Transport across nanogaps using semiclassically consistent boundary conditions

Charge particle transport across nanogaps is studied theoretically within the Schrodinger-Poisson mean field framework and the existence of limiting current investigated. It is shown that the choice of a first order WKB wavefunction as the transmitted wave leads to self consistent boundary conditions and gives results that are significantly different in the non-classical regime from those obtained using a plane transmitted wave. At zero injection energies, the quantum limiting current density, J_c, is found to obey the local scaling law J_c ~ (V_g)^alpha/(D)^{5-2alpha} with the gap separation D and voltage V_g. The exponent alpha > 1.1 with alpha --> 3/2 in the classical regime of small de Broglie wavelengths. These results are consistent with recent experiments using nanogaps most of which are found to be in a parameter regime where classical space charge limited scaling holds away from the emission dominated regime.Comment: 4 pages, 4 ps figure

Finite size and intrinsic field effect on the polar-active properties of the 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 inhomogeneous electric field induced by the nanosized tip of the Scanning Probe Microscope (SPM) probe) the thickness and charge of the interface layer drastically changes, it 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.Comment: 35 pages, 12 figures, 1 table, 2 appendices, to be submitted to Phys. Rev.

Controlling the stereochemistry and regularity of butanethiol self-assembled monolayers on Au(111)

© 2014 American Chemical Society. The rich stereochemistry of the self-assembled monolayers (SAMs) of four butanethiols on Au(111) is described, the SAMs containing up to 12 individual C, S, or Au chiral centers per surface unit cell. This is facilitated by synthesis of enantiomerically pure 2-butanethiol (the smallest unsubstituted chiral alkanethiol), followed by in situ scanning tunneling microscopy (STM) imaging combined with density functional theory molecular dynamics STM image simulations. Even though butanethiol SAMs manifest strong headgroup interactions, steric interactions are shown to dominate SAM structure and chirality. Indeed, steric interactions are shown to dictate the nature of the headgroup itself, whether it takes on the adatom-bound motif RS•Au(0)S•R or involves direct binding of RS• to face-centered-cubic or hexagonal-close-packed sites. Binding as RS• produces large, organizationally chiral domains even when R is achiral, while adatom binding leads to rectangular plane groups that suppress long-range expression of chirality. Binding as RS• also inhibits the pitting intrinsically associated with adatom binding, desirably producing more regularly structured SAMs

Enhanced electric conductivity at ferroelectric vortex cores in BiFeO3

In many large ensembles, the property of the system as a whole cannot be understood from studying the individual entities alone ¿ these ensembles can be made up by neurons in the brain, transport users in traffic networks or data packages in the Internet. The past decade has seen important progress in our fundamental understanding of what such seemingly disparate 'complex systems' have in common; some of these advances are surveyed here

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. © 2010 The American Physical Society.Authors are grateful to E. Tsymbal and E. Tsymbal for valuable critical remarks. Research is sponsored by Ministry of Science and Education of Ukraine and National Science Foundation(Materials World Network, Grant No. DMR-0908718). S.V.K. and A.B. acknowledge the DOE SISGR program. P.M. is supported by the Division of Scientific User Facilities, US DOE

Thermodynamics of Nanodomain Formation and Breakdown in Scanning Probe Microscopy: Landau-Ginzburg-Devonshire Approach

Thermodynamics of tip-induced nanodomain formation in scanning probe microscopy of ferroelectric films and crystals is studied using the analytical Landau-Ginzburg-Devonshire approach and phase-field modeling. 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 a "subcritical" nucleus of the domain preceding the nucleation event is shown to be "soft" (i.e., smooth without domain walls) and localized below the probe, and the electrostatic field distribution is dominated by the tip. In contrast, polarization distribution inside a stable domain is "hard" (i.e., sharp contrast with delineated domain walls) and the spontaneous polarization reorientation takes place inside a localized spatial region, where the absolute value of the resulting electric field is larger than the thermodynamic coercive field. The calculated coercive biases corresponding to formation of switched domains are in a good agreement with available experimental results for typical ferroelectric materials. The microscopic origin of the observed domain-tip elongation in the region where the probe electric field is much smaller than the intrinsic coercive field is the positive depolarization field in front of the moving-counter domain wall. For infinitely thin domain wall the depolarization field outside the semiellipsoidal domain tip is always higher than the intrinsic coercive field that must initiate the local domain breakdown through the sample depth while the domain length is finite in the energetic approach evolved by Landauer and Molotskii (we refer the phenomenon as Landauer-Molotskii paradox). Our approach provides the solution of the paradox: the domain vertical growth should be accompanied by the increase in the charged domain-wall width. © 2009 The American Physical Society.Research sponsored by Ministry of Science and Education of Ukraine (Grant No. UU30/004) and National Science Foundation (Grants No. DMR-0908718 and No. DMR-0820404). A.N.M. and S.V.S. gratefully acknowledge financial support from National Academy of Science of Ukraine, joint Russian-Ukrainian under Grants No. NASU N 17-Ukr_a and No. RFBR N 08-02-90434. The research is supported in part (S.V.K.) by the Division of Scientific User Facilities, U.S. DOE

Electrical half-wave rectification at ferroelectric domain walls

Ferroelectric domain walls represent multifunctional 2D-elements with great potential for novel device paradigms at the nanoscale. Improper ferroelectrics display particularly promising types of domain walls, which, due to their unique robustness, are the ideal template for imposing specific electronic behavior. Chemical doping, for instance, induces p- or n-type characteristics and electric fields reversibly switch between resistive and conductive domain-wall states. Here, we demonstrate diode-like conversion of alternating-current (AC) into direct-current (DC) output based on neutral 180$^{\circ}$ domain walls in improper ferroelectric ErMnO$_3$. By combining scanning probe and dielectric spectroscopy, we show that the rectification occurs for frequencies at which the domain walls are fixed to their equilibrium position. The practical frequency regime and magnitude of the output is controlled by the bulk conductivity. Using density functional theory we attribute the transport behavior at the neutral walls to an accumulation of oxygen defects. Our study reveals domain walls acting as 2D half-wave rectifiers, extending domain-wall-based nanoelectronic applications into the realm of AC technology

Tunneling electroresistance effect in ferroelectric tunnel junctions at the nanoscale

Stable and switchable polarization of ferroelectric materials opens a possibility to electrically control their functional behavior. A particularly promising approach is to employ ferroelectric tunnel junctions where the polarization reversal in a ferroelectric barrier changes the tunneling current across the junction. Here, we demonstrate the reproducible tunneling electroresistance effect using a combination of Piezoresponse Force Microscopy (PFM) and Conducting Atomic Force Microscopy (C-AFM) techniques on nanometer-thick epitaxial BaTiO3 single crystal thin films on SrRuO3 bottom electrodes. Correlation between ferroelectric and electronic transport properties is established by the direct nanoscale visualization and control of polarization and tunneling current in BaTiO3 films. The obtained results show a change in resistance by about two orders of magnitude upon polarization reversal on a lateral scale of 20 nm at room temperature. These results are promising for employing ferroelectric tunnel junctions in non-volatile memory and logic devices, not involving charge as a state variable.Comment: 18 pages, 4 figure

Orbital redistribution in molecular nanostructures mediated by metal-organic bonds

Dicyanovinyl-quinquethiophene (DCV5T-Me) is a prototype conjugated oligomer for highly efficient organic solar cells. This class of oligothiophenes are built up by an electron-rich donor (D) backbone and terminal electron-deficient acceptor (A) moieties. Here, we investigated its structural and electronic properties when it is adsorbed on a Au(111) surface using low temperature scanning tunneling microscopy/spectroscopy (STM/STS) and atomic force microscopy (AFM). We find that DCV5T-Me self-assembles in extended chains, stabilized by intercalated Au atoms. The effect of metal-ligand hybridization with Au adatoms causes an energetic downshift of the DCV5T-Me lowest unoccupied molecular orbital (LUMO) with respect to the uncoordinated molecules on the surface. The asymmetric coordination of a gold atom to only one molecular end group leads to an asymmetric localization of the LUMO and LUMO+1 states at opposite sides. Using model density functional theory (DFT) calculations, we explain such orbital reshaping as a consequence of linear combinations of the original LUMO and LUMO+1 orbitals, mixed by the attachment of a bridging Au adatom. Our study shows that the alignment of molecular orbitals and their distribution within individual molecules can be modified by contacting them to metal atoms in specific sites