Piezoresponse Force Spectroscopy (PFS) has emerged as a powerful technique for probing highly localized switching behavior and the role of microstructure and defects on switching. The application of a dc bias to a scanning probe microscope tip in contact with a ferroelectric surface results in the nucleation and growth of a ferroelectric domain below the

Thermodynamics of tip-induced nanodomain formation in scanning probe microscopy of ferroelectric films and crystals is studied using the Landau-Ginzburg-Devonshire phenomenological approach. The local redistribution of polarization induced by the biased probe apex is analyzed including the effects of polarization gradients, field dependence of dielectric properties, intrinsic domain wall width, and film thickness. The polarization distribution inside "subcritical" nucleus of the domain preceding the nucleation event is very smooth and localized below the probe, and the electrostatic field distribution is dominated by the tip. In contrast, polarization distribution inside the stable domain is rectangular-like, and

Using Landau-Ginzburg-Devonshire approach we calculated the equilibrium distributions of electric field, polarization, and space charge in the ferroelectric-semiconductor heterostructures containing proper or incipient ferroelectric thin films. The role of the polarization gradient and intrinsic surface energy, interface dipoles, and free charges on polarization dynamics are specifically explored. The intrinsic field effects, which originated at the ferroelectric-semiconductor interface, lead to the surface band bending and result into the formation of depletion space-charge layer near the semiconductor surface. During the local polarization reversal ͑caused by the electric field of the nanosized tip of the scanning probe microscope͒ the thickness and charge of the interface layer drastically changes, in particular, the sign of the screening carriers is determined by the polarization direction. Obtained analytical solutions could be extended to analyze polarization-mediated electronic transport.

Domain-wall dynamics in ferroic materials underpins functionality of data storage and information technology devices. Using localized electric field of a scanning probe microscopy tip, we experimentally demonstrate a surprisingly rich range of polarization reversal behaviors in the vicinity of the initially flat 180°ferroelectric domain wall. The nucleation bias is found to increase by an order of magnitude from a two-dimensional ͑2D͒ nucleus at the wall to three-dimensional nucleus in the bulk. The wall is thus significantly ferroelectrically softer than the bulk. The wall profoundly affects switching on length scales on the order of micrometers. The mechanism of correlated switching is analyzed using analytical theory and phase-field modeling. The longrange effect is ascribed to wall bending under the influence of a tip with bias that is well below the bulk nucleation level at large distances from the wall. These studies provide an experimental link between the macroscopic and mesoscopic physics of domain walls in ferroelectrics and atomistic models of 2D nucleation.

The thermodynamics and kinetics of tip-induced polarization switching in Piezoresponse Force Microscopy in the presence of surface charge defects is studied using the combination of analytical and numerical techniques. The signature of the defects in hysteresis loop fine structure and Switching Spectroscopy PFM images is identified and compared to experimental observations. An approach for the deconvolution of PFM spectroscopy measurements to extract relevant defect parameters is derived. This methodology is universal and can be extended to switching in other ferroics and in reversible electrochemical processes, establishing a pathway for the understanding of the thermodynamics and kinetics of phase transitions at a single defect level.