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At least 1,423 records · Page 79

Anomalously Suppressed Thermal Conduction by Electron-Phonon Coupling in Charge-Density-Wave Tantalum Disulfide

Charge and thermal transport in a crystal is carried by free electrons and phonons (quantized lattice vibration), the two most fundamental quasiparticles. Above the Debye temperature of the crystal, phonon-mediated thermal conductivity ( κ L ) is typically limited by mutual scattering of phonons, which results in κ L decreasing with inverse temperature, whereas free electrons play a negligible role in κ L . Here, an unusual case in charge-density-wave tantalum disulfide (1T-TaS 2 ) is reported, in which κ L is limited instead by phonon scattering with free electrons, resulting in a temperature-independent κ L . In this system, the conventional phonon–phonon scattering is alleviated by its uniquely structured phonon dispersions, while unusually strong electron-phonon (e-ph) coupling arises from its Fermi surface strongly nested at wavevectors in which phonons exhibit Kohn anomalies. The unusual temperature dependence of thermal conduction is found as a consequence of these effects. The finding reveals new physics of thermal conduction, offers a unique platform to probe e-ph interactions, and provides potential ways to control heat flow in materials with free charge carriers. The temperature-independent thermal conductivity may also find thermal management application as a special thermal interface material between two systems when the heat conduction between them needs to be maintained at a constant level.

36 MATERIALS SCIENCE↗

Advances in Rare-Earth Tritelluride Quantum Materials: Structure, Properties, and Synthesis

A distinct class of 2D layered quantum materials with the chemical formula of RTe 3 (R = lanthanide) has gained significant attention owing to the occurrence of collective quantum states, superconductivity, charge density waves (CDW), spin density waves, and other advanced quantum properties. To study the Fermi surface nesting driven CDW formation, the layered RTe 3 family stages an excellent low dimensional genre system. In addition to the primary energy gap feature observed at higher energy, optical spectroscopy study on some RTe 3 evidence a second CDW energy gap structure indicating the occurrence of multiple CDW ordering even with light and intermediate RTe 3 compounds. Here, a comprehensive review of the fundamentals of RTe 3 layered tritelluride materials is presented with a special focus on the recent advances made in electronic structure, CDW transition, superconductivity, magnetic properties of these unique quantum materials. A detailed description of successful synthesis routes including the flux method, self-flux method, and CVT along with potential applications is summarized.

36 MATERIALS SCIENCE↗

Correlating Electronic Structure and Device Physics with Mixing Region Morphology in High-Efficiency Organic Solar Cells

The donor/acceptor interaction in non-fullerene organic photovoltaics leads to the mixing domain that dictates the morphology and electronic structure of the blended thin film. Initiative effort is paid to understand how these domain properties affect the device performances on high-efficiency PM6:Y6 blends. Different fullerenes acceptors are used to manipulate the feature of mixing domain. It is seen that a tight packing in the mixing region is critical, which could effectively enhance the hole transfer and lead to the enlarged and narrow electron density of state (DOS). As a result, short-circuit current (J SC ) and fill factor (FF) are improved. The distribution of DOS and energy levels strongly influences open-circuit voltage (V OC ). The raised filling state of electron Fermi level is seen to be key in determining device V OC . Energy disorder is found to be a key factor to energy loss, which is highly correlated with the intermolecular distance in the mixing region. A 17.53% efficiency is obtained for optimized ternary devices, which is the highest value for similar systems. The current results indicate that a delicate optimization of the mixing domain property is an effective route to improve the V OC , J SC , and FF simultaneously, which provides new guidelines for morphology control toward high-performance organic solar cells.

36 MATERIALS SCIENCE↗

Electronic Topological Transition as a Route to Improve Thermoelectric Performance in Bi 0.5 Sb 1.5 Te 3

The electronic structure near the Fermi surface determines the electrical properties of the materials, which can be effectively tuned by external pressure. Bi0.5Sb1.5Te3 is a p-type thermoelectric material which holds the record high figure of merit at room temperature. Here it is examined whether the figure of merit of this model system can be further enhanced through some external parameter. With the application of pressure, it is surprisingly found that the power factor of this material exhibits λ behavior with a high value of 4.8 mW m –1 K –2 at pressure of 1.8 GPa. Such an enhancement is found to be driven by pressure-induced electronic topological transition, which is revealed by multiple techniques. Together with a low thermal conductivity of about 0.89 W m –1 K –1 at the same pressure, a figure of merit of 1.6 is achieved at room temperature. The results and findings highlight the electronic topological transition as a new route for improving the thermoelectric properties.

36 MATERIALS SCIENCE↗

Metal–Organic Framework Integrating Ionic Framework and Bimetallic Coupling Effect for Highly Efficient Oxygen Evolution Reaction

Metal–organic frameworks (MOFs) are recognized as promising electrocatalysts for the oxygen evolution reaction (OER) because of their permanent porosity and rich architectural diversity; however, ionic MOFs enabling fast ions exchange during OER are rarely explored. Here, an ionic MOF (Ni-btz) constructed with an azolate ligand is selected, and continuous 3D bimetallic MOF (NiFe-btz) films deriving from high-degree intergrowth of microsized MOFs particles are fabricated. The as-prepared NiFe-btz/NF-OH electrode exhibits excellent OER performance with a low overpotential of 239 mV at 10 mA cm –2 under alkaline condition. The OER charge transfer process and bimetallic coupling effect in ionic NiFe-btz are probed by density functional theory calculations and confirmed via X-ray photoelectron spectroscopy and in situ Raman measurements. The partial density of states of NiFe-btz indicates that the main contribution for electron density around the Fermi level is from Cl ions clarifying the profitable impact of ionic MOF framework. This work systematically demonstrates the relationship of electronic structure and OER activity in ionic, bimetallic MOFs and expands the scope of 3D MOF films for efficient OER.

36 MATERIALS SCIENCE↗

Unconventional Anomalous Hall Effect Driven by Self‐Intercalation in Covalent 2D Magnet Cr 2 Te 3

Covalent 2D magnets such as Cr 2 Te 3 , which feature self-intercalated magnetic cations located between monolayers of transition-metal dichalcogenide material, offer a unique platform for controlling magnetic order and spin texture, enabling new potential applications for spintronic devices. Here, it is demonstrated that the unconventional anomalous Hall effect (AHE) in Cr 2 Te 3 , characterized by additional humps and dips near the coercive field in AHE hysteresis, originates from an intrinsic mechanism dictated by the self-intercalation. This mechanism is distinctly different from previously proposed mechanisms such as topological Hall effect, or two-channel AHE arising from spatial inhomogeneities. Crucially, multiple Weyl-like nodes emerge in the electronic band structure due to strong spin-orbit coupling, whose positions relative to the Fermi level is sensitively modulated by the canting angles of the self-intercalated Cr cations. These nodes contribute strongly to the Berry curvature and AHE conductivity. This component competes with the contribution from bands that are less affected by the self-intercalation, resulting in a sign change in AHE with temperature and the emergence of additional humps and dips. The findings provide compelling evidence for the intrinsic origin of the unconventional AHE in Cr 2 Te 3 and further establish self-intercalation as a control knob for engineering AHE in complex magnets.

2D magnets↗

2D Mg-Cu Intermetallic Compounds with Nontrivial Band Topology and Dirac Nodal Lines

Synthesis of vertical heterostructures that include atomically thin layers of materials with topologically nontrivial energy bands is desirable for exploring exotic quantum states. In this study, the authors report on atomic-layer-by-layer deposition of magnesium on copper(111) surface by molecular beam epitaxy, monitored in situ by low-energy electron microscopy and diffraction, and modeled by ab initio theory. It is found that a 2D MgCu 2 intermetallic compound forms during initial Mg deposition and persists till a full monolayer of Mg is formed. Deposition of additional Mg triggers a phase transition from the commensurate MgCu 2 to an incommensurate Mg 2 Cu layer and enables growth of the second layer of Mg. Ab initio calculations indicate non-trivial topology of the electron bands in the interfacial Mg 2 Cu layer and the existence of Dirac nodal lines near the Fermi level. The new 2D Mg 2 Cu material emerges as a promising platform to study new topological states of matter.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

CeO 2 Doping of Hf 0.5 Zr 0.5 O 2 Thin Films for High Endurance Ferroelectric Memories

Ferroelectric switching is demonstrated in CeO 2 -doped Hf 0.5 Zr 0.5 O 2 (HZCO) thin films with application in back-end-of-line compatible embedded memories. At low cerium oxide doping concentrations (2.0–5.6 mol%), the ferroelectric orthorhombic phase is stabilized after annealing at temperatures below 400 °C. HZCO ferroelectrics show reliable switching characteristics beyond 10 11 cycles in TiN/HZCO/TiN capacitors, several orders of magnitude greater than identically processed Hf 0.5 Zr 0.5 O 2 (HZO) capacitors, without sacrificing polarization and retention. Internal photoemission and photoconductivity experiments show that CeO 2 -doping introduces in-gap states in HZCO that are nearly aligned with TiN Fermi level, facilitating electron injection through these states. Furthermore, the enhanced average bulk conduction, which may lead to more uniform thermal dissipation in the HZCO films, delays irreversible degradation via breakdown that leads to device failure after repeated programming cycles.

36 MATERIALS SCIENCE↗

Enhancement of the Magnetoresistance in the Mobility‐Engineered Compensated Metal Pt 5 P 2

Abstract The magnetoresistance (MR) in nonmagnetic materials continues to be a fertile research area in materials science. The search for giant, positive MR has been limited to a rather small window of materials such as high‐mobility semimetals in single‐crystalline form. Here, the observation of a very large positive MR in metallic Pt 5 P 2 in polycrystalline form is reported. The observations reveal that improvement of the crystallinity results in a significant enhancement of the positive MR, exceeding 10 000% at 9 T, comparable to high‐mobility semimetals. Based on first‐principles calculations combined with magnetotransport and thermoelectric measurements, the Fermi surface of Pt 5 P 2 is found to consist of a collection of multiple electron and hole pockets compensating one another, along with a characteristic pocket continuously connected to the adjacent Brillouin zone, together with possible topologically protected band crossings. This work extends the landscape of high MR candidate materials to polycrystalline metals, which demonstrates the importance of crystallinity and purity of the samples for the optimization of the MR.

36 MATERIALS SCIENCE↗

Reducing the Barrier Height in Organic Transistors

Abstract Reducing the Schottky barrier height and Fermi level de‐pinning in metal‐organic semiconductor contacts are crucial for enhancing the performance of organic transistors. The reduction of the Schottky barrier height in bottom‐contact top‐gate organic transistors is demonstrated by adding 1 nm thick atomic layer deposited Al 2 O 3 on the source and drain contacts. By using two different donor‐acceptor copolymers, both p‐ and n‐ type transistors are investigated. Temperature‐dependent current–voltage measurements from non‐treated, self‐assembled monolayer treated, and Al 2 O 3 treated Au source‐drain contact field‐effect transistors with varying channel lengths are carried out. The drain current versus drain voltage near zero gate voltage, which may be described by the thermionic emission model at temperatures above 150 K, allows the estimation of the Schottky barrier height ( φ B ). The Al 2 O 3 contact‐treated transistors show more than 40% lower φ B compared with the non‐treated contacts in the p ‐type transistor. Similarly, an isoindigo‐based transistor, with n ‐type transport, shows a reduction in φ B with Al 2 O 3 treated contacts suggesting that such ultrathin oxide layers provide a universal method for reducing the barrier height.

Ghobadi, Arash↗

Extreme Enhancement-Mode Operation Accumulation Channel Hydrogen-Terminated Diamond FETs with V th < -6 V and High on-Current

In this work, a new Field Effect Transistor device concept based on hydrogen-terminated diamond (H-diamond) is demonstrated that operates in an Accumulation Channel rather than a Transfer Doping regime. The FET devices demonstrate both extreme enhancement-mode operation and high on-current with improved channel charge mobility compared to Transfer-Doped equivalents. Electron-beam evaporated Al 2 O 3 is used on H-diamond to suppress the Transfer Doping mechanism and produce an extremely high ungated channel resistance. A high-quality H-diamond surface with an unpinned Fermi level is crucially achieved, allowing for the formation of a high-density hole accumulation layer by gating the entire device channel which is encapsulated in dual-stacks of Al 2 O 3 . Completed devices with gate/channel length of 1 µm demonstrate record threshold voltage < -6 V with on-current > 80 mA mm -1 . Carrier density and mobility figures extracted by CV analysis indicate a high 2D charge density of ≈ 2 × 10 12 cm -2 and increased hole mobility of 110 cm 2 V -1 s -1 in comparison with more traditional Transfer-Doped H-diamond FETs. These results demonstrate the most negative threshold voltage yet reported for H-diamond FETs and highlight a powerful new strategy to greatly improve carrier mobility and enable enhanced high power and high frequency diamond transistor performance.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Uranium Doped Gallium Nitride Epitaxial Thin Films

Gallium nitride (GaN) is near ubiquitous in modern day technologies, forming the backbone of solid-state lighting and high-power electronics. Engineering the physical properties of GaN has been investigated to some degree by the incorporation or doping of most of the elements of the periodic table, but the actinides remain unexplored. Molecular beam epitaxy is used to demonstrate uranium doping of GaN single crystals. High structural quality of the host matrix is maintained despite partial elemental segregation of the uranium dopant into 1D structures at the levels presented here. Electronic transport measurements reveal relatively high conductivity, which persists down to cryogenic temperature and is characterized by the formation of narrow gaps in the electronic band structures very close to the Fermi level. Photoluminescence measurements reveal that the U-doped GaN exhibits optical behavior similar to that of the GaN substrate. The addition of actinide materials to a non-centrosymmetric, optically active, radiation-hard, and electronically tunable host matrix opens a world of possibilities for investigating and leveraging elements with high electron correlations in the pursuit of novel devices.

36 - MATERIALS SCIENCE↗

Heterometallic Actinide‐Containing Photoresponsive Metal‐Organic Frameworks: Dynamic and Static Tuning of Electronic Properties

Abstract Acquiring fundamental knowledge of properties of actinide‐based materials is a necessary step to create new possibilities for addressing the current challenges in the nuclear energy and nuclear waste sectors. In this report, we established a photophysics–electronics correlation for actinide‐containing metal‐organic frameworks (An‐MOFs) as a function of excitation wavelength, for the first time. A stepwise approach for dynamically modulating electronic properties was applied for the first time towards actinide‐based heterometallic MOFs through integration of photochromic linkers. Optical cycling, modeling of density of states near the Fermi edge, conductivity measurements, and photoisomerization kinetics were employed to shed light on the process of tailoring optoelectronic properties of An‐MOFs. Furthermore, the first photochromic MOF‐based field‐effect transistor, in which the field‐effect response could be changed through light exposure, was constructed. As a demonstration, the change in current upon light exposure was sufficient to operate a two‐LED fail‐safe indicator circuit.

Martin, Corey R.↗

f‐ block MOFs: A Pathway to Heterometallic Transuranics

Abstract A novel series of heterometallic f ‐block‐frameworks including the first examples of transuranic heterometallic 238 U/ 239 Pu‐metal–organic frameworks (MOFs) and a novel monometallic 239 Pu‐analog are reported. In combination with theoretical calculations, we probed the kinetics and thermodynamics of heterometallic actinide(An)‐MOF formation and reported the first value of a U‐to‐Th transmetallation rate. We concluded that formation of uranyl species could be a driving force for solid‐state metathesis. Density of states near the Fermi edge, enthalpy of formation, band gap, proton affinity, and thermal/chemical stability were probed as a function of metal ratios. Furthermore, we achieved 97 % of the theoretical maximum capacity for An‐integration. These studies shed light on fundamental aspects of actinide chemistry and also foreshadow avenues for the development of emerging classes of An‐containing materials, including radioisotope thermoelectric generators or metalloradiopharmaceuticals.

Park, Kyoung Chul↗

Toward Complete Transformation of Sodium Polysulfides by Regulating the Second-Shell Coordinating Environment of Atomically Dispersed Fe

Room temperature sodium-sulfur (RT Na-S) batteries are highly competitive as potential energy storage devices. Nevertheless, their actually achieved reversible capacities are far below the theoretical value due to incomplete transformation of polysulfides. Herein, atomically dispersed Fe-N/S active center by regulating the second-shell coordinating environment of Fe single atom is proposed. The Fe-N4S2 coordination structure with enhanced local electronic concentration around the Fermi level is revealed via synchrotron radiation X-ray absorption spectroscopy (XAS) and theoretical calculations, which can not only significantly promote the transformation kinetics of polysulfides, but induce uniform Na deposition for dendrite-free Na anode. Here as a result, the obtained S cathode delivers a high initial reversible capacity of 1590 mAh g-1, nearly the theoretical value. Here this work opens up a new avenue to facilitate the complete transformation of polysulfides for RT Na-S batteries.

25 ENERGY STORAGE↗

2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO 2 to Formic Acid

Abstract Efficiently transforming CO 2 into renewable energy sources is crucial for decarbonization efforts. Formic acid (HCOOH) holds great promise as a hydrogen storage compound due to its high hydrogen density, non‐toxicity, and stability under ambient conditions. However, the electrochemical reduction of CO 2 (CO 2 RR) on conventional carbon black‐supported metal catalysts faces challenges such as low stability through dissolution and agglomeration, as well as suffering from high overpotentials and the necessity to overcome the competitive hydrogen evolution reaction (HER). In this study, we modify the physical/chemical properties of metal surfaces by depositing metal monolayers on graphene (M/G) to create highly active and stable electrocatalysts. Strong covalent bonding between graphene and metal is induced by the hybridization of sp and d orbitals, especially the sharp , , and orbitals of metals near the Fermi level, playing a decisive role. Moreover, charge polarization on graphene in M/G enables the deposition of another thin metallic film, forming metal/graphene/metal (M/G/M) structures. Finally, evaluating overpotentials required for CO 2 reduction to HCOOH, CO, and HER, we find that Pd/G, Pt/G/Ag, and Pt/G/Au exhibit excellent activity and selectivity toward HCOOH production. Our novel 2D hybrid catalyst design methodology may offer insights into enhanced electrochemical reactions through the electronic mixing of metal and other p‐block elements.

Cho, Jinwon↗

Heterometallic Actinide-Containing Photoresponsive Metal-Organic Frameworks: Dynamic and Static Tuning of Electronic Properties

Acquiring fundamental knowledge of properties of actinide-based materials is a necessary step to create new possibilities for addressing the current challenges in the nuclear energy and nuclear waste sectors. Here in this report, we established a photophysics–electronics correlation for actinide-containing metal-organic frameworks (An-MOFs) as a function of excitation wavelength, for the first time. A stepwise approach for dynamically modulating electronic properties was applied for the first time towards actinide-based heterometallic MOFs through integration of photochromic linkers. Optical cycling, modeling of density of states near the Fermi edge, conductivity measurements, and photoisomerization kinetics were employed to shed light on the process of tailoring optoelectronic properties of An-MOFs. Furthermore, the first photochromic MOF-based field-effect transistor, in which the field-effect response could be changed through light exposure, was constructed. As a demonstration, the change in current upon light exposure was sufficient to operate a two-LED fail-safe indicator circuit.

36 MATERIALS SCIENCE↗