Nanoscale Electric Phenomena at Oxide Surfaces and Interfaces by Scanning Probe Microscopy

Scanning Probe Microscopy is used to study and quantify the nanoscale electric phenomena in the two classes of oxide systems, namely transport at electroactive grain boundaries and surface behavior of ferroelectric materials. Scanning Impedance Microscopy is developed to study the capacitance and local C-V characteristic of the interfaces combining the spatial resolution of traditional SPMs with the precision of conventional electrical measurements. SPM of SrTiO3 grain boundaries in conjunction with variable temperature impedance spectroscopy and I-V measurements allowed to find and theoretically justify the effect of field suppression of dielectric constant in the vicinity of the electroactive interfaces in strontium titanate. Similar approaches were used to study ferroelectric properties and ac and dc transport behavior in a number of polycrystalline oxides. In the second part, the effects of local charge density on the chemistry and physics of ferroelectric surfaces are studied. The kinetics and thermodynamics parameters of adsorption are assessed by variable temperature SPM. Piezoresponse force microscopy is used to engineer domain patterns on ferroelectric surfaces. Localized photochemical activity of ferroelectric surfaces is explored as a new tool for metallic nanostructures fabrication.Comment: Ph.D. Thesis, September 2002, 304 pages, 108 figures, 2.4 MB PDF file, Higher quality version available at sergei2.kalininweb.co

Scanning Impedance Microscopy: From Impedance Spectra to Impedance Images

Impedance spectroscopy has long been recognized as one of the major techniques for the characterization of ac transport in materials. The primary limitation of this technique is the lack of spatial resolution that precludes the equivalent circuit elements from being unambiguously associated with individual microstructural features. Here we present a scanning probe microscopy technique for quantitative imaging of ac and dc transport properties of electrically inhomogeneous materials. This technique, referred to as Scanning Impedance Microscopy (SIM), maps the phase and amplitude of local potential with respect to an electric field applied across the sample. Amplitude and phase behavior of individual defects can be correlated with their transport properties. The frequency dependence of the voltage phase shift across an interface yields capacitance and resistance. SIM of single interfaces is demonstrated on a model metal-semiconductor junction. The local interface capacitance and resistance obtained from SIM measurements agrees quantitatively with macroscopic impedance spectroscopy. Superposition of a dc sample bias during SIM probes the C-V characteristics of the interface. When combined with Scanning Surface Potential Microscopy (SSPM), which can be used to determine interface I-V characteristic, local transport properties are completely determined. SIM and SSPM of polycrystalline materials are demonstrated on BiFeO3 and p-doped silicon. An excellent agreement between the properties of a single interface determined by SIM and traditional impedance spectra is demonstrated. Finally, the applicability of this technique for imaging transport behavior in nanoelectronic devices is illustrated with carbon nanotube circuit

Carbon nanotubes as a tip calibration standard for electrostatic scanning probe microscopies

Scanning Surface Potential Microscopy (SSPM) is one of the most widely used techniques for the characterization of electrical properties at small dimensions. Applicability of SSPM and related electrostatic scanning probe microscopies for imaging of potential distributions in active micro- and nanoelectronic devices requires quantitative knowledge of tip surface contrast transfer. Here we demonstrate the utility of carbon-nanotube-based circuits to characterize geometric properties of the tip in the electrostatic scanning probe microscopies (SPM). Based on experimental observations, an analytical form for the differential tip-surface capacitance is obtained.Comment: 14 pages, 4 figure

Tip-gating Effect in Scanning Impedance Microscopy of Nanoelectronic Devices

Electronic transport in semiconducting single-wall carbon nanotubes is studied by combined scanning gate microscopy and scanning impedance microscopy (SIM). Depending on the probe potential, SIM can be performed in both invasive and non-invasive mode. High-resolution imaging of the defects is achieved when the probe acts as a local gate and simultaneously an electrostatic probe of local potential. A class of weak defects becomes observable even if they are located in the vicinity of strong defects. The imaging mechanism of tip-gating scanning impedance microscopy is discussed.Comment: 11 pages, 3 figures, to be published in Appl. Phys. Let

Imaging mechanism of piezoresponse force microscopy of ferroelectric surfaces

In order to determine the origin of image contrast in piezoresponse force microscopy (PFM), analytical descriptions of the complex interactions between a small tip and ferroelectric surface are derived for several sets of limiting conditions. Image charge calculations are used to determine potential and field distributions at the tip-surface junction between a spherical tip and an anisotropic dielectric half plane. Methods of Hertzian mechanics are used to calculate the response amplitude in the electrostatic regime. In the electromechanical regime, the limits of strong (classical) and weak (field-induced) indentation are established and the relative contributions of electroelastic constants are determined. These results are used to construct ‘‘piezoresponse contrast mechanism maps’’ that correlate the imaging conditions with the PFM contrast mechanisms. Conditions for quantitative PFM imaging are set forth. Variable-temperature PFM imaging of domain structures in BaTiO3 and the temperature dependence of the piezoresponse are compared with Ginzburg-Devonshire theory. An approach to the simultaneous acquisition of piezoresponse and surface potential images is proposed

Contrast mechanism maps for piezoresponse force microscopy

Piezoresponse force microscopy (PFM) is one of the most established techniques for the observation and local modification of ferroelectric domain structures on the submicron level. Both electrostatic and electromechanical interactions contribute at the tip-surface junction in a complex manner, which has resulted in multiple controversies in the interpretation of PFM. Here we analyze the influence of experimental conditions such as tip radius of curvature, indentation force, and cantilever stiffness on PFM image contrast. These results are used to construct contrast mechanism maps, which correlate the imaging conditions with the dominant contrast mechanisms. Conditions under which materials properties can be determined quantitatively are elucidated

Local Polarization, Charge Compensation, and Chemical Interactions on Ferroelectric Surfaces: a Route Toward New Nanostructures

The local potential at domains on ferroelectric surfaces results from the interplay between atomic polarization and screening charge. The presence of mobile charge affects surface domain configuration, switching behavior, and surface chemical reactions. By measuring the temperature and time dependence of surface potential and piezo response with scanning probe microscopies, thermodynamic parameters associated with charge screening are determined. This is illustrated for the case of BaTiO3 (100) in air, for which the charge compensation mechanism is surface adsorption and enthalpy and entropy of adsorption are determined. The local electrostatic fields in the vicinity of the domains have a dominant effect on chemical reactivity. Photoreduction of a large variety of metals can be localized to domains with the appropriate surface charge. It has been demonstrated that proximal probe tips can be used to switch polarization direction locally. Combining the ability to \u27write\u27 domains of local polarization with domain specific reactivity of metals, vapors of small molecules, and organic compounds leads to a new approach to fabricating complex nanostructures