Junsoo Shin

Vector Piezoresponse Force Microscopy

A novel approach for nanoscale imaging and characterization of the orientation dependence of electromechanical properties-vector piezoresponse force microscopy (Vector PFM)-is described. The relationship between local electromechanical response, polarization, piezoelectric constants, and crystallographic orientation is analyzed in detail. The image formation mechanism in vector PFM is discussed. Conditions for complete three-dimensional (3D) reconstruction of the electromechanical response vector and evaluation of the piezoelectric constants from PFM data are set forth. The developed approach can be applied to crystallographic orientation imaging in piezoelectric materials with a spatial resolution below 10 nm. Several approaches for data representation in 2D-PFM and 3D-PFM are presented. The potential of vector PFM for molecular orientation imaging in macroscopically disordered piezoelectric polymers and biological systems is discussed.

Electronic transport imaging in a multiwire SnO2 chemical field-effect transistor device

The electronic transport and the sensing performance of an individual SnO2 crossed-nanowires device in a three-terminal field-effect transistor configuration were investigated using a combination of macroscopic transport measurements and scanning surface-potential microscopy (SSPM). The structure of the device was determined using both scanning electron- and atomic force microscopy data. The SSPM images of two crossed one-dimensional nanostructures, simulating a prototypical nanowire network sensors, exhibit large dc potential drops at the crossed-wire junction and at the contacts, identifying them as the primary electroactive elements in the circuit. The gas sensitivity of this device was comparable to those of sensors formed by individual homogeneous nanostructures of similar dimensions. Under ambient conditions, the dc transport measurements were found to be strongly affected by field-induced surface charges on the nanostructure and the gate oxide. These charges result in a memory effect in transport m...

Nanoelectromechanics of polarization switching in piezoresponse force microscopy

Nanoscale polarization switching in ferroelectric materials by piezoresponse force microscopy in weak and strong indentation limits is analyzed using exact solutions for coupled electroelastic fields under the tip. Tip-induced domain switching is mapped on the Landau theory of phase transitions, with domain size as an order parameter. For a point charge interacting with a ferroelectric surface, switching by both first and the second order processes is possible, depending on the charge–surface separation. For a realistic tip, the domain nucleation process is first order in charge magnitude and polarization switching occurs only above a certain critical tip bias. In pure ferroelectric or ferroelastic switching, the late stages of the switching process can be described using a point charge model and arbitrarily large domains can be created. However, description of domain nucleation and the early stages of growth process when the domain size is comparable with the tip curvature radius (weak indentation) or th...

Real space imaging of the microscopic origins of the ultrahigh dielectric constant in polycrystalline CaCu3Ti4O12

The origins of an ultrahigh dielectric constant in polycrystalline CaCu3Ti4O12 (CCTO) were studied using the combination of impedance spectroscopy, electron microscopy, and scanning probe microscopy (SPM). Impedance spectra indicate that the transport properties in the 0.1Hz–1MHz frequency range are dominated by a single parallel resistive-capacitive (RC) element with a characteristic relaxation frequency of 16Hz. dc potential distributions measurements by SPM illustrate that significant potential drops occur at the grain boundaries, which thus can be unambiguously identified as the dominant RC element. High frequency ac amplitude and phase distributions illustrate very weak grain boundary contrast in SPM, indicative of strong capacitive coupling across the interfaces. These results demonstrate that the ultrahigh dielectric constant reported for polycrystalline CCTO materials is related to grain-boundary behavior.

Atomistic screening mechanism of ferroelectric surfaces: an in situ study of the polar phase in ultrathin BaTiO3 films exposed to H2O.

The polarization screening mechanism and ferroelectric phase stability of ultrathin BaTiO(3) films exposed to water molecules is determined by first principles theory and in situ experiment. Surface crystallography data from electron diffraction combined with density functional theory calculations demonstrate that small water vapor exposures do not affect surface structure or polarization. Large exposures result in surface hydroxylation and rippling, formation of surface oxygen vacancies, and reversal of the polarization direction. Understanding interplay between ferroelectric phase stability, screening, and atomistic processes at surfaces is a key to control low-dimensional ferroelectricity.

Simultaneous elastic and electromechanical imaging by scanning probe microscopy : Theory and applications to ferroelectric and biological materials

An approach for combined imaging of elastic and electromechanical properties of materials, referred to as piezoacoustic scanning probe microscopy (PA-SPM), is presented. Applicability of this technique for elastic and electromechanical imaging with nanoscale resolution in such dissimilar materials as ferroelectrics and biological tissues is demonstrated. The PA-SPM signal formation is analyzed based on the theory of nanoelectromechanics of piezoelectric indentation and signal sensitivity to materials properties and imaging conditions. It is shown that simultaneous measurements of local indentation stiffness and indentation piezocoefficient provide the most complete description of the local electroelastic properties for transversally isotropic materials, thus making piezoacoustic SPM a comprehensive imaging and analysis tool. The contrast formation mechanism in the low frequency regime is described in terms of tip-surface contact mechanics. Signal generation volumes for electromechanical and elastic signal...

Oxygen-Induced Surface Reconstruction of SrRuO3 and Its Effect on the BaTiO3 Interface

Atomically engineered oxide multilayers and superlattices display unique properties responsive to the electronic and atomic structures of the interfaces. We have followed the growth of ferroelectric BaTiO3 on SrRuO3 electrode with in situ atomic scale analysis of the surface structure at each stage. An oxygen-induced surface reconstruction of SrRuO3 leads to formation of SrO rows spaced at twice the bulk periodicity. This reconstruction modifies the structure of the first BaTiO3 layers grown subsequently, including intermixing observed with cross-section spectroscopy. These observations reveal that this common oxide interface is much more interesting than previously reported and provide a paradigm for oxygen engineering of oxide structure at an interface.

Layer-by-layer and pseudo-two-dimensional growth modes for heteroepitaxial BaTiO3 films by exploiting kinetic limitations

Pulsed laser deposition has enabled formation of highly oxidized and strained BaTiO3 films on SrTiO3 substrates in a layer-by-layer growth mode to thicknesses of 125nm. Balancing thermodynamics and diffusion lengths enables controlled growth at the higher oxygen pressures required. Growth above 800°C produces an array of uniform pseudo-two-dimensional islands on single-step terraces which are independent of film thickness and correlated with threading dislocations. Control over growth modes is enabled by the manipulation of diffusion lengths and produces films with morphologies with broad applicability for fabrication of high-quality oxide films and self-assembled nanostructures.

Scanning probe microscopy imaging of frequency dependent electrical transport through carbon nanotube networks in polymers

Frequency dependent electrical transport in the conducting networks of single walled carbon nanotubes embedded in polymers was studied by scanning impedance microscopy (SIM). SIM allows current flow in the nanotubes inside the polymer matrix at up to 100 nm below the surface to be imaged directly, providing a non-invasive approach for studying transport in these materials. The conductance of the composite is shown to be limited by a small number of bundle–bundle and bundle–contact junctions. For high frequencies, the SIM phase distribution along the networks is governed by the capacitive interaction between the nanotubes and the substrate and is in agreement with a transmission line model. For low driving frequencies the capacitive coupling to the back gate can be minimized and an approach for determining the potential distribution along the network by accounting for tip–surface capacitance variations is demonstrated. Thus, SIM provides a direct method for characterizing electrical transport through percolation networks formed by nanotube bundles in polymers or, more generally, nanorods in various matrices.

Single-crystal-like, c-axis oriented BaTiO3 thin films with high-performance on flexible metal templates for ferroelectric applications

Epitaxial, c-axis oriented BaTiO3 thin films were deposited using pulsed laser ablation on flexible, polycrystalline Ni alloy tape with biaxially textured oxide buffer multilayers. The high quality of epitaxial BaTiO3 thin films with P4mm group symmetry was confirmed by x-ray diffraction. The microscopic ferroelectric domain structure and the piezoelectric domain switching in these films were confirmed via spatially resolved piezoresponse mapping and local hysteresis loops. Macroscopic measurements demonstrate that the films have well-saturated hysteresis loops with a high remanent polarization of ∼11.5 μC/cm2. Such high-quality, single-crystal-like BaTiO3 films on low-cost, polycrystalline, flexible Ni alloy substrates are attractive for applications in flexible lead-free ferroelectric devices.