Molecule-electrode Contact Research Articles

Thermopower in Underpotential Deposition-Based Molecular Junctions.

Underpotential deposition (UPD) is an intriguing means for tailoring the interfacial electronic structure of an adsorbate at a substrate. Here we investigate the impact of UPD on thermoelectricity occurring in molecular tunnel junctions based on alkyl self-assembled monolayers (SAMs). We observed noticeable enhancements in the Seebeck coefficient of alkanoic acid and alkanethiol monolayers, by up to 2- and 4-fold, respectively, upon replacement of a conventional Au electrode with an analogous bimetallic electrode, Cu UPD on Au. Quantum transport calculations indicated that the increased Seebeck coefficients are due to the UPD-induced changes in the shape or position of transmission resonances corresponding to gateway orbitals, which depend on the choice of the anchor group. Our work unveils UPD as a potent means for altering the shape of the tunneling energy barrier at the molecule-electrode contact of alkyl SAM-based junctions and hence enhancing thermoelectric performance.

Tailoring single-molecule conductance with structured graphene electrodes

Modulation of electric currents through single-molecule junctions is usually achieved by synthesis of molecules with desired functionalities, in conjunction with suitable molecule–electrode contacts through specific anchoring groups. An alternative to this approach, barely explored so far, is to use structured electrodes, where conductivity could eventually be controlled by changing the specific anchoring site within the very same electrode. Here, we theoretically investigate how to exploit the pronounced anisotropy of corrugated graphene deposited on Ru(0001) (Gr/Ru) to tailor single-molecule conductivity in 4-aminophenyl and 4-aminobenzonitrile. We show that currents induced in the upper and lower anchoring positions in the Gr/Ru moiré are substantially different, irrespective of the chosen molecule. The magnitude of these currents can differ by as much as an order of magnitude at specific bias voltages. We also show that both molecules display rectifying properties, which can differ by up to a factor of five in different anchoring sites. Interestingly, the observed modulations strongly depend on the chemical binding nature between the molecule and the electrode, (strong) covalent bond for 4-aminophenyl and (weak) physisorption for 4-aminobenzonitrile. All this suggests that Gr/Ru can be an ideal electrode to modulate single-molecule electric conductivity under experimental conditions that are available in many laboratories.

Spin-selectivity effect of G-quadruplex DNA molecules.

Chirality-induced spin selectivity has been attracting extensive interest in recent years and is demonstrated in a variety of chiral molecules, all of which arise from inherent molecular chirality. Here, we first propose a theoretical model to study the spin-dependent electron transport along guanine-quadruplex (G4) DNA molecules, connected to two nonmagnetic electrodes, by considering the molecule-electrode contact and weak spin-orbit coupling. Our results indicate that the G4-DNA molecular junctions exhibit pronounced spin-selectivity effect, and the asymmetric contact-induced external chirality, instead of the inherent molecular chirality, dominates their spin filtration efficiency. Furthermore, the spin-selectivity effect is robust against the disorder and hold in a wide range of model parameters. These results could be checked by charge transport measurements and provide an alternative way to improve the spin-selectivity effect of chiral nanodevices.

Electrochemically fabricated molecule–electrode contacts for molecular electronics

Connecting molecules to electrodes is key for a range of applications. Conventional methods typically involve a spontaneous reaction of thiol/disulfide-terminated molecules with metal surfaces. Although modifying metal surfaces with thiol chemistry is simple, it is limited to forming a specific S–metal bonding, which is labile and hence there are concerns regarding its mechanical instability. In addition, spontaneous grafting requires long processing times to achieve high molecular coverages on the surface, which adds challenges for manufacturing devices comprising molecular films. Electrochemical methods for forming molecular films on surfaces offer powerful advantages over traditional methods, including reaction acceleration, molecular coverage control, and guiding the chemical bonding at the molecule‒electrode interface. Electrochemical grafting enables connecting molecules to various types of electrodes including those that cannot be functionalized by other methods. More recently, electrochemical approaches were expanded to enable connecting 2D materials to electrodes, opening a realm of possibilities for hybrid technologies. In this opinion, we survey the recent progress in electrochemical methods for connecting (bio) molecules to electrodes for advancing molecular and bioelectronics.

Thermopower of Molecular Junction in Harsh Thermal Environments.

Molecular junctions can be miniaturized devices for heat-to-electricity conversion application, yet these operate only in mild thermal environments (less than 323 K) because thiol, the most widely used anchor moiety for chemisorption of active molecules onto surface of electrode, easily undergoes thermal degradation. N-Heterocyclic carbene (NHC) can be an alternative to traditional thiol anchor for producing ultrastable thermoelectric molecular junctions. Our experiments showed that the NHC-based molecular junctions withstood remarkably high temperatures up to 573 K, exhibiting consistent Seebeck effect and thermovoltage up to approximately |1900 μV|. Our work advances our understanding of molecule-electrode contact in the Seebeck effect, providing a roadmap for constructing robust and efficient organic thermoelectric devices.

The Unusual Dielectric Response of Large Area Molecular Tunnel Junctions Probed with Impedance Spectroscopy

AbstractThe dielectric behavior of organic materials at molecular dimensions can be vastly different than their bulk counterparts and therefore it is important to investigate and control the dielectric response of molecular‐scale materials for a large variety of applications. Large‐area molecular junctions are explored to study the charge transport mechanisms with unprecedented detail and to demonstrate novel functionalities. Therefore, large‐area molecular junctions are, in principle, a promising platform to study the dielectric effects at the molecular scale. This review summarizes recent progress on the measurements and understanding of the dielectric behavior of molecular systems and how they behave differently from their bulk properties. This review introduces, briefly, the concepts of impedance spectroscopy (IS) and how this technique can be applied to study the dielectric response of solid‐state large‐area molecular junctions. This analysis gives new insights in the factors that determine the dielectric constant of monolayers (including collective electrostatic effects and how the dielectric constant increases with monolayer thickness), how IS gives new insights into the role of defects, and the factors that contribute to the molecule–electrode contact resistance. This review ends with an outlook highlighting interesting future directions.

Room‐Temperature Spin‐Dependent Transport in Metalloporphyrin‐Based Supramolecular Wires

AbstractHere we present room‐temperature spin‐dependent charge transport measurements in single‐molecule junctions made of metalloporphyrin‐based supramolecular assemblies. They display large conductance switching for magnetoresistance in a single‐molecule junction. The magnetoresistance depends acutely on the probed electron pathway through the supramolecular wire: those involving the metal center showed marked magnetoresistance effects as opposed to those exclusively involving the porphyrin ring which present nearly complete absence of spin‐dependent charge transport. The molecular junction magnetoresistance is highly anisotropic, being observable when the magnetization of the ferromagnetic junction electrode is oriented along the main molecular junction axis, and almost suppressed when it is perpendicular. The key ingredients for the above effect to manifest are the electronic structure of the paramagnetic metalloporphyrin, and the spinterface created at the molecule–electrode contact.

Room-Temperature Spin-Dependent Transport in Metalloporphyrin-Based Supramolecular Wires.

Here we present room‐temperature spin‐dependent charge transport measurements in single‐molecule junctions made of metalloporphyrin‐based supramolecular assemblies. They display large conductance switching for magnetoresistance in a single‐molecule junction. The magnetoresistance depends acutely on the probed electron pathway through the supramolecular wire: those involving the metal center showed marked magnetoresistance effects as opposed to those exclusively involving the porphyrin ring which present nearly complete absence of spin‐dependent charge transport. The molecular junction magnetoresistance is highly anisotropic, being observable when the magnetization of the ferromagnetic junction electrode is oriented along the main molecular junction axis, and almost suppressed when it is perpendicular. The key ingredients for the above effect to manifest are the electronic structure of the paramagnetic metalloporphyrin, and the spinterface created at the molecule–electrode contact.

Amine-Anchored Aromatic Self-Assembled Monolayer Junction: Structure and Electric Transport Properties.

We studied the structure and transport properties of aromatic amine self-assembled monolayers (NH2-SAMs) on an Au surface. The oligophenylene and oligoacene amines with variable lengths can form a densely packed and uniform monolayer under proper assembly conditions. Molecular junctions incorporating an eutectic Ga-In (EGaIn) top electrode were used to characterize the charge transport properties of the amine monolayer. The current density J of the junction decreases exponentially with the molecular length (d), as J = J0 exp(-βd), which is a sign of tunneling transport, with indistinguishable values of J0 and β for NH2-SAMs of oligophenylene and oligoacene, indicating a similar molecule-electrode contact and tunneling barrier for two groups of molecules. Compared with the oligophenylene and oligoacene molecules with thiol (SH) as the anchor group, a similar β value (∼0.35 Å-1) of the aromatic NH2-SAM suggests a similar tunneling barrier, while a lower (by 2 orders of magnitude) injection current J0 is attributed to lower electronic coupling Γ of the amine group with the electrode. These observations are further supported by single-level tunneling model fitting. Our study here demonstrates the NH2-SAMs can work as an effective active layer for molecular junctions, and provide key physical parameters for the charge transport, paving the road for their applications in functional devices.

Using the Electrode Potential to Orient Single Molecules in Nanoscale Electrical Junctions and Determine Charge Transport Mechanism

Charge transport through and between molecules is central to important processes in nature. Studying the conductivity of single molecules can contribute to a better understanding of charge transport, and also help to develop building blocks of molecular electronics, light harvesting devices, etc. We measure the conductivity of molecules using the Scanning Tunneling Microscope break-junction (STM-BJ) method that utilizes repeatedly formed circuits where one or a few molecules are trapped between two electrodes, at least one of which has nanoscale dimensions. The statistical analysis of thousands of measurements yields the conductance of single molecules.One particular interest is the role of the molecule-electrode contact and orientation in charge transport. In the simplest analysis this contact can present a substantial barrier to charge injection, which can have important consequences in devices such as dye sensitized semiconductor nanoparticle solar cells. Our most recent developments include controlling the orientation of the molecule in the junction using the electrode potential so that we can measure conductance along different molecular axes, accessing elements of the anisotropy of the molecular conductance tensor. Specifically, when the molecule is oriented flat, with the molecular plane parallel to the electrode surface, charge transport is measured perpendicular to the molecular plane. Furthermore, the electrode dependence of the molecular conductivity provides insight into the transport mechanism. This approach can be applied to molecules that do not have suitable molecular anchoring groups for traditional STM-BJ measurements, and allows us to determine the importance of anchoring groups in charge transport in molecular junctions.

Using the Electrode Potential to Orient Single Molecules in Nanoscale Electrical Junctions

Charge transport through and between molecules is central to important processes in nature. Studying the conductivity of single molecules can contribute to a better understanding of charge transport, and also help to develop building blocks of molecular electronics, light harvesting devices, etc. We measure the conductivity of molecules using the Scanning Tunneling Microscope break-junction (STM-BJ) method that utilizes repeatedly formed circuits where one or a few molecules are trapped between two electrodes, at least one of which has nanoscale dimensions. The statistical analysis of thousands of measurements yields the conductance of single molecules.One particular interest is the role of the molecule-electrode contact and orientation in charge transport. In the simplest analysis this contact can present a substantial barrier to charge injection, which can have important consequences in devices such as dye sensitized semiconductor nanoparticle solar cells. Our most recent developments include controlling the orientation of the molecule in the junction using the electrode potential so that we can measure conductance along different molecular axes, accessing elements of the anisotropy of the molecular conductance tensor. Specifically, when the molecule is oriented flat, with the molecular plane parallel to the electrode surface, charge transport is measured perpendicular to the molecular plane. This approach can be applied to molecules that do not have suitable molecular anchoring groups for traditional STM-BJ measurements, and allows us to determine the importance of anchoring groups in charge transport in molecular junctions.

Metal-Single-Molecule-Semiconductor Junctions Formed by a Radical Reaction Bridging Gold and Silicon Electrodes.

Here we report molecular films terminated with diazonium salts moieties at both ends which enables single-molecule contacts between gold and silicon electrodes at open circuit via a radical reaction. We show that the kinetics of film grafting is crystal-facet dependent, being more favorable on ⟨111⟩ than on ⟨100⟩, a finding that adds control over surface chemistry during the device fabrication. The impact of this spontaneous chemistry in single-molecule electronics is demonstrated using STM-break junction approaches by forming metal-single-molecule-semiconductor junctions between silicon and gold source and drain, electrodes. Au-C and Si-C molecule-electrode contacts result in single-molecule wires that are mechanically stable, with an average lifetime at room temperature of 1.1 s, which is 30-400% higher than that reported for conventional molecular junctions formed between gold electrodes using thiol and amine contact groups. The high stability enabled measuring current-voltage properties during the lifetime of the molecular junction. We show that current rectification, which is intrinsic to metal-semiconductor junctions, can be controlled when a single-molecule bridges the gap in the junction. The system changes from being a current rectifier in the absence of a molecular bridge to an ohmic contact when a single molecule is covalently bonded to both silicon and gold electrodes. This study paves the way for the merging of the fields of single-molecule and silicon electronics.

Non-chemisorbed gold-sulfur binding prevails in self-assembled monolayers.

Gold-thiol contacts are ubiquitous across the physical and biological sciences in connecting organic molecules to surfaces. When thiols bind to gold in self-assembled monolayers (SAMs) the fate of the hydrogen remains a subject of profound debate-with implications for our understanding of their physical properties, spectroscopic features and formation mechanism(s). Exploiting measurements of the transmission through a molecular junction, which is highly sensitive to the nature of the molecule-electrode contact, we demonstrate here that the nature of the gold-sulfur bond in SAMs can be probed via single-molecule conductance measurements. Critically, we find that SAM measurements of dithiol-terminated molecular junctions yield a significantly lower conductance than solution measurements of the same molecule. Through numerous control experiments, conductance noise analysis and transport calculations based on density functional theory, we show that the gold-sulfur bond in SAMs prepared from the solution deposition of dithiols does not have chemisorbed character, which strongly suggests that under these widely used preparation conditions the hydrogen is retained.

Transmission mechanism and quantum interference in fused thienoacenes coupling to Au electrodes through the thiophene rings.

So far, quantum interference in molecular devices where the anchors are inseparable parts of the whole molecule has been seldom discussed. In this article, we perform first-principles calculations on the electronic transmission properties of a series of Au-thienoacene-Au junctions where the molecule interacts with electrodes through the S atoms in thiophene rings in a fused-ring system. The calculated binding energy of the Au-S interaction is highly dependent on the substitution sites of the thiophene rings, which agrees with the experimental report that the Au-S interaction is too weak to form a junction for some molecules. The electronic coupling at the molecule-electrode contact is also affected by the molecular structure. To distinguish the coupling mechanism, we show the importance of investigating the electron distribution of frontier molecular orbitals in combination with the percentage of the π system in the partial density of states on the S atoms. Because of the difference in electronic coupling, comparison between molecules should be done with care. On the other hand, conductance suppression due to the destructive quantum interference originating from the molecular topology is demonstrated by comparing the properties of isomers with similar molecule-electrode coupling.

First principle study on stretching and breaking process of single-molecule junction: Terminal group effect

The stretching and breaking processes of stilbene-based molecular junctions, which contain S or N atoms in the terminal groups, are studied by using density functional theory. The numerical results show that for pyramid-shaped gold electrodes, a stretching force of about 0.59 nN is needed to break the molecular junction with —S terminals, which is larger than the force of 0.25 nN that is required by the molecule to stretch —SH terminals away from pyramid-shaped gold electrode. However, it is obviously smaller than the force of about 1.5 nN that is needed by the molecule to break —S terminals from planar-shaped gold electrode. If the terminal group is —NH<sub>2</sub> or —NO<sub>2</sub>, the force for breaking the molecular junction is about 0.45 nN or 0.33 nN, respectively. More delocalized molecular orbitals formed by the coupling between the frontier occupied orbitals of molecule and electrodes, higher stretching force for breaking molecular junction is required. The natural bond orbital (NBO) analysis shows that more NBO net charges that the terminal atom possesses can enhance the stability of the molecule-electrode contact if there is no bonding orbital formed between end group of molecule and electrode. Based on the numerical results and the combination with previous studies, it can be found that —S terminal and —NH<sub>2</sub> terminal show evident properties in distinguishing tip structures of gold electrodes, which provides useful information for precisely controlling the interactions and interface structures between molecule and electrodes.

Potential Dependence of Mechanical Stability and Electronic Coupling of Single S–Au Bonds

Providing a mechanically stable and electronically efficient coupling between a molecule and an electrode is critical to the study of charge transfer and conductance of the molecule. A common method is to link the molecule to Au electrodes via a linker (e.g., thiol terminal of the molecule). Here we study the mechanical stability and electronic coupling of a S-Au bond in single-molecule junctions over a broad range of electrode potentials. Our results show that the mechanical and electromechanical properties of molecule-electrode contact undergo a systematic change with the potential involving Au oxidation at positive potentials and S protonation at negative potentials. The study establishes the potential range for a stable S-Au bond and determines the potential dependence of the mechanical and electromechanical properties of the molecule-electrode contact, which is crucial to the interpretation of potential-dependent charge transfer in electrochemistry and electrochemical gating of charge transport in molecular electronics.

An Electromechanical Approach to Understanding Binding Configurations in Single-Molecule Devices.

The configuration of the molecule-electrode contact region plays an important role in determining the conductance of a single-molecule junction, and the variety of possible contact configurations have yielded multiple conductance values for a number of molecular families. In this report, we perform simultaneous conductance and electromechanical coupling parameter measurements on a series of oligophenylene-dithiol single-molecule junctions. These molecules show two distinct conductance values, and by examining the conductance changes, the electromechanical coupling, and the changes in the I- V characteristics coupled with a combination of analytical mechanical models and density functional theory (DFT) structure calculations, we are able to determine the most-probable binding configuration in each of the conductance states. We find that the lower-conductance state is likely due to the thiols binding to each electrode at a gold top site, and in the higher-conductance state, the phenylene π orbitals interact with electrodes, drastically modifying the transport behavior. This approach provides an expanded methodology for exploring the relationship between the molecule-electrode contact configuration and molecular conductance.

Technical Effects of Molecule–Electrode Contacts in Graphene-Based Molecular Junctions

This study focuses on comparing methods for capturing and measuring the charge transport properties of single molecules in gold–graphene contact gaps. We have attempted to measure the single-molecule conductance of a series of 1,n-alkanedithiols (n = 4, 6, 8) tethered between a gold and a graphene contact with three different methods. The conducting probe atomic force microscopy break junction (CP-AFM BJ), scanning tunneling microscopy (STM) break junction (STM BJ), and STM-based I(s) techniques for forming molecular junctions with graphene lower contacts were compared. In each case, the upper contact was gold, with a gold-coated AFM probe in the CP-AFM BJ method and a gold STM tip for both the STM BJ and I(s) techniques. Both the CP-AFM BJ and the STM-based I(s) methods yielded similar values for the conductance decay constant values, with βN = 0.56 and 0.40, respectively. In line with previous observations, these are much smaller than values recorded for the same alkanedithiol series in symmetric gold–m...

Can aromaticity enhance the electron transport in molecular wires?

Abstract An interesting debate has been recently raised around the role played by aromaticity in the electron transport ability of molecular wires. Normally, it is associated to destructive interference effects, so that the more aromatic the wire the less conductor. This rule was observed experimentally in a series of homologous wires containing ring units of different aromaticity, but theoretical calculations and other recent experiments demonstrate the rule cannot be generalized and depends, for instance, in the type of molecule-electrode contact. However, neither chemical explanation nor qualitative rules were given yet to allow predicting the specific behavior of different molecular junctions. In this work, using series of polymeric molecular wires of different length and formed by different aromatic units, it is proven how it is possible to change from an expected destructive to a constructive interference effect of the aromaticity in the electron transport. Thus, aromaticity may be also employed to enhance the electron transport in a molecular wire. A chemical explanation to the experimental and theoretical observations is given and a simple way of tuning the response of a molecular wire to an external electric voltage by increasing/decreasing its aromaticity and changing its type of molecule-electrode contact is provided.

Stretching-Induced Conductance Variations as Fingerprints of Contact Configurations in Single-Molecule Junctions.

Molecule-electrode contact atomic structures are a critical factor that characterizes molecular devices, but their precise understanding and control still remain elusive. Based on combined first-principles calculations and single-molecule break junction experiments, we herein establish that the conductance of alkanedithiolate junctions can both increase and decrease with mechanical stretching, and the specific trend is determined by the S-Au linkage coordination number (CN) or the molecule-electrode contact atomic structure. Specifically, we find that the mechanical pulling results in the conductance increase for the junctions based on S-Au CN two and CN three contacts, while the conductance is minimally affected by stretching for junctions with the CN one contact and decreases upon the formation of Au monatomic chains. Detailed analysis unravels the mechanisms involving the competition between the stretching-induced upshift of the highest occupied molecular orbital-related states toward the Fermi level of electrodes and the deterioration of molecule-electrode electronic couplings in different contact CN cases. Moreover, we experimentally find a higher chance to observe the conductance enhancement mode under a faster elongation speed, which is explained by ab initio molecular dynamics simulations that reveal an important role of thermal fluctuations in aiding deformations of contacts into low-coordination configurations that include monatomic Au chains. Pointing out the insufficiency in previous notions of associating peak values in conductance histograms with specific contact atomic structures, this work resolves the controversy on the origins of ubiquitous multiple conductance peaks in S-Au-based single-molecule junctions.