Petro Maksymovych

Differentiating Ferroelectric and Nonferroelectric Electromechanical Effects with Scanning Probe Microscopy

Ferroelectricity in functional materials remains one of the most fascinating areas of modern science in the past several decades. In the last several years, the rapid development of piezoresponse force microscopy (PFM) and spectroscopy revealed the presence of electromechanical hysteresis loops and bias-induced remnant polar states in a broad variety of materials including many inorganic oxides, polymers, and biosystems. In many cases, this behavior was interpreted as the ample evidence for ferroelectric nature of the system. Here, we systematically analyze PFM responses on ferroelectric and nonferroelectric materials and demonstrate that mechanisms unrelated to ferroelectricity can induce ferroelectric-like characteristics through charge injection and electrostatic forces on the tip. We will focus on similarities and differences in various PFM measurement characteristics to provide an experimental guideline to differentiate between ferroelectric material properties and charge injection. In the end, we apply the developed measurement protocols to an unknown ferroelectric material.

Exploring Local Electrostatic Effects with Scanning Probe Microscopy: Implications for Piezoresponse Force Microscopy and Triboelectricity

The implementation of contact mode Kelvin probe force microscopy (cKPFM) utilizes the electrostatic interactions between tip and sample when the tip and sample are in contact with each other. Surprisingly, the electrostatic forces in contact are large enough to be measured even with tips as stiff as 4.5 N/m. As for traditional noncontact KPFM, the signal depends strongly on electrical properties of the sample, such as the dielectric constant, and the tip properties, such as the stiffness. Since the tip is in contact with the sample, bias-induced changes in the junction potential between tip and sample can be measured with higher lateral and temporal resolution compared to traditional noncontact KPFM. Significant and reproducible variations of tip-surface capacitance are observed and attributed to surface electrochemical phenomena. Observations of significant surface charge states at zero bias and strong hysteretic electromechanical responses at a nonferroelectric surface have significant implications for fields such as triboelectricity and piezoresponse force microscopy.

Phase Transitions, Phase Coexistence, and Piezoelectric Switching Behavior in Highly Strained BiFeO 3 Films

Highly strained BiFeO3 films transition into a true tetragonal state at 430 °C but remain polar to much higher temperatures (∼800 °C). Piezoelectric switching is only possible up to 300 °C, i.e., at temperatures for which strain stabilizes the stripe-like coexistence of multiple polymorphs.

Domain Wall Geometry Controls Conduction in Ferroelectrics

A new paradigm of domain wall nanoelectronics has emerged recently, in which the domain wall in a ferroic is itself an active device element. The ability to spatially modulate the ferroic order parameter within a single domain wall allows the physical properties to be tailored at will and hence opens vastly unexplored device possibilities. Here, we demonstrate via ambient and ultrahigh-vacuum (UHV) scanning probe microscopy (SPM) measurements in bismuth ferrite that the conductivity of the domain walls can be modulated by up to 500% in the spatial dimension as a function of domain wall curvature. Landau-Ginzburg-Devonshire calculations reveal the conduction is a result of carriers or vacancies migrating to neutralize the charge at the formed interface. Phase-field modeling indicates that anisotropic potential distributions can occur even for initially uncharged walls, from polarization dynamics mediated by elastic effects. These results are the first proof of concept for modulation of charge as a function of domain wall geometry by a proximal probe, thereby expanding potential applications for oxide ferroics in future nanoscale electronics.

Finite size and intrinsic field effect on the polar-active properties of ferroelectric-semiconductor heterostructures

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 Microscope) 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 conduction in multiaxial ferroelectrics

The conductance of domain wall structures consisting of either stripes or cylindrical domains in multiaxial ferroelectric-semiconductors is analyzed. The effects of the flexoelectric coupling, domain size, wall tilt, and curvature on charge accumulation are analyzed using the Landau-Ginsburg Devonshire theory for polarization vector combined with the Poisson equation for charge distributions. The proximity and size effect of the electron and donor accumulation/depletion by thin stripe domains and cylindrical nanodomains are revealed. In contrast to thick domain stripes and wider cylindrical domains, in which the carrier accumulation (and so the static conductivity) sharply increases at the domain walls only, small nanodomains of radii less than 5-10 correlation lengths appeared conducting across the entire cross-section. Implications of such conductive nanosized channels may be promising for nanoelectronics.

Microwave a.c. conductivity of domain walls in ferroelectric thin films

Ferroelectric domain walls are of great interest as elementary building blocks for future electronic devices due to their intrinsic few-nanometre width, multifunctional properties and field-controlled topology. To realize the electronic functions, domain walls are required to be electrically conducting and addressable non-destructively. However, these properties have been elusive because conducting walls have to be electrically charged, which makes them unstable and uncommon in ferroelectric materials. Here we reveal that spontaneous and recorded domain walls in thin films of lead zirconate and bismuth ferrite exhibit large conductance at microwave frequencies despite being insulating at d.c. We explain this effect by morphological roughening of the walls and local charges induced by disorder with the overall charge neutrality. a.c. conduction is immune to large contact resistance enabling completely non-destructive walls read-out. This demonstrates a technological potential for harnessing a.c. conduction for oxide electronics and other materials with poor d.c. conduction, particularly at the nanoscale.

Formation, Migration, and Reactivity of Au-CO Complexes on Gold Surfaces

We report experimental as well as theoretical evidence that suggests Au-CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au-CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10(-8) to 10(-4) Torr (dosage up to 10(6) langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au-CO complex formation and diffusion, and Au adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au-CO complex result from the reduced Au-Au bonding at elbows and step edges leading to stronger Au-CO bonding and to the formation of a more positively charged CO (CO(δ+)) on Au. Our studies indicate that the mobile Au-CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers.

Electronic control over attachment and self-assembly of alkyne groups on gold.

Self-assembled monolayers are the basis for molecular nanodevices, flexible surface functionalization, and dip-pen nanolithography. Yet self-assembled monolayers are typically created by a rather inefficient process involving thermally driven attachment reactions of precursor molecules to a metal surface, followed by a slow and defect-prone molecular reorganization. Here we demonstrate a nonthermal, electron-induced approach to the self-assembly of phenylacetylene molecules on gold that allows for a previously unachievable attachment of the molecules to the surface through the alkyne group. While thermal excitation can only desorb the parent molecule due to prohibitively high activation barriers for attachment reactions, localized injection of hot electrons or holes not only overcomes this barrier but also enables an unprecedented control over the size and shape of the self-assembly, defect structures, and the reverse process of molecular disassembly from a single molecule to a mesoscopic length scale. Electron-induced excitation may therefore enable new and highly controlled approaches to molecular self-assembly on a surface.

Giant elastic tunability in strained BiFeO3 near an electrically induced phase transition

Elastic anomalies are signatures of phase transitions in condensed matters and have traditionally been studied using various techniques spanning from neutron scattering to static mechanical testing. Here, using band-excitation elastic/piezoresponse spectroscopy, we probed sub-MHz elastic dynamics of a tip bias-induced rhombohedral−tetragonal phase transition of strained (001)-BiFeO3 (rhombohedral) ferroelectric thin films from ∼103 nm3 sample volumes. Near this transition, we observed that the Youngs modulus intrinsically softens by over 30% coinciding with two- to three-fold enhancement of local piezoresponse. Coupled with phase-field modelling, we also addressed the influence of polarization switching and mesoscopic structural heterogeneities (for example, domain walls) on the kinetics of this phase transition, thereby providing fresh insights into the morphotropic phase boundary in ferroelectrics. Furthermore, the giant electrically tunable elastic stiffness and corresponding electromechanical properties observed here suggest potential applications of BiFeO3 in next-generation frequency-agile electroacoustic devices, based on the utilization of the soft modes underlying successive ferroelectric phase transitions.