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All sourcesNASA NTRSDOE OSTI
NASA NTRS2022

STITCH: A Subgrid-Scale Model for Energy Buildup in the Solar Corona

The solar corona routinely exhibits explosive activity, in particular coronal mass ejections and their accompanying eruptive ares, that have global-scale consequences. These events and their smaller counterparts, coronal jets, originate in narrow, sinuous lament channels. The key processes that form and evolve the channels operate on still smaller spatial scales and much longer time scales, culminating in a vast separation of characteristic lengths and times that govern these explosive phenomena. In this article, we describe implementation and tests of an efficient subgrid-scale model for generating eruptive structures in magnetohydrodynamics (MHD) coronal simulations. STITCH {STatistical InjecTion of Condensed Helicity { is a physics-based, reduced representation of helicity condensation: a process wherein small-scale vortical surface convection forms ubiquitous current sheets, and pervasive reconnection across the sheets mediates an inverse cascade of magnetic helicity and free energy, thereby forming the lament channels. We have developed a formalism, STITCH, that abstracts these complex processes into a single term in Ohm's law and the induction equation that directly injects tangential magnetic flux into the low corona. We show that our approach is in very good agreement with a full helicity-condensation calculation that treats all of the dynamics explicitly, while enabling substantial reductions in temporal duration and spatial resolution. In addition, we illustrate the flexibility of STITCH at forming localized lament channels and at energizing complex surface flux distributions that have sinuous boundaries. STITCH is simple to implement and computationally ecient, making it a powerful technique for physics-based modeling of solar eruptive events.

J T Dahlin↗
DOE OSTI2019

Perspective on identifying and characterizing the processes controlling iron speciation and residence time at the atmosphere-ocean interface

It is well recognized that the atmospheric deposition of iron (Fe) affects ocean productivity, atmospheric CO 2 uptake, ecosystem diversity, and overall climate. Despite significant advances in measurement techniques and modeling efforts, discrepancies persist between observations and models that hinder accurate predictions of processes and their global effects. Here, we provide an assessment report on where the current state of knowledge is and where future research emphasis would have the highest impact in furthering the field of Fe atmosphere-ocean biogeochemical cycle. These results were determined through consensus reached by diverse researchers from the oceanographic and atmospheric science communities with backgrounds in laboratory and in situ measurements, modeling, and remote sensing. We discuss i) novel measurement methodologies and instrumentation that allow detection and speciation of different forms and oxidation states of Fe in deliquesced mineral aerosol, cloud/rainwater, and seawater; ii) oceanic models that treat Fe cycling with several external sources and sinks, dissolved, colloidal, particulate, inorganic, and organic ligand-complexed forms of Fe, as well as Fe in detritus and phytoplankton; and iii) atmospheric models that consider natural and anthropogenic sources of Fe, mobilization of Fe in mineral aerosols due to the dissolution of Fe-oxides and Fe-substituted aluminosilicates through proton-promoted, organic ligand-promoted, and photo-reductive mechanisms. In addition, the study identifies existing challenges and disconnects (both fundamental and methodological) such as i) inconsistencies in Fe nomenclature and the definition of bioavailable Fe between oceanic and atmospheric disciplines, and ii) the lack of characterization of the processes controlling Fe speciation and residence time at the atmosphere-ocean interface. Such challenges are undoubtedly caused by extremely low concentrations, short lifetime, and the myriad of physical, (photo)chemical, and biological processes affecting global biogeochemical cycling of Fe. However, we also argue that the historical division (separate treatment of Fe biogeochemistry in oceanic and atmospheric disciplines) and the classical funding structures (that often create obstacles for transdisciplinary collaboration) are also hampering the advancement of knowledge in the field. Finally, the study provides some specific ideas and guidelines for laboratory studies, field measurements, and modeling research required for improved characterization of global biogeochemical cycling of Fe in relationship with other trace elements and essential nutrients. In conclusion, the report is intended to aid scientists in their work related to Fe biogeochemistry as well as program managers at the relevant funding agencies

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

2,3,7,8-Tetrachlorodibenzo-p-dioxin has both pro-carcinogenic and anti-carcinogenic effects on neuroendocrine prostate carcinoma formation in TRAMP mice

It is well established that the prototypical aryl hydrocarbon receptor (AHR) agonist 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) can both cause and protect against carcinogenesis in non-transgenic rodents. But because these animals almost never develop prostate cancer with old age or after carcinogen exposure, whether AHR activation can affect cancer of the prostate remained unknown. We used animals designed to develop this disease, Transgenic Adenocarcinoma of the Mouse Prostate (TRAMP) mice, to investigate the potential role of AHR signaling in prostate cancer development. We previously reported that AHR itself has prostate tumor suppressive functions in TRAMP mice; i.e., TRAMP mice in which Ahr was knocked out developed neuroendocrine prostate carcinomas (NEPC) with much greater frequency than did those with both Ahr alleles. In the present study we investigated effects of AHR activation by three different xenobiotics. In utero and lactational TCDD exposure significantly increased NEPC tumor incidence in TRAMP males, while chronic TCDD treatment in adulthood had the opposite effect, a significant reduction in NEPC incidence. Chronic treatment of adult TRAMP mice with the low-toxicity selective AHR modulators indole-3-carbinol or 3,3′-diindolylmethane did not significantly protect against these tumors. Thus, we demonstrate, for the first time, that ligand-dependent activation of the AHR can alter prostate cancer incidence. The nature of the responses depended on the timing of AHR activation and ligand structures. - Highlights: • TRAMP mice model aggressive neuroendocrine prostate carcinomas in men • In utero/lactational TCDD exposure raised prostate cancer incidence in TRAMP mice. • TCDD treatment in adulthood lowered prostate cancer incidence in TRAMP mice. • No significant protection was seen in TRAMP mice given I3C or DIM in adulthood. • This is the first report that TCDD alters prostate cancer incidence in lab animals.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2019

Modification of Carbon Nitride/Reduced Graphene Oxide van der Waals Heterostructure with Copper Nanoparticles To Improve CO 2 Sensitivity

Carbon nitride/reduced graphene oxide (rGO) van der Waals heterostructures (vdWH) have previously shown exceptional oxygen sensitivity via a photoredox mechanism, making it a potential material candidate for various applications such as oxygen reduction reaction catalysis and oxygen sensing. In this work, the electronic structure of a carbon nitride/rGO composite is modified through the introduction of copper nanoparticles (NPs). When incorporated into a chemiresistor device, this vdWH displayed a newfound CO 2 sensitivity. The effects of humidity and light were investigated and found to be crucial components for the CO 2 sensitivity. Density functional theory calculations performed on a carbon nitride/copper NP@rGO model system found an enhanced stabilization of CO 2 caused by H-bonds between the carbon nitride layer and chemisorbed CO 2 on copper, pointing to the important role played by humidity. The synergetic effect between the carbon nitride layer interfaced with CuNP@rGO, in combination with humidity and light (395 nm) irradiation, is found to be responsible for the newfound sensitivity toward CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Dry Reforming of Ethane and Butane with CO 2 over PtNi/CeO 2 Bimetallic Catalysts

Dry reforming is a potential process to convert CO 2 and light alkanes into syngas (H 2 and CO), which can be subsequently transformed to chemicals and fuels. Here in this work, PtNi bimetallic catalysts have been investigated for dry reforming of ethane and butane using both model surfaces and supported powder catalysts. The PtNi bimetallic catalyst shows an improvement in both activity and stability as compared to the corresponding monometallic catalysts. The formation of PtNi alloy and the partial reduction of Ce 4+ to Ce 3+ under reaction conditions are demonstrated by in-situ Ambient Pressure X-ray Photoemission Spectroscopy (AP-XPS), X-ray Diffraction (XRD) and X-ray Absorption Fine Structure (XAFS) measurements. A Pt-rich bimetallic surface is revealed by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) following CO adsorption. Combined in-situ experimental results and Density Functional Theory (DFT) calculations suggest that the Pt-rich PtNi bimetallic surface structure would weaken the binding of surface oxygenates/carbon species and reduce the activation energy for C-C bond scission, leading to an enhanced dry reforming activity.

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

Defect filtering for thermal expansion induced dislocations in III–V lasers on silicon

Epitaxially integrated III–V semiconductor lasers for silicon photonics have the potential to dramatically transform information networks, but currently, dislocations limit performance and reliability even in defect-tolerant InAs quantum dot (QD)-based lasers. Despite being below the critical thickness, QD layers in these devices contain previously unexplained misfit dislocations, which facilitate non-radiative recombination. We demonstrate here that these misfit dislocations form during post-growth cooldown due to the combined effects of (1) thermal-expansion mismatch between the III–V layers and silicon and (2) mechanical hardening in the active region. By incorporating an additional sub-critical thickness, indium-alloyed “misfit dislocation trapping layer,” we leverage these mechanical hardening effects to our advantage, displacing 95% of misfit dislocations from the QD layer in model structures. Unlike conventional dislocation mitigation strategies, the trapping layer reduces neither the number of threading dislocations nor the number of misfit dislocations. It simply shifts the position of misfit dislocations away from the QD layer, reducing the defects' impact on luminescence. In full lasers, adding a misfit dislocation trapping layer both above and below the QD active region displaces misfit dislocations and substantially improves performance: we measure a twofold reduction in lasing threshold currents and a greater than threefold increase in output power. Overall, our results suggest that devices employing both traditional threading dislocation reduction techniques and optimized misfit dislocation trapping layers may finally lead to fully integrated, commercially viable silicon-based photonic integrated circuits.

36 MATERIALS SCIENCE↗
DOE OSTI2014

SU-D-16A-02: A Novel Methodology for Accurate, Semi-Automated Delineation of Oral Mucosa for Radiation Therapy Dose-Response Studies

Purpose: The significant morbidity caused by radiation-induced acute oral mucositis means that studies aiming to elucidate dose-response relationships in this tissue are a high priority. However, there is currently no standardized method for delineating the mucosal structures within the oral cavity. This report describes the development of a methodology to delineate the oral mucosa accurately on CT scans in a semi-automated manner. Methods: An oral mucosa atlas for automated segmentation was constructed using the RayStation Atlas-Based Segmentation (ABS) module. A radiation oncologist manually delineated the full surface of the oral mucosa on a planning CT scan of a patient receiving radiotherapy (RT) to the head and neck region. A 3mm fixed annulus was added to incorporate the mucosal wall thickness. This structure was saved as an atlas template. ABS followed by model-based segmentation was performed on four further patients sequentially, adding each patient to the atlas. Manual editing of the automatically segmented structure was performed. A dose comparison between these contours and previously used oral cavity volume contours was performed. Results: The new approach was successful in delineating the mucosa, as assessed by an experienced radiation oncologist, when applied to a new series of patients receiving head and neck RT. Reductions in the mean doses obtained when using the new delineation approach, compared with the previously used technique, were demonstrated for all patients (median: 36.0%, range: 25.6% – 39.6%) and were of a magnitude that might be expected to be clinically significant. Differences in the maximum dose that might reasonably be expected to be clinically significant were observed for two patients. Conclusion: The method developed provides a means of obtaining the dose distribution delivered to the oral mucosa more accurately than has previously been achieved. This will enable the acquisition of high quality dosimetric data for use in dose-response studies. We would like to thank the Engineering and Physical Sciences Research Council for funding. We acknowledge support from the NIHR RM/ICR Biomedical Research Centre. RayStatation was used under an evaluation agreement with RaySearch Laboratories AB.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Recycling Disassembled Automotive Plastic Components for New Vehicle Components: Enabling the Automotive Circular Economy

As the automotive industry increasingly relies on plastic components to meet fuel efficiency and emissions targets, the challenge of managing end-of-life vehicle (ELV) plastics continues to grow. Currently, more than 80% of ELV plastics in the U.S. are landfilled due to limited economic incentives and technical barriers to recycling. This study examines a mechanical recycling pathway for thermoplastic components disassembled from ELVs and assesses their usability for reintegration into new vehicle parts. Four representative materials were chosen based on material labels embedded in recovered parts and aligned with their virgin industrial equivalents: polypropylene (PP), 10% talc-filled PP (PP-T10), 20% talc-filled PP (PP-T20), and a 20% glass-/mineral-filled polyamide (PA6 + GF7 + MF13). The materials underwent shredding, drying, and injection molding before being characterized by particle size analysis, density measurement, thermal analysis (TGA, DSC), mechanical testing, and heat deflection temperature (HDT) evaluation. The results in this work indicated that minor differences in crystallinity were observed and small differences between model materials and ELV materials could have contributed to these changes. Mechanical testing revealed that neat polypropylene suffered a 15–20% reduction in stiffness and tensile strength, but talc-filled polypropylene and glass/mineral-filled nylon retained >90% of their modulus, strength, and heat deflection temperature values relative to virgin controls. Differences between virgin and ELV materials could have been attributed to use life degradation, contamination during use life, or even chemical/processing differences in model materials and ELV materials. However, these findings suggest that mechanically recycled, disassembled ELV plastics can retain sufficient structural performance to support circularity efforts in the automotive sector.

automotive recycling↗
NASA NTRS1979

Preliminary noise tradeoff study of a Mach 2.7 cruise aircraft

NASA computer codes in the areas of preliminary sizing and enroute performance, takeoff and landing performance, aircraft noise prediction, and economics were used in a preliminary noise tradeoff study for a Mach 2.7 design supersonic cruise concept. Aerodynamic configuration data were based on wind-tunnel model tests and related analyses. Aircraft structural characteristics and weight were based on advanced structural design methodologies, assuming conventional titanium technology. The most advanced noise prediction techniques available were used, and aircraft operating costs were estimated using accepted industry methods. The 4-engines cycles included in the study were based on assumed 1985 technology levels. Propulsion data was provided by aircraft manufacturers. Additional empirical data is needed to define both noise reduction features and other operating characteristics of all engine cycles under study. Data on VCE design parameters, coannular nozzle inverted flow noise reduction and advanced mechanical suppressors are urgently needed to reduce the present uncertainties in studies of this type.

Mascitti, V. R.↗
NASA NTRS1983

Algorithm development for the control design of flexible structures

The critical problems associated with the control of highly damped flexible structures are outlined. The practical problems include: high performance; assembly in space, configuration changes; on-line controller software design; and lack of test data. Underlying all of these problems is the central problem of modeling errors. To justify the expense of a space structure, the performance requirements will necessarily be very severe. On the other hand, the absence of economical tests precludes the availability of reliable data before flight. A design algorithm is offered which: (1) provides damping for a larger number of modes than the optimal attitude controller controls; (2) coordinates the rate of feedback design with the attitude control design by use of a similar cost function; and (3) provides model reduction and controller reduction decisions which are systematically connected to the mathematical statement of the control objectives and the disturbance models.

Skelton, R. E.↗
NASA NTRS1984

Waveform inversion of mantle Love waves - The Born seismogram approach

Normal mode theory, extended to the slightly laterally heterogeneous earth by the first-order Born approximation, is applied to the waveform inversion of mantle Love waves (200-500 sec) for the earth's lateral heterogeneity at l = 2 and a spherically symmetric anelasticity (Q sub mu) structure. The data are from the Global Digital Seismograph Network (GDSN). The l = 2 pattern is very similar to the results of other studies that used either different methods, such as phase velocity measurements and multiplet location measurements, or a different data set, such as mantle Rayleigh waves from different instruments. The results are carefully analyzed for variance reduction and are most naturally explained by heterogeneity in the upper 420 km. Because of the poor resolution of the data set for the deep interior, however, a fairly large heterogeneity in the transition zones, of the order of up to 3.5 percent in shear wave velocity, is allowed. It is noteworthy that Love waves of this period range can not constrain the structure below 420 km and thus any model presented by similar studies below this depth are likely to be constrained by Rayleigh waves (spheroidal modes) only.

Tanimoto, T.↗
NASA NTRS1993

Compressive behavior of undulations in filament-wound composites

The compressive performance of a filament-wound cylinder can be severely degraded by unavoidable fiber curvatures due to the presence of crossover bands. These crossover bands contain fiber undulations which influence the compressive strength, stiffness, and associated failure mechanisms of a filament-wound structure. The primary objectives of this study were to identify failure mechanisms and measure the compressive strength and stiffness of test specimens which model the microundulations. Compressive tests were conducted on flat-panel coupons which were developed to model the mechanics of large-scale fiber undulation regions in filament-wound composite cylinders. The primary effect of the undulation regions within a filament-wound structure is to initiate failure. Depending on the overall laminate configuration, the failure process includes various combinations of failure mechanisms, such as delaminations, matrix splitting and/or fiber fracture. These failure mechanisms are aggravated by the presence of large deformations caused by the reduction in local compressive stiffness and the introduction of complex material couplings due to the fiber undulation. Furthermore, the adjacent layers have been shown to strongly influence the compressive strength, stiffness, and associated failure mechanisms by weakening or reinforcing the laminate.

Jensen, David W.↗
NASA NTRS1994

Structural design criteria for filament-wound composite shells

Advanced composite cylinders, manufactured by filament winding, provide a cost effective solution to many present structural applications; however, the compressive performance of filament-wound cylinders is lower than comparable shells fabricated from unidirectional tape. The objective of this study was to determine the cause of this reduction in thin filament-wound cylinders by relating the manufacturing procedures to the quality of the cylinder and to its compressive performance. The experiments on cylinder buckling were complemented by eigenvalue buckling analysis using a detailed geometric model in a finite element analysis. The applicability of classical buckling analyses was also investigated as a design tool.

Hahn, H. T.↗
NASA NTRS2002

Acoustic Benefits of Stator Sweep and Lean for a High Tip Speed Fan

A model high-speed fan stage was acoustically tested in the NASA Glenn 9- by 15-Foot Low Speed Wind Tunnel at takeoff/approach flight conditions. The fan was designed for a corrected rotor tip speed of 442 m/s (1450 ft/s), and had a powered core, or booster stage, giving the model a nominal bypass ratio of 5. The model also had a simulated engine pylon and nozzle bifurcation contained within the bypass duct. The fan was tested with three stator sets to evaluate acoustic benefits associated with a swept and leaned stator and with a swept integral vane/frame stator which incorporated some of the swept and leaned features as well as eliminated some of the downstream support structure. The baseline fan with the wide chord rotor and baseline stator approximated a current GEAE CF6 engine. A flyover effective perceived noise level (EPNL) code was used to generate relative EPNL values for the various configurations. Flyover effective perceived noise levels (EPNL) were computed from the model data to help project noise benefits. A tone removal study was also performed. The swept and leaned stator showed a 3 EPNdB reduction at lower fan speeds relative to the baseline stator; while the swept integral vane/frame stator showed lowest noise levels at intermediate fan speeds. Removal of the bypass blade passage frequency rotor tone (BPF) showed a 4 EPNdB reduction for the baseline and swept and leaned stators, and a 6 EPNdB reduction for the swept integral vane/ frame stator. Therefore, selective tone removal techniques such as active noise control and/or tuned liner could be particularly effective in reducing noise levels for certain fan speeds.

Woodward, Richard P.↗
NASA NTRS2004

NASA's Quiet Aircraft Technology Project

NASA's Quiet Aircraft Technology Project is developing physics-based understanding, models and concepts to discover and realize technology that will, when implemented, achieve the goals of a reduction of one-half in perceived community noise (relative to 1997) by 2007 and a further one-half in the far term. Noise sources generated by both the engine and the airframe are considered, and the effects of engine/airframe integration are accounted for through the propulsion airframe aeroacoustics element. Assessments of the contribution of individual source noise reductions to the reduction in community noise are developed to guide the work and the development of new tools for evaluation of unconventional aircraft is underway. Life in the real world is taken into account with the development of more accurate airport noise models and flight guidance methodology, and in addition, technology is being developed that will further reduce interior noise at current weight levels or enable the use of lighter-weight structures at current noise levels.

Whitfield, Charlotte E.↗
NASA NTRSDate not supplied

Urban Air Mobility Noise: Current Practice, Gaps, and Recommendations

AN Air Mobility (UAM) is an opportunity for aviation to improve transportation systems across the world. Representative UAM vehicle attributes include electrical vertical takeoff and landing (eVTOL) vehicles that can accommodate up to 6 passengers (or equivalent cargo), are possibly autonomous, perform missions of up to 100 nautical miles at altitudes up to 3000 ft. above ground level, have flight speeds up to 200 knots, and weigh between 800 and 8000 pounds. Along with the many anticipated benefits, there will be noise issues that need to be addressed. In 2018, NASA formed an Urban Air Mobility Noise Working Group (UNWG) to assemble noise experts from industry, universities and government agencies to identify, discuss, and address UAM noise issues. This oral presentation summarizes technology gaps and goals associated with four areas of interest: Tools & Technologies, Ground & Flight Testing, Human Response & Metrics, and Regulation & Policy, and is drawn from a draft white paper [1] by the same title. Tools & Technologies include noise prediction tools and noise reduction technologies that have been developed for conventional rotorcraft and fixed-wing vehicles that may be applicable or need to be modified for UAM. Prediction tools need to be able to account for variable speed rotors and other temporal variation effects that impact community noise. A reprioritization of noise sources needs to be done since UAM vehicles include multiple rotors/propellers, often in proximity to one another and/or the airframe, with dynamic transition, and new noise sources such as electric motors or hybrid-electric propulsion. Scattering and propagation methods need to be developed that include the vehicle components and surfaces near a receiver such as buildings and vertiports. Validation databases are needed to quantify prediction uncertainties. Prediction tools used to evaluate community noise will need source models appropriate for a wide range of UAM vehicles. Existing noise reduction technologies need to be evaluated and new noise reduction technologies should be developed in anticipation of future noise requirements. Although the prediction and treatment of interior cabin noise is a secondary goal, it is recognized that new tools and methods may be needed due to the uniqueness of the vehicle design and the presence of both acoustic and structure-borne loads. Ground & Flight Testing has been a critical part of validating noise reduction technologies and verifying that an air vehicle is ready for certification. UAM vehicles introduce new challenges for test procedures such as different source noise directivity, unsteady sources due to maneuvers, and a variety of takeoff and approach trajectories. The operating environment will be more complex than current aircraft with the introduction of vertiports in populated areas with “urban canyons” making reflections an important part of noise prediction and annoyance. It is expected that new test procedures and measurement methods will be necessary. Consideration will need to be given for both piloted and autonomous operations. Human Response & Metrics may be very different for UAM noise compared to current experience with airport noise. Current metrics used to certify rotorcraft and fixed-wing aircraft may not be as useful for evaluating UAM noise. Operations at lower altitudes may influence annoyance. Psychoacoustic and community testing will be needed to quantify annoyance and assess appropriate metrics. In addition to conventional noise level metrics, considerations such as audibility and temporal variation of the sound may be required. Differences between indoor or outdoor exposure will have an impact with dependence on urban and residential flight paths. Aircraft noise is currently regulated at a national level and typically involves partnerships with the industry to establish regulations. Regulators realize that current policies and procedures may not be appropriate for some of the emerging air vehicles and new procedures may be needed to address UAM noise. Development of new policies and procedures are needed so that local communities do not hastily attempt to establish their own restrictions that will both limit growth of the market and create an inconsistent and confusing regulatory environment. To expedite this development, it is crucial early measurement data are shared through partnership arrangements to support both noise certification and noise modeling/noise assessment. At the same time, an effective engagement strategy should be developed to address local community noise issues associated with UAM vehicles and flight operations as they arise.

urban air mobility↗
NASA NTRS1993

Evaluation of CSI enhancements for jitter reduction on the EOS AM-1 observatory

A collaborative study between the Goddard Space Flight Center and the Langley Research Center is now underway to investigate the application of Control-Structure Integration (CSI) technologies to the EOS AM-1 spacecraft. Preliminary GN&C pointing studies of EOS AM-1, performed in 1991 and 1992, have indicated the potential for low pointing jitter and stability margins. Hence, a detailed baseline and CSI enhanced jitter assessment has been undertaken. This paper describes the spacecraft jitter pointing requirements, finite element models, and on-board disturbances. The jitter assessment approach being used by the NASA LaRC and various tools developed for efficient simulation and analysis of jitter are presented. In addition, preliminary results are given to show the potential need of CSI technologies for improving pointing performance of the spacecraft.

Belvin, W. K.↗
DOE OSTI2015

Electronic structure and optical properties of α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} solid-solution thin films

We have examined the effect of V doping on the electronic and optical properties of epitaxial hematite (α-Fe{sub 2}O{sub 3}) thin films, by employing several characterization techniques and computational modeling. The conductivity of α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} (0 ≤ x ≤ ∼0.5) is enhanced by several orders of magnitude as x is increased, as evidenced by electrical resistivity measurements and x-ray photoelectron spectroscopy core-level and valence-band spectra. Optical absorption shows a reduction in the direct band gap by as much as 0.64 eV for x = 0.53 (E{sub g} = 1.46 eV) relative to that of α-Fe{sub 2}O{sub 3} (E{sub g} = 2.10 eV). Detailed understanding of the character of the optical transitions in the alloys is achieved using first-principles calculations of the ground and excited states. These calculations reveal that V doping results in occupied V 3d orbitals hybridized with Fe orbitals and located at approximately mid-gap in α-Fe{sub 2}O{sub 3}. The lowest energy transitions involve charge transfer from occupied V 3d to unoccupied Fe 3d* orbitals. With a low band gap and high conductivity, α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} is a promising material for photovoltaic and photoelectrochemical applications.

36 MATERIALS SCIENCE↗