The effects of contact configurations on the rectification of dipyrimidinylben diphenyl diblock molecular junctions

The transport properties of a conjugated dipyrimidinyl-diphenyl diblock oligomer sandwiched between two gold electrodes, as recently reported by [Díez-Pérez et al. Nature Chem. 1 635 (2009)], are theoretically investigated using the fully self-consistent nonequilibrium Green's function method combined with density functional theory. Two kinds of symmetrical anchoring geometries are considered. Calculated current-voltage curves show that the contact structure has a strong effect on the rectification behaviour of the molecular diode. For the equilateral triangle configuration, pronounced rectification behaviour comparable to the experimental measurement is revealed, and the theoretical analysis indicates that the observed rectification characteristic results from the asymmetric shift of the perturbed molecular energy levels under bias voltage. While for the tetrahedron configuration, both rectification and negative differential conductivity behaviours are observed. The calculated results further prove the close dependence of the transporting characteristics of molecular junctions on contact configuration.     

Readout of the qubit state with a dc-SQUID

The states of a flux qubit with three Josephson junctions were observed with a dc-SQUID. The qubit is an aluminium superconductor loop surrounded by a dc-SQUID for readout. It has two states, which have persistent currents flowing in opposite directions. The system potentially offers the advantage of allowing single-shot/single-system measurements of macroscopic superposition of the two states. We have developed a highly sensitive, low-noise, single-shot detection system, and here we report the first direct observation of a macroscopic quantum superposition. The measured ground and the first excited state showed the same behaviour as the theoretical ones. We also showed that the measured behaviour of the switching current in a dc-SQUID was the same as that of the quantum-mechanically expected value of the switching current in the qubit.     

A comparative study of electron transport in benzene molecule covalently bonded to gold and silicon electrodes for pioneering the electron transport properties of silicon quantum dot-molecule hybrid polymers

In order to pioneer the electron transport properties of silicon (Si) quantum dot-molecule hybrid polymers, we investigate the electron transport properties of the benzene molecule in silicon (Si) semiconductor electrodes, based on nonequilibrium Green's function (NEGF) method coupled with density functional theory (DFT), in comparison with conventional gold (Au) metal electrodes, with three different anchoring linker groups: thiol for dithiol-benzene (DTB), methylene for dimethyl-benzene (DMB), and direct bonding for benzene (Ph). It is interestingly found that, due to band gap nature of the Si semiconductor electrodes, the molecular junctions with the Si electrodes show no current up to the bias voltage of around 0.8 V. In addition, the DTB molecular junctions in the Si semiconductor electrodes connected with Si–S bond show higher conducting properties than other DMB and Ph molecular junctions directly coupled to the electrodes with the Si–C bonds (DMB < Ph < DTB). The electron transport properties of the molecules in the two different electrodes are analyzed on the basis of the understanding transmission spectra, projected density of states (PDOS), and molecular orbitals. We believe that the use of thiol linker may open new possibility in the molecular electronics with the Si semiconductor electrodes and the Si QD-molecule hybrid polymers concept.     

The observer-based synchronization and parameter estimation of a class of chaotic system via a single output

The conductance of a single molecule transport junction comprising anthracene molecular junction (AMJ) with fullerene as alligator clips was investigated using ab-initio density functional theory (DFT) in the Landauer–Imry regime of coherent tunnelling transport. In our previous research, we have already calculated the electrical transport properties of aromatic molecules with thiol, amine, hydroxyl and selenol end groups concluding the exceptional assistance in the formation of robust molecular junctions. In this article, we have presented the suitability of fullerene anchoring in coupling anthracene molecule with gold electrodes. AMJ with boron-20 (B-20) and C-20 alligator clips exhibited strongest conduction in contrast to nitrogen, oxygen, fluorine and neon alligator clips.     

Anchoring group effects in molecular devices: An ab initio study on the electronic transport of a carbon-dimer

The conductance of a molecular device is sensitive to the contact geometry between the molecules and the probing electrodes. Taking a carbon-dimer C₂ as an example and connecting it to the electrodes by different linking atoms H, Cu and S, we investigate the anchoring group effect in molecular devices by the first-principles approaches. The results exhibit that, depending on the anchoring groups and the subsequent different metal-molecule chemical bonds, the current varies over more than two orders of magnitude under the same bias. This emphasizes the great importance of the anchoring groups in molecular devices.     

An approach to measure electromechanical properties of atomic and molecular junctions

We describe a new setup for simultaneous measurements of force and current in conductive nanocontacts in a liquid environment with a high sampling rate and resolution. A lab-built current-to-voltage converter allows measurements of the current over seven orders of magnitude. As examples, we studied conductances and mechanical forces upon formation and breaking of gold atomic contacts and of two molecular junctions containing 1,2-di(4-pyridyl)ethyne (M1) and 1,4-di(4-pyridyl)buta-1,3-diyne (M2). We found that the forces required to deform or break gold atomic contacts depend critically on the surrounding medium. Further, they show non-linear behaviour in dependence of the number N of gold atoms detached. The electromechanical properties of the two types of molecular junctions upon stretching were analysed by correlating breaking forces with simultaneously measured junction conductances. A rather complex behaviour in a wide range of forces was discovered. Comparison of the current-probe atomic force microscopy experiments on the rupture of molecular junctions with STM-based break junction experiments enables the assignment of breaking forces of molecular junctions to the corresponding junction conductances.     

Some remarks on the chain segment dynamics in confined polymers

Recently, the chain dynamics of molten polymers in confined geometries has been investigated, using NMR. Some of these experiments have been performed on poydimethylsiloxane (PDMS) confined in planar nanolayers involving non-adsorbant solid surfaces. Here the data obtained on various PDMS systems are compared. The common property to these systems is that the local dynamics is anisotropic and the chain segments are undergoing uniaxial fluctuations around the normal n to the layers. Our data clearly show that the sign of the degree of orientational order S ( i.e. the direction of the fluctuations around n) and the broadening of the order distribution P( S) both result from the relative influence of the impenetrable interfaces and anchoring junctions on the segment behaviour.     

Electronic transport properties in benzene-based heterostructure: Effects of anchoring groups

Using density functional theory (DFT) combined with nonequilibrium Green?s functions (NEGF), the electronic transport properties of benzene-based heterostructure molecular devices have been investigated. We focus on the contact geometry between molecules and electrodes, and several different anchoring groups have been considered. The current–voltage characteristics were calculated for positive and negative bias voltages, and discussed in terms of transmission spectra, transferred charges, and molecular projected self-consistent Hamiltonian (MPSH) states. Our results show that the anchoring groups play a crucial role in determining the overall conductivity of the molecular devices. Negative differential resistance (NDR) and rectifying effect can be observed.     

Effect of Chirality on the Electronic Transport Properties of the Thioxanthene-Based Molecular Switch

Based on the nonequilibrium Green function method and density functional theory calculations,we theoretically investigate the effect of chirality on the electronic transport properties of thioxanthene-based molecular switch.The molecule comprises the switch which can exhibit different chiralities,that is,cis-form and trans-form by ultraviolet or visible irradiation.The results clearly reveal that the switching behaviors can be realized when the molecule converts between cis-form and trans-form.Furthermore,the on-off ratio can be modulated by the chirality of the carbon nanotube electrodes.The maximum on-off ratio can reach 109 at 0.4 V for the armchair junction,suggesting potential applications of this type of junctions in future design of functional molecular devices.     

Electrical-thermal switching in carbon-black-polymer composites as a local effect

Following the lack of microscopic information about the intriguing well-known electrical-thermal switching mechanism in carbon-black-polymer composites, we applied atomic force microscopy in order to reveal the local nature of the process and correlated it with the characteristics of the widely used commercial switches. We conclude that the switching events take place in critical interparticle tunneling junctions that carry most of the current. The macroscopic switched state is then a result of a dynamic-stationary state of fast switching and slow reconnection of the corresponding junctions.     

Design of switching junctions for two-dimensional discrete soliton networks

The performance of switching junctions in two-dimensional discrete-soliton networks is analyzed theoretically by coupled-mode theory. Our analysis can be used for the design of routing junctions with specified operational characteristics. Appropriately engineering the intersection site can further improve the switching efficiency of these junctions. Our analytical results are verified by numerical simulations.     

Effect of resistance feedback on spin torque-induced switching of nanomagnets

In large magnetoresistance devices spin torque-induced changes in resistance can produce GHz current and voltage oscillations which can affect magnetization reversal. In addition, capacitive shunting in large resistance devices can further reduce the current, adversely affecting spin torque switching. Here, we simultaneously solve the Landau-Lifshitz-Gilbert equation with spin torque and the transmission line telegrapher's equations to study the effects of resistance feedback and capacitance on magnetization reversal of both spin valves and magnetic tunnel junctions. While for spin valves parallel (P) to anti-parallel (AP) switching is adversely affected by the resistance feedback due to saturation of the spin torque, in low resistance magnetic tunnel junctions P-AP switching is enhanced. We study the effect of resistance feedback on the switching time of magnetic tunnel junctions, and show that magnetization switching is only affected by capacitive shunting in the pF range.     

Current-induced conformational switching in single-molecule junctions

Current-induced conformational switching in single-molecule junctions constitutes a fundamental process in molecular electronics. Motivated by recent experiments on azobenzene derivatives, we study this process for molecules which exhibit two (meta)stable conformations in the neutral state but only a single stable conformation in the ionic state. We derive and analyze appropriate Fokker–Planck equations obtained from a density-matrix formalism starting from a generic model and present comprehensive analytical and numerical results for the switching dynamics in general and the quantum yield in particular.     

Negative differential resistance behaviour in N-doped crossed graphene nanoribbons

By using first-principles calculations and nonequilibrium Green’s function technique, we study elastic transport properties of crossed graphene nanoribbons. The results show that the electronic transport properties of molecular junctions can be modulated by doped atoms. Negative differential resistance (NDR) behaviour can be observed in a certain bias region, when crossed graphene nanoribbons are doped with nitrogen atoms at the shoulder, but it cannot be observed for pristine crossed graphene nanoribbons at low biases. A mechanism for the negative differential resistance behaviour is suggested.     

Current induced exchange switching of magnetic junctions with cubic anisotropy of a free layer

The stability of equilibrium configurations of magnetic junctions with a free layer of cubic anisotropy with two axes in the layer plane has been analyzed. Variants of switching between different configurations have been considered. It has been demonstrated that the possibility exists of considerably decreasing the threshold current density necessary for switching. Numerical simulation of the dynamics of switching between different configurations has been performed.     

Resistive switching behaviour of highly epitaxial CeO2 thin film for memory application

We report on the remarkable potential of highly epitaxial and pure (001)‐oriented CeO₂ thin films grown on conducting Nb‐doped SrTiO₃ (NSTO) substrates by laser molecular beam epitaxy for nonvolatile memory application. Resistive switching (RS) devices with the structure of Au/epi‐CeO₂/NSTO exhibit reversible and steady bipolar RS behaviour with large high/low resistance ratio and a narrow dispersion of the resistance values. Detailed analysis of the conduction mechanisms reveals that the trapping/detrapping processes and oxygen vacancies migration play important roles in the switching behaviour. In the light of XPS measurement results, the CeO₂/NSTO interface with oxygen vacancies or defects is responsible for the RS effect. Furthermore, a model is proposed to explain this resistance switching behaviour. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A possible salicylideneanilines-based optical molecular switch induced by a reversible hydrogen transfer: an ab initio study

The electronic transport properties of the salicylideneanilines-based molecular optical switch are investigated using a nonequilibrium Green's function formalism combined with first-principles density functional theory. The molecule that comprises the switch can convert between the enol and keto tautomeric forms upon photoinduced excited state hydrogen transfer in the molecular bridge. Theoretical results show that the current through the enol form is significantly larger than that through the keto form, which realize the on and off states of the molecular switch. The physical origin of the switching behaviour is interpreted based on the spatial distributions of molecular orbitals and the HOMO-LUMO gap. Furthermore the effect of the donor/acceptor substituent on the electronic transport through the molecular device is also discussed in detail. The switching performance can be improved to some extent through the acceptor substituent.     

Static and dynamic electro-optic properties of a SmC* phase in surface stabilized geometry and dispersed in the polymer matrix

Comparative electro-optical measurements have been made on a ferroelectric liquid crystal (FLC) in surface stabilized geometry and confined to an ellipsoidal cavity within a polymer matrix. The static and dynamic electro-optical characteristics were measured for both systems and show qualitatively similar behaviours. A fast switching and important bistability were observed and characterized as a function of the applied electric field strength. The switching time between the two stable states of the surface stabilized cell was found to be longer than that found for the composite films. We argue that the faster switching dynamic of the FLC in cavities is due to the enhance of the rotational mobility of the molecules, probably (and partly) because of the soft anchoring character of the molecules at the cavity walls. Using a collective switching model in the high field regime, which assume a linear coupling between the spontaneous polarization and the local cavity electric field, we give an estimate of the rotational viscosity of the FLC molecules in the droplets.Received: 5 October 2003, Published online: 5 February 2004PACS: 61.30.Pq Microconfined liquid crystals: droplets, cylinders, randomly confined liquid crystals, polymer dispersed liquid crystals, and porous systems - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions - 77.80.Fm Switching phenomena     

溶液酸碱性对低聚苯亚乙炔基分子结电输运性质的影响

结合密度泛函理论和非平衡格林函数方法计算了溶液酸碱性对低聚苯亚乙炔基分子结电输运性质的影响,此低聚苯亚乙炔基分子中两个不同位置的H原子被氨基和羧基取代.通过质子化和去质子化模拟酸性溶液和碱性溶液对分子结构的影响.计算结果表明:中性环境下分子器件具有良好的导电性和微弱的整流效应;碱性溶液中羧基去质子化后,分子器件电流值增长近一倍,但整流效应变化不明显;酸性溶液中氨基质子化后,分子器件正向偏压导电性能略微降低,但整流方向发生明显反转,且与中性环境下的情况相比,整流比提高了近三倍.提出了一种利用化学手段控制分子结导电能力和整流性能的方法.     

Computational study of new azo dyes with different anchoring groups for dye-sensitised solar cells

Some of new azo dyes with different anchoring groups, such as biscarbodithiolic acid, hydroxamic acid, phosphonic acid, carboxcylic acid and sulfonic acid have been investigated theoretically to evaluate the effects of various anchoring groups on the optical and electronic properties of the dyes in dye-sensitised solar cells. Optical and electronic properties, UV–Vis absorption spectra, light-harvesting efficiency, lifetime of the excited state, chemical hardness and lowest unoccupied molecular orbital (LUMO) orbital weight of the dyes on the anchoring groups, have been studied to shed light on how the various anchoring groups influence the properties of the dyes. The biscarbodithiolic acid-based dye shows the longest maximum absorption wavelength and the widest absorption spectra together with the highest light-harvesting efficiency, the longest lifetime of the excited state and the highest the LUMO orbital weight of the dye on the atoms of the anchoring group, suggesting the good ability in electron injection. Theoretical calculations have been also performed on the adsorption of these dyes on the TiO₂ anatase (101) surface. These results show that the biscarbodithiolic acid-based dye has the highest adsorption energy and the largest negative shift of the conduction band of TiO₂ due to the adsorption of the dye onto the TiO₂.