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Formic acid oxidation (FAO) is a typical anode reaction in fuel cells that can be facilitated by modulating its direct and indirect reaction pathways. Herein, PtAu bimetallic nanoparticles loaded onto Co and N co-doping carbon nanoframes (CoNC NFs) were designed to improve the selectivity of the direct reaction pathway for efficient FAO. Based on these subtle nanomaterials, the influences of elemental composition and carbon-support materials on the two pathways of FAO were investigated in detail. The results of fuel cell tests verified that the appropriate amount of Au in PtAu/CoNC can promote a direct reaction pathway for FAO, which is crucial for enhancing the oxidation efficiency of formic acid. In particular, the obtained PtAu/CoNC with an optimal Pt/Au atomic ratio of 1:1 (PtAu/CoNC-3) manifests the best catalytic performance among the analogous obtained Pt-based electrocatalysts. The FAO mass activity of the PtAu/CoNC-3 sample reached 0.88 A·mgPt−1, which is 26.0 times higher than that of Pt/C. The results of first-principles calculation and CO stripping jointly demonstrate that the CO adsorption of PtAu/CoNC is considerably lower than that of Pt/CoNC and PtAu/C, which indicates that the synergistic effect of Pt, Au, and CoNC NFs is critical for the resistance of Pt to CO poisoning. This work is of great significance for a deeper understanding of the oxidation mechanism of formic acid and provides a feasible and promising strategy for enhancing the catalytic performance of the catalyst by improving the direct reaction pathway for FAO.

It is well known that the phase stability of CsPb(I1−xBrx)3 (0 ≤ x ≤ 1) perovskite materials is enhanced under humid environments with the increase of Br− concentration in film, however, the bandgap (Eg) is also widened synchronously, resulted in limiting the light harvesting and then reducing the power conversion efficiency (PCE) of devices. Hence, how to realize the compatibility of high stability and high PCE is a challenge for device based on CsPb(I1−xBrx)3. In this work, the two- (2-T) and four-terminal (4-T) tandem solar cells (TSCs) consisting of a CsPb(I1−xBrx)3 top sub-cell and a crystalline silicon (c-Si) bottom sub-cell are constructed and compared. It is found that in the case of 2-T configuration, performance of device is very sensitive to the Eg and the thickness of top sub-cell, and a maximum PCE of 29.23% is achieved only for the CsPbI3 top sub-cell at an optimum thickness of 275 nm. However, in the 4-T formation, devices present a weak dependence on the Eg and the thickness of top sub-cell, and PCEs above 28.5% can be obtained when CsPbBr3 is used as top sub-cell. These results highly underline the application potential of 4-T CsPb(I1−xBrx)3/Si TSCs, especially for CsPbBr3/Si TSC.

In recent years, inorganic CsPbBr3-based perovskites have accomplished considerable progress owing to their superior stability under harsh humid environment. The power conversion efficiency (PCE) of CsPbBr3 perovskite solar cells (PSCs) has seen an unprecedented development from 5.74% to 10.91% with the improvement of the CsPbBr3 crystal quality. Despite extensive research efforts, the device efficiency of the CsPbBr3-based PSCs still lags behind that of other hybrid perovskite materials. Therefore, there is a significant interest in further boosting the performance of all-inorganic CsPbBr3 PSCs by the synergic optimization of films and device interfaces. In this review, we have discussed and summarized recent advances and methodologies related to CsPbBr3 films and PSCs. Furthermore, we discuss different fabrication strategies such as solution-based and vapor-based methods and their influence on the properties of CsPbBr3, particularly the morphology of films. Moreover, the timeline of improvement of the device efficiency from 2015 to 2020 is comprehensively addressed and developments are clearly sorted out by addressing critical factors influencing the photovoltaic performance. We further highlight state-of-the-art engineering strategies for CsPbBr3 PSCs that facilitate the crystallization control, charge extraction, suppression of charge recombination, and defect passivation in a systematic manner. At the end of the review, the summary and perspectives are presented along with beneficial guidelines for developing highly efficient and stable CsPbBr3 PSCs.

Recently, inorganic perovskite solar cells (PSCs) based on CsPbBr3 have triggered incredible interest due to the demonstrated excellent stability against thermal and high humidity environmental conditions. However, the power conversion efficiency (PCE) of the CsPbBr3-based PSCs is still lower than that of the organic-inorganic hybrid one, because of the large band gap and serious charge recombination at the interface or inside the device. Here, the working mechanism of the devices with normal n-i-p planar structure is modeled and investigated using SCAPS 1D simulation software. The simulation results state that the proper band structure of PSCs is crucial to carrier separation and transport. The high interface recombination, originated from the large band offsets of the electron transport material (ETM)/absorber and absorber/hole transport material (HTM) respectively, can be effectively diminished with the continuous gradient junction design of the absorber, and a PCE of 11.58% is obtained with a high open-circuit voltage (VOC) of 1.68 V. Moreover, by building a heterojunction bilayer absorption scenario of CsPbIBr2/CsPbBr3 and employing ZnOS and Cu2ZnSnS4 films as the ETM and HTM respectively, the PCE of PSCs is further increased to 15.89%, caused mainly by the enhancement in short-current density (JSC). Moreover, reducing the interface defect density is also very important to improve the performance of PSCs. These results will provide theoretical guidance for improving the performance of the CsPbBr3-based PSCs.

Nanoscale phase mixtures in transition-metal oxides (TMOs) often render these materials susceptible to external stimuli (electric field, mechanical stress, etc.), which can lead to rich functional properties and device applications. Here, direct observation and multifield manipulation of a nanoscale mixture of brownmillerite SrFeO

CuxO (Cupric Oxide) nanotubes (NTs) were synthesized by using thermal oxidation of Cu nanowires (NWs) for 2 and 4 hours, respectively, and the effect of the components on their photo-electrical properties due to the infrared (IR) light with a wavelength of 1064 nm were investigated. In the 2-h CuxO NTs, the main component was Cu2O; however, the 4-h CuxO NTs were composed of a mixture of CuO and Cu2O. The photoelectric properties showed that the voltage difference and the sensitivity of 4-h CuxO NTs were more than 3 times those of the 2-h CuxO NTs, and its linear range was only about one-third that of the 2-h CuxO NTs. The above results were caused by the 4-h CuxO NTs containing a higher content of CuO, which had a suitable bandgap of 1.2 eV for light with a wavelength of 1064 nm. In addition, the response and the recovery times for the 4-h NTs were on the same order as those of the 2-h NTs. The conclusions from this article indicated that 4-h and 2-h NTs were very promising for the design of IR photodetector device with higher sensitivity and a larger detection range respectively.

Formamidinium tin iodide (FASnI3), as one promising Pb-free halide perovskite, has received extensive attention. But perovskite solar cells (PSCs) based on FASnI3 films have yet to realize the high power conversion efficiency (PCE) achieved in its Pb-based counterparts. To investigate the limitation of FASnI3-based perovskite solar cells with inverted p-i-n planar structures, the influences of various parameters on the device performance are analyzed through device simulation. The results reveal that defect density at front hole transport material (HTM)/absorber interface is critical for high efficiency. And it is interesting to note that the doping density, rather than the doping type and its space distribution, dominates the device properties, and an upper limit of 1 × 1016 cm−3 is achieved. In addition, the response of device to band offset is investigated, and an optimum electron affinity of 3.9 eV is obtained. Finally, the effects of relative permittivity and thickness of the absorber with different carrier lifetime are studied. A maximum PCE of 9.75% is achieved at absorber thickness of 300 nm with carrier lifetime of 0.1 ns? These results show that optimizing the interface property and band offset, improving the stability of Sn2+ and reducing the defect density of absorber layer are the main challenges for high-performance FASnI3-based PSCs in the future research.

Single-atom catalysts (SACs) are of great scientific and technical importance due to their low cost, high site density, and high specificity to enhance chemical reactions. Nevertheless, a major issue that severely limits the practical exploration of SACs is their instability, i.e., the preference of sintering and clustering over a defect-free substrate during operation. Here, we employ first-principles calculations to investigate how substrate engineering can stabilize SACs by strain-tuning the electronic interactions between the metal and the substrate using two Pd adatoms on a defect-free, single-layer MoS2 as a typical example. It is identified that the Pd2 dimer is prone to dissociate and form highly efficient SACs for CO oxidation due to the enhanced charge transfer and orbital hybridization with the MoS2 substrate under a suitable tensile strain. The straining induces a semiconductive-to-metallic phase transition of the substrate. Moreover, low-cost elements, such as Ag, Ni, Cu, and Cr, can also be stabilized into high-performance SACs for CO oxidation with tunable reaction barriers by straining. The present findings offer a new avenue to inhibit the transition metal atoms from clustering into nanoclusters/particles and provide a clear guidance for the development of highly cost-efficient and stable SACs on defect-free substrates.

Photocatalytic studies performed on well-defined epitaxial thin films and heterostructures allow the direct investigation of crystallographic-dependent reactivity, and can provide fundamental insights into the reaction mechanisms. In this work, we show that phase-pure, monoclinic BiVO4 nanoislands with a truncated pyramid shape with the (010) top surface and {110} sidewalls can be grown on (001)-oriented yttria-stabilized zirconia (YSZ) substrates with an epitaxial relationship of BiVO4(010)[001] // YSZ(001)[100]. The resulting nanostructures show a strong size-dependent mass-normalized photocatalytic activity, with highly dispersed nanoislands at low coverage being the most active. Pb(NO3)2 photooxidation or photoreduction reactions can be controlled in aqueous solution with and without adding NaIO3 as a electron scavenger, leading to the selective deposition of PbO2 or Pb on {110} or (010) surfaces of BiVO4, respectively.

Ionic defects, such as oxygen vacancies, play a crucial role in the magnetic and electronic states of transition metal oxides. Control of oxygen vacancy is beneficial to the technological applications, such as catalysis and energy conversion. Here, we investigate the electronic structure of SrCoO3−x as a function of oxygen content (x). We found that the hybridization extent between Co 3d and O 2p increased with the reduction of oxygen vacancies. The valence band maximum of SrCoO2.5+δ has a typical O 2p characteristic. With further increasing oxygen content, the Co ions transform from a high spin Co3+ to an intermediate spin Co4+, resulting in a transition of SrCoO3−x from insulator to metal. Our results on the electronic structure evolution with the oxygen vacancies in SrCoO3−x not only illustrate a spin state transition of Co ions, but also indicate a perspective application in catalysis and energy field.

For ferroelectric photovoltaics, it is challenging to enhance the power conversion efficiency (PCE) without sacrificing the photoresponse switchability. Here, we demonstrate that enhanced PCE and good photoresponse switchability can be simultaneously achieved in perovskite heterostructures comprising narrow-gap semiconductor LaVO3 (LVO) and ferroelectric Pb(Zr0.2Ti0.8)O3 (PZT). The LVO(24 nm)/PZT(120 nm) based device exhibits a ∼5-fold enhancement in PCE compared with the PZT-only based device, which is attributed to the enhanced absorption from the LVO layer and the built-in field at the LVO/PZT interface facilitating the separation of photo-generated e–h pairs. In addition, the switched photovoltage of the LVO/PZT based device is above 1 V, which is as large as that of the PZT-only based device. This persisted photoresponse switchability is obtained because the polarization can be fully switched in the LVO/PZT based devices when the LVO thickness is less than 24 nm. Our finding therefore provides a promising route for the development of high-efficiency and highly switchable ferroelectric photovoltaic devices.

Since the first report in 2009, the certified power conversion efficiency (PCE) of organic-inorganic halide perovskite solar cells (PSCs) has rapidly risen to 23.3%, which successfully demonstrates the importance of film morphology and quality management, especially for the planar heterojunction architecture based on solution-processed method. In this paper, the morphology, structure, optical and electrical properties of perovskite films treated by two different multi-step thermal annealing methods have been studied and compared. For the conventional multi-step (CMS) annealing method, the surface morphologies and optical properties of films are significantly influenced by the annealing temperature due to the decomposition of CH3NH3PbI3. When the modified multi-step (MMS) method is adopted, the decomposition of CH3NH3PbI3 can be effectively suppressed. The best device treated by MMS method at 180 °C showed a short circuit current density of 20.85 mA/cm2, an open circuit voltage of 0.96 V, a fill factor of 72.7%, and a PCE of 14.7%, which is a 23.5% enhancement in PCE relative to the maximum 11.9% treated by CMS method at 160 °C. These findings suggest that the efficiency of PSCs can be further improved by optimizing the preparation process.

Electronic states of a correlated material can be effectively modified by structural variations delivered from a single-crystal substrate. In this letter, we show that the CrN films grown on MgO (001) substrates have a (001) orientation, whereas the CrN films on {\alpha}-Al2O3 (0001) substrates are oriented along (111) direction parallel to the surface normal. Transport properties of CrN films are remarkably different depending on crystallographic orientations. The critical thickness for the metal-insulator transition (MIT) in CrN 111 films is significantly larger than that of CrN 001 films. In contrast to CrN 001 films without apparent defects, scanning transmission electron microscopy results reveal that CrN 111 films exhibit strain-induced structural defects, e. g. the periodic horizontal twinning domains, resulting in an increased electron scattering facilitating an insulating state. Understanding the key parameters that determine the electronic properties of ultrathin conductive layers is highly desirable for future technological applications., Comment: 19 pages, 4 figures

Manipulation of octahedral distortion at atomic length scale is an effective means to tune the physical ground states of functional oxides. Previous work demonstrates that epitaxial strain and film thickness are variable parameters to modify the octahedral rotation and tilt. However, selective control of bonding geometry by structural propagation from adjacent layers is rarely studied. Here we propose a new route to tune the ferromagnetic response in SrRuO3 (SRO) ultrathin layers by oxygen coordination of adjacent SrCuO2 (SCO) layers. The infinite-layered CuO2 in SCO exhibits a structural transformation from "planar-type" to "chain-type" as reducing film thickness. These two orientations dramatically modify the polyhedral connectivity at the interface, thus altering the octahedral distortion of SRO. The local structural variation changes the spin state of Ru and hybridization strength between Ru 4d and O 2p orbitals, leading to a significant change in the magnetoresistance and anomalous Hall resistivity of SRO layers. These findings could launch further investigations into adaptive control of magnetoelectric properties in quantum oxide heterostructures using oxygen coordination.

Materials with large perpendicular magnetic anisotropy (PMA) are candidates for spintronic devices, such as magnetic random-access memory, etc., due to their stable magnetic reference states. Because of shape anisotropy, the magnetic easy axis of oxide thin films favors in-plane orientation. In this Paper, we demonstrate a convenient means to control the magnetic anisotropy of ${\mathrm{Sr}\mathrm{Ru}\mathrm{O}}_{3}$ (SRO) ultrathin layers from in-plane to out-of-plane by capping with nonmagnetic materials. Tuning the anisotropy is achieved by imposition of symmetry mismatch at the interface-induced structural transition of SRO with suppressed octahedral tilt. These results suggest a potential direction for engineering magnetic oxide thin films with flexible tunable PMA using capping-layer-induced dissimilar symmetry.

Lead‐free halide double perovskites (HDPs) are promising candidates for high‐performance solar cells because of their environmentally‐friendly property and chemical stability in air. The power conversion efficiency of HDPs‐based solar cells needs to be further improved before their commercialization in the market. It requires a thoughtful understanding of the correlation between their specific structure and property. Here, the structural and optical properties of an important HDP‐based (NH4)2SeBr6 are investigated under high pressure. A dramatic piezochromism is found with the increase in pressure. Optical absorption spectra reveal the pressure‐induced red‐shift in bandgap with two distinct anomalies at 6.57 and 11.18 GPa, and the energy tunability reaches 360 meV within 20.02 GPa. Combined with structural characterizations, Raman and infrared spectra, and theoretical calculations using density functional theory, results reveal that, the first anomaly is caused by the formation of a Br‐Br bond among the [SeBr6]2− octahedra, and the latter is attributed to a cubic‐to‐tetragonal phase transition. These results provide a clear correlation between the chemical bonding and optical properties of (NH4)2SeBr6. It is believed that the proposed strategy paves the way to optimize the optoelectronic properties of HDPs and further stimulate the development of next‐generation clear energy based on HDPs solar cells., Pressure‐induced optical properties variation of lead‐free halide double perovskite (NH4)2SeBr6 is strongly correlated with the re‐organization of Br‐Br bonds and the rotation and distortion of [SeBr6]2− octahedra. The structure–optical property relationship constructed here is a straightforward approach to optimize the optoelectronic properties of halide double perovskites (HDPs) and further stimulate the development of next‐generation clear energy based on HDPs solar cells.

Low-dimensional quantum materials that remain strongly ferromagnetic down to mono layer thickness are highly desired for spintronic applications. Although oxide materials are important candidates for next generation of spintronic, ferromagnetism decays severely when the thickness is scaled to the nano meter regime, leading to deterioration of device performance. Here we report a methodology for maintaining strong ferromagnetism in insulating LaCoO3 (LCO) layers down to the thickness of a single unit cell. We find that the magnetic and electronic states of LCO are linked intimately to the structural parameters of adjacent "breathing lattice" SrCuO2 (SCO). As the dimensionality of SCO is reduced, the lattice constant elongates over 10% along the growth direction, leading to a significant distortion of the CoO6 octahedra, and promoting a higher spin state and long-range spin ordering. For atomically thin LCO layers, we observe surprisingly large magnetic moment (0.5 uB/Co) and Curie temperature (75 K), values larger than previously reported for any mono layer oxide. Our results demonstrate a strategy for creating ultra thin ferromagnetic oxides by exploiting atomic hetero interface engineering,confinement-driven structural transformation, and spin-lattice entanglement in strongly correlated materials., 24 pages, 5 figures, 1 supporting information with 13 figures

Despite the booming research in organometal halide perovskite solar cells (PSCs) of recent years, considerable roadblocks remain for their large-scale deployment, ranging from undesirable current-voltage hysteresis to inferior device stability. Among various plausible origins of hysteresis, interfacial ferroelectricity is particularly intriguing and warrants a close scrutiny. Here, we examine interfacial ferroelectricity in MAPbI

Strain engineering provides the ability to control the ground states and associated phase transition in the epitaxial films. However, the systematic study of intrinsic characters and their strain dependency in transition-metal nitrides remains challenging due to the difficulty in fabricating the stoichiometric and high-quality films. Here we report the observation of electronic state transition in highly crystalline antiferromagnetic CrN films with strain and reduced dimensionality. Shrinking the film thickness to a critical value of ~ 30 unit cells, a profound conductivity reduction accompanied by unexpected volume expansion is observed in CrN films. The electrical conductivity is observed surprisingly when the CrN layer as thin as single unit cell thick, which is far below the critical thickness of most metallic films. We found that the metallicity of an ultrathin CrN film recovers from an insulating behavior upon the removal of as-grown strain by fabrication of first-ever freestanding nitride films. Both first-principles calculations and linear dichroism measurements reveal that the strain-mediated orbital splitting effectively customizes the relatively small bandgap at the Fermi level, leading to exotic phase transition in CrN. The ability to achieve highly conductive nitride ultrathin films by harness strain-controlling over competing phases can be used for utilizing their exceptional characteristics., Comment: 24 pages, 5 figures

Spin state transition in perovskite cobaltite is delicately controlled by the competition between exchange interaction energy and crystal-field energy. The latter is mainly governed by the change of bond length and bonding angle. Previous work has revealed that the electronic configuration associated with spin state transition in $\mathrm{LaCo}{\mathrm{O}}_{3}$ (LCO) thin films can be effectively modulated by epitaxial strain. However, a systematic study on the spin state transition of $\mathrm{C}{\mathrm{o}}^{3+}$ ions in LCO films with different crystallographic symmetry is still missing. Here, keeping the in-plane strain unchanged, we report that the magnetization of LCO films can be manipulated with crystallographic symmetry. The ultrathin LCO layers, constrained by the cubic substrate, have pseudotetragonal structure and small magnetization. Upon increasing the layer thickness, the monoclinic structure dominates the LCO film and maximizes its ferromagnetism. For the LCO films with a thickness beyond 35 unit cells, the symmetry relaxes gradually towards its rhombohedral bulk form, and meanwhile the magnetization reduces. These results highlight the importance of spin-lattice entanglement in a ferroelastic material and provide a concise way to maximize its functionality using symmetry engineering.

The development of artificial synapses has enabled the establishment of brain-inspired computing systems, which provides a promising approach for overcoming the inherent limitations of current computer systems. The two-terminal memristors that faithfully mimic the function of biological synapses have intensive prospects in the neural network field. Here, we propose a high-performance artificial synapse based on oxide tunnel junctions with oxygen vacancy migration. Both short-term and long-term plasticities are mimicked in one device. The oxygen vacancy migration through oxide ultrathin films is utilized to manipulate long-term plasticity. Essential synaptic functions, such as paired pulse facilitation, post-tetanic potentiation, as well as spike-timing-dependent plasticity, are successfully implemented in one device by finely modifying the shape of the pre- and postsynaptic spikes. Ultralow femtojoule energy consumption comparable to that of the human brain indicates its potential application in efficient neuromorphic computing. Oxide tunnel junctions proposed in this work provide an alternative approach for realizing energy-efficient brain-like chips.

Structure determines material's functionality, and strain tunes the structure. Tuning the coherent epitaxial strain by varying the thickness of the films is a precise route to manipulate the functional properties in the low-dimensional oxide materials. Here, to explore the effects of the coherent epitaxial strain on the properties of SrCoO2.5 thin films, thickness-dependent evolutions of the structural properties and electronic structures were investigated by X-ray diffraction, Raman spectra, optical absorption spectra, scanning transmission electron microscopy (STEM), and first-principles calculations. By increasing the thickness of the SrCoO2.5 films, the c-axis lattice constant decreases, indicating the relaxation of the coherent epitaxial strain. The energy band gap increases and the Raman spectra undergo a substantial softening with the relaxation of the coherent epitaxial strain. From the STEM results, it can be concluded that the strain causes the variation of the oxygen content in the BM-SCO2.5 films, which results in the variation of band gaps with varying the strain. First-principles calculations show that strain-induced changes in bond lengths and angles of the octahedral CoO6 and tetrahedral CoO4 cannot explain the variation band gap. Our findings offer an alternative strategy to manipulate structural and electronic properties by tuning the coherent epitaxial strain in transition-metal oxide thin films.

The effects of target stoichiometry and growth conditions on the structure and properties of the monoclinic bismuth vanadate (BiVO4) (010) epitaxial films created using pulsed laser deposition were studied systematically. It is shown that phase-pure monoclinic BiVO4 epitaxial films were fabricated from a nonstoichiometric target with a bismuth/vanadium (Bi : V) ratio of 6 at 680 °C. The three-dimensional and adsorption-controlled growth process was confirmed using X-ray diffraction and atomic force microscopy. The valence states of Bi3+ and V5+ were determined from the results of X-ray photoelectron spectroscopy (XPS), indicating that the BiVO4 film has substantial stoichiometry. The results of the valence band XPS indicated that the Bi 6s energy level of the BiVO4 (010) film was located much deeper than that of the polycrystalline sample. The direct optical band gap of the BiVO4 film was found to be 2.59 eV. The photocatalytic oxidization activity of the single crystal BiVO4 film for rhodamine B degradation is about one order of magnitude higher in comparison with the polycrystalline sample, indicating that the nanostructured BiVO4 film is a promising material for obtaining better photocatalytic activity.

This work was supported by the Natural Sciences and Engineering Research Council of Canada (NSERC) Discovery Grant RGPIN-04178, the Ministry of Research, Innovation and Science (MRIS) Early Researcher Award, the National Natural Science Foundation of China (NSFC) Grant Nos. 11504192, 11674187, and 52001232, Shanghai Sailing Program (20YF1452000), the Shanghai Scientific and Technological Innovation Project (20ZR1460200) and the Fundamental Research Funds for the Central Universities. The work was also in part supported by the Canada First Research Excellence Fund. Work at MIT was supported by Army Research Office (W911NF-20-2-0061), the National Science Foundation (NSF-DMR 1700137), Office of Naval Research (N00014-20-1-2306) and Center for Integrated Quantum Materials (NSF-DMR 1231319) for financial support.

Recently, inspired by natural biological motor behavior, various actuators emerge at the historic moment. Actuator is a kind of device that converts input energy into mechanical motion, and the input energy can be triggered by various stimuli such as heat, light, and electric fields. However, present actuators usually are driven by a single stimulus, often showing poor performance with high power consumption. Here, a MXene and Low-Density Polyethylene based actuator with multiresponsive functions was fabricated via a facile drop-casting method. The electrically driven actuator shows a large offset distance (20 mm), with a low driving voltage of 1.5 V. The heat driven actuator can sense temperature gradient and capture object in the same way that flytraps do. Especially, finite element analysis was used to successfully verify the working mechanism. The light driven actuator is able to perform like a walking robot with a speed up to 16.52 mm min−1. It can perform as a light-controlled (or heat-controlled) switch and be integrated into a circuit being applied to some extreme occasions that require non-contact switches, for example, the current need for non-contact scenarios with COVID-19. This work also provides a new paradigm for expanding MXene applications.

Inorganic perovskites (CsPbX3, X = I−, Br− or Cl−) have got researchers attention in the photovoltaic community due to their exceptional photoelectric properties and high thermal stability. In this work, we have explained a two-step vapor deposition approach to fabricate the CsPbCl3 films. To improve the properties of CsPbCl3 perovskite, different reaction conditions and their influence on the structural, morphological and optical properties of resultant films were systematically examined. We found that the proposed deposition strategy has a wide reaction window and is viable for the preparation of uniform CsPbCl3 films. The optimal reaction conditions resulted in improved crystallinity, morphology and photoluminescence. The present work will provide beneficial guidance for high-quality CsPbCl3 and other CsPbX3 perovskite films for future optoelectronic applications.

Distinct from the conductive filament-type counterparts, the interface-type resistive switching (RS) devices are electroforming-free and exhibit bidirectionally continuous conductance changes, making them promising candidates as analog synapses. While the interface-type RS devices typically operate through the interfacial oxygen migration, materials which can tolerate a wide range of oxygen non-stoichiometry and possess high oxygen mobility are therefore demanded. SrFeOx (SFO), which can easily transform between a conductive, oxygenated perovskite SrFeO3 (PV-SFO) phase and an insulating, oxygen-vacancy-rich brownmillerite SrFeO2.5 (BM-SFO) phase under electric field, emerges as a suitable material. Herein, an interface-type RS device is ingeniously structured by two epitaxial SFO layers: a PV-SFO matrix layer and an ultrathin BM-SFO interfacial layer, aiming to leverage the oxygen migration-induced interfacial BM-PV phase transformation to realize the gradual conductance modulation. Experimentally, the fabricated device exhibits electroforming-free, analog memristive behavior. This device also emulates essential synaptic functions, including excitatory postsynaptic current, paired-pulse facilitation, transition from short-term memory to long-term memory, spike-timing-dependent plasticity, and potentiation/depression. A simulated neural network built from the SFO-based synapses achieves accuracies above 88% for image recognition. This work provides a novel approach to use the SFO family of topotactic materials for developing analog synapses as building blocks for neuromorphic computing circuits.

In this work, the surface structure of a single-domain epitaxial BiFeO3 film with (111) orientation was investigated by in situ grazing incidence X-ray diffraction and X-ray reflectivity. We found that a large strain gradient exists in the surface region (2–3 nm) of the BiFeO3 film. The strain gradient is approximately 107 m–1, which is 2 or 3 orders of magnitude larger than the value inside the film. Moreover, we found that a surface layer with a lower electron density compared with the underlying BiFeO3 layer exists on the surface of BiFeO3 film, and this layer exhibits an irreversible surface structure transition occurs at 500 K, which should be associated with the surface flexoelectric field. We considered that this large strain gradient is originated from the surface depolarization field of ferroelectrics. Our results suggest a coupling between the surface structure and the flexoelectricity and imply that the surface layer and properties would be controlled by the strain gradient in ferroelectric films.

The high aspect ratio nickel nanowires (NWs) with the different sizes and morphologies were synthesized by the improved chemical reduction method, dropping method. By simply adjusting the reaction conditions of the Ni2+ concentration and the precursor solution addition, the average diameter of Ni NWs can be tuned from 85 nm to 350 nm, and the length was about 40 μm. Moreover, the diameter of Ni NWs was more influenced by the Ni2+ concentration than the precursor solution addition and a simple empirical model has been proposed for this dependency. Meanwhile, the morphology change was also systematically investigated. Magnetic measurements showed that the diameter and aspect ratio of Ni NWs have no regular impact on the saturation magnetization and the squareness of Ni NWs. The Hc of Ni NWs was, however, a function of the aspect ratio rather than diameter, which is different from that of Ni NWs prepared by template method. The variation of Hc of Ni NWs can be described using the chain-of-sphere model.

The defect chemistry of perovskite oxides involves the cause to most of their abundant functional properties, including interface magnetism, charge transport, ionic exchange, and catalytic activity. The possibility to achieve dynamic control over oxygen anion vacancies offers a unique opportunity for the development of appealing switchable devices, which at present are commonly based on ferroelectric materials. Herein, we report the discovery of a switchable photovoltaic effect, that the sign of the open voltage and the short circuit current can be reversed by inverting the polarity of the applied field, upon electrically tailoring the distribution of oxygen vacancies in perovskite oxide films. This phenomenon is demonstrated in lateral photovoltaic devices based on both ferroelectric BiFeO3 and paraelectric SrTiO3 films, under a reversed applied field whose magnitude is much smaller than the coercivity value of BiFeO3. The migration of oxygen vacancies was directly observed by employing an advanced annul...

Despite of the tremendous efforts spent on the oxygen vacancy migration in determining the property optimization of oxygen-vacancy enrichment transition metal oxides, few has focused on their dynamic behaviors non-equilibrium states. In this work, we performed multi-timescale ultrafast X-ray diffraction measurements by using picosecond synchrotron X-ray pulses and femtosecond table-top X-ray pulses to monitor the structural dynamics in the oxygen-vacancy ordered SrCoO2.5 thin films. A giant photoinduced strain ({\Delta}c/c > 1%) was observed, whose distinct correlation with the pump photon energy indicates a non-thermal origin of the photoinduced strain. The sub-picosecond resolution X-ray diffraction reveals the formation and propagation of the coherent acoustic phonons inside the film. We also simulate the effect of photoexcited electron-hole pairs and the resulting lattice changes using the Density Function Theory method to obtain further insight on the microscopic mechanism of the measured photostriction effect. Comparable photostrictive responses and the strong dependence on excitation wavelength are predicted, revealing a bonding to anti-bonding charge transfer or high spin to intermediate spin crossover induced lattice expansion in the oxygen-vacancy films., Comment: 12 pages, 4 figures, support material

Nickel oxide (NiO) nanotubes were synthesized via a thermal oxidation process from Ni nanowires. The effects of oxidation temperature on the morphology, microstructures, and composition of nanowires were investigated using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results show that the Ni nanowires convert initially to Ni/NiO core-shell nanowires with increasing annealing temperatures, and then to the nanotubes at the critical transition temperature of about 425 &deg, C. Our findings provide useful information for the preparation of NiO nanotubes to meet the required applications.

Oxygen vacancies (Vo) play significant roles in determining the properties of transition-metal oxides. However, the concentration of Vo cannot be tuned quantitatively by optimizing the preparation conditions, and the precise control of Vo distribution at the atomic scale is even more challenging. Here, by controlling the reversible phase transitions between perovskite LaCoO3 (PV-LCO) and brownmillerite LaCoO2.5, we realize the tuning of Vo in PV-LCO, including the concentration with quantitative precision and the spatial distribution at the atomic scale. With the first principles calculations, we clarify that two thirds of Vo in PV-LCO can be eliminated after a cycle of the reversible phase transitions, and all the residual Vo are confined in specific lattice sites in PV-LCO. Such an ordered distribution of Vo can help to enhance the ferromagnetism of PV-LCO.

Organometal halide perovskite solar cells (PSCs) have emerged as one of the most promising photovoltaic technologies with efficiencies exceeding 20.3%. However, device stability problems including hysteresis in current–voltage scans must be resolved before the commercialization of PSCs. Transient absorption measurements and first-principles calculations indicate that the migration of oxygen vacancies in the TiO2 electrode under electric field during voltage scans contributes to the anomalous hysteresis in PSCs. The accumulation of oxygen vacancies at the electrode/perovskite interface slows down charge extraction while significantly speeding up charge recombination at the interface. Moreover, nonadiabatic molecular dynamics simulations reveal that the charge recombination rates at the interface depend sensitively (with 1 order of magnitude difference) on the locations of oxygen vacancies. By intentionally reducing oxygen vacancies in the TiO2 electrode, we substantially suppress unfavorable hysteresis in ...

The impact behavior of Fe-based amorphous coatings with various thicknesses fabricated by high-velocity-air-fuel thermal spraying was systematically investigated via 3D X-ray tomography. The results showed that the impact damage occurred principally by cracking in the coating, plastic deformation in the substrate, and delamination at the coating/substrate interface. It was found that the size of the interfacial delamination was a nonlinear function of the normalized coating thickness tc/a (i.e. the ratio of coating thickness (tc) to the contact radius (a)). Three thickness regions of distinctive damage modes were identified: thin coating region (tc/a ≤ 0.33), intermediate-thickness region (0.33 0.54). For tc/a ≤ 0.33, no delamination appeared in the coating/substrate interface. With an increase from tc/a = 0.33 to tc/a = 0.54, the extent of interfacial delamination increased quickly and reached a maximum. Finally, when tc/a > 0.54, the extent of delamination decreased when tc/a increased. In addition, it was indicated that the residual stress was found to decrease with the coating thickness, reflecting that the residual stress was excluded as a predominant factor of impact damage. Furthermore, a good agreement with the Hertz impact theory and finite element modeling was identified in the case of interfacial damage: significant delamination was observed in the 600 μm coating when the maximum shear stress occurred close to the coating/substrate interface. This finding can be used to assist the design of coated components in load-bearing applications.

Strontium substituted barium hexaferrites i.e., Ba 1 - x Sr x Fe 11 Cr 1 O 19 with x = 0.0–0.8 were prepared via co-precipitation technique. Single-phase magnetoplumbite structure was confirmed for all samples by X-ray diffraction, whereas scanning electron microscopy showed the variation in microstructure on Sr2+ substitution. Magnetic measurements revealed that the substitution causes prominent enhancement in saturation magnetization and coercive field for x = 0.4 sample. However, under same condition, decrease in real part of dielectric permittivity, dielectric loss tangent and ac conductivity were observed by impedance spectroscopy, while these parameters started to increase for x > 0.4. The dielectric permittivity exhibited frequency-dependent dispersive behavior due to Maxwell-Wagner interfacial polarization whereas weak ferroelectric hysteresis loops were obtained for the prepared samples. Moreover, it was found that the Sr2+ substitution substantially enhanced the resistive properties which is elucidated in term of localization of charge carrier’s mobility due to reduction in Fe 3 + - O - Fe 2 + network and microstructural variations. Here, it is proposed that x = 0.4 sample exhibits maximum magnetization (64 emu/g), moderate real part of dielectric permittivity at low frequency (>103), diminished dielectric loss tangent (~0.05) and colossal value of resistance (~1010 Ω) which makes this material interesting for high frequency applications.

Molybdenum disulfide (MoS2), as a classic two-dimensional material, is limited in applications with its relatively poor conductivity and chemical instability due to its single morphology/phase structure in electrocatalytic activity and specific capacitance. Moreover, up to date, it is still an open area in establishing cost-effective approaches to fabricate exotic MoS2 nanostructures with desired morphology and phase component for exhibiting excellent performance in energy conversion and storage. Herein, only using extremely ordinary sources of molybdenum and sulfur and a simple one-pot hydrothermal method, we efficiently and economically synthesized two types of stable MoS2 nanostructures with a certain percentage of the metastable metallic (1T) phase, i.e., spherical nanoflowers (SNF) and random nanosheets (RNS). Both SNF–MoS2 and RNS-MoS2 exhibited excellent electrocatalytic activity for hydrogen evolution reaction with ultra-high stability and high specific capacitance. These remarkable properties are due to the dramatically increased number of active sites in these unique nanostructures and their enhanced electric conductivities due to the metallic 1T phase. Furthermore, when these two types of nanostructures are physical decorated with carbon black, their electrocatalysis is further enhanced. Our findings offer an economical approach to fabricate stable MoS2-based nanomaterials for practical applications with highly efficient energy conversion and energy storage.

Nickel sulfides (NiSx) as promising catalysts for hydrogen evolution reaction (HER) have attracted much interest. However, the HER catalytic activities of NiSx reported are relatively low for their poor electrical conductivity. The HER catalytic performance of NiSx is expected to be further enhanced by increasing their electronic conductivity. Constructing heterostructures consisting of noble metal and semiconductor has been proven to be an efficient method to promote their physicochemical performances benefitting from synergistic effects along the metal-semiconductor interface. Here, Au-NiSx heterostructures including core@shell, yolk-shell, and oligomer-like structures have been designed and synthesized by different solvothermal methods. A formation mechanism involving the Kirkendall effect has been proposed for the yolk-shell structure with an empty space around the Au core rather than the seeded grown core@shell structure. Catalytic performance measurements indicate that the Au@NiSx core@shell nanoparticles (NPs) exhibit superior HER catalytic property to Au-NiSx yolk-shell, oligomer-like structures, and “pure” NiSx NPs, resulting from the electron transfer between Au and NiSx interfaces. The overpotentials of Au-NiSx NPs with core@shell and yolk-shell nanostructures are 253 mV and 263 mV at 10 mA/cm2, respectively, which are lower than those of oligomer-like Au-NiSx (283 mV) and pure NiSx (321 mV) NPs. The Tafel slope of Au@NiSx core@shell structure (43.7 mV/dec) is also the lowest. These results demonstrate that the core@shell NPs possess the best HER performances, followed by their yolk-shell and oligomer-like counterparts. These findings confirm that the physicochemical performances of the metal-semiconductor heterostructures can be efficiently optimized by adjusting the electron transfer through the interface structure control.

The SnO thin films have been deposited on quartz glass substrates using an e-beam evaporation system at room temperature and different post-deposition thermal treatments have been carried out. In case of annealing in air, n-type polycrystalline SnO films are obtained after annealing at 300 °C and 400 °C, respectively. For the 500 °C annealed film, SnO2 phase is generated due to the strong oxidation. However, when annealed in vacuum, pure p-type polycrystalline SnO films are produced. The feasible and controllable methods of p- and n-type SnO films contributes to the development of high performance devices.

Organic-inorganic hybrid perovskite solar cells have shown great prospect as a low-cost and high efficiency photovoltaic technology. The quality of the perovskite absorber layer is most critical to the performance of the device, and the stability remains one of the challenging issues. In this paper, the Cesium (Cs) doping perovskite film was prepared from nonstoichiometric precursor solution in ambient and humidity-controlled conditions. The results showed that the crystallinity, uniformity, absorption, Photo-luminescence intensity and the thermal stability of these films can be effectively improved compared with the films fabricated from stoichiometric one, which is attributed to the combined effect of the Cs doping and excess methylammonium cations passivation. Finally, the highest efficiency of the perovskite solar cells fabricated from nonstoichiometric solution reached to 14.1%, which is 12.8% higher than that of the control device from stoichiometric solution (12.5%). Furthermore, the device displayed the high stability and efficiency degradation of only 2% occurring over a period of 5 weeks in ambient air without encapsulation. This reported work provides a pathway for further improving the performance of perovskite solar cells with higher stability.

Perovskite-structured (ABO3) transition metal oxides are promising bifunctional electrocatalysts for efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). In this paper, a set of epitaxial rare-earth nickelates (RNiO3) thin films is investigated with controlled A-site isovalent substitution to correlate their structure and physical properties with ORR/OER activities, examined by using a three-electrode system in O2-saturated 0.1 m KOH electrolyte. The ORR activity decreases monotonically with decreasing the A-site element ionic radius which lowers the conductivity of RNiO3 (R = La, La0.5Nd0.5, La0.2Nd0.8, Nd, Nd0.5Sm0.5, Sm, and Gd) films, with LaNiO3 being the most conductive and active. On the other hand, the OER activity initially increases upon substituting La with Nd and is maximal at La0.2Nd0.8NiO3. Moreover, the OER activity remains comparable within error through Sm-doped NdNiO3. Beyond that, the activity cannot be measured due to the potential voltage drop across the film. The improved OER activity is ascribed to the partial reduction of Ni3+ to Ni2+ as a result of oxygen vacancies, which increases the average occupancy of the eg antibonding orbital to more than one. The work highlights the importance of tuning A-site elements as an effective strategy for balancing ORR and OER activities of bifunctional electrocatalysts. MOE (Min. of Education, S’pore)

Aligned Ni nanowire (NW) arrays were investigated for terahertz (THz) wave modulation. By adjusting the NW density and order of the NW arrays, the resonant frequency and intensity of the THz waves can be effectively tuned. The tuning range of the resonant frequency is about 0.29 THz, and a transmittance of less than 40% in the frequency region from 0.5 to 2 THz is achieved by changing the NW density. Although the order of the NW arrays has no influence on the resonant frequency, the transmittance can be tuned about 21%. The ability to tune the intensity and resonant frequency effectively and the ease of fabrication of the Ni-NW arrays make them the potential candidates for THz tunable filters, intensity modulators, and spatial light modulators.

Ferroelectricity has been believed unable to coexist with metallicity since the free carriers can screen the internal Coulomb interactions of dipoles. Very recently, one kind of material called ferroelectric metal was reexamined. Here, we report the coexistence of metallicity and polar distortion in a candidate for ferroelectric metal $\mathrm{PbT}{\mathrm{i}}_{1\text{\ensuremath{-}}x}\mathrm{N}{\mathrm{b}}_{x}{\mathrm{O}}_{3}$ via doping engineering. The ferroelectriclike polar distortion in all the doped $\mathrm{PbT}{\mathrm{i}}_{1\text{\ensuremath{-}}x}\mathrm{N}{\mathrm{b}}_{x}{\mathrm{O}}_{3}$, with $x$ ranging from 0.04 to 0.12, was observed by the piezoresponse force microscopy and the scanning transmission electron microscopy measurements. $\mathrm{PbT}{\mathrm{i}}_{1\text{\ensuremath{-}}x}\mathrm{N}{\mathrm{b}}_{x}{\mathrm{O}}_{3}$ films become more conductive with more doping density, and a metallic behavior emerges when $x$ reaches 0.12. Our first-principles calculations further revealed that the doped Nb ions in the films can only provide free electrons, but are not able to damage the dipoles in unit cells even with the heaviest doping density of 0.12. We believe that these results confirm a feasibility of realizing the coexistence of metallicity and polar distortion for other ferroelectrics in a common way, and motivate the synthesis of some new materials with artificially designed properties even incompatible in nature.

Controlling functionalities, such as magnetism or ferroelectricity, by means of oxygen vacancies (${V}_{\mathrm{O}}$) is a key issue for the future development of transition-metal oxides. Progress in this field is currently addressed through ${V}_{\mathrm{O}}$ variations and their impact on mainly one order parameter. Here we reveal a mechanism for tuning both magnetism and ferroelectricity simultaneously by using ${V}_{\mathrm{O}}$. Combining experimental and density-functional theory studies of $\mathrm{E}{\mathrm{u}}_{0.5}\mathrm{B}{\mathrm{a}}_{0.5}\mathrm{Ti}{\mathrm{O}}_{3\ensuremath{-}\ensuremath{\delta}}$, we demonstrate that oxygen vacancies create $\mathrm{T}{\mathrm{i}}^{3+}\phantom{\rule{4pt}{0ex}}3{d}^{1}$ defect states, mediating the ferromagnetic coupling between the localized Eu $4{f}^{7}$ spins, and increase an off-center displacement of Ti ions, enhancing the ferroelectric Curie temperature. The dual function of Ti sites also promises a magnetoelectric coupling in the $\mathrm{E}{\mathrm{u}}_{0.5}\mathrm{B}{\mathrm{a}}_{0.5}\mathrm{Ti}{\mathrm{O}}_{3\ensuremath{-}\ensuremath{\delta}}$.

Artificial superlattices constructed with ferromagnetic La0.7Sr0.3MnO3 layer and ferroelectric Ba0.7Sr0.3TiO3 layer were designed and fabricated on SrTiO3 substrates. An epitaxial growth with sharp interfaces between La0.7Sr0.3MnO3 and Ba0.7Sr0.3TiO3 layers was confirmed by scanning transmission electron microscopy and x-ray diffraction. An unambiguous charge transfer involving an electron transferring from the La0.7Sr0.3MnO3 layers to Ba0.7Sr0.3TiO3 layers (Mn3+→Mn4+; Ti4+→Ti3+) across the interface were resolved by electron energy loss spectra analysis. These observations are attributed to the possible modification in the stereochemistry of the Ti and Mn ions in the interfacial region. The out-of-plane lattice parameter, Curie temperature, and magnetoresistance are strongly affected by the thicknesses of the La0.7Sr0.3MnO3 and Ba0.7Sr0.3TiO3 layers. Huge magnetoresistance subsisting to low temperature was also observed in the La0.7Sr0.3MnO3/Ba0.7Sr0.3TiO3 superlattices. All spectral changes identified at a nanometer scale and their potential effect on the degradation of magnetic and transport properties at a macroscopic level. These findings highlight the importance of dependence on sublayer thickness, illustrating the high degree of tenability in these artificially low-dimensional oxide materials.

BiFeO 3 (BFO) thin films with BaTiO 3 (BTO) or SrTiO 3 (STO) as buffer layer were epitaxially grown on SrRuO 3 -covered SrTiO 3 substrates. X-ray diffraction measurements show that the BTO buffer causes tensile strain in the BFO films, whereas the STO buffer causes compressive strain. Different ferroelectric domain structures caused by these two strain statuses are revealed by piezoelectric force microscopy. Electrical and magnetical measurements show that the tensile-strained BFO/BTO samples have reduced leakage current and large ferroelectric polarization and magnetization, compared with compressively strained BFO/STO. These results demonstrate that the electrical and magnetical properties of BFO thin films can be artificially modified by using a buffer layer.

We investigated the effects of oxygen vacancies on the structural, magnetic, and transport properties of La1– x Sr x MnO3 ( x =0.1, 0.2, 0.33, 0.4, and 0.5) grown around a critical point (without/with oxygen vacancies) under low oxygen pressure (10 Pa) and high oxygen pressure (40 Pa). We found that all films exhibit ferromagnetic behavior below the magnetic critical temperature, and that the films grown under low oxygen pressures have degraded magnetic properties with lower Curie temperatures and smaller magnetic moments. These results show that in epitaxial La1– x Sr x MnO3 thin films, the magnetic and transport properties are very sensitive to doping concentration and oxygen vacancies. Phase diagrams of the films based on the doping concentration and oxygen vacancies were plotted and discussed.

The ultrafast laser-excited magnetization dynamics of ferromagnetic (FM) La0.67Sr0.33MnO3 (LSMO) thin films with BiFeO3 (BFO) coating layers grown by laser molecular beam epitaxy are investigated using the optical pump-probe technique. Uniform magnetization precessions are observed in the films under an applied external magnetic field by measuring the time-resolved magneto-optical Kerr effect. The magnetization precession frequencies of the LSMO thin films with the BFO coating layers are lower than those of uncoated LSMO films, which is attributed to the suppression of the anisotropy field induced by the exchange interaction at the interface between the antiferromagnetic order of BFO and the FM order of LSMO.

The properties of perovskite nickelates are very sensitive to their oxygen content, which allows us to tune their electronic structures by varying the oxygen partial pressure during film deposition. Under the optimized condition, we have obtained GdNiO3 films that are sensitive to a wide spectrum of light. By combining the GdNiO3 film with Nb-doped SrTiO3 to form a heterojunction, we design a self-powered photodetector with high sensitivity toward light with a wavelength between 650 nm and 365 nm. Under 365 nm illumination (50 μW/cm2), the device shows a responsivity of 0.23 A/W at 0 V bias, comparable to or even better than the ultraviolet photodetectors made of semiconductor materials such as GaN or ZnO. The photo-dark ratio can be close to 103 when the power light density reaches 0.6 mW/cm2. Moreover, the device performance is very stable without any decay after 6 months. MOE (Min. of Education, S’pore) Published version