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Abstract 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 LaCoO 3 with paramagnetism in bulk. In contrast, unexpected ferromagnetism is observed in tensile-strained LaCoO 3 films, however, its origin remains controversial. Here we simultaneously reveal the formation of ordered oxygen vacancies and previously unreported long-range suppression of CoO 6 octahedral rotations throughout LaCoO 3 films. Supported by density functional theory calculations, we find that the strong modification of Co 3 d -O 2 p 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 LaCoO 3 films while suggesting potential applications toward low-power spintronic devices. 

Highly promising performance for future computing applications is achieved based on a new materials design. 

We report the dielectric Properties of HfO 2 -based films in the optical–high frequency range. The demonstrated tunability of the optical dielectric constant of HfO 2 -based compounds is of great relevance for optoelectronic applications, e.g., high-refractive index dielectrics for nanoantenna and optical coatings for electronic displays. Since the optical dielectric constant of HfO 2 is determined by the electronic structure and its crystal environment, we tune the physical properties of HfO 2 films on MgO by adding different dopants. In this work, we aim to determine the influence of doping together with the resulting crystal structure on the optical dielectric constant. Hence, we studied 20 mol. % Y-doped HfO 2 (HYO), Hf 0.5 Zr 0.5 O 2 (HZO), and Hf 0.5 Ce 0.5 O 2 (HCO). Among the dopants, Y 2 O 3 has the lowest, ZrO 2 an intermediate, and CeO 2 the highest real part of the optical dielectric constant. The optical dielectric constant is found to be lowest in the cubic HYO films. An intermediate dielectric constant is found in HZO films that is predominantly in the monoclinic phase, but additionally hosts the cubic phase. The highest dielectric constant is observed in HCO films that are predominantly in the cubic phase with inclusions of the monoclinic phase. The observed trend is in good agreement with the dominant role of the dopant type in setting the optical dielectric constant. 

Vertically aligned nanocomposite (VAN) thin films have shown strong potential in oxide nanoionics but are yet to be explored in detail in solid-state battery systems. Their 3D architectures are attractive because they may allow enhancements in capacity, current, and power densities. In addition, owing to their large interfacial surface areas, the VAN could serve as models to study interfaces and solid-electrolyte interphase formation. Here, we have deposited highly crystalline and epitaxial vertically aligned nanocomposite films composed of a Li x La 0.32±0.05 (Nb 0.7±0.1 Ti 0.32±0.05 )O 3±δ -Ti 0.8±0.1 Nb 0.17±0.03 O 2±δ -anatase [herein referred to as LL(Nb, Ti)O-(Ti, Nb)O 2 ] electrolyte/anode system, the first anode VAN battery system reported. This system has an order of magnitude increased Li + ionic conductivity over that in bulk Li 3x La 1/3−x NbO 3 and is comparable with the best available Li 3x La 2/3−x TiO 3 pulsed laser deposition films. Furthermore, the ionic conducting/electrically insulating LL(Nb, Ti)O and electrically conducting (Ti, Nb)O 2 phases are a prerequisite for an interdigitated electrolyte/anode system. This work opens up the possibility of incorporating VAN films into an all solid-state battery, either as electrodes or electrolytes, by the pairing of suitable materials. 

δ-Bi 2 O 3 has long been touted as a potential material for use in solid oxide fuel cells (SOFC) due to its intrinsically high ionic conductivity. However, its limited operational temperature has led to stabilising the phase from >725 °C to room temperature either by doping, albeit with a compromise in conductivity, or by growing the phase confined within superlattice thin films. Superlattice architectures are challenging to implement in functional μSOFC devices owing to their ionic conducting channels being in the plane of the film. Vertically aligned nanocomposites (VANs) have the potential to overcome these limitations, as their nanocolumnar structures are perpendicular to the plane of the film, hence connecting the electrodes at top and bottom. Here, we demonstrate for the first time the growth of epitaxially stabilised δ-Bi 2 O 3 in VAN films, stabilised independently of substrate strain. The phase is doped with Dy and is formed in a VAN film which incorporates DyMnO 3 as a vertically epitaxially stabilising matrix phase. Our VAN films exhibit very high ionic conductivity, reaching 10 −3 S cm −1 at 500 °C. This work opens up the possibility to incorporate thin film δ-Bi 2 O 3 based VANs into functional μSOFC devices, either as cathodes (by pairing δ-Bi 2 O 3 with a catalytically active electronic conductor) and/or electrolytes (by incorporating δ-Bi 2 O 3 with an insulator). 

The emerging field of self-assembled vertically aligned nanocomposite (VAN) thin films effectively enables strain, interface, and microstructure engineering as well as (multi)functional improvements in electric, magnetic, optical, and energy-related properties. Well-ordered or patterned microstructures not only empower VAN thin films with many new functionalities but also enable VAN thin films to be used in nanoscale devices. Comparative ordered devices formed via templating methods suffer from critical drawbacks of processing complexity and potential contamination. Therefore, VAN thin films with spontaneous ordering stand out and display many appealing features for next-generation technological devices, such as electronics, optoelectronics, ultrahigh-density memory systems, photonics, and 3D microbatteries. The spontaneous ordering described in this review contains ordered/patterned structures in both in-plane and out-of-plane directions. In particular, approaches to obtaining spontaneously ordered/patterned structures in-plane are systematically reviewedfrom both thermodynamic and kinetic perspectives. Out-of-plane ordering is also discussed in detail. In addition to reviewing the progress of VAN films with spontaneous ordering, this article also highlights some recent developments in spontaneous ordering approaches and proposes future directions.