Recombination dynamics and manybody effect of excitons in large-area monolayer MoS2capped with (111) NiO epitaxial layer.

CVD grown monolayer MoS2films on c-sapphire substrates are vacuum annealed and capped with (111) NiO epitaxial films using pulsed laser deposition technique. Time, energy and polarization resolved optical techniques are used to understand the effect of capping on the excitonic properties of the monolayer MoS2. It has been observed that trion contribution in the photoluminescence (PL) spectra increases after the capping, suggesting an enhancement of electron concentration in the conduction band. This has been attributed to the capping driven reduction of physisorbed air molecules from the sulphur vacancy (VS) sites. Note that the air molecules act as passivating agents for theVS-donors. Low temperature polarization resolved PL spectroscopy and ultrafast pump and probe transient absorption spectroscopy (TAS) show an increase of the biexcitonic population in the system after the encapsulation. The TAS study further reveals longer lifetime for both A and B excitons in capped samples implying a reduction of non-radiative recombination rate of the excitons after the capping. It has also been observed that in the capped samples,K/K'valleys are populated with trions under sufficiently high pump powers. This has been attributed to the lower non-radiative recombination rates of the high energy photoexcited carriers and the faster transfer of either electrons or holes from the high energy pockets to theK/K'valleys. The study further reveals different many-body effects in excitons and trions.

Guided acoustic waves in thin epitaxial films: Experiment and inverse problem solution for NiTi.

Despite the fundamental and technological importance of the elastic constants, a suitable method for their full characterization in epitaxial films is missing. Here we show that transient grating spectroscopy (TGS) with highly k-vector-selective generation and detection of acoustic waves is capable of determination of all independent elastic coefficients of an epitaxial thin film grown on a single-crystalline substrate. This experimental setup enables detection of various types of guided acoustic waves and evaluation of the directional dependence of their speeds of propagation. For the studied model system, which is a 3µm thin epitaxial film of the NiTi shape memory alloy on an MgO substrate, the TGS angular maps include Rayleigh-type surface acoustic waves as well as Sezawa-type and Love-type modes, delivering rich information on the elastic response of the film under different straining modes. The resulting inverse problem, which means the calculation of the elastic constants from the TGS maps, is subsequently solved using the Ritz-Rayleigh numerical method. Using this approach, tetragonal elastic constants of the NiTi film and their changes with the austenite→martensite phase transition are analyzed.

High Entropy Nonlinear Dielectrics with Superior Thermally Stable Performance.

A high configurational entropy, achieved through a proper design of compositions, can minimize the Gibbs free energy and stabilize the quasi-equilibrium phases in a solid-solution form. This leads to the development of high-entropy materials with unique structural characteristics and excellent performance, which otherwise could not be achieved through conventional pathways. This work develops a high-entropy nonlinear dielectric system, based on the expansion of lead magnesium niobate-lead titanate. A dense and uniform distribution of nano-polar regions is observed in the samples owing to the addition of Ba, Hf, and Zr ions, which lead to enhanced performance of nonlinear dielectrics. The fact that no structural phase transformation is detected up to 250 °C, and no noticeable change or a steep drop in structural and electrical characteristics is observed at high temperatures suggests a robust thermal stability of the dielectric systems developed. With these advantages, these materials hold vast potential for applications such as dielectric energy storage, dielectric tunability, and electrocaloric effect. Thus, this work offers a new high-entropy configuration with elemental modulation, with enhanced dielectric material features.

Real-space imaging of periodic nanotextures in thin films via phasing of diffraction data.

New properties and exotic quantum phenomena can form due to periodic nanotextures, including Moire patterns, ferroic domains, and topologically protected magnetization and polarization textures. Despite the availability of powerful tools to characterize the atomic crystal structure, the visualization of nanoscale strain-modulated structural motifs remains challenging. Here, we develop nondestructive real-space imaging of periodic lattice distortions in thin epitaxial films and report an emergent periodic nanotexture in a Mott insulator. Specifically, we combine iterative phase retrieval with unsupervised machine learning to invert the diffuse scattering pattern from conventional X-ray reciprocal-space maps into real-space images of crystalline displacements. Our imaging in PbTiO3/SrTiO3 superlattices exhibiting checkerboard strain modulation substantiates published phase-field model calculations. Furthermore, the imaging of biaxially strained Mott insulator Ca2RuO4 reveals a strain-induced nanotexture comprised of nanometer-thin metallic-structure wires separated by nanometer-thin Mott-insulating-structure walls, as confirmed by cryogenic scanning transmission electron microscopy (cryo-STEM). The nanotexture in Ca2RuO4 film is induced by the metal-to-insulator transition and has not been reported in bulk crystals. We expect the phasing of diffuse X-ray scattering from thin crystalline films in combination with cryo-STEM to open a powerful avenue for discovering, visualizing, and quantifying the periodic strain-modulated structures in quantum materials.

Bending Modulated Ultralarge Magnetoresistance in Flexible La0.67Ba0.33MnO3 Thin Film Based Device.

Magnetoresistance based information devices have attracted much attention due to the ability to utilize spins as information carriers. To promote the magnetoresistance-based devices, ultrahigh magnetoresistance ratios are highly desirable for magnetic sensing, memory, and artificial intelligent devices, etc. However, today the magnetoresistance devices are facing the challenge of limited magnetoresistance ratio, low work temperature, or high magnetic field, which calls for proper theories and mechanisms. To address it, we first introduce the flexible bending-controlled magnetoresistance device based on the La0.67Ba0.33MnO3 film. Due to the anisotropic resistance of the La0.67Ba0.33MnO3 film and the nonlinear amplification effect of the Zener diode, the device has exhibited strong magnetoresistive performance (∼8725% at 1 T, 300 K). Combining the assist from mechanical bending and diode, high magnetic field sensitivity with large magnetoresistance ratio (∼1.7 × 104% at 1 T, 300 K) and low work current (∼0.15 mA) is simultaneously achieved at room temperature, which is over 104 times larger than that of the planar La0.67Ba0.33MnO3 film. Based on the above results, we propose one but not the only possible application as tunable multistage switch. Our findings may pave a strategy to develop flexible diode-enhanced magnetoresistance device with ultrahigh magnetoresistance ratios and bending tunable performances.

Ionic Rectification across Ionic and Mixed Conductor Interfaces.

In electrochemical devices, it is important to control the ionic transport between the electrodes and solid electrolytes. However, it is difficult to tune the transport without applying an electric field. This paper presents a method to modulate the transport via tuning of the electrochemical potential difference by controlling the electronic states at the interfaces. We fabricated thin-film solid-state Li batteries using LiTi2O4 thin films as positive electrodes. The spontaneous Li-ion transport between the solid electrolyte and LiTi2O4 is controlled by tuning the electrochemical potential difference via use of an electrically conducting Nb-doped SrTiO3 substrate. This study establishes the foundation for rectifying the ionic transport via electronic energy band alignment.

Polarization and Dielectric Properties of BiFeO3-BaTiO3 Superlattice-Structured Ferroelectric Films.

Superlattice-structured epitaxial thin films composed of Mn(5%)-doped BiFeO3 and BaTiO3 with a total thickness of 600 perovskite (ABO3) unit cells were grown on single-crystal SrTiO3 substrates by pulsed laser deposition, and their polarization and dielectric properties were investigated. When the layers of Mn-BiFeO3 and BaTiO3 have over 25 ABO3 unit cells (N), the superlattice can be regarded as a simple series connection of their individual capacitors. The superlattices with an N of 5 or less behave as a unified ferroelectric, where the BaTiO3 and Mn-BiFeO3 layers are structurally and electronically coupled. Density functional theory calculations can explain the behavior of spontaneous polarization for the superlattices in this thin regime. We propose that a superlattice formation comprising two types of perovskite layers with different crystal symmetries opens a path to novel ferroelectrics that cannot be obtained in a solid solution system.

Strain-Induced Atomic-Scale Building Blocks for Ferromagnetism in Epitaxial LaCoO3.

The origin of strain-induced ferromagnetism, which is robust regardless of the type and degree of strain in LaCoO3 (LCO) thin films, is enigmatic despite intensive research efforts over the past decade. Here, by combining scanning transmission electron microscopy with ab initio density functional theory plus U calculations, we report that the ferromagnetism does not emerge directly from the strain itself but rather from the creation of compressed structural units within ferroelastically formed twin-wall domains. The compressed structural units are magnetically active with the rocksalt-type high-spin/low-spin order. Our study highlights that the ferroelastic nature of ferromagnetic structural units is important for understanding the intriguing ferromagnetic properties in LCO thin films.

Reactions of the Li2MnO3 Cathode in an All-Solid-State Thin-Film Battery during Cycling.

We evaluated the structural change of the cathode material Li2MnO3 that was deposited as an epitaxial film with an (001) orientation in an all-solid-state battery. We developed an in situ surface X-ray diffraction (XRD) technique, where X-rays are incident at a very low grazing angle of 0.1°. An X-ray with wavelength of 0.82518 Å penetrated an ∼2 µm-thick amorphous Li3PO4 solid-state electrolyte and ∼1 µm-thick metal Li anode on the Li2MnO3 cathode. Experiments revealed a structural change to a high-capacity (activated) phase that proceeded gradually and continuously with cycling. The activated phase barely showed any capacity fading. First-principles calculations suggested that the activated phase has O1 stacking, which is attained by first delithiating to an intermediate phase with O3 stacking and tetrahedral Li. This intermediate phase has a low Li migration barrier path in the [001] direction, but further delithiation causes an energetically favorable and irreversible transition to the O1 phase. We propose a mechanism of structural change with cycling: charging to a high voltage at a sufficiently low Li concentration typically induces irreversible transition to a phase detrimental to cycling that could, but not necessarily, be accompanied by the dissolution of Mn and/or the release of O into the electrolyte, while a gradual irreversible transition to an activated phase happens at a similar Li concentration under a lower voltage.

Clean Solid-Electrolyte/Electrode Interfaces Double the Capacity of Solid-State Lithium Batteries.

Solid-state lithium (Li) batteries using spinel-oxide electrode materials such as LiNi0.5Mn1.5O4 are promising power supplies for mobile devices and electric vehicles. Here, we demonstrate stable battery cycling between the Li0Ni0.5Mn1.5O4 and Li2Ni0.5Mn1.5O4 phases with working voltages of approximately 2.9 and 4.7 V versus Li/Li+ in solid-state Li batteries with contamination-free clean Li3PO4/LiNi0.5Mn1.5O4 interfaces. This clean interface has the effect of doubling the capacity of conventional battery cycling between the Li0Ni0.5Mn1.5O4 and Li1Ni0.5Mn1.5O4 phases. We also investigated the structural changes between the Li0Ni0.5Mn1.5O4 and Li2Ni0.5Mn1.5O4 phases during battery cycling. Furthermore, we found an inhomogeneous distribution of the Li2Ni0.5Mn1.5O4 phase in the LiNi0.5Mn1.5O4 electrode, induced by spontaneous Li migration after the formation of the Li3PO4/LiNi0.5Mn1.5O4 interface. These results indicate that the formation of a contamination-free clean Li3PO4/LiNi0.5Mn1.5O4 interface is key to increase the battery capacity.

Route to High-Performance Micro-solid Oxide Fuel Cells on Metallic Substrates.

Micro-solid oxide fuel cells based on thin films have strong potential for use in portable power devices. However, devices based on silicon substrates typically involve thin-film metallic electrodes which are unstable at high temperatures. Devices based on bulk metal substrates overcome these limitations, though performance is hindered by the challenge of growing state-of-the-art epitaxial materials on metals. Here, we demonstrate for the first time the growth of epitaxial cathode materials on metal substrates (stainless steel) commercially supplied with epitaxial electrolyte layers (1.5 µm (Y2O3)0.15(ZrO2)0.85 (YSZ) + 50 nm CeO2). We create epitaxial mesoporous cathodes of (La0.60Sr0.40)0.95Co0.20Fe0.80O3 (LSCF) on the substrate by growing LSCF/MgO vertically aligned nanocomposite films by pulsed laser deposition, followed by selectively etching out the MgO. To enable valid comparison with the literature, the cathodes are also grown on single-crystal substrates, confirming state-of-the-art performance with an area specific resistance of 100 Ω cm2 at 500 °C and activation energy down to 0.97 eV. The work marks an important step toward the commercialization of high-performance micro-solid oxide fuel cells for portable power applications.

Tuning Optical Properties by Controlled Aggregation: Electroluminescence Assisted by Thermally-Activated Delayed Fluorescence from Thin Films of Crystalline Chromophores.

Several photophysical properties of chromophores depend crucially on intermolecular interactions. Thermally-activated delayed fluorescence (TADF) is often influenced by close packing of the chromophore assembly. In this context, the metal-organic framework (MOF) approach has several advantages: it can be used to steer aggregation such that the orientation within aggregated structures can be predicted using rational approaches. We demonstrate this design concept for a DPA-TPE (diphenylamine-tetraphenylethylene) chromophore, which is non-emissive in its solvated state due to vibrational quenching. Turning this DPA-TPE into a ditopic linker makes it possible to grow oriented MOF thin films exhibiting pronounced green electroluminescence with low onset voltages. Measurements at different temperatures clearly demonstrate the presence of TADF. Finally, this work reports that the layer-by-layer process used for MOF thin film deposition allows the integration of the TADF-DPA-TPE in a functioning LED device.

Stable and Tunable Current-Induced Phase Transition in Epitaxial Thin Films of Ca2RuO4.

Owing to the recent discovery of the current-induced metal-insulator transition and unprecedented electronic properties of the concomitant phases of calcium ruthenate Ca2RuO4, it is emerging as an important material. To further explore the properties, the growth of epitaxial thin films of Ca2RuO4 is receiving more attention, as high current densities can be applied to thin-film samples and the amount can be precisely controlled in an experimental environment. However, it is difficult to grow high-quality thin films of Ca2RuO4 due to the easy formation of the crystal defects originating from the sublimation of RuO4; therefore, the metal-insulator transition of Ca2RuO4 is typically not observed in the thin films. Herein, a stable current-induced metal-insulator transition is achieved in the high-quality thin films of Ca2RuO4 grown by solid-phase epitaxy under high growth temperatures and pressures. In the Ca2RuO4 thin films grown by ex situ annealing at >1200 °C and 1.0 atm, continuous changes in the resistance of over 2 orders of magnitude are induced by currents with a precise dependence of the resistance on the current amplitude. A hysteretic, abrupt resistive transition is also observed in the thin films from the resistance-temperature measurements conducted under constant-voltage (variable-current) conditions with controllability of the transition temperature. A clear resistive switching by the current-induced transition is demonstrated in the current-electric-field characteristics, and the switching currents and fields are shown to be very stable. These results represent a significant step toward understanding the high-current-density properties of Ca2RuO4 and the future development of Mott-electronic devices based on electricity-driven transitions.

Synthesis, Characterization, and Magnetoresistive Properties of the Epitaxial Pd0.96Fe0.04/VN/Pd0.92Fe0.08 Superconducting Spin-Valve Heterostructure.

A thin-film superconductor(S)/ferromagnet(F) F1/S/F2-type Pd0.96Fe0.04(20 nm)/VN(30 nm)/Pd0.92Fe0.08(12 nm) heteroepitaxial structure was synthesized on (001)-oriented single-crystal MgO substrate utilizing a combination of the reactive magnetron sputtering and the molecular-beam epitaxy techniques in ultrahigh vacuum conditions. The reference VN film, Pd0.96Fe0.04/VN, and VN/Pd0.92Fe0.08 bilayers were grown in one run with the target sample. In-situ low-energy electron diffraction and ex-situ X-ray diffraction investigations approved that all the Pd1-xFex and VN layers in the series grew epitaxial in a cube-on-cube mode. Electric resistance measurements demonstrated sharp transitions to the superconducting state with the critical temperature reducing gradually from 7.7 to 5.4 K in the sequence of the VN film, Pd0.96Fe0.04/VN, VN/Pd0.92Fe0.08, and Pd0.96Fe0.04/VN/Pd0.92Fe0.08 heterostructures due to the superconductor/ferromagnet proximity effect. Transition width increased in the same sequence from 21 to 40 mK. Magnetoresistance studies of the trilayer Pd0.96Fe0.04/VN/Pd0.92Fe0.08 sample revealed a superconducting spin-valve effect upon switching between the parallel and antiparallel magnetic configurations, and anomalies associated with the magnetic moment reversals of the ferromagnetic Pd0.92Fe0.08 and Pd0.96Fe0.04 alloy layers. The moderate critical temperature suppression and manifestations of superconducting spin-valve properties make this kind of material promising for superconducting spintronics applications.

Magnetotransport Anomaly in Room-Temperature Ferrimagnetic NiCo2 O4 Thin Films.

The inverse spinel ferrimagnetic NiCo2 O4 presents a unique model system for studying the competing effects of crystalline fields, magnetic exchange, and various types of chemical and lattice disorder on the electronic and magnetic states. Here, magnetotransport anomalies in high-quality epitaxial NiCo2 O4 thin films resulting from the complex energy landscape are reported. A strong out-of-plane magnetic anisotropy, linear magnetoresistance, and robust anomalous Hall effect above 300 K are observed in 5-30 unit cell NiCo2 O4 films. The anomalous Hall resistance exhibits a nonmonotonic temperature dependence that peaks around room temperature, and reverses its sign at low temperature in films thinner than 20 unit cells. The scaling relation between the anomalous Hall conductivity and longitudinal conductivity reveals the intricate interplay between the spin-dependent impurity scattering, band intrinsic Berry phase effect, and electron correlation. This study provides important insights into the functional design of NiCo2 O4 for developing spinel-based spintronic applications.

Fabrication and Characterization of PZT Fibered-Epitaxial Thin Film on Si for Piezoelectric Micromachined Ultrasound Transducer.

This paper presents a fibered-epitaxial lead zirconate titanate (PZT) thin film with intermediate features between the monocrystalline and polycrystalline thin films for piezoelectric micromachined ultrasound transducer (pMUT). The grain boundaries confirmed by scanning electron microscopy, but it still maintained the in-plane epitaxial relationship found by X-ray diffraction analyses. The dielectric constant (εr33 = 500) was relatively high compared to those of the monocrystalline thin films, but was lower than those of conventional polycrystalline thin films near the morphotropic phase boundary composition. The fundamental characterizations were evaluated through the operation tests of the prototyped pMUT with the fibered-epitaxial thin film. As a result, its piezoelectric coefficient without poling treatment was estimated to be e31,f = -10⁻-11 C/m², and thus reasonably high compared to polycrystalline thin films. An appropriate poling treatment increased e31,f and decreased εr33. In addition, this unique film was demonstrated to be mechanically tougher than the monocrystalline thin film. It has the potential ability to become a well-balanced piezoelectric film with both high signal-to-noise ratio and mechanical toughness for pMUT.

Investigating Metal⁻Insulator Transition and Structural Phase Transformation in the (010)-VO2/(001)-YSZ Epitaxial Thin Films.

The VO2 thin films with sharp metal⁻insulator transition (MIT) were epitaxially grown on (001)-oriented Yttria-stabilized zirconia substrates (YSZ) using radio-frequency (RF) magnetron sputtering techniques. The MIT and structural phase transition (SPT) were comprehensively investigated under in situ temperature conditions. The amplitude of MIT is in the order of magnitude of 104, and critical temperature is 342 K during the heating cycle. It is interesting that both electron concentration and mobility are changed by two orders of magnitude across the MIT. This research is distinctively different from previous studies, which found that the electron concentration solely contributes to the amplitude of the MIT, although the electron mobility does not. Analysis of the SPT showed that the (010)-VO2/(001)-YSZ epitaxial thin film presents a special multi-domain structure, which is probably due to the symmetry matching and lattice mismatch between the VO2 and YSZ substrate. The VO2 film experiences the SPT from the M1 phase at low temperature to a rutile phase at a high temperature. Moreover, the SPT occurs at the same critical temperature as that of the MIT. This work may shed light on a new MIT behavior and may potentially pave the way for preparing high-quality VO2 thin films on cost-effective YSZ substrates for photoelectronic applications.

Anion-Substitution-Induced Nonrigid Variation of Band Structure in SrNbO3- xN x (0 ≤ x ≤ 1) Epitaxial Thin Films.

Pervoskite oxynitrides exhibit rich functionalities such as colossal magnetoresistance and high photocatalytic activity. The wide tunability of physical properties by the N/O ratio makes perovskite oxynitrides promising as optical and electrical materials. However, composition-dependent variation of the band structure, especially under partially substituted composition, is not yet well understood. In this study, we quantitatively analyzed the composition-dependent variation of band structure of a series of SrNbO3- xN x (0 ≤ x ≤ 1.02) epitaxial thin films. Electrical conductivity decreased along with the increase of N content x as a result of an increase in Nb valence from 4+ to 5+. Optical measurements revealed that the N 2p band is formed at a critical composition between 0.07 < x < 0.38, which induces charge-transfer transition (CTT) in the visible-light region. These variations in the band structure were explained by first-principles calculations. However, the CTT energy slightly increased at higher N contents (i.e., lower carrier density) on contrary to the expectation based on the rigid-band-like shift of the Fermi level, which suggests a complex combination of the following band-shifting effects induced by N-substitution: whereas (1) reduction of the Burstein-Moss effect causes CTT energy reduction, (2) enhancement of hybridization between Nb 4d and N 2p orbitals and/or (3) suppression of many-body effects enlarge the band gap energy at larger N content. The band structure variation in perovskite oxynitride as presently elucidated would be a guidepost for future material design.

Extremely Low Resistance of Li3PO4 Electrolyte/Li(Ni0.5Mn1.5)O4 Electrode Interfaces.

Solid-state Li batteries containing Li(Ni0.5Mn1.5)O4 as a 5 V-class positive electrode are expected to revolutionize mobile devices and electric vehicles. However, practical applications of such batteries are hampered by the high resistance at their solid electrolyte/electrode interfaces. Here, we achieved an extremely low electrolyte/electrode interface resistance of 7.6 Ω cm2 in solid-state Li batteries with Li(Ni0.5Mn1.5)O4. Furthermore, we observed spontaneous migration of Li ions from the solid electrolyte to the positive electrode after the formation of the electrolyte/electrode interface. Finally, we demonstrated stable fast charging and discharging of the solid-state Li batteries at a current density of 14 mA/cm2. These results provide a solid foundation to understand and fabricate low-resistance electrolyte/electrode interfaces.

Directing Oxygen Vacancy Channels in SrFeO2.5 Epitaxial Thin Films.

Transition-metal oxides (TMOs) with brownmillerite (BM) structures possess one-dimensional oxygen vacancy channels (OVCs), which play a key role in realizing high ionic conduction at low temperatures. The controllability of the vacancy channel orientation, thus, possesses a great potential for practical applications and would provide a better visualization of the diffusion pathways of ions in TMOs. In this study, the orientations of the OVCs in BM-SrFeO2.5 are stabilized along two crystallographic directions of the epitaxial thin films. The distinctively orientated phases are found to be highly stable and exhibit a considerable difference in their electronic structures and optical properties, which could be understood in terms of orbital anisotropy. The control of the OVC orientation further leads to modifications in the hydrogenation of the BM-SrFeO2.5 thin films. The results demonstrate a strong correlation between crystallographic orientations, electronic structures, and ionic motion in the BM structure.