Stretch Evolution of Electronic Coupling of the Thiophenyl Anchoring Group with Gold in Mechanically Controllable Break Junctions.

The current-voltage characteristics of a single-molecule junction are determined by the electronic coupling Γ between the electronic states of the electrodes and the dominant transport channel(s) of the molecule. Γ is profoundly affected by the choice of the anchoring groups and their binding positions on the tip facets and the tip-tip separation. In this work, mechanically controllable break junction experiments on the N,N'-bis(5-ethynylbenzenethiol-salicylidene)ethylenediamine are presented, in particular, the stretch evolution of Γ with increasing tip-tip separation. The stretch evolution of Γ is characterized by recurring local maxima and can be related to the deformation of the molecule and sliding of the anchoring groups above the tip facets and along the tip edges. A dynamic simulation approach is implemented to model the stretch evolution of Γ, which captures the experimentally observed features remarkably well and establishes a link to the microscopic structure of the single-molecule junction.

Proximity-Induced Gap Opening by Twisted Plumbene in Epitaxial Graphene.

Besides graphene, further honeycomb 2D structures were successfully synthesized on various surfaces. However, almost flat plumbene hosting topologically protected edge states could not yet be realized. In this Letter, we investigated the intercalation of Pb on buffer layers on SiC(0001). Thereby, suspended and charge neutral graphene emerged, and the intercalated Pb formed plumbene honeycomb lattices, which are rotated by ±7.5° with respect to graphene. Along with this twist, a proximity-induced modulation of the hopping parameter in graphene opens a band gap of around 30 meV at the Fermi energy, giving rise to a metal-insulator transition. Moreover, the edges of the intercalated plumbene layers revealed edge states within the gap of the conduction bands at around 1 eV as expected for charge neutral plumbene.

Deposition of Nanosized Amino Acid Functionalized Bismuth Oxido Clusters on Gold Surfaces.

Bismuth compounds are of growing interest with regard to potential applications in catalysis, medicine, and electronics, for which their environmentally benign nature is one of the key factors. One thing that currently hampers the further development of bismuth oxido-based materials, however, is the often low solubility of the precursors, which makes targeted immobilisation on substrates challenging. We present an approach towards the solubilisation of bismuth oxido clusters by introducing an amino carboxylate as a functional group. For this purpose, the bismuth oxido cluster [Bi38O45(NO3)20(dmso)28](NO3)4·4dmso (dmso = dimethyl sulfoxide) was reacted with the sodium salt of tert-butyloxycabonyl (Boc)-protected phenylalanine (L-Phe) to obtain the soluble and chiral nanocluster [Bi38O45(Boc-Phe-O)24(dmso)9]. The exchange of the nitrates by the amino carboxylates was proven by nuclear magnetic resonance, Fourier-transform infrared spectroscopy, as well as elemental analysis and X-ray photoemission spectroscopy. The solubility of the bismuth oxido cluster in a protic as well as an aprotic polar organic solvent and the growth mode of the clusters upon spin, dip, and drop coating on gold surfaces were studied by a variety of microscopy, as well as spectroscopic techniques. In all cases, the bismuth oxido clusters form crystalline agglomerations with size, height, and distribution on the substrate that can be controlled by the choice of the solvent and of the deposition method.

Describing chain-like assembly of ethoxygroup-functionalized organic molecules on Au(111) using high-throughput simulations.

Due to the low corrugation of the Au(111) surface, 1,4-bis(phenylethynyl)-2,5-bis(ethoxy)benzene (PEEB) molecules can form quasi interlocked lateral patterns, which are observed in scanning tunneling microscopy experiments at low temperatures. We demonstrate a multi-dimensional clustering approach to quantify the anisotropic pair-wise interaction of molecules and explain these patterns. We perform high-throughput calculations to evaluate an energy function, which incorporates the adsorption energy of single PEEB molecules on the metal surface and the intermolecular interaction energy of a pair of PEEB molecules. The analysis of the energy function reveals, that, depending on coverage density, specific types of pattern are preferred which can potentially be exploited to form one-dimensional molecular wires on Au(111).

Tunable Magnetic Vortex Dynamics in Ion-Implanted Permalloy Disks.

Nanoscale, low-phase-noise, tunable transmitter-receiver links are key for enabling the progress of wireless communication. We demonstrate that vortex-based spin-torque nano-oscillators, which are intrinsically low-noise devices because of their topologically protected magnetic structure, can achieve frequency tunability when submitted to local ion implantation. In the experiments presented here, the gyrotropic mode is excited with spin-polarized alternating currents and anisotropic magnetoresistance measurements yield discrete frequencies from a single device. Indeed, chromium-implanted regions of permalloy disks exhibit different saturation magnetization than neighboring, non-irradiated areas, and thus different resonance frequency, corresponding to the specific area where the core is gyrating. Our study proves that such devices can be fabricated without the need for further lithographical steps, suggesting ion irradiation can be a viable and cost-effective fabrication method for densely packed networks of oscillators.

Field-responsive colloidal assemblies defined by magnetic anisotropy.

Particle dispersions provide a promising tool for the engineering of functional materials that exploit self-assembly of complex structures. Dispersion made from magnetic colloidal particles is a great choice; they are biocompatible and remotely controllable among many other advantages. However, their dominating dipolar interaction typically limits structural complexity to linear arrangements. This paper shows how a magnetostatic equilibrium state with noncollinear arrangement of the magnetic moments, as reported for ferromagnetic Janus particles, enables the controlled self-organization of diverse structures in two dimensions via constant and low-frequency external magnetic fields. Branched clusters of staggered chains, compact clusters, linear chains, and dispersed single particles can be formed and interconverted reversibly in a controlled way. The structural diversity is a consequence of both the inhomogeneity and the spatial extension of the magnetization distribution inside the particles. We draw this conclusion from calculations based on a model of spheres with multiple shifted dipoles. The results demonstrate that fundamentally new possibilities for responsive magnetic materials can arise from interactions between particles with a spatially extended, anisotropic magnetization distribution.

Electron transport through NiSi2-Si contacts and their role in reconfigurable field-effect transistors.

A model is presented which describes reconfigurable field-effect transistors (RFETs) with metal contacts, whose switching is controlled by manipulating the Schottky barriers at the contacts. The proposed modeling approach is able to bridge the gap between quantum effects on the atomic scale and the transistor switching. We apply the model to transistors with a silicon channel and NiSi2 contacts. All relevant crystal orientations are compared, focusing on the differences between electron and hole current, which can be as large as four orders of magnitude. Best symmetry is found for the [Formula: see text] orientation, which makes this orientation most advantageous for RFETs. The observed differences are analyzed in terms of the Schottky barrier height at the interface. Our study indicates that the precise orientation of the interface relative to a given transport direction, perpendicular or tilted, is an important technology parameter, which has been underestimated during the previous development of RFETs. Most of the conclusions regarding the studied metal-semiconductor interface are also valid for other device architectures.

Probing interlayer excitons in a vertical van der Waals p-n junction using a scanning probe microscopy technique.

Two dimensional (2D) semiconductors feature exceptional optoelectronic properties controlled by strong confinement in one dimension. In this contribution, we studied interlayer excitons in a vertical p-n junction made of bilayer n-type MoS2 and few layers of p-type GaSe using current sensing atomic force microscopy (CSAFM). The p-n interface is prepared by mechanical exfoliation onto highly ordered pyrolytic graphite (HOPG). Thus the heterostructure creates an ideal layered system with HOPG serving as the bottom contact for the electrical characterization. Home-built Au tips are used as the top contact in CSAFM mode. During the basic diode characterization, the p-n interface shows strong rectification behavior with a rectification ratio of 104 at ±1 V. The I-V characteristics reveal pronounced photovoltaic effects with a fill factor of 0.55 by an excitation below the band gap. This phenomenon can be explained by the dissociation of interlayer excitons at the interface. The possibility of the interlayer exciton formation is indicated by density functional theory (DFT) calculations on this heterostructure: the valence band of GaSe and the conduction band of MoS2 contribute to an interface-specific state at an energy of about 1.5 eV. The proof of excitonic transitions to that state is provided by photoluminescence measurements at the p-n interface. Finally, photocurrent mapping at the interface under an excitation wavelength of 785 nm provides evidence of efficient extraction of such excitons. Our results demonstrate a pathway towards a 2D device for future optoelectronics and light harvesting assisted by interlayer excitons in a van der Waals (vdW) heterostructure.

Tuning the conductance of a molecular wire by the interplay of donor and acceptor units.

We investigate the conductance of optimized donor-acceptor-donor molecular wires obtained by on-surface synthesis on the Au(111) surface. A careful balance between acceptors and donors is achieved using a diketopyrrolopyrrole acceptor and two thiophene donors per unit along the wire. Scanning tunneling microscopy imaging, spectroscopy, and conductance measurements done by pulling a single molecular wire at one end are presented. We show that the conductance of the obtained wires is among the highest reported so far in a tunneling transport regime, with an inverse decay length of 0.17 Å-1. Using complex band structure calculations, different donor and acceptor groups are discussed, showing how a balanced combination of donor and acceptor units along the wire can further minimize the decay of the tunneling current with length.

Percolated Si:SiO2 Nanocomposites: Oven- vs. Millisecond Laser-Induced Crystallization of SiOx Thin Films.

Three-dimensional nanocomposite networks consisting of percolated Si nanowires in a SiO2 matrix, Si:SiO2, were studied. The structures were obtained by reactive ion beam sputter deposition of SiOx (x ≈ 0.6) thin films at 450 ∘C and subsequent crystallization using conventional oven, as well as millisecond line focus laser treatment. Rutherford backscattering spectrometry, Raman spectroscopy, X-ray diffraction, cross-sectional and energy-filtered transmission electron microscopy were applied for sample characterization. While oven treatment resulted in a mean Si wire diameter of 10 nm and a crystallinity of 72% within the Si volume, almost single-domain Si structures of 30 nm in diameter and almost free of amorphous Si were obtained by millisecond laser application. The structural differences are attributed to the different crystallization processes: conventional oven tempering proceeds via solid state and millisecond laser application via liquid phase crystallization of Si. The five orders of magnitude larger diffusion constant in the liquid phase is responsible for the three-times larger Si nanostructure diameter. In conclusion, laser treatment offers not only significantly shorter process times, but moreover, a superior structural order of nano-Si compared to conventional heating.

Cluster Tool for In Situ Processing and Comprehensive Characterization of Thin Films at High Temperatures.

A new cluster tool for in situ real-time processing and depth-resolved compositional, structural and optical characterization of thin films at temperatures from -100 to 800 °C is described. The implemented techniques comprise magnetron sputtering, ion irradiation, Rutherford backscattering spectrometry, Raman spectroscopy, and spectroscopic ellipsometry. The capability of the cluster tool is demonstrated for a layer stack MgO/amorphous Si (∼60 nm)/Ag (∼30 nm), deposited at room temperature and crystallized with partial layer exchange by heating up to 650 °C. Its initial and final composition, stacking order, and structure were monitored in situ in real time and a reaction progress was defined as a function of time and temperature.

Functional thiols as repair and doping agents of defective MoS2 monolayers.

Recent experimental and theoretical studies indicate that thiols (R-SH) can be used to repair sulfur vacancy defects in MoS2 monolayers (MLs). This density functional theory study investigates how the thiol repair mechanism process can be used to dope MoS2 MLs. Fluorinated thiols as well as amine-containing ones are used to p- and n-dope the MoS2 ML, respectively. It is shown that functional groups are only physisorbed on the repaired MoS2 surface. This explains the reversible doping with fluorinated thiols.

Chemical and Electronic Repair Mechanism of Defects in MoS2 Monolayers.

Using ab initio density functional theory calculations, we characterize changes in the electronic structure of MoS2 monolayers introduced by missing or additional adsorbed sulfur atoms. We furthermore identify the chemical and electronic function of substances that have been reported to reduce the adverse effect of sulfur vacancies in quenching photoluminescence and reducing electronic conductance. We find that thiol-group-containing molecules adsorbed at vacancy sites may reinsert missing sulfur atoms. In the presence of additional adsorbed sulfur atoms, thiols may form disulfides on the MoS2 surface to mitigate the adverse effect of defects.

Universality of (2+1)-dimensional restricted solid-on-solid models.

Extensive dynamical simulations of restricted solid-on-solid models in D=2+1 dimensions have been done using parallel multisurface algorithms implemented on graphics cards. Numerical evidence is presented that these models exhibit Kardar-Parisi-Zhang surface growth scaling, irrespective of the step heights N. We show that by increasing N the corrections to scaling increase, thus smaller step-sized models describe better the asymptotic, long-wave-scaling behavior.

Rotational friction of dipolar colloids measured by driven torsional oscillations.

Despite its prominent role in the dynamics of soft materials, rotational friction remains a quantity that is difficult to determine for many micron-sized objects. Here, we demonstrate how the Stokes coefficient of rotational friction can be obtained from the driven torsional oscillations of single particles in a highly viscous environment. The idea is that the oscillation amplitude of a dipolar particle under combined static and oscillating fields provides a measure for the Stokes friction. From numerical studies we derive a semi-empirical analytic expression for the amplitude of the oscillation, which cannot be calculated analytically from the equation of motion. We additionally demonstrate that this expression can be used to experimentally determine the rotational friction coefficient of single particles. Here, we record the amplitudes of a field-driven dipolar Janus microsphere with optical microscopy. The presented method distinguishes itself in its experimental and conceptual simplicity. The magnetic torque leaves the local environment unchanged, which contrasts with other approaches where, for example, additional mechanical (frictional) or thermal contributions have to be regarded.

Carbon : nickel nanocomposite templates - predefined stable catalysts for diameter-controlled growth of single-walled carbon nanotubes.

Carbon : nickel (C : Ni) nanocomposite templates (NCTs) were used as catalyst precursors for diameter-controlled growth of single-walled carbon nanotubes (SWCNTs) by chemical vapor deposition (CVD). Two NCT types of 2 nm thickness were prepared by ion beam co-sputtering without (type I) or with assisting Ar(+) ion irradiation (type II). NCT type I comprised Ni-rich nanoparticles (NPs) with defined diameter in an amorphous carbon matrix, while NCT type II was a homogenous C : Ni film. Based on the Raman spectra of more than 600 individual SWCNTs, the diameter distribution obtained from both types of NCT was determined. SWCNTs with a selective, monomodal diameter distribution are obtained from NCT type I. About 50% of the SWCNTs have a diameter of (1.36 ± 0.10) nm. In contrast to NCT type I, SWCNTs with a non-selective, relatively homogeneous diameter distribution from 0.80 to 1.40 nm covering 88% of all SWCNTs are obtained from NCT type II. From both catalyst templates predominantly separated as-grown SWCNTs are obtained. They are free of solvents or surfactants, exhibit a low degree of bundling and contain negligible amounts of MWCNTs. The study demonstrates the advantage of predefined catalysts for diameter-controlled SWCNT synthesis in comparison to in situ formed catalysts.

Non-equilibrium dynamics of magnetically anisotropic particles under oscillating fields.

In this article, we demonstrate how magnetic anisotropy of colloidal particles can give rise to unusual dynamics and controllable rearrangements under time-dependent fields. As an example, we study spherical particles with a radially off-centered net magnetic moment in an oscillating field. Based on complementary data from a numerical simulation of spheres with shifted dipole and experimental observations from particles with hemispherical ferromagnetic coating, it is explained on a two particle basis how this magnetic anisotropy causes nontrivial rotational motion and magnetic reorientation. We further present the behavior of larger ensembles of coated particles. It illustrates the potential for controlled reconfiguration based on the presented two-particle dynamics.

High Conductivity in Molecularly p-Doped Diketopyrrolopyrrole-Based Polymer: The Impact of a High Dopant Strength and Good Structural Order.

[3]-Radialene-based dopant CN6-CP studied herein, with its reduction potential of +0.8 versus Fc/Fc+ and the lowest unoccupied molecular orbital level of -5.87 eV, is the strongest molecular p-dopant reported in the open literature, so far. The efficient p-doping of the donor-acceptor dithienyl-diketopyrrolopyrrole-based copolymer having the highest unoccupied molecular orbital level of -5.49 eV is achieved. The doped films exhibit electrical conductivities up to 70 S cm(-1) .

Carbon p electron ferromagnetism in silicon carbide.

Ferromagnetism can occur in wide-band gap semiconductors as well as in carbon-based materials when specific defects are introduced. It is thus desirable to establish a direct relation between the defects and the resulting ferromagnetism. Here, we contribute to revealing the origin of defect-induced ferromagnetism using SiC as a prototypical example. We show that the long-range ferromagnetic coupling can be attributed to the p electrons of the nearest-neighbor carbon atoms around the VSiVC divacancies. Thus, the ferromagnetism is traced down to its microscopic electronic origin.

Optics, mechanics, and energetics of two-dimensional MoS2 nanostructures from a theoretical perspective.

CONSPECTUS: Nanostructures based on molybdenum disulfide (MoS2) are by far the most common and well-studied systems among two-dimensional (2D) semiconducting materials. Although still being characterized as a "promising material", catalytic activity of MoS2 nanostructures has been found, and applications in lubrication processes are pursued. Because exfoliation techniques have improved over the past years, monolayer MoS2 is easily at hand; thus, experimental studies on its electronic properties and applicability are in scientific focus, and some MoS2-based electronic devices have been reported already. Additionally, the improvement of atomic force microscopy led to nanoindentation experiments, in which the exceptional mechanical properties of MoS2 could be confirmed. In this Account, we review recent results from density-functional based calculations on several MoS2-based nanostructures; we have chosen to follow several experimental routes focusing on different nanostructures and their specific properties. MoS2-based triangular nanoflakes are systems that are experimentally well described and studied with a special focus on their optical absorption. The interpretation of our calculations fits well to the experimental picture: the absorption peaks in the visible light range show a quantum-confinement effect; they originate from excitations into the edge states. Additionally, delocalized metallic-like states are present close to the Fermi level, which do not contribute to photoabsorption in the visible range. Additionally, nanoindentation experiments have been simulated to obtain mechanical properties of the MoS2 material and to study the influence of deformation on the system's electronics. In these molecular-dynamics simulations, a tip penetrates a MoS2 monolayer, and the obtained Young's modulus and breaking stress agree very well with experimentally obtained values. Whereas the structural properties, such as bond lengths and layer contraction, vary locally differently upon indentation, the electronic structure in terms of the density of states, the gap between occupied and unoccupied states, or the quantum transport change only slightly. The robustness of the material with respect to electronic and mechanical properties makes monolayer MoS2 special. However, it is important to note that this robustness refers to a local disturbance through deformation and still seems to be dependent on the defect concentration. Finally, we present a comparison of the thermodynamic stabilities of different MoS2-based nanostructures with a focus on nanoflakes, fullerene-like nanooctahedra, and smaller Chevrel-type and non-Chevrel-type clusters (nanowires). All studied systems are stable in comparison to MoS2, Mo bulk, and the S8 crown, but only the studied nanoflakes and nanowires show specific stoichiometries, either sulfur-rich or sulfur-poor, whereas the nanooctahedra may adopt both. From the thermodynamic stabilities, it should be possible to deliberately choose specific nanostructures by thoughtful choices of the synthesis conditions. In conclusion, we present in this Account exceptional properties of MoS2-based nanostructures studied by means of density-functional theory. The focus lies on optical absorption in the visible range observed in triangular nanoflakes, which originate in the system's edge states, the robustness of monolayer MoS2 with respect to punctual loads regarding both mechanical and electronic properties, and the thermodynamic stability of most studied MoS2-based nanosystems revealing a correlation between composition and preferred morphology, particularly for 2D systems.