Single-molecule Transistors Research Articles

Rotation and Anisotropic Molecular Orbital Effect in a SingleH2TPPMolecule Transistor

Electron transport through a single molecule is determined not only by the intrinsic properties of the molecule but also by the configuration of the molecule with respect to the lead electrodes. Here, we show how electron transport through a single H2TPP molecule is modulated by changes in the configuration. The Coulomb stability diagram of a single H2TPP molecule transistor exhibited a few different patterns in different measurement scans. Furthermore, the sample exhibited negative differential resistance, the magnitude of which changed with the pattern in the Coulomb stability diagram. Such behavior can be explained by the rotation of the molecule with anisotropic molecular orbitals in the gap electrodes induced by electrical stress. Moreover, we find that the energy separations between molecular orbitals are also affected by the rotation, confirming that the metal-molecule interface configuration renormalizes the electronic levels in the molecule.

Phonon-assisted zero bias anomaly in a single-molecule quantum dot coupled to the Luttinger liquid leads

Abstract The joint effects of the electron–phonon interaction and electron–electron interaction in the Luttinger liquid leads on nonequilibrium transport through a single-molecule transistor in the Kondo regime are investigated by using the improved canonical transformation scheme and equation of motion approach. For weak intralead electron interaction, a pronounced dip around zero bias, accompanied by a series of discrete single-electron tunneling peaks is observed in the differential conductance. With the increase of the intralead interaction, the phonon-assisted peaks turn into dips, which demonstrates a phonon-assisted two-channel Kondo physics. For a certain region of interaction strength the inelastic electron tunneling can dominate electron transport. Our results well explain the experiments of zero bias anomaly.

Fast optical modulation of the fluorescence from a single nitrogen–vacancy centre

The much sought after optical transistor --the photonic counterpart of the electronic transistor-- is poised to become a central ingredient in the development of optical signal processing. The motivation for using photons rather than electrons not only comes from their faster dynamics but also from their lower crosstalk and minor environmental decoherence, which enable a high degree of integration and the realization of quantum operations. A single-molecule transistor has been recently demonstrated at cryogenic temperatures. Here, we demonstrate that a single NV centre at room temperature can operate as an optical switch under non-resonant CW illumination. We show optical modulation of more than 80% and time response faster than 100 ns in the green-laser-driven fluorescence signal, which we control through an independent near-infrared (NIR) gating laser. Our study indicates that the NIR laser triggers a fast-decay channel of the NV mediated by promotion of the excited state to a dark band. This simple concept opens a new approach towards the implementation of nanoscale optical switching devices.

Electrical Readout of Individual Nuclear Spin Trajectories in a Single-Molecule Magnet Spin Transistor

We present the electrical readout of time trajectories obtained from an isolated nuclear spin. The device, a TbPc(2) single-molecule magnet spin transistor, detects the four different nuclear spin states of the Tb(3+) ion with fidelities better than 69%, allowing us to measure individual relaxation times (T(1)) of several tens of seconds. A good agreement with quantum Monte Carlo simulations suggests that the relaxation times are limited by the current tunneling through the transistor, which opens up the possibility to tune T(1) electrically by means of bias and gate voltages.

Three-Terminal Single-Molecule Junctions Formed by Mechanically Controllable Break Junctions with Side Gating

Molecules are promising candidates for electronic device components because of their small size, chemical tunability, and ability to self-assemble. A major challenge when building molecule-based electronic devices is forming reliable molecular junctions and controlling the electrical current through the junctions. Here, we report a three-terminal junction that combines both the ability to form a stable single-molecule junction via the mechanically controllable break junction (MCBJ) technique and the ability to shift the energy levels of the molecule by gating. Using a noncontact side-gate electrode located a few nanometers away from the molecular junction, the conductance of the molecule could be dramatically modulated because the electrical field applied to the molecular junction from the side gate changed the molecular electronic structure, as confirmed by the ab initio calculations. Our study will provide a new design for mechanically stable single-molecule transistor junctions fabricated by the MCBJ method.

Crossover from adiabatic to antiadiabatic phonon-assisted tunneling in single-molecule transistors

The crossover between two customary limits of phonon-assisted tunneling, the adiabatic and antiadiabatic regimes, is studied systematically in the framework of a minimal model for molecular devices: a resonant level coupled by displacement to a localized vibrational mode. Conventionally associated with the limits where the phonon frequency is either sufficiently small or sufficiently large as compared to the bare electronic hopping rate, we show that the crossover between the two regimes is governed for strong electron-phonon interactions primarily by the polaronic shift rather than the phonon frequency. In particular, the perturbative adiabatic limit is approached only as the bare hopping rate \Gamma exceeds the polaronic shift, leaving an extended window of couplings where \Gamma well exceeds the phonon frequency and yet the physics is basically that of the antiadiabatic regime. We term this intermediate regime the extended antiadiabatic regime. The effective low-energy Hamiltonian in the traditional and the extended antiadiabatic regime is shown to be the (purely fermionic) interacting resonant-level model, with parameters that we extract from numerical renormalization-group calculations. The extended antiadiabatic regime is followed in turn by a true crossover region where the polaron gets progressively undressed. The renormalized tunneling rate, which serves as the low-energy scale in the problem and thus sets the width of the tunneling resonance, is found to follow an approximate scaling form on going from the adiabatic to the antiadiabatic regime. Charging properties are governed by two distinct mechanisms at the extended antiadiabatic and into the crossover region, giving rise to distinctive shoulders in the low-temperature conductance as a function of gate voltage.

Gate-Tunable Large Negative Tunnel Magnetoresistance in Ni–C60–Ni Single Molecule Transistors

We have fabricated single C(60) molecule transistors with ferromagnetic Ni leads (FM-SMTs) by using an electrical break junction method and investigated their magnetotransport. The FM-SMTs exhibited clear gate-dependent hysteretic tunnel magnetoresistance (TMR) and the TMR values reached as high as -80%. The polarity of the TMR was found to be always negative over the entire bias range studied here. Density functional theory calculations show that hybridization between the Ni substrate states and the C(60) molecular orbitals generates an antiferromagnetic configuration in the local density of states near the Fermi level, which gives a reasonable explanation for the observed negative TMR.

Manipulation of organic polyradicals in a single-molecule transistor

Inspired by cotunneling spectroscopy of spin-states in a single OPE5-based molecule, we investigate the prospects for electric control of magnetism in purely organic molecules contacted in a three-terminal geometry. Using the gate electrode, the molecule is reversibly switched between three different redox states, with magnetic spectra revealing both ferromagnetic and antiferromagnetic exchange couplings on the molecule. These observations are shown to be captured by an effective low-energy Heisenberg model, which we substantiate microscopically by a simple valence bond description of the molecule. These preliminary findings suggest an interesting route towards functionalized all-organic molecular magnetism.

An electrostatic gate for mechanically controlled single-molecule junctions

We present a fabrication scheme for a tunable single-molecule transistor that allows for controlling the electrode separation and provides an electrostatic gate. The experimental approach is based on the mechanically controlled break junction technique but integrates an additional bottom gate electrode and an uninterrupted high-κ gate dielectric. The device performance is demonstrated for a single-molecule junction showing Coulomb blockade characteristics.

Single-Molecule Phenyl-Acetylene-Macrocycle-Based Optoelectronic Switch Functioning as a Quantum-Interference-Effect Transistor

This work proposes a new type of optoelectronic switch, the phenyl-acetylene-macrocycle-based single-molecule transistor, which utilizes photon-assisted tunneling and destructive quantum interference. The analysis uses single-particle Green's functions along with Floquet theory. Without the optical field, phenyl-acetylene-macrocycle exhibits a wide range of strong antiresonance between its frontier orbitals. The simulations show large on-off ratios (over 10(4)) and measurable currents (~10(-11) A) enabled by photon-assisted tunneling in a weak optical field (~2 × 10(5) V/cm) and at a small source-drain voltage (~0.05 V). Field amplitude power scaling laws and a range of field intensities are given for operating one- and two-photon assisted tunneling in phenyl-acetylene-macrocycle-based single-molecule transistors. This development opens up a new direction for creating molecular switches.

Finite-bias conductance anomalies at a singlet-triplet crossing

Quantum dots and single-molecule transistors may exhibit level crossings induced by tuning external parameters such as magnetic field or gate voltage. For Coulomb blockaded devices, this shows up as an inelastic cotunneling threshold in the differential conductance, which can be tuned to zero at the crossing. Here we show that, in addition, level crossings can give rise to a nearly vertical step-edge, ridge or even a Fano-like ridge-valley feature in the differential conductance inside the relevant Coulomb diamond. We study a gate-tunable quasidegeneracy between singlet and triplet ground states, and demonstrate how these different shapes may result from a competition between nonequilibrium occupations and weak (spin-orbit) mixing of the states. Our results are shown to be in qualitative agreement with recent transport measurements on a Mn complex [E. A. Osorio, et al., Nano Lett. 10, 105 (2010)]. The effect remains entirely general and should be observable in a wide range of Coulomb blockaded devices.

Single-Molecule Electrochemical Gating in Ionic Liquids

The single-molecular conductance of a redox active molecular bridge has been studied in an electrochemical single-molecule transistor configuration in a room-temperature ionic liquid (RTIL). The redox active pyrrolo-tetrathiafulvalene (pTTF) moiety was attached to gold contacts at both ends through -(CH(2))(6)S- groups, and gating of the redox state was achieved with the electrochemical potential. The water-free, room-temperature, ionic liquid environment enabled both the monocationic and the previously inaccessible dicationic redox states of the pTTF moiety to be studied in the in situ scanning tunneling microscopy (STM) molecular break junction configuration. As the electrode potential is swept to positive potentials through both redox transitions, an ideal switching behavior is observed in which the conductance increases and then decreases as the first redox wave is passed, and then increases and decreases again as the second redox process is passed. This is described as an "off-on-off-on-off" conductance switching behavior. This molecular conductance vs electrochemical potential relation could be modeled well as a sequential two-step charge transfer process with full or partial vibrational relaxation. Using this view, reorganization energies of ~1.2 eV have been estimated for both the first and second redox transitions for the pTTF bridge in the 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BMIOTf) ionic liquid environment. By contrast, in aqueous environments, a much smaller reorganization energy of ∼0.4 eV has been obtained for the same molecular bridge. These differences are attributed to the large, outer-sphere reorganization energy for charge transfer across the molecular junction in the RTIL.

Ambipolar Transport in an Electrochemically Gated Single-Molecule Field-Effect Transistor

Charge transport is studied in single-molecule junctions formed with a 1,7-pyrrolidine-substituted 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) molecular block using an electrochemical gate. Compared to an unsubstituted-PTCDI block, spectroscopic and electrochemical measurements indicate a reduction in the highest occupied (HOMO)-lowest unoccupied (LUMO) molecular orbital energy gap associated with the electron donor character of the substituents. The small HOMO-LUMO energy gap allows for switching between electron- and hole-dominated charge transports as a function of gate voltage, thus demonstrating a single-molecule ambipolar field-effect transistor. Both the unsubstituted and substituted molecules display similar n-type behaviors, indicating that they share the same n-type conduction mechanism. However, the substituted-PTCDI block shows a peak in the source-drain current vs gate voltage characteristics for the p-type transport, which is attributed to a two-step incoherent transport via the HOMO of the molecule.

Quantum quenches and driven dynamics in a single-molecule device

The nonequilibrium dynamics of molecular devices is studied in the framework of a generic model for single-molecule transistors: a resonant level coupled by displacement to a single vibrational mode. In the limit of a broad level and in the vicinity of the resonance, the model can be controllably reduced to a form quadratic in bosonic operators, which in turn is exactly solvable. The response of the system to a broad class of sudden quenches and ac drives is thus computed in a nonperturbative manner, providing an asymptotically exact solution in the limit of weak electron-phonon coupling. From the analytic solution, we are able to (1) explicitly show that the system thermalizes following a local quantum quench, (2) analyze in detail the time scales involved, (3) show that the relaxation time in response to a quantum quench depends on the observable in question, and (4) reveal how the amplitude of long-time oscillations evolves as the frequency of an ac drive is tuned across the resonance frequency. Explicit analytical expressions are given for all physical quantities and all nonequilibrium scenarios under study.

Unconventional Kondo effect in redox active single organic macrocyclic transistors.

Cyclo[6]- and cyclo[8]pyrrole, two aromatic expanded porphyrins, were studied in a single-molecule transistor (SMT) setup. The analyses of these compounds allowed us to observe an uncommon absence of an even-odd effect in the Kondo resonance in discrete, metal-free organic macrocyclic compounds. The findings from the SMT measurements of these cyclopyrroles were in accord with those from cyclic voltammetry (CV) studies and theoretical analyses. These findings provide support for the notion that SMT measurements could be useful as a tool for the characterization of similar types of aromatic macrocyclic compounds.

Fabrication of nanogap electrodes via nano-oxidation mask by scanning probe microscopy nanolithography

In this study, a simple technique was introduced for the fabrication of nanogap electrodes by using nano-oxidation scanning probe microscopy lithography with a Cr/Pt coated silicon tip. Silicon electrodes with a gap of sub-31 nm were fabricated successfully by this technique. The current-voltage measurements (I-V) of the electrodes demonstrated excellent insulating characteristics. This technique is simple, controllable, inexpensive, and faster than common methods. The results showed that silicon electrodes have a great potential for the fabrication of single molecule transistors, single electron transistors, and other nanoelectronic devices.

Image charge effects in single-molecule junctions: Breaking of symmetries and negative-differential resistance in a benzene single-electron transistor

Both experiments and theoretical studies have demonstrated that the interaction between the current-carrying electrons and the induced polarization charge in single-molecule junctions leads to a strong renormalization of molecular charging energies. However, the effect on electronic excitations and molecular symmetries remain unclear. Using a theoretical framework developed for semiconductor-nanostructure-based single-electron transistors (SETs), we demonstrate that the image charge interaction breaks the molecular symmetries in a benzene-based single-molecule transistor operating in the Coulomb blockade regime. This results in the appearance of a so-called blocking state, which gives rise to negative-differential resistance (NDR). We show that the appearance of NDR and its magnitude in the symmetry-broken benzene SET depends in a complicated way on the interplay between the many-body matrix elements, the lead tunnel coupling asymmetry, and the bias polarity. In particular, the current reducing property of the blocking state causing the NDR is shown to vanish under strongly asymmetric tunnel couplings, when the molecule is coupled stronger to the drain electrode. The calculated I-V characteristic may serve as an indicator for image charge broken molecular symmetries in experimental situations.

Transient electron dynamics in a vibrating quantum dot in the Kondo regime

We employ the time-dependent non-crossing approximation to investigate the joint effect ofstrong electron–electron and electron–phonon interaction on the instantaneousconductance of a single-molecule transistor which is abruptly moved into the Kondoregime by means of a gate voltage. We find that the instantaneous conductanceexhibits decaying sinusoidal oscillations on the long timescale for infinitesimal bias.The ambient temperature and electron–phonon coupling strength influence theamplitude of these oscillations. The frequency of the oscillations is found to beequal to the phonon frequency. We argue that the origin of these oscillations canbe attributed to the interference between the emerging Kondo resonance andits phonon sidebands. We discuss the effect of finite bias on these oscillations.

Cotunneling through a magnetic single-molecule transistor based on N@C60

We present an experimental and theoretical study of a magnetic single-molecule transistor based on N@C60 connected to gold electrodes. Particular attention is paid to the regime of intermediate molecule-lead coupling, where cotunneling effects manifest themselves in the Coulomb-blockade regime. The experimental results for the differential conductance as a function of bias, gate voltage, and external magnetic field are in agreement with our analysis of the tunneling rates and provide evidence of magnetic signatures in single-N@C60 devices arising from an antiferromagnetic exchange interaction between the C60 spin and the nitrogen spin.

Influencing the Electronic Interaction in Diferrocenyl-1-Phenyl-1H-Pyrroles

Functionalised diferrocenyl-1-phenyl-1H-pyrroles were synthesised using Negishi C,C cross-coupling reactions. The influence of different substituents at the phenyl moiety on the electronic interaction was studied using electrochemistry (cyclic and square-wave voltammetry) and spectro-electrochemistry (in situ UV/Vis-NIR spectroscopy). The ferrocenyl moieties gave rise to two sequential, reversible redox processes in each of the diferrocenyl-1-phenyl-1H-pyrroles. The observed ΔE(1/2) values (ΔE(1/2) = difference between first and second oxidation) range between 420 and 480 mV. A linear relationship between the Hammett constants σ of the substituents and the separation of the redox potentials exists. The NIR measurements confirm electronic communication between the iron centers as intervalence charge transfer (IVCT) absorptions were observed in the corresponding mixed-valent monocationic species. All compounds were classified as class II systems according to Robin and Day (M. B. Robin and P. Day, Adv. Inorg. Chem., 1967, 10, 247-423). The oscillator strength of the charge transfer transition highly depends on the electron donating or electron withdrawing character of the phenyl substituents. This enables direct tuning of the intermetallic communication by simple modification of the molecule's functional group. Hence, this series of molecules may be regarded as model compounds for single molecule transistors.