Acceleration of radiative recombination for efficient perovskite LEDs.

The increasing demands for more efficient and brighter thin-film light-emitting diodes (LEDs) in flat-panel display and solid-state lighting applications have promoted research into three-dimensional (3D) perovskites. These materials exhibit high charge mobilities and low quantum efficiency droop1-6, making them promising candidates for achieving efficient LEDs with enhanced brightness. To improve the efficiency of LEDs, it is crucial to minimize nonradiative recombination while promoting radiative recombination. Various passivation strategies have been used to reduce defect densities in 3D perovskite films, approaching levels close to those of single crystals3. However, the slow radiative (bimolecular) recombination has limited the photoluminescence quantum efficiencies (PLQEs) of 3D perovskites to less than 80% (refs. 1,3), resulting in external quantum efficiencies (EQEs) of LED devices of less than 25%. Here we present a dual-additive crystallization method that enables the formation of highly efficient 3D perovskites, achieving an exceptional PLQE of 96%. This approach promotes the formation of tetragonal FAPbI3 perovskite, known for its high exciton binding energy, which effectively accelerates the radiative recombination. As a result, we achieve perovskite LEDs with a record peak EQE of 32.0%, with the efficiency remaining greater than 30.0% even at a high current density of 100 mA cm-2. These findings provide valuable insights for advancing the development of high-efficiency and high-brightness perovskite LEDs.

In-plane charged domain walls with memristive behaviour in a ferroelectric film.

Domain-wall nanoelectronics is considered to be a new paradigm for non-volatile memory and logic technologies in which domain walls, rather than domains, serve as an active element. Especially interesting are charged domain walls in ferroelectric structures, which have subnanometre thicknesses and exhibit non-trivial electronic and transport properties that are useful for various nanoelectronics applications1-3. The ability to deterministically create and manipulate charged domain walls is essential to realize their functional properties in electronic devices. Here we report a strategy for the controllable creation and manipulation of in-plane charged domain walls in BiFeO3 ferroelectric films a few nanometres thick. By using an in situ biasing technique within a scanning transmission electron microscope, an unconventional layer-by-layer switching mechanism is detected in which ferroelectric domain growth occurs in the direction parallel to an applied electric field. Based on atomically resolved electron energy-loss spectroscopy, in situ charge mapping by in-line electron holography and theoretical calculations, we show that oxygen vacancies accumulating at the charged domain walls are responsible for the domain-wall stability and motion. Voltage control of the in-plane domain-wall position within a BiFeO3 film gives rise to multiple non-volatile resistance states, thus demonstrating the key functional property of being a memristor a few unit cells thick. These results promote a better understanding of ferroelectric switching behaviour and provide a new strategy for creating unit-cell-scale devices.

Two-Dimensional Superconductivity at the LaAlO_{3}/KTaO_{3}(110) Heterointerface.

We report on the observation of a T_{c}∼0.9 K superconductivity at the interface between LaAlO_{3} film and the 5d transition metal oxide KTaO_{3}(110) single crystal. The interface shows a large anisotropy of the upper critical field, and its superconducting transition is consistent with a Berezinskii-Kosterlitz-Thouless transition. Both facts suggest that the superconductivity is two-dimensional (2D) in nature. The carrier density measured at 5 K is ∼7×10^{13} cm^{-2}. The superconducting layer thickness and coherence length are estimated to be ∼8 and ∼30 nm, respectively. Our result provides a new platform for the study of 2D superconductivity at oxide interfaces.

Atomic-Scale Control of Magnetism at the Titanite-Manganite Interfaces.

Complex oxide thin-film heterostructures often exhibit magnetic properties different from those known for bulk constituents. This is due to the altered local structural and electronic environment at the interfaces, which affects the exchange coupling and magnetic ordering. The emergent magnetism at oxide interfaces can be controlled by ferroelectric polarization and has a strong effect on spin-dependent transport properties of oxide heterostructures, including magnetic and ferroelectric tunnel junctions. Here, using prototype La2/3Sr1/3MnO3/BaTiO3 heterostructures, we demonstrate that ferroelectric polarization of BaTiO3 controls the orbital hybridization and magnetism at heterointerfaces. We observe changes in the enhanced orbital occupancy and significant charge redistribution across the heterointerfaces, affecting the spin and orbital magnetic moments of the interfacial Mn and Ti atoms. Importantly, we find that the exchange coupling between Mn and Ti atoms across the interface is tuned by ferroelectric polarization from ferromagnetic to antiferromagnetic. Our findings provide a viable route to electrically control complex magnetic configurations at artificial multiferroic interfaces, taking a step toward low-power spintronics.

Selective Exposure of Robust Perovskite Layer of Aurivillius-Type Compounds for Stable Photocatalytic Overall Water Splitting.

Aurivillius-type compounds ((Bi2 O2 )2+ (An -1 Bn O3 n +1 )2- ) with alternately stacked layers of bismuth oxide (Bi2 O2 )2+ and perovskite (An -1 Bn O3 n +1 )2- are promising photocatalysts for overall water splitting due to their suitable band structures and adjustable layered characteristics. However, the self-reduction of Bi3+ at the top (Bi2 O2 )2+ layers induced by photogenerated electrons during photocatalytic processes causes inactivation of the compounds as photocatalysts. Here, using Bi3 TiNbO9 as a model photocatalyst, its surface termination is modulated by acid etching, which well suppresses the self-corrosion phenomenon. A combination of comprehensive experimental investigations together with theoretical calculations reveals the transition of the material surface from the self-reduction-sensitive (Bi2 O2 )2+ layer to the robust (BiTiNbO7 )2- perovskite layer, enabling effective electron transfer through surface trapping and effective hole transfer through surface electric field, and also efficient transfer of the electrons to the cocatalyst for greatly enhanced photocatalytic overall water splitting. Moreover, this facile modification strategy can be readily extended to other Aurivillius compounds (e.g., SrBi2 Nb2 O9 , Bi4 Ti3 O12 , and SrBi4 Ti4 O15 ) and therefore justify its usefulness in rationally tailoring surface structures of layered photocatalysts for high photocatalytic overall water-splitting activity and stability.

Interface-engineered ferroelectricity of epitaxial Hf0.5Zr0.5O2 thin films.

Ferroelectric hafnia-based thin films have attracted intense attention due to their compatibility with complementary metal-oxide-semiconductor technology. However, the ferroelectric orthorhombic phase is thermodynamically metastable. Various efforts have been made to stabilize the ferroelectric orthorhombic phase of hafnia-based films such as controlling the growth kinetics and mechanical confinement. Here, we demonstrate a key interface engineering strategy to stabilize and enhance the ferroelectric orthorhombic phase of the Hf0.5Zr0.5O2 thin film by deliberately controlling the termination of the bottom La0.67Sr0.33MnO3 layer. We find that the Hf0.5Zr0.5O2 films on the MnO2-terminated La0.67Sr0.33MnO3 have more ferroelectric orthorhombic phase than those on the LaSrO-terminated La0.67Sr0.33MnO3, while with no wake-up effect. Even though the Hf0.5Zr0.5O2 thickness is as thin as 1.5 nm, the clear ferroelectric orthorhombic (111) orientation is observed on the MnO2 termination. Our transmission electron microscopy characterization and theoretical modelling reveal that reconstruction at the Hf0.5Zr0.5O2/ La0.67Sr0.33MnO3 interface and hole doping of the Hf0.5Zr0.5O2 layer resulting from the MnO2 interface termination are responsible for the stabilization of the metastable ferroelectric phase of Hf0.5Zr0.5O2. We anticipate that these results will inspire further studies of interface-engineered hafnia-based systems.

Surface Oxygen Vacancies Confined by Ferroelectric Polarization for Tunable CO Oxidation Kinetics.

Surface oxygen vacancies have been widely discussed to be crucial for tailoring the activity of various chemical reactions from CO, NO, to water oxidation by using oxide-supported catalysts. However, the real role and potential function of surface oxygen vacancies in the reaction remains unclear because of their very short lifetime. Here, it is reported that surface oxygen vacancies can be well confined electrostatically for a polarization screening near the perimeter interface between Pt {111} nanocrystals and the negative polar surface (001) of ferroelectric PbTiO3. Strikingly, such a catalyst demonstrates a tunable catalytic CO oxidation kinetics from 200 °C to near room temperature by increasing the O2 gas pressure, accompanied by the conversion curve from a hysteresis-free loop to one with hysteresis. The combination of reaction kinetics, electronic energy loss spectroscopy (EELS) analysis, and density functional theory (DFT) calculations, indicates that the oxygen vacancies stabilized by the negative polar surface are the active sites for O2 adsorption as a rate-determining step, and then dissociated O moves to the surface of the Pt nanocrystals for oxidizing adsorbed CO. The results open a new pathway for tunable catalytic activity of CO oxidation.

Electric field control of superconductivity at the LaAlO3/KTaO3(111) interface.

The oxide interface between LaAlO3 and KTaO3(111) can harbor a superconducting state. We report that by applying a gate voltage (V G) across KTaO3, the interface can be continuously tuned from superconducting into insulating states, yielding a dome-shaped T c-V G dependence, where T c is the transition temperature. The electric gating has only a minor effect on carrier density but a strong one on mobility. We interpret the tuning of mobility in terms of change in the spatial profile of the carriers in the interface and hence, effective disorder. As the temperature is decreased, the resistance saturates at the lowest temperature on both superconducting and insulating sides, suggesting the emergence of a quantum metallic state associated with a failed superconductor and/or fragile insulator.

Interface-engineered electron and hole tunneling.

Although the phenomenon of tunneling has been known since the advent of quantum mechanics, it continues to enrich our understanding of many fields of science. Commonly, this effect is described in terms of electrons traversing the potential barrier that exceeds their kinetic energy due to the wave nature of electrons. This picture of electron tunneling fails, however, for tunnel junctions, where the Fermi energy lies sufficiently close to the insulator valence band, in which case, hole tunneling dominates. We demonstrate the deterministic control of electron and hole tunneling in interface-engineered Pt/BaTiO3/La0.7Sr0.3MnO3 ferroelectric tunnel junctions by reversal of tunneling electroresistance. Our electrical measurements, electron microscopy and spectroscopy characterization, and theoretical modeling unambiguously point out to electron or hole tunneling regimes depending on interface termination. The interface control of the tunneling regime offers designed functionalities of electronic devices.

Overcoming the Limits of the Interfacial Dzyaloshinskii-Moriya Interaction by Antiferromagnetic Order in Multiferroic Heterostructures.

Topologically protected magnetic states have a variety of potential applications in future spintronics owing to their nanoscale size (<100 nm) and unique dynamics. These fascinating states, however, usually are located at the interfaces or surfaces of ultrathin systems due to the short interaction range of the Dzyaloshinskii-Moriya interaction (DMI). Here, magnetic topological states in a 40-unit cells (16 nm) SrRuO3 layer are successfully created via an interlayer exchange coupling mechanism and the interfacial DMI. By controlling the thickness of an antiferromagnetic and ferromagnetic layer, interfacial ionic polarization, as well as the transformation between ferromagnetic and magnetic topological states, can be modulated. Using micromagnetic simulations, the formation and stability of robust magnetic skyrmions in SrRuO3 /BiFeO3 heterostructures are elucidated. Magnetic skyrmions in thick multiferroic heterostructures are promising for the development of topological electronics as well as rendering a practical approach to extend the interfacial topological phenomena to bulk via antiferromagnetic order.

Electronic and nanostructure engineering of bifunctional MoS2 towards exceptional visible-light photocatalytic CO2 reduction and pollutant degradation.

With recently increasing environmental issues and foreseeable energy crisis, it is desirable to design cheap, efficient, and visible-light responsive nano-photocatalyst for CO2 conversion and pollutant degradation. Herein, we report a flower-like of MoS2-based hybrid photocatalyst with high efficiency through nanostructure and electronic structure engineering. Nanostructure control is used to fabricate MoS2 in to flower-like nanosheets (NSs) with large surface active area. Then MoS2 is coupled with conduction-band edge matched tin dioxide (SnO2) and decorated with Ag nanoparticles for suitable work function to create a unique cascade band alignment electronic structure to facilitate photoexcited charge transfer. It is shown that the amount-optimized nanocomposite of SnO2/Ag/MoS2 exhibits exceptional visible-light photocatalytic activities for conversion of carbon dioxide (CO2) to methane (CH4), approximately one order of magnitude enhancement than original MoS2 with the apparent quantum efficiency 2.38% at 420 nm. Similarly, the optimized sample also shows high activities for 2,4-diclorophenol, Methylene-Blue, Rhodamine-B and Methyl-Orange degradation as compared to pure MoS2. It is clearly demonstrated through combination of hydroxyl radical evaluation, photoelectrochemical and electrochemical impedance, that the enhanced photoactivities are attributed to the increased specific surface area, optimized band alignment for charge transfer and suppressed recombination. Our current work provides feasible routes for further research.