Effect of length and contact chemistry on the electronic structure and thermoelectric properties of molecular junctions

We present a combined experimental and computational study that probes the thermoelectric and electrical transport properties of molecular junctions. Experiments were performed on junctions created by trapping aromatic molecules between gold electrodes. The end groups (-SH, -NC) of the aromatic molecules were systematically varied to study the effect of contact coupling strength and contact chemistry. When the coupling of the molecule with one of the electrodes was reduced by switching the terminal chemistry from -SH to -H, the electrical conductance of molecular junctions decreased by an order of magnitude, whereas the thermopower varied by only a few percent. This has been predicted computationally in the past and is experimentally demonstrated for the first time. Further, our experiments and computational modeling indicate the prospect of tuning thermoelectric properties at the molecular scale. In particular, the thiol-terminated aromatic molecular junctions revealed a positive thermopower that increased linearly with length. This positive thermopower is associated with charge transport primarily through the highest occupied molecular orbital, as shown by our computational results. In contrast, a negative thermopower was observed for a corresponding molecular junction terminated by an isocyanide group due to charge transport primarily through the lowest unoccupied molecular orbital.     

Electron Transport through Single π‐Conjugated Molecules Bridging between Metal Electrodes

Understanding electron transport through a single molecule bridging between metal electrodes is a central issue in the field of molecular electronics. This review covers the fabrication and electron‐transport properties of single π‐conjugated molecule junctions, which include benzene, fullerene, and π‐stacked molecules. The metal/molecule interface plays a decisive role in determining the stability and conductivity of single‐molecule junctions. The effect of the metal–molecule contact on the conductance of the single π‐conjugated molecule junction is reviewed. The characterization of the single benzene molecule junction is also discussed using inelastic electron tunneling spectroscopy and shot noise. Finally, electron transport through the π‐stacked system using π‐stacked aromatic molecules enclosed within self‐assembled coordination cages is reviewed. The electron transport in the π‐stacked systems is found to be efficient at the single‐molecule level, thus providing insight into the design of conductive materials.     

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.     

A theoretical study of molecular conduction. III. A nonequilibrium-Green's-function-based Hartree-Fock approach

Many recent experimental and theoretical studies have paid attention to the conductivity of single molecule transport junctions, both because it is fundamentally important and because of its significance in the development of molecular-based electronics. In this paper, we discuss a nonequilibrium Green's function (NEGF)-based Hartree-Fock (HF) approach; the NEGF method can appropriately accommodate charge distributions in molecules connected to electrodes. In addition, we show that a NEGF-based density matrix can reduce to an ordinary HF density matrix for an isolated molecule if the molecule does not interact with electrodes. This feature of the NEGF-based density matrix also means that NEGF-based Mulliken charges can be reduced to ordinary Mulliken charges in those cases. Therefore, the NEGF-based HF approach can directly compare molecules that are connected to electrodes with isolated ones, and is useful in investigating complicated features of molecular conduction. We also calculated the transmission probability and conduction for benzenedithiol under finite electrode biases. The coupling between the electrodes and molecule causes electron transfer from the molecule to the electrodes, and the applied bias modifies this electron transfer. In addition, we found that the molecule responds capacitively to the applied bias, by shifting the molecular orbital energies.     

Study of molecular junctions with a combined surface-enhanced Raman and mechanically controllable break junction method

We have developed a combined surface-enhanced Raman spectroscopy (SERS) and break junction method to detect and characterize molecules between two microfabricated electrodes separated with a gap that can be continuously adjusted from a few angstroms to nanometers. It allows us to obtain a vibrational fingerprint of the adjustable molecular junction while performing electron transport measurements on the molecule simultaneously. This new approach will provide not only new insights into electron transport properties of molecule junctions on a chip but also the mechanism of single-molecule-SERS.     

Orbital views of molecular conductance perturbed by anchor units

Site-specific electron transport phenomena through benzene and benzenedithiol derivatives are discussed on the basis of a qualitative Hu?ckel molecular orbital analysis for better understanding of the effect of anchoring sulfur atoms. A recent work for the orbital control of electron transport through aromatic hydrocarbons provided an important concept for the design of high-conductance connections of a molecule with anchoring atoms. In this work the origin of the frontier orbitals of benzenedithiol derivatives, the effect of the sulfur atoms on the orbitals and on the electron transport properties, and the applicability of the theoretical concept on aromatic hydrocarbons with the anchoring units are studied. The results demonstrate that the orbital view predictions are applicable to molecules perturbed by the anchoring units. The electron transport properties of benzene are found to be qualitatively consistent with those of benzenedithiol with respect to the site dependence. To verify the result of the Hu?ckel molecular orbital calculations, fragment molecular orbital analyses with the extended Hu?ckel molecular orbital theory and electron transport calculations with density functional theory are performed. Calculated results are in good agreement with the orbital interaction analysis. The phase, amplitude, and spatial distribution of the frontier orbitals play an essential role in the design of the electron transport properties through aromatic hydrocarbons.     

Orbital views of the electron transport through heterocyclic aromatic hydrocarbons

Electron-transport properties of heterocyclic aromatic hydrocarbons are investigated with theoretical methods. The present study is based on a previously derived concept for orbital control of electron transport through aromatic hydrocarbons. The orbital control concept provided crucial basic understanding for the best conductance channels in the aromatic hydrocarbons and was successfully applied in the design of molecular devices. That concept was proven to hold true for small aromatic molecules, large polycyclic aromatic hydrocarbons with different edge structures, and in weak and strong coupling with the electrodes junctions. The polycyclic aromatic hydrocarbons and nanographenes used in the molecular electronics are often immobilized with different types of defects, which require the application of the orbital control concept on heterocyclic aromatic hydrocarbons. In this work, the effect of the heteroatoms in aromatic hydrocarbons on their electron-transport properties and the applicability of the orbital control concept on heterocyclic aromatic hydrocarbons are studied. Effective routes for electron transport are predicted in weak coupling junctions by analyzing the phase and amplitude of the frontier orbitals. The qualitative predictions are made with the nonequilibrium Green??s function method combined with the Hückel approximation. Quantitative, first principle calculations are performed with the nonequilibrium Green??s function method combined with density functional theory. The obtained results are in good agreement with the expectations on the basis of the orbital control concept, which proves its applicability in heterocyclic aromatic hydrocarbons.     

Studying single molecule electrochemistry with scanning tunneling microscope break-junction technique

The fundamental principle of molecular electronics is to comprehend electrical properties of single molecules connected between two probe electrodes. In recent years, substantial advances in this field have been made to underpin experimental and theoretical understanding of single molecule electrochemistry. By using scanning tunneling microscope (STM) break-junction technique, the switching events of electrical current from single molecule bridge tuning by electrochemical gating are investigated to uncover the relationship between electrochemical electron transfer and charge transport processes in chemical and biological molecule junctions. In this short review, we outline the latest works of single molecule electrochemistry studied with STM break-junction technique from Nongjian Tao's group, and share the insights on the opportunities and challenges for future research.     

Low-Bias Conductance Mechanism of Diarylethene Isomers:a First-Principle Study

The structure-property relationship of diarylethene (DAE)-derivative molecular isomers, which involve ring-closed and ring-open forms, is investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. Molecular junctions are formed by the isomers connecting to Au(111) electrodes through flanked pyridine groups. The difference in electronic structures caused by different geometry structures for the two isomers, particularly the interatomic alternative single bond and double bond of the ring-closed molecule, contributes to the vastly different low-bias conductance values. The lowest unoccupied molecular orbital (LUMO) of the isomers is the main channel for electron transport. In addition, more electrons transferred to the ring-closed molecular junction in the equilibrium condition, thereby decreasing the LUMO energy to near the Fermi energy, which may contribute to a larger conductance value at the Fermi level. Our findings are helpful for understanding the mechanism of low-bias conductance and are conducive to the design of high-performance molecular switching based on diarylethene or diarylethene-derivative molecules.     

单分子电导测量技术及其影响因素

Molecular electronics is an important field for the application of nanotechnologies with an ultimate goal of building functional devices using single molecules or molecular arrays to realize the same functionality as macroscopic devices. To attain this goal, reliable techniques for measuring and manipulating electron transfer processes through single molecules are essential. There are various techniques and many environmental factors influencing single-molecule electronic conductance measurements. In this review, we first provide a detailed introduction and classification of the current well-accepted techniques in this field for measuring single-molecule conductance. All available techniques are summarized into two categories: the fixed junction technique and break junction technique. The break junction technique involves repeatedly forming and breaking molecular junctions by mechanically controlling a pair of electrodes moving into and out of contact in the presence of target molecules. Single-molecule conductance can be determined from the conductance plateaus that appear in typical conductance decay traces when molecules bind two electrodes during their separation process. In contrast, the fixed junction technique is to fix the distance between a pair of electrodes and measure the conductance fluctuations when a single molecule binds the two electrodes stochastically. Both techniques comprise different application methods and have been employed preferentially by different groups. Specific features of both techniques and their intrinsic advantages are compared and summarized in Section 4.     

Electron-beam evaporated silicon as a top contact for molecular electronic device fabrication

This paper discusses the electronic properties of molecular devices made using covalently bonded molecular layers on carbon surfaces with evaporated silicon top contacts. The Cu "top contact" of previously reported carbon/molecule/Cu devices was replaced with e-beam deposited Si in order to avoid Cu oxidation or electromigration, and provide further insight into electron transport mechanisms. The fabrication and characterization of the devices is detailed, including a spectroscopic assessment of the molecular layer integrity after top contact deposition. The electronic, optical, and structural properties of the evaporated Si films are assessed in order to determine the optical gap, work function, and film structure, and show that the electron beam evaporated Si films are amorphous and have suitable conductivity for molecular junction fabrication. The electronic characteristics of Si top contact molecular junctions made using different molecular layer structures and thicknesses are used to evaluate electron transport in these devices. Finally, carbon/molecule/silicon devices are compared to analogous carbon/molecule/metal junctions and the possible factors that control the conductance of molecular devices with differing contact materials are discussed.     

Functional Molecular Junctions Derived from Double Self‐Assembled Monolayers

Information processing using molecular junctions is becoming more important as devices are miniaturized to the nanoscale. Herein, we report functional molecular junctions derived from double self‐assembled monolayers (SAMs) intercalated between soft graphene electrodes. Newly assembled molecular junctions are fabricated by placing a molecular SAM/(top) electrode on another molecular SAM/(bottom) electrode by using a contact‐assembly technique. Double SAMs can provide tunneling conjugation across the van der Waals gap between the terminals of each monolayer and exhibit new electrical functions. Robust contact‐assembled molecular junctions can act as platforms for the development of equivalent contact molecular junctions between top and bottom electrodes, which can be applied independently to different kinds of molecules to enhance either the structural complexity or the assembly properties of molecules.     

Electron transport through rectifying self-assembled monolayer diodes on silicon: Fermi-level pinning at the molecule-metal interface

We report the synthesis and characterization of molecular rectifying diodes on silicon using sequential grafting of self-assembled monolayers of alkyl chains bearing a pi group at their outer end (Si/sigma-pi/metal junctions). We investigate the structure-performance relationships of these molecular devices, and we examine the extent to which the nature of the pi end group (change in the energy position of their molecular orbitals) drives the properties of these molecular diodes. Self-assembled monolayers of alkyl chains (different chain lengths from 6 to 15 methylene groups) functionalized by phenyl, anthracene, pyrene, ethylene dioxythiophene, ethylene dioxyphenyl, thiophene, terthiophene, and quaterthiophene were synthesized and characterized by contact angle measurements, ellipsometry, Fourier transform infrared spectroscopy, and atomic force microscopy. We demonstrate that reasonably well-packed monolayers are obtained in all cases. Their electrical properties were assessed by dc current-voltage characteristics and high-frequency (1-MHz) capacitance measurements. For all of the pi groups investigated here, we observed rectification behavior. These results extend our preliminary work using phenyl and thiophene groups (Lenfant et al., Nano Lett. 2003, 3, 741). The experimental current-voltage curves were analyzed with a simple analytical model, from which we extracted the energy position of the molecular orbital of the pi group in resonance with the Fermi energy of the electrodes. We report experimental studies of the band lineup in these silicon/alkyl pi-conjugated molecule/metal junctions. We conclude that Fermi-level pinning at the pi group/metal interface is mainly responsible for the observed absence of a dependence of the rectification effect on the nature of the pi groups, even though the groups examined were selected to have significant variations in their electronic molecular orbitals.     

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.     

Conductance of a single molecule C60-SnPc heterojunction

Geometries of molecule-molecule interfaces strongly influence the current passing from one molecule to another. The contact conductance of molecule-molecule junctions which consist of fullerene and tin phthalocyanine molecules is investigated with a low-temperature scanning tunneling microscope. Two types of molecules are deposited onto Cu(111). Fullerene molecules are transferred to tips through controlled contact of STM tips on molecules. The molecule-molecule junctions are formed by approachi...     

Changes of coupling between the electrodes and the molecule under external bias bring negative differential resistance

We report a first-principles study of electrical transport and negative differential resistance (NDR) in a single molecular conductor consisting of a borazine ring sandwiched between two Au(100) electrodes with a finite cross section. The projected density of states (PDOS) and transmission coefficients under various external voltage biases are analyzed, and it suggests that the variation of the coupling between the molecule and the electrodes with external bias leads to NDR. Therefore, we propose that one origin of NDR in molecular devices is caused by the characteristics of both the molecule and the electrodes as well as their cooperation, not necessarily only by the inherent properties of certain species of molecules themselves. The changes of charge state of the molecule have minor effects on NDR in this device because the Mulliken population analysis shows that electron occupation variation on the molecule is very small when different external biases are applied.     

Ab initio electron transport study of carbon and boron-nitrogen nanowires

We report first-principles calculations on the electrical transport properties of two kinds of one-dimensional nanowires: (a) a carbon nanowire (CNW) with alternating single and triple bonds and (b) a boron-nitrogen nanowire (BNNW) with equidistant bonds. We demonstrate the similarity and difference between the carbon nanowire and its boron-nitrogen analogue in the molecular orbital and transport properties, and then explore the potential innovations. The effects of molecular orbitals and nanowire-electrode coupling on the transport properties are analyzed. The cases of the nanowires sandwiched between both nanoscale and bulk electrodes are considered. It suggests that the characteristics of the transmission spectra and the current-voltage characteristics (I-V curves) are determined both by the electrodes and by the molecule as well as their coupling. In particular, the negative differential resistance (NDR) phenomenon is more apparent when the nanowires are positioned between two nanoscale electrodes. The tuning of the transport properties is also probed through the changes of nanowire-electrode separation and the inclusion of a gate voltage. These lead to dramatic variations in the equilibrium conductance, which can be understood from the shift and alignment of the molecular orbital relative to the Fermi level of the electrodes. In the analysis of the effects of nanowire-electrode separation, it shows that the equilibrium conductance has the same variation behavior as that of the projected density of states (PDOS) for CNW, while the localized molecular orbitals of BNNW result in its conductance varies differently from its PDOS. The different molecular orbital characteristics near the Fermi level of these two kinds of nanowires underlie their different transport properties.     

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.     

Single molecule electron transport junctions: charging and geometric effects on conductance

A p-benzenedithiolate (BDT) molecule covalently bonded between two gold electrodes has become one of the model systems utilized for investigating molecular transport junctions. The plethora of papers published on the BDT system has led to varying conclusions with respect to both the mechanism and the magnitude of transport. Conductance variations have been attributed to difficulty in calculating charge transfer to the molecule, inability to locate the Fermi energy accurately, geometric dispersion, and stochastic switching. Here we compare results obtained using two transport codes, TRANSIESTA-C and HUCKEL-IV, to show that upon Au-S bond lengthening, the calculated low bias conductance initially increases by up to a factor of 30. This increase in highest occupied molecular orbital (HOMO) mediated conductance is attributed to charging of the terminal sulfur atom and a corresponding decrease in the energy gap between the Fermi level and the HOMO. Addition of a single Au atom to each terminal of the extended BDT molecule is shown to add four molecular states near the Fermi energy, which may explain the varying results reported in the literature.     

Controlling the transmission line shape of molecular t-stubs and potential thermoelectric applications

Asymmetric line shapes can occur in the transmission function describing electron transport in the vicinity of a minimum caused by quantum interference effects. Such asymmetry can be used to increase the thermoelectric efficiency of molecular junctions. So far, however, asymmetric line shapes have been only empirically found for just a few rather complex organic molecules where the origins of the line shapes relation to molecular structure were not resolved. In the present, work we introduce a method to analyze the structure dependence of the asymmetry of interference dips from simple two site tight-binding models, where one site corresponds to a molecular π orbital of the wire and the other to an atomic p(z) orbital of a side group, which allows us to characterize analytically the peak shape in terms of just two parameters. We assess our scheme with first-principles electron transport calculations for a variety of t-stub molecules and also address their suitability for thermoelectric applications.