Reconfigurable Resistive Switching in VO2/La0.7Sr0.3MnO3/Al2O3 (0001) Memristive Devices for Neuromorphic Computing.

The coexistence of nonvolatile and volatile switching modes in a single memristive device provides flexibility to emulate both neuronal and synaptic functions in the brain. Furthermore, such a device structure may eliminate the need for additional circuit elements such as transistor-based selectors, enabling low-power consumption and high-density device integration in fully memristive spiking neural networks. In this work, we report dual resistive switching (RS) modes in VO2/La0.7Sr0.3MnO3 (LSMO) bilayer memristive devices. Specifically, the nonvolatile RS is driven by the movement of oxygen vacancies (Vo) at the VO2/LSMO interface and requires a higher biasing voltage, whereas the volatile RS is controlled by the metal-insulator transition (MIT) of VO2 under a lower biasing voltage. The simple device structure is electrically driven between the two RS modes and thus can operate as a one selector-one resistor (1S1R) cell, which is a desirable feature in memristive crossbar arrays to avoid the sneak-path current issue. The RS modes are found to be stable and repeatable and can be reconfigured by exploiting the interfacial and phase transition properties, and thus, they hold great promise for applications in memristive neural networks and neuromorphic computing.

Hydrogen-Driven Low-Temperature Topotactic Transition in Nanocomb Cobaltite for Ultralow Power Ionic-Magnetic Coupled Applications.

We reversibly control ferromagnetic-antiferromagnetic ordering in an insulating ground state by annealing tensile-strained LaCoO3 films in hydrogen. This ionic-magnetic coupling occurs due to the hydrogen-driven topotactic transition between perovskite LaCoO3 and brownmillerite La2Co2O5 at a lower temperature (125-200 °C) and within a shorter time (3-10 min) than the oxygen-driven effect (500 °C, tens of hours). The X-ray and optical spectroscopic analyses reveal that the transition results from hydrogen-driven filling of correlated electrons in the Co 3d-orbitals, which successively releases oxygen by destabilizing the CoO6 octahedra into CoO4 tetrahedra. The transition is accelerated by surface exchange, diffusion of hydrogen in and oxygen out through atomically ordered oxygen vacancy "nanocomb" stripes in the tensile-strained LaCoO3 films. Our ionic-magnetic coupling with fast operation, good reproducibility, and long-term stability is a proof-of-principle demonstration of high-performance ultralow power magnetic switching devices for sensors, energy, and artificial intelligence applications, which are keys for attaining carbon neutrality.

Growth of emergent simple pseudo-binary ferroelectrics and their potential in neuromorphic computing devices.

Ferroelectric memory devices such as ferroelectric memristors, ferroelectric tunnel junctions, and field-effect transistors are considered among the most promising candidates for neuromorphic computing devices. The promise arises from their defect-independent switching mechanism, low energy consumption and high power efficiency, and important properties being aimed for are reliable switching at high speed, excellent endurance, retention, and compatibility with complementary metal-oxide-semiconductor (CMOS) technology. Binary or doped binary materials have emerged over conventional complex-composition ferroelectrics as an optimum solution, particularly in terms of CMOS compatibility. The current state-of-the-art route to achieving superlative ferroelectric performance of binary oxides is to induce ferroelectricity at the nanoscale, e.g., in ultra-thin films of doped HfO2, ZrO2, Zn1-xMgxO, Al-xScxN, and Bi1-xSmxO3. This short review article focuses on the materials science of emerging new ferroelectric materials, including their different properties such as remanent polarization, coercive field, endurance, etc. The potential of these materials is discussed for neuromorphic applications.

High-performance and self-powered visible light photodetector using multiple coupled synergetic effects.

In this work, we demonstrate, for the first time, that coupling together the pyroelectric effect, the photovoltaic effect and the plasmonic effect is a novel method to significantly enhance the performance of self-powered photodetectors in the visible region. Photodetectors based on tri-layered heterojunction of n-Si/p-SnO/n-ZnO through the inclusion of silver (Ag) nanoparticles (NPs) at the SnO/ZnO interface were fabricated. The photo-response of the device, with excitation from a chopped 650 nm wavelength laser, was carefully investigated, and it was shown that the photodetector performance is enhanced the most with the inclusion of spheroidal Ag NPs with ∼70 nm diameter. The Al/Si/SnO/Ag NPs/ZnO/ITO device exhibited an optimum responsivity, detectivity and sensitivity of 210.2 mA W-1, 5.47 × 109 Jones and 15.0 × 104, respectively, together with a rise and fall time of 2.3 and 51.3 µs, respectively, at a laser power density of 317 mW cm-2 and at a chopper frequency of 10 Hz. The present photodetectors are more than twice as responsive as the current best-performing ZnO-based pyro-phototronic photodetectors and they also exhibit other competitive features, such as detectivity, and fall and rise times. Therefore, by exploiting the plasmonic effect of the Ag NPs together with the pyroelectric effect in a ZnO film, and the photovoltaic effect at a Si/SnO junction, all in a single device, photodetectors were developed with state-of-the-art performance for the visible region.

La-doped BaSnO3 for electromagnetic shielding transparent conductors.

In this work, we find that La-doped BaSnO3 (BLSO) is shown to be a promising electromagnetic shielding transparent conductor. While films grown on industrially practical optoelectronic MgAl2O4 substrates have higher sheet resistance by three orders of magnitude than in previous reports, we show how to recover the sheet resistance close to the single-crystal level by use of an MgO template layer which enables high quality (001)-oriented BLSO epitaxial film growth on (001) MgAl2O4. There is a positive correlation between crystallinity and conductivity; high crystallinity minimizes scattering of free electrons. By applying this design principle to 5-20% doped films, we find that highly crystalline 5% La-doped BLSO films exhibit low sheet resistance of ~ 8.7 Ω â–¯ -1, high visible transmittance of ~ 80%, and high X-band electromagnetic shielding effectiveness of ~ 25.9 dB, thus outperforming transparent conducting oxides films of Sn-doped In2O3 and SrMoO3.

Self-Assembled Au Nanoelectrodes: Enabling Low-Threshold-Voltage HfO2-Based Artificial Neurons.

Filamentary-type resistive switching devices, such as conductive bridge random-access memory and valence change memory, have diverse applications in memory and neuromorphic computing. However, the randomness in filament formation poses challenges to device reliability and uniformity. To overcome this issue, various defect engineering methods have been explored, including doping, metal nanoparticle embedding, and extended defect utilization. In this study, we present a simple and effective approach using self-assembled uniform Au nanoelectrodes to controll filament formation in HfO2 resistive switching devices. By concentrating the electric field near the Au nanoelectrodes within the BaTiO3 matrix, we significantly enhanced the device stability and reduced the threshold voltage by up to 45% in HfO2-based artificial neurons compared to the control devices. The threshold voltage reduction is attributed to the uniformly distributed Au nanoelectrodes in the insulating matrix, as confirmed by COMSOL simulation. Our findings highlight the potential of nanostructure design for precise control of filamentary-type resistive switching devices.

Comprehensive study of Raman optical response of typical substrates for thin-film growth under 633†nm and 785†nm laser excitation.

Raman spectroscopy is one of the most efficient and non-destructive techniques for characterizing materials. However, it is challenging to analyze thin films using Raman spectroscopy since the substrates beneath the thin film often obscure its optical response. Here, we evaluate the suitability of fourteen commonly employed single-crystal substrates for Raman spectroscopy of thin films using 633 nm and 785 nm laser excitation systems. We determine the optimal wavenumber ranges for thin-film characterization by identifying the most prominent Raman peaks and their relative intensities for each substrate and across substrates. In addition, we compare the intensity of background signals across substrates, which is essential for establishing their applicability for Raman detection in thin films. The substrates LaAlO3 and Al2O3 have the largest free spectral range for both laser systems, while Al2O3 has the lowest background levels, according to our findings. In contrast, the substrates SrTiO3 and Nb:SrTiO3 have the narrowest free spectral range, while GdScO3, NGO and MgO have the highest background levels, making them unsuitable for optical investigations.

Low Temperature Epitaxial LiMn2O4 Cathodes Enabled by NiCo2O4 Current Collector for High-Performance Microbatteries.

Epitaxial cathodes in lithium-ion microbatteries are ideal model systems to understand mass and charge transfer across interfaces, plus interphase degradation processes during cycling. Importantly, if grown at <450 °C, they also offer potential for complementary metal-oxide-semiconductor (CMOS) compatible microbatteries for the Internet of Things, flexible electronics, and MedTech devices. Currently, prominent epitaxial cathodes are grown at high temperatures (>600 °C), which imposes both manufacturing and scale-up challenges. Herein, we report structural and electrochemical studies of epitaxial LiMn2O4 (LMO) thin films grown on a new current collector material, NiCo2O4 (NCO). We achieve this at the low temperature of 360 °C, ∼200 °C lower than existing current collectors SrRuO3 and LaNiO3. Our films achieve a discharge capacity of >100 mAh g-1 for ∼6000 cycles with distinct LMO redox signatures, demonstrating long-term electrochemical stability of our NCO current collector. Hence, we show a route toward high-performance microbatteries for a range of miniaturized electronic devices.

Bandlike Transport and Charge-Carrier Dynamics in BiOI Films.

Following the emergence of lead halide perovskites (LHPs) as materials for efficient solar cells, research has progressed to explore stable, abundant, and nontoxic alternatives. However, the performance of such lead-free perovskite-inspired materials (PIMs) still lags significantly behind that of their LHP counterparts. For bismuth-based PIMs, one significant reason is a frequently observed ultrafast charge-carrier localization (or self-trapping), which imposes a fundamental limit on long-range mobility. Here we report the terahertz (THz) photoconductivity dynamics in thin films of BiOI and demonstrate a lack of such self-trapping, with good charge-carrier mobility, reaching ∼3 cm2 V-1 s-1 at 295 K and increasing gradually to ∼13 cm2 V-1 s-1 at 5 K, indicative of prevailing bandlike transport. Using a combination of transient photoluminescence and THz- and microwave-conductivity spectroscopy, we further investigate charge-carrier recombination processes, revealing charge-specific trapping of electrons at defects in BiOI over nanoseconds and low bimolecular band-to-band recombination. Subject to the development of passivation protocols, BiOI thus emerges as a superior light-harvesting semiconductor among the family of bismuth-based semiconductors.

Stable Supercapacity of Binder-Free TiO2(B) Epitaxial Electrodes for All-Solid-State Nanobatteries.

Owing to its pseudocapacitive, unidimensional, rapid ion channels, TiO2(B) is a promising material for application to battery electrodes. In this study, we align these channels by epitaxially growing TiO2(B) films with the assistance of an isostructural VO2(B) template layer. In a liquid electrolyte, binder-free TiO2(B) epitaxial electrodes exhibit a supercapacity near the theoretical value of 335 mA h g-1 and an excellent charge-discharge reproducibility for ≥200 cycles, which outperform those of other TiO2(B) nanostructures. For the all-solid-state configuration employing the LiPON solid electrolyte, excellent stability persists. Our findings suggest excellent potential for miniaturizing all-solid-state nanobatteries in self-powered integrated circuits.

Emergent and robust ferromagnetic-insulating state in highly strained ferroelastic LaCoO3 thin films.

Transition metal oxides are promising candidates for the next generation of spintronic devices due to their fascinating properties that can be effectively engineered by strain, defects, and microstructure. An excellent example can be found in ferroelastic LaCoO3 with paramagnetism in bulk. In contrast, unexpected ferromagnetism is observed in tensile-strained LaCoO3 films, however, its origin remains controversial. Here we simultaneously reveal the formation of ordered oxygen vacancies and previously unreported long-range suppression of CoO6 octahedral rotations throughout LaCoO3 films. Supported by density functional theory calculations, we find that the strong modification of Co 3d-O 2p hybridization associated with the increase of both Co-O-Co bond angle and Co-O bond length weakens the crystal-field splitting and facilitates an ordered high-spin state of Co ions, inducing an emergent ferromagnetic-insulating state. Our work provides unique insights into underlying mechanisms driving the ferromagnetic-insulating state in tensile-strained ferroelastic LaCoO3 films while suggesting potential applications toward low-power spintronic devices.

Local symmetry breaking drives picosecond spin domain formation in polycrystalline halide perovskite films.

Photoinduced spin-charge interconversion in semiconductors with spin-orbit coupling could provide a route to optically addressable spintronics without the use of external magnetic fields. However, in structurally disordered polycrystalline semiconductors, which are being widely explored for device applications, the presence and role of spin-associated charge currents remains unclear. Here, using femtosecond circular-polarization-resolved pump-probe microscopy on polycrystalline halide perovskite thin films, we observe the photoinduced ultrafast formation of spin domains on the micrometre scale formed through lateral spin currents. Micrometre-scale variations in the intensity of optical second-harmonic generation and vertical piezoresponse suggest that the spin-domain formation is driven by the presence of strong local inversion symmetry breaking via structural disorder. We propose that this leads to spatially varying Rashba-like spin textures that drive spin-momentum-locked currents, leading to local spin accumulation. Ultrafast spin-domain formation in polycrystalline halide perovskite films provides an optically addressable platform for nanoscale spin-device physics.

Thin-film design of amorphous hafnium oxide nanocomposites enabling strong interfacial resistive switching uniformity.

A design concept of phase-separated amorphous nanocomposite thin films is presented that realizes interfacial resistive switching (RS) in hafnium oxide-based devices. The films are formed by incorporating an average of 7% Ba into hafnium oxide during pulsed laser deposition at temperatures ≤400°C. The added Ba prevents the films from crystallizing and leads to ∼20-nm-thin films consisting of an amorphous HfOx host matrix interspersed with ∼2-nm-wide, ∼5-to-10-nm-pitch Ba-rich amorphous nanocolumns penetrating approximately two-thirds through the films. This restricts the RS to an interfacial Schottky-like energy barrier whose magnitude is tuned by ionic migration under an applied electric field. Resulting devices achieve stable cycle-to-cycle, device-to-device, and sample-to-sample reproducibility with a measured switching endurance of ≥104 cycles for a memory window ≥10 at switching voltages of ±2 V. Each device can be set to multiple intermediate resistance states, which enables synaptic spike-timing-dependent plasticity. The presented concept unlocks additional design variables for RS devices.

Layered BiOI single crystals capable of detecting low dose rates of X-rays.

Detecting low dose rates of X-rays is critical for making safer radiology instruments, but is limited by the absorber materials available. Here, we develop bismuth oxyiodide (BiOI) single crystals into effective X-ray detectors. BiOI features complex lattice dynamics, owing to the ionic character of the lattice and weak van der Waals interactions between layers. Through use of ultrafast spectroscopy, first-principles computations and detailed optical and structural characterisation, we show that photoexcited charge-carriers in BiOI couple to intralayer breathing phonon modes, forming large polarons, thus enabling longer drift lengths for the photoexcited carriers than would be expected if self-trapping occurred. This, combined with the low and stable dark currents and high linear X-ray attenuation coefficients, leads to strong detector performance. High sensitivities reaching 1.1 × 103 µC Gyair-1 cm-2 are achieved, and the lowest dose rate directly measured by the detectors was 22 nGyair s-1. The photophysical principles discussed herein offer new design avenues for novel materials with heavy elements and low-dimensional electronic structures for (opto)electronic applications.

Ferroelectric Orthorhombic ZrO2 Thin Films Achieved Through Nanosecond Laser Annealing.

A new approach for the stabilization of the ferroelectric orthorhombic ZrO2 films is demonstrated through nanosecond laser annealing (NLA) of as-deposited Si/SiOx /W(14 nm)/ZrO2 (8 nm)/W(22 nm), grown by ion beam sputtering at low temperatures. The NLA process optimization is guided by COMSOL multiphysics simulations. The films annealed under the optimized conditions reveal the presence of the orthorhombic phase, as confirmed by X-ray diffraction, electron backscatter diffraction, and transmission electron microscopy. Macroscopic polarization-electric field hysteresis loops show ferroelectric behavior, with saturation polarization of 12.8 µC cm-2 , remnant polarization of 12.7 µC cm-2 and coercive field of 1.2 MV cm-1 . The films exhibit a wake-up effect that is attributed to the migration of point defects, such as oxygen vacancies, and/or a transition from nonferroelectric (monoclinic and tetragonal phase) to the ferroelectric orthorhombic phase. The capacitors demonstrate a stable polarization with an endurance of 6.0 × 105 cycles, demonstrating the potential of the NLA process for the fabrication of ferroelectric memory devices with high polarization, low coercive field, and high cycling stability.

Interface-related phenomena in epitaxial complex oxide ferroics across different thin film platforms: opportunities and challenges.

Interfaces in complex oxides give rise to fascinating new physical phenomena arising from the interconnected spin, lattice, charge and orbital degrees of freedom. Most commonly, interfaces are engineered in epitaxial superlattice films. Of growing interest also are epitaxial vertically aligned nanocomposite films where interfaces form by self-assembly. These two thin film forms offer different capabilities for materials tuning and have been explored largely separately from one another. Ferroics (ferroelectric, ferromagnetic, multiferroic) are among the most fascinating phenomena to be manipulated using interface effects. Hence, in this review we compare and contrast the ferroic properties that arise in these two different film forms, highlighting exemplary materials combinations which demonstrate novel, enhanced and/or emergent ferroic functionalities. We discuss the origins of the observed functionalities and propose where knowledge can be translated from one materials form to another, to potentially produce new functionalities. Finally, for the two different film forms we present a perspective on underexplored/emerging research directions.

Charge transport in mixed metal halide perovskite semiconductors.

Investigation of the inherent field-driven charge transport behaviour of three-dimensional lead halide perovskites has largely remained challenging, owing to undesirable ionic migration effects near room temperature and dipolar disorder instabilities prevalent specifically in methylammonium-and-lead-based high-performing three-dimensional perovskite compositions. Here, we address both these challenges and demonstrate that field-effect transistors based on methylammonium-free, mixed metal (Pb/Sn) perovskite compositions do not suffer from ion migration effects as notably as their pure-Pb counterparts and reliably exhibit hysteresis-free p-type transport with a mobility reaching 5.4 cm2 V-1 s-1. The reduced ion migration is visualized through photoluminescence microscopy under bias and is manifested as an activated temperature dependence of the field-effect mobility with a low activation energy (~48 meV) consistent with the presence of the shallow defects present in these materials. An understanding of the long-range electronic charge transport in these inherently doped mixed metal halide perovskites will contribute immensely towards high-performance optoelectronic devices.

Floating perovskite-BiVO4 devices for scalable solar fuel production.

Photoelectrochemical (PEC) artificial leaves hold the potential to lower the costs of sustainable solar fuel production by integrating light harvesting and catalysis within one compact device. However, current deposition techniques limit their scalability1, whereas fragile and heavy bulk materials can affect their transport and deployment. Here we demonstrate the fabrication of lightweight artificial leaves by employing thin, flexible substrates and carbonaceous protection layers. Lead halide perovskite photocathodes deposited onto indium tin oxide-coated polyethylene terephthalate achieved an activity of 4,266 µmol H2 g-1 h-1 using a platinum catalyst, whereas photocathodes with a molecular Co catalyst for CO2 reduction attained a high CO:H2 selectivity of 7.2 under lower (0.1 sun) irradiation. The corresponding lightweight perovskite-BiVO4 PEC devices showed unassisted solar-to-fuel efficiencies of 0.58% (H2) and 0.053% (CO), respectively. Their potential for scalability is demonstrated by 100 cm2 stand-alone artificial leaves, which sustained a comparable performance and stability (of approximately 24 h) to their 1.7 cm2 counterparts. Bubbles formed under operation further enabled 30-100 mg cm-2 devices to float, while lightweight reactors facilitated gas collection during outdoor testing on a river. This leaf-like PEC device bridges the gulf in weight between traditional solar fuel approaches, showcasing activities per gram comparable to those of photocatalytic suspensions and plant leaves. The presented lightweight, floating systems may enable open-water applications, thus avoiding competition with land use.

Heterostrain-enabled ultrahigh electrostrain in lead-free piezoelectric.

Piezoelectric materials provide high strain and large driving forces in actuators and can transform electrical energy into mechanical energy. Although they were discovered over 100 years ago, scientists are still searching for alternative lead-free piezoelectrics to reduce their environmental impact. Developing high-strain piezoelectric materials has been a long-term challenge, particularly challenging for the design of high-strain polycrystalline piezoelectrics containing no toxic lead element. In this work, we report one strategy to enhance the electrostrain via designing "heterostrain" through atomic-scale defect engineering and mesoscale domain engineering. We achieve an ultrahigh electrostrain of 2.3% at high temperature (220 °C) in lead-free polycrystalline ceramics, higher than all state-of-the-art piezoelectric materials, including lead-free and lead-based ceramics and single crystals. We demonstrate practical solutions for achieving high electrostrain in low-cost environmentally piezoelectric for various applications.