Peter Maksymovych

Perovskite-fullerene hybrid materials suppress hysteresis in planar diodes

Solution-processed planar perovskite devices are highly desirable in a wide variety of optoelectronic applications; however, they are prone to hysteresis and current instabilities. Here we report the first perovskite–PCBM hybrid solid with significantly reduced hysteresis and recombination loss achieved in a single step. This new material displays an efficient electrically coupled microstructure: PCBM is homogeneously distributed throughout the film at perovskite grain boundaries. The PCBM passivates the key PbI3− antisite defects during the perovskite self-assembly, as revealed by theory and experiment. Photoluminescence transient spectroscopy proves that the PCBM phase promotes electron extraction. We showcase this mixed material in planar solar cells that feature low hysteresis and enhanced photovoltage. Using conductive AFM studies, we reveal the memristive properties of perovskite films. We close by positing that PCBM, by tying up both halide-rich antisites and unincorporated halides, reduces electric field-induced anion migration that may give rise to hysteresis and unstable diode behaviour.

Polarization Control of Electron Tunneling into Ferroelectric Surfaces

Ferroelectric Patterning with High Fields Ferroelectric oxides have a net polarization that can switch direction upon application of a sufficiently high electric field. In principle, a ferroelectric thin film should be able to act as a polar switch—tunneling an electron through the film would effectively switch on or off depending on the direction of the polarization. In practice, the length scale needed for a sufficiently small tunneling barrier is nearly the same as the scale at which films no longer support ferroelectricity. Maksymovych et al. (p. 1421) now show that the tip of an atomic force microscope can be used to pattern polarization domains in a thin film of lead zirconate titanate in high electric fields similar to those for field emission tips. High electric fields delivered with an atomic force microscope tip pattern polarization domains in ferroelectric thin films. We demonstrate a highly reproducible control of local electron transport through a ferroelectric oxide via its spontaneous polarization. Electrons are injected from the tip of an atomic force microscope into a thin film of lead-zirconate titanate, Pb(Zr0.2Ti0.8)O3, in the regime of electron tunneling assisted by a high electric field (Fowler-Nordheim tunneling). The tunneling current exhibits a pronounced hysteresis with abrupt switching events that coincide, within experimental resolution, with the local switching of ferroelectric polarization. The large spontaneous polarization of the PZT film results in up to 500-fold amplification of the tunneling current upon ferroelectric switching. The magnitude of the effect is subject to electrostatic control via ferroelectric switching, suggesting possible applications in ultrahigh-density data storage and spintronics.

The Role of Gold Adatoms and Stereochemistry in Self-Assembly of Methylthiolate on Au(111)

On the basis of high resolution STM images and DFT modeling, we have resolved low- and high-coverage structures of methylthiolate (CH(3)S) self-assembled on the Au(111) surface. The key new finding is that the building block of all these structures has the same stoichiometry of two thiolate species joined by a gold adatom. The self-arrangement of the methylthiolate-adatom complexes on the surface depends critically on their stereochemical properties. Variations of the latter can produce local ordering of adatom complexes with either (3 x 4) or (3 x 4 square root(3)) periodicity. A possible structural connection between the (3 x 4 square root(3)) structure and commonly observed (square root(3) x square root(3))R30 degrees phase in methylthiolate self-assembled monolayers is developed by taking into account the reduction in the long-range order and stereochemical isomerization at high coverage. We also suggest how the observed self-arrangements of methylthiolate may be related to the c(4 x 2) phase of its longer homologues.

Dynamic Conductivity of Ferroelectric Domain Walls in BiFeO3

Topological walls separating domains of continuous polarization, magnetization, and strain in ferroic materials hold promise of novel electronic properties, that are intrinsically localized on the nanoscale and that can be patterned on demand without change of material volume or elemental composition. We have revealed that ferroelectric domain walls in multiferroic BiFeO(3) are inherently dynamic electronic conductors, closely mimicking memristive behavior and contrary to the usual assumption of rigid conductivity. Applied electric field can cause a localized transition between insulating and conducting domain walls, tune domain wall conductance by over an order of magnitude, and create a quasicontinuous spectrum of metastable conductance states. Our measurements identified that subtle and microscopically reversible distortion of the polarization structure at the domain wall is at the origin of the dynamic conductivity. The latter is therefore likely to be a universal property of topological defects in ferroelectric semiconductors.

Au adatoms in self-assembly of benzenethiol on the Au(111) surface.

Self-assembly of benzenethiol at low coverage on Au(111) was studied using low-temperature scanning tunneling microscopy. Phenylthiolate species (PhS), formed by thermal dehydrogenation of the parent PhSH molecule, was found to self-assemble into surface-bonded complexes with gold adatoms. Each complex involves two PhS species and one gold adatom. The PhS species form either cis- or trans-geometry relative to each other. At a higher coverage, the complexes coalesce, most likely due to the formation of weak C-H...S hydrogen bonds facilitated by the spatial arrangement of the PhS groups. Our findings thus establish that the self-assembly of arenethiols on the Au(111) surface is driven by gold adatom chemistry, which has recently been found to be the key ingredient in the self-assembly of alkanethiols on gold.

Tunable Metallic Conductance in Ferroelectric Nanodomains

Metallic conductance in charged ferroelectric domain walls was predicted more than 40 years ago as the first example of an electronically active homointerface in a nonconductive material. Despite decades of research on oxide interfaces and ferroic systems, the metal-insulator transition induced solely by polarization charges without any additional chemical modification has consistently eluded the experimental realm. Here we show that a localized insulator-metal transition can be repeatedly induced within an insulating ferroelectric lead-zirconate titanate, merely by switching its polarization at the nanoscale. This surprising effect is traced to tilted boundaries of ferroelectric nanodomains, that act as localized homointerfaces within the perovskite lattice, with inherently tunable carrier density. Metallic conductance is unique to nanodomains, while the conductivity of extended domain walls and domain surfaces is thermally activated. Foreseeing future applications, we demonstrate that a continuum of nonvolatile metallic states across decades of conductance can be encoded in the size of ferroelectric nanodomains using electric field.

Rapid multidimensional data acquisition in scanning probe microscopy applied to local polarization dynamics and voltage dependent contact mechanics

A rapid multidimensional spectroscopic imaging approach in scanning probe microscopy is developed and applied to piezoresponse force spectroscopy. Evolution of resonance frequency, dissipation, and piezoresponse signal at each point during acquisition of local hysteresis loops provides information on polarization dynamics and voltage dependent contact mechanics of ferroelectric surfaces. The measurements illustrate significant frequency shifts during piezoresponse force spectroscopy, necessitating the use of frequency-tracking methods. The method is universal and can be extended to other scanning probe microscopy techniques.

Defect-Mediated Polarization Switching in Ferroelectrics and Related Materials: From Mesoscopic Mechanisms to Atomistic Control

The plethora of lattice and electronic behaviors in ferroelectric and multiferroic materials and heterostructures opens vistas into novel physical phenomena including magnetoelectric coupling and ferroelectric tunneling. The development of new classes of electronic, energy-storage, and information-technology devices depends critically on understanding and controlling field-induced polarization switching. Polarization reversal is controlled by defects that determine activation energy, critical switching bias, and the selection between thermodynamically equivalent polarization states in multiaxial ferroelectrics. Understanding and controlling defect functionality in ferroelectric materials is as critical to the future of oxide electronics and solid-state electrochemistry as defects in semiconductors are for semiconductor electronics. Here, recent advances in understanding the defect-mediated switching mechanisms, enabled by recent advances in electron and scanning probe microscopy, are discussed. The synergy between local probes and structural methods offers a pathway to decipher deterministic polarization switching mechanisms on the level of a single atomically defined defect.

Local bias-induced phase transitions

Electrical bias-induced phase transitions underpin a wide range of applications from data storage to energy generation and conversion. The mechanisms behind these transitions are often quite complex and in many cases are extremely sensitive to local defects that act as centers for local transformations or pinning. Using ferroelectrics as an example, we review methods for probing bias-induced phase transitions and discuss the current limitations and challenges for extending the methods to field-induced phase transitions and electrochemical reactions in energy storage, biological and molecular systems.

Electronic Properties of Isosymmetric Phase Boundaries in Highly Strained Ca‐Doped BiFeO3

Anisotropic electronic conductivity is reported for isosymmetric phase boundaries in highly strained bismuth ferrite, which are the (fully epitaxial) connecting regions between two different structural variants of the same material. Strong correlations between nanoscale phase transition and local electronic conductivity are found. A high degree of control over their electronic properties can be attained through non-local electrical switching.