Joshua Hihath

Measurement and Statistical Analysis of Single-Molecule Current–Voltage Characteristics, Transition Voltage Spectroscopy, and Tunneling Barrier Height

We report on the measurement and statistical study of thousands of current-voltage characteristics and transition voltage spectra (TVS) of single-molecule junctions with different contact geometries that are rapidly acquired using a new break junction method at room temperature. This capability allows one to obtain current-voltage, conductance voltage, and transition voltage histograms, thus adding a new dimension to the previous conductance histogram analysis at a fixed low-bias voltage for single molecules. This method confirms the low-bias conductance values of alkanedithiols and biphenyldithiol reported in literature. However, at high biases the current shows large nonlinearity and asymmetry, and TVS allows for the determination of a critically important parameter, the tunneling barrier height or energy level alignment between the molecule and the electrodes of single-molecule junctions. The energy level alignment is found to depend on the molecule and also on the contact geometry, revealing the role of contact geometry in both the contact resistance and energy level alignment of a molecular junction. Detailed statistical analysis further reveals that, despite the dependence of the energy level alignment on contact geometry, the variation in single-molecule conductance is primarily due to contact resistance rather than variations in the energy level alignment.

Transition from Tunneling to Hopping in Single Molecular Junctions by Measuring Length and Temperature Dependence

The charge transport characteristics of a family of long conjugated molecular wires have been studied using the scanning tunneling microscope break junction technique. The family consists of four wires ranging from 3.1 to 9.4 nm in length. The two shortest wires show highly length dependent and temperature invariant conductance behavior, whereas the longer two wires show weakly length dependent and temperature variant behavior. This trend is consistent with a model whereby conduction occurs by two different mechanisms in the family of wires: by a coherent tunneling mechanism in the shorter two and by an incoherent charge hopping process in the longer wires. The temperature dependence of the two conduction mechanisms gives rise to a phenomenon whereby at elevated temperatures longer molecules that conduct via charge hopping can yield a higher conductance than shorter wires that conduct via tunneling. The evolution of molecular junctions as the tip retracts has been studied and explained in context of the characteristics of individual transient current decay curves.

Controlling single-molecule conductance through lateral coupling of [pi] orbitals

In recent years, various single-molecule electronic components have been demonstrated. However, it remains difficult to predict accurately the conductance of a single molecule and to control the lateral coupling between the π orbitals of the molecule and the orbitals of the electrodes attached to it. This lateral coupling is well known to cause broadening and shifting of the energy levels of the molecule; this, in turn, is expected to greatly modify the conductance of an electrode-molecule-electrode junction. Here, we demonstrate a new method, based on lateral coupling, to mechanically and reversibly control the conductance of a single-molecule junction by mechanically modulating the angle between a single pentaphenylene molecule bridged between two metal electrodes. Changing the angle of the molecule from a highly tilted state to an orientation nearly perpendicular to the electrodes changes the conductance by an order of magnitude, which is in qualitative agreement with theoretical models of molecular π-orbital coupling to a metal electrode. The lateral coupling is also directly measured by applying a fast mechanical perturbation in the horizontal plane, thus ruling out changes in the contact geometry or molecular conformation as the source for the conductance change.

Study of electron-phonon interactions in a single molecule covalently connected to two electrodes

Presented here is a study of electron-phonon interactions in a single molecule junction where the molecule is covalently connected to two electrodes. In this system, vibration modes in a single molecule junction are measured by sweeping the bias voltage between the two electrodes and recording the differential conductance while the strain in the junction is changed by separating the two electrodes. This unique approach allows changes in conductance to be compared to changes in the configuration of a single molecule junction. This system opens a new door for characterizing single molecule junctions and a better understanding of the relationship between molecular conductance, electron-phonon interactions, and configuration.

Gate-controlled electron transport in coronenes as a bottom-up approach towards graphene transistors

Graphene is considered to be a large aromatic molecule, the limiting case of the family of polycyclic aromatic hydrocarbons. This fascinating two-dimensional material has many potential applications, including field effect transistors (FETs). However, the graphene sheets in these devices have irregular shapes and variable sizes, and contain various impurities and defects, which are undesirable for applications. Moreover, the bandgap of graphene is zero and, consequently, the on/off ratios of graphene FETs are small, making it difficult to build logic circuits. To overcome these difficulties, we report here a bottom-up attempt to fabricate nanoscale graphene FETs. We synthesize structurally well-defined coronene molecules (consisting of 13 benzene rings) terminated with linker groups, bridge each molecule to source and drain electrodes through the linkers, measure conductance and demonstrate the FET behaviour of the molecule.

Inelastic Transport and Low-Bias Rectification in a Single-Molecule Diode

Designing, controlling, and understanding rectification behavior in molecular-scale devices has been a goal of the molecular electronics community for many years. Here we study the transport behavior of a single molecule diode, and its nonrectifying, symmetric counterpart at low temperatures, and at both low and high biases to help elucidate the electron-phonon interactions and transport mechanisms in the rectifying system. We find that the onset of current rectification occurs at low biases, indicating a significant change in the elastic transport pathway. However, the peaks in the inelastic electron tunneling (IET) spectrum are antisymmetric about zero bias and show no significant changes in energy or intensity in the forward or reverse bias directions, indicating that despite the change in the elastic transmission probability there is little impact on the inelastic pathway. These results agree with first principles calculations performed to evaluate the IETS, which also allow us to identify which modes are active in the single molecule junction.

Binding configurations and intramolecular strain in single-molecule devices

The development of molecular-scale electronic devices has made considerable progress over the past decade, and single-molecule transistors, diodes and wires have all been demonstrated. Despite this remarkable progress, the agreement between theoretically predicted conductance values and those measured experimentally remains limited. One of the primary reasons for these discrepancies lies in the difficulty to experimentally determine the contact geometry and binding configuration of a single-molecule junction. In this Article, we apply a small-amplitude, high-frequency, sinusoidal mechanical signal to a series of single-molecule devices during junction formation and breakdown. By measuring the current response at this frequency, it is possible to determine the most probable binding and contact configurations for the molecular junction at room temperature in solution, and to obtain information about how an applied strain is distributed within the molecular junction. These results provide insight into the complex configuration of single-molecule devices, and are in excellent agreement with previous predictions from theoretical models.

Electron-phonon interactions in single octanedithiol molecular junctions.

We study the charge transport properties and electron-phonon interactions in single molecule junctions, each consisting of an octanedithiol molecule covalently bound to two electrodes. Conductance measurements over a wide temperature range establish tunneling as the dominant charge transport process. Inelastic electron tunneling spectroscopy performed on individual molecular junctions provides a chemical signature of the molecule and allows electron-phonon interaction induced changes in the conductance to be explored. By fitting the conductance changes in the molecular junction using a simple model for inelastic transport, it is possible to estimate the phonon damping rates in the molecule. Finally, changes in the inelastic spectra are examined in relation to conductance switching events in the junction to demonstrate how changes in the configuration of the molecule or contact geometry can affect the conductance of the molecular junction.

The role of molecule?electrode contact in single-molecule electronics

Creating complex electronic systems from individual molecular components is one of the most formidable challenges in nanotechnology today. To achieve this goal it is necessary not only to design the functionality of the molecular system to create devices, but also to control the interface between bulk contacts and molecular systems. In this brief perspective we discuss the role of molecule–electrode contact in single-molecule systems. This contact is responsible for making the system mechanically stable enough to perform measurements, and can also have profound impacts on both the contact resistance and the energy level alignment in the system. We will discuss a variety of different linker groups that have been explored, note the advantages and disadvantages of various contact chemistries, and discuss new methodologies used for understanding the impact that the molecule–electrode contact has on the energetics of single-molecule devices.

Conformational gating of DNA conductance

DNA is a promising molecule for applications in molecular electronics because of its unique electronic and self-assembly properties. Here we report that the conductance of DNA duplexes increases by approximately one order of magnitude when its conformation is changed from the B-form to the A-form. This large conductance increase is fully reversible, and by controlling the chemical environment, the conductance can be repeatedly switched between the two values. The conductance of the two conformations displays weak length dependencies, as is expected for guanine-rich sequences, and can be fit with a coherence-corrected hopping model. These results are supported by ab initio electronic structure calculations that indicate that the highest occupied molecular orbital is more disperse in the A-form DNA case. These results demonstrate that DNA can behave as a promising molecular switch for molecular electronics applications and also provide additional insights into the huge dispersion of DNA conductance values found in the literature.