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Two-dimensional (2D) transition metal dichalcogenides have emerged as promising quantum functional blocks benefitting from their unique combination of spin, valley, and layer degrees of freedom, particularly for the tremendous flexibility of moiré superlattices formed by van der Waals stacking. These degrees of freedom coupled with the enhanced Coulomb interaction in 2D structures allow excitons to serve as on-chip information carriers. However, excitons are spatially circumscribed due to their low mobility and limited lifetime. One way to overcome these limitations is through the coupling of excitons with surface plasmon polaritons (SPPs), which facilitates an interaction between remote quantum states. Here, we showcase the successful coupling of SPPs with interlayer excitons in molybdenum diselenide/tungsten diselenide heterobilayers. Our results indicate that the valley polarization can be efficiently transferred to SPPs, enabling preservation of polarization information even after propagating tens of micrometers. [ABSTRACT FROM AUTHOR]

Transition metal catalysts supported on topological insulators are predicted to show improved catalytic properties due to the presence of topological surface states, which may float up to the catalysts and provide robust electron transfer. However, experimental studies of surface structures and corresponding catalytic properties of transition metal/topological insulator heterostructures have not been demonstrated so far. Here, we report the structures, chemical states, and adsorption behaviors of two conventional transition metal catalysts, Pt and Pd, on the surface of Bi2Se3, a common topological insulator material. We reveal that Pt forms nanoparticles on the Bi2Se3 surface. Moreover, the interaction between Pt and surface Se is observed. Furthermore, thermal dosing of O2 onto the Pt/Bi2Se3 heterostructure leads to no oxygen adsorption. Detailed scanning tunneling microscopy study indicates that Pt transforms into PtSe2 after the thermal process, thus preventing O2 from adsorption. For another transition metal Pd, it exhibits approximate layer-island growth on Bi2Se3, and Pd–Se interaction is also observed. Our work provides significant insights into the behaviors of transition metals on top of a common topological insulator material and will assist in the future design of catalysts built with topological materials. [ABSTRACT FROM AUTHOR]

PtS2, a member of the group 10 transition metal dichalcogenides (TMDs), has received extensive attention because of its excellent electrical properties and air stability. However, there are few reports on the preparation of single-crystal PtS2 in the literature, and the growth mechanism of single crystal PtS2 is not well elucidated. In this work, we proposed a method of preparation that combines magnetron sputtering and chemical vapor transport to obtain monocrystalline PtS2 on a SiO2/Si substrate. By controlling the growth temperature and time, we have synthesized a single crystalline PtS2 of hexagonal shape and size of 1–2 μm on a silicon substrate. Combining the molecular dynamics simulation, the growth mechanism of single crystal PtS2 was investigated both experimentally and theoretically. The synthesis method has a short production cycle and low cost, which opens the door for the fabrication of other TMDs single crystals. [ABSTRACT FROM AUTHOR]

The prospect of creating ferroelectric or high permittivity nanomaterials provides motivation for investigating complex transition metal oxides of the form Ba(Ti, MV)O3, where M = Nb or Ta. Solid state processing typically produces mixtures of crystalline phases, rarely beyond minimally doped Nb/Ta. Using a modified sol-gel method, we prepared single phase nanocrystals of Ba(Ti, M)O3. Compositional and elemental analysis puts the empirical formulas close to BaTi0.5Nb0.5O3−δ and BaTi0.5Ta0.5O3−δ. For both materials, a reversible temperature dependent phase transition (non-centrosymmetric to symmetric) is observed in the Raman spectrum in the region 533–583 K (260–310 °C); for Ba(Ti, Nb)O3, the onset is at 543 K (270 °C); and for Ba(Ti, Ta)O3, the onset is at 533 K (260 °C), which are comparable with 390–393 K (117–120 °C) for bulk BaTiO3. The crystal structure was resolved by examination of the powder x-ray diffraction and atomic pair distribution function (PDF) analysis of synchrotron total scattering data. It was postulated whether the structure adopted at the nanoscale was single or double perovskite. Double perovskites (A2B′B″O6) are characterized by the type and extent of cation ordering, which gives rise to higher symmetry crystal structures. PDF analysis was used to examine all likely candidate structures and to look for evidence of higher symmetry. The feasible phase space that evolves includes the ordered double perovskite structure Ba2(Ti, MV)O6 (M = Nb, Ta) Fm-3m, a disordered cubic structure, as a suitable high temperature analog, Ba(Ti, MV)O3Pm-3m, and an orthorhombic Ba(Ti, MV)O3Amm2, a room temperature structure that presents an unusually high level of lattice displacement, possibly due to octahedral tilting, and indication of a highly polarized crystal. [ABSTRACT FROM AUTHOR]

VO2 is renowned for its electric transition from an insulating monoclinic (M1) phase, characterized by V–V dimerized structures, to a metallic rutile (R) phase above 340 K. This transition is accompanied by a magnetic change: the M1 phase exhibits a non-magnetic spin-singlet state, while the R phase exhibits a state with local magnetic moments. Simultaneous simulation of the structural, electric, and magnetic properties of this compound is of fundamental importance, but the M1 phase alone has posed a significant challenge to the density functional theory (DFT). In this study, we show none of the commonly used DFT functionals, including those combined with on-site Hubbard U to treat 3d electrons better, can accurately predict the V–V dimer length. The spin-restricted method tends to overestimate the strength of the V–V bonds, resulting in a small V–V bond length. Conversely, the spin-symmetry-breaking method exhibits the opposite trends. Each of these two bond-calculation methods underscores one of the two contentious mechanisms, i.e., Peierls lattice distortion or Mott localization due to electron–electron repulsion, involved in the metal–insulator transition in VO2. To elucidate the challenges encountered in DFT, we also employ an effective Hamiltonian that integrates one-dimensional magnetic sites, thereby revealing the inherent difficulties linked with the DFT computations. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) transition metal dichalcogenides (TMDs) hold immense promise as ultrathin-body semiconductors for cutting-edge electronics and optoelectronics. In particular, their sustained charge mobility even at atomic-level thickness as well as their absence of surface dangling bonds, versatile band structures, and silicon-compatibility integration make them a prime candidate for device applications in both academic and industrial domains. Despite such high expectations, group-VI TMDs reportedly exhibit a range of enigmatic properties, such as substantial contact resistance, Fermi level pinning, and limited unipolar charge transport, which are all rooted in their inherent defects. In other words, intrinsic physical properties resulting from their native defects extend their influence beyond the material level. Bridging point-defect-induced material properties and their behavior at the device level, this Perspective sheds light on the significance of crystalline defects beyond a rather simple defect–property relationship. As a distinctive approach, we briefly review the well-established defect model of conventional III–V semiconductors and further apply it to the emergent defect behaviors of 2D TMDs such as their defect-induced gap states. Within the main discussion, we survey a range of behaviors caused by the most prevalent intrinsic defect, namely, vacancies, within 2D TMDs, and their implications for electronic and optoelectronic properties when employed at the device level. This review presents an in-depth summary of complexities in material properties as well as device characteristics arising from intrinsic point defects and provides a solid foundation for the cross-links among native defects and material/device properties. [ABSTRACT FROM AUTHOR]

Molybdenum disulfide (MoS2), a semiconducting two-dimensional layered transition metal dichalcogenide (2D TMDC), with attractive properties enables the opening of a new electronics era beyond Si. However, the notoriously high contact resistance (RC) regardless of the electrode metal has been a major challenge in the practical applications of MoS2-based electronics. Moreover, it is difficult to lower RC because the conventional doping technique is unsuitable for MoS2 due to its ultrathin nature. Therefore, the metal–insulator–semiconductor (MIS) architecture has been proposed as a method to fabricate a reliable and stable contact with low RC. Herein, we introduce a strategy to fabricate MIS contact based on atomic layer deposition (ALD) to dramatically reduce the RC of single-layer MoS2 field effect transistors (FETs). We utilize ALD Al2O3 as an interlayer for the MIS contact of bottom-gated MoS2 FETs. Based on the Langmuir isotherm, the uniformity of ALD Al2O3 films on MoS2 can be increased by modulating the precursor injection pressures even at low temperatures of 150 °C. We discovered, for the first time, that film uniformity critically affects RC without altering the film thickness. Additionally, we can add functionality to the uniform interlayer by adopting isopropyl alcohol (IPA) as an oxidant. Tunneling resistance across the MIS contact is lowered by n-type doping of MoS2 induced by IPA as the oxidant in the ALD process. Through a highly uniform interlayer combined with strong doping, the contact resistance is improved by more than two orders of magnitude compared to that of other MoS2 FETs fabricated in this study. [ABSTRACT FROM AUTHOR]

The capacity to externally manipulate magnetic properties is highly desired from both fundamental and technological perspectives, particularly in the development of magnetoelectronics and spintronics devices. Here, using first-principles calculations, we have demonstrated the ability of controlling the magnetism of magnetized graphene monolayers by interfacing them with a two-dimensional ferroelectric material. When the 3d transition metal (TM) is adsorbed on the graphene monolayer, its magnetization easy axis can be flipped from in-plane to out-of-plane by the ferroelectric polarization reversal of In2Se3, and the magnetocrystalline anisotropy energy (MAE) can be high to −0.692 meV/atom when adopting the Fe atom at bridge site with downward polarization. This may be a universal method since the 3d TM-adsorbed graphene has a very small MAE, which can be easily manipulated by the ferroelectric polarization. As a result, the inherent mechanism is analyzed by the second variation method. [ABSTRACT FROM AUTHOR]

The ionization energies (IEs) of RuC, RhC, OsC, IrC, and PtC are assigned by the measurement of their two-photon ionization thresholds. Although late transition metal–carbon bonds are of major importance in organometallic chemistry and catalysis, accurate and precise fundamental thermochemical data on these chemical bonds are mainly lacking in the literature. Based on their two-photon ionization thresholds, in this work, we assign IE(RuC) = 7.439(40) eV, IE(RhC) = 7.458(32) eV, IE(OsC) = 8.647(25) eV, IE(IrC) = 8.933(74) eV, and IE(PtC) = 9.397(32) eV. These experimentally derived IEs are further confirmed through quantum chemical calculations using coupled-cluster single double perturbative triple methods that are extrapolated to the complete basis set limit using a three-parameter mixed Gaussian/exponential extrapolation scheme and corrected for spin–orbit effects using a semiempirical method. The electronic structure and chemical bonding of these MC species are discussed in the context of these ionization energy measurements. The IEs of RuC, RhC, OsC, and IrC closely mirror the IEs of the corresponding transition metal atoms, suggesting that for these species, the (n + 1)s electrons of the transition metals are not significantly involved in chemical bonding. [ABSTRACT FROM AUTHOR]

Negative differential resistance (NDR) is observed in various emerging electronic devices. As compared to the conventional silicon-based field effect transistor (FET), the NDR is widely investigated in two-dimensional (2D) transition metal dichalcogenide (TMD) FETs. In this work, we study the NDR effect for the TMD-based metal-edge-contact MoS 2 double-gate FET with 10 nm channel length. The multiscale atomistic simulation is demonstrated for the lateral heterostructure of a metal–semiconductor–metal FET by density functional theory, maximally localized Wannier function tight-binding Hamiltonian, and non-equilibrium Green's function methods. The quantum transport model in the given lateral heterostructure resulted in NDR in a double-gate FET. Here, we focus on the NDR by the systematic study of the transmission spectrum of the metal-edge-contact MoS 2 channel FET and finally compare it with zero NDR ideal highly doped FET. The peak-to-valley ratio in the NDR response can be modulated with the change in the gate-to-source voltage and can be used to explore various future electronic applications. [ABSTRACT FROM AUTHOR]

To control the growth of layered two-dimensional structures, such as transition metal dichalcogenide materials or heterostructures, understanding the growth mechanism is crucial. Here, we report the synthesis of ultra-thin MoO2 nanoplatelets through the sublimation of MoO3. Rhombus MoO2 nanoplatelets with the P21/c space group were characterized using various microscopic and spectroscopic techniques. Introducing sulfur sources into the chemical vapor deposition system also leads to the formation of monoclinic MoO2 nanoflakes due to the incomplete sulfurization of MoO3. With a gradual increase in the vapor concentration of sulfur, MoO3 undergoes stepwise reduction into MoS2/MoO2 and eventually into MoS2. Additionally, utilizing MoO2 as a precursor for Mo sources enables the formation of monolayer MoS2 single crystals. This work provides an effective approach for growing MoO2 nanoplatelets and elucidates the mechanism behind the stepwise sulfurization of MoO3. [ABSTRACT FROM AUTHOR]

The acidic (pKa ≈ 1.5 – 2.5) and hygroscopic nature of poly(3,4-ethylene dioxythiophene) polystyrene sulfonate, used as a common hole-injection layer in optoelectronic devices, has a detrimental effect on device stability and is associated with well established device failure mechanisms. In this work, a process with a high green index hole-injection layer material (V 2 O 5) and low surface roughness (RMS roughness ≈ 1.3 nm) was developed for demonstrating a hybrid polymer–inorganic perovskite light-emitting diode. Test devices with the new hole-injection layer demonstrate nearly identical maximum current efficiencies (4.23 vs 4.19 cd/A), and luminous efficacies (2.99 vs 2.32 lm/W) when compared to a control device fabricated with the conventional hole-injection layer. Furthermore, the peak brightness was achieved at a current density one-third of the value for the control device. To examine the transport of holes in the above hole-injection layer, we carried out device simulations based on a physical charge control model, including defect-assisted tunneling for hole injection. Close agreement for current–voltage characteristics is observed. Experimentally measured mobility in the device and measured radiative lifetimes were found to be sufficient to achieve this agreement without resorting to the introduction of a sheet charge at the injection interface. Despite the use of a bulk-heterojunction device architecture, the model predicts high radiative recombination rates [ ≈ 5.6 × 10 22 /(cm 3 s)] in the emissive layer, consistent with the measured photophysical properties for the active film, suggesting effective passivation of non-radiative surface states. [ABSTRACT FROM AUTHOR]

The recent development of accurate and efficient semilocal density functionals on the third rung of Jacob's ladder of density functional theory, such as the revised regularized strongly constrained and appropriately normed (r2SCAN) density functional, could enable rapid and highly reliable prediction of the elasticity and temperature dependence of thermophysical parameters of refractory elements and their intermetallic compounds using the quasi-harmonic approximation (QHA). Here, we present a comparative evaluation of equilibrium cell volumes, cohesive energy, mechanical moduli, and thermophysical properties (Debye temperature and thermal expansion coefficient) for 22 transition metals using semilocal density functionals, including the local density approximation (LDA), Perdew–Burke–Ernzerhof (PBE) and PBEsol generalized gradient approximations (GGAs), and the r2SCAN meta-GGA. PBEsol and r2SCAN deliver the same level of accuracies for structural, mechanical, and thermophysical properties. PBE and r2SCAN perform better than LDA and PBEsol for calculating cohesive energies of transition metals. Among the tested density functionals, r2SCAN provides an overall well-balanced performance for reliably computing cell volumes, cohesive energies, mechanical properties, and thermophysical properties of various 3d, 4d, and 5d transition metals using QHA. Therefore, we recommend that r2SCAN could be employed as a workhorse method to evaluate thermophysical properties of transition metal compounds and alloys in high throughput workflows. [ABSTRACT FROM AUTHOR]

Tuning of ferroic phases provides great opportunities for material functionalities, especially in two-dimensional materials. Here, a 4f rare-earth carbide Gd2C monolayer is predicted to be a ferromagnetic metal with large magnetization, inherited from its bulk property. Based on first-principles calculations, we propose a strategy that the surface passivation can effectively tune its ferroicity, namely, switching among ferromagnetic, antiferromagnetic, and ferroelectric phases. Metal–insulator transition also occurs accompanying these ferroic transitions. Our calculation also suggests that the magneto-optic Kerr effect and second harmonic generation are effective methods in monitoring these phase transitions. [ABSTRACT FROM AUTHOR]

We demonstrate modulation of insulator metal transition (IMT) of VO2 films grown on single crystalline substrates through the effect of in-plane compression with crystallization of capping chalcogenide layer on the targeted VO2 films. Chalcogenide germanium–antimony–telluride (Ge2Sb2Te5: GST), which shows large volume reduction of 6.8% with its phase change from amorphous to crystal, was deposited on VO2 films grown on Al2O3 (001) and TiO2 (001) substrates, where V–V atoms along the cR-axis in the tetragonal VO2 phase align parallel and perpendicular to the substrate surfaces, respectively. As a result, counter shifts in temperature-dependence of resistance characteristics, to lower and higher directions, were observed for VO2 films on Al2O3 (001) and TiO2 (001), consistent with the lattice modulation of VO2 films by the in-plane compression introduced by GST crystallization. The obtained results open a way to realize large resistance change of IMT under constant temperature by controlling GST phases. [ABSTRACT FROM AUTHOR]

A guided ion beam tandem mass spectrometer was employed to study the reactions of U+ + CO2, UO+ + O2, and the reverse of the former, UO+ + CO. Reaction cross sections as a function of kinetic energy over about a three order of magnitude range were studied for all systems. The reaction of U+ + CO2 proceeds to form UO+ + CO with an efficiency of 118% ± 24% as well as generating UO2+ + C and UCO+ + O. The reaction of UO+ + O2 forms UO2+ in an exothermic, barrierless process and also results in the collision-induced dissociation of UO+ to yield U+. In the UO+ + CO reaction, the formation of UO2+ in an endothermic process is the dominant reaction, but minor products of UCO+ + O and U+ + (O + CO) are also observed. Analysis of the kinetic energy dependences observed provides the bond energies, D0(U+–O) = 7.98 ± 0.22 and 8.05 ± 0.14 eV, D0(U+–CO) = 0.73 ± 0.13 eV, and D0(OU+–O) = 7.56 ± 0.12 eV. The values obtained for D0(U+–O) and D0(OU+–O) agree well with the previously reported literature values. To our knowledge, this is the first experimental measurement of D0(U+–CO). An analysis of the oxide bond energies shows that participation of 5f orbitals leads to a substantial increase in the thermodynamic stability of UO2+ relative to ThO2+ and especially transition metal dioxide cations. [ABSTRACT FROM AUTHOR]

In this paper, we investigated the properties of transition metal (TM)-doped α - G a 2 O 3 using first-principles calculations and Monte Carlo simulations. α - G a 2 O 3 is a wide-bandgap semiconductor material with enhanced performance and lower fabrication costs on sapphire substrates compared to β - G a 2 O 3 . Doping with TMs can modify electrical transport, optical absorption, and magnetic properties, yet theoretical studies on this are scarce. Our study focused on V, Cr, Mn, and Fe impurities. We introduced a newly proposed scheme for efficiently determining the ground-state defect configuration during structural relaxation. We adopt a recent, novel image charge correction method to accurately calculate formation enthalpy and thermodynamic transition levels for spin-polarized transition metal ion doping, without employing the empirical dielectric constant. Results showed Cr ions tend to neutral substitutional Ga, while V, Mn, and Fe impurity ions tend to carry a negative charge in common n-type α - G a 2 O 3 . Magnetic moments and spin-splitting impurity levels primarily arise from transition metal impurities and their d orbitals. We used the generalized four-state method to calculate exchange interaction constants between substitution lattice sites and identified (anti) ferromagnetic couplings at specific distances in a 120-atom supercell, which are negligible in total energy calculations. Monte Carlo simulations indicated a Curie temperature of 360 K in n-type α - G a 2 O 3 : Mn system with 12.5% doping, suggesting intrinsic ferromagnetic ordering based on the Heisenberg model. Our study contributes to understanding TM-doped α - G a 2 O 3 electronic structure and magnetic properties through improved methodologies. The approach can be applied in research involving other TM-doped oxides or wide-bandgap semiconductors. [ABSTRACT FROM AUTHOR]

Two-dimensional ferromagnetic materials hold great promise to develop energy-efficient magnetoelectric memory devices and next-generation spintronics. However, one of the crucial challenges for these materials is the realization of tunable magnetocrystalline anisotropy (MCA) to balance thermal stability and energy efficiency. Here, we systematically study the adsorption effects of 3d transition metals (3d-TMs) on the electronic structure and magnetic property of the Fe3GeTe2 (FGT) monolayer. The adsorption systems exhibit different ground state configurations depending on the adatoms, while the controlled perpendicular magnetic anisotropy has also been achieved. Notably, the Mn/FGT system can maintain the out-of-plane magnetic orientation with a changing amplitude of MCA energy up to 3.057 erg/cm2 as the external strain varies from −4% to 1%. In contrast, the Fe/FGT structure undergoes spin reorientation from in-plane to out-of-plan magnetization with a distinct modification behavior of MCA. We elucidate that the underlying atomistic mechanism mainly arises from the alteration of Fe-derived 3d-orbital states in response to the strain effect, leading to competitive changes in the different coupling states. These findings can not only provide useful guidance to optimize two-dimensional magnets for fundamental research but also reveal the promising potential of TMs/FGT materials for the development of ultra-low energy spintronic devices. [ABSTRACT FROM AUTHOR]

Real-time (RT) electronic structure methods provide a natural framework for describing light–matter interactions in arbitrary time-dependent electromagnetic fields (EMF). Optically induced excited state transitions are of particular interest, which require tuned EMF to drive population transfer to and from the specific state(s) of interest. Intersystem crossing, or spin-flip, may be driven through shaped EMF or laser pulses. These transitions can result in long-lived "spin-trapped" excited states, which are especially useful for materials requiring charge separation or protracted excited state lifetimes. Time-dependent configuration interaction (TDCI) is unique among RT methods in that it may be implemented in a basis of eigenstates, allowing for rapid propagation of the time-dependent Schrödinger equation. The recent spin–orbit TDCI (TD-SOCI) enables a real-time description of spin-flip dynamics in an arbitrary EMF and, therefore, provides an ideal framework for rational pulse design. The present study explores the mechanism of multiple spin-flip pathways for a model transition metal complex, FeCO, using shaped pulses designed to drive controlled intersystem crossing and charge transfer. These results show that extremely tunable excited state dynamics can be achieved by considering the dipole transition matrix elements between the states of interest. [ABSTRACT FROM AUTHOR]

Motivated by the recent experimental study on hydrogen storage in MXene multilayers [Liu et al., Nat. Nanotechnol. 16, 331 (2021)], for the first time we propose a workflow to computationally screen 23 857 compounds of MXene to explore the general relation between the activated H2 bond length and adsorption distance. By using density functional theory we generate a dataset to investigate the adsorption geometries of hydrogen on MXenes, based on which we train physics-informed atomistic line graph neural networks (ALIGNNs) to predict adsorption parameters. To fit the results, we further derived a formula that quantitatively reproduces the dependence of H2 bond length on the adsorption distance from MXenes within the framework of Pauling's resonating valence bond theory, revealing the impact of transition metal's ligancy and valence on activating dihydrogen in H2 storage. [ABSTRACT FROM AUTHOR]

Intercalation has attracted considerable attention due to its extensive ability to modify the electronic, optical, and magnetic properties of two-dimensional (2D) layered nanomaterials. Typically, dispersed atoms or molecules are inserted into the van der Waals gap of the 2D materials. Recently, Guo et al. experimentally reported the novel VS2–VS superlattice, where the intercalation takes the form of atomic chain arrays. In this study, we employed the first-principles calculations based on density functional theory to investigate a series of analogous 2D MX2–MX–MX2 nanomaterials, which, consisting of 2D transition metal dichalcogenide bilayers, intercalated with a one-dimensional transition metal chalcogenide MX chain array, forming a hotdog-like structure. Some of the 2D MX2–MX–MX2 are thermally and dynamically stable, suggesting their potential for experimental fabrication similar to VS2–VS–VS2. MnS2–MnS–MnS2 and MnSe2–MnSe–MnSe2 have been found to exhibit ferromagnetic half-metallic properties. In addition, VSe2–VSe–VSe2, CrS2–CrS–CrS2, and CrSe2–CrSe–CrSe2 have been found to be thermally and dynamically stable. Under appropriate external stress, doping, or bias, they could become ferromagnetic half-metals, revealing their potential for spintronic applications. [ABSTRACT FROM AUTHOR]

Despite its simplicity and relatively low computational cost, second-order Møller-Plesset perturbation theory (MP2) is well-known to overbind noncovalent interactions between polarizable monomers and some organometallic bonds. In such situations, the pairwise-additive correlation energy expression in MP2 is inadequate. Although energy-gap dependent amplitude regularization can substantially improve the accuracy of conventional MP2 in these regimes, the same regularization parameter worsens the accuracy for small molecule thermochemistry and density-dependent properties. Recently, we proposed a repartitioning of Brillouin-Wigner perturbation theory that is size-consistent to second order (BW-s2), and a free parameter (α) was set to recover the exact dissociation limit of H2 in a minimal basis set. Alternatively α can be viewed as a regularization parameter, where each value of α represents a valid variant of BW-s2, which we denote as BW-s2(α). In this work, we semi-empirically optimize α for noncovalent interactions, thermochemistry, alkane conformational energies, electronic response properties, and transition metal datasets, leading to improvements in accuracy relative to the ab initio parameterization of BW-s2 and MP2. We demonstrate that the optimal α parameter (α = 4) is more transferable across chemical problems than energy-gap-dependent regularization parameters. This is attributable to the fact that the BW-s2(α) regularization strength depends on all of the information encoded in the t amplitudes rather than just orbital energy differences. While the computational scaling of BW-s2(α) is iterative O ( N 5 ) , this effective and transferable approach to amplitude regularization is a promising route to incorporate higher-order correlation effects at second-order cost. [ABSTRACT FROM AUTHOR]

Nanosheets of transition metal dichalcogenides with prospects of photocatalysis and optoelectronics applications have significant potential in device fabrication due to their low-cost production and easily controllable morphology. Here, non-degenerate pump-probe differential transmission studies with varying pump-fluence have been carried out on single-phase 2H–MoSe2 and mixed-phase 1T/2H–MoSe2 nanosheets to characterize their excited carrier dynamics. For both the samples, the differential probe transmission data show photo-induced bleaching at earlier pump-probe delay followed by photo-induced absorption unveiling signatures of exciton-state filling, exciton trapping, defect-mediated photo-induced probe absorption and recombination of defect bound excitons. The exciton trapping and photo-induced absorption by the trapped-carriers are estimated to occur with time constant of ∼430 to 500 fs based on multi-exponential modelling of the differential transmission till pump-probe delay of ∼3.5 ps. Biexponential modeling of the subsequent slow-recovery of the negative differential transmission at pump-probe delay ≳3.5 ps reveals that the exciton recombination happens via two distinct decay channels with ∼25 to 55 ps (τ1) and ≳1 ns (τ2) time constants. Pump-fluence dependent reduction in τ1 and further modelling of exciton population using higher order kinetic rate equation reveals that the two-body exciton-exciton annihilation governs the exciton recombination initially with a decay rate of ∼ 10 − 8 cm3s−1. The detailed analysis suggests that the fraction of total excitons that decay via long decay channel decreases with increasing exciton density for 2H–MoSe2, in contrast to 1T/2H–MoSe2 where the fraction of excitons decaying via long decay channel remains constant. [ABSTRACT FROM AUTHOR]

Constructing metal-semiconductor interfaces by loading metal atoms onto two-dimensional material to build atomically dispersed single-atom catalysts (SACs) has emerged as a new frontier for improving atom utilization and designing multifunctional electrocatalysts. Nowadays, studies on black phosphorus nanosheets in electrocatalysis have received much attention and the successful preparation of metal nanoparticle/black phosphorus (BP) hybrid electrocatalysts indicates BP nanosheets can serve as a potential support platform for SACs. Herein, by using large-scale ab initio calculations, we explored a large composition space of SACs with transition metal atoms supported on BP monolayer (M-BP) and built a comprehensive picture of activity trend, stability, and electronic origin towards oxygen reduction and evolution reaction (ORR and OER) and hydrogen evolution reaction (HER). The results show that the catalytic activity can be widely tuned by reasonable regulation of metal atoms. Ni-, Pd-, and Pt-BP could effectively balance the binding strength of the target intermediates, thus achieving efficient bifunctional activity for OER and ORR. Favorable bifunctional catalytic performance for OER and HER can be realized on Rh-BP. Especially, Pt-BP exhibits promising trifunctional activity towards OER, ORR, and HER. Multiple-level corrections among overpotential, Gibbs free energy, orbital population, and d-band center reveal that the trend and origin of catalytic activity are intrinsically determined by the d-band center of metal sites. The thermodynamic and dynamic stability simulations demonstrate that the active metal centers are firmly anchored on BP substrate with intact M-P bonds. These findings provide a theoretical basis for the rational design of BP-based SACs toward promising multifunctional activity. [ABSTRACT FROM AUTHOR]

Pseudopotential locality errors have hampered the applications of the diffusion Monte Carlo (DMC) method in materials containing transition metals, in particular oxides. We have developed locality error free effective core potentials, pseudo-Hamiltonians, for transition metals ranging from Cr to Zn. We have modified a procedure published by some of us in Bennett et al. [J. Chem. Theory Comput. 18, 828 (2022)]. We carefully optimized our pseudo-Hamiltonians and achieved transferability errors comparable to the best semilocal pseudopotentials used with DMC but without incurring in locality errors. Our pseudo-Hamiltonian set (named OPH23) bears the potential to significantly improve the accuracy of many-body-first-principles calculations in fundamental science research of complex materials involving transition metals. [ABSTRACT FROM AUTHOR]

Despite widespread interest in the phase-change applications of vanadium dioxide (VO2), the fabrication of high-quality VO2 thin films with elevated transition temperatures (TIMT) and high insulator–metal-transition resistance switching still remains a challenge. This study introduces a two-step atmospheric oxidation approach to fabricate bilayer VO2−x/VO2 films on a c-plane sapphire substrate. To quantify the impact of the VO2 buffer layer, a single-layer VO2 film of the same thickness was also fabricated. The bilayer VO2−x/VO2 films, wherein the top VO2−x film was under-oxidized, demonstrated an elevation in TIMT reaching ∼97 °C, one of the highest reported to date for VO2 films and is achieved in a doping-free manner. Our results also reveal a one-order increase in resistance switching, with the optimum bilayer VO2/VO2 film exhibiting ∼3.6 orders of switching from 25 to 110 °C, compared to the optimum single-layer VO2 reference film. This is accompanied by a one-order decrease in the on-state resistance in its metallic phase. The elevation in TIMT, coupled with increased strain extracted from the XRD characterization of the bilayer film, suggests the possibility of compressive strain along the c-axis. These VO2−x/VO2 films also demonstrate a significant change in the slope of their resistance vs temperature curves contrary to the conventional smooth transition. This feature was ascribed to the rutile/monoclinic quasi-heterostructure formed due to the top VO2−x film having a reduced TIMT. Our findings carry significant implications for both the lucid fabrication of VO2 thin film devices as well as the study of phase transitions in correlated oxides. [ABSTRACT FROM AUTHOR]

A real-space method using generating integers is used to determine possible commensurate lattice Moiré patterns for a bilayer of two equal hexagonal lattices, which can in principle be extended to lattice mismatched bilayers. These Moiré patterns can be classified by a pair of relatively prime integers (n , m) , wherein a rotation θ (n , m) of the top hexagonal lattice maps its lattice vector (n , m) to (m , n) of the bottom lattice. Within this formulation, the area of the commensurate supercell is proportional to (n 2 + m 2 + n m) and the number of coincident lattice sites per supercell is given by (n − m) 2. Taking bilayer boron nitride (BN) as an example, we present how to systematically generate Moiré patterns and explore the differences in local chemistry in the interstitial region by impurity intercalation. Systematic calculations of the properties of intercalated 3d transition metals were performed in an h-BN (4 , 3) bilayer, corresponding to a rotation of 9.43 degrees. These calculations reveal that local symmetry in the intercalated region significantly affect the energetics and magnetization of the intercalated species. These results highlight that Moiré pattern physics is not limited to optoelectronic/electronic phenomena, such as interfacial exciton formation or magic angle superconductivity, but it also produces chemical and magnetic atomic site selectivity, which may play important roles in adsorption, catalysis, or quantum information. [ABSTRACT FROM AUTHOR]

The activity of Li-intercalated MoS2 phases for the hydrogen evolution reaction is investigated using density functional theory. The most stable semiconducting 2H phase, the metallic 1T′ phase, and a polymorphous surface composed of alternating H and T′ phases (1T″) are investigated. The local structure of the MoS2 surface is found to define its reactivity. In all cases, active sites for the hydrogen evolution process are restricted to T-like sulphur sites. Li-intercalation is found to promote hydrogen evolution reaction reactivity for the H phase whilst having little effect on the T phase. While improved compared to the non-intercalated phase, the Li-intercalated H phase MoS2 still has minimal activity for the hydrogen evolution reaction. The same effect of intercalation is also found for another transition metal dichalcogenide, MoSe2. The ability to improve reactivity in this way makes ion intercalation a promising space for designing new 2D catalysts for the hydrogen evolution reaction. [ABSTRACT FROM AUTHOR]

Optoelectronic functional materials with flexible and in-plane anisotropic properties has been a significant development direction of nanotechnology due to wearable and polarized optoelectronic applications. Herein, the elasticity, global band dispersion, optical dielectric properties of environmentally friendly IVB-VIA layered transition metal trichalcogenides (MX3, M = Zr, Hf; X = S, Se) are investigated systematically by density functional theory with different kinds of van der Waals correction and hybrid functional. The low elastic modulus suggests that they are appropriate for the design of flexible optoelectronic devices. Originating from the effect of d states of chalcogens and s states of transition metals, the dispersion of the valence band edge of monolayer MX3 shows that the effective mass of carriers along the wave vector kx is much heavier than that of carriers along the wave vector ky. This means that the mobility of carriers exhibits obvious in-plane anisotropy. Meanwhile, the optical dielectric properties of monolayer MX3 as well as absorbed photon flux (Jabs) of the related heterostructures display noteworthy in-plane anisotropy in the visible-IR region. The ratio of Jabs from different direction reaches up to 1.7. This work could not only promote understanding of rich photophyiscal properties of transition metal trichalcogenides, but also provide a theoretical reference for the invention of high-performance optoelectronic devices with high flexibility and anisotropy. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) transition metal dihalides (TMDHs) have attracted great interest owing to their unique magnetic and semiconductor properties. Compared with the mirror/inversion symmetric materials, 2D Janus materials possess vertical intrinsic dipole moment, which offer a versatile platform for the fundamental physics and future spintronic devices. Here, we systematically explore the magnetic and electronic properties of the 2D Janus transition metal dihalides MXY (M = Co and Ni; X ≠ Y = Cl, Br, and I) monolayers and bilayers by using density functional theory. The monolayer CoClBr, NiClBr, and NiBrI are bipolar ferromagnetic semiconductors that possess the valence and conduction band edges of different spin channels. The magnetism of the bilayer CoClBr, NiClBr, and NiBrI is highly dependent on the accumulated dipole moments of the two adjacent layers. When the dipole moments in both layers are aligned in the same direction and the accumulated dipole moments are nonzero, the systems are antiferromagnetic half semiconductors. However, when the dipole moments in the two layers are opposite and the accumulated dipole moments are zero, the systems are A-type antiferromagnetic semiconductors. Our findings are helpful to understand the magnetism of Janus TMDHs and guide experiments in exploring their potential application in spintronic devices. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) ultra-thin materials are more crucial than their bulk counterparts for the covalent functionalization of their surface owing to atomic thinness, large surface-to-volume ratio, and high reactivity of surface atoms having unoccupied orbitals. Since the surface of a 2D material is composed of atoms having unoccupied orbitals, covalent functionalization enables one to improve or precisely modify the properties of the ultra-thin materials. Chemical functionalization of 2D materials not only modifies their intrinsic properties but also makes them adapted for nanotechnology applications. Such engineered materials have been used in many different applications with their improved properties. In the present Perspective, we begin with a brief history of functionalization followed by the introduction of functionalized 2D materials. Our Perspective is composed of the following sections: the applications areas of 2D graphene and graphene oxide crystals, transition metal dichalcogenides, and in-plane anisotropic black phosphorus, all of which have been widely used in different nanotechnology applications. Finally, our Perspectives on the future directions of applications of functionalized 2D materials are given. The present Perspective sheds light on the current progress in nanotechnological applications of engineered 2D materials through surface functionalization. [ABSTRACT FROM AUTHOR]

We have conducted the study of structural, magnetic, magnetothermal, and magnetoelastic properties of four rare-earth compounds: Gd4.5Tb0.5Si2Ge2, Gd4TbSi2Ge2, Gd4.4Tb0.5Ti0.1Si2Ge2, and Gd3.9TbTi0.1Si2Ge2 in the vicinity of magnetically induced phase transitions. We demonstrate that the introduction of Ti into the rare-earth sublattice separates the structural and magnetic phase transitions and changes the order of magnetic phase transition from type I to II, while preserving high values of magnetocaloric effect (MCE). Additionally, incorporating a small quantity of Tb enables the creation of compounds with enhanced MCE values over a specific temperature range of 240–290 K. The observed phenomena can be attributed to the combined effects of forced magnetization and alteration of magnetic susceptibility during the structural phase transition that accompany the magnetic phase changes in these compounds. [ABSTRACT FROM AUTHOR]

We present the chemical bonding and electronic properties of liquid methane at temperatures from 2000 to 4000 K and high densities of up to 3.0 g/cm3, calculated using ab initio molecular dynamics simulations in combination with the Mulliken population analysis. Bond-overlap populations and pair distribution functions are studied to investigate the evolution of electron delocalization accompanying atomic structure change as the density is increased. In addition, we also investigated the bandgap energy, electronic density of states, and spatial distribution of electron density. We observed that molecular hydrogen and C‒C bonds are formed after methane dissociates, and then the system undergoes a nonmetal–metal transition coinciding with hydrogen being transformed from the molecular to the atomic state. The C‒C bonds in the system retain covalent character, even at the highest density of 3.0 g/cm3. [ABSTRACT FROM AUTHOR]

The interaction between adjacent active sites is crucial to balance the efficiency and utilization of functional atoms in single-atom catalysts. Herein, the catalytic activity of hydrogen evolution reaction at different site (nitrogen coordinated transition metal centers embedded in graphene) distances was comprehensively investigated by density functional theory calculations. The results show that a proximity effect of reactivity and site spacing can be identified in the Co-series single-atom catalysts. Although the proximity effect is more linearly responded with the site spacing along x direction, an optimal distance of ∼0.8 and ∼2.8 nm are found for Co and Rh, Ir atoms, respectively. An in-depth analysis of the electronic property reveals that the proximity effect is caused by the distinct net charge of the active site, which is affected by the d z 2 position relative to EF. Subsequently, an excess electron nodal channel in x direction was found to serve as a communication pathway between the active sites. Through the finding in this work, an optimal Fe-N2C2 structure was deliberately designed and has shown prominent proximity effect as Co-series do. The results reported in this work provide a simple and effective tuning method for the reactivity of a single-atom catalyst. [ABSTRACT FROM AUTHOR]

We present a simplified tight-binding (TB) model to describe the low-energy physics of monolayer 1T' transition metal dichalcogenides (TMDCs). The TB model is constructed by combining symmetry analysis and first-principle calculations. Our TB model accurately reproduces the electronic structures near the Fermi energy and provides a better representation of energy band inversion. By considering spin–orbit coupling (SOC), our TB model successfully reproduces the opening of the bandgap, characterizes nontrivial topology, and predicts corresponding helical edge states. Additionally, using this TB model, we observe that quantized electronic conductance remains robust under significant disorder intensity. However, the robustness of the edge states can be suppressed by the Zeeman fields and SOC strength in the scattering zone. Furthermore, moderate concentrations of vacancy disorder destroy the topological protection and eliminate quantized conductance. Our TB model serves as a starting point for a comprehensive understanding of the properties of these materials and can guide future research on superconductivity, strain, and correlation effects. [ABSTRACT FROM AUTHOR]

Although the d-band center theory can well describe the interaction between gas molecules and transition metal surfaces, the detailed reaction process and specific adsorption conditions are unclear. Hence, in this work, we systematically studied the adsorption mechanism, adsorption conditions, and recovery time of NO and NO2 molecules on different transition metals (Cu, Ag, Au, Ni, Pd, Pt, Rh, Ru, Tc, Mo, Nb, and Zr) surfaces by first-principles. The results indicated that the charge transfers from the dz2, dxz, and dyz orbitals of substrate atoms to the HOMOs/LUMOs of NO and NO2. Moreover, we demonstrate that the interaction orbitals between the NO/NO2 and the metal atoms excellently correspond with the match of energy level and parity, and the maximum overlap of the orbital wave function. Interestingly, the excellent linear scaling between charge transfer and the d-band center, work function, and matrix element (V2ad) of metals has been confirmed. Specifically, the different recovery times of these systems at different temperatures were explored. Our results can provide a feasible way for exploring gas-sensitive materials in the experiments. [ABSTRACT FROM AUTHOR]

Recent experiments performed on chiral molecules, comprising transition metal or rare earth elements, indicate temperature reinforced chiral induced spin selectivity. In these compounds, spin selectivity is suppressed in the low temperature regime but grows by one to several orders of magnitude as the temperature is increased to room temperature. By relating temperature to nuclear motion, it is proposed that nuclear displacements acting on the local spin moments, through indirect exchange interactions, generate an anisotropic magnetic environment that is enhanced with temperature. The induced local anisotropy field serves as the origin of a strongly increased spin selectivity at elevated temperature. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) perovskites have gained much attention lately owing to their excellent optoelectronic properties, chemical tunability, and environmental stability. Multiple methods have been devised to synthesize high quality 2D perovskite single crystals, and recent progress in fabricating its heterostructures is notable as well. In particular, with growing interest in 2D van der Waals heterostructures, 2D perovskites have become a strong candidate as a new building block for heterostructures to reveal unique physical properties across different interfaces. Until now, various heterostructure devices of 2D perovskite single crystals with other types of 2D materials such as transition metal dichalcogenides (TMDs) and graphene have been studied, which have shown intriguing results including interlayer excitons and enhanced electronic properties. Here, we introduce various synthetic approaches to realize 2D perovskite single crystals and unique characteristics of their single crystal heterostructures fabricated with precision, possessing sharp interfaces. Moreover, recent studies of semiconductor devices based on 2D perovskite single crystal heterostructures are discussed in-depth. New perspectives to further the horizon in the field of 2D perovskite heterostructures are suggested in this work including the consideration of metal–2D material van der Waals contact, application of dry transfer techniques, electric bias driven ion diffusion studies, and nanocrystal array fabrication. 2D perovskite heterostructure single crystal devices factoring in these novel perspectives will further uncover the true potential of these materials for highly efficient and stable semiconductor devices. [ABSTRACT FROM AUTHOR]

The conventional theory of superconductivity holds that Cooper pairs form due to electron–phonon coupling; however, this description may not be adequate to describe certain unconventional superconductors such as cuprates and iron chalcogenides. In these unconventional superconductors, it has been proposed that spin fluctuations may be responsible for the formation of Cooper pairs. In this study, we explore spin interactions in the transition metal, dichalcogenide niobium disulfide, induced through proximity effects by fabricating antiferromagnet/NbS2 heterostructures. We tested three different 2D antiferromagnetic materials, each with different spin textures: anganese phosphorus trisulfide, manganese phosphorus triselenide, and chromium trichloride. Our results showed a substantial reduction in the critical temperature in the case of NbS2/MnPSe3. We hypothesize that this could be due to spin fluctuations in MnPSe3 inducing proximity effects in NbS2. [ABSTRACT FROM AUTHOR]

Vanadium dioxide (VO2) undergoes a metal–insulator phase transition at ∼70 °C and has attracted substantial interest for potential applications in electronics, including those in neuromorphic computing. The vanadium–oxygen system has a rather complicated phase diagram, and controlling the stoichiometry and the phase of thin films of vanadium oxides is a well-known challenge. We explore the novel combination of two methods of VO2 thin film deposition using off-axis RF magnetron sputtering on (100)- and (111)-oriented yttria-stabilized zirconia (YSZ) substrates: reactive sputtering of vanadium in an oxygen environment and sputtering of vanadium metal followed by oxidation to VO2. Interestingly, the reactive sputtering process on both substrate orientations yields the metastable semiconducting VO2 (B) phase, which is structurally stabilized by the YSZ surface. The metal sputtering and oxidation process on YSZ produces mainly the equilibrium monoclinic (or M1) phase of VO2 that exhibits a metal–insulator transition. Using this method, we obtained thin films of (010)-textured polycrystalline VO2 (M1) that show a metal–insulator transition with an on/off ratio larger than 1000. [ABSTRACT FROM AUTHOR]

We study the electronic coupling between an adsorbate and a metal surface by calculating tunneling matrix elements Had directly from first principles. For this, we employ a projection of the Kohn–Sham Hamiltonian upon a diabatic basis using a version of the popular projection-operator diabatization approach. An appropriate integration of couplings over the Brillouin zone allows the first calculation of a size-convergent Newns–Anderson chemisorption function, a coupling-weighted density of states measuring the line broadening of an adsorbate frontier state upon adsorption. This broadening corresponds to the experimentally observed lifetime of an electron in the state, which we confirm for core-excited A r * (2 p 3 / 2 − 1 4 s) atoms on a number of transition metal (TM) surfaces. Yet, beyond just lifetimes, the chemisorption function is highly interpretable and encodes rich information on orbital phase interactions on the surface. The model thus captures and elucidates key aspects of the electron transfer process. Finally, a decomposition into angular momentum components reveals the hitherto unresolved role of the hybridized d-character of the TM surface in the resonant electron transfer and elucidates the coupling of the adsorbate to the surface bands over the entire energy scale. [ABSTRACT FROM AUTHOR]

The chemical synthesis of (CdSe)13 magic-sized clusters (MSCs) allows the replacement of host atoms by individual transition metals such as Mn. By analyzing the spectral fingerprints of the Mn2+ photoluminescence (PL) in MSCs with different dopant concentrations, we are able to distinguish between single Mn2+ ions and coupled Mn2+ pairs. In case of Mn2+ pair emission, temperature-dependent studies show a pronounced red shift, followed by a distinct blue shift of the PL energy upon heating. This is related to a spin ladder formation of the ground and excited states due to Mn2+–Mn2+ exchange interaction at cryogenic temperatures, which is assumed to vanish at higher temperatures. In contrast, single Mn2+ ion PL exhibits a unique redshift with increasing temperature, which can be attributed to a particularly strong coupling to vibronic modes due to the ultimate small size of the MSCs. [ABSTRACT FROM AUTHOR]

Some chemical reactions proceed on multiple potential energy surfaces and are often accompanied by a change in spin multiplicity, being called spin-forbidden reactions, where the spin–orbit coupling (SOC) effects play a crucial role. In order to efficiently investigate spin-forbidden reactions with two spin states, Yang et al. [Phys. Chem. Chem. Phys. 20, 4129–4136 (2018)] proposed a two-state spin-mixing (TSSM) model, where the SOC effects between the two spin states are simulated by a geometry-independent constant. Inspired by the TSSM model, we suggest a multiple-state spin-mixing (MSSM) model in this paper for the general case with any number of spin states, and its analytic first and second derivatives have been developed for locating stationary points on the mixed-spin potential energy surface and estimating thermochemical energies. To demonstrate the performance of the MSSM model, some spin-forbidden reactions involving 5d transition elements are calculated using the density functional theory (DFT), and the results are compared with the two-component relativistic ones. It is found that MSSM DFT and two-component DFT calculations may provide very similar stationary-point information on the lowest mixed-spin/spinor energy surface, including structures, vibrational frequencies, and zero-point energies. For the reactions containing saturated 5d elements, the reaction energies by MSSM DFT and two-component DFT agree very well within 3 kcal/mol. As for the two reactions OsO+ + CH4 → OOs(CH2)+ + H2 and W + CH4 → WCH2 + H2 involving unsaturated 5d elements, MSSM DFT may also yield good reaction energies of similar accuracy but with some counterexamples. Nevertheless, the energies may be remarkably improved by a posteriori single point energy calculations using two-component DFT at the MSSM DFT optimized geometries, and the maximum error of about 1 kcal/mol is almost independent of the SOC constant used. The MSSM method as well as the developed computer program provides an effective utility for studying spin-forbidden reactions. [ABSTRACT FROM AUTHOR]

Transition metal oxide (TMO) anodes show inferior sodium ion storage performance compared with that of lithium ion storage owing to the larger radium size and heavier elemental mass of Na+ than Li+. Effective strategies are highly desired to improve the Na+ storage performance of TMOs for applications. In this work, using ZnFe2O4@xC nanocomposites as model materials for investigation, we found that by manipulating the particle sizes of the inner TMOs core and the features of outer carbon coating, the Na+ storage performance can be significantly improved. The ZnFe2O4@1C with a diameter of the inner ZnFe2O4 core of around 200 nm coated by a thin carbon layer of around 3 nm shows a specific capacity of only 120 mA h g−1. The ZnFe2O4@6.5C with a diameter of the inner ZnFe2O4 core of around 110 nm embedding in a porous interconnected carbon matrix displays a significantly improved specific capacity of 420 mA h g−1 at the same specific current. Furthermore, the latter shows an excellent cycling stability of 1000 cycles with a capacity retention of 90% of the initial 220 mA h g−1 specific capacity at 1.0 A g−1. TEM, electrochemical impedance spectroscopy, and kinetic analysis show that the inner ZnFe2O4 core with reduced particle size and the outer thicker and interconnected carbon matrix synergistically improve the active reaction sites, integrity, electric conductivity, and pseudocapacitive-controlled contribution of ZnFe2O4@xC nanocomposites, thus leading to an overall enhanced Na+ storage performance. Our findings create a universal, facile, and effective method to enhance the Na+ storage performance of the TMO@C nanomaterials. [ABSTRACT FROM AUTHOR]

Transmission electron microscope image and electronic transport of La0.7Sr0.3MnO3 (LSMO) films grown on (001) oriented Si using the sputtered pulsed plasma method confirmed the presence of around 8 nm thick, less dense, and highly resistive LSMO at the interface below the conducting phase. Thicker LSMO films, in addition to metal-insulator transition, show an anomaly around the Curie temperature in temperature-dependent resistivity and magnetoresistance (MR), which is a unique observation. The conduction in these LSMO films at temperatures below low-temperature resistivity minimum is dominated by Kondo-like scattering over electron–electron scattering, established using the phenomenological model. At 20 K, the maximum positive MR is ∼ 12% for the in-plane field, while it is ∼ 7.2% for the out-of-plane field. The maximum negative in-plane MR is found to be ∼ 42.5%, which becomes ∼ 30% when the orientation of the field changes to the out-of-plane direction. The two-dimensional field-dependent change in the magneto-conductance model evidenced the quantum interference effect (QIE). The existence of QIE is associated with magnetic scattering and scattering due to spin–orbit coupling. These results may be used to modulate the electrical properties of future electronic devices and can encourage scientists to explore the multi-functionalities of complex oxides grown on bare Si substrates. [ABSTRACT FROM AUTHOR]

The peculiar potential transition metal dichalcogenides in regard to sensor and device applications have been exhibited by both experimental and theoretical studies. The use of these materials, thermodynamically stable even at elevated temperatures, particularly in nano- and optoelectronic technology, is about to come true. On the other hand, the distinct electronic and thermal transport properties possessing unique coherency, which may result in higher thermoelectric efficiency, have also been reported. However, exploiting this potential in terms of power generation and cooling applications requires a deeper understanding of these materials in this regard. This perspective study, concentrated with this intention, summarizes thermoelectric research based on transition metal dichalcogenides from a broad perspective and also provides a general evaluation of future theoretical investigations inevitable to shed more light on the physics of electronic and thermal transport in these materials and to lead future experimental research. [ABSTRACT FROM AUTHOR]

Heterovalent ion doping has been playing a remarkably significant role in the microwave dielectric performances of columbite A2+Nb 2 O 6 (A2+ = Zn, Ca, or transition metal). Here, the Q × f value of MgNb 2 O 6 ceramics can be effectively enhanced from 32,893 GHz to 117,659 GHz by doping with 1 mol% (TiW)5+. Based on the high Q value of Mg(Nb 0.98 Ti 0.01 W 0.01) 2 O 6 , TiO 2 was selected to further adjust the τ f value of the matrix material prepared by the conventional solid-state reaction method. The results show that the Mg(Nb 0.98 Ti 0.01 W 0.01) 2 O 6 ceramics undergo three phase zones with increasing TiO 2 content: columbite (MgNb 2 O 6) solid solution, a mixture of columbite and rutile (Ti 0.5 Mg 0.167 Nb 0.333 O 2), and Ti 0.5 Mg 0.167 Nb 0.333 O 2 solid solution. This variation in phase formation has an essential effect on the microwave dielectric behavior of Mg(Nb 0.98 Ti 0.01 W 0.01) 2 O 6 @xTiO 2 (0.03 ≤ x ≤ 0.25) ceramics. It is important to note that at x = 0.17, the specimen has excellent microwave dielectric performances, with ε r = 34.79, Q × f = 24,103 GHz, and the τ f of the specimen may be adjust to zero. It is anticipated that these materials will be utilised in contemporary microwave and telecommunication equipment. [ABSTRACT FROM AUTHOR]

We investigated the effects of various transition metal dopants on the changes in B-site ion-oxygen (B–O) bonding characteristics and the subsequent effects on the electrochemical properties of PrCoO 3 (PCMe, PrCo 0.9 Me 0.1 O 3-δ , Me = Cu, Mn, Nb). The lattice constants of Mn, Cu, and Nb-doped PrCoO 3 were increased compared with that of pure PrCoO 3 (PCO), and the B–O–B bond angles were determined to be 163.709°, 167.323°, 165.149°, and 161.765° for PCO, PCCu, PCMn, and PCNb, respectively, by Rietveld refinement. The pre-edge peak of the O K-edge shifted to 0.7 eV of lower energy in PCCu as compared with PCO, and to 0.2 eV of lower energy in PCMn. By contrast, PCNb shifted to 0.3 eV of higher energy. Considering the B–O–B bond angle and pre-edge peak shift, the overlap between B 3d and O 2p orbitals can be expected to be the largest in PCCu, indicating the strongest covalency, whereas PCNb has the weakest covalency. The polarization resistance, as an indicator of the ORR activity, was 7.63, 6.67, 8.05, and 9.56 Ω cm2 in PCO, PCCu, PCMn and PCNb, respectively. [ABSTRACT FROM AUTHOR]