Thermal multiferroics in all-inorganic quasi-two-dimensional halide perovskites.

Multiferroic materials, particularly those possessing simultaneous electric and magnetic orders, offer a platform for design technologies and to study modern physics. Despite the substantial progress and evolution of multiferroics, one priority in the field remains to be the discovery of unexplored materials, especially those offering different mechanisms for controlling electric and magnetic orders1. Here we demonstrate the simultaneous thermal control of electric and magnetic polarizations in quasi-two-dimensional halides (K,Rb)3Mn2Cl7, arising from a polar-antipolar transition, as evidenced using both X-ray and neutron powder diffraction data. Our density functional theory calculations indicate a possible polarization-switching path including a strong coupling between the electric and magnetic orders in our halide materials, suggesting a magnetoelectric coupling and a situation not realized in oxide analogues. We expect our findings to stimulate the exploration of non-oxide multiferroics and magnetoelectrics to open access to alternative mechanisms, beyond conventional electric and magnetic control, for coupling ferroic orders.

Large Perpendicular Magnetic Anisotropy Induced by an Intersite Charge Transfer in Strained EuVO2H Films.

Perovskite oxides ABO3 continue to be a major focus in materials science. Of particular interest is the interplay between A and B cations as exemplified by intersite charge transfer (ICT), which causes novel phenomena including negative thermal expansion and metal-insulator transition. However, the ICT properties were achieved and optimized by cationic substitution or ordering. Here we demonstrate an anionic approach to induce ICT using an oxyhydride perovskite, EuVO2H, which has alternating layers of EuH and VO2. A bulk EuVO2H behaves as a ferromagnetic insulator with a relatively high transition temperature (TC) of 10 K. However, the application of external pressure to the EuIIVIIIO2H bulk or compressive strain from the substrate in the thin films induces ICT from the EuIIH layer to the VIIIO2 layer due to the extended empty V dxy orbital. The ICT phenomenon causes the VO2 layer to become conductive, leading to an increase in TC that is dependent on the number of carriers in the dxy orbitals (up to a factor of 4 for 10 nm thin films). In addition, a large perpendicular magnetic anisotropy appears with the ICT for the films of <100 nm, which is unprecedented in materials with orbital-free Eu2+, opening new perspectives for applications. The present results provide opportunities for the acquisition of novel functions by alternating transition metal/rare earth layers with heteroanions.

In Situ Transformation of Metal Molybdates into Polymetallic Sulfides with Enriched Edge Sites for High-Performance Supercapacitors.

An effective approach to synthesize polycrystalline Ni-Co-Mo sulfide (NiCoMoS) is developed through doping engineering coupled with chemical transformation. The polycrystalline NiCoMoS with enriched active edge sites is designed and fabricated on a Ni foam (NF) via a facile hydrothermal calcination and post-sulfidation approach, where the polycrystalline NiCoMoO4 precursor is elaborately prepared by doping Co ions into the NiMoO4 lattice and subsequently in-situ-converted into NiCoMoS with 3D architectures of ordered nanoneedle arrays. Benefiting from the unique 3D structure and synergistic effects of each component, the optimized needle-like NiCoMoS(2.0) arraying on a NF as a self-standing electrode exhibits superior electrochemical performances with a high specific charge (920.0 C g-1 at 1.0 A g-1), excellent rate capability, and good long-term stability. Furthermore, the assembled NiCoMoS//activated carbon hybrid device presents a satisfactory supercapacitor performance, affording an energy density of 35.2 W h kg-1 at a power density of 800.0 W kg-1 and competitive long-term stability (83.8% retention at 15 A g-1 after 10,000 cycles). Such a novel strategy may pave a new route for exploring other polymetallic sulfides with enriched, exposed active edge sites for energy-related applications.

Construction of NiCoZnS materials with controllable morphology for high-performance supercapacitors.

A facile two-step hydrothermal approach with post-sulfurization treatment was put forward to construct the mixed transition metal sulfide (NiCoZnS) with a high electrochemical performance. The different morphologies of NiCoZnS materials were successfully fabricated by adjusted the Ni/Co molar ratio of the NiCoZn(OH)F precursor. Moreover, thein situphase transformation from the NiCoZn(OH)F phase to Zn0.76Co0.24S and NiCo2S4phases and lattice defects via the S2-ion-exchange were determined by x-ray diffractometer, transmission electron microscopy and x-ray photoelectron spectroscopy techniques, which improved electric conductivity and interfacial active sites of the NiCoZnS, and so promoted the reaction kinetics. Significantly, the urchin-like NiCoZnS1/1prepared at the Ni/Co molar ratio of 1.0 exhibited promising electrochemical performances with high capacitance and excellent cycling stability. Furthermore, the asymmetric device (NiCoZnS//AC) using NiCoZnS1/1as the positive electrode had excellent supercapacitor performances with an energy density of 57.8 Wh·kg-1at a power density of 750 W·kg-1as well as a long cycle life (79.2% capacity retention after 10 000 cycles), indicating the potential application in high-performance supercapacitors.

Dehydration of Electrochemically Protonated Oxide: SrCoO2 with Square Spin Tubes.

Controlling oxygen deficiencies is essential for the development of novel chemical and physical properties such as high-Tc superconductivity and low-dimensional magnetic phenomena. Among reduction methods, topochemical reactions using metal hydrides (e.g., CaH2) are known as the most powerful method to obtain highly reduced oxides including Nd0.8Sr0.2NiO2 superconductor, though there are some limitations such as competition with oxyhydrides. Here we demonstrate that electrochemical protonation combined with thermal dehydration can yield highly reduced oxides: SrCoO2.5 thin films are converted to SrCoO2 by dehydration of HSrCoO2.5 at 350 °C. SrCoO2 forms square (or four-legged) spin tubes composed of tetrahedra, in contrast to the conventional infinite-layer structure. Detailed analyses suggest the importance of the destabilization of the SrCoO2.5 precursor by electrochemical protonation that can greatly alter reaction energy landscape and its gradual dehydration (H1-xSrCoO2.5-x/2) for the SrCoO2 formation. Given the applicability of electrochemical protonation to a variety of transition metal oxides, this simple process widens possibilities to explore novel functional oxides.

High-sensitive sensor for the simultaneous determination of phenolics based on multi-walled carbon nanotube/NiCoAl hydrotalcite electrode material.

The ternary NiCoAl hydrotalcite (NiCoAl-LDH) was combined with carboxylic multi-walled carbon nanotube (MWCNT) to fabricate a novel electrochemical sensor for simultaneously determining the co-existing trace phenolic substances. The morphology, structure, and electrochemical behavior of the as-prepared materials were characterized by various techniques. Benefitting from the great conductivity of MWCNT and high electrocatalytic activity of NiCoAl-LDH for phenolic substances, the advanced MWCNT/NiCoAl-LDH sensor presented a fast response, high sensitivity, excellent stability, and satisfactory replicability. The sensor offered good linear responses in the ranges1.50~600 µM to hydroquinone (HQ), 5.00~1.03 × 103 µM to catechol (CC), and 6.00 × 10-2~250 µM to bisphenol A (BPA). The detection limits of HQ, CC, and BPA were 0.4, 0.8, and 6. × 10-3 µM (S/N = 3), respectively. In environmental water, the sensor achieved satisfactory recoveries for the simultaneous detection of HQ (98.6~101%), CC (98.0~101%), and BPA (97.5~101%), with relative standard deviations less than 4.4%.

Controllable architecture of the NiCoZnS@NiCoFe layered double hydroxide coral-like structure for high-performance supercapacitors.

The rational design of the morphological structure of electrode materials is considered as an important strategy to obtain high-performance supercapacitors. So, NiCoZnS materials with different Ni/Co/Zn molar ratios on Ni foam (NF) were synthesized, in which the Ni/Co/Zn molar ratio plays a key role in the morphological structure and electrochemical performances. Furthermore, the pre-prepared NiCoZnS materials act as substrates to guide the self-assembling of NiCoFe layered double hydroxide (LDH) nanosheets on the substrate surface to form core-shell electrode materials (NiCoZnS@NiCoFe-LDH) with a 3D mesoporous hierarchical network structure for further improving electrochemical performances. The unique interconnected coral-like NiCoZnS1@NiCoFe-LDH with a large specific surface area (93.1 m2 g-1) and high specific capacitance is achieved at the Ni/Co/Zn molar ratio of 1 : 1 : 1. Benefiting from the unique structural feature and respective merits of the NiCoZnS and NiCoFe-LDH, the NiCoZnS1@NiCoFe-LDH demonstrates an ultrahigh specific capacitance of 1524.0 C g-1 (3386.7 F g-1) at 1.0 A g-1 and excellent 95.0% capacitance retention at 10 A g-1 after 5000 cycles. As for practical application, the assembled NiCoZnS1@NiCoFe-LDH//AC delivers a favorable energy density of 66.25 W h kg-1 at 1500 W kg-1 and a long-term cycling lifetime (86.04% retention at 5.0 A g-1 after 10 000 cycles), which suggests promising potential in energy storage and conversion.

A selective control of volatile and non-volatile superconductivity in an insulating copper oxide via ionic liquid gating.

Manipulating the superconducting states of high transition temperature (high-Tc) cuprate superconductors in an efficient and reliable way is of great importance for their applications in next-generation electronics. Here, employing ionic liquid gating, a selective control of volatile and non-volatile superconductivity is achieved in pristine insulating Pr2CuO4±Î´ (PCO) films, based on two distinct mechanisms. Firstly, with positive electric fields, the film can be reversibly switched between superconducting and non-superconducting states, attributed to the carrier doping effect. Secondly, the film becomes more resistive by applying negative bias voltage up to - 4 V, but strikingly, a non-volatile superconductivity is achieved once the gate voltage is removed. Such phenomenon represents a distinctive route of manipulating superconductivity in PCO, resulting from the doping healing of oxygen vacancies in copper-oxygen planes as unravelled by high-resolution scanning transmission electron microscope and in situ X-ray diffraction experiments. The effective manipulation of volatile/non-volatile superconductivity in the same parent cuprate brings more functionalities to superconducting electronics, as well as supplies flexible samples for investigating the nature of quantum phase transitions in high-Tc superconductors.

Preparation of a NiAl-Oxide@Polypyrrole Composite for High-Performance Supercapacitors.

A core-shell NiAlO@polypyrrole composite (NiAlO@PPy) with a 3D "sand rose"-like morphology was prepared via a facile in situ oxidative polymerization of pyrrole monomer, where the role of PPy coating thickness was investigated for high-performance supercapacitors. Microstructure analyses indicated that the PPy was successfully coated onto the NiAlO surface to form a core-shell structure. The NiAlO@PPy exhibited a better electrochemical performance than pure NiAlO, and the moderate thickness of the PPy shell layer was beneficial for expediting the electron transfer in the redox reaction. It was found that the NiAlO@PPy5 prepared at 5.0 mL L-1 addition amount of pyrrole monomer demonstrated the best electrochemical performance with a high specific capacitance of 883.2 F g-1 at a current density of 1 A g-1 and excellent capacitance retention of 91.82 % of its initial capacitance after 1000 cycles at 3 A g-1 . The outstanding electrochemical performance of NiAlO@PPy5 were due to the synergistic effect of NiAlO and PPy, where the uniform network-like PPy shell with the optimal thickness made electrolyte ions more easily accessible for faradic reactions. This work provided a simple approach for designing organic-inorganic core-shell materials as high-performance electrode materials for electrochemical supercapacitors.

Electric Field-Controlled Multistep Proton Evolution in H x SrCoO2.5 with Formation of H-H Dimer.

Ionic evolution-induced phase transformation can lead to wide ranges of novel material functionalities with promising applications. Here, using the gating voltage during ionic liquid gating as a tuning knob, the brownmillerite SrCoO2.5 is transformed into a series of protonated H x SrCoO2.5 phases with distinct hydrogen contents. The unexpected electron to charge-neutral doping crossover along with the increase of proton concentration from x = 1 to 2 suggests the formation of exotic charge neutral H-H dimers for higher proton concentration, which is directly visualized at the vacant tetrahedron by scanning transmission electron microscopy and then further supported by first principles calculations. Although the H-H dimers cause no change of the valency of Co2+ ions, they result in clear enhancement of electronic bandgap and suppression of magnetization through lattice expansion. These results not only reveal a hydrogen chemical state beyond anion and cation within the complex oxides, but also suggest an effective pathway to design functional materials through tunable ionic evolution.

Manipulate the Electronic and Magnetic States in NiCo2 O4 Films through Electric-Field-Induced Protonation at Elevated Temperature.

Ionic-liquid-gating- (ILG-) induced proton evolution has emerged as a novel strategy to realize electron doping and manipulate the electronic and magnetic ground states in complex oxides. While the study of a wide range of systems (e.g., SrCoO2.5 , VO2 , WO3 , etc.) has demonstrated important opportunities to incorporate protons through ILG, protonation remains a big challenge for many others. Furthermore, the mechanism of proton intercalation from the ionic liquid/solid interface to whole film has not yet been revealed. Here, with a model system of inverse spinel NiCo2 O4 , an increase in system temperature during ILG forms a single but effective method to efficiently achieve protonation. Moreover, the ILG induces a novel phase transformation in NiCo2 O4 from ferrimagnetic metallic into antiferromagnetic insulating with protonation at elevated temperatures. This study shows that environmental temperature is an efficient tuning knob to manipulate ILG-induced ionic evolution.

Publisher Correction: Electric-field control of ferromagnetism through oxygen ion gating.

In the original version of this Article, Figs. 4c and 4d contained incorrectly sized error bars. This has now been corrected in both the PDF and HTML versions of the Article.

Electric-field control of ferromagnetism through oxygen ion gating.

Electric-field-driven oxygen ion evolution in the metal/oxide heterostructures emerges as an effective approach to achieve the electric-field control of ferromagnetism. However, the involved redox reaction of the metal layer typically requires extended operation time and elevated temperature condition, which greatly hinders its practical applications. Here, we achieve reversible sub-millisecond and room-temperature electric-field control of ferromagnetism in the Co layer of a Co/SrCoO2.5 system accompanied by bipolar resistance switching. In contrast to the previously reported redox reaction scenario, the oxygen ion evolution occurs only within the SrCoO2.5 layer, which serves as an oxygen ion gating layer, leading to modulation of the interfacial oxygen stoichiometry and magnetic state. This work identifies a simple and effective pathway to realize the electric-field control of ferromagnetism at room temperature, and may lead to applications that take advantage of both the resistance switching and magnetoelectric coupling.

Electric-Field-Controlled Phase Transformation in WO3 Thin Films through Hydrogen Evolution.

Field-effect transistors with ionic-liquid gating (ILG) have been widely employed and have led to numerous intriguing phenomena in the last decade, due to the associated excellent carrier-density tunability. However, the role of the electrochemical effect during ILG has become a heavily debated topic recently. Herein, using ILG, a field-induced insulator-to-metal transition is achieved in WO3 thin films with the emergence of structural transformations of the whole films. The subsequent secondary-ion mass spectrometry study provides solid evidence that electrochemically driven hydrogen evolution dominates the discovered electrical and structural transformation through surface absorption and bulk intercalation.

Electric-field control of tri-state phase transformation with a selective dual-ion switch.

Materials can be transformed from one crystalline phase to another by using an electric field to control ion transfer, in a process that can be harnessed in applications such as batteries, smart windows and fuel cells. Increasing the number of transferrable ion species and of accessible crystalline phases could in principle greatly enrich material functionality. However, studies have so far focused mainly on the evolution and control of single ionic species (for example, oxygen, hydrogen or lithium ions). Here we describe the reversible and non-volatile electric-field control of dual-ion (oxygen and hydrogen) phase transformations, with associated electrochromic and magnetoelectric effects. We show that controlling the insertion and extraction of oxygen and hydrogen ions independently of each other can direct reversible phase transformations among three different material phases: the perovskite SrCoO3-δ (ref. 12), the brownmillerite SrCoO2.5 (ref. 13), and a hitherto-unexplored phase, HSrCoO2.5. By analysing the distinct optical absorption properties of these phases, we demonstrate selective manipulation of spectral transparency in the visible-light and infrared regions, revealing a dual-band electrochromic effect that could see application in smart windows. Moreover, the starkly different magnetic and electric properties of the three phases-HSrCoO2.5 is a weakly ferromagnetic insulator, SrCoO3-δ is a ferromagnetic metal, and SrCoO2.5 is an antiferromagnetic insulator-enable an unusual form of magnetoelectric coupling, allowing electric-field control of three different magnetic ground states. These findings open up opportunities for the electric-field control of multistate phase transformations with rich functionalities.

Postoperative Evaluation of Reduction Loss in Proximal Humeral Fractures: A Comparison of Plain Radiographs and Computed Tomography.

OBJECTIVE: To compare postoperative CT images with plain radiographs for measuring prognostic factors of reduction loss of fractures of the proximal part of the humerus. METHODS: A total of 65 patients who sustained fractures of the proximal humerus treated with locking plates from June 2012 to October 2015 were retrospectively analyzed. There were 24 men and 41 women, with a mean age of 60.0 years (range, 22-76 years). According to the Neer classification system of proximal humeral fracture, there were 26 two-part, 27 three-part and 12 four-part fractures of the proximal part of the humerus, and all fractures were treated with open reduction and internal fixation (ORIF) using locked plating. All postoperative CT images and plain radiographs of the patients were obtained. Prognostic factors of the reduction loss were the change of neck shaft angle (NSA) and the change of humeral head height (HHH). The change of NSA and HHH were evaluated by the difference between postoperative initial and final follow-up measurement. Reduction loss was defined as the change ≥10° for NSA or ≥5 mm for HHH. The NSA and HHH were measured using plain radiographs and 3-D CT images, both initially and at final follow-up. The paired t-test was used for comparison of NSA, change of NSA, HHH, and change of HHH between two image modalities. The differences between two image modalities in the assessment of reduction loss were examined using the χ2 -test (McNemar test). Intraclass correlation coefficients (ICC) were used to assess the intra-observer and inter-observer reliability. RESULTS: 3-D CT images (ICC range, 0.834-0.967) were more reliable in all parameters when compared with plain radiographs (ICC range, 0.598-0.915). Significant differences were found between the two image modalities in all parameters (plain radiographs: initial NSA = 133.6° ± 3.8°, final NSA = 130.0° ± 1.9°, initial HHH = 17.9 ± 0.9 mm, final HHH = 15.8 ± 1.5 mm; 3-D CT: initial NSA = 131.4° ± 3.4°, final NSA = 128.8° ± 1.7°, initial HHH = 16.8 ± 1.2 mm, final HHH = 14.5 ± 1.1 mm; all P < 0.05). In the assessment of reduction loss, the percentage was 16.9% (11/65) for the plain radiographs and 7.7% (5/65) for the 3-D CT scans (P < 0.05). For the 5 patients with reduction loss, which were observed by two imaging modalities, the mean Constant-Murley score was 61.0 ± 1.6. The patients with reduction loss, observed only in plain radiographs but not CT images, had good shoulder function (Constant-Murley score: 82.7 ± 1.0). CONCLUSIONS: Our data reveal that 3-D CT images are more reliable than plain radiographs in the assessment of the prognostic factors of reduction loss of fractures of the proximal part of the humerus with treatment of locking plates; this reliable CT technique can serve as an effective guideline for the subsequent clinical management of patients.

Heteroepitaxy of Fe3O4/Muscovite: A New Perspective for Flexible Spintronics.

Spintronics has captured a lot of attention since it was proposed. It has been triggering numerous research groups to make their efforts on pursuing spin-related electronic devices. Recently, flexible and wearable devices are in a high demand due to their outstanding potential in practical applications. In order to introduce spintronics into the realm of flexible devices, we demonstrate that it is feasible to grow epitaxial Fe3O4 film, a promising candidate for realizing spintronic devices based on tunneling magnetoresistance, on flexible muscovite. In this study, the heteroepitaxy of Fe3O4/muscovite is characterized by X-ray diffraction, high-resolution transmission electron microscopy, and Raman spectroscopy. The chemical composition and magnetic feature are investigated by a combination of X-ray photoelectron spectroscopy and X-ray magnetic circular dichroism. The electrical and magnetic properties are examined to show the preservation of the primitive properties of Fe3O4. Furthermore, various bending tests are performed to show the tunability of functionalities and to confirm that the heterostructures retain the physical properties under repeated cycles. These results illustrate that the Fe3O4/muscovite heterostructure can be a potential candidate for the applications in flexible spintronics.

Electronic Structure and Ferromagnetism Modulation in Cu/Cu2O Interface: Impact of Interfacial Cu Vacancy and Its Diffusion.

Cu/Cu2O composite structures have been discovered to show sizable ferromagnetism (FM) with the potential applications in spintronic devices. To date, there is no consensus on the FM origin in Cu/Cu2O systems. Here, first principles calculations are performed on the interface structure to explore the microscopic mechanism of the FM. It is found that only the Cu vacancy (V(Cu)) adjacent to the outermost Cu2O layer induces a considerable magnetic moment, mostly contributed by 2p orbitals of the nearest-neighbor oxygen atom (O(NN)) with two dangling bonds and 3d orbitals of the Cu atoms bonding with the O(NN). Meanwhile, the charge transfer from Cu to Cu2O creates higher density of states at the Fermi level and subsequently leads to the spontaneous FM. Furthermore, the FM could be modulated by the amount of interfacial V(Cu), governed by the interfacial Cu diffusion with a moderate energy barrier (~1.2 eV). These findings provide insights into the FM mechanism and tuning the FM via interfacial cation diffusion in the Cu/Cu2O contact.

GaN as an interfacial passivation layer: tuning band offset and removing fermi level pinning for III-V MOS devices.

The use of an interfacial passivation layer is one important strategy for achieving a high quality interface between high-k and III-V materials integrated into high-mobility metal-oxide-semiconductor field-effect transistor (MOSFET) devices. Here, we propose gallium nitride (GaN) as the interfacial layer between III-V materials and hafnium oxide (HfO2). Utilizing first-principles calculations, we explore the structural and electronic properties of the GaN/HfO2 interface with respect to the interfacial oxygen contents. In the O-rich condition, an O8 interface (eight oxygen atoms at the interface, corresponding to 100% oxygen concentration) displays the most stability. By reducing the interfacial O concentration from 100 to 25%, we find that the interface formation energy increases; when sublayer oxygen vacancies exist, the interface becomes even less stable compared with O8. The band offset is also observed to be highly dependent on the interfacial oxygen concentration. Further analysis of the electronic structure shows that no interface states are present at the O8 interface. These findings indicate that the O8 interface serves as a promising candidate for high quality III-V MOS devices. Moreover, interfacial states are present when such interfacial oxygen is partially removed. The interface states, leading to Fermi level pinning, originate from unsaturated interfacial Ga atoms.

Expression of human DNA mismatch-repair protein, hMSH2, in patients with oral lichen planus.

hMSH2 is one of the human DNA mismatch repair genes that plays an important role in reducing mutations and maintaining genomic stability. The aim of the present study was to detect the expression and significance of hMSH2 protein in patients with oral lichen planus (OLP). The expression levels of hMSH2 in the OLP group (n=51) and control group with normal oral mucosa (NM; n=40) were detected using an immunohistochemical method and subsequently assessed. The positive rate of hMSH2 expression in the OLP group was 52.94%, while the rate was 80% in the control group, exhibiting a statistically significant difference (χ2=7.1993; P<0.05). However, the expression of hMSH2 in the OLP tissues was not shown to significantly correlate with the patient gender, age and type of OLP (P>0.05). In conclusion, the protein expression levels of hMSH2 in the OLP tissues were significantly reduced as compared with that in the NM tissues, indicating that hMSH2 plays a role in the development of OLP. Therefore, hMSH2 may be used as a biomarker for evaluating the cancer risk of patients with OLP.