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Understanding how doping influences physicochemical properties of ABO 3 perovskite oxides is critical for tailoring their functionalities. In this study, SrFe 0.67 Cr 0.33 O 3-δ epitaxial thin films were used to examine the effects of Fe and Cr competition on structure and B-site cation oxidation states. The films exhibit a perovskite-like structure near the film/substrate interface, while a brownmillerite-like structure with horizontal oxygen vacancy channels predominates near the surface. Electron energy loss spectroscopy shows Fe remains Fe 3+ , while Cr varies from ∼Cr 3+ (tetrahedral layers) to ∼Cr 4+ (octahedral layers) within brownmillerite phases and becomes ∼Cr 4.5+ in perovskite-like phases. Theoretical simulations indicate that Cr-O bond arrangements and the way oxygen vacancies interact with Cr and Fe drive Cr charge disproportionation. High-valent Cr cations introduce additional densities of states near the Fermi level, reducing the optical bandgap from ∼2.0 eV (SrFeO 2.5 ) to ∼1.7 eV (SrFe 0.67 Cr 0.33 O 3-δ ). These findings offer insights into B-site cation doping in the perovskite oxide framework.

The cubic perovskite SrMoO 3 with a paramagnetic ground state and remarkably low room-temperature resistivity has been considered as a suitable candidate for the new-era oxide-based technology. However, the difficulty of preparing single-phase SrMoO 3 thin films by hydrogen-free sputtering has hindered their practical use, especially due to the formation of thermodynamically favorable SrMoO 4 impurity. In this work, we developed a radio frequency sputtering technology enabling the reduction reaction and achieved conductive epitaxial SrMoO 3 films with pure phase from a SrMoO 4 target in a hydrogen-free, pure argon environment. We demonstrated the significance of controlling the target-to-substrate distance (TSD) on the synthesis of SrMoO 3 ; the film resistivity drastically changes from 1.46 × 10 5 μΩ·cm to 250 μΩ·cm by adjusting the TSD. Cross-sectional microstructural analyses demonstrated that films with the lowest resistivity, deposited for TSD = 2.5 cm, possess a single-phase SrMoO 3 with an epitaxial perovskite structure. The formation mechanism of the conductive single-phase SrMoO 3 films can be attributed to the plasma-assisted growth process by tuning the TSD. Temperature-dependent resistivity and Hall effect studies revealed metal-like conducting properties for low-resistive SrMoO 3 films, while the high-resistive ones displayed semiconductor-like behavior. Our approach makes hydrogen-free, reliable and cost-efficient scalable deposition of SrMoO 3 films possible, which may open up promising prospects for a wide range of future applications of oxide materials., Competing Interests: No potential conflict of interest was reported by the author(s)., (© 2024 The Author(s). Published by National Institute for Materials Science in partnership with Taylor & Francis Group.)

Piezoelectric and ferroelectric wurtzite are promising to reshape modern microelectronics because they can be easily integrated with mainstream semiconductor technology. Sc doped AlN (Al 1- x Sc x N) has attracted much attention for its enhanced piezoelectric and emerging ferroelectric properties, yet the commonly used sputtering results in polycrystalline Al 1- x Sc x N films with high leakage current. Here, the pulsed laser deposition of single crystalline epitaxial Al 1- x Sc x N thin films on sapphire and 4H-SiC substrates is reported. Pure wurtzite phase is maintained up to x = 0.3 with ≤0.1 at% oxygen contamination. Polarization is estimated to be 140 µC cm -2 via atomic scale microscopy imaging and found to be switchable via a scanning probe. The piezoelectric coefficient is found to be five times of the undoped one when x = 0.3, making it desirable for high-frequency radiofrequency (RF) filters and 3D nonvolatile memories., (© 2024 Wiley‐VCH GmbH.)

Light is an effective tool to probe the polarization and domain distribution in ferroelectric materials passively, that is, non-invasively, for example, via optical second harmonic generation (SHG). With the emergence of oxide electronics, there is now a strong demand to expand the role of light toward active control of the polarization. In this work, optical control of the ferroelectric polarization is demonstrated in prototypical epitaxial PbZr x Ti 1-x O 3 (PZT)-based heterostructures. This is accomplished in three steps, using above-bandgap UV light, while tracking the response of the polarization with optical SHG. First, it is found that UV-light exposure induces a transient enhancement or suppression of the ferroelectric polarization in films with an upward- or downward-oriented polarization, respectively. This behavior is attributed to a modified charge screening driven by the separation of photoexcited charge carriers at the Schottky interface of the ferroelectric thin film. Second, by taking advantage of this optical handle on electrostatics, remanent optical poling from a pristine multi-domain into a single-domain configuration is accomplished. Third, via thermal annealing or engineered electrostatic boundary conditions, a complete reversibility of the optical poling is further achieved. Hence, this work paves the way for the all-optical control of the spontaneous polarization in ferroelectric thin films., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

The concept of multiphysics, where materials respond to diverse external stimuli, such as magnetic fields, electric fields, light irradiation, stress, heat, and chemical reactions, plays a fundamental role in the development of innovative devices. Nanomanufacturing, especially in low-dimensional systems, enhances the synergistic interactions taking place on the nanoscale. Light-matter interaction, rather than electric fields, holds great promise for achieving low-power, wireless control over magnetism, solving two major technological problems: the feasibility of electrical contacts at smaller scales and the undesired heating of the devices. Here, we shed light on the remarkable reversible modulation of magnetism using visible light in epitaxial Fe 3 O 4 /BaTiO 3 heterostructure. This achievement is underpinned by the convergence of two distinct mechanisms. First, the magnetoelastic effect, triggered by ferroelectric domain switching, induces a proportional change in coercivity and remanence upon laser illumination. Second, light-matter interaction induces charged ferroelectric domain walls' electrostatic decompensations, acting intimately on the magnetization of the epitaxial Fe 3 O 4 film by magnetoelectric coupling. Crucially, our experimental results vividly illustrate the capability to manipulate magnetic properties using visible light. This concomitant mechanism provides a promising avenue for low-intensity visible-light manipulation of magnetism, offering potential applications in multiferroic devices.

Ba-rich compositions in the Ba x Sr 1- x MnO 3 (BSMO) cubic perovskite (3C) system are magnetic ferroelectrics and are of interest for their strong magnetoelectric coupling. Beyond x = 0.5, they only form in hexagonal polymorphs. Here, the 3C phase boundary is pushed to Ba 0.6 Sr 0.4 MnO 3 for the thin films. Using regular pulsed laser deposition (rPLD), 3C Ba 0.6 Sr 0.4 MnO 3 could be epitaxially stabilized on DyScO 3 (101) o substrates by using a 0.1% O 2 /99.9% N 2 gas mixture. However, the 3C phase was mixed with the 4H polymorph for films 24 nm thick and above, and the films were relatively rough. To improve flatness and phase purity, changes in growth kinetics were investigated and interval PLD (iPLD) was especially effective. In iPLD, deposition is interrupted after completion of approximately one monolayer, and the deposit is annealed for a specific period of time before repeating. Both film flatness and, more importantly, the volume of the 3C polymorph improved with iPLD, resulting in 40 nm single-phase films. The results imply that iPLD improves the persistent nucleation of highly metastable phases and offers a new approach to epitaxial stabilization of novel materials, including more Ba-rich BSMO compositions in the 3C structure.

The growth of epitaxial thin films from the Ruddlesden-Popper series of strontium iridates by magnetron sputtering is analyzed. It was found that, even using a non-stoichiometric target, the films formed under various conditions were consistently of the perovskite-like n = ∞ SrIrO 3 phase, with no evidence of other RP series phases. A detailed inspection of the temperature-oxygen phase diagram underscored that kinetics mechanisms prevail over thermodynamics considerations. The analysis of the angular distribution of sputtered iridium and strontium species indicated clearly different spatial distribution patterns. Additionally, significant backsputtering was detected at elevated temperatures. Thus, it is assumed that the interplay between these two kinetic phenomena is at the origin of the preferential nucleation of the SrIrO 3 phase. In addition, strategies for controlling cation stoichiometry off-axis have also been explored. Finally, the long-term stability of the films has been demonstrated.

Spin-orbit torques generated by a spin current are key to magnetic switching in spintronic applications. The polarization of the spin current dictates the direction of switching required for energy-efficient devices. Conventionally, the polarizations of these spin currents are restricted to be along a certain direction due to the symmetry of the material allowing only for efficient in-plane magnetic switching. Unconventional spin-orbit torques arising from novel spin current polarizations, however, have the potential to switch other magnetization orientations such as perpendicular magnetic anisotropy, which is desired for higher density spintronic-based memory devices. Here, it is demonstrated that low crystalline symmetry is not required for unconventional spin-orbit torques and can be generated in a nonmagnetic high symmetry material, iridium dioxide (IrO 2 ), using epitaxial design. It is shown that by reducing the relative crystalline symmetry with respect to the growth direction large unconventional spin currents can be generated and hence spin-orbit torques. Furthermore, the spin polarizations detected in (001), (110), and (111) oriented IrO 2 thin films are compared to show which crystal symmetries restrict unconventional spin transport. Understanding and tuning unconventional spin transport generation in high symmetry materials can provide a new route towards energy-efficient magnetic switching in spintronic devices., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

The luminescent properties of epitaxial Cu 2 O thin films were studied in 10-300 K temperature range and compared with the luminescent properties of Cu 2 O single crystals. Cu 2 O thin films were deposited epitaxially via the electrodeposition method on either Cu or Ag substrates at different processing parameters, which determined the epitaxial orientation relationships. Cu 2 O (100) and (111) single crystal samples were cut from a crystal rod grown using the floating zone method. Luminescence spectra of thin films contain the same emission bands as single crystals around 720, 810 and 910 nm, characterizing VO2+, VO+ and VCu defects, correspondingly. Additional emission bands, whose origin is under discussion, are observed around 650-680 nm, while the exciton features are negligibly small. The relative mutual contribution of the emission bands varies depending on the thin film sample. The existence of the domains of crystallites with different orientations determines the polarization of luminescence. The PL of both Cu 2 O thin films and single crystals is characterized by negative thermal quenching in the low-temperature region; the reason of this phenomenon is discussed.

The discovery of superconductivity in the infinite-layer nickelate Nd 0.8 Sr 0.2 NiO 2 has motivated tremendous efforts for its significance toward the understanding of high-temperature superconductivity. However, the synthesis of infinite-layer nickelates is instable and has become a hindrance to experimental progress. Optimizing the growth of precursor Nd 0.8 Sr 0.2 NiO 3 by pulsed laser deposition is crucial for obtaining infinite-layer nickelates. By systematically investigating the growth of Nd 0.8 Sr 0.2 NiO 3 with wide range of conditions, we found that the laser fluence plays a critical role in determining the stoichiometry, lattice structure, and electronic properties. A higher Ni deficiency and larger c -axis lattice constant appeared with the lower laser fluence. At 0.6 J/cm 2 , the Ni deficiency is as large as 25%. According to X-ray absorption spectra and X-ray linear dichroism, we further find that (i) there are no obvious changes of the Ni valence and (ii) the energy level of the d x 2 - y 2 orbital gradually increases relative to the d 3 z 2 - r 2 orbital with increasing Ni deficiency. What is more, the onset temperature and magnitude of the resistivity change at the metal-to-insulator transitions (MITs) also are found to decrease with increasing laser fluence during the growth.

Multiferroic thin films are a promising class of multifunctional materials, since they allow the integration of multiple functionalities within a single device. In order to overcome the scarcity of single phase multiferroics, it is crucial to develop novel multiferroic heterostructures, combining good ferroelectric and ferromagnetic properties as well as a strong coupling between them. For this purpose, Ba 2 EuFeNb 4 O 15 /BaFe 12 O 19 multiferroic magnetoelectric bilayers have been epitaxially grown on niobium doped SrTiO 3 (100) single crystal substrates by pulsed laser deposition. The simultaneous presence of both ferroelectric and magnetic properties-due, respectively, to the Ba 2 EuFeNb 4 O 15 and BaFe 12 O 19 components-was demonstrated at room temperature, attesting the multiferroic nature of the heterostructure. More interestingly, a strong magnetoelectric coupling was demonstrated (i) by manipulating the ferroelectric properties via an external magnetic field, and conversely, (ii) by tuning the magnetic properties via an external electric field. This strong magnetoelectric coupling shows the high interdependence of both ferroic orders in the Ba 2 EuFeNb 4 O 15 /BaFe 12 O 19 heterostructure, mediated by elastic (epitaxial) strain at the interfaces.

In condensed matter physics, oxide materials show various intriguing physical properties. Therefore, many efforts are made in this field to develop functional oxides. Due to the excellent potential for tin-based perovskite oxides, an expansion of new related functional compounds is crucial. This work uses a heteroepitaxial approach supported by theoretical calculation to stabilize PbSnO 3 thin films with different orientations. The analyses of X-ray diffraction and transmission electron microscopy unveil the structural information. A typical antiferroelectric feature with double hysteresis and butterfly loops is observed through electrical characterizations consistent with the theoretical prediction. The phase transition is monitored, and the transition temperatures are determined based on temperature-dependent structural and electrical characterizations. Furthermore, the microscopic antiferroelectric order is noticed under atomic resolution images via scanning transmission electron microscopy. This work offers a breakthrough in synthesizing epitaxial PbSnO 3 thin films and comprehensively understanding its anisotropic antiferroelectric behavior., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Antiferroelectric PbZrO 3 has attracted renewed interest in recent years because of its unique properties and wide range of potential applications. However, the nature of antiferroelectricity and its evolution with the electric field and temperature remain controversial, mostly due to the difficulty of obtaining high-quality single-crystal samples. The lack of consensus regarding the phase transition in PbZrO 3 is not only important on a fundamental side but also greatly hinders further applications. Herein, high-quality PbZrO 3 epitaxial thin films are successfully fabricated by pulsed laser deposition. The structural and physical properties of the films are systematically studied via a combination of electric property measurements, X-ray diffraction, scanning transmission electron microscopy imaging, and second-harmonic generation studies. Our studies unveil the noncentrosymmetric nature of PbZrO 3 films at room temperature. Moreover, the Curie temperature increased to 270°, ∼40° higher than that in the bulk, and no intermediate ferroelectric phase was observed. Besides, an incipient ferroelectric with relaxor-like behavior above the Curie temperature due to the existence of a local polar cluster in the high-temperature paraelectric phase is experimentally observed for the first time. Our studies provide a better understanding of PbZrO 3 thin films and pave the way for practical applications of antiferroelectric material in modern electronic devices.

Magnetic perovskite films have promising properties for use in energy-efficient spintronic devices and magnetic refrigeration. Here, an epitaxial ferromagnetic La 0.67 Ba 0.33 Mn 0.95 Ti 0.05 O 3 (LBMTO-5) thin film was grown on SrTiO 3 (001) single crystal substrate by pulsed laser deposition. High-resolution X-ray diffraction proved the high crystallinity of the film with tetragonal symmetry. The magnetic, magnetocaloric and magnetoresistance properties at different directions of the applied magnetic field with respect to the ab plane of the film were investigated. An in-plane uni-axial magnetic anisotropy was evidenced. The LBMTO-5 epilayer exhibits a second-order ferromagnetic-paramagnetic phase transition around 234 K together with a metal-semiconductor transition close to this Curie temperature (T C ). The magnetic entropy variation under 5 T induction of a magnetic field applied parallel to the film surface reaches a maximum of 17.27 mJ/cm 3 K. The relative cooling power is 1400 mJ/cm 3 K (53% of the reference value reported for bulk Gd) for the same applied magnetic field. Giant magnetoresistance of about 82% under 5 T is obtained at a temperature close to T C . Defined as the difference between specific resistivity obtained under 5 T with the current flowing along the magnetic easy axis and the magnetic field oriented transversally to the current, parallel and perpendicular to the sample plane, respectively, the in-plane magneto-resistance anisotropy in 5 T is about 9% near the T C .

Epitaxial strain modifies the physical properties of thin films deposited on single-crystal substrates. In a previous work, we demonstrated that in the case of La 2/3 Ca 1/3 MnO 3 thin films the strain induced by the substrate can produce the segregation of a non-ferromagnetic layer (NFL) at the top surface of ferromagnetic epitaxial La 2/3 Ca 1/3 MnO 3 for a critical value of the tetragonality τ, defined as τ = | c - a | a , of τ C ≈ 0.024. Although preliminary analysis suggested its antiferromagnetic nature, to date a complete characterization of the magnetic state of such an NFL has not been performed. Here, we present a comprehensive magnetic characterization of the strain-induced segregated NFL. The field-cooled magnetic hysteresis loops exhibit an exchange bias mechanism below T ≈ 80 K, which is well below the Curie temperature of the ferromagnetic La 2/3 Ca 1/3 MnO 3 layer. The exchange bias and coercive fields decay exponentially with temperature, which is commonly accepted to describe spin-glass (SG) behavior. The signatures of slow dynamics were confirmed by slow spin relaxation over a wide temperature regime. Low-energy muon spectroscopy experiments directly evidence the slowing down of the magnetic moments below ~100 K in the NFL. The experimental results indicate the SG nature of the NFL. This SG state can be understood within the context of the competing ferromagnetic and antiferromagnetic interactions of similar energies.

Disordered superconducting nitrides with kinetic inductance have long been considered to be leading material candidates for high-inductance quantum-circuit applications. Despite continuing efforts toward reducing material dimensions to increase the kinetic inductance and the corresponding circuit impedance, achieving further improvements without compromising material quality has become a fundamental challenge. To this end, a method to drastically increase the kinetic inductance of superconducting materials via spinodal decomposition while maintaining a low microwave loss is proposed. Epitaxial Ti 0.48 Al 0.52 N is used as a model system and the utilization of spinodal decomposition to trigger the insulator-to-superconductor transition with a drastically enhanced material disorder is demonstrated. The measured kinetic inductance increases by two to three orders of magnitude compared with the best disordered superconducting nitrides reported to date. This work paves the way for substantially enhancing and deterministically controlling the inductance for advanced superconducting quantum circuits., (© 2022 Wiley-VCH GmbH.)

The magnetic Weyl fermion originates from the time reversal symmetry (TRS)-breaking in magnetic crystalline structures, where the topology and magnetism entangle with each other. Therefore, the magnetic Weyl fermion is expected to be effectively tuned by the magnetic field and electrical field, which holds promise for future topologically protected electronics. However, the electrical field control of the magnetic Weyl fermion has rarely been reported, which is prevented by the limited number of identified magnetic Weyl solids. Here, the electric field control of the magnetic Weyl fermion is demonstrated in an epitaxial SrRuO 3 (111) thin film. The magnetic Weyl fermion in the SrRuO 3 films is indicated by the chiral anomaly induced magnetotransport, and is verified by the observed Weyl nodes in the electronic structures characterized by the angle-resolved photoemission spectroscopy (ARPES) and first-principles calculations. Through the ionic-liquid gating experiment, the effective manipulation of the Weyl fermion by electric field is demonstrated, in terms of the sign-change of the ordinary Hall effect, the nonmonotonic tuning of the anomalous Hall effect, and the observation of the linear magnetoresistance under proper gating voltages. The work may stimulate the searching and tuning of Weyl fermions in other magnetic materials, which are promising in energy-efficient electronics., (© 2021 Wiley-VCH GmbH.)

Several aspects such as the growth relation between the layers of the GaN/AlN/SiC heterostructure, the consistency of the interfaces, and elemental diffusion are achieved by High Resolution Transmission Electron Microscopy (HR-TEM). In addition, the dislocation densities together with the defect correlation lengths are investigated via High-Resolution X-ray Diffraction (HR-XRD) and the characteristic positron diffusion length is achieved by Doppler Broadening Spectroscopy (DBS). Moreover, a comparative analysis with our previous work (i.e., GaN/AlN/Si and GaN/AlN/Al 2 O 3 ) has been carried out. Within the epitaxial GaN layer defined by the relationship F4¯3m (111) 3C-SiC || P63mc (0002) AlN || P63mc (0002) GaN, the total dislocation density has been assessed as being 1.47 × 10 10 cm -2 . Compared with previously investigated heterostructures (on Si and Al 2 O 3 substrates), the obtained dislocation correlation lengths ( L e = 171 nm and L s =288 nm) and the mean distance between two dislocations ( r d = 82 nm) are higher. This reveals an improved crystal quality of the GaN with SiC as a growth template. In addition, the DBS measurements upheld the aforementioned results with a higher effective positron diffusion length LeffGaN2 = 75 ± 20 nm for the GaN layer.

Solid-gas interactions at electrode surfaces determine the efficiency of solid-oxide fuel cells and electrolyzers. Here, the correlation between surface-gas kinetics and the crystal orientation of perovskite electrodes is studied in the model system La 0.8 Sr 0.2 Co 0.2 Fe 0.8 O 3 . The gas-exchange kinetics are characterized by synthesizing epitaxial half-cell geometries where three single-variant surfaces are produced [i.e., La 0.8 Sr 0.2 Co 0.2 Fe 0.8 O 3 /La 0.9 Sr 0.1 Ga 0.95 Mg 0.05 O 3-δ /SrRuO 3 /SrTiO 3 (001), (110), and (111)]. Electrochemical impedance spectroscopy and electrical conductivity relaxation measurements reveal a strong surface-orientation dependency of the gas-exchange kinetics, wherein (111)-oriented surfaces exhibit an activity >3-times higher as compared to (001)-oriented surfaces. Oxygen partial pressure ( p O 2 )-dependent electrochemical impedance spectroscopy studies reveal that while the three surfaces have different gas-exchange kinetics, the reaction mechanisms and rate-limiting steps are the same (i.e., charge-transfer to the diatomic oxygen species). First-principles calculations suggest that the formation energy of vacancies and adsorption at the various surfaces is different and influenced by the surface polarity. Finally, synchrotron-based, ambient-pressure X-ray spectroscopies reveal distinct electronic changes and surface chemistry among the different surface orientations. Taken together, thin-film epitaxy provides an efficient approach to control and understand the electrode reactivity ultimately demonstrating that the (111)-surface exhibits a high density of active surface sites which leads to higher activity., (© 2021 Wiley-VCH GmbH.)

Bismuth ferrite (BiFeO 3 ) has recently become interesting as a room-temperature multiferroic material, and a variety of prototype devices have been designed based on its thin films. A low-cost and simple processing technique for large-area and high-quality BiFeO 3 thin films that is compatible with current semiconductor technologies is therefore urgently needed. Development of BiFeO 3 thin films is summarized with a specific focus on the chemical solution route. By a systematic analysis of the recent progress in chemical-route-derived BiFeO 3 thin films, the challenges of these films are highlighted. An all-solution chemical-solution deposition (AS-CSD) for BiFeO 3 thin films with different orientation epitaxial on various oxide bottom electrodes is introduced and a comprehensive study of the growth, structure, and ferroelectric properties of these films is provided. A facile low-cost route to prepare large-area high-quality epitaxial BFO thin films with a comprehensive understanding of the film thickness, stoichiometry, crystal orientation, ferroelectric properties, and bottom electrode effects on evolutions of microstructures is provided. This work paves the way for the fabrication of devices based on BiFeO 3 thin films., (© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Atomic layer deposition (ALD) was used to control the stoichiometry of thin lithium aluminosilicate films, thereby enabling crystallization into the ion-conducting β-eucryptite LiAlSiO 4 phase. The rapid thermal annealed ALD film developed a well-defined epitaxial relationship to the silicon substrate: β-LiAlSiO 4 (12̅10)||Si (100) and β-LiAlSiO 4 (101̅0)||Si (001). The extrapolated room temperature ionic conductivity was found to be 1.2 × 10 -7 S/cm in the [12̅10] direction. Because of the unique 1-D channel along the c axis of β-LiAlSiO 4 , the epitaxial thin film has the potential to facilitate ionic transport if oriented with the c axis normal to the electrode surface, making it a promising electrolyte material for three-dimensional lithium-ion microbatteries.

The study of ionic materials on nanometer scale is of great relevance for efficient miniaturized devices for energy applications. The epitaxial growth of thin films can be a valid route to tune the properties of the materials and thus obtain new degrees of freedom in materials design. High crystal quality Sm x Ce 1- x O 2-δ films are here reported at a high doping level up to x = 0.4, thanks to the good lattice matching with the (110) oriented NdGaO 3 substrate. X-ray diffraction and transmission electron microscopy demonstrate the ordered structural quality and absence of Sm segregation at the macroscopic and atomic level, respectively. Therefore, in epitaxial thin films, the homogeneous doping can be obtained even with the high dopant content not always approachable in bulk form, getting even an improvement of the structural properties. In situ spectroscopic measurements by X-ray photoemission and X-ray absorption show the O 2p band shift toward the Fermi level, which can favor the oxygen exchange and vacancy formation on the surface when the Sm doping is increased to x = 0.4. X-ray absorption spectroscopy also confirms the absence of ordered oxygen vacancy clusters and further reveals that the 5d e g and t 2g states are well separated by the crystal field in the undistorted local structure even in the case of a high doping level up to x = 0.4.

Heusler-type magnetic shape memory alloys (MSMAs) exhibit a martensitic transformation (MT) accompanied by a complex magnetic reordering, strongly affected by an intricate martensitic microstructure. The hierarchic twin structure of martensite, formed as a result of minimization of elastic energy down to atomic scale, is under intensive study nowadays. On the other hand, the much more sophisticated problem of the relationship between nanoscale twin structure and the magnetism in MSMAs has being tackled only recently. It will be shown in this topical review that the nanotwin structure affects not only the basic magnetic parameters of MSMAs, but also can change qualitatively its magnetic nature and related magnetodynamic and magnetoresistance properties. This will be primarily illustrated, both theoretically and experimentally, on the prototype Ni-Mn-Ga and Ni(Co)-Mn-Sn MSMAs in the form of epitaxial thin films, but the conclusions are also valid for other Heusler-type MSMAs, both in the form of thin films, ribbons and bulk single crystals and polycrystals. The following new and remarkable phenomena will be highlighted. (i) A strong ferromagnetic exchange coupling is observed between the submicron twin components in Ni-Mn-Ga ferromagnetic martensite. It results in the modification of the average magnetic anisotropy and the formation of a non-collinear magnetic structure, whereby a negative magnetoresistance appears in a wide temperature range. (ii) Weak antiferromagnetic coupling occurs between the ferromagnetically ordered twin components in Ni(Co)-Mn-Sn martensite. This coupling enabled to explain the exchange bias and magnetic resonance spectra in the same terms as for artificial antiferromagnetically coupled multilayered structures., (© 2020 IOP Publishing Ltd.)

In quantum matters hosting electron-electron correlation and spin-orbit coupling, spatial inhomogeneities, arising from competing ground states, can be essential for understanding exotic topological properties. A prominent example is Hall anomalies observed in SrRuO 3 films, which were interpreted in terms of either magnetic skyrmion-induced topological Hall effect or inhomogeneous anomalous Hall effect (AHE). To clarify this ambiguity, we systematically investigated the evolution of AHE with controllable inhomogeneities in SrRuO 3 film thickness ( t SRO ). By exploiting the step-flow growth of SrRuO 3 films, we induced a microscopically ordered stripe pattern with one-unit-cell differences in t SRO . The associated spatial distribution of momentum-space Berry curvatures enables a two-channel AHE with hump-like Hall anomalies, which can be continuously engineered according to non-integer t SRO . We further microscopically characterized the stripe-like ferromagnetic domains and two-step magnetic switching behavior in the inhomogeneous SrRuO 3 film. These unique features can be utilized to identify the two-channel AHE model and understand its microscopic origin.

Mixed-valance manganites with strong electron correlation exhibit strong potential for spintronics, where emergent magnetic behaviors, such as propagation of high-frequency spin waves and giant topological Hall Effects can be driven by their mesoscale spin textures. Here, we create magnetic vortex clusters with flux closure spin configurations in single-crystal La 0.67 Sr 0.33 MnO 3 wire. A distinctive transformation from out-of-plane domains to a vortex state is directly visualized using magnetic force microscopy at 4 K in wires when the width is below 1.0 μm. The phase-field modeling indicates that the inhomogeneous strain, accompanying with shape anisotropy, plays a key role for stabilizing the flux-closure spin structure. This work offers a new perspective for understanding and manipulating the non-trivial spin textures in strongly correlated systems., (Copyright © 2019 Science China Press. Published by Elsevier B.V. All rights reserved.)

The present article evaluates, in qualitative and quantitative manners, the characteristics (i.e., thickness of layers, crystal structures, growth orientation, elemental diffusion depths, edge, and screw dislocation densities), within two GaN/AlN/Si heterostructures, that alter their efficiencies as positron moderators. The structure of the GaN film, AlN buffer layer, substrate, and their growth relationships were determined through high-resolution transmission electron microscopy (HR-TEM). Data resulting from high-resolution X-ray diffraction (HR-XRD) was mathematically modeled to extract dislocation densities and correlation lengths in the GaN film. Positron depth profiling was evaluated through an experimental Doppler broadening spectroscopy (DBS) study, in order to quantify the effective positron diffusion length. The differences in values for both edge (ρde) and screw (ρds) dislocation densities, and correlation lengths ( L e , L s ) found in the 690 nm GaN film, were associated with the better effective positron diffusion length ( L eff ) of LeffGaN2 = 43 ± 6 nm., Competing Interests: The authors declare no conflicts of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results.

This study assesses the characteristics (edge and screw dislocation density) of a commercially available GaN/AlN/Al 2 O 3 wafer. The heterostructure was evaluated by means of high-resolution X-ray diffraction (HR-XRD), high-resolution transmission electron microscopy (HR-TEM), and Doppler-Broadening Spectroscopy (DBS). The results were mathematically modeled to extract defect densities and defect correlation lengths in the GaN film. The structure of the GaN film, AlN buffer, Al 2 O 3 substrate and their growth relationships were determined through HR-TEM. DBS studies were used to determine the effective positron diffusion length of the GaN film. Within the epitaxial layers, defined by a [GaN P 63 m c (0 0 0 2) || P 63 m c AlN (0 0 0 2) || (0 0 0 2) R 3 ¯ c Al 2 O 3 ] relationship, regarding the GaN film, a strong correlation between defect densities, defect correlation lengths, and positron diffusion length was assessed. The defect densities ρ d e = 6.13 × 10 10 cm -2 , ρ d s = 1.36 × 10 10 cm -2 , along with the defect correlation lengths L e = 155 nm and L s = 229 nm found in the 289 nm layer of GaN, account for the effective positron diffusion length L eff ~60 nm.

Spin-orbit coupling (SOC), the interaction between the electron spin and the orbital angular momentum, can unlock rich phenomena at interfaces, in particular interconverting spin and charge currents. Conventional heavy metals have been extensively explored due to their strong SOC of conduction electrons. However, spin-orbit effects in classes of materials such as epitaxial 5 d -electron transition-metal complex oxides, which also host strong SOC, remain largely unreported. In addition to strong SOC, these complex oxides can also provide the additional tuning knob of epitaxy to control the electronic structure and the engineering of spin-to-charge conversion by crystalline symmetry. Here, we demonstrate room-temperature generation of spin-orbit torque on a ferromagnet with extremely high efficiency via the spin-Hall effect in epitaxial metastable perovskite SrIrO 3 We first predict a large intrinsic spin-Hall conductivity in orthorhombic bulk SrIrO 3 arising from the Berry curvature in the electronic band structure. By manipulating the intricate interplay between SOC and crystalline symmetry, we control the spin-Hall torque ratio by engineering the tilt of the corner-sharing oxygen octahedra in perovskite SrIrO 3 through epitaxial strain. This allows the presence of an anisotropic spin-Hall effect due to a characteristic structural anisotropy in SrIrO 3 with orthorhombic symmetry. Our experimental findings demonstrate the heteroepitaxial symmetry design approach to engineer spin-orbit effects. We therefore anticipate that these epitaxial 5 d transition-metal oxide thin films can be an ideal building block for low-power spintronics., Competing Interests: The authors declare no conflict of interest.

Complex multiphase nanocomposite designs present enormous opportunities for developing next-generation integrated photonic and electronic devices. Here, a unique three-phase nanostructure combining a ferroelectric BaTiO 3 , a wide-bandgap semiconductor of ZnO, and a plasmonic metal of Au toward multifunctionalities is demonstrated. By a novel two-step templated growth, a highly ordered Au-BaTiO 3 -ZnO nanocomposite in a unique "nanoman"-like form, i.e., self-assembled ZnO nanopillars and Au nanopillars in a BaTiO 3 matrix, is realized, and is very different from the random three-phase ones with randomly arranged Au nanoparticles and ZnO nanopillars in the BaTiO 3 matrix. The ordered three-phase "nanoman"-like structure provides unique functionalities such as obvious hyperbolic dispersion in the visible and near-infrared regime enabled by the highly anisotropic nanostructures compared to other random structures. Such a self-assembled and ordered three-phase nanocomposite is obtained through a combination of vapor-liquid-solid (VLS) and two-phase epitaxy growth mechanisms. The study opens up new possibilities in the design, growth, and application of multiphase structures and provides a new approach to engineer the ordering of complex nanocomposite systems with unprecedented control over electron-light-matter interactions at the nanoscale., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

With the advances in artificial intelligence and communication technologies, flexible microwave magnetic materials have become essential for flexible microwave detectors, wearable microwave sensors, and flexible spintronics. Here, a highly stable in-plane (IP) ferromagnetic resonance (FMR) and a tunable out-of-plane (OOP) FMR character are demonstrated in the flexible microwave magnetic Li 0.35 Zn 0.3 Fe 2.35 O 4 (LZFO) (111) epitaxial thin films under external mechanical bending. Both the IP FMR line width and resonance field ( H r ) are basically unchanged when the sample was bent under an external tensile or compressive bending strain and deformation. However, the OOP FMR spectra (including H r and absorption peak) could be tuned by mechanical bending, i.e., the LZFO sample possesses two OOP FMR absorption peaks at an external bending curvature. Meanwhile, excellent mechanical antifatigue and mechanical retention characteristics have also been obtained in the LZFO sample. The highly stable IP and the tunable OOP FMR spectra in the same LZFO sample with excellent mechanical antifatigue character have a promising prospect in microwave magnetic devices and flexible spintronics.

Perovskite multiferroic oxides are promising materials for the realization of sensitive and switchable photodiodes because of their favorable band gap (<3.0 eV), high absorption coefficient, and tunable internal ferroelectric (FE) polarization. A high-speed switchable photodiode based on multiferroic Bi 2 FeCrO 6 (BFCO)/SrRuO 3 (SRO)-layered heterojunction was fabricated by pulsed laser deposition. The heterojunction photodiode exhibits a large ideality factor ( n = ∼5.0) and a response time as fast as 68 ms, thanks to the effective charge carrier transport and collection at the BFCO/SRO interface. The diode can switch direction when the electric polarization is reversed by an external voltage pulse. The time-resolved photoluminescence decay of the device measured at ∼500 nm demonstrates an ultrafast charge transfer (lifetime = ∼6.4 ns) in BFCO/SRO heteroepitaxial structures. The estimated responsivity value at 500 nm and zero bias is 0.38 mA W -1 , which is so far the highest reported for any FE thin film photodiode. Our work highlights the huge potential for using multiferroic oxides to fabricate highly sensitive and switchable photodiodes.

Oxygen vacancy dynamic behavior at room temperature in complex oxides was carefully explored by using a combined approach of ion liquid gating technique and resistance measurements. Heterostructures of PrBaCo 2 O 5+δ /Gd 2 O 3 -doped CeO 2 epitaxial thin films were fabricated on (001) Y 2 O 3 -stabilized ZrO 2 single crystal substrates for systematically investigating the oxygen redox dynamics. The oxygen dynamic changes as response to the gating voltage and duration were precisely detected by in situ resistance measurements. A reversible and nonvolatile resistive switching dynamics was detected at room temperature under the gating voltage >13.5 V with pulse duration >1 s.

Phase transitions in correlated materials can be manipulated at the nanoscale to yield emergent functional properties, promising new paradigms for nanoelectronics and nanophotonics. Vanadium dioxide (VO 2 ), an archetypal correlated material, exhibits a metal-insulator transition (MIT) above room temperature. At the thicknesses required for heterostructure applications, such as an optical modulator discussed here, the strain state of VO 2 largely determines the MIT dynamics critical to the device performance. We develop an approach to control the MIT dynamics in epitaxial VO 2 films by employing an intermediate template layer with large lattice mismatch to relieve the interfacial lattice constraints, contrary to conventional thin film epitaxy that favors lattice match between the substrate and the growing film. A combination of phase-field simulation, in situ real-time nanoscale imaging, and electrical measurements reveals robust undisturbed MIT dynamics even at preexisting structural domain boundaries and significantly sharpened MIT in the templated VO 2 films. Utilizing the sharp MIT, we demonstrate a fast, electrically switchable optical waveguide. This study offers unconventional design principles for heteroepitaxial correlated materials, as well as novel insight into their nanoscale phase transitions.

A variety of emergent phenomena have been enabled by interface engineering in complex oxides. The existence of an intrinsic interfacial layer has often been found at oxide heterointerfaces. However, the role of such an interlayerin controlling functionalities is not fully explored. Here, we report the control of the exchange bias (EB) in single-phase manganite thin films with nominallyuniform chemical composition across the interfaces. The sign of EB depends on the magnitude of the cooling field. A pinned layer, confirmed by polarized neutron reflectometry, provides the source of unidirectional anisotropy. The origin of the exchange bias coupling is discussed in terms of magnetic interactions between the interfacial ferromagnetically reduced layer and the bulk ferromagnetic region. The sign of EB is related to the frustration of antiferromagnetic coupling between the ferromagnetic region and the pinned layer. Our results shed new light on using oxide interfaces to design functional spintronic devices., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We present a promising technology for nonvolatile flexible electronic devices: A direct fabrication of epitaxial lead zirconium titanate (PZT) on flexible mica substrate via van der Waals epitaxy. These single-crystalline flexible ferroelectric PZT films not only retain their performance, reliability, and thermal stability comparable to those on rigid counterparts in tests of nonvolatile memory elements but also exhibit remarkable mechanical properties with robust operation in bent states (bending radii down to 2.5 mm) and cycling tests (1000 times). This study marks the technological advancement toward realizing much-awaited flexible yet single-crystalline nonvolatile electronic devices for the design and development of flexible, lightweight, and next-generation smart devices with potential applications in electronics, robotics, automotive, health care, industrial, and military systems.

Quantum Hall conductance in monolayer graphene on an epitaxial SrTiO 3 (STO) thin film is studied to understand the role of oxygen vacancies in determining the dielectric properties of STO. As the gate-voltage sweep range is gradually increased in the device, systematic generation and annihilation of oxygen vacancies, evidenced from the hysteretic conductance behavior in the graphene, are observed. Furthermore, based on the experimentally observed linear scaling relation between the effective capacitance and the voltage sweep range, a simple model is constructed to manifest the relationship among the dielectric properties of STO with oxygen vacancies. The inherent quantum Hall conductance in graphene can be considered as a sensitive, robust, and noninvasive probe for understanding the electronic and ionic phenomena in complex transition-metal oxides without impairing the oxide layer underneath., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The coexistence and coupling of ferromagnetic and ferroelectric orders in a single material is crucial for realizing next-generation multifunctional applications. The coexistence of such orders is confirmed at room temperature in epitaxial thin films of BiFe 1- x Co x O 3 (x ≤ 0.15), which manifests a spin structure change from a low-temperature cycloidal one to a high-temperature collinear one with canted ferromagnetism., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Metastable polymorphs, many of which have never been fabricated, have been predicted to exhibit interesting and technologically relevant properties. Epitaxial synthesis is a powerful structure-directing method that can produce metastable polymorphs but is typically done in a trial and error fashion. Unfortunately, the relevant thermodynamic terms governing epitaxial synthesis of new materials are unknown. Accurate calculation of the relevant thermodynamic terms and their incorporation into predictive models would accelerate the synthesis of metastable polymorphs by identifying thermodynamically favorable paths. Using density functional theory with three different functionals, we computed several relevant terms for TiO 2 anatase (A) and rutile (R) film growth on low-index surfaces of SrTiO 3 (STO) and BaTiO 3 (BTO) cubic perovskites. After identifying potential coherent epitaxial interfaces based on experimental observations, the volumetric formation, volumetric strain, and areal substrate-film interface energies were calculated for (001) A ∥(001) (S/B)TO , (102) A ∥(011) (S/B)TO , (100) R ∥(111) (S/B)TO , and (112) A ∥(111) (S/B)TO coherent interfaces. These terms were integrated into a standard model of epitaxial nucleation, and the results yielded reasonable agreement between experimental observations and DFT predictions of the preferred epitaxial polymorph. Predicted trends in epitaxial stability were essentially independent of the three functionals used in the calculations. These results are discussed in light of their promise that DFT-informed epitaxial film growth can accelerate fabrication of new polymorphs. These results also validate the recently proposed 20 kJ/mol stability window for predicting which polymorphs could be epitaxially stabilized.

Self-assembly via nanoscale phase separation offers an elegant route to fabricate nanocomposites with physical properties unattainable in single-component systems. One important class of nanocomposites are optical metamaterials which exhibit exotic properties and lead to opportunities for agile control of light propagation. Such metamaterials are typically fabricated via expensive and hard-to-scale top-down processes requiring precise integration of dissimilar materials. In turn, there is a need for alternative, more efficient routes to fabricate large-scale metamaterials for practical applications with deep-subwavelength resolution. Here, we demonstrate a bottom-up approach to fabricate scalable nanostructured metamaterials via spinodal decomposition. To demonstrate the potential of such an approach, we leverage the innate spinodal decomposition of the VO 2 -TiO 2 system, the metal-to-insulator transition in VO 2 , and thin-film epitaxy, to produce self-organized nanostructures with coherent interfaces and a structural unit cell down to 15 nm (tunable between horizontally and vertically aligned lamellae) wherein the iso-frequency surface is temperature-tunable from elliptic to hyperbolic dispersion producing metamaterial behavior. These results provide an efficient route for the fabrication of nanostructured metamaterials and other nanocomposites for desired functionalities.

The nanoscale origins of ferroelastic domain wall motion in ferroelectric multilayer thin films that lead to giant electromechanical responses are investigated. We present direct evidence for complex underpinning factors that result in ferroelastic domain wall mobility using a combination of atomic-level aberration corrected scanning transmission electron microscopy and phase-field simulations in model epitaxial (001) tetragonal (T) PbZr x Ti 1-x O 3 (PZT)/rhombohedral (R) PbZr x Ti 1-x O 3 (PZT) bilayer heterostructures. The local electric dipole distribution is imaged on an atomic scale for a ferroelastic domain wall that nucleates in the R-layer and cuts through the composition breaking the T/R interface. Our studies reveal a highly complex polarization rotation domain structure that is nearly on the knife-edge at the vicinity of this wall. Induced phases, namely tetragonal-like and rhombohedral-like monoclinic were observed close to the interface, and exotic domain arrangements, such as a half-4-fold closure structure, are observed. Phase field simulations show this is due to the minimization of the excessive elastic and electrostatic energies driven by the enormous strain gradient present at the location of the ferroelastic domain walls. Thus, in response to an applied stimulus, such as an electric field, any polarization reorientation must minimize the elastic and electrostatic discontinuities due to this strain gradient, which would induce a dramatic rearrangement of the domain structure. This insight into the origins of ferroelastic domain wall motion will allow researchers to better "craft" such multilayered ferroelectric systems with precisely tailored domain wall functionality and enhanced sensitivity, which can be exploited for the next generation of integrated piezoelectric technologies.

Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as microsolid oxide fuel cells, electrolyzers, sensors, and memristors. In this paper, we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol % of samaria, an enhancement in the defect association is observed by Raman spectroscopy. The role of such associated defects on the films̀ oxygen ion transport and exchange is investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has a sharp maximum in ionic conductivity and drops in its activation energy down to 0.6 eV for 20 mol % doping. Increasing the doping concentration further up to 40 mol %, it raises the activation energy substantially by a factor of 2. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first-order reversal curve measurements indicates that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol % of samaria. In a model experiment, through a solid solution series of samaria doped ceria epitaxial films, we reveal that the occurrence of associated defects in the bulk affects the surface charging state of the SDC films to increase the exchange rates. The implication of these findings is the design of coatings with tuned oxygen surface exchange by controlling the bulk associated clusters for future electrocatalytic applications.

Employing atomic layer deposition, we have grown p-type epitaxial undoped and N-doped anatase TiO2(001) thin films on c-axis Al2O3 substrate. From X-ray diffraction and transmission electron microscopy studies, crystallographic relationships between the film and the substrate are found to be (001)TiO2//(0001)Al2O3 and [1̅10]TiO2//[011̅0]Al2O3. N-doping in TiO2 thin films enhances the hole concentration and mobility. The optical band gap of anatase TiO2 (3.23 eV) decreases to 3.07 eV upon N-doping. The epitaxial films exhibit room-temperature ferromagnetism and photoresponse. A TiO2-based homojunction diode was fabricated with rectification from the p-n junction formed between N-doped p-TiO2 and n-TiO2.

The evolution of interface between the epitaxial thin film LiCoO2 (LCO) electrode and liquid electrolyte and inside the LCO film during electrochemical cycling has been analyzed by high resolution scanning transmission electron microscopy. Relaxation of sharp translational domain boundaries with mismatched layers of CoO2 octahedra occurs during cycling and results in formation of continuous CoO2 layers across the boundaries. The original trigonal layered structure of LiCoO2 tends to change into a spinel structure at the electrode/electrolyte interface after significant extraction of Li from LCO. This change is more pronounced at 4.2 V peak of CV, indicating lower stability of the layered LCO structure near its surface after Li is extracted above 60%. The transformed structure is identified to be close to Co3O4, with Co both on tetrahedral and octahedral sites, rather than to LiCo2O4 as it was suggested in earlier publications. Electron energy-loss spectroscopy measurements also show that Co ions oxidation state is reduced to mixed valence state Co(2+)/Co(3+) during the structure changes to spinel rather than oxidized.

Epitaxial LiCoO2 (LCO) thin films of different orientations were fabricated by pulsed laser deposition (PLD) in order to model single-crystal behavior during electrochemical reaction. This paper demonstrates that deposition of conductive SrRuO3 between a SrTiO3 (STO) substrate and an LCO film allows (1) epitaxial growth of LCO with orientation determined by STO and (2) electrochemical measurements, such as cyclic voltammetry and impedance spectroscopy. Scanning transmission electron microscopy (S/TEM and SEM) has demonstrated an orientation relationship between LCO and STO of three orientations, (111), (110) and (100), and identified a LCO/electrolyte surface as consisting of two crystallographic facets of LCO, (001) and {104}. The difference in the orientation of LCO accounts for the difference in the exposed area of {104} planes to the electrolyte, where lithium ions have easy access to fast diffusion planes. The resistance for lithium ion transfer measured by electrochemical impedance spectroscopy had inverse correlation with exposed area of {104} plane measured by TEM. Chemical diffusivity of lithium ions in LCO was measured by fitting electrochemical impedance spectroscopy data to a modified Randles equivalent circuit and allowed us to determine its dependence on film orientation.

Epitaxial strain alters the physical properties of thin films grown on single crystal substrates. Thin film oxides are particularly apt for strain engineering new functionalities in ferroic materials. In the case of La(2/3)Ca(1/3)MnO(3) (LCMO) thin films, here we show the first experimental images obtained by electron holography demonstrating that epitaxial strain induces the segregation of a flat and uniform nonferromagnetic layer with antiferromagnetic (AFM) character at the top surface of a ferromagnetic (FM) layer, the whole film being chemical and structurally homogeneous at room temperature. For different substrates and growth conditions the tetragonality of LCMO at room temperature, defined as τ = |c - a|/a, is the driving force for a phase coexistence above an approximate critical value of τC ≈ 0.024. Theoretical calculations prove that the increased tetragonality changes the energy balance of the FM and AFM ground states in strained LCMO, enabling the formation of magnetically inhomogeneous states. This work gives the key evidence that opens a new route to synthesize strain-induced exchanged-biased FM-AFM bilayers in single thin films, which could serve as building blocks of future spintronic devices.

Next-generation devices will rely on exotic functional properties not found in traditional systems. One class of materials of particular interest for applications are those possessing metal-to-insulator transitions (MITs). In this work, we probe the relationship between variations in the growth process, subsequent variations in cation stoichiometry, and the MIT in NdNiO3 thin films. Slight variations in the growth conditions, in particular the laser fluence, during pulsed-laser deposition growth of NdNiO3 produces films that are both single-phase and coherently strained to a range of substrates despite possessing as much as 15% Nd-excess. Subsequent study of the temperature-dependence of the electronic transport reveals dramatic changes in both the onset and magnitude of the resistivity change at the MIT with increasing cation nonstoichiometry giving rise to a decrease (and ultimately a suppression) of the transition and the magnitude of the resistivity change. From there, the electronic transport of nearly ideal NdNiO3 thin films are studied as a function of epitaxial strain, thickness, and orientation. Overall, transitioning from tensile to compressive strain results in a systematic reduction of the onset and magnitude of the resistivity change across the MIT, thinner films are found to possess sharper MITs with larger changes in the resistivity at the transition, and (001)-oriented films exhibit sharper and larger MITs as compared to (110)- and (111)-oriented films as a result of highly anisotropic in-plane transport in the latter.

Using pulsed laser deposition, TiO2 (-) B and its recently discovered variant Ca:TiO2 (-) B (CaTi5O11) are synthesized as highly crystalline thin films for the first time by a completely water-free process. Significant enhancement in the Li-ion battery performance is achieved by manipulating the crystal orientation of the films, used as anodes, with a demonstration of extraordinary structural stability under extreme conditions., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A multipurpose six-axis κ-diffractometer, together with the brilliance of the ESRF light source and a CCD area detector, has been explored for studying epitaxial relations and crystallinity in thin film systems. The geometrical flexibility of the six-axis goniometer allows measurement of a large volume in reciprocal space, providing an in-depth understanding of sample crystal relationships. By a set of examples of LaAlO3 thin films deposited by the atomic layer deposition technique, the possibilities of the set-up are presented. A fast panoramic scan provides determination of the crystal orientation matrices, prior to more thorough inspection of single Bragg nodes. Such information, in addition to a broadening analysis of families of single reflections, is shown to correlate well with the crystallinity, crystallite size, strain and epitaxial relationships in the thin films. The proposed set-up offers fast and easy sample mounting and alignment, along with crucial information on key features of the thin film structures.