flare X-ray source’s spatial Fourier components (the visibilities), which are sensitive to the presence of the sharp edge at the lower boundary of the occulted source. We have found a suitable flare event for analysis, SOL2011-10-20T03:25 (M1.7), and report a first result from this novel technique here. Using a four-minute integration over the 3–25 keV photon energy range, we find R{sub X-ray}=960.11±0.15±0.29 arcsec, at 1 au, where the uncertainties include statistical uncertainties from the method and a systematic error. The standard VAL-C model predicts a value of 959.94 arcsec, which is about 1σ below our value.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Spectroscopic and dielectric response of zinc bismuth phosphate glasses as a function of chromium content

Graphical abstract: 20ZnF{sub 2}–(20 − x)Bi{sub 2}O{sub 3}–60P{sub 2}O{sub 5}:xCr{sub 2}O{sub 3} (0 ≤ x ≤2 mol%) glasses are prepared by melt quenching technique. The optical absorption spectra of present glasses are analyzed as a function of chromium content. The absorption bands are assigned to {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 1g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 2g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 2}T{sub 1g}(G) and {sup 4}A{sub 2g}(F) ⟶ {sup 2}E{sub g}(G) transitions of Cr{sup 3+} ions. - Highlights: • ZnF{sub 2}–Bi{sub 2}O{sub 3}–P{sub 2}O{sub 5}:Cr{sub 2}O{sub 3} glasses were prepared by melt quenching and annealing. • Spectroscopic and dielectric properties of chromium ions were investigated. • ESR and optical absorption spectra indicate the co-existence of Cr{sup 6+} ions with Cr{sup 5+} ions and Cr{sup 3+} ions. • Cr{sup 3+} ions act as modifiers and influence the semiconducting nature of the glass system. - Abstract: 20ZnF{sub 2}–(20 − x)Bi{sub 2}O{sub 3}–60P{sub 2}O{sub 5}:xCr{sub 2}O{sub 3} (0 ≤ x ≤2 mol%) glasses are prepared by melt quenching technique. Amorphous nature of these samples is confirmed by X-ray diffraction (XRD) analysis. FTIR study reveals bands due to CrO{sub 6}(o{sub d}) and CrO{sub 4}{sup 2−}(T{sub d}) units along with conventional phosphate groups. The optical absorption and ESR studies of present glasses are analyzed as a function of chromium content. The absorption bands are assigned to {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 1g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 2g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 2}T{sub 1g}(G) and {sup 4}A{sub 2g}(F) ⟶ {sup 2}E{sub g}(G) transitions of Cr{sup 3+} ions. The highest concentration of Cr{sup 3+} ions (in octahedral sites, with network modifying positions) is found in the sample with 2.0 mol% of Cr{sub 2}O{sub 3}. The analysis of dielectric properties indicates a gradual increase in semiconducting character with increase in the concentration of Cr{sub 2}O{sub 3} from 0.2 to 2.0 mol%. The studies on dielectric breakdown strength identify the highest insulating strength for lowest mol% of Cr{sub 2}O{sub 3} in the present samples.

36 MATERIALS SCIENCE↗