Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Optical conductivity”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Improved Manufacturability and Throughput of Ultra- Transparent, Super-Insulating Aerogels

AeroShield Materials produces a novel silica aerogel material with exemplary thermal performance and unprecedented optical clarity, offering the potential for super-insulating fenestration and insulated glass to reduce thermal losses in the built environment by billions of dollars every year. One of the most significant challenges facing AeroShield today is the total amount of time that is required to produce large monolithic aerogel samples. This overall process can require as much as 144 hours total, which can significantly hinder scale-up to an economically viable product. The purpose of this Phase 1 research was to continue development of our novel aerogel manufacturing process to reduce material processing time by up to 10x, greatly improving product throughput and reducing cost. AeroShield’s manufacturing process can be divided into 4 major stages, each with their own distinct set of parameters and time requirements. Under this Phase 1 award, AeroShield was able to identify and optimize a number of these parameters, including molding materials, solvent rinse conditions, critical point drying time, and annealing conditions. AeroShield also performed thorough analyses on how these optimized parameters affected important final characteristics of the gels, including optical clarity, thermal conductivity, and dimensional stability. This campaign culminated in the production of laboratory scale aerogel samples using significantly lower process times of both 36 and 18 total hours, which represent Phase 1 Target and Stretch goals. In order to achieve widespread market adoption, monolithic sheets of the aerogel material must be made to industry-standard sizes (8’ x 12’) at a cost that provides 5-7 year or less breakeven energy savings for consumers (<$2 sq/ft). The work performed under this Phase 1 award shows that time and materials required to make aerogel samples, which make up a significant portion of their overall cost, can be greatly reduced without sacrificing quality. AeroShield plans to use these optimized processes to produce larger, product-relevant sized aerogels in order to achieve target final material costs.

Wilke, Kyle↗
DOE OSTI2026

Plasma-Assisted Pre-Chamber Ignition System for Highly Dilute Stoichiometric Heavy-Duty Natural Gas Engines (Final Technical Report)

This project explored advanced ignition technologies to significantly enhance efficiency and reduce operating costs for heavy-duty natural gas engines operating at stoichiometric conditions, while meeting ultra-low NOx emission standards. The main goal was to develop and validate a plasma-assisted pre-chamber ignition system that could deliver at least a 2% increase in brake thermal efficiency (BTE) and a 4% decrease in total cost of ownership (TCO) compared to a typical multi-cylinder engine with three-way catalyst aftertreatment, ensuring compatibility with the expected 2027 EPA/CARB regulations. In the first half of the project, the research team concentrated on developing and testing plasma-assisted pre-chamber ignition using nanosecond pulsed discharges. Extensive experiments were conducted in an optically accessible rapid-compression and expansion machine, a constant-volume chamber, and an optical single-cylinder engine. Experiments were coupled with CFD simulations. The work produced unique insights into pre-chamber flame formation, jet ignition, dilution effects, and flame quenching at pressures, temperatures, and dilution levels relevant to engines. Although plasma-assisted ignition showed promise in controlled lab settings, the research also identified fundamental and practical challenges when applying this technology to real engine conditions. Midway through the project, a crucial pivot was made, guided by three key findings. First, the power electronics required for nanosecond plasma discharges were found to be too costly for commercial use, undermining the project’s cost-of-ownership goals. Second, nanosecond plasma ignition was highly sensitive to turbulent flow in the pre-chamber, resulting in lower ignition reliability than traditional spark under engine-like conditions. Third, achieving a truly diffuse low-temperature plasma at high pressures near top dead center was not possible, reducing the anticipated chemical enhancement benefits. These results collectively suggested that continuing with plasma-assisted ignition was unlikely to meet both efficiency and cost objectives. In response, the project shifted focus to a more realistic approach: enhancing traditional spark-based pre-chamber ignition with significantly less spark energy. Using insights gained earlier in the project, the team redesigned the pre-chamber to maintain high dilution tolerance and quick combustion, even with lower ignition energy. Testing confirmed that with optimized pre-chamber design and combustion timing, a lower-energy spark could reliably ignite highly diluted stoichiometric mixtures, reduce burn time, and boost thermal efficiency. Final engine testing and techno-economic analysis verified that this revised approach successfully achieved the project goals. The optimized pre-chamber ignition system provided over a 2% increase in calculated brake thermal efficiency compared to the baseline engine. Notably, the lower ignition energy and simplified hardware reduced component stress, extended maintenance intervals, and lowered the total cost of ownership. When used with stoichiometric operation and traditional three-way aftertreatment, the system remained compatible with near-zero NOx emissions targets without increasing cost or complexity in the emissions control system. In summary, although the project deviated from its initial plasma-assisted ignition idea, the work produced a more practical and commercially viable solution. The results show that precisely optimized, low-energy pre-chamber spark ignition can significantly improve efficiency and reduce overall ownership costs for heavy-duty natural gas engines. This directly aligns with DOE goals for cleaner, more efficient, and cost-effective transportation technologies.

03 NATURAL GAS↗
DOE OSTI2024

High-Speed OH-PLIF Diagnostics of Flame Flashback in Low Swirl Hydrogen-Enriched Flames

This paper reports flashback events observed in hydrogen-enriched flames stabilized in a low swirl burner (LSB) at atmospheric pressure and temperature conditions. The fundamentals of hydrogen-rich stable flames and spatiotemporal investigation of flashback phenomena were observed experimentally using a high-repetition-rate nanosecond (ns)-duration hydroxyl radical planar laser-induced fluorescence (OH-PLIF) diagnostic. Testing was conducted in an optically accessible pre-mixing section of a LSB with inlet pre-mixing velocities ranging from 5 to 10 m/s for methane and hydrogen (50 – 90% by mole) blends. Swirlers with two different turning angles, 26o and 33o, and three different perforated plate hole diameters, 1.08, 1.12 and 1.16 mm, with measured swirl numbers varying from 0.43 to 0.49 were used in this study at atmospheric temperature and pressure inlet conditions. The flashback propensity showed a dependence on the proximity of the lifted flame to the burner exit (termed as lift-off length, L) which was dependent on the pre-mixer velocity (V), hydrogen content (XH2) and equivalence ratio (ϕ) at constant temperature and pressure conditions. High-speed OH-PLIF images revealed lifted flames were first observed at low ϕ/ XH2 condition which then changed to a M-shaped flame attached to burner rim with the increase in ϕ/ XH2. Further increases in ϕ/XH2, depending upon other inlet parameters, triggered flame flashback into the pre-mixing section. Flashback occurred when burning began in the outer shear layer and the leading flame brush propagated into the nozzle. Such spatiotemporally resolved high-speed OH-PLIF imaging provides insights on different stages of flashback in a LSB – flashback initiation, transition of flame propagation from burner exit to the swirler and flashback to flame holding transition. Flame ϕ at flashback showed an expected linearly increasing trend with increasing V and decreasing XH2 and the conclusions drawn aligned well with detailed investigations. For identical inlet conditions, flashback propensity decreased with increasing perforated-plate hole diameter and increasing swirler vane angle.

Parajuli, Pradeep↗
DOE OSTI2026

The pathfinder X-Ray axion telescope for the International Axion Observatory (IAXO) and axion searches at the CERN Axion Solar Telescope (CAST)

The axion, a hypothetical pseudo-scalar particle proposed by Peccei and Quinn to resolve the strong CP problem in quantum chromodynamics, remains one of the most compelling dark matter candidates. Axions and Axion-Like Particles (ALPs) are characterized by a broad and largely unconstrained parameter space in mass and coupling strength, motivating extensive experimental searches. The International Axion Observatory (IAXO) is a next-generation axion helioscope designed to achieve over an order of magnitude improvement in sensitivity to the axion-photon coupling constant gaγ relative to previous experiments such as the CERN Axion Solar Telescope (CAST). IAXO will employ large-scale superconducting magnets, precision x-ray optics, and ultra-low-background detectors to search for solar axions produced primarily via the Primakoff effect. This work presents the design and performance of the IAXO pathfinder x-ray optic, a technological demonstrator that validated the optical concepts for IAXO through axion searches at CAST. Comprehensive ray-tracing simulations and experimental measurements were conducted to assess the optic's effective area, detection efficiency, and background suppression capabilities. Deployed at CAST in conjunction with Micromegas and GridPix detectors, the Pathfinder demonstrated record-setting sensitivity to both gaγ and the axion-electron coupling gae, establishing the most stringent laboratory constraints on solar axions to date. These results confirm the viability of the IAXO optical design and detector concept, providing a critical technological benchmark that informs the ongoing development of the BabyIAXO and full-scale IAXO telescopes.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Harnessing complexity: Nonlinear optical phenomena in L-shapes, nanocrescents, and split-ring resonators

Here, we conduct systematic studies of the optical characteristics of plasmonic nanoparticles that exhibit C 2v symmetry. In particular, we analyze three distinct geometric configurations: an L-type shape, a crescent, and a split-ring resonator shaped like the Greek letter π. Optical properties are examined using the finite-difference time-domain method. It is demonstrated that all three shapes exhibit two prominent plasmon modes associated with the two axes of symmetry. This is in addition to a wide range of resonances observed at high frequencies corresponding to quadrupole modes and peaks due to sharp corners. Next, to facilitate nonlinear analysis, we employ a semiclassical hydrodynamic model, where the electron pressure term is explicitly accounted for. This model goes beyond the standard Drude description and enables capturing nonlocal and nonlinear effects. Employing this model enables us to rigorously examine the second-order angular resolved nonlinear optical response of these nanoparticles in each of the three configurations. Two pumping regimes are considered, namely, continuous wave (CW) and pulsed excitations. For CW pumping, we explore the properties of the second harmonic generation (SHG). Polarization and angle-resolved SHG spectra are obtained, revealing strong dependence on the nanoparticle geometry and incident wave polarization. The C 2v symmetry is shown to play a key role in determining the polarization states and selection rules of the SHG signal. For pulsed excitations, we discuss the phenomenon of broadband terahertz (THz) generation induced by the difference-frequency generation . It is shown that the THz emission spectra exhibit unique features attributed to the plasmonic resonances and symmetry of the nanoparticles. The polarization of the generated THz waves is also examined, revealing interesting patterns tied to the nanoparticle geometry. To gain deeper insight, we propose an analytical theory that agrees very well with the numerical experiments. The theory shows that the physical origin of the THz radiation is the mixing of various frequency components of the fundamental pulse by the second-order nonlinear susceptibility. An expression for the far-field THz intensity is derived in terms of the incident pulse parameters and the nonlinear response tensor of the nanoparticle. The results presented in this work offer new insights into the linear and nonlinear optical properties of nanoparticles with C 2v symmetry. The demonstrated strong SHG response and efficient broadband THz generation hold great promise for applications in nonlinear spectroscopy, nanophotonics, and optoelectronics. The proposed theoretical framework also provides a valuable tool for understanding and predicting the nonlinear behavior of other related nanostructures.

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

Optically induced quantum transitions in direct probed mesoscopic NbSe 2 for prototypical bolometers

Superconducting transition-edge sensors (TES) have emerged as fascinating devices to detect broadband electromagnetic radiation with low thermal noise. The advent of metallic transition metal dichalcogenides, such as NbSe 2 , has also created an impetus to understand their low-temperature properties, including superconductivity. Interestingly, NbSe 2 -based sensor within the TES framework remains unexplored. In this work, direct-probed superconducting NbSe 2 absorbers led to a proof-of-concept demonstration for the transduction of incoming light to heat, where a thermodynamic superconducting phase transition in NbSe 2 was evident to switch it to the normal-state, when biased below its superconducting transition temperature. A wavelength-dependent response of its optical absorption properties was observed, based on the incident optical excitation source used. Furthermore, extensive optical characterization studies were conducted using Raman spectroscopy, where the in-plane and out-of-plane thermal conductivity was empirically determined. Our results open new possibilities for the use of NbSe 2 in superconducting radiation detectors, including in a TES framework

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Height-resolved emission spectroscopy and high-speed imaging of the TiAl6V4 vapor plume under laser powder bed fusion conditions

Optical emission spectroscopy is increasingly used as an in situ monitoring technique during laser powder bed fusion (LPBF) because plume emission holds elemental information not found in other in situ sensing techniques. This work explores the shape, stability, and temperature of the emission plume above the melt pool of Ti6Al4 V undergoing laser scans under LPBF-like processing conditions, using high-speed video and height-resolved spectroscopy to study the details of plume dynamics. Optical emission spectroscopy is conducted in the 480 nm to 525 nm region, where Ti emission is strong, with 0.3 mm vertical resolution above the baseplate. The Boltzmann plot method is used to determine temperature at each probed elevation, which indicates that the hottest location of the plume is occasionally elevated 0.3 mm to 0.6 mm above the scanning surface. The results show that the plume shape, stability, temperature, and spectra are highly dependent on the processing conditions. We highlight some of the complexities of optical emission spectroscopy and discuss potential challenges for implementing optical emission spectroscopy across an entire build.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Development of an Optical Library for Coevaporated CdSe x Te 1– x

The conversion efficiency of CdTe solar cells may be improved by bandgap engineering, i.e., changing the bandgap value through the addition of Se in the absorber. The Se alloying enables a short-circuit current density improvement, as it leads to a bandgap energy value decrease. Furthermore, it has been associated with increased minority carrier lifetimes, assuring high open-circuit voltage values. An Se gradient profile control can further optimize the solar cell performance. Thus, an optical model baseline of the CdSe x Te 1–x (CST) compound was developed. Spectroscopic ellipsometry measurements were conducted to accurately extract the optical constants of ten CST layers deposited through coevaporation with x varying from 0 to 1. Using the measured dielectric function spectra from the discrete CST layers with varying x, and considering the composition-induced shift in the critical point energies, an energy-shift model was employed to develop the accurate optical library for the CST compound for any x value to provide data for future modeling and optimization. Furthermore, the library accuracy was validated through optical simulations of the quantum efficiency of a graded CST solar cell using the finite-difference time-domain method by replicating the Se profile in the absorber layer measured through secondary ion mass spectrometry.

14 SOLAR ENERGY↗
DOE OSTI2025

Towards satellite tests combining general relativity and quantum mechanics through quantum optical interferometry: progress on the deep space quantum link

The Deep Space Quantum Link (DSQL) is a space-mission concept that aims to explore the interplay between general relativity and quantum mechanics using quantum optical interferometry. This mission concept was formally presented to the United States National Academy of Science Decadal Survey as a research campaign for Fundamental Physics in 2022. Since then, advances have been made in the space-based quantum optical technologies required to conduct a DSQL-type mission. In addition, other research efforts have defined alternative measurement concepts to explore the same scientific questions motivating the DSQL mission. This paper serves as an update to the community on the status of the DSQL mission concept and related research and technology development efforts.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Physical Modeling and Design of a Nonvolatile Optically Gated High‐Power Diamond Transistor

In this work, we present the theory and modeling framework of a diamond optically gated junction field‐effect transistor (DOGFET). The device utilizes nitrogen substitutional centers in type‐1b diamond to optically modulate a p‐ boron doped diamond channel. Using sub‐gap lasers with intensities as low as 100 W/cm 2 , electrons are optically excited from substitutional nitrogen sites to the conduction band of the diamond substrate, thus enabling the optical gate to exercise control on modulating the space‐charge region at the junction and therefore the channel conductivity. We show that the device can deliver a current of 7 μA/μm, or equivalently 1750 A/cm 2 , while switching at a frequency greater than 100 kHz, in a form factor of 5 μm 2 . The breakdown voltage is found to be greater than 1850 V, with a breakdown field strength of ~13 MV/cm. Moreover, the device supports nonvolatile operation with a “memory effect” enabling single transistor state retention. The presented simulation framework provides a physically grounded insight into the limits and opportunities of optoelectronic diamond systems.

Engineering - Electronic and electrical engineerin↗
DOE OSTI2026

Tracking Thermal Transport in Colloidal Quantum Dot Films Using in Situ Time-Resolved X-ray Diffraction

Colloidal quantum dots (QDs) and their thin films are increasingly used in electronic and photonic devices replacing traditional bulk semiconductors. However, thermal properties of QDs remain underexplored relative to device development efforts. This study shows the use of time-resolved X-ray diffraction as a contact-free method to probe the thermal response of QDs in environments representative of the active layer in QD optoelectronic devices, providing in situ insights for future thermal management strategies. Through the extraction of Debye–Waller factors on a subnanosecond time scale, we directly capture the heating and cooling of core/shell CdSe/CdS QDs following pulsed optical excitation. In a QD thin film that actively provides optical gain, the thermal conductivity is found to be as low as 0.13 W m –1 K –1 , because of the poor heat flow between close-packed QD solids. For QDs dispersed in liquids, interfacial thermal conductance dominates thermal relaxation, with a conductance of 15 MW m –2 K –1 .

36 MATERIALS SCIENCE↗
DOE OSTI2025

Enhanced production of active species and NH 3 using non-equilibrium ferroelectric barrier discharge

Non-equilibrium plasma-assisted ammonia synthesis is investigated through enhanced active species production with ferroelectric discharge. Time-resolved in-situ diagnostics of femtosecond two-photon absorption laser-induced fluorescence, coherent anti-Stokes Raman scattering, and laser absorption spectroscopy, as well as optical emission spectroscopy, were conducted to probe the key intermediate species, such as H and N radicals as well as N 2 (ν), ions, and NH 3 to achieve better understanding of non-equilibrium energy transfer and ammonia formation. The results reveal that ferroelectric discharge improved ammonia yield by four times. Results also show that ferroelectrics not only enhanced ions (N 2 + ) production, radicals (N, H) number density, but also increased the N 2 vibrational temperature. Further plasma modeling identified the couplings between elevated radical and ion production and enhanced vibrational excitation reactions, e.g., N + H 2 (ν)→NH + H, N 2 (ν)+H → NNH, N 2 + + H 2 → H + N 2 H + , and N 2 H + +e→NH + N, facilitated by ferroelectric discharge. These findings provide critical insight into the mechanism of ferroelectric plasma catalysis and highlight their potential in advancing energy-efficient chemical synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Local charge-screening and polarization switching in a ferroelectric ionic-superconductor

For ferroelectric ionic-conductors, polarization switching is complicated by the interplay between ion mobility and charge screening effects. When the ionic charge carriers also play a key role in the domain reversal, such as in Rb-doped KTiOPO 4 (RKTP), a higher level of complexity is introduced. RKTP provides an ideal platform for investigating the relationship between ionic conductivity and polarization reversal because its highly anisotropic crystal properties allow selective modification of material characteristics through diffusive cation doping. Here, we use indiffused Ba/K doping to create a significant increase in the ionic conductivity. Time-of-flight secondary ion mass spectrometry is employed to map Ba/K doping within the RKTP crystal and correlate it to changes in ionic mobility and polarization switching characteristics under an external field applied to the nonpolar face. Using band-excitation piezoresponse force microscopy, we demonstrate a selective switching-inhibition mechanism driven by the enhanced charge screening.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Efficacy of Gadolinium Gallium Garnet (GGG) as a High-Impedance Optical Window for Shock Wave Experiments

We conducted a series of plate impact experiments to examine the efficacy of < 111>-oriented gadolinium gallium garnet (GGG) single crystals as high-impedance optical window for Photonic Doppler velocimetry (PDV) under shock and double-shock loading. At ~ 123 GPa, shocked GGG remains fully transparent to 1550 nm light for at least 250 ns without any signal degradation. Above 135 GPa, PDV data measured through GGG exhibit a gradual loss of fringe contrast following shock entrance, which eventually leads to transparency loss. The duration for which shocked GGG remains transparent decreases with increasing pressure, and at ~ 148 GPa, it becomes opaque within ~ 20–30 ns. This limits the use of GGG as an interferometry window between ~ 110–140 GPa under single shock loading. Within this pressure range, the refractive index of GGG increases linearly with density: n = 1.552 + 0.054ρ. In contrast to single shock loading, where GGG becomes opaque rapidly above ~ 140 GPa, double-shocked GGG remains optically transparent for over 100 ns when it is first shocked to ~ 123 GPa and then reshocked to significantly higher pressures (215–233 GPa). Our findings raise the exciting possibility of GGG being used as a high-impedance optical window in multi-shock and shock-ramp loading experiments.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Bandgap Engineering of Ga 2 O 3 by MOCVD Through Alloying with Indium

Ga 2 O 3 and In 2 O 3 are vital semiconductors with current and future electronic device applications. Here, we study the alloying of In 2 O 3 and Ga 2 O 3 (IGO) and the associated changes in structure, morphology, band gap, and electrical transport properties. Undoped films of IGO were deposited on sapphire substrates with varying indium (In) percentage from zero to 100% by metal-organic chemical vapor deposition (MOCVD). Some films were annealed in H 2 to induce electrical conductivity. The measurements showed the optical band gap decreased by adding In; this was confirmed by density functional (DFT) calculations, which revealed that the nature of the valence band maximum and conduction band minimum strongly relate to the chemistry and that the band gap drops by adding In. The as-grown films were highly resistive except for pure In 2 O 3 , which possesses p-type conductivity, likely arising from In vacancy-related acceptor states. N-type conductivity was induced in all films after H-anneal. DFT calculations revealed that the presence of In decreases the electron effective mass, which is consistent with the electrical transport measurements that showed higher electron mobility for higher In percentage. The work revealed the successful band gap engineering of IGO and the modification of its band structure while maintaining high-quality films by MOCVD.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Conducting polymer-based electrochemical sensors: Progress, challenges, and future perspectives

Conducting polymers are promising due to their unique properties, such as excellent electrical and optical properties, physical and chemical stability, high conductivity, and effective redox properties with high-temperature stability and biocompatibility. Due to these properties, conducting polymers are useful in diverse applications like sensors, batteries, oil industries, biosensors, biomedicines, catalysis, cancer treatment, etc. This review article aims to discuss the recent trends and analysis of conducting polymer-based electrochemical sensors in diverse areas with all required sensor characteristics, such as the derived limit of detection, utilized techniques for the sensing analysis and derived linear dynamic range with the stability of the sensors. Conducting polymers and their nanocomposites-based electrochemical sensors have demonstrated exceptional capabilities towards detecting various biomolecules, heavy metals, pesticides, and viruses like SARS-COV-2. Incorporation of redox mediators, use of conducting hydrogels, and molecular imprinting are promising strategies for better performance of the derived sensor. The article has demonstrated the existing challenges and limitations and provided solutions in the field. In the future, conducting polymers-based electrochemical sensors can be utilized in wearable sensors and integrated with IoT devices for better reach in real-time applications. They can also be made more accessible with precise control and data output by following specific methodologies. Utilizing green and sustainable conducting polymers can be crucial in advancing eco-friendly practices in the future. Conducting polymer-based electrochemical sensors has affectivity in neurochemical and pathogen sensing, which is essential for brain function and mental health.

42 ENGINEERING↗
DOE OSTI2024

Proton surface exchange kinetics of perovskite triple conducting thin films for protonic ceramic electrolysis cells: BaPr 0.9 Y 0.1 O 3–δ (BPY) vs. Ba 1–x Co 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3–δ (BCFZY)

Protonic ceramic electrolysis cells (PCECs) are an attractive green H 2 production technology, given their intermediate-temperature operating range and ability to produce dry H 2 . However, PCECs will benefit from development of more efficient and durable “triple conducting” anodes where steam is split, H incorporated, and oxygen evolved. In this work, we evaluated the kinetics of the steam-splitting/H incorporation reaction on BaPr 0.9 Y 0.1 O 3–δ (BPY) in comparison to the benchmark Ba 1–x Co 0.4 Fe 0.4 Z r0.1 Y 0.1 O 3–δ (BCFZY) composition, replacing most of the transition metal elements (Co, Fe, Zr) with the lanthanide Pr. We prepared geometrically well-defined perovskite BPY and BCFZY thin films by pulsed laser deposition and performed simultaneous optical transmission relaxation and electrical conductivity relaxation measurements at 400–500 °C in 0.21 atm O 2 during switching of the steam partial pressure to isolate and compare their proton surface exchange coefficients (k). The k values of BPY were comparable to those of BCFZY and more stable over time. According to angle-resolved XPS and STEM-EDS mapping of FIB cross-sections, the surface of BPY exhibited Ba enrichment, Pr deficiency, and Si contamination. In contrast, BCFZY exhibited Ba deficiency throughout, no obvious surface segregation, and less Si contamination. The Ba segregation on the BPY film appears to have promoted steam splitting/H incorporation kinetics even though the more basic surface reacted with the acidic environmental SiO x H y . Faster kinetics observed on stoichiometric BCFZY vs. Ba-deficient BCFZY confirmed the benefit of a high A-site Ba concentration. This result contrasts with most work on perovskites applied in solid oxide electrolysis cell anodes, in which A-site segregation is considered deleterious for surface reaction kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗