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.     

Effect of the anchoring groups on the switching behaviour of the dihydroazulene/vinylheptafulvene molecular junction with zigzag-edged graphene nanoribbons electrodes

The switching behaviour of dihydroazulene/vinylheptafulvene molecule with different anchoring groups sandwiched between two zigzag-edged graphene nanoribbons (ZGNRs) electrodes is investigated by applying nonequilibrium Green's function formalism combined with first-principles density functional theory. The calculated results show that the anchoring groups play a significant role in determining the electronic transport properties and switching behaviour of the molecular junctions. A higher current switching ratio without any oscillation can be obtained for the molecular junctions with carbon atom anchoring group, which suggests that this system has a broader application in future logic and memory devices.     

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.     

Effect of torsion angle on electronic transport through different anchoring groups in molecular junction

By applying nonequilibrium Green's function formalism combined with first-principles density functional theory, we investigate effect of torsion angle on electronic transport properties of 4,^4′-biphenyl molecule connected with different anchoring groups (dithiocarboxylate and thiol group) to Au(111) electrodes. The influence of the HOMO-LUMO gaps and the spatial distributions of molecular orbitals on the quantum transport through the molecular device are discussed. Theoretical results show that the torsion angle plays important role in conducting behavior of molecular devices. By changing the torsion angle between two phenyl rings, namely changing the magnitude of the intermolecular coupling effect, a different transport behavior can be observed in these two systems.     

Characteristics of electrical properties of wide temperature range TGB phases in liquid crystal dimers

4-n-decyloxy-4′-(cholesteryloxycarbonyl-1-butyloxy) chalcone and its two successive homologous are optically active dimeric compound derived from cholesterol. They possess wide temperature ranges of two twist grain boundary (TGB) phases namely TGBA and TGBC*. Comprehensive dielectric studies have been carried out for these compounds in the frequency range of 1 Hz to 10 MHz for different conditions of molecular anchoring. Various electrical parameter viz. dielectric permittivity, dielectric anisotropy, dc conductivity, and activation energy have been determined for these two TGB phases. Weak relaxation processes have been detected under planar anchoring of molecules in the TGBA and TGBC* phases presumably due to amplitude (soft mode) and phase (Goldstone mode) fluctuations.     

An AFM, XPS and electrochemical study of molecular electroactive monolayers formed by wet chemistry functionalization of H-terminated Si(1 0 0) with vinylferrocene

Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η⁵-C₅H₅)Fe²⁺(η⁵-C₅H₄)-CH₂-CH₂-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe³⁺ at the expenses of Fe²⁺ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO⁻ groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe³⁺ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing.     

Study of intrinsic anchoring in nematic liquid crystals based on modified Gruhn-Hess pair potential

A nematic liquid crystal slab composed of N molecular layers is investigated using a simple cubic lattice model, based upon the molecular pair potential which is spatially anisotropic and dependent on elastic constants of liquid crystals. A perfect nematic order is assumed in the theoretical treatment, which means the orientation of the molecular long axis coincides with the director of liquid crystal and the total free energy equals to the total interaction energy. We present a modified Gruhn-Hess model, which is relative to the splay-bend elastic constant K₁₃. Furthermore, we have studied the free nematic interfacial behavior (intrinsic anchoring) by this model in the assumption of the perfect nematic order. We find that the preferred orientation at the free interface and the intrinsic anchoring strength change with the value of modification, and that the director profile can be determined by the competition of the intrinsic anchoring with external forces present in the system. Also we simulate the intrinsic anchoring at different temperatures using Monte Carlo method and the simulation results show that the intrinsic anchoring favors planar alignment and the free interface is more disordered than the bulk.     

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.     

Influence of the order parameter on the anchoring energy of liquid crystals

No theory of the polar and azimuthal anchoring energies of liquid crystals (LCs) has been developed on a molecular level, despite the scientific and practical topicality of the problem. The interaction energies of mesogenic molecules with graphite and polyethylene surfaces calculated previously by the method of atom-atom potentials are in good agreement with the experimental data, but, at the same time, the calculated polar and azimuthal anchoring energies are larger than their experimental values by one and two orders of magnitude, respectively. To explain these values, the anchoring energy has been assumed to depend not only on the interaction with the surface but also on the interaction between the LC molecules arranged in the model in the form of quasi-layers. The mesogenic molecules have been modeled by rods with virtual C’ atoms (carbon atoms with hydrogen atoms attached to them) “threaded” on them. The molecule orientation has been specified by the polar and azimuthal angles θ _i , φ _i and θ _j , φ _j relative to the directors of the ith and jth layers. The derived polar and azimuthal anchoring energies as well as their dependences on the order parameter have turned out to be close to the experimental data.     

Anchoring and structural transitions as a function of molecular length in confined liquid crystals

Using deuteron nuclear magnetic resonance to study liquid crystals confined to cylindrical pores, an anchoring transition has been found. The transition exhibits an unexpected sharp dependence of the anchoring strength on cyanobiphenyl liquid crystal molecular length. A structural transition from a parallel axial to a planar radial configuration occurs due to an anchoring transition from planar to weakly homeotropic orientation at the walls. The anchoring strength is at a minimum near the decylcyanobiphenyl (10CB) liquid crystal length. Long chain liquid crystal configurations depend on thermal cycling and on the equilibrium atmosphere leading to a bistable SmA structure. Orientational order wetting in the isotropic phase also depends on molecular length.     

Induced twisted-grain-boundary phases in the binary mixtures of a cholesteric and a nematic compound

Thermodynamical, optical-texture and dielectric studies have been performed to study the phase diagram of the binary system of 5-cholesten-3β-ol-octanoate and 4-n-nonyloxybenzoic acid. It is observed that low concentrations of 5-cholesten-3β-ol-octanoate (2–30?mol?%) in 4-n-nonyloxybenzoic acid induce a mean-field phase diagram derived by Renn within the framework of the chiral Chen–Lubenski model. Various optical textures of the twisted-grain-boundary (TGB) phases under different conditions of molecular anchoring have been observed. Weak transitions related to the TGB phases have been detected by temperature dependent dielectric spectroscopy.     

Theoretical study of electronic structure and excited states properties of two dyes for dye-sensitized solar cells

Two conjugated organic dyes comprising the benzo[b]furan moieties as the electron donor and cyanoacetic acid moieties as the electron acceptor/anchoring groups have been investigated using a quantum chemical method. The molecular equilibrium geometries and ground state character were studied using density functional theory. Absorption spectra were obtained using time-dependent density functional theory and semiempirical ZINDO. The nature of absorption spectra was further studied using 2D and 3D real-space analysis; here, 2D real-space analysis showed electron–hole coherence, and 3D real-space analysis showed intramolecular charge transfer during photo-excitation. As important parameters, excited state oxidation potential and driving force energy were obtained to reveal the relationship between molecular structure and performance of two compounds.     

Twisted Grain Boundary Phases in the Binary Mixtures of 3ß-Chloro-5-Cholestene and 4-N-Decyloxybenzoic Acid

From the thermodynamical, optical texture and dielectric studies of the binary mixtures of 3β-chloro-5-cholestene (ChCl) and 4-n-decyloxybenzoic acid (DOBA), the phase diagram has been drawn. It has been observed that low concentrations of ChCl (1 to 7 mol%) in DOBA induce various types of twisted grain boundary (TGB) submesophases, whereas higher concentrations induce a smectic A (SmA) mesophase. Various optical textures of the TGB phases under different conditions of molecular anchoring have been observed. Weak transitions related with TGB phases have been detected from the temperature dependence of dielectric permittivity. The observed phase diagram of ChCl-DOBA binary system is in complete conformity with the theoretically predicted mean-field phase diagram derived by Renn within the framework of the chiral Chen-Lubenski model     

Thermodynamic and electrical characteristics of the twisted grain boundary phases of 4-n-dodecyloxy-4′-(cholesteryloxycarbonyl-1-butyloxy) chalcone

The investigated optically active dimeric compound, 4-n-dodecyloxy-4′-(cholesteryloxycarbonyl-1-butyloxy) chalcone, shows wide temperature ranges of two twisted grain boundary (TGB) phases, namely TGBA and TGBC*. The dielectric spectroscopy has been carried out for this compound in the frequency range of 1?Hz to 35?MHz for two different conditions of molecular anchoring. A relaxation mode has been detected in the TGBA and TGBC* phases for the planar anchoring of the molecules. This mode lies in the MHz region and has the characteristics of amplitude fluctuation of directors (soft mode). Results are supportive of the theory developed for the soft modes of TGBA and TGBC* phases. Dielectric anisotropy shows an unusual but characteristic (of TGB phases) variation with temperature.     

Nematic ordering in a cell with modulated surface anchoring: effects of flexoelectricity

We have analyzed molecular ordering in a nematic sample sandwiched between two parallel substrates, characterized by a periodically varying anchoring easy axis. If the periodicity lambda is smaller than the Debye screening length l(D) and the nematic material possesses flexoelectric properties, it is necessary to take into account also the electrostatic and flexoelectric contributions in the thermodynamical potential when the actual director field is determined. In this framework, for small deviations from the homeotropic alignment we have derived analytical expressions for the tilt angle (theta) and the electrical potential. To establish a connection with experimentally observable quantities, we have related the theta profile to the average and investigated its behavior for different values of lambda, the flexoelectric coefficient, and the anchoring strength w. Our results indicate that in a nematic with pronounced flexoelectric properties for small enough lambda, a kind of subsurface deformation appears, which substantially decreases . Therefore, effects of flexoelectricity cannot be neglected in treating nematic cells with modulated anchoring which allows bistable ordering.     

Inhomogeneous threshold director reorientation in a planar nematic flexoelectric cell with finite anchoring energy

The dependence of the threshold parameters and the period of the electric-field-induced spatially periodic reorientation of the director in a flexoelectric nematic liquid crystal (NLC) on the anchoring conditions at the surface of a planar NLC cell has been studied. The threshold electric field and the corresponding wave-number of the periodic structure of the director field have been numerically calculated for arbitrary values of the anchoring energy. In the case of strong anchoring, the corresponding analytical expressions are obtained in a single-constant approximation. A decrease in the azimuthal anchoring energy leads to an increase in the intervals of possible values of the flexoelectric parameter ν and the ratio K₂/K₁ of the Frank elastic constants. A decrease in the polar anchoring energy leads to narrowing of these intervals as compared to the case of infinitely strong anchoring at the NLC cell surface.     

Controlling the self-ordering behaviour of nanostructures on patterned substrates

We use molecular dynamics simulations to show how 2D anchoring patterns on a substrate can be utilised to accurately control the placement and morphology of nucleating 3D nanostructures. The 2D anchoring patterns for our model system consisted of a Pt ad-atom island on a Pt substrate with a surrounding monolayer of Ag atoms. The crystallographic direction of the Pt/Ag boundaries comprising the 2D anchoring pattern and the shape of the pattern was found to have a significant effect on the resultant 3D nanostructures to the extent that one can force nanostructures to have unstable facets, changing the appearance of nanostructures completely. We used the Pt/Ag system as a model to study the effects of square, rectangular and triangular anchoring patterns on Pt(111) and Pt(100) substrates. However, the processes observed are thought to result from the successful altering of the growth mode from Frank–Van der Merwe to Volmer–Weber growth; hence, these processes should be quite general and applicable to other systems.     

On the threshold characteristics of the flexoelectric domains arising in a homogeneous electric field: The case of anisotropic elasticity

Precise solutions for the threshold voltage U_c and wave number q_c that feature the appearance of longitudinal flexoelectric domains of Vistin’-Pikin-Bobylev at strong anchoring have been derived. Based on the formulated expressions, we present and analyze computer calculations for a planar nematic layer with anisotropic elasticity and both negative and positive dielectric anisotropy under the action of a homogeneous flexoelectrically deforming d.c. electric field. The obtained relations allow a selection of particular values of physical parameters, in order to improve the performance of devices exploiting flexoelectrcity in nematics.     

分子整流器的相关技术

分子整流器的相关技术是研究器件基础理论和未来付诸应用的关键问题之一。由于分子材料的特殊物理化学性质,原本成熟的普通半导体工艺不再适用。本文综述了目前在分子整流器研究领域广泛使用的相关技术,介绍了分子有序排列的各种组装技术,ＳＴＭ技术,电极制备技术等。分子器件的深入研究将会引起信息处理系统和材料科学的发展,对未来科学技术和社会发展产生深远的影响。     

Theoretical insights into the effects of the diameter and helicity on the adsorption of formic acid on silicon carbide nanotube

The anchoring of small organic molecules onto the semiconductor surface has a great application for developing various molecular devices, such as novel solar cells, fuel cells, hybrid systems, sensors, and so on. In the present work, by carrying out detailed density-functional theory calculations, we have investigated the adsorption of the formic acid (HCOOH) molecule on planar and various curved silicon carbide (SiC) nanotubes. By considering both the molecular and dissociative adsorptions of HCOOH on these SiC nanomaterials, we found that the HCOOH molecule prefers to dissociate into HCOO and H group. Interestingly, different adsorption modes were found for HCOOH on SiC nanotubes, i.e. dissociative monodentate or bidentate adsorption, which depends on the tube diameter and helicity. For (n, 0) SiC nanotube, the monodentate adsorption mode is energetically favorable when n is less than 10. However, HCOOH prefers to be adsorbed on other (n, 0) SiC nanotubes in a bridged bidentate mode, which is similar to those of on (n, n) SiC nanotubes or planar SiC sheet. Moreover, upon HCOOH adsorption, these SiC nanomaterials remain to be of the semiconducting nature and their band gaps are decreased to different degrees. In addition, we also explored the effects of HCOOH coverage on its adsorption on SiC nanotube.