Enhanced thermopower in covalent graphite-molecule contacts.

The Seebeck effect is very attractive for technological applications as it leads to the direct conversion of heat into electricity. One of the key quantities determining the efficiency of such conversion is the thermopower S. In this paper we explore theoretically what electronic properties are responsible for the Seebeck effect in molecular junctions with graphite or graphene electrodes. We propose that S can be enhanced because of the combined effect of the dip in the density of states at the Fermi energy of these materials and the molecular resonance. Then to understand the impact of the covalent vs. non-covalent molecule-carbon bonding we calculate from first principles the electronic and transport properties of graphite/molecule/Au junctions, where both types of bonding have been reported experimentally. We ultimately predict that S is about 120 µV K-1 at room temperature for a 3,5-dimethyl-4-aminobenzene (DMAB) molecule covalently attached to the graphite electrode. This value is one order of magnitude larger than the typical values measured to date for molecular junctions and it is a signature of the direct C-C molecule-graphite bond. Finally we also demonstrate how one can control not just the absolute magnitude of S, but also its sign by designing the graphite-molecule contact. Our results lead the way towards the use of junctions with molecules covalently attached to a C-based substrate as possible new improved platforms for molecular thermoelectric devices.

Robust Organic Radical Molecular Junctions Using Acetylene Terminated Groups for C-Au Bond Formation.

Organic paramagnetic and electroactive molecules are attracting interest as core components of molecular electronic and spintronic devices. Currently, further progress is hindered by the modest stability and reproducibility of the molecule/electrode contact. We report the synthesis of a persistent organic radical bearing one and two terminal alkyne groups to form Au-C σ bonds. The formation and stability of self-assembled monolayers and the electron transport through single-molecule junctions at room temperature have been studied. The combined analysis of both systems demonstrates that this linker forms a robust covalent bond with gold and a better-defined contact when compared to traditional sulfur-based linkers. Density functional theory and quantum transport calculations support the experimental observation highlighting a reduced variability of conductance values for the C-Au based junction. Our findings advance the quest for robustness and reproducibility of devices based on electroactive molecules.

Femtosecond Spin Current Pulses Generated by the Nonthermal Spin-Dependent Seebeck Effect and Interacting with Ferromagnets in Spin Valves.

Using the sensitivity of optical second harmonic generation to currents, we demonstrate the generation of 250-fs long spin current pulses in Fe/Au/Fe/MgO(001) spin valves. The temporal profile of these pulses indicates ballistic transport of hot electrons across a sub-100 nm Au layer. The pulse duration is primarily determined by the thermalization time of laser-excited hot carriers in Fe. Considering the calculated spin-dependent Fe/Au interface transmittance we conclude that a nonthermal spin-dependent Seebeck effect is responsible for the generation of ultrashort spin current pulses. The demonstrated rotation of spin polarization of hot electrons upon interaction with noncollinear magnetization at Au/Fe interfaces holds high potential for future spintronic devices.

Covalent Modification of Highly Ordered Pyrolytic Graphite with a Stable Organic Free Radical by Using Diazonium Chemistry.

A novel, persistent, electrochemically active perchlorinated triphenylmethyl (PTM) radical with a diazonium functionality has been covalently attached to highly ordered pyrolytic graphite (HOPG) by electrografting in a single-step process. Electrochemical scanning tunneling microscopy (EC-STM) and Raman spectroscopy measurements revealed that PTM molecules had a higher tendency to covalently react at the HOPG step edges. The cross-section profiles from EC-STM images showed that there was current enhancement at the functionalized areas, which could be explained by redox-mediated electron tunneling through surface-confined redox-active molecules. Cyclic voltammetry clearly demonstrated that the intrinsic properties of the organic radical were preserved upon grafting and DFT calculations also revealed that the magnetic character of the PTM radical was preserved.

The effect of a Ta oxygen scavenger layer on HfO2-based resistive switching behavior: thermodynamic stability, electronic structure, and low-bias transport.

Reversible resistive switching between high-resistance and low-resistance states in metal-oxide-metal heterostructures makes them very interesting for applications in random access memories. While recent experimental work has shown that inserting a metallic "oxygen scavenger layer" between the positive electrode and oxide improves device performance, the fundamental understanding of how the scavenger layer modifies the heterostructure properties is lacking. We use density functional theory to calculate thermodynamic properties and conductance of TiN/HfO2/TiN heterostructures with and without a Ta scavenger layer. First, we show that Ta insertion lowers the formation energy of low-resistance states. Second, while the Ta scavenger layer reduces the Schottky barrier height in the high-resistance state by modifying the interface charge at the oxide-electrode interface, the heterostructure maintains a high resistance ratio between high- and low-resistance states. Finally, we show that the low-bias conductance of device on-states becomes much less sensitive to the spatial distribution of oxygen removed from the HfO2 in the presence of the Ta layer. By providing a fundamental understanding of the observed improvements with scavenger layers, we open a path to engineer interfaces with oxygen scavenger layers to control and enhance device performance. In turn, this may enable the realization of a non-volatile low-power memory technology with concomitant reduction in energy consumption by consumer electronics and offering significant benefits to society.

A redox-active radical as an effective nanoelectronic component: stability and electrochemical tunnelling spectroscopy in ionic liquids.

A redox-active persistent perchlorotriphenylmethyl (PTM) radical chemically linked to gold exhibits stable electrochemical activity in ionic liquids. Electrochemical tunnelling spectroscopy in this medium demonstrates that the PTM radical shows a highly effective redox-mediated current enhancement, demonstrating its applicability as an active nanometer-scale electronic component.

Single-atom based coherent quantum interference device structure.

We describe the fabrication, operation principles, and simulation of a coherent single-atom quantum interference device (QID) structure on Si(100) controlled by the properties of single atoms. The energy and spatial distribution of the wave functions associated with the device are visualized by scanning tunneling spectroscopy and the amplitude and phase of the evanescent wave functions that couple into the quantum well states are directly measured, including the action of an electrostatic gate. Density functional theory simulations were employed to simulate the electronic structure of the device structure, which is in excellent agreement with the measurements. Simulations of device transmission demonstrate that our coherent single-atom QID can have ON-OFF ratios in excess of 10(3) with potentially minimal power dissipation.

Spin-Valve Effect in NiFe/MoS2/NiFe Junctions.

Two-dimensional (2D) layered transition metal dichalcogenides (TMDs) have been recently proposed as appealing candidate materials for spintronic applications owing to their distinctive atomic crystal structure and exotic physical properties arising from the large bonding anisotropy. Here we introduce the first MoS2-based spin-valves that employ monolayer MoS2 as the nonmagnetic spacer. In contrast with what is expected from the semiconducting band-structure of MoS2, the vertically sandwiched-MoS2 layers exhibit metallic behavior. This originates from their strong hybridization with the Ni and Fe atoms of the Permalloy (Py) electrode. The spin-valve effect is observed up to 240 K, with the highest magnetoresistance (MR) up to 0.73% at low temperatures. The experimental work is accompanied by the first principle electron transport calculations, which reveal an MR of ∼9% for an ideal Py/MoS2/Py junction. Our results clearly identify TMDs as a promising spacer compound in magnetic tunnel junctions and may open a new avenue for the TMDs-based spintronic applications.

Controlling the Spin Texture of Topological Insulators by Rational Design of Organic Molecules.

We present a rational design approach to customize the spin texture of surface states of a topological insulator. This approach relies on the extreme multifunctionality of organic molecules that are used to functionalize the surface of the prototypical topological insulator (TI) Bi2Se3. For the rational design we use theoretical calculations to guide the choice and chemical synthesis of appropriate molecules that customize the spin texture of Bi2Se3. The theoretical predictions are then verified in angular-resolved photoemission experiments. We show that, by tuning the strength of molecule-TI interaction, the surface of the TI can be passivated, the Dirac point can energetically be shifted at will, and Rashba-split quantum-well interface states can be created. These tailored interface properties-passivation, spin-texture tuning, and creation of hybrid interface states-lay a solid foundation for interface-assisted molecular spintronics in spin-textured materials.

Enhancing Electron Correlation at a 3d Ferromagnetic Surface.

Spin-resolved momentum microscopy and theoretical calculations are combined beyond the one-electron approximation to unveil the spin-dependent electronic structure of the interface formed between iron (Fe) and an ordered oxygen (O) atomic layer, and an adsorbate-induced enhancement of electronic correlations is found. It is demonstrated that this enhancement is responsible for a drastic narrowing of the Fe d-bands close to the Fermi energy (EF ) and a reduction of the exchange splitting, which is not accounted for in the Stoner picture of ferromagnetism. In addition, correlation leads to a significant spin-dependent broadening of the electronic bands at higher binding energies and their merging with satellite features, which are manifestations of a pure many-electron behavior. Overall, adatom adsorption can be used to vary the material parameters of transition metal surfaces to access different intermediate electronic correlated regimes, which will otherwise not be accessible. The results show that the concepts developed to understand the physics and chemistry of adsorbate-metal interfaces, relevant for a variety of research areas, from spintronics to catalysis, need to be reconsidered with many-particle effects being of utmost importance. These may affect chemisorption energy, spin transport, magnetic order, and even play a key role in the emergence of ferromagnetism at interfaces between non-magnetic systems.

Coexistance of giant tunneling electroresistance and magnetoresistance in an all-oxide composite magnetic tunnel junction.

We propose, by performing advanced ab initio electron transport calculations, an all-oxide composite magnetic tunnel junction, within which both large tunneling magnetoresistance (TMR) and tunneling electroresistance (TER) effects can coexist. The TMR originates from the symmetry-driven spin filtering provided by an insulating BaTiO(3) barrier to the electrons injected from the SrRuO(3) electrodes. Following recent theoretical suggestions, the TER effect is achieved by intercalating a thin insulating layer, here SrTiO(3), at one of the SrRuO(3)/BaTiO(3) interfaces. As the complex band structure of SrTiO(3) has the same symmetry as that of BaTiO(3), the inclusion of such an intercalated layer does not negatively alter the TMR and in fact increases it. Crucially, the magnitude of the TER also scales with the thickness of the SrTiO(3) layer. The SrTiO(3) thickness becomes then a single control parameter for both the TMR and the TER effect. This protocol offers a practical way to the fabrication of four-state memory cells.

Maximally localized dynamical quantum embedding for solving many-body correlated systems.

Quantum computing opens new avenues for modeling correlated materials, which are notoriously challenging to solve due to the presence of large electronic correlations. Quantum embedding approaches, such as dynamical mean-field theory, provide corrections to first-principles calculations for strongly correlated materials, which are poorly described at lower levels of theory. Such embedding approaches are computationally demanding on classical computing architectures and hence remain restricted to small systems, limiting the scope of their applicability. Hitherto, implementations on quantum computers have been limited by hardware constraints. Here, we derive a compact representation, where the number of quantum states is reduced for a given system while retaining a high level of accuracy. We benchmark our method for archetypal quantum states of matter that emerge due to electronic correlations, such as Kondo and Mott physics, both at equilibrium and for quenched systems. We implement this approach on a quantum emulator, demonstrating a reduction of the required number of qubits.

Electronic transport calculations for the conductance of Pt-1,4-phenylene diisocyanide-Pt molecular junctions.

The low-bias transport properties of a single 1,4-phenylene diisocyanide (PDI) molecule connected to two platinum (Pt) electrodes are investigated using a self-consistent ab initio approach that combines the non-equilibrium Green's function formalism with density functional theory. Our calculations demonstrate that the zero-bias conductance of an asymmetric Pt-PDI-Pt junction, where the PDI molecule is attached to the atop site at one Pt(111) electrode and to a Pt adatom at the other, is 2.6 x 10( - 2)G(0), in good agreement with the experimental value (3 x 10( - 2)G(0)) measured with break junctions. Although the highest occupied and the lowest unoccupied molecule orbitals in PDI are both pi-type, delocalized along the entire molecule, their electronic coupling with the highly conducting states of the Pt electrode is blocked at the atop site, leading to the small transmission. This indicates that more efficient electronic contacts are needed to fabricate molecular devices with a high conductance using Pt electrodes and aromatic isocyanides such as PDI.

Application of conserved thermal-noise energy model to damped resonant behavior in cryogenic current comparators.

Measurements of the resonant behavior of a cryogenic current comparator (CCC) under a range of damping conditions have been made. A model of conserved thermal-noise energy in resonant systems has been applied showing that, regardless of the value of the damping resistor, the energy stored in the resonance is constant. This finding is presented in the context of the design of high turn CCCs for use in the measurement of small currents where there is an increasing requirement to understand and reduce noise. Various damping methods for CCCs are described and experimental results compared with the theory.

An Experimental and Theoretical Study of Laser Postionization of Femtosecond-Laser-Desorbed Drug Molecules.

Femtosecond laser desorption postionization mass spectrometry using 7.9 eV single-photon ionization (7.9 eV fs-LDPI-MS) detected three of four drug compounds previously found to have very low ionization efficiencies by secondary ion mass spectrometry. Electronic structure calculations of the ionization energies and other properties of these four drug compounds predicted that all display ionization energies below the 7.9 eV photon energy, as required for single-photon ionization. The 7.9 eV fs-LDPI-MS of carbamazepine, imipramine, and verapamil all showed significant precursor (M+) ion signal, but no representative signal was observed for ciprofloxacin. Furthermore, 7.9 eV fs-LDPI-MS displayed higher M+ signals and mostly similar fragment ions compared with 70 eV electron impact mass spectrometry. Ionization and fragmentation patterns are discussed in terms of calculated wave functions for the highest occupied molecular orbitals. The implications for improving lateral resolution and sensitivity of MS imaging of drug compounds are also considered.

Resistive switching mechanism of GeTe-Sb2Te3 interfacial phase change memory and topological properties of embedded two-dimensional states.

A theoretical study of an interfacial phase change memory made of a GeTe-Sb2Te3 superlattice with W electrodes is presented to identify the high and low resistance states and the switching mechanism. The ferro structure of the GeTe layer block in the Te-Ge-Te-Ge sequence can be in the low resistance state only if the SET/RESET mode consists of a two step dynamical process, corresponding to a vertical flip of the Ge layer with respect to the Te layer, followed by lateral motion driven by thermal relaxation. The importance of spin-orbit coupling at the GeTe/Sb2Te3 interface to the "bias polarity-dependent" SET/RESET operation is shown, and an analysis of the two-dimensional states confined at the GeTe/Sb2Te3 interface inside the resistive switching layer is presented. Our results allow us to propose a phase diagram for the transition from a topologically nontrivial to a trivial gap state of these two-dimensional compounds.

Stable anchoring chemistry for room temperature charge transport through graphite-molecule contacts.

An open challenge for single-molecule electronics is to find stable contacts at room temperature with a well-defined conductance. Common coinage metal electrodes pose fabrication and operational problems due to the high mobility of the surface atoms. We demonstrate how molecules covalently grafted onto mechanically robust graphite/graphene substrates overcome these limitations. To this aim, we explore the effect of the anchoring group chemistry on the charge transport properties of graphite-molecule contacts by means of the scanning tunneling microscopy break-junction technique and ab initio simulations. Molecules adsorbed on graphite only via van der Waals interactions have a conductance that decreases exponentially upon stretching the junctions, whereas the molecules bonded covalently to graphite have a single well-defined conductance and yield contacts of unprecedented stability at room temperature. Our results demonstrate a strong bias dependence of the single-molecule conductance, which varies over more than one order of magnitude even at low bias voltages, and show an opposite rectification behavior for covalent and noncovalent contacts. We demonstrate that this bias-dependent conductance and opposite rectification behavior is due to a novel effect caused by the nonconstant, highly dispersive density of states of graphite around the Fermi energy and that the direction of rectification is governed by the detailed nature of the molecule/graphite contact. Combined with the prospect of new functionalities due to a strongly bias-dependent conductance, these covalent contacts are ideal candidates for next-generation molecular electronic devices.

Spin-Polarized Tunneling through Chemical Vapor Deposited Multilayer Molybdenum Disulfide.

The two-dimensional (2D) semiconductor molybdenum disulfide (MoS2) has attracted widespread attention for its extraordinary electrical-, optical-, spin-, and valley-related properties. Here, we report on spin-polarized tunneling through chemical vapor deposited multilayer MoS2 (∼7 nm) at room temperature in a vertically fabricated spin-valve device. A tunnel magnetoresistance (TMR) of 0.5-2% has been observed, corresponding to spin polarization of 5-10% in the measured temperature range of 300-75 K. First-principles calculations for ideal junctions result in a TMR up to 8% and a spin polarization of 26%. The detailed measurements at different temperature, bias voltages, and density functional theory calculations provide information about spin transport mechanisms in vertical multilayer MoS2 spin-valve devices. These findings form a platform for exploring spin functionalities in 2D semiconductors and understanding the basic phenomena that control their performance.

Excitonic Effects in Tungsten Disulfide Monolayers on Two-Layer Graphene.

Light emission in atomically thin heterostructures is known to depend on the type of materials and the number and stacking sequence of the constituent layers. Here we show that the thickness of a two-dimensional substrate can be crucial in modulating the light emission. We study the layer-dependent charge transfer in vertical heterostructures built from monolayer tungsten disulfide (WS2) on one- and two-layer epitaxial graphene, unravelling the effect that the interlayer electronic coupling has on the excitonic properties of such heterostructures. We bring evidence that the excitonic properties of WS2 can be effectively tuned by the number of supporting graphene layers. Integrating WS2 monolayers with two-layer graphene leads to a significant enhancement of the photoluminescence response, up to 1 order of magnitude higher compared to WS2 supported on one-layer graphene. Our findings highlight the importance of substrate engineering when constructing atomically thin-layered heterostructures.

Dynamic spin filtering at the Co/Alq3 interface mediated by weakly coupled second layer molecules.

Spin filtering at organic-metal interfaces is often determined by the details of the interaction between the organic molecules and the inorganic magnets used as electrodes. Here we demonstrate a spin-filtering mechanism based on the dynamical spin relaxation of the long-living interface states formed by the magnet and weakly physisorbed molecules. We investigate the case of Alq3 on Co and, by combining two-photon photoemission experiments with electronic structure theory, show that the observed long-time spin-dependent electron dynamics is driven by molecules in the second organic layer. The interface states formed by physisorbed molecules are not spin-split, but acquire a spin-dependent lifetime, that is the result of dynamical spin-relaxation driven by the interaction with the Co substrate. Such spin-filtering mechanism has an important role in the injection of spin-polarized carriers across the interface and their successive hopping diffusion into successive molecular layers of molecular spintronics devices.