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At least 1,261 records · Page 70
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Spectroscopic Investigation into P(NDI2OD-T2) Charge Localization

P(NDI2OD-T2), commonly referred to as N2200, stands out as a promising electron-transporting (n-type) polymer for low-cost, flexible (photo)electrochemical applications due to its reversible two-electron reduction and high electron mobility. UV–vis spectroelectrochemistry in the tetrabutyl ammonium hexafluorophosphate/acetonitrile electrolyte shows two sets of chemically reversible redox signals in the cyclic voltammetry corresponding to the reduction of the neutral polymer film to polaronic and bipolaronic species. These electrochemical signatures suggest a distinct electronic reorganization upon reduction (polaron/bipolaron formation), highlighting the need for molecular-level insights into how charges are accommodated within the polymer backbone. While it has been previously hypothesized that charge predominantly localizes on the naphthalene diimide (NDI) unit during reductive charging, specific changes in atomic environments that confirm this localization have not been characterized in n-type polymers. Herein, we use near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to probe electronic transitions in an electrochemically charged polymer to deduce charge localization. The O K-edge (1s) spectra exhibit two distinct π* peaks; the intensity of the lower-energy π* a peak that corresponds to an excitation to a largely localized carbonyl state decreases with reductive potentials relative to the higher-energy π* b peak. We corroborate this with Raman spectroscopy at different potentials, which shows a decrease in intensity on the C–C/C═C and C═O stretching bands of NDI as well as a red shift of the carbonyl band due to the formation of a polaron on the NDI. Additionally, new Raman active NDI signals associated with elongated C═O and C═C bonds are observed at lower energy during the formation of charged states. Together with theoretical calculations, these findings show that the injected charge spatially localizes on the NDI units and is dominantly distributed on the carbonyl groups. In conclusion, the combination of NEXAFS, optical and vibrational spectroscopies, and theoretical calculations is generalizable to other pi-conjugated polymers and can identify charge localization for the further development of organic semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Controlled and Selective Photo-oxidation of Amyloid-β Fibrils by Oligomeric p-Phenylene Ethynylenes

Photodynamic therapy (PDT) has been explored as a therapeutic strategy to clear toxic amyloid aggregates involved in neurodegenerative disorders such as Alzheimer’s disease. A major limitation of PDT is off-target oxidation, which can be lethal for the surrounding cells. In this work, we have shown that a novel class of oligo-p-phenylene ethynylenes (OPEs) exhibit selective binding and fluorescence turn-on in the presence of prefibrillar and fibrillar aggregates of disease-relevant proteins such as amyloid-β (Aβ) and α-synuclein. Concomitant with fluorescence turn-on, OPE also photosensitizes singlet oxygen under illumination through the generation of a triplet state, pointing to the potential application of OPEs as photosensitizers in PDT. Herein, we investigated the photosensitizing activity of an anionic OPE for the photo-oxidation of Aβ fibrils and compared its efficacy to the well-known but nonselective photosensitizer methylene blue (MB). Our results show that, while MB photo-oxidized both monomeric and fibrillar conformers of Aβ40, OPE oxidized only Aβ40 fibrils, targeting two histidine residues on the fibril surface and a methionine residue located in the fibril core. Oxidized fibrils were shorter and more dispersed but retained the characteristic β-sheet rich fibrillar structure and the ability to seed further fibril growth. Importantly, the oxidized fibrils displayed low toxicity. We have thus discovered a class of novel theranostics for the simultaneous detection and oxidization of amyloid aggregates. Importantly, the selectivity of OPE’s photosensitizing activity overcomes the limitation of off-target oxidation of traditional photosensitizers and represents an advancement of PDT as a viable strategy to treat neurodegenerative disorders.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

P-Type Doping of Mixed Tin–Lead Halide Perovskites Using Electron Transfer to Mo(tfd-COCF3) 3 and F 4 TCNQ

Mixed tin-lead halide perovskites are emerging as promising candidates to address the toxicity issues of lead-based perovskites and to provide additional bandgap tunability for optoelectronic applications. Electron-transfer doping offers a prospective pathway to modulate electronic properties of metal-halide perovskites, while not disturbing the underlying crystal structure. However, limited research exists comparing molecular dopants for these systems. Here, our study investigates the p-type electron-transfer doping of the mixed tin-lead halide perovskite MAPb 0.5 Sn 0.5 I 3 (MA = methylammonium) using a sequential deposition approach (perovskite film followed by dopant incorporation) and the molecular dopants F 4 TCNQ and Mo(tfd-COCF 3 ) 3 . Up to 3 orders of magnitude higher carrier density and up to 2 orders of magnitude greater conductivity are achieved relative to the undoped samples, with F 4 TCNQ and Mo(tfd-COCF 3 ) 3 demonstrating similar doping efficiencies (associated with the ratio of mobile charges added to the number of dopant molecules incorporated) of 0.031(3) % and 0.024(3) %, respectively. Differences in the doping effectiveness for a given molarity doping solution likely follow from variations in dopant incorporation within the film during the spin coating deposition step.

14 SOLAR ENERGY↗
DOE OSTI2024

Recovery of p -Hydroxybenzoic Acid from Cu-Catalyzed Alkaline Hydrogen Peroxide Pretreatment of Hybrid Poplar

p-Hydroxybenzoic acid (pHBA) is present in some hardwood biomass feedstocks as an ester attached to the polymeric lignin subunits. Here, we report the isolation and recovery of pHBA from alkaline liquor waste streams obtained from fractionation of hybrid poplar using the “Cu-AHP process”. This process features two stages: alkaline pre-extraction (AP) of the biomass and copper-catalyzed alkaline hydrogen peroxide pretreatment. On a biomass scale of 100 g, 0.5 g of pHBA with a purity of 96% was obtained after decolorization and crystallization. The scalability of the purification process was demonstrated by using liquor obtained from the first-stage AP with 900 g of poplar biomass to afford 3.5 g of crystalline pHBA with 97% purity. Altogether, these results show that pHBA may be isolated and purified from waste streams generated in the two-stage Cu-AHP process without any alteration of the process conditions or impact on carbohydrate and lignin fractionation.

09 BIOMASS FUELS↗
DOE OSTI2024

Oxidative Catalytic Fractionation of Lignocellulosic Biomass Using a Co-N-P-C Catalyst and One-Step Isolation of Aromatic Monomers via Centrifugal Partition Chromatography

Methods for catalytic fractionation of biomass provide a means to convert lignin directly into monomers while generating a high-quality cellulosic stream, contrasting conventional biomass pretreatment strategies that prioritize the cellulosic fraction. Here, a nonprecious-metal Co-N-P-C catalyst is identified for aerobic oxidative catalytic fractionation (OCF) of poplar feedstock in dimethyl carbonate that achieves significantly higher yields of aromatic monomers (24 wt %) relative to those obtained with a recently reported Co-N-C catalyst in acetone solvent (15 wt %). Mechanistic studies indicate that the acidic properties of the catalyst contribute to its improved performance by promoting extraction of lignin from insoluble polysaccharides. This OCF process is complemented by the development of a new centrifugal partition chromatography (CPC) method that supports isolation of all five major aromatic monomers (syringic acid, syringaldehyde, vanillic acid, vanillin, and para-hydroxybenzoic acid) in a single liquid–liquid extraction purification step. Furthermore, this OCF/CPC sequence has important implications for future lignin valorization efforts.

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

Evidence for a Solid-Electrolyte Inductive Effect in the Superionic Conductor Li 10 Ge 1– x Sn x P 2 S 12

Strategies to enhance ionic conductivities in solid electrolytes typically focus on the effects of modifying their crystal structures or of tuning mobile-ion stoichiometries. A less-explored approach is to modulate the chemical bonding interactions within a material to promote fast lithium-ion diffusion. Recently, the idea of a solid-electrolyte inductive effect has been proposed, whereby changes in bonding within the solid-electrolyte host framework modify the potential energy landscape for the mobile ions, resulting in an enhanced ionic conductivity. Direct evidence for a solid-electrolyte inductive effect, however, is lacking—in part because of the challenge of quantifying changes in local bonding interactions within a solid-electrolyte host framework. Here, we consider the evidence for a solid-electrolyte inductive effect in the archetypal superionic lithium-ion conductor Li 10 Ge 1–x Sn x P 2 S 12 . Substituting Ge for Sn weakens the {Ge,Sn}–S bonding interactions and increases the charge density associated with the S 2– ions. This charge redistribution modifies the Li + substructure causing Li + ions to bind more strongly to the host framework S 2– anions, which in turn modulates the Li + ion potential energy surface, increasing local barriers for Li + ion diffusion. Each of these effects is consistent with the predictions of the solid-electrolyte inductive effect model. Density functional theory calculations predict that this inductive effect occurs even in the absence of changes to the host framework geometry due to Ge → Sn substitution. These results provide direct evidence in support of a measurable solid–electrolyte inductive effect and demonstrate its application as a practical strategy for tuning ionic conductivities in superionic lithium-ion conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Multi-Electron Transfer at H-Terminated p-Si Electrolyte Interfaces: Large Photovoltages under Inversion Conditions

Here, photovoltages for hydrogen terminated p-Si(111) in an acetonitrile electrolyte were quantified with methyl viologen [1,1'-(CH 3 ) 2 -4,4'-bipyridinium](PF 6 ) 2 , abbreviated MV 2+ , and [Ru(bpy) 3 ](PF 6 ) 2 , where bpy is 2,2'-bipyridine, that respectively undergo two and three one-electron transfer reductions. The reduction potentials, E°, of the two MV 2+ reductions occurred at energies within the forbidden bandgap, while the three [Ru(bpy) 3 ] 2+ reductions occurred within the continuum of conduction band states. Bandgap illumination resulted in reduction that were more positive than that measured with a degenerately doped n + -Si demonstrative of a photovoltage, Vph, that increased in the order: MV 2+/+ (260 mV) < MV +/0 (400 mV) < Ru 2+/+ (530 mV) ~ Ru +/0 (540 mV) ~ Ru 0/– (550 mV). Pulsed 532 nm excitation generated electron-hole pairs whose dynamics were nearly constant under depletion conditions and increased markedly as the potential was raised or lowered. A long wavelength absorption feature assigned to conduction band electrons provided additional evidence for the presence of an inversion layer. Collectively, the data reveal that the most optimal photovoltage, as well at the longest electron-hole pair lifetime and the highest surface electron concentration, occur when E° lies energetically within the unfilled conduction band states where an inversion layer is present. The bell-shaped dependence for electron-hole pair recombination with the surface potential was predicted by the time-honored SRH model providing a clear indication that this interface provides access to all four bias conditions, i.e., accumulation, flat band, depletion, and inversion. The implications of these findings for photocatalysis applications and solar energy conversion are discussed.

14 SOLAR ENERGY↗
DOE OSTI2020

Electrochemical studies of a high voltage Na 4 Co 3 (PO 4 ) 2 P 2 O 7 –MWCNT composite through a selected stable electrolyte

Na 4 Co 3 (PO 4 ) 2 P 2 O 7 –MWCNT composites in 1 M NaPF 6 in EC:DMC electrolytes deliver stable discharge capacities of 80 mA h g −1 and 78 mA h g −1 at normal and elevated temperatures, respectively. In a full cell configuration vs. NaTi 2 (PO 4 ) 3 –MWCNT, they deliver an initial discharge capacity of 78 mA h g −1 at 0.2C rate.

25 ENERGY STORAGE↗
DOE OSTI2021

p-Type molecular doping by charge transfer in halide perovskite

Efficient p-type doping is achieved in a halide perovskite through energy band tuning to allow charge transfer with the acceptor molecule F4TCNQ. Complementary characterization confirms doping and assesses the impact on optoelectronic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2020

High voltage GaN p-n diodes formed by selective area regrowth

GaN p-n diodes were formed by selective area regrowth on freestanding GaN substrates using a dry etch, followed by post-etch surface treatment to reduce etch-induced defects, and subsequent regrowth into wells. Etched-and-regrown diodes with a 150 gm diameter achieved 840 V operation at 0.5 A/cm 2 reverse current leakage and a specific on-resistance of 1.2 mΩ•cm 2 . Etched-and-regrown diodes were compared with planar, regrown diodes without etching on the same wafer. Both types of diodes exhibited similar forward and reverse electrical characteristics, which indicate that etch-induced defectivity of the junction was sufficiently mitigated soas not to be the primary cause for leakage. An area dependence for forward and reverse leakage current density was observed, suggesting that the mesa sidewall provided a leakage path.

42 ENGINEERING↗
DOE OSTI2021

Role of microtearing mode in DIII-D and future high- β p core plasmas

This paper provides modeling evidence for a new variant of microturbulence instability that regulates the electron thermal fluxes in the transport barrier region of DIII-D "high β p " discharges. This scenario is being investigated as a possible scenario for future steady-state reactors, and thus it is essential to understand the physics processes which govern its performance in order to confidently extrapolate to future devices. Additional analysis examining the extrapolation of this scenario to ITER shows that while the new microtearing mode identified here is unlikely to be unstable in that regime (due to increased temperatures and reduced collisionality), the large shift in magnetic axis (Shafranov shift) that arises in these plasmas may still favor stabilization of common ballooning instabilities which peak on the low field side, but destabilize electrostatic slab modes on the high field side.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Unravel unusual hardening behavior of a Pd–Ni–P metallic glass in its supercooled liquid region

Monolithic metallic glasses often exhibit work softening induced by high atom mobility in the supercooled liquid region in tension. In this work, we report an unusual viscous flow of the Pd 42.5 Ni 42.5 P 15 metallic glass in its supercooled liquid region, which is characterized by a remarkable hardening behavior with decent plasticity during tension. To unravel the causes of this unusual hardening, we conducted structural and thermodynamic analyses by employing several experiments, including dynamic mechanical analysis, differential scanning calorimetry, high-resolution transmission electron microscopy, and in situ heating synchrotron high-energy x-ray diffraction. It was found that the unusual hardening behavior was attributed to structural ordering during deformation, rather than nanocrystallization or structural relaxation observed, sometimes, in metallic glasses deformed in supercooled liquid region. We also incorporated an additional work hardening region in the modified deformation map for metallic glasses.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Breakdown characteristics of deep-ultraviolet Al 0.6 Ga 0.4 N p-i-n avalanche photodiodes

A top-illuminated deep-ultraviolet Al 0.6 Ga 0.4 N p-i-n avalanche photodiode (APD) structure was designed and grown by metalorganic chemical vapor deposition on an AlN bulk substrate and on two different quality AlN/sapphire templates, and APDs were fabricated and tested. The APD devices with a circular diameter of 20 μm have demonstrated a distinctive reverse-bias breakdown behavior. The reverse breakdown voltage of the APDs is approximately -140 V, which corresponds to a breakdown electric field of 6–6.2 MV/cm for the Al 0.6 Ga 0.4 N material as estimated by Silvaco TCAD simulation. The APDs grown on the AlN bulk substrate show the lowest leakage current density of < 1 × 10 -8 A/cm 2 (at low reverse bias) compared to that of the devices grown on the AlN templates. From the photocurrent measurement, a maximum gain (current limited) of 1.2 × 10 4 is calculated. The average temperature coefficients of the breakdown voltage are negative for APD devices fabricated from both the AlN bulk substrate and the AlN templates, but these data show that the coefficient is the least negative for the APD devices grown on the low-dislocation-density AlN bulk substrate.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Steady-state junction current distribution in p-n GaN diodes measured using low-energy electron microscopy (LEEM)

Here, we report on the measurement of the lateral distribution of the junction current of an electrical biased p-n GaN diode by electron emission microscopy using a low-energy electron microscope. The vacuum level at the surface of the diode was lowered by deposition of cesium to achieve negative electron affinity, allowing overflow electrons at the surface of the biased diodes to be emitted and their spatial distribution imaged. The results were compared to the literature, and a good match with analytical solutions by Joyce and Wemple was obtained.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Dissolution of Mg-enriched defects in implanted GaN and increased p-type dopant activation

Annealing Mg-implanted homoepitaxial GaN at temperatures above 1400 °C eliminates the formation of inversion domains and leads to improved dopant activation efficiency. Extended defects, in the form of inversion domains, contain electrically inactive Mg after post-implantation annealing at temperatures as high as 1300 °C (one GPa N 2 overpressure), which results in a low dopant activation efficiency. Triple-axis x-ray data reveal that implant-induced strain is fully relieved after annealing at 1300 °C for 10 min, indicating that strain-inducing point defects formed during implantation have reconfigured and inversion domains are formed. However, annealing at temperatures of 1400–1500 °C (one GPa N 2 overpressure) eliminates the presence of the inversion domains. While residual defects, such as dislocation loops, still exist after annealing at and above 1400 °C, chemical analysis at multiple dislocation loops shows no sign of Mg segregation. Meanwhile, an overall decreasing trend in the dislocation loop density is observed after annealing at the higher temperatures and longer times. Additionally, once inversion domains are formed and the samples are cooled to room temperature, they are shown to dissolve with subsequent annealing above 1400 °C. While such defects have been observed before, the important finding that such defects can be dissolved with a short, higher temperature step is key. Earlier work [Breckenridge et al., J. Appl. Phys. Lett. 118, 022101 (2021)] addressing electrical measurements of these types of samples showed that annealing at 1400 °C leads to a dopant activation efficiency that is an order of magnitude higher than that observed at 1300 °C. In conclusion, this work complements earlier work by identifying the inversion domains, which incorporate Mg, and points to the benefits, in terms of defect density and p-type dopant activation, of using higher temperature (>1400 °C) annealing cycles to activate Mg in GaN, even if the Mg-containing inversion domains had been formed during lower temperature annealing.

36 MATERIALS SCIENCE↗
DOE OSTI2022

DFT simulation of conductivity of the p-type doped and charge-injected cis-polyacetylene

Semiconducting conjugated polymers (CPs) have shown great potential in organic solar cells and organic field-effect transistors (OFETs), due to their tunable electronic and optical properties. In this study, we compare computational predictions of electronic and optical properties of ensembles of cis-polyacetylene (cis-PA) multiple oligomers in two different forms (a) undoped cis-PA and (b) cis-PA doped by phosphorous fluoride (PF¯ 6 ) via density functional theory (DFT) with hybrid functionals. The comparison of undoped cis-PA under the constraint of injected charge carrier and cis-PA doped by PF¯ 6 shows that either doping or injection provides very similar features in electronic structure and optical properties. Doped and injected are similar to each other and different from the pristine, undoped PA. Computed results also indicate that the injection of charge carriers and adding p-type doping into the semiconducting CP model both greatly affect the conductivity. Furthermore, these observations provide a better understanding and practical use of the properties of polyacetylene films for flexible electronic applications.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Exploring charge transport dynamics in a cryogenic P-type germanium detector

Abstract This study explores the dynamics of charge transport within a cryogenic P-type Ge particle detector, fabricated from a crystal cultivated at the University of South Dakota. By subjecting the detector to cryogenic temperatures and an Am-241 source, we observe evolving charge dynamics and the emergence of cluster dipole states, leading to the impact ionization process at 40 mK. Our analysis focuses on crucial parameters: the zero-field cross-section of cluster dipole states and the binding energy of these states. For the Ge detector in our investigation, the zero-field cross-section of cluster dipole states is determined to be 8.45 × 10 −11 ± 4.22 × 10 −12 cm 2 . Examination of the binding energy associated with cluster dipole states, formed by charge trapping onto dipole states during the freeze-out process, reveals a value of 0.034 ± 0.0017 meV. These findings shed light on the intricate charge states influenced by the interplay of temperature and electric field, with potential implications for the sensitivity in detecting low-mass dark matter.

Physics↗