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At least 1,675 records · Page 93

Phase Transition in a Memristive Suspended MoS 2 Monolayer Probed by Opto- and Electro-Mechanics

Semiconducting monolayers of a 2D material are able to concatenate multiple interesting properties into a single component. Here, by combining opto-mechanical and electronic measurements, we demonstrate the presence of a partial 2H–1T' phase transition in a suspended 2D monolayer membrane of MoS 2 . Electronic transport shows unexpected memristive properties in the MoS 2 membrane, in the absence of any external dopants. A strong mechanical softening of the membrane is measured concurrently and may only be related to the 2H–1T' phase transition, which imposes a 3% directional elongation of the topological 1T' phase with respect to the semiconducting 2H. We note that only a few percent 2H–1T' phase switching is sufficient to observe measurable memristive effects. Our experimental results combined with first-principles total energy calculations indicate that sulfur vacancy diffusion plays a key role in the initial nucleation of the phase transition. Our study clearly shows that nanomechanics represents an ultrasensitive technique to probe the crystal phase transition in 2D materials or thin membranes. Lastly, a better control of the microscopic mechanisms responsible for the observed memristive effect in MoS 2 is important for the implementation of future devices.

2D materials↗

Vacancy-Induced Formation and Growth of Inversion Domains in Transition-Metal Dichalcogenide Monolayer

Sixty degree grain boundaries in semiconducting transition-metal dichalcogenide (TMDC) monolayers have been shown to act as conductive channels that have profound influence on both the transport properties and exciton behavior of the monolayers. We show that annealing TMDC monolayers at high temperature induces the formation of large-scale inversion domains surrounded by such 60° grain boundaries. To study the formation mechanism of such inversion domains, we use the electron beam in a scanning transmission electron microscope to activate the dynamic process within pristine TMDC monolayers. Moreover, the electron beam acts to generate chalcogen vacancies in TMDC monolayers and provide energy for them to undergo structural evolution. We directly visualize the nucleation and growth of such inversion domains and their 60° grain boundaries atom-by-atom within a MoSe 2 monolayer and explore their formation mechanism. Combined with density functional theory, we conclude that the nucleation of the inversion domains and migration of their 60° grain boundaries are driven by the collective evolution of Se vacancies and subsequent displacement of Mo atoms, where such a dynamical process reduces the vacancy-induced lattice shrinkage and stabilizes the system. Our results can help to understand the performance of such materials under severe conditions (e.g., high temperature).

36 MATERIALS SCIENCE↗

Direct Observation of Ammonia Storage in UiO-66 Incorporating Cu(II) Binding Sites

The presence of active sites in metal–organic framework (MOF) materials can control and affect their performance significantly in adsorption and catalysis. However, revealing the interactions between the substrate and active sites in MOFs at atomic precision remains a challenging task. Here, we report the direct observation of binding of NH 3 in a series of UiO-66 materials containing atomically dispersed defects and open Cu(I) and Cu(II) sites. While all MOFs in this series exhibit similar surface areas (1111–1135 m 2 g –1 ), decoration of the -OH site in UiO-66-defect with Cu(II) results in a 43% enhancement of the isothermal uptake of NH 3 at 273 K and 1.0 bar from 11.8 in UiO-66-defect to 16.9 mmol g –1 in UiO-66-Cu II . A 100% enhancement of dynamic adsorption of NH 3 at a concentration level of 630 ppm from 2.07 mmol g –1 in UiO-66-defect to 4.15 mmol g –1 in UiO-66-Cu II at 298 K is observed. In situ neutron powder diffraction, inelastic neutron scattering, and electron paramagnetic resonance, solid-state nuclear magnetic resonance, and infrared spectroscopies, coupled with modeling reveal that the enhanced NH 3 uptake in UiO-66-Cu II originates from a {Cu(II)···NH 3 } interaction, with a reversible change in geometry at Cu(II) from near-linear to trigonal coordination. This work represents the first example of structural elucidation of NH 3 binding in MOFs containing open metal sites and will inform the design of new efficient MOF sorbents by targeted control of active sites for NH 3 capture and storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Temperature Fluctuations on Surface Mobility of Atomic Steps and Oxidation Dynamics in High-Temperature Alloys

In contrast to the traditional perspective that thermal fluctuations are insignificant in surface dynamics, here we report their influence on surface reaction dynamics. Using real-time low-energy electron microscopy imaging of NiAl(100) under both vacuum and O 2 atmospheres, we demonstrate that transient temperature variations substantially alter the direction of atom diffusion between the surface and bulk, leading to markedly different oxidation outcomes. During heating, substantial outward diffusion of atoms from the bulk to the surface results in step growth. Conversely, cooling induces considerable inward diffusion of adatoms, producing a distinct oxide morphology. In both scenarios, initially formed oxide islands impede local atomic step mobility, thereby increasing step length due to mass transfer between the surface and bulk, with atomic steps acting as adatom sinks during heating and sources during cooling. Furthermore, we show that this pinning effect on atomic step mobility can be mitigated by applying persistent temperature fluctuations. As a result, understanding these nuances is vital for accurately predicting and dynamically manipulating the performance of active materials in various chemical processes under transient thermal conditions.

36 MATERIALS SCIENCE↗

Thermodynamically Guided Synthesis of Mixed-Linker Zr-MOFs with Enhanced Tunability

Guided by thermodynamics, we have synthesized two mixed-linker zirconium-based metal–organic frameworks (Zr-MOFs), namely, PCN-133 and PCN-134. Both of them possess a layer-pillar structure, in which the connection between Zr 6 clusters and primary BTB linkers form a (3,6)-connected kdg layer that is further extended into 3D frameworks by auxiliary DCDPS/TCPP linkers (BTB = benzene tribenzoate, DCDPS = 4,4'-dicarboxydiphenyl sulfone, TCPP = tetrakis(4-carboxyphenyl)porphyrin). PCN-134 demonstrates high porosity (N 2 uptake of 717 cm 3 ·g –1 and BET surface area of 1946 cm 2 ·g –1 ) and excellent chemical stability in aqueous solutions with pH values ranging from 0 to 13. More importantly, PCN-134 tolerates the partial absence of auxiliary linkers leading to structural defects during the assembly process while preserving its framework integrity. Furthermore, the defect density can be systematically controlled by tuning the occupancy of the auxiliary linker, which in turn affects the MOF properties. For instance, the dichromate uptake of PCN-134 is tuned by adjusting the BTB/TCPP ratios, which gives rise to an efficient dichromate absorbent when the TCPP molar ratio in linkers is set as 22%. Additionally, the photocatalytic reduction of Cr(VI) in aqueous solution was also performed by PCN-134–22%TCPP which exhibits excellent catalytic activity. This work not only opens up a new synthetic route toward mixed-linker MOFs, but also provides tunable control of MOF defects and, in turn, the properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Molecular Silane-Derivatized Ru(II) Catalyst for Photoelectrochemical Water Oxidation

Photoanodes in dye-sensitized photoelectrosynthesis cells integrate molecular chromophore/catalyst assemblies on mesoporous n-type metal oxide electrodes for light-driven water oxidation. One limitation for sustainable photoanodes is the stability of chromophore/catalyst assembly on electrode surfaces for long periods. Progress has been made in stabilizing chromophores based on atomic layer deposition, polymer dip coating, C–C cross-coupling by electropolymerization, and silane surface binding, but little progress has been made on catalyst stabilization. We report here the silane-derivatized catalyst, Ru(bda)(L) 2 (bda = 2,2'-bipyridine-6,6'-dicarboxylate, L = 4-(6-(triethoxysilyl)hexyl)pyridine), catalyst 1, which is stabilized on metal oxide electrode surfaces over an extended pH range. A surface stabilization study shows that it maintains its reactivity on the electrode surface toward electrochemical oxidation over a wide range of conditions. Its electrochemical stability on electrode surfaces has been systematically evaluated, and its role as a catalyst for water oxidation has been explored. On surfaces of mesoporous nanostructured core/shell SnO 2 /TiO 2 , with a TiO 2 stabilized inner layer of the Ru(II) polypyridyl chromophore, [Ru(4,4'-(PO 3 H 2 ) 2 bpy)(bpy) 2 ] 2+ (RuP 2+ ; bpy = 2,2'-bipyridine), highly efficient photoelectrochemical water oxidation catalysis occurs to produce O 2 with a maximum efficiency of ~1.25 mA/cm 2 . Furthermore, long-term loss of catalytic activity occurs with time owing to catalyst loss from the electrode surface by axial ligand dissociation in the high oxidation states of the catalyst.

25 ENERGY STORAGE↗

Electronic properties of the bulk and surface states of Fe 1+y Te 1-x Se x

The idea of employing non-Abelian statistics for error-free quantum computing ignited interest in reports of topological surface superconductivity and Majorana zero modes (MZMs) in FeTe 0.55 Se 0.45 . However, the topological features and superconducting properties are not observed uniformly across the sample surface. The understanding and practical control of these electronic inhomogeneities present a prominent challenge for potential applications. Here, we combine neutron scattering, scanning angle-resolved photoemission spectroscopy, and microprobe composition and resistivity measurements to characterize the electronic state of Fe 1+y Te 1-x Se x . Furthermore, we establish a phase diagram in which the superconductivity is observed only at sufficiently low Fe concentration, in association with distinct antiferromagnetic correlations, whereas the coexisting topological surface state occurs only at sufficiently high Te concentration. We find that FeTe 0.55 Se 0.45 is located very close to both phase boundaries, which explains the inhomogeneity of superconducting and topological states. Our results demonstrate the compositional control required for use of topological MZMs in practical applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Charge transport in mixed metal halide perovskite semiconductors

Investigation of the inherent field-driven charge transport behaviour of three-dimensional lead halide perovskites has largely remained challenging, owing to undesirable ionic migration effects near room temperature and dipolar disorder instabilities prevalent specifically in methylammonium-and-lead-based high-performing three-dimensional perovskite compositions. Here, in this paper, we address both these challenges and demonstrate that field-effect transistors based on methylammonium-free, mixed metal (Pb/Sn) perovskite compositions do not suffer from ion migration effects as notably as their pure-Pb counterparts and reliably exhibit hysteresis-free p-type transport with a mobility reaching 5.4 cm 2 V –1 s -1 . The reduced ion migration is visualized through photoluminescence microscopy under bias and is manifested as an activated temperature dependence of the field-effect mobility with a low activation energy (~48 meV) consistent with the presence of the shallow defects present in these materials. An understanding of the long-range electronic charge transport in these inherently doped mixed metal halide perovskites will contribute immensely towards high-performance optoelectronic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Characterising local environments in high energy density Li-ion battery cathodes: a combined NMR and first principles study of LiFe x Co 1-x PO 4

Olivine-type LiCoPO4 (LCP) is a high energy density lithium ion battery cathode material due to the high voltage of the Co2+/Co3+ redox reaction. However, it displays a significantly poorer electrochemical performance than its more widely investigated isostructural analogue LiFePO4 (LFP). The co-substituted LiFexCo1-xPO4 olivines combine many of the positive attributes of each end member compound and are promising next-generation cathode materials. Here, the fully lithiated x = 0, 0.25, 0.5, 0.75 and 1 samples are extensively studied using 31P solid-state nuclear magnetic resonance (NMR). Practical approaches to broadband excitation and for the resolution of the isotropic resonances are described. First principles hybrid density functional calculations are performed on the Fermi contact shift (FCS) contributions of individual M–O–P pathways in the end members LFP and LCP and compared with the fitted values extracted from the LiFexCo1-xPO4 experimental data. Combining both data sets, the FCS for the range of local P environments expected in LiFexCo1-xPO4 have been calculated and used to assign the NMR spectra. Due to the additional unpaired electron in d6 Fe2+ as compared with d7 Co2+ (both high spin), LFP is expected to have larger Fermi contact shifts than LCP. However, two of the Co–O–P pathways in LCP give rise to noticeably larger shifts and the unexpected appearance of peaks outside the range delimited by the pure LFP and LCP 31P shifts. This behaviour contrasts with that observed previously in LiFexMn1-xPO4, where all 31P shifts lay within the LiMnPO4–LFP range. Although there are 24 distinct local P environments in LiFexCo1-xPO4, these group into seven resonances in the NMR spectra, due to significant overlap of the isotropic shifts. The local environments that give rise to the largest contributions to the spectral intensity are identified and used to simplify the assignment. This provides a tool for future studies of the electrochemically-cycled samples, which would otherwise be challenging to interpret.

36 MATERIALS SCIENCE↗

Chemomechanical behaviors of layered cathode materials in alkali metal ion batteries

Layered cathode materials (LCMs), because of their high energy density and relatively stable performance, represent an important class of cathode materials for alkali metal ion ( e.g. , Li + and Na + ) batteries. Chemomechanical behaviors of LCMs, which affect battery performance dramatically, have drawn extensive attention in recent years. Most chemomechanical processes have some common chemical and structural origins that are at the center of materials chemistry, for example, defects and local bonding environments in the solid state. In this review, we first discuss the chemomechanical breakdown of LCMs by introducing their categories and negative effects on the battery performance. We then systematically analyze factors that govern the initiation and propagation of chemomechanical breakdown and summarize their formation mechanisms. Strategies that can enhance the chemomechanical properties of LCMs or reduce the destructive effects of chemomechanical breakdown are then discussed. Lastly, light is shed on the new state-of-the-art techniques that have been applied to study chemomechanical breakdown. This review virtually includes most aspects of the chemomechanical behaviors of LCMs and provides some insights into the important chemical motifs that determine the chemomechanical properties. Thus, we believe that advanced design protocols of LCMs can be developed to effectively address the chemomechanical breakdown issue of LCMs.

25 ENERGY STORAGE↗

Nonstoichiometry, structure, and properties of Ba 1-x TiO y thin films

The effects of growth conditions on the chemistry, structure, electrical leakage, dielectric response, and ferroelectric behavior of Ba 1-x TiO y thin films are explored. Although single-phase, coherently-strained films are produced in all cases, small variations in the laser fluence during pulsed-laser deposition growth result in films with chemistries ranging from BaTiO 3 to Ba 0.93 TiO 2.87 . As the laser fluence increases, the films become more barium deficient and the out-of-plane lattice parameter expands (as much as 5.4% beyond the expected value for Ba 0.93 TiO 2.87 films). Stoichiometric BaTiO 3 films are found to be three orders of magnitude more conducting than Ba 0.93 TiO 2.87 films and the barium-deficient films exhibit smaller low-field permittivity, lower loss tangents, and higher dielectric maximum temperatures. Although large polarization is observed in all cases, large built-in potentials (shifted loops) and hysteresis-loop pinching are present in barium-deficient films – suggesting the presence of defect dipoles. The effects of these defect dipoles on ferroelectric hysteresis are studied using first-order reversal curves. Temperature-dependent current–voltage and deep-level transient spectroscopy studies show at least two defect states, which grow in concentration with increasing deficiency of both barium and oxygen, at ~0.4 eV and ~1.2 eV above the valence band edge, which are attributed to V$^{"}_{Ba}$ defect–V$_{Ö}$dipole complexes and V$^{"}_{Ba}$ defect states, respectively. The defect states can additionally be removed via ex post facto processing. Such work to understand and control defects in this important material could provide a pathway to enable better control over its properties and highlight new avenues to manipulate functions in these complex materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unzipping and folding of graphene by swift heavy ions

We show that graphene on a dielectric substrate sustains major modifications if irradiated with swift heavy ions under oblique angles. Due to a combination of defect creation in the graphene layer and hillock creation in the substrate, graphene is split and folded along the ion track yielding double layer nanoribbons. The folded parts are up to several 100 nm in length. Our results indicate that the radiation hardness of graphene devices is questionable but also open up a new way of introducing extended low-dimensional defects in a controlled way.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Inspection of Nickel Alloy Welds: Results from Five Year International Program

The U.S. Nuclear Regulatory Commission established and coordinated the international Program for the Inspection of Nickel alloy Components (PINC). The goal of PINC was to evaluate the capabilities of various nondestructive examination (NDE) techniques to detect and characterize primary water stress corrosion cracking (PWSCC) in dissimilar metal welds. Round-robin results showed that a combination of conventional and phased-array ultrasound provide the highest performance for flaw detection and depth sizing in dissimilar metal piping welds. The effective detection of flaws in bottom-mounted instrumentation penetrations by eddy current and ultrasound shows that it may be possible to reliably inspect these components in the field.

36 MATERIALS SCIENCE↗

Pulse-echo phased array ultrasonic inspection of pultruded rod stitched efficient unitized structure (PRSEUS)

A PRSEUS test article was subjected to controlled impact on the skin face followed by static and cyclic axial compressions. Phased array ultrasonic inspection was conducted before impact, and after each of the test conditions. A linear phased array probe with a manual X-Y scanner was used for interrogation. Ultrasound showed a delamination between the skin and stringer flange adjacent to the impact. As designed, the stitching in the flange arrested the lateral flaw formation. Subsequent ultrasonic data showed no delamination growth due to continued loading.

42 ENGINEERING↗

Defect modes in one-dimensional magnetized plasma photonic crystals with a dielectric defect layer

By using transfer matrix method, properties of one-dimensional magnetized plasma photonic crystals with a dielectric defect layer are studied. Results show that several defect modes appear within the photonic band gaps; periodic number and collision frequency only affect transmission magnitude of the defect modes; the external magnetic field and incident angle control both the transmission magnitude and frequency of the defect modes; thickness and dielectric constant of the defect layer determine both the number and frequency of the defect modes. This phenomenon may be useful in designing of narrow band filters or multi-channel filters.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗