Functionality in single-molecule devices: model calculations and applications of the inelastic electron tunneling signal in molecular junctions

We analyze how functionality could be obtained within single-molecule devices by using a combination of non-equilibrium Green's functions and ab initio calculations to study the inelastic transport properties of single-molecule junctions. First, we apply a full non-equilibrium Green's function technique to a model system with electron-vibration coupling. We show that the features in the inelastic electron tunneling spectra (IETS) of the molecular junctions are virtually independent of the nature of the molecule-lead contacts. Since the contacts are not easily reproducible from one device to another, this is a very useful property. The IETS signal is much more robust versus modifications at the contacts and hence can be used to build functional nanodevices. Second, we consider a realistic model of a organic conjugated molecule. We use ab initio calculations to study how the vibronic properties of the molecule can be controlled by an external electric field which acts as a gate voltage. The control, through the gate voltage, of the vibron frequencies and (more importantly) of the electron-vibron coupling enables the construction of functionality: nonlinear amplification and/or switching is obtained from the IETS signal within a single-molecule device.     

First-principles study of the triwing graphene nanoribbons: junction-dependent electronic structures and electric field modulations

Using first-principles calculations, we investigate the structural, electronic and magnetic properties of triwing zigzag graphene nanoribbons (TW-ZGNRs), as well as the electric field effects on their electronic structures. The TW-ZGNRs have comparable energetic stabilities to the normal ZGNRs and exhibit fascinating junction-dependent electronic properties. With the sp(2) hybridized junctions, the TW-ZGNRs undergo a Peierls distortion and behave as ferromagnetic metals. While the TW-ZGNRs with sp(3) hybridized junctions become semiconductors, which have a ferrimagnetic ground state. An external electric field can further modulate the band structures of semiconducting TW-ZGNRs. The parallel electric field directly moves the flat bands around the Fermi level, while the perpendicular field controls the edge states at the ribbon wings. By these electric field modulations, the band gaps are effectively tuned and half-metallicity can be induced into TW-ZGNRs. Our studies demonstrate that the junctions play an important role in the electronic structures of TW-ZGNRs, which have well-tunable electronic and magnetic properties for potential applications in nanoelectronics and spintronics.     

Gate-controlled current and inelastic electron tunneling spectrum of benzene: a self-consistent study

We use density functional theory based nonequilibrium Green's function to self-consistently study the current through the 1,4-benzenedithiol (BDT). The elastic and inelastic tunneling properties through this Au-BDT-Au molecular junction are simulated, respectively. For the elastic tunneling case, it is found that the current through the tilted molecule can be modulated effectively by the external gate field, which is perpendicular to the phenyl ring. The gate voltage amplification comes from the modulation of the interaction between the electrodes and the molecules in the junctions. For the inelastic case, the electron tunneling scattered by the molecular vibrational modes is considered within the self-consistent Born approximation scheme, and the inelastic electron tunneling spectrum is calculated.     

Ab initio investigations of the electric field dependence of the geometric and electronic structures of molecular wires

Theoretical investigations on the typical molecular wire, polyacetylene, which bridges two chemically inert electrodes, have been carried out at the Hartree-Fock level by incorporating the external electric field into the calculations. The results demonstrate that both the geometric and the electronic structures of the conjugated molecular wires are sensitive to the electric field. When the electric field increases, the carbon-carbon single bonds become shorter and the double bonds become longer, leading to a higher conjugation. The electric field reduces the HOMO-LUMO gap and increases the dipole moment. The spatial distributions of the molecular orbitals are used to analyze the electrical properties of the molecular wire. All of these features are more pronounced with increasing conjugation chain length. Quantitative correlations between most of these features and the electric field have been discussed as well.     

Electronic characteristics of fluorene/TiO2 molecular heterojunctions

The electronic properties of molecular junctions of the general type carbon/molecule/TiO2Au were examined as examples of "molecular heterojunctions" consisting of a molecular monolayer and a semiconducting oxide. Junctions containing fluorene bonded to pyrolyzed photoresist film (PPF) were compared to those containing Al2O3 instead of fluorene, and those with only the TiO2 layer. The responses to voltage sweep and pulse stimulation were strongly dependent on junction composition and temperature. A transient current response lasting a few milliseconds results from injection and trapping of electrons in the TiO2 layer, and occurred in all three junction types studied. Conduction in PPFTiO2Au junctions is consistent with space charge limited conduction at low voltage, then a sharp increase in current once the space charge fills all the traps. With fluorene present, there is a slower, persistent change in junction conductance which may be removed by a reverse polarity pulse. This "memory" effect is attributed to a redox process in the TiO2 which generates TiIII and/or TiII, which have much higher conductance than TiO2 due to the presence of conduction band electrons. The redox process amounts to "dynamic doping" of the TiO2 layer by the imposed electric field. The memory effect arises from a combination of the properties of the molecular and oxide layers, and is a special property of the molecular heterojunction configuration.     

Molecular interface effect of heterogeneous molecular junctions consisting of nonfluorinated and fluorinated phthalocyanines

We report the tunneling behavior of homogeneous and heterogeneous molecular junctions using p-type molecules of iron phthalocyanine (FePc), phthalocyanine (H(2)Pc), and copper(II) octaalkoxyl substituted phthalocyanine (CuPcOC8) and n-type molecule of copper hexadecafluorophthalocyanine (F(16)CuPc). The molecular films formed on the electrode surfaces were inspected by X-ray photoelectron spectroscopy (XPS). The measured characteristic tunneling curves of single-component phthalocyanines revealed comparable energy gaps for homogeneous tunneling junctions using the photoemission method. In contrast, for the heterogeneous tunnel junctions of mixed phthalocyanines including fluorinated phthalocyanine a distinctive offset of the energy gaps to the positive bias voltage direction can be clearly identified. It is suggested that the substitution of phthalocyanines and surface affinity of phthalocyanines could contribute to the controlled phase separation within the heterogeneous tunneling junctions. The apparent shift of the tunneling spectra is attributed to the existence of an internal electric field originated with the phase separation of the binary mixture of p-type and n-type phthalocyanines within the tunneling junction.     

Intramolecular charge transfer in π-conjugated oligomers: a theoretical study on the effect of temperature and oxidation state

Intramolecular charge transfer (ICT) of gaseous π-conjugated oligo-phenyleneethynylenes (OPE) induced by a homogeneous applied electric field has been theoretically investigated using a combined approach integrating molecular dynamics (MD) simulations and Perturbed Matrix Method calculations. In line with recent investigations, our results indicate the peculiar role of conformational transitions on OPE electronic properties which reflects on a strong temperature effect on ICT. Electron transfer reactions inducing chemical alteration on OPE, also taken into account in this study, revealed extremely important for explaining non-linear ICT effects and probably plays a central role in the mechanisms underlying molecular transport junctions. Our study further points out the necessity of using MD-based approach for modelling molecular electronics, even when relatively rigid molecular systems are concerned.     

Photoswitching Molecular Junctions: Platforms and Electrical Properties

Remarkable advances in technology have enabled the manipulation of individual molecules and the creation of molecular electronic devices utilizing single and ensemble molecules. Maturing the field of molecular electronics has led to the development of functional molecular devices, especially photoswitching or photochromic molecular junctions, which switch electronic properties under external light irradiation. This review introduces and summarizes the platforms for investigating the charge transport in single and ensemble photoswitching molecular junctions as well as the electronic properties of diverse photoswitching molecules such as diarylethene, azobenzene, dihydropyrene, and spiropyran. Furthermore, the article discusses the remaining challenges and the direction for moving forward in this area for future photoswitching molecular devices.     

金属-分子-金属结器件研究进展

有机功能分子是新型纳光电器件研究热门材料之一, 多用金属-分子-金属结方法研究其荷电输运特性.本文从无损制备、微纳尺度及可寻址性等方面, 综述了金属-分子-金属结器件研究进展. 将制备方法归为软接触法、扫描探针显微镜法、对电极法、交叉线法、角沉积法和纳米孔法等六大类, 并分析了不同方法及实验参数对荷电输运特性的影响. 总的来说, 扫描探针法可用于分子电学特性的快速统计分析, 但可寻址性差; 纳米孔分子结具有良好的可寻址性, 可用于分子输运特性的变温研究, 但上电极沉积可导致分子层破坏或界面特性不确定; 角度沉积法和软接触法可有效减少电极热沉积对分子层的烧蚀, 但器件尺度较大; 对电极法可获得纳米级可寻址分子结, 若结合模板压印交叉纳米线法制备电极, 则在无损分子器件研究及其集成方面有很好的前景.     

基于吡嗪连接的石墨烯电极单分子场效应晶体管

In single-molecule junctions, anchoring groups that connect the central molecule to the electrodes have profound effects on the mechanical and electrical properties of devices. The mechanical strength of the anchoring groups affects the device stability, while their electronic coupling strength influences the junction conductance and the conduction polarity. To design and fabricate high-performance single-molecule devices with graphene electrodes, it is highly desirable to explore robust anchoring groups that bond the central molecule to the graphene electrodes. Condensation of ortho-phenylenediamine terminated molecules with ortho-quinone moieties at the edges of graphene generates graphene-conjugated pyrazine units that can be employed as anchoring groups for the construction of molecular junctions with graphene electrodes. In this study, we investigated the fabrication and electrical characterization of single-molecule field-effect transistors (FETs) with graphene as the electrodes, pyrazine as the anchoring groups, and a heavily doped silicon substrate as the back-gate electrode. Graphene nano-gaps were fabricated by a high-speed feedback-controlled electro-burning method, and their edges were fully oxidized; thus, there were many ortho-quinone moieties at the edges. After the deposition of phenazine molecules with ortho-phenylenediamine terminals at both ends, a large current increase was observed, indicating that molecular junctions were formed with covalent pyrazine anchoring groups. The yield of the single-molecule devices was as high as 26%, demonstrating the feasibility of pyrazine as an effective anchoring group for graphene electrodes. Our electrical measurements show that the ten fabricated devices exhibited a distinct gating effect when a back-gate voltage was applied. However, the gate dependence of the conductance varied considerably from device to device, and three types of different gate modulation behaviors, including p-type, ambipolar, and n-type conduction, were observed. Our observations can be understood using a modified single-level model that takes into account the linear dispersion of graphene near the Dirac point; the unique band structure of graphene and the coupling strength of pyrazine with the graphene electrode both crucially affect the conduction polarity of single-molecule FETs. When the coupling strength of pyrazine with the graphene electrode is weak, the highest occupied molecular orbital (HOMO) of the central molecule dominates charge transport. Depending on the gating efficiencies of the HOMO level and the graphene states, devices can exhibit p-type or ambipolar conduction. In contrast, when the coupling is strong, the redistribution of electrons around the central molecule and the graphene electrodes leads to a realignment of the molecular levels, resulting in the lowest unoccupied molecular orbital (LUMO)-dominated n-type conduction. The high yield and versatility of the pyrazine anchoring groups are beneficial for the construction of single-molecule devices with graphene electrodes.     

Light‐Driven Reversible Intermolecular Proton Transfer at Single‐Molecule Junctions

Photoresponsive molecular systems are essential for molecular optoelectronic devices, but most molecular building blocks are non‐photoresponsive. Employed here is a photoinduced proton transfer (PIPT) strategy to control charge transport through single‐molecule azulene junctions with visible light under ambient conditions, which leads to a reversible and controllable photoresponsive molecular device based on non‐photoresponsive molecules and a photoacid. Also demonstrated is the application of PIPT in two single‐molecule AND gate and OR gate devices with electrical signal as outputs.     

I/V characteristics of a molecular switch

We present a study of the conduction properties of a class of aromatic compounds, whose conformation can be modulated with a transverse electric field, with strong effects on the molecular transport properties. The theoretical method includes the molecule–electrode interaction in a simple, although effective way: the coupling matrix elements are considered independent from the energy of the continuum spectrum of the lead. This results in a simple expression for the molecular Green’s function with a significant simplification in the expression of the transmission function. The effects of the voltage bias on the electronic molecular density is included through a uniform effective electric field. A simplified but accurate method for the evaluation of the molecular response to the field, which spares lengthy computations for each value of the voltage, is presented. The proposed method is calibrated on the widely studied benzene-1,4-dithiol molecule. The calculations on the selected molecular wire (a tetracyano derivative of 4,4′-di(mercaptoethynyl)tolan) show that conductivity is low for perpendicular rings, whereas conduction is allowed for the planar conformation, which corresponds to the equilibrium geometry in the absence of the transverse electric field.     

噻吩低聚物分子器件电输运特性的理论研究

Based on the first-principles computational method and the elastic scattering Green's func-tion theory, we have investigated the electronic transport properties of different oligothio-phene molecular junctions theoretically. The numerical results show that the difference of geometric symmetries of the oligothiophene molecules leads to the difference of the contact configurations between the molecule and the electrodes, which results in the difference of the coupling parameters between the molecules and electrodes as well as the delocalization properties of the molecular orbitals. Hence, the series of oligothiophene molecular junctions display unusual conductive properties on the length dependence.     

Application of electric fields in NMR

Anisotropic orientation states in materials such as liquid crystals, liquid crystalline polymers or polymeric electrets can be induced by the application of electric fields. This behaviour is exploited extensively in displays or sensors. Anisotropic optical properties induced by relatively high electric field strengths are used in the well known displays made from liquid crystalline materials. The anisotropy of electric properties in polymeric materials gives rise to properties such as the high piezoelectricity of fluorine containing electrets. Attempts have been made to investigate the orientational state induced by electric fields after poling using NMR techniques. However, there is only access to the irreversible part of the electrically induced orientation. In-situ application of (high) voltages during NMR experiments enables the investigation of the influence of the electric field on molecular orientational states or electrically-induced morphological changes. The NMR methods have been modified to investigate the dynamics of reorientation processes in electric fields and to extend the possible time range towards below1ms. The application of high voltages in NMR experiments requires experimental specifications. Some of our experiences are outlined in this paper.     

Transport properties of graphene nanoribbon-based molecular devices

The electronic and transport properties of an edge-modified prototype graphene nanoribbon (GNR) slice are investigated using density functional theory and Green's function theory. Two decorating functional group pairs are considered, such as hydrogen-hydrogen and NH(2)-NO(2) with NO(2) and NH(2) serving as a donor and an acceptor, respectively. The molecular junctions consist of carbon-based GNR slices sandwiched between Au electrodes. Nonlinear I-V curves and quantum conductance have been found in all the junctions. With increasing the source-drain bias, the enhancement of conductance is quantized. Several key factors determining the transport properties such as the electron transmission probabilities, the density of states, and the component of Frontier molecular orbitals have been discussed in detail. It has been shown that the transport properties are sensitive to the edge type of carbon atoms. We have also found that the accepter-donor functional pairs can cause orders of magnitude changes of the conductance in the junctions.     

Electrically Controlled Eight‐Spin‐Qubit Entangled‐State Generation in a Molecular Break Junction

The generation of spin‐based multi‐qubit entangled states in the presence of an electric field is one of the most challenging tasks in current quantum‐computing research. Such examples are still elusive. By using non‐equilibrium Green′s function‐based quantum‐transport calculations in combination with non‐collinear spin density functional theory, we report that an eight‐spin‐qubit entangled state can be generated with the high‐spin state of a dinuclear Fe(II) complex when the system is placed in a molecular break junction. The possible gate operation scheme, gating time, and decoherence issues have been carefully addressed. Furthermore, our calculations reveal that the preservation of the high spin state of this complex is possible if the experimentalists keep the electric‐field strength below 0.78 V nm^?1. In brief, the present study offers a unique way to realize the first example of a multi‐qubit entangled state by electrical means only.     

The determination of molecular parameters from dielectric measurements on nematic liquid crystals

The physical properties of liquid crystal phases (mesophases) depend in a very sensitive manner on the structure of the constituent liquid crystal-forming molecules (mesogens). Thus a small change in molecular structure can result in a dramatic change in the corresponding liquid crystal properties. The dielectric responses of materials reflect the electric properties of molecules, and so analysis of dielectric measurements on liquid crystals in terms of molecular properties should lead to the development of structure/property relationships for such mesophases. This paper explores the problems of determining molecular parameters from dielectric measurements on nematic liquid crystals. Specifically, the difficulties in defining the internal electric field and knowing the value of the order parameter are addressed. Experimental results on a range of liquid crystals show that short range correlations are important in determining both the dielectric and optical response of nematic liquid crystals. It is concluded therefore that more sophisticated molecular theories, which take account of molecular shape and volume, need to be developed before reliable structure/property relationships can be established for liquid crystals.     

单分子结的构筑及分子电导性质的测试

分子电子学已成为21世纪研究的热点. 通过将具有特定功能的分子连接在纳米尺度金属电极之间从而构筑包括分子导线、开关、整流器在内的各种分子尺度电子器件, 这引起了科学家们广泛的研究兴趣. 在分子电子学研究中, 构筑金属/分子/金属(MMM)分子结是研究分子器件中电子传输性质的关键. 尽管已经取得了很大的进展, 目前在纳米尺度下构筑稳定可靠的MMM分子结并测试单个分子的电学性质仍然面临很多挑战. 本文着重对单分子电学性质的测试技术和相关理论研究的最新进展以及存在的挑战做了概述.