Heng-Jui Liu

Epitaxial Photostriction-Magnetostriction Coupled Self-Assembled Nanostructures

Self-assembled vertical nanostructures take advantage of high interface-to-volume ratio and can be used to design new functionalities by the choice of a proper combination of constituents. However, most of the studies to date have emphasized the functional controllability of the nanostructures using external electric or magnetic fields. In this study, to introduce light (or photons) as an external control parameter in a self-assembled nanostructure system, we have successfully synthesized oxide nanostructures with CoFe(2)O(4) nanopillars embedded in a SrRuO(3) matrix. The combination of photostrictive SrRuO(3) and magnetostrictive CoFe(2)O(4) in the intimately assembled nanostructures leads to a light-induced, ultrafast change in magnetization of the CoFe(2)O(4) nanopillars. Our work demonstrates a novel concept on oxide nanostructure design and opens an alternative pathway for the explorations of diverse functionalities in heteroepitaxial self-assembled oxide nanostructures.

Interface control of surface photochemical reactivity in ultrathin epitaxial ferroelectric films

Asymmetrical electrical boundary conditions in (001)-oriented Pb(Zr0.2TiO0.8)O3 (PZT) epitaxial ultrathin ferroelectric films are exploited to control surface photochemical reactivity determined by the sign of the surface polarization charge. It is shown that the preferential orientation of polarization in the as-grown PZT layer can be manipulated by choosing an appropriate type of bottom electrode material. PZT films deposited on the SrRuO3 electrodes exhibit preferential upward polarization (C+) whilst the same films grown on the (La,Sr)CoO3-electrodes are polarized downward (C−). Photochemical activity of the PZT surfaces with different surface polarization charges has been tested by studying deposition of silver nanoparticles from AgNO3 solution under UV irradiation. PZT surfaces with preferential C+ orientation possess a more active surface for metal reduction than their C− counterparts, evidenced by large differences in the concentration of deposited silver nanoparticles. This effect is attributed t...

Origin of metallic behavior in NiCo2O4 ferrimagnet.

Predicting and understanding the cation distribution in spinels has been one of the most interesting problems in materials science. The present work investigates the effect of cation redistribution on the structural, electrical, optical and magnetic properties of mixed-valent inverse spinel NiCo2O4(NCO) thin films. It is observed that the films grown at low temperatures (T < 400 °C) exhibit metallic behavior while that grown at higher temperatures (T > 400 °C) are insulators with lower ferrimagnetic-paramagnetic phase transition temperature. So far, n-type Fe3O4 has been used as a conducting layer for the spinel thin films based devices and the search for a p-type counterpart still remains elusive. The inherent coexistence and coupling of ferrimagnetic order and the metallic nature in p-type NCO makes it a promising candidate for spintronic devices. Detailed X-ray Absorption and X–ray Magnetic Circular Dichroism studies revealed a strong correlation between the mixed-valent cation distribution and the resulting ferrimagnetic-metallic/insulating behavior. Our study clearly demonstrates that it is the concentration of Ni3+ions and the Ni3+–O2−Ni2+ double exchange interaction that is crucial in dictating the metallic behavior in NCO ferrimagnet. The metal-insulator and the associated magnetic order-disorder transitions can be tuned by the degree of cation site disorder via growth conditions.

Revealing the flexoelectricity in the mixed-phase regions of epitaxial BiFeO3 thin films

Understanding the elastic response on the nanoscale phase boundaries of multiferroics is an essential issue in order to explain their exotic behaviour. Mixed-phase BiFeO3 films, epitaxially grown on LaAlO3 (001) substrates, have been investigated by means of scanning probe microscopy to characterize the elastic and piezoelectric responses in the mixed-phase region of rhombohedral-like monoclinic (MI) and tilted tetragonal-like monoclinic (MII,tilt) phases. Ultrasonic force microscopy reveal that the regions with low/high stiffness values topologically coincide with the MI/MII,tilt phases. X-ray diffraction strain analysis confirms that the MI phase is more compliant than the MII,tilt one. Significantly, the correlation between elastic modulation and piezoresponse across the mixed-phase regions manifests that the flexoelectric effect results in the enhancement of the piezoresponse at the phase boundaries and in the MI regions. This accounts for the giant electromechanical effect in strained mixed-phase BiFeO3 films.

Structural study in highly compressed BiFeO3 epitaxial thin films on YAlO3

We report a study on the thermodynamic stability and structure analysis of the epitaxial BiFeO3 (BFO) thin films grown on YAlO3 (YAO) substrate. First, we observe a phase transition of MC–MA–T occurs in thin sample (<60 nm) with an utter tetragonal-like phase (denoted as MII here) with a large c/a ratio (∼1.23). Specifically, MII phase transition process refers to the structural evolution from a monoclinic MC structure at room temperature to a monoclinic MA at higher temperature (150 °C) and eventually to a presence of nearly tetragonal structure above 275 °C. This phase transition is further confirmed by the piezoforce microscopy measurement, which shows the rotation of polarization axis during the phase transition. A systematic study on structural evolution with thickness to elucidate the impact of strain state is performed. We note that the YAO substrate can serve as a felicitous base for growing T-like BFO because this phase stably exists in very thick film. Thick BFO films grown on YAO substrate exhi...

Van der Waals epitaxy of functional MoO2 film on mica for flexible electronics

Flexible electronics have a great potential to impact consumer electronics and with that our daily life. Currently, no direct growth of epitaxial functional oxides on commercially available flexible substrates is possible. In this study, in order to address this challenge, muscovite, a common layered oxide, is used as a flexible substrate that is chemically similar to typical functional oxides. We fabricated epitaxial MoO2 films on muscovite via pulsed laser deposition technique. A combination of X-ray diffraction and transmission electron microscopy confirms van der Waals epitaxy of the heterostructures. The electrical transport properties of MoO2 films are similar to those of the bulk. Flexible or free-standing MoO2 thin film can be obtained and serve as a template to integrate additional functional oxide layers. Our study demonstrates a remarkable concept to create flexible electronics based on functional oxides.

Large Magnetoresistance in Magnetically Coupled SrRuO3 –CoFe2O4 Self-Assembled Nanostructures

A new way to induce a large magnetoresistance has been achieved by self-assembled nanostructures consisting of ferromagnetic spinel CoFe₂O₄ (CFO) and metallic perovskite SrRuO₃ (SRO). The interdiffused Fe³⁺ ions in SRO have paved the way to strong magnetic couplings with CFO nanopillars, resulting in the suppression of spin-polarized electron scattering.

Atomic mechanism of polarization-controlled surface reconstruction in ferroelectric thin films

At the ferroelectric surface, the broken translational symmetry induced bound charge should significantly alter the local atomic configurations. Experimentally revealing the atomic structure of ferroelectric surface, however, is very challenging due to the strong spatial variety between nano-sized domains, and strong interactions between the polarization and other structural parameters. Here, we study surface structures of Pb(Zr0.2Ti0.8)O3 thin film by using the annular bright-field imaging. We find that six atomic layers with suppressed polarization and a charged 180° domain wall are at negatively poled surfaces, no reconstruction exists at positively poled surfaces, and seven atomic layers with suppressed polarization and a charged 90° domain wall exist at nominally neutral surfaces in ferroelastic domains. Our results provide critical insights into engineering ferroelectric thin films, fine grain ceramics and surface chemistry devices. The state-of-the-art methodology demonstrated here can greatly advance our understanding of surface science for oxides.

Complex oxide-noble metal conjugated nanoparticles.

Hybrid nanoparticles (NPs) composed of multiple components offer new opportunities for next-generation materials. In this study, a paradigm for the noble metal/ternary complex oxide hybrid NPs is reported by adopting pulsed laser ablation in liquids. As model hybrids, gold-spinel heterodimer (Au-CoFe2O4) and gold-pervoskite heterodimer (Au-SrTiO3) NPs are investigated. This work has demonstrated the diverse playgroup of NP conjugation enlarged by complex oxides.

Flexible ferroelectric element based on van der Waals heteroepitaxy

A flexible ferroelectric memory element based on oxide heteroepitaxy has been demonstrated with superior performance. 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.