Metamaterials present great potential in the applications of solar cells and nanophotonics, such as super lenses and other meta devices, owing to their superior optical properties. In particular, hyperbolic metamaterials (HMMs) with exceptional optical anisotropy offer improved manipulation of light–matter interactions as well as a divergence in the density of states and thus show enhanced performances in related fields. Recently, the emerging field of oxide–metal vertically aligned nanocomposites (VANs) suggests a new approach to realize HMMs with flexible microstructural modulations. In this work, a new oxide–metal metamaterial system, CeO 2 –Au, has been demonstrated with variable Au phase morphologies from nanoparticle-in-matrix (PIM), nanoantenna-in-matrix, to VAN. The effective morphology tuning through deposition background pressure, and the corresponding highly tunable optical performance of three distinctive morphologies, were systematically explored and analyzed. A hyperbolic dispersion at high wavelength has been confirmed in the nano-antenna CeO 2 –Au thin film, proving this system as a promising candidate for HMM applications. More interestingly, a new and abnormal in-plane epitaxy of Au nanopillars following the large mismatched CeO 2 matrix instead of the well-matched SrTiO 3 substrate, was discovered. Additionally, the tilting angle of Au nanopillars, α , has been found to be a quantitative measure of the balance between kinetics and thermodynamics during the depositions of VANs. All these findings provide valuable information in the understanding of the VAN formation mechanisms and related morphology tuning.
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Induced ferroelectric phases in SrTiO 3 by a nanocomposite approach
Inducing new phases in thick films via vertical lattice strain is one of the critical advantages of vertically aligned nanocomposites (VANs). In SrTiO 3 (STO), the ground state is ferroelastic, and the ferroelectricity in STO is suppressed by the orthorhombic transition. Here, we explore whether vertical lattice strain in three-dimensional VANs can be used to induce new ferroelectric phases in SrTiO 3 :MgO (STO:MgO) VAN thin films. The STO:MgO system incorporates ordered, vertically aligned MgO nanopillars into a STO film matrix. Strong lattice coupling between STO and MgO imposes a large lattice strain in the STO film. We have investigated ferroelectricity in the STO phase, existing up to room temperature, using piezoresponse force microscopy, phase field simulation and second harmonic generation. We also serendipitously discovered the formation of metastable TiO nanocores in MgO nanopillars embedded in the STO film matrix. Our results emphasize the design of new phases via vertical epitaxial strain in VAN thin films.
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- NSF-PAR ID:
- 10230955
- Date Published:
- Journal Name:
- Nanoscale
- Volume:
- 12
- Issue:
- 35
- ISSN:
- 2040-3364
- Page Range / eLocation ID:
- 18193 to 18199
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract To investigate the role of interlayers on the growth, microstructure, and physical properties of 3D nanocomposite frameworks, a set of novel 3D vertically aligned nanocomposite (VAN) frameworks are assembled by a relatively thin interlayer (M) sandwiched by two consecutively grown La0.7Sr0.3MnO3(LSMO)‐ZnO VANs layers. ZnO nanopillars from the two VAN layers and the interlayer (M) create a heterogeneous 3D frame embedded in the LSMO matrix. The interlayer (M) includes yttria‐stabilized zirconia (YSZ), CeO2, SrTiO3, BaTiO3, and MgO with in‐plane matching distances increasing from ≈3.63 to ≈4.21 Å, and expected in‐plane strains ranging from tensile (≈8.81% on YSZ interlayer) to compressive (≈–6.23% on MgO interlayer). The metal‐insulator transition temperature increases from ≈133 K (M = YSZ) to ≈252 K (M = MgO), and the low‐field magnetoresistance peak value is tuned from ≈36.7% to ≈20.8%. The 3D heterogeneous frames empower excellent tunable magnetotransport properties and promising potentials for microstructure‐enabled applications.
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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).more » « less
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null (Ed.)Due to environmental concerns and the increasing drive towards miniaturization of electronic circuits and devices, lead-free ferroelectric films with low leakage current and robust ferroelectric and piezoelectric properties are highly desired. The preferred alternative, BaTiO 3 , is non-toxic and has ferroelectric properties, but its high leakage current, poor ferroelectricity and piezoelectricity and low Curie temperature of ∼130 °C in thin film form are obstacles for high-temperature practical applications. Here, we report that a negative-pressure-driven enhancement of ferroelectric Curie temperature and effective piezoelectric coefficient are achieved in (111)-oriented BaTiO 3 nanocomposite films. The enhanced ferroelectric and piezoelectric properties in the emergent monoclinic BaTiO 3 are attributed to the sharp vertical interface and 3D tensile strain that develops upon interspersing stiff and self-assembled vertical Sm 2 O 3 nanopillars through the film thickness. Our work also demonstrates that fabricating oxide films through (111)-oriented epitaxy opens up new avenues for the creation of new phase components and exploration of novel functionalities for developing oxide quantum electronic devices.more » « less
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null (Ed.)Integration of highly anisotropic multiferroic thin films on silicon substrates is a critical step towards low-cost devices, especially high-speed and low-power consumption memories. In this work, an oxide–metal vertically aligned nanocomposite (VAN) platform has been used to successfully demonstrate self-assembled multiferroic BaTiO 3 –Fe (BTO–Fe) nanocomposite films with high structural anisotropy on Si substrates. The effects of various buffer layers on the crystallinity, microstructure, and physical properties of the BTO–Fe films have been explored. With an appropriate buffer layer design, e.g. SrTiO 3 /TiN bilayer buffer, the epitaxial quality of the BTO matrix and the anisotropy of the Fe nanopillars can be improved greatly, which in turn enhances the physical properties, including the ferromagnetic, ferroelectric, and optical response of the BTO–Fe thin films. This unique combination of properties integrated on Si offers a promising approach in the design of multifunctional nanocomposites for Si-based memories and optical devices.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D0NR03460F
