Extreme phonon anharmonicity underpins superionic diffusion and ultralow thermal conductivity in argyrodite Ag8SnSe6.

Ultralow thermal conductivity and fast ionic diffusion endow superionic materials with excellent performance both as thermoelectric converters and as solid-state electrolytes. Yet the correlation and interdependence between these two features remain unclear owing to a limited understanding of their complex atomic dynamics. Here we investigate ionic diffusion and lattice dynamics in argyrodite Ag8SnSe6 using synchrotron X-ray and neutron scattering techniques along with machine-learned molecular dynamics. We identify a critical interplay of the vibrational dynamics of mobile Ag and a host framework that controls the overdamping of low-energy Ag-dominated phonons into a quasi-elastic response, enabling superionicity. Concomitantly, the persistence of long-wavelength transverse acoustic phonons across the superionic transition challenges a proposed 'liquid-like thermal conduction' picture. Rather, a striking thermal broadening of low-energy phonons, starting even below 50 K, reveals extreme phonon anharmonicity and weak bonding as underlying features of the potential energy surface responsible for the ultralow thermal conductivity (<0.5 W m-1 K-1) and fast diffusion. Our results provide fundamental insights into the complex atomic dynamics in superionic materials for energy conversion and storage.

Sm, Nd doped BiFeO3epitaxial film for photodetector with extremely large on-off current ratio.

BiFeO3is one of the star materials in the field of ferroelectric photovoltaic for its relatively narrow bandgap (2.2-2.7 eV) and better visible light absorption. However, a high temperature over 600 °C is indispensable in the usual BiFeO3growth process, which may lead to impure phase, interdiffusion of components near the interface, oxygen vacancy and ferrous iron ions, which will result in large leakage current and greatly aggravate the ferroelectricity and photoelectric response. Here we prepared Sm, Nd doped epitaxial BiFeO3film via a rapid microwave assisted hydrothermal process at low temperature. The Bi0.9Sm0.5Nd0.5FeO3film exhibits narrow bandgap (1.35 eV) and photo response to red light, the on-off current ratio reaches over 105. The decrease in band gap and +2/+3 variable element doping are responsible for the excellent photo response. The excellent photo response performances are much better than any previously reported BiFeO3films, which has great potential for applications in photodetection, ferroelectric photovoltaic and optoelectronic devices.

Ultra-High-Density Ferroelectric Array Formed by Sliding Ferroelectric Moiré Superlattices.

2D van der Waals (vdW) materials offer infinite possibilities for constructing unique ferroelectrics through simple layer stacking and rotation. In this work, we stack nonferroelectric GeS2 and ferroelectric CuInP2S6 to form heterostructures by combining sliding ferroelectric polarization with displacement ferroelectric polarization to achieve multiple polarization states. First-principles calculations reveal that the polarization reversal of the CuInP2S6 component in the GeS2/CuInP2S6/GeS2 heterostructure can simultaneously drive the switching of sliding ferroelectric polarization, displaying a robust coupling of the two polarizations and leading to the overall polarization switching. Based on this, ferroelectric arrays with a density of 6.55 × 1012 cm-2 (equivalent to a storage density of 0.7 TB cm-2) were constructed in a moiré superlattice, and the polarization strength of array elements was 11.77 pC/m, higher than that of all reported 2D vdW out-of-plane ferroelectrics. High density, large polarization, and electrically switchable array elements in ferroelectric arrays provide unprecedented opportunities to design 2D high-density nonvolatile ferroelectric memories.

Temperature dependence of magnetic moment of rare earth ions in ErFeO3 and NdFeO3 single crystals.

The interaction between rare earth and iron spins in rare earth orthoferrites leads to remarkable phenomena, such as the spin-flip process. This is despite the rare earth spins not being magnetically ordered. Instead, they are polarized by the ordered iron spins. The interaction between the two spin families is not well understood. This study reports the temperature dependence of the net magnetic moment for rare earth spins, by measuring the overall magnetization for ErFeO3 and NdFeO3 single crystals. The obtained temperature dependence can be described well using a model based on the mean field theory, giving tanh(const./T) temperature dependence. This functional dependence is not disrupted by the spin-flip transition as the crystals are cooled.

A Disordered Rubik's Cube-Inspired Framework for Sodium-Ion Batteries with Ultralong Cycle Lifespan.

Sodium-ion batteries (SIBs) with fast-charge capability and long lifespan could be applied in various sustainable energy storage systems, from personal devices to grid storage. Inspired by the disordered Rubik's cube, here, we report that the high-entropy (HE) concept can lead to a very substantial improvement in the sodium storage properties of hexacyanoferrate (HCF). An example of HE-HCF has been synthesized as a proof of concept, which has achieved impressive cycling stability over 50 000 cycles and an outstanding fast-charging capability up to 75 C. Remarkable air stability and all-climate performance are observed. Its quasi-zero-strain reaction mechanism and high sodium diffusion coefficient have been measured and analyzed by multiple in situ techniques and density functional theory calculations. This strategy provides new insights into the development of advanced electrodes and provides the opportunity to tune electrochemical performance by tailoring the atomic composition.

Wearable Photo-Thermo-Electrochemical Cells (PTECs) Harvesting Solar Energy.

Solar induced thermal energy is a vital heat source supplementing body heat to realize thermo-to-electric energy supply for wearable electronics. Thermo-electrochemical cells, compared to the widely investigated thermoelectric generators, show greater potential in wearable applications due to the higher voltage output from low-grade heat and the increased option range of cheap and flexible electrode/electrolyte materials. A wearable photo-thermo-electrochemical cell (PTEC) is first fabricated here through the introduction of a polymer-based flexible photothermal film as a solar-absorber and hot electrode, followed by a systematic investigation of wearable device design. The as-prepared PTEC single device shows outstanding output voltage and current density of 15.0 mV and 10.8 A m-2 and 7.1 mV and 8.57 A m-2 , for the device employing p-type and n-type gel electrolytes, respectively. Benefiting from the equivalent performance in current density, a series connection containing 18 pairs of p-n PTEC devices is effectively made, which can harvest solar energy and charge supercapacitors to above 250 mV (1 sun solar illumination). Meanwhile, a watch-strap shaped flexible PTEC (eight p-n pairs) that can be worn on a wrist is fabricated and the realized voltage above 150 mV under light shows the potential for use in wearable applications.

Enhanced thermoelectric performance of In-doped and AgCuTe-alloyed SnTe through band engineering and endotaxial nanostructures.

Endotaxial nanostructures can reduce lattice thermal conductivity through enhancing phonon scattering without affecting electrical transport, leading to a high thermoelectric performance. On the other hand, band engineering can enhance electrical transport by improving the Seebeck coefficient through valence band convergence and the resonance level. In this paper, the synergistic effect of band engineering and endotaxial nanostructures was implemented in SnTe thermoelectric materials by alloying with AgCuTe and doping with Indium. The positron annihilation lifetime spectra show that the vacancy concentration in SnTe was reduced after alloying with AgCuTe, which led to a decreasing hole concentration and improved carrier mobility. Additionally, the diffusion of Ag in the matrix during the preparation can facilitate valence band convergence. Therefore, the power factor of SnTe is greatly increased to 18 µW cm-1 K-2 at 800 K, which can be further increased to 21.4 µW cm-1 K-2 at 800 K after In doping due to resonance level formation. Meanwhile, Cu2Te endotaxial nanostructures also can be observed in the TEM image after SnTe alloying with AgCuTe. So, the lattice thermal conductivity significantly reduced to 0.93 W m-1 K -1 in In-doped and AgCuTe-alloyed SnTe. Finally, we obtain an enhanced ZT value of 1.14 in Sn1.02In0.01Te-1%AgCuTe at 800 K.

Chemical Solution Route for High-Quality Multiferroic BiFeO3 Thin Films.

Bismuth ferrite (BiFeO3 ) has recently become interesting as a room-temperature multiferroic material, and a variety of prototype devices have been designed based on its thin films. A low-cost and simple processing technique for large-area and high-quality BiFeO3 thin films that is compatible with current semiconductor technologies is therefore urgently needed. Development of BiFeO3 thin films is summarized with a specific focus on the chemical solution route. By a systematic analysis of the recent progress in chemical-route-derived BiFeO3 thin films, the challenges of these films are highlighted. An all-solution chemical-solution deposition (AS-CSD) for BiFeO3 thin films with different orientation epitaxial on various oxide bottom electrodes is introduced and a comprehensive study of the growth, structure, and ferroelectric properties of these films is provided. A facile low-cost route to prepare large-area high-quality epitaxial BFO thin films with a comprehensive understanding of the film thickness, stoichiometry, crystal orientation, ferroelectric properties, and bottom electrode effects on evolutions of microstructures is provided. This work paves the way for the fabrication of devices based on BiFeO3 thin films.

Magnetization reversal on different time-scales for ErFeO3 and NdFeO3 single crystals.

The dynamics of the magnetic moment reversal is studied for ErFeO3 and NdFeO3 single crystals. The reversal occurs at 41 and 5.1 K for ErFeO3 and NdFeO3, respectively, at a field of 300 Oe. The dynamics of the magnetization reversal process depends on the temperature at which the reversal occurs. The reversal is abrupt if the thermal energy is far higher than the energy of Zeeman splitting of the rare earth ion levels by internal fields, as observed for ErFeO3. A gradual magnetization reversal occurs for NdFeO3 over 64 s, when the thermal energy at the temperature of the reversal is well below the Zeeman splitting energy of Nd3+ spins. A mechanism for this gradual magnetization reversal is proposed in terms of the thermal re-population of Zeeman doublets of Nd3+ ions, the splitting energy of which continuously changes during the magnetization reversal.

Quantitative source apportionment of heavy metals in cultivated soil and associated model uncertainty.

To estimate spatial distribution, source analysis and uncertainty of heavy metals (Pb, Cd, Cr, Hg, As, Cu, Zn, and Ni) based on geographic information system (GIS), positive matrix factorization model (PMF) and bootstrap (BS) using 382 soil samples collected from cultivated soils in Lanzhou. The mean contents of Cd, Hg, Cu, Zn and Ni were high as 1.7,1.7, 2.1, 1.5 and 1.3 times local background values, mean contents of Pb, Cr and As were lower than local background values. However, the mean contents of eight heavy metals were lower environmental quality risk control standard for soil contamination of agricultural soil. Proportions of four sources were identified: Cr was predominantly contributed by natural sources (29.14%), Cu, Zn and Ni was primarily from industrial sources (25.26%), Hg and As were mainly of agricultural sources (27.49%), Pb and Cd mainly came from traffic source and smelting-related activities (18.09%). Uncertainties analysis contained three aspects: bootstrap runs, factor contributions in the PMF solution, and coefficient of variation (CV) values. By combining the four pollution source factors with bootstrap runs, the accuracy of the four pollution source factors were reliable based on PMF model. The median values in the BS runs was considered the most true factor contribution, and the 5th-95th quartile interval represents the variability of each factor, Factor 4 (traffic source) R2 was 0.70 and lower variability. The highest CV value usually means a significantly deviation degree. In this study, the CV values of Cr in Factor 1, Cu, Zn, and Ni in Factor 2, Hg, and As in Factor 3, Pb, and Cd in Factor 4 were lower, indicates a lower deviation degree. and with the lowest content among heavy metals usually was also with the greatest uncertainties. In this study improves understanding of the reduction of heavy metal pollution in cultivated soil, and also serves as reference for pollution source apportionment in other regions.

Strain tuning of closed topological nodal lines and opposite pockets in quasi-two-dimensional α-phase FeSi2.

Following topological nodal point semimetals, topological nodal line semimetals with one dimensional (1D) topological elements have recently aroused great interest worldwide in the fields of quantum chemistry and condensed matter physics. In this study, by means of first-principles, we predict that quasi-two-dimensional (2D) α-FeSi2 with a P4/mmm space group is a topological nodal line semimetal with two nodal lines close to the Fermi level, in the kz = 0 and kz = π planes. Usually, topological nodal line semimetals can be classified into type I, type II, and hybrid-type categories, each type with different physical properties. Importantly, for the first time, we find that type I, type II, and hybrid-type nodal lines can be realized in a realistic material, i.e., quasi-2D α-FeSi2, by strain switching. The realization of tunable nodal line types occurs because quasi-2D α-FeSi2 has special opposite-pocket-behaving bands around the Fermi level. The results presented herein reflect that α-FeSi2 is a valuable candidate for spintronics application by utilization of type I, type II, and hybrid-type topological nodal line semimetals in a single material tuned by mechanical strain.

van der Waals force layered multiferroic hybrid perovskite (CH3NH3)2CuCl4 single crystals.

In inorganic-organic perovskites, the three-dimensional arrangement of the organic group results in more subtle balance of charge, spin and space, thereby providing an attractive route toward new multiferroics. Here we report the existing of multiple ferroic orderings in inorganic-organic layered perovskites with relative strong hydrogen bond ordering of the organic chains intra plane. In addition, the inter plane in perovskite is stacking via van der Waals force. However, such magnetoelectric coupling properties for this compound have not been reported since it is difficult to characterize the properties in single crystals since most of the hybrid perovskites are usually deliquescent and unstable when exposed to air. To deal with these problems, we synthesized a (CH3NH3)2CuCl4 single crystal by using a simple evaporation technique, and demonstrated ferroelectric, magnetic and magneto-electric properties of (CH3NH3)2CuCl4. The internal hydrogen bonding of easily tunable organic unit combined with 3d transition-metal layers in such hybrid perovskites make (CH3NH3)2CuCl4 a multiferroic crystal with magnetoelectrical coupling and offer an new way to engineer multifunctional multiferroic.

Multifunctional Active-Center-Transferable Platinum/Lithium Cobalt Oxide Heterostructured Electrocatalysts towards Superior Water Splitting.

Designing cost-effective and efficient electrocatalysts plays a pivotal role in advancing the development of electrochemical water splitting for hydrogen generation. Herein, multifunctional active-center-transferable heterostructured electrocatalysts, platinum/lithium cobalt oxide (Pt/LiCoO2 ) composites with Pt nanoparticles (Pt NPs) anchored on LiCoO2 nanosheets, are designed towards highly efficient water splitting. In this electrocatalyst system, the active center can be alternatively switched between Pt species and LiCoO2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Specifically, Pt species are the active centers and LiCoO2 acts as the co-catalyst for HER, whereas the active center transfers to LiCoO2 and Pt turns into the co-catalyst for OER. The unique architecture of Pt/LiCoO2 heterostructure provides abundant interfaces with favorable electronic structure and coordination environment towards optimal adsorption behavior of reaction intermediates. The 30 % Pt/LiCoO2 heterostructured electrocatalyst delivers low overpotentials of 61 and 285 mV to achieve 10 mA cm-2 for HER and OER in alkaline medium, respectively.

Optimized Electronic Configuration to Improve the Surface Absorption and Bulk Conductivity for Enhanced Oxygen Evolution Reaction.

The composition and structure are crucial for stabilizing an appropriate electronic configuration (unit eg electron for example) in high-efficiency electrocatalysts for the oxygen evolution reaction (OER). Here, an excellent platform to investigate the roles of the composition and structure in tuning the electron configuration for higher OER efficiency is provided by layered perovskite oxides with subtle variations of composition and structure (doping with 0%, 50%, and 100% cobalt in the Bi7Fe3Ti3O21). The crystal structures were analyzed by X-ray diffraction refinement, and the electronic structures were calculated based on X-ray absorption spectroscopy and magnetization vs temperature plots according to the Curie-Weiss law. The results indicate that the elongation of oxygen octahedra along the c-axis in layered perovskite could stabilize Co ions in the intermediate spin (IS) ( t2g)5( eg)1 state, resulting in dramatically enhanced electronic conductivity and absorption capacity. Subsequently, the OER efficiency of sample with 100% Co was found to be (incredibly) 100 times higher than that of the sample with 0% Co, with the current density increased from 0.13 to 43 mA/cm2 (1.8 V vs reversible hydrogen electrode); the Tafel slope was reduced from 656 to 87 mV/dec; and double-layer capacity enhanced from 174 to 4193 µF/cm2. This work reveals that both the composition and structure should be taken into account to stabilize a suitable electronic structure such as IS Co ions with moderate absorption and benign electronic conductivity for high-efficiency catalysis of the OER.

Ultrahigh piezoelectricity in ferroelectric ceramics by design.

Piezoelectric materials, which respond mechanically to applied electric field and vice versa, are essential for electromechanical transducers. Previous theoretical analyses have shown that high piezoelectricity in perovskite oxides is associated with a flat thermodynamic energy landscape connecting two or more ferroelectric phases. Here, guided by phenomenological theories and phase-field simulations, we propose an alternative design strategy to commonly used morphotropic phase boundaries to further flatten the energy landscape, by judiciously introducing local structural heterogeneity to manipulate interfacial energies (that is, extra interaction energies, such as electrostatic and elastic energies associated with the interfaces). To validate this, we synthesize rare-earth-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT), as rare-earth dopants tend to change the local structure of Pb-based perovskite ferroelectrics. We achieve ultrahigh piezoelectric coefficients d33 of up to 1,500 pC N-1 and dielectric permittivity ε33/ε0 above 13,000 in a Sm-doped PMN-PT ceramic with a Curie temperature of 89 °C. Our research provides a new paradigm for designing material properties through engineering local structural heterogeneity, expected to benefit a wide range of functional materials.

Magneto-Seebeck effect in Co2FeAl/MgO/Co2FeAl: first-principles calculations.

The magneto-Seebeck effect has recently attracted considerable attention because of its novel fundamental physics and future potential application in spintronics. Herein, employing first-principles calculations and the spin-resolved Boltzmann transport theory, we have systematically investigated the electronic structures and spin-related transport properties of Co2FeAl/MgO/Co2FeAl multilayers with parallel (P) and anti-parallel (AP) magnetic alignment. Our results indicate that the sign of tunneling magneto-Seebeck (TMS) value with Co2/O termination is consistent with that of the measured experimental result although its value (-221%) at room temperature is smaller than the experimental one (-95%). The calculated spin-Seebeck coefficients of the Co2/O termination with P and AP states and the FeAl/O termination with the AP state are all larger than other typical Co2MnSi/MgO/Co2MnSi heterostructures. By analyzing the geometries, electronic structures, and magnetic behaviors of two different terminations (Co2/O and FeAl/O terminations), we find that the two terminations in the interface region form anti-bonding and bonding states, reconstructing the energy gap, changing the magnetic moment of O atoms, and improving the spin-polarization (-82%). This phenomenon can be ascribed to the charge transfer and hybridization between Co/Fe 3d and O 2p states, which also results in a bowknot orbital shape of Co atoms with Co2/O termination and an ankle shape of Co atoms with FeAl/O termination far away from the interface. Moreover, there are spin-splitting transmission gaps with the Co2/O-termination around the Fermi level, while the transmission gaps with the FeAl/O-termination are closed and thus show a typical metallic character. Our findings will guide the experimental design of magneto-Seebeck devices for future spintronic applications.

Tuning the magnetism of two-dimensional hematene by ferroelectric polarization.

Magnetism in two-dimensional (2D) materials, that is, a 2D version of the magnetism of three-dimensional bulk materials, and the associated novel physics have recently been the focus of many spintronics researchers. Here we investigate the manipulation of 2D magnetism at the interfaces of ferromagnetic/ferroelectric hematene/BaTiO3(001) heterostructures (HSs) fabricated via a precisely chosen sequence. By introducing four types of interfaces of 2D hematene and three-dimensional BaTiO3 that induce different oxygen environments, the control of magnetism is directly demonstrated from first-principles. An obvious 2D electron gas originates from the Fe-3d and O-2p hybridization; the electron gas is sensitive to the interfacial atomic displacements. Robust control of both the direction and magnitude of the net magnetization has been realized for an Fe/TiO2 terminated bilayer HS. The electron occupancies of the dxy and dxz orbitals and changes to the Fe-O bond play a key role in determining the magnetism of our systems. Our work not only demonstrates the technique's potential for manipulating magnetism in 2D hematene, but also sheds light on the underlying mechanism and the fundamental properties of hematene HSs.

Understanding of transition metal (Ru, W) doping into Nb for improved thermodynamic stability and hydrogen permeability: density functional theory calculations.

Hydrogen solubility and diffusivity are the key features of hydrogen permeable membrane materials. To characterize the hydrogen permeation performance of NbTM (TM = W, Ru) phases, their hydrogen diffusion coefficient and solution coefficient, thermodynamic stability and chemical bonding are studied by a series of first principles calculations. The phonon spectra and elastic constants show that NbTM is dynamically stable. The TM-H chemical bonds have an ionic/covalent mixed character and are stronger than the Nb-H bond. The preferential diffusion paths of H in both Nb16H and Nb15TMH are from a tetrahedral interstitial site (TIS) to another TIS. The TM doping in Nb16H lowers the solubility and energy barrier of H diffusion and enhances the H diffusion coefficient (D), with Nb16RuH exhibiting the highest D value for TIS to TIS diffusion (2.14 × 10-8 m2 s-1) at 600 K. This study shows that alloying and temperature could significantly affect the solubility and diffusivity of hydrogen in Nb. Moreover, TM doping could greatly improve the hydrogen diffusion performance with good control of hydrogen embrittlement.

Seeking large Seebeck effects in LaX(X = Mn and Co)O3/SrTiO3 superlattices by exploiting high spin-polarized effects.

SrTiO3-based transition-metal oxide heterostructures with superconducting, ferromagnetic, ferroelectric, and ferroelastic properties exhibit high application potential in the fields of energy storage, energy conversion, and spintronic devices. Meanwhile, high effective (charge)-Seebeck coefficient materials composed of a ferromagnetic layer and SrTiO3 insulator layer have been achieved but we still have blocks to pursuing high spin-Seebeck coefficient materials. Here, we use first-principles calculations combined with spin-resolved Boltzmann transport theory to investigate the spin- and effective-Seebeck coefficients in the LaX(X = Mn and Co)O3/SrTiO3 superlattice. Compared with the LaMnO3/SrTiO3 superlattice, LaCoO3/SrTiO3 with ferromagnetic ordering has high spin polarization, relatively low valence valley degeneracy but high effective mass. Utilizing these characteristics, the maximum spin-Seebeck coefficient of LaMnO3/SrTiO3 is -152 µV K-1 at 450 K along the cross-plane direction, while LaCoO3/SrTiO3 reaches -247 µV K-1 under the same conditions. Interestingly, the spin- and effective-Seebeck coefficients are amazingly consistent with each other below 200 K, which indicates that one spin channel (spin-up or spin-down) dominates the carrier transport, and the other one (spin-down or spin-up) is filtered out. These characteristics are mainly associated with the magnetic MnO2/CoO2 layers with distinct dxy and dz2 orbitals near the Fermi level. Our results clarify the relationship of spin- and effective-Seebeck coefficients and indicate that SrTiO3-based transition metal oxide heterointerfaces are a key candidate for spin caloritronics.

Engineering electrical transport in α-MgAgSb to realize high performances near room temperature.

α-MgAgSb shows promise as a potential new low-temperature thermoelectric (TE) material and has been widely researched recently. We explored the effects of sintering conditions on the properties of MgAgSb-based thermoelectric materials through manipulating a spark plasma sintering system (SPS), where Ag vacancies and Mg point defects play a dominant role. The transport properties of MgAgSb were optimized effectively and efficiently, especially for electrical transport. As a result, we obtained a steady power factor (PF) of ∼17 µW cm-1 K-2, owing to the optimal carrier concentration of 9.8 × 1019 cm-3. Additionally, α-MgAgSb exhibits an ultralow lattice thermal conductivity of around 0.45 Wm-1 K-1 at 375 K. More importantly, a high ZT value of 0.85 was achieved below 375 K, approaching room temperature.