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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Proton Traffic Jam: Effect of Nanoconfinement and Acid Concentration on Proton Hopping Mechanism

Abstract The properties of the water network in concentrated HCl acid pools in nanometer‐sized reverse nonionic micelles were probed with TeraHertz absorption, dielectric relaxation spectroscopy, and reactive force field simulations capable of describing proton hopping mechanisms. We identify that only at a critical micelle size of W 0 =9 do solvated proton complexes form in the water pool, accompanied by a change in mechanism from Grotthuss forward shuttling to one that favors local oscillatory hopping. This is due to a preference for H + and Cl − ions to adsorb to the micelle interface, together with an acid concentration effect that causes a “traffic jam” in which the short‐circuiting of the hydrogen‐bonding motif of the hydronium ion decreases the forward hopping rate throughout the water interior even as the micelle size increases. These findings have implications for atmospheric chemistry, biochemical and biophysical environments, and energy materials, as transport of protons vital to these processes can be suppressed due to confinement, aggregation, and/or concentration.

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

Tuning Interface Electronic Properties via Chiral Two‐Dimensional Metal‐Organic Frameworks

Control over structural symmetries in nanomaterials offers a powerful approach to engineer electronic properties. For instance, breaking of mirror symmetries in two-dimensional (2D) materials with a hexagonal lattice can lead to nontrivial electronic topologies and correlated-electron phenomena. Yet, the impact of structural chirality on the electronic properties of 2D materials and interfaces remains underexplored. Here, how chiral phases of a 2D metal-organic framework (MOF) with a hexagonal lattice—consisting of hexaazatriphenylene molecules coordinated to Cu atoms—scatter, confine, and perturb the Shockley surface state (SS) electrons of an underlying Ag(111) substrate is investigated. Via low-temperature scanning tunneling microscopy and spectroscopy, noncontact atomic force microscopy, and numerical calculations based on an electronic plane-wave expansion method, modifications of the Ag(111) SS band structure are shown and quantified, including gap openings and lifts of band degeneracies, driven exclusively by the structural chirality of the 2D MOF phases. These findings highlight how structural symmetries, in particular chirality, affect electronic states at material interfaces, expanding on the toolkit for designing 2D materials with tailored electronic properties.

band structure engineering↗
DOE OSTI2020

Direct processing of PbZr 0.53 Ti 0.47 O 3 films on glass and polymeric substrates

This work reports on direct crystallization of PbZr 0.53 Ti 0.47 O 3 (PZT) thin films on glass and polymeric substrates, using pulsed thermal processing (PTP). Specifically, xenon flash lamps deliver pulses of high intensity, short duration, broadband light to the surface of a chemical solution deposited thin film, resulting in the crystallization of the film. Structural analysis by X-ray diffraction (XRD) and transmission electron microscopy show the existence of perovskite structure in nano-sized grains (≤5 nm). Local functional analysis by band excitation piezoelectric spectroscopy and electrostatic force microscopy confirm the presence of a ferroelectric phase and retention of voltage-written polarization for multiple days. Based on structural and functional analyses, strategies are discussed for optimization of pulse voltage and duration for the realization of crystalline ferroelectric thin films. For ~200 nm-thick PZT films on glass substrates, 500 μs-long pulses were required for crystallization, starting with 100 pulses at 350 V, 10 or 25 pulses at 400 V and in general lower number of pulses at higher voltages (resulting in higher radiant energy). Overall power densities of >6.4 kW/cm 2 were needed for appearance of peaks corresponding to the perovskite phase in the XRD. Films on glass processed at 350–400 V had a higher degree of 111-oriented perovskite grains. Higher applied radiant energy (through increased pulse voltage or count) resulted in more random and/or partially 001-oriented films. For ~1 μm-thick PZT films on polymeric substrates, 10 to 25 250 μs-long pulses at voltages ranging between 200 to 250 V, corresponding to power densities of ~2.8 kW/cm 2 , were optimal for maximized perovskite phase crystallization, while avoiding substrate damage.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Hollow-cathode chemical vapor deposition of thick, low-stress diamond-like carbon films

A radio-frequency (RF), hollow-cathode plasma source with confining magnetic field is described for the chemical vapor deposition of thick ( > 10 µm), amorphous diamond-like carbon ablator films for inertial confinement fusion applications. Plasma is characterized by optical emission spectroscopy, while properties of the resultant films are measured by a combination of profilometry, Rutherford backscattering spectrometry, elastic recoil detection analysis, X-ray diffraction, Raman spectroscopy, and atomic force microscopy. The dependence of the deposition rate, film density, elemental composition, self-bias and residual stress is reported as a function of RF power. Higher density films were found when using Ar plasma, than N 2 or H 2 plasma. The coatings produced are x-ray amorphous, exhibit low compressive stress ( ~ 100 MPa), high density ( < 1.7 g/cm 3 ), hydrogen content of ~ 30 at.%, and a low average roughness of 0.75 nm. Finally, applications of these films as tunable-density ablators for inertial confinement fusion experiments are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Annealing Controls Ultrafast Dynamics of Carrier Production in Organic Photovoltaics Incorporating a Nonfullerene Acceptor

Nonfullerene acceptors have emerged as leading candidates in organic photovoltaics pushing past some of the limitations of their fullerene counterparts with absorption extending in the visible and NIR, decreased air-sensitivity, and tunable energy levels. Significant progress has been made in demonstrating the potential of nonfullerene acceptor-based devices to reach high efficiencies; however, a photophysical and mechanistic understanding of charge generation in these nonfullerene acceptors lags behind. In particular, the effects of annealing on carrier production have not been previously examined. Here, we use transient absorption spectroscopy and atomic force microscopy to examine the effect of solvent vapor annealing on a perylene diimide-based nonfullerene acceptor, PDI-DPP-PDI. We find that when mixed with the donor PTB7-Th, the effect of solvent vapor annealing on PDI-DPP-PDI is to reduce geminate recombination, leading to balanced exciton generation and charge separation.

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

Impact of Backbone Rigidity on the Thermomechanical Properties of Semiconducting Polymers with Conjugation Break Spacers

There remains a lack of fundamental understanding in theroleofbackbonerigidityonthe thermomechanical properties of conjugated polymers. Here, we provide the first holistic approach to understand the fundamental influence of backbone rigidity on an n-type naphthalene diimide-based conjugated polymer, denoted by PNDI-Cx, through insertion of a flexible conjugation break spacer (CBS). CBS lengths are varied from fully conjugated with zero alkyl spacer (PNDI-C0) to a seven- carbon alkyl spacer (PNDI-C 7 ), with the CBS engineered into each repeat unit for systematic evaluation. Solution small-angle neutron scattering and oscillatory shear rheometry were employed to provide the first quantitative evidence of CBS influence over conjugated polymer chain rigidity and entanglement molecular weight (M e ), demonstrating a reduction in the Kuhn length from 521 to 36 Å for fully conjugated PNDI-C0 and PNDI-C6, respectively, as well as a nearly consistent Me of ~15 kDa upon the addition of CBS. Thermomechanical properties, such as elastic modulus and glass-transition temperature, were shown to decrease with an increasing length of CBS. An extraordinary ductility, upwards of 400% tensile strain before fracture, was observed for high-molecular-weight PNDI-C4, which we attribute to a high number of entanglements and disruption of crystallization. Furthermore, the deformation mechanism for PNDI-Cx was studied under strain through X-ray diffraction, polarized UV-vis spectroscopy, and atomic force microscopy. Overall, this work sheds light on the important role of backbone rigidity in designing flexible and stretchable conjugated polymers.

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

Imaging Ferroelastic Domain Walls in Hybrid Improper Ferroelectric Sr 3 Sn 2 O 7

For this work, we combined synchrotron-based near field infrared spectroscopy and atomic force microscopy to image the properties of ferroelastic domain walls in Sr 3 Sn 2 O 7 . Although frequency shifts at the walls are near the limit of our sensitivity, we can confirm semiconducting rather than metallic character and widths between 20 and 60 nm. The latter is significantly narrower than in other hybrid improper ferroelectrics like Ca 3 Ti 2 O 7 . We attribute this trend to the softer lattice in Sr 3 Sn 2 O 7 , which may enable the octahedral tilt and rotation order parameters to evolve more quickly across the wall without significantly increased strain. These findings are crucial for the understanding of phononic properties at interfaces and the development of domain wall-based devices.

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

LiNi0.8Mn0.1Co0.1O2 Thin Films Prepared by Polymer-Assisted Deposition for the Study of Cathode-Electrolyte Interphases in Lithium-Ion Batteries

High-nickel layered oxide cathodes such as LiNi0.8Mn0.1Co0.1O2 (NMC811) are critical for next-generation lithium-ion batteries (LIBs) due to their superior energy density and reduced reliance on cobalt. However, many Ni-rich cathodes suffer from rapid capacity fade and structural instability originating from complex interfacial reactions at the cathode-electrolyte interface. Traditional composite electrodes exhibit degradation mechanisms that are challenging to quantitatively understand due to additives, including binders and carbon black. In this study, we demonstrate a new synthesis approach for binder- and additive-free NMC811 thin films using polymer-assisted deposition (PAD). PAD-NMC811 are model thin-film cathodes for investigating interfacial phenomena that can be obscured in composite cathodes. Structural and chemical characterization by X-ray diffraction, soft X-ray absorption spectroscopy, and atomic force microscopy show that PAD-NMC811 films possess high phase purity, crystallinity, chemical homogeneity, and morphological uniformity. Electrochemical analyses using cyclic voltammetry and galvanostatic cycling revealed electrochemical behavior consistent with that of composite electrodes, along with a moderate capacity fade indicative of cathode-electrolyte interphase (CEI) formation. Our findings illustrate the effectiveness of PAD synthesis of thin films tailored for detailed mechanistic studies, which offer critical insights into CEI evolution and cathode degradation pathways.

25 ENERGY STORAGE↗
DOE OSTI2022

Channel Scaling Dependent Photoresponse of Copper-Based Flexible Photodetectors Fabricated Using Laser-Induced Oxidation

Copper (Cu) oxide compounds (Cu x O), which include cupric (CuO) and cuprous (Cu 2 O) oxide, have been recognized as a promising p-channel material with useful photovoltaic properties and superior thermal conductivity. Typically, deposition methods or thermal oxidation can be used to obtain Cu x O. However, these processes are difficult to apply to flexible substrates because plastics have a comparatively low glass transition temperature. Also, additional patterning steps are needed to fabricate applications. In this work, we fabricated a metal–semiconductor–metal photodetector using laser-induced oxidation of thin Cu films under ambient conditions. Raman spectroscopy, scanning electron microscopy–energy-dispersive X-ray spectroscopy, and atomic force microscopy were used to study the composition and morphology of our devices. Moreover, the photoresponse of this device is reported herein. We performed an in-depth analysis of the relationship between the channel size and number of carriers using scanning photocurrent microscopy. The carrier transport behaviors were identified; the photocurrent decreased as the length and width of the channel increased. Furthermore, we verified the suitability of the device as a flexible photodetector using a variety of bending tests. Our in-depth analysis of this Cu-based flexible photodetector could play an important role in understanding the mechanisms of other flexible photovoltaic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Millimeter-Scale Exfoliation of hBN with Tunable Flake Thickness for Scalable Encapsulation

As a two-dimensional (2D) dielectric material, hexagonal boron nitride (hBN) is in high demand for applications in photonics, nonlinear optics, and nanoelectronics. Unfortunately, the high-throughput preparation of macroscopic-scale, high-quality hBN flakes with controlled thickness is an ongoing challenge, limiting device fabrication and technological integration. In this report we present a metal thin-film exfoliation method to prepare hBN flakes with millimeter-scale dimension, near-unity yields, and tunable flake thickness distribution from 1-7 layers, a substantial improvement over scotch tape exfoliation. The single crystallinity and high quality of the exfoliated hBN are demonstrated with optical microscopy, atomic force microscopy, Raman spectroscopy, and second harmonic generation. We further explore a possible mechanism for the effectiveness and selectivity based on thin-film residual stress measurements, density functional theory calculations, and transmission electron microscopy imaging of the deposited metal films. We find that the magnitude of the residual tensile stress induced by thin film deposition plays a key role in determining exfoliated flake thickness in a manner which closely resembles 3D semiconductor spalling. Lastly, we demonstrate that our exfoliated, large-area hBN flakes can be readily incorporated as encapsulating layers for other 2D monolayers. Altogether, this method brings us one step closer to the high throughput, mass production of hBN-based 2D photonic, optoelectronic, and quantum devices.

2D materials↗
DOE OSTI2021

Inhibition of Amyloid β-Induced Lipid Membrane Permeation and Amyloid β Aggregation by K162

Alzheimer's disease (AD) is characterized by progressive neurodegeneration associated with amyloid β (Aβ) peptide aggregation. The aggregation of Aβ monomers (AβMs) leads to the formation of Aβ oligomers (AβOs), the neurotoxic Aβ form, capable of permeating the cell membrane. Here, we investigated the effect of a fluorene-based active drug candidate, named K162, on both Aβ aggregation and AβO toxicity toward the bilayer lipid membrane (BLM). Electrochemical impedance spectroscopy (EIS), atomic force microscopy (AFM), and molecular dynamics (MD) were employed to show that K162 inhibits AβOs-induced BLM permeation, thus preserving BLM integrity. In the presence of K162, only shallow defects on the BLM surface were formed. Apparently, K162 modifies Aβ aggregation by bypassing the formation of toxic AβOs, and only nontoxic AβMs, dimers (AβDs), and fibrils (AβFs) are produced. Unlike other Aβ toxicity inhibitors, K162 preserves neurologically beneficial AβMs. This unique K162 inhibition mechanism provides an alternative AD therapeutic strategy that could be explored in the future.

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

Thermal Conversion of Ultrathin Nickel Hydroxide for Wide Band Gap 2D Nickel Oxides

Wide band gap (WBG) semiconductors (E g > 2.0 eV) are integral to the advancement of next-generation electronics, optoelectronics, and power industries owing to their capability for high-temperature operation, high breakdown voltage, and efficient light emission. Enhanced power efficiency and functional performance can be attained through miniaturization, specifically via the integration of device fabrication into a two-dimensional (2D) structure enabled by WBG 2D semiconductors. However, as an essential subgroup of WBG semiconductors, 2D transition metal oxides (TMOs) remain largely underexplored in terms of physical properties and applications in 2D optoelectronic devices, primarily due to the scarcity of sufficiently large 2D crystals. Thus, our goal is to develop synthesis pathways for 2D TMOs possessing large crystal domains (e.g., >10 μm), expanding the 2D TMO family and providing insights for future engineering of 2D TMOs. Here, we demonstrate the synthesis of WBG 2D nickel oxide (NiO) (E g > 2.7 eV) thermally converted from 2D nickel hydroxide (Ni(OH) 2 ) with a lateral domain size larger than 10 μm. Moreover, the conversion process is investigated using various microscopic techniques, such as atomic force microscopy, Raman spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy, providing significant insights into morphology and structural variations under different oxidative conditions. The electronic structure of the converted Ni x O y is further investigated using multiple soft X-ray spectroscopies, such as X-ray absorption and emission spectroscopies.

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

Scalable Synthesis and Characterization of Multilayer γ-Graphyne, New Carbon Crystals with a Small Direct Band Gap

γ-Graphyne is the most symmetric sp 2 /sp 1 allotrope of carbon, which can be viewed as graphene uniformly expanded through the insertion of two-carbon acetylenic units between all the aromatic rings. To date, synthesis of bulk γ-graphyne has remained a challenge. In this work, we report the synthesis of multilayer γ-graphyne through crystallization-assisted irreversible cross-coupling polymerization. A comprehensive characterization of this new carbon phase is described, including synchrotron powder X-ray diffraction, electron diffraction, lateral force microscopy, Raman spectroscopy, infrared spectroscopy, and cyclic voltammetry. Experiments indicate that γ-graphyne is a 0.48 eV band gap semiconductor, with a hexagonal a-axis spacing of 6.88 Å and an interlayer spacing of 3.48 Å, which is consistent with theoretical predictions. The observed crystal structure has an aperiodic sheet stacking. The material is thermally stable up to 240 °C but undergoes transformation at higher temperatures. While conventional 2D polymerization and reticular chemistry rely on error correction through reversibility, we demonstrate that a periodic covalent lattice can be synthesized under purely kinetic control. The reported methodology is scalable and inspires extension to other allotropes of the graphyne family.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Low resistance p-type contacts to monolayer WSe2 through chlorinated solvent doping

Tungsten diselenide (WSe 2 ) is a promising p-type semiconductor limited by high contact resistance (R C ) and the lack of a reliable doping strategy. Here, we demonstrate that exposing WSe 2 to chloroform provides simple and stable p-type doping. In monolayer WSe 2 transistors with Pd contacts, chloroform increases the maximum hole current by over 100× (>200 µA/µm), reduces R C to ~ 2.5 kΩ·μm, and retains an on/off ratio of 10 10 at room temperature. These improvements persist for over 8 months, survive a 150 °C thermal anneal, and remain effective down to 10 K, enabling a cryogenic R C of ~ 1 kΩ·μm. Density functional theory indicates that chloroform strongly physisorbs to WSe 2 , inducing hole doping with minimal impact on the electronic states between the valence band and conduction band edges. Auger electron spectroscopy and atomic force microscopy suggest that chloroform intercalates at the WSe 2 interface with the gate oxide, contributing to doping stability and mitigating interfacial dielectric disorder, though further studies are needed to conclusively confirm this mechanism. This robust, scalable approach enables high-yield WSe 2 transistors with good p-type performance.

42 ENGINEERING↗
DOE OSTI2021

Introduction of Chalcogenide Glasses to Additive Manufacturing: Nanoparticle Ink Formulation, Inkjet Printing, and Phase Change Devices Fabrication

Abstract Chalcogenide glasses are one of the most versatile materials that have been widely researched because of their flexible optical, chemical, electronic, and phase change properties. Their application is usually in the form of thin films, which work as active layers in sensors and memory devices. In this work, we investigate the formulation of nanoparticle ink of Ge–Se chalcogenide glasses and its potential applications. The process steps reported in this work describe nanoparticle ink formulation from chalcogenide glasses, its application via inkjet printing and dip-coating methods and sintering to manufacture phase change devices. We report data regarding nanoparticle production by ball milling and ultrasonication along with the essential characteristics of the formed inks, like contact angle and viscosity. The printed chalcogenide glass films were characterized by Raman spectroscopy, X-ray diffraction, energy dispersive spectroscopy and atomic force microscopy. The printed films exhibited similar compositional, structural, electronic and optical properties as the thermally evaporated thin films. The crystallization processes of the printed films are discussed compared to those obtained by vacuum thermal deposition. We demonstrate the formation of printed thin films using nanoparticle inks, low-temperature sintering and proof for the first time, their application in electronic and photonic temperature sensors utilizing their phase change property. This work adds chalcogenide glasses to the list of inkjet printable materials, thus offering an easy way to form arbitrary device structures for optical and electronic applications.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Experimental discovery of structure–property relationships in ferroelectric materials via active learning

Emergent functionalities of structural and topological defects in ferroelectric materials underpin an extremely broad spectrum of applications ranging from domain wall electronics to high dielectric and electromechanical responses. Many of these functionalities have been discovered and quantified via local scanning probe microscopy methods. However, the search has until now been based on either trial and error, or using auxiliary information such as the topography or domain wall structure to identify potential objects of interest on the basis of the intuition of operator or pre-existing hypotheses, with subsequent manual exploration. Here we report the development and implementation of a machine learning framework that actively discovers relationships between local domain structure and polarization-switching characteristics in ferroelectric materials encoded in the hysteresis loop. The hysteresis loops and their scalar descriptors such as nucleation bias, coercive bias and the hysteresis loop area (or more complex functionals of hysteresis loop shape) and corresponding uncertainties are used to guide the discovery of these relationships via automated piezoresponse force microscopy and spectroscopy experiments. As such, this approach combines the power of machine learning methods to learn the correlative relationships between high-dimensional data, as well as human-based physics insights encoded into the acquisition function. For ferroelectric materials, this automated workflow demonstrates that the discovery path and sampling points of on- and off-field hysteresis loops are largely different, indicating that on- and off-field hysteresis loops are dominated by different mechanisms. Here, the proposed approach is universal and can be applied to a broad range of modern imaging and spectroscopy methods ranging from other scanning probe microscopy modalities to electron microscopy and chemical imaging.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effects of growth substrate on the nucleation of monolayer MoTe 2

The discovery and characterization of two-dimensional (2D) materials beyond graphene has increased dramatically over the past decade with increasingly fine control over the growth dynamics of these materials. MoTe 2 represents a model material for studying phase change properties of 2D materials due to small energy differences between its 2H semiconducting phase and 1T' semimetallic phase. Although some substrates are demonstrated to be better than others for the wafer-scale growth of high quality MoTe 2 films, substrate effects on the nucleation and growth of MoTe 2 are still not well understood. Here, we grow monolayer MoTe 2 by converting MoO x thin films deposited on three different substrates: sapphire Al 2 O 3 (0001), amorphous SiO 2 , and amorphous AlO x , and examine the early stages of the conversion reaction to elucidate the substrate effects on the nucleation of MoTe 2 . We observe that the chemical composition of the substrate is more important than the surface topography and crystallinity of the substrate, with high quality monolayer 2H MoTe 2 formed on both Al 2 O 3 (0001) and AlO x in contrast to mixed phase 2H/1T' MoTe 2 formed on SiO 2 , as determined by Raman spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Ultrafast charge transfer and carrier dynamics in a WS 2 /MoSe 2 few-layer van der Waals heterostructure

Photocarrier dynamics including interlayer charge transfer and intralayer valley scattering are studied in a heterostructure formed by trilayer WS 2 and MoSe 2 . The sample is fabricated by mechanical exfoliation and dry transfer and characterized by atomic force microscopy, Raman spectroscopy, and photoluminescence measurements. The conduction band minima of the two materials are nearly degenerate, representing a unique band alignment. Layer-selective pump–probe measurements are performed with three configurations to reveal a complete picture of the photocarrier dynamics. By comparing the heterostructure with the two individual trilayer materials in each experimental configuration, ultrafast interlayer charge transfer is unambiguously observed, which occurs on the same time scale as the intralayer valley scattering of the photocarriers. The quasi-equilibrium distribution of electrons in the two layers mediate the fast carrier recombination process. Furthermore, these results show that the band structures of the few-layer transition metal dichalcogenides can enable rich photocarrier dynamics with intermediate band alignments that are complementary to the previously studied monolayer–monolayer heterostructures.

36 MATERIALS SCIENCE↗