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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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At least 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Rate Controlling in Low-Temperature Standard NH 3 -SCR: Implications from Operando EPR Spectroscopy and Reaction Kinetics

Here, a series of seven Cu/SSZ-13 catalysts with Si/Al = 6.7 are used to elucidate key rate-controlling factors during low-temperature standard ammonia-selective catalytic reduction (NH 3 -SCR), via a combination of SCR kinetics and operando electron paramagnetic resonance (EPR) spectroscopy. Strong Cu-loading-dependent kinetics, with Cu atomic efficiency increasing nearly by an order of magnitude, is found when per chabazite cage occupancy for Cu ion increases from ~0.04 to ~0.3. This is due mainly to the release of intercage Cu transfer constraints that facilitates the redox chemistry, as evidenced from detailed Arrhenius analysis. Operando EPR spectroscopy studies reveal strong connectivity between Cu-ion dynamics and SCR kinetics, based on which it is concluded that under low-temperature steady-state SCR, kinetically most relevant Cu species are those with the highest intercage mobility. Transient binuclear Cu species are mechanistically relevant species, but their splitting and cohabitation are indispensable for low-temperature kinetics.

catalytic reactions↗
DOE OSTI2025

Electrochemical Random-Access Memory: Progress, Perspectives, and Opportunities

Non-von Neumann computing using neuromorphic systems based on analogue synaptic and neuronal elements has emerged as a potential solution to tackle the growing need for more efficient data processing, but progress toward practical systems has been stymied due to a lack of materials and devices with the appropriate attributes. Recently, solid state electrochemical ion-insertion, also known as electrochemical random access memory (ECRAM) has emerged as a promising approach to realize the needed device characteristics. ECRAM is a three terminal device that operates by tuning electronic conductance in functional materials through solid-state electrochemical redox reactions. This mechanism can be considered as a gate-controlled bulk modulation of dopants and/or phases in the channel. Early work demonstrating that ECRAM can achieve nearly ideal analogue synaptic characteristics has sparked tremendous interest in this approach. More recently, the realization that electrochemical ion insertion can be used to tune the electronic properties of many types of materials including transition metal oxides, layered two-dimensional materials, organic and coordination polymers, and that the changes in conductance can span orders of magnitude has further attracted interest in ECRAM as the basis for analogue synaptic elements for inference accelerators as well as for dynamical devices that can emulate a wide range of neuronal characteristics for implementation in analogue spiking neural networks. At its core, ECRAM shares many fundamental aspects with rechargeable batteries, where ion insertion materials are used extensively for their ability to reversibly store charge and energy. Computing applications, however, present drastically different requirements: systems will require many millions of devices, scaled down to tens of nanometers, all while achieving reliable electronic-state tuning at scaled-up rates and endurances, and with minimal energy dissipation and noise. Further, in this review, we discuss the history, basic concepts, recent progress, as well as the challenges and opportunities for different types of ECRAM, broadly grouped by their primary mobile ionic charge carrier, including Li, protons, and oxygen vacancies.

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

Low-temperature failure mechanism of [001] niobium micropillars under uniaxial tension

The plasticity of body-centered cubic (bcc) metals is dependent of temperature as well as sample dimension at the micrometer scale, but the effects of cryogenic temperature on the plasticity and the related failure process in micron-sized bcc metals have not been studied under uniaxial tension. In this work, we utilized in situ cryogenic micro-tensile tests, transmission electron microscopy, and dislocation dynamic simulations to examine the plasticity and failure processes of [001]-oriented bcc niobium micropillars. Our study reveals that a strong suppression of cross-slip at low temperatures prevents dislocation multiplication and leads to a dislocation starvation state, at which no mobile dislocation exists due to the rapid annihilation of dislocations at free surfaces. New dislocations are then nucleated until stress concentration at a slip step creates a micro-crack, the propagation of which leads to catastrophic failure. As a result, this unique failure process results from the combined effects of sample dimension and temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Nozzle-Free Printing of CNT Electronics Using Laser-Generated Focused Ultrasound

Printed electronics have made remarkable progress in recent years and inkjet printing (IJP) has emerged as one of the leading methods for fabricating printed electronic devices. However, challenges such as nozzle clogging, and strict ink formulation constraints have limited their widespread use. To address this issue, a novel nozzle-free printing technology is explored, which is enabled by laser-generated focused ultrasound, as a potential alternative printing modality called Shock-wave Jet Printing (SJP). Specifically, the performance of SJP-printed and IJP-printed bottom-gated carbon nanotube (CNT) thin film transistors (TFTs) is compared. While IJP required ten print passes to achieve fully functional devices with channel dimensions ranging from tens to hundreds of micrometers, SJP achieved comparable performance with just a single pass. For optimized devices, SJP demonstrated six times higher maximum mobility than IJP-printed devices. Furthermore, the advantages of nozzle-free printing are evident, as SJP successfully printed stored and unsonicated inks, delivering moderate electrical performance, whereas IJP suffered from nozzle clogging due to CNT agglomeration. Moreover, SJP can print significantly longer CNTs, spanning the entire range of tube lengths of commercially available CNT ink. The findings from this study contribute to the advancement of nanomaterial printing, ink formulation, and the development of cost-effective printable electronics.

47 OTHER INSTRUMENTATION↗
DOE OSTI2026

Efficient and Robust p-Type Transistor Based on Ultrawide-Bandgap Semiconductor

The p-type transistor is an indispensable component of semiconductor technology, enabling a complementary operation with n-channel transistors for computation, storage, and communication. Achieving both high robustness and high efficiency is highly desirable but challenging for p-type transistors due to the limited semiconductors with reliable hole transport and their high activation energies. Here, in this study, we achieved a robust yet efficient p-type transistor by heterogeneously integrating an ultrawide-bandgap semiconductor and a high-κ dielectric layer through van der Waals integration. The p-type transistor employs a two-dimensional hole channel on hydrogenated diamond (bandgap 5.6 eV) combined with a high-κ (30.5) SrTiO 3 perovskite membrane. At room temperature, the transistor exhibits stable operation with a high on-current (∼200 mA/mm), low subthreshold swing (70 mV/dec), high hole mobility (566 cm 2 /(V·s) to 572 cm 2 /(V·s)), and high on–off ratio (∼10 9 ). Furthermore, tuning the annealing temperature allows operation in either enhancement or depletion mode. The robust p-type transistor with high efficiency holds great potential for future power electronics, ultraviolet (UV) optoelectronics, and harsh-environment electronic applications.

high-κ membrane↗
DOE OSTI2024

Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling

Thin films of poly(arylene ethynylene)-conjugated polymers, including low-energy-gap donor–acceptor polymers, can be prepared via stepwise polymerization utilizing surface-confined Sonogashira cross-coupling. This robust and efficient polymerization protocol yields conjugated polymers with a precise molecular structure and with nanometer-level control of the organization and the uniform alignment of the macromolecular chains in the densely packed film. In addition to high stability and predictable and well-defined molecular organization and morphology, the surface-confined conjugated polymer chains experience significant interchain electronic interactions, resulting in dominating intermolecular π-electron delocalization which is primarily responsible for the electronic and spectroscopic properties of polymer films. The fluorescent films demonstrate remarkable performance in chemosensing applications, showing a turn-off fluorescent response on the sub-ppt (part per trillion) level of nitroaromatic explosives in water. This unique sensitivity is likely related to the enhanced exciton mobility in the uniformly aligned and structurally monodisperse polymer films.

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

Microstructural characterization of phase-separated co-deposited Cu–Ta immiscible alloy thin films

Elevated temperature co-sputtering of immiscible elements ends in a variety of self-organized morphologies due to phase separation. Cu–Ta is used as a model system to understand the evolution of phase-separated microstructural morphologies by co-sputtering thin films with nominal 50–50 at.% composition at four temperatures: 25, 400, 600, and 800 °C. Scanning/transmission electron microscopy of the film cross sections showed the microstructure morphology varied from nanocrystalline Cu–Ta at 25 °C to a wavy ribbon-like structure at 400 °C, to Cu-rich agglomerates surrounded by Ta-rich veins at 600 and 800 °C. In the agglomerate-vein morphology, microstructural features were present on two length scales, from a few nanometers to a few tens of nanometers, thus making the structures hierarchical. On the nanoscale, the Cu-rich agglomerates contained Ta precipitates, whereas the Ta-rich veins had embedded Cu nanocrystals. The various microstructures can be attributed to the highly disparate constituent element interdiffusion at the deposition temperatures with the Cu having orders of magnitude higher mobility than Ta at the deposition temperatures. This research of processing–microstructure relationship will be useful in guiding the design of hierarchical multiphase microstructures in binary or multicomponent thin films with tailored mechanical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Quantized electronic transitions in electrodeposited copper indium selenide nanocrystalline homojunctions

Pairing semiconductors with electrochemical processing offers an untapped opportunity to create novel nanostructures for practical devices. Here we report the results of one such pairing: the in-situ formation of highly-doped, interface-matched, sharp nanocrystalline homojunctions (NHJs) with single step electrodeposition of two copper-indium-selenide (CISe) compounds on flexible foil. It produces a homogenous film, comprising inherently ordered, 3-dimensional interconnected network of pn -CISe NHJs. These CISe NHJs exhibit surprising non-linear emissions, quantized transitions, large carrier mobility, low trap-state-density, long carrier lifetime and possible up-conversion. They facilitate efficient separation of minority carriers, reduce recombination and essentially function like quantum materials. This approach mitigates the material issues and complex fabrication of incumbent nanoscale heterojunctions; it also overcomes the flexibility and scale-up challenges of conventional planar pn junctions. The self-stabilized CISe NHJ film can be roll-to-roll processed in ambient atmosphere, thus providing a promising platform for a range of optoelectronic technologies. This concept exemplified by CISe compounds can be adapted to create nano-scale pn junctions with other inorganic semiconductors.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Dynamic Deformation in Nuclear Graphite and Underlying Mechanisms

Time-dependent deformation in nuclear graphite is influenced by the creation and migration of radiation-induced defects in the reactor environment. This study investigates the role of pre-existing defects such as point defect clusters and Mrozowski cracks in nuclear graphite IG-110. Separate specimens were irradiated with a 2.8 MeV Au 2+ beam with a fluence of 4.38 × 10 14 cm −2 and an 8 MeV C 2+ beam with a fluence of 1.24 × 10 16 cm −2 . Microscopic specimens were either mechanically loaded inside a transmission electron microscope (TEM) or subjected to ex situ indentation-based creep loading. In situ TEM tests showed significant plasticity in regions highly localized around the Mrozowski cracks, resembling slip or ripplocation bands. Slip bands were also seen near regions without pre-existing defects but at very high stresses. Ex situ self-ion irradiation embrittled the specimens and decreased the creep displacement and rate, while heavy ion irradiation resulted in the opposite behavior. We hypothesize that the large-sized gold ions (compared to the carbon atoms) induced interplanar swelling as well as cross-plane channels for increased defect mobility. These findings illustrate the role of pre-existing defects in the dynamic relaxation of stresses during irradiation and the need for more studies into the radiation environment’s impact on the mechanical response of nuclear graphite.

creep deformation↗
DOE OSTI2024

Investigating Gadolinium-Lined Sodium-Iodide Neutron Detectors for Mobile Applications

For enhancing the effectiveness of nonproliferation efforts in neutron detection, most portable instruments rely on 6 Li scintillators, 10 B-based detectors, or gas-filled 3 He proportional counters. Additionally, gamma-ray detectors based on scintillators and semiconductors are often employed for search applications to find radioactive material in the field. These systems typically include dedicated detectors along with separate high voltage supplies and processing electronics for the gamma-ray and neutron detectors. Ideally, a portable radiation detection system should be lightweight, compact, and cost-effective. In the field, scintillators can serve a dual purpose: (1) detecting gamma-rays and (2) detecting neutrons. Gamma-ray detection with scintillators is based on the interaction of gamma-rays within the scintillating material, whereas neutron detection depends indirectly on neutron capture events. These capture events generate conversion electrons and gamma-rays, which can interact with the scintillator. For enhancing neutron capture, the scintillator can be surrounded by neutron absorber materials with a high neutron cross section. The resulting secondary electrons and gamma-rays from neutron interactions, depending on the absorber material used, can then be analyzed to detect the presence of neutron sources. Similarly, semiconductor-based detectors can be employed along with neutron absorbers as liners for neutron detection. 158 Gd has a significantly larger neutron cross section than 3 He, commonly used in gas-filled proportional counters, as shown in Figure 1. For thermal (0.025 eV) neutrons, the absorption cross section of 158 Gd is 10,000 times greater than that of 3 He (refer to Figure 1). This feature makes naturally occurring gadolinium, which consists of 24.8% 158 Gd, a promising neutron absorber material for use in combination with gamma-ray detectors–yielding a hybrid detector–for neutron detection.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2021

Helium causing disappearance of a/2<111> dislocation loops in binary Fe-Cr ferritic alloys

In this work, single and dual-beam self-ion irradiations were performed at 500°C on ultra-high purity Fe14%Cr alloy to ~0.33 displacements-per-atom (dpa), and 0 or 3030 atomic-parts-per-million (appm) helium/dpa, respectively. Using transmission electron microscopy, we reveal that helium can drastically modify the dislocation loop Burgers vector in Fe-Cr alloys. Helium co-implantation caused complete disappearance of a/2<111> type dislocation loops, and the microstructure consisted of only a<100> loops. Conversely, a/2<111> type loops were predominant without He co-implantation. The total loop density remained largely unaffected. The results strikingly contrast literature asserting that helium stabilizes a/2<111> type loops in bcc Fe alloys, based on low temperature irradiations. Collectively analyzing the results with literature suggest that the small positive interaction between helium and self-interstitial atoms (SIA) in Fe predicted by atomistic simulations maybe insufficient to holistically explain the dislocation loop microstructure development in presence of helium. Helium-SIA positive binding inadvertently implies elevated a/2<111> loop fraction and higher loop densities that the present results contradict. Helium induced high cavity density causing a preferential loss of highly glissile <111> clusters, leaving the matrix saturated with <100> type clusters is proposed as a potential mechanism. Further, the in-situ irradiations combined with Burgers vector analysis strengthened the evidence of Cr-induced dislocation loop mobility reduction that appears to stabilize the a/2<111> type loops and causes higher loop densities in Fe-Cr alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Significant Efficiency Enhancements in Non‐Y Series Acceptors by the Addition of Outer Side Chains

Abstract Most current highly efficient organic solar cells utilize small molecules like Y6 and its derivatives as electron acceptors in the photoactive layer. In this work, a small molecule acceptor, SC8‐IT4F, is developed through outer side chain engineering on the terminal thiophene of a conjugated 6,12‐dihydro‐dithienoindeno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene (IDTT) central core. Compared to the reference molecule C8‐IT4F, which lacks outer side chains, SC8‐IT4F displays notable differences in molecule geometry (as shown by simulations), thermal behavior, single‐crystal packing, and film morphology. Blend films of SC8‐IT4F and the polymer donor PM6 exhibit larger carrier mobilities, longer carrier lifetimes, and reduced recombination compared to C8‐IT4F, resulting in improved device performance. Binary photovoltaic devices based on the PM6:SC8‐IT4F films reveal an optimal efficiency over 15%, which is one of the best values for non‐Y type small molecule acceptors (SMAs). The resultant devices also show better thermal and operational stability than the control PM6:L8‐BO devices. SC8‐IT4F and its blend exhibit a higher relative degree of crystallinity and π coherence length, compared to C8‐IT4F samples, beneficial for charge transport and device performance. The results indicate that outer side chain engineering on existing small electron acceptors can be a promising molecular design strategy for further pursuing high‐performance organic solar cells.

He, Qiao [Department of Chemistry and Centre for P↗
DOE OSTI2023

Electron–phonon physics from first principles using the EPW code

EPW is an open-source software for ab initio calculations of electron–phonon interactions and related materials properties. The code combines density functional perturbation theory and maximally localized Wannier functions to efficiently compute electron–phonon coupling matrix elements, and to perform predictive calculations of temperature-dependent properties and phonon-assisted quantum processes in bulk solids and low-dimensional materials. Here, we report on significant developments in the code since 2016, namely: a transport module for the calculation of charge carrier mobility under electric and magnetic fields using the Boltzmann transport equation; a superconductivity module for calculations of phonon-mediated superconductors using the anisotropic multi-band Eliashberg theory; an optics module for calculations of phonon-assisted indirect transitions; a module for the calculation of small and large polarons without supercells; and a module for calculating band structure renormalization and temperature-dependent optical spectra using the special displacement method. For each capability, we outline the methodology and implementation and provide example calculations.

36 MATERIALS SCIENCE↗
DOE OSTI2026

In situ transmission electron microscopy observations of CaCO 3 crystallization onto polysaccharide-coated nanoparticles

Polysaccharides and proteoglycans are widely associated with the organic matrix at sites of CaCO 3 biomineralization, and previous studies indicate that these macromolecules may confer greater roles in mineral nucleation than previously recognized. This investigation uses in situ liquid-phase transmission electron microscopy (LP-TEM) to observe CaCO 3 nucleation onto aminated silica (SiO 2 –NH 3 + ) nanoparticles treated with a layer of chitosan (near-neutral derivative of chitin) or heparin (a carboxylated and highly sulfated glycosaminoglycan). In the absence of polysaccharides, few CaCO 3 particles formed and exhibited mobility. However, the SiO 2 –NH 3 + nanoparticles were enveloped in a region of higher mass density relative to the bulk solution, suggesting the development of a local solute-rich environment that surrounds the charged NH 3 + groups. The heparin- or chitosan-coated silica particles also exhibited regions of higher mass density around the nanoparticles. In the presence of these polysaccharide coatings, we observed the nucleation of abundant CaCO 3 particles whereby the polyanionic heparin promoted more nucleation than the weakly cationic chitosan. Many crystallites appeared to form at the polysaccharide–TEM cell membrane–solution interface, further indicating interfacial and macromolecule-specific control on crystallization. The combined results demonstrate that chitosan and heparin have an appreciable effect on the timing, size, and location of CaCO 3 nucleation compared to the polysaccharide-free nanoparticles.

15 GEOTHERMAL ENERGY↗
DOE OSTI2022

Integration of Omics into a New Comprehensive Rate Law for Competitive Terminal Electron-Accepting Processes in Reactive Transport Models: Application to N, Fe, S, and Contaminant Transformations in Stream and Wetland Sediments

Surface waters represent important sources of alternate energy and drinking water in the United States, and characterizing the biogeochemical processes that affect surface water quality is relevant to the DOE-BER mission. Sediment biogeochemical processes regulate the release of carbon (C), nutrients, and contaminants to surface waters and thus influence water quality. Sediment biogeochemical processes are dynamic and affected by the deposition and remobilization of solid material and changes in environmental conditions driven by water discharge variations. Wetlands are important natural filters of surface waters which may either trap, metabolize, or mobilize nutrients and contaminants. Despite their importance, biogeochemical processes regulating nutrient and contaminant release and C transformation in stream and wetland sediments cannot be predicted accurately by current mathematical models. These reactive transport models largely rely on detectable changes in geochemical conditions to activate metabolic processes, do not accurately account for the competition between microbial processes, and poorly constrain effects of hydrological perturbations on biogeochemical processes. In this BER-SBR exploratory project, metagenomic and geochemical signatures were combined to identify microbially-mediated redox processes in anaerobic stream and wetland sediments from the Savannah River Site (SRS, ANL SFA) and East Fork Poplar Creek (EFPC, ORNL SFA) that play important roles in C, uranium (U), and mercury (Hg) transformations. In addition, sediment incubations were conducted to examine the competition between anaerobic respiration processes Finally, new rate laws were developed for reactive transport models that rely on complementary metagenomic and geochemical signatures to identify the underlying anaerobic microbial processes in stream and wetland sediments, describe the competition between the dominant metabolic processes involved in nutrient release and U and Hg mobilization, and more accurately quantify carbon transformation and the response of microbial processes to changes in redox conditions associated with hydrological forcing. These rate laws were optimized in batch reactors with SRS wetland sediments, where iron and sulfate reduction dominate. Anaerobic carbon remineralization processes followed the expected thermodynamic sequence of microbial respiration with depth in both sediments, except that geochemical signals indicated that sulfate reduction was inactive in EFPC sediments and moderate in SRS wetland sediments. Estimates indicated that microbial iron reduction contributed to at least half of the production of reduced iron in these sediments. Incubations demonstrated that nitrate reduction, denitrification, and dissimilatory nitrate reduction to ammonium were active in the natural EFPC sediment and activated upon nitrate amendment in these nitrate-rich sediments. In turn, these processes were outcompeted by the addition of either iron oxides or sulfate as alternative terminal electron acceptors. Although geochemical products of sulfate reduction were not detected in the incubations, the abundance of sulfate reduction genes increased with depth in the sediment and was equally more pronounced in treatments amended with either iron oxides or sulfate. Simultaneously, anaerobic sulfide oxidizing bacteria coupling sulfide oxidation to DNRA (and not conventional denitrification) were apparently enriched over time, regardless of the treatments. These findings indicate that sulfate reduction is important in freshwater stream sediments and probably catalyzed by a cryptic sulfur cycle involving nitrogen species, in which the sulfur products from sulfate reduction are immediately removed by side reactions and not detectable by geochemical measurements alone. Similar experiments in SRS sediments, however, demonstrated little interaction between nitrogen and sulfur cycling microorganisms. Sulfate reduction was impacted by the addition of more thermodynamically favorable electron acceptors, suggesting either that iron-reducing microorganisms outcompeted sulfate-reducing microorganisms for organic substrate, depleting the stock of electron donor available for sulfate reduction, or that the cryptic sulfur cycle was shunted by the precipitation of FeS generated as a result of the abiotic reduction of iron oxides by dissolved sulfide. A diagnostic modeling exercise was conducted to further investigate the competition between terminal electron accepting processes. As conventional kinetic models typically do not account for cryptic cycles and used inaccurate formulations to describe competition between microbial communities, new metabolic rate laws were developed that explicitly express the electron acceptor-specific enzyme of each energetically favorable metabolic process based on gene abundance detected in the incubations. The model was tested with the sediment slurry incubation data to determine whether substrate competition could explain the decrease in sulfate reduction observed in the presence of iron oxide competitor. The model was able to reproduce geochemical concentrations really well in each treatment once the model was calibrated with the unamended control, suggesting that microbial competition was indeed driven by thermodynamic considerations. Overall, carbon remineralization processes and rates will be reproduced much more realistically with the new metabolic rate laws.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Structural Heterogeneity in Medium-Entropy AgMnSbPbTe 4 for Glassy Thermal Transport and High Thermoelectric Performance

Medium-entropy semiconductors represent a unique category of entropy-engineered materials. They possess a considerable level of randomness in atomic mixing, although this is not sufficient to conclusively achieve single-phase structure stabilization, in contrast to high-entropy materials. This introduces strong competition between the formation of different phases, which can potentially lead to structural heterogeneity. Here, in this work, we uncover endotaxial nanoprecipitates in the microscopically identified homogeneous medium-entropy semiconductor AgMnSbPbTe 4 . These nanoprecipitates initially crystallize in a cubic phase $(Fm\bar{3}m)$ within kinetically stabilized AgMnSbPbTe 4 , subsequently evolving into a thermodynamically stable monoclinic phase $(P2_1/c)$ during thermal annealing while maintaining an endotaxial relationship with the matrix lattice. This nanophase segregation and the resultant lattice mismatch at interfaces introduce strain fluctuations up to 5% at intervals of 20 nm across the entire microstructure. Within the matrix phase, atomic displacement of up to 23 pm was observed. This structural heterogeneity results in glass-like thermal transport behavior, achieving an ultralow lattice thermal conductivity κ L = 0.312 Wm –1 K –1 at 800 K, which is in accordance with the amorphous limit predicted by the Cahill model. The synergy of band convergence effect and well-maintained carrier mobility leads to a maximum ZT of 1.72 at 800 K and an average ZT avg of 1.02 over the temperature range of 300–825 K. This study highlights that the underexplored structural heterogeneity in medium-entropy semiconductors can potentially yield beneficial phenomena, such as the phonon-glass electron-crystal transport behavior in this case, which holds promise for advancing thermoelectric applications.

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

Spectroelectrochemical insights into the intrinsic nature of lead halide perovskites

Abstract Lead halide perovskites have emerged as a new class of semiconductor materials with exceptional optoelectronic properties, sparking significant research interest in photovoltaics and light-emitting diodes. However, achieving long-term operational stability remains a critical hurdle. The soft, ionic nature of the halide perovskite lattice renders them vulnerable to various instabilities. These instabilities can be triggered by factors such as photoexcitation, electrical bias, and the surrounding electrolyte/solvent or atmosphere under operating conditions. Spectroelectrochemistry offers a powerful approach to bridge the gap between electrochemistry and photochemistry (or spectroscopy), by providing a comprehensive understanding of the band structure and excited-state dynamics of halide perovskites. This review summarizes recent advances that highlight the fundamental principles, the electronic band structure of halide perovskite materials, and the photoelectrochemical phenomena observed upon photo- and electro-chemical charge injections. Further, we discuss halide instability, encompassing halide oxidation, vacancy formation, ion migration, degradation, and sequential expulsion under electrical bias. Spectroelectrochemical studies that provide a deeper understanding of interfacial processes and halide mobility can pave the way for the design of more robust perovskites, accelerating future research and development efforts. Graphical Abstract

Min, Seonhong↗
DOE OSTI2020

Water stable molecular n-doping produces organic electrochemical transistors with high transconductance and record stability

From established to emergent technologies, doping plays a crucial role in all semiconducting devices. Doping could, theoretically, be an excellent technique for improving repressively low transconductances in n-type organic electrochemical transistors – critical for advancing logic circuits for bioelectronic and neuromorphic technologies. However, the technical challenge is extreme: n-doped polymers are unstable in electrochemical transistor operating environments, air and water (electrolyte). Here, the first demonstration of doping in electron transporting organic electrochemical transistors is reported. The ammonium salt tetra-n-butylammonium fluoride is simply admixed with the conjugated polymer poly(N,N’-bis(7-glycol)-naphthalene-1,4,5,8-bis(dicarboximide)-co-2,2’-bithiophene-co-N,N’-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide), and found to act as a simultaneous molecular dopant and morphology-additive. The combined effects enhance the n-type transconductance with improved channel capacitance and mobility. Furthermore, operational and shelf-life stability measurements showcase the first example of water-stable n-doping in a polymer. Overall, the results set a precedent for doping/additives to impact organic electrochemical transistors as powerfully as they have in other semiconducting devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗