Nagarajan Valanoor

Enhanced nonvolatile resistive switching in dilutely cobalt doped TiO2

Incorporation of dilute concentration of dopant having a valence state different than that of the host cation enables controlled incorporation proximity vacancy defects for local charge balance. Since nonvolatile resistive switching is a phenomenon tied to such defects, it can be expected to be influenced by dilute doping. In this work, we demonstrate that enhanced nonvolatile resistive switching is realized in dilutely cobalt doped TiO2 films grown at room temperature. We provide essential characterizations and analyses. We suggest that the oxygen vacancies in the proximity of immobile dopants provide well distributed anchors for the development of systematic filamentary tracks.

Interface mediated resistive switching in epitaxial NiO nanostructures

We report on the non-volatile resistive switching properties of epitaxial nickel oxide (NiO) nanostructures, 10-100 nm wide and up to 30 nm high grown on (001)-Nb:SrTiO3 substrates. Conducting-atomic force microscopy on individual nano-islands confirms prominent bipolar switching with a maximum ON/OFF ratio of ∼103 at a read voltage of ∼+0.4 V. This ratio is found to decrease with increasing height of the nanostructure. Linear fittings of I-V loops reveal that low and high resistance states follow Ohmic-conduction and Schottky-emission mechanism, respectively. The switching behavior (dependence on height) is attributed to the modulation of the carrier density at the nanostructure-substrate interface due to the applied electric field.

A Template and Catalyst-Free Metal-Etching-Oxidation Method to Synthesize Aligned Oxide Nanowire Arrays: NiO as an Example

Although NiO is one of the canonical functional binary oxides, there has been no report so far on the effective fabrication of aligned single crystalline NiO nanowire arrays. Here we report a novel vapor-based metal-etching-oxidation method to synthesize high-quality NiO nanowire arrays with good vertical alignment and morphology control. In this method, Ni foils are used as both the substrates and the nickel source; NiCl(2) powder serves as the additional Ni source and provides Cl(2) to initiate mild etching. No template is deliberately employed; instead a nanograined NiO scale formed on the NiO foil guides the vapor infiltration and assists the self-assembled growth of NiO nanowires via a novel process comprising simultaneous Cl(2) etching and gentle oxidation. Furthermore, using CoO nanowires and Co-doped NiO as examples, we show that this general method can be employed to produce nanowires of other oxides as well as the doped counterparts.

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...

Epitaxial (001) BiFeO3 thin-films with excellent ferroelectric properties by chemical solution deposition-the role of gelation

High-quality phase-pure (001) epitaxial bismuth ferrite (BiFeO3; BFO) thin films have been realized by chemical solution deposition. A thorough chemical investigation of the precursor molecular changes during gelation reveals that control of the delicate balance between gelation and salt (metal nitrate) precipitation through solvent evaporation is the key to a homogenous gel, necessary to ultimately obtain high-quality films. Spin-coating at 3000 rpm for 30 seconds on a preheated STO(001) substrate (∼70 °C) and subsequent heating at 90 °C leads to a suitable gel, which is then heated to 650 °C for crystallization. Pure phase BFO thin films of 150 nm thickness prepared by this route on lanthanum strontium manganite (La0.67Sr0.33MnO3; LSMO) buffered (001)-SrTiO3 (STO) substrates are shown to have not only epitaxial nature, but also robust ferroelectric properties with low coercive field. Critically, we show that these films can be achieved using stoichiometric 0.25 M precursors (with no Bi excess), thus obviating complexities typically arising from secondary phases associated with precursors having excess Bi. Square hysteresis loops with a high remanent polarization of 2Pr = 97.8 μC cm−2 and a low coercive field of 2Ec = 203.5 kV cm−1 are obtained at room temperature. Frequency-dependent hysteresis loops reveal a switching mechanism that is nucleation dominated. In addition, polarization direction dependent resistive switching behavior is also observed. The findings here thus show it is possible to realize high-quality bismuth ferrite thin films via chemical process techniques.

Robust polarization and strain behavior of sm-modified BiFeO 3 piezoelectric ceramics

The route to phase-pure BiFeO3 (BFO) ceramics with excellent ferroelectric and electromechanical properties is severely impeded by difficulties associated with the perovskite phase stability during synthesis. This has meant that dopants and solid solutions with BFO have been investigated as a means of not only improving the functional properties, but also of improving the perovskite phase formation of BFO-based ceramics. The present work focuses on Sm-modified BFO ceramics of composition Bi0.88Sm0.12FeO3. The polarization and strain behaviors were investigated as a function of the phase composition, microstructure, and chemical composition. Addition of Sm reduces the susceptibility of the BFO perovskite to phase degradation by Si impurities. Si was observed to react into Sm-rich grains dispersed within the microstructure, with no large increases in the amount of bismuth-parasitic phases, namely Bi25FeO39 and Bi2Fe4O9. These as-prepared ceramics exhibited robust polarization behavior showing maximum remnant polarizations of ~40 to 50 μC/cm2. The electric-fieldinduced strain showed an appreciable stability in terms of the driving field frequency with maximum peak-to-peak strains of ~0.3% and a coercive field of ~130 kV/cm.

Chemical solution deposition derived (001)-oriented epitaxial BiFeO3 thin films with robust ferroelectric properties using stoichiometric precursors (invited)

Phase pure bismuth ferrite (BiFeO3) thin films with (001)-oriented epitaxial structure are realized on lanthanum strontium manganite (La0.67Sr0.33MnO3) buffered (001)-SrTiO3 substrates by chemical solution deposition. The annealing process is optimized such that a stoichiometric precursor can be used to accurately control the Bi:Fe ratio. Ferroelectric, dielectric, and resistive switching behaviours are investigated for 40 nm, 70 nm, and 150 nm BFO thin films. While the thinnest film (40 nm) shows very leaky loops, square and fully saturated polarization hysteresis loops are shown for the thicker films. The highest remanent polarization (2Pr = 100 μC/cm2) and relative dielectric constant (er = 613) are obtained in the 150 nm BFO thin film. High cycle fatigue tests show that the thick films are resistant to polarization fatigue. Piezoresponse force microscopy results show that the domain structure varies with thickness. Resistive switching and polarization mediated diode effects are also observed. These ro...

Higher order harmonic detection for exploring nonlinear interactions with nanoscale resolution

Nonlinear dynamics underpin a vast array of physical phenomena ranging from interfacial motion to jamming transitions. In many cases, insight into the nonlinear behavior can be gleaned through exploration of higher order harmonics. Here, a method using band excitation scanning probe microscopy (SPM) to investigate higher order harmonics of the electromechanical response, with nanometer scale spatial resolution is presented. The technique is demonstrated by probing the first three harmonics of strain for a Pb(Zr1-xTix)O3 (PZT) ferroelectric capacitor. It is shown that the second order harmonic response is correlated with the first harmonic response, whereas the third harmonic is not. Additionally, measurements of the second harmonic reveal significant deviations from Rayleigh-type models in the form of a much more complicated field dependence than is observed in the spatially averaged data. These results illustrate the versatility of nth order harmonic SPM detection methods in exploring nonlinear phenomena in nanoscale materials.

Nanoscale modulation of electronic states across unit cell steps on the surface of an epitaxial colossal magnetoresistance manganite film

The nature of electronic states near the edge of unit cell steps on the surface of epitaxial La0.7Sr0.3MnO3 (LSMO) thin films grown by real-time reflection high energy electron diffraction monitored pulsed laser deposition is examined by scanning tunneling microscopy and scanning tunneling spectroscopy techniques. It is observed that the electronic states are strongly modulated near the step edge with considerably high gap at the edge and low gap on the terrace. This modulation weakens at low temperature. The temperature evolution of the density of states and the nature of gap in deep metallic state of LSMO are also discussed.

Microstructural analysis of interfaces in a ferromagnetic-multiferroic epitaxial heterostructure

We report a study on multiferroic bismuth ferrite (BiFeO3, BFO)-ferromagnetic lanthanum strontium manganese oxide (La0.7Sr0.3MnO3, LSMO) epitaxial interfaces by scanning transmission electron microscopy-energy dispersive spectroscopy (STEM-EDS) and energy-filtered transmission electron microscopy (EFTEM). Epitaxial (001) oriented LSMO/BFO heterostructures were fabricated on a (001) strontium titanate (SrTiO3, STO) substrate using pulsed laser deposition (PLD). Different cooling conditions to room temperature (rapid or slow) were used to investigate the effect of fabrication conditions on the structural quality of the interfaces. The combined analysis of bright field transmission electron microscopy imaging, STEM-EDS and EFTEM data reveals that the LSMO-BFO heterostructure interface is free from any defects but the phases are chemically interdiffused over a length scale of ∼4 nm.