Mechanically Controllable Break Junction Research Articles

Halide adsorption influences snapback distance in Scanning Tunnelling Microscope break junctions

‘Snapback distance’ refers to the rapid increase in the size of the gap formed immediately after breaking an atomic-scale metallic contact. It is a commonly observed phenomenon in Scanning Tunnelling Microscope break junction (STM-BJ) and mechanically controlled break junction (MCBJ) experiments. Here, we show that the snapback distance measured for a gold break junction in pure water was significantly reduced in an electrolyte containing halide anions. In the case of Br−, experiments under electrochemical control provided clear evidence that this reduction was caused by halide adsorption on the surface of the gold.

Benchmarking break-junction techniques: electric and thermoelectric characterization of naphthalenophanes.

Break-junction techniques provide the possibility to study electric and thermoelectric properties of single-molecule junctions in great detail. These techniques rely on the same principle of controllably breaking metallic contacts in order to create single-molecule junctions, whilst keeping track of the junction's conductance. Here, we compare results from mechanically controllable break junction (MCBJ) and scanning tunneling microscope (STM) methods, while characterizing conductance properties of the same novel mechanosensitive para- and meta-connected naphtalenophane compounds. In addition, thermopower measurements are carried out for both compounds using the STM break junction (STM-BJ) technique. For the conductance experiments, the same data processing using a clustering analysis is performed. We obtain to a large extent similar results for both methods, although values of conductance and stretching lengths for the STM-BJ technique are slightly larger in comparison with the MCBJ. STM-BJ thermopower experiments show similar Seebeck coefficients for both compounds. An increase in the Seebeck coefficient is revealed, whilst the conductance decreases, after which it saturates at around 10 μV K-1. This phenomenon is studied theoretically using a tight binding model. It shows that changes of molecule-electrode electronic couplings combined with shifts of the resonance energies explain the correlated behavior of conductance and Seebeck coefficient.

An experimental set-up to probe the quantum transport through a single atomic$$/$$molecular junction at room temperature

Understanding the transport characteristics at the atomic limit is the prerequisite for futuristic nanoelectronic applications. Among various experimental procedures, mechanically controllable break junction (MCBJ) is a well-adopted experimental technique to study and control atomic or molecular scale devices. Here, we present the details of developing a piezo-controlled table-top MCBJ set-up, working at ambient conditions, along with the necessary data acquisition technique and analysis of the data. We performed the conductance experiment on a macroscopic gold wire, which exhibits a quantised conductance plateau upon pulling the wire. Conductance peak up to ~ 20G0 (G0 = 2e2\(/\)h where e is the electronic charge and h is the Planck’s constant) could be resolved at room temperature. A well-known test bed molecule, 4,4′-bipyridine, was introduced between the gold electrodes and the conductance histogram exhibits two distinctive conductance peaks, confirming the formation of a single molecular junction, in line with the previous reports. This demonstrates that our custom-designed MCBJ set-up can measure the quantum transport of a single molecular junction at ambient conditions.

Optical Trapping of a Single Molecule of Length Sub-1 nm in Solution

Optical Trapping of a Single Molecule of Length Sub-1 nm in Solution

Over-the-Gap Conductance Oscillations in Superconducting Vanadium Nanocontacts Induced by Hydrogen Impurities.

We have investigated the current-voltage (I-V) characteristics of Josephson junctions made by a low-temperature superconductor of vanadium (V) with a small amount of hydrogen (H) and deuterium (D) impurities using a mechanically controllable break junction (MCBJ) technique. Below the superconducting transition temperature TC, the differential conductance dI/dV spectra show distinct peaks within the superconducting gap, known as the subgap structure, which result from multiple Andreev reflections in pure V nanocontacts. Additionally, the H and D impurities in V nanocontacts induce several new conductance peaks outside the gap, referred to as an over-the-gap structures (OGSs). We found that the OGS peaks exhibit strong temperature dependence until the temperature is close to TC and follow the gap function predicted by BCS theory. When the contact diameter is changed at low temperature using the MCBJ technique, the OGS anomalies change almost linearly with the inverse of the contact diameter. In addition, the gap anomalies are significantly shifted outward by changing the positions of the H atoms through application of a high bias voltage between the contacts. The above features suggest that the OGS peaks are caused by the superconducting quasiparticle interference induced by H or D impurities and/or inhomogeneous structures in the nanocontacts.

Conductance Growth of Single-Cluster Junctions with Increasing Sizes.

Quantum-tunneling-based nanoelectronics has the potential for the miniaturization of electronics toward the sub-5 nm scale. However, the nature of phase-coherent quantum tunneling leads to the rapid decays of the electrical conductance with tunneling transport distance, especially in organic molecule-based nanodevices. In this work, we investigated the conductance of the single-cluster junctions of a series of atomically well-defined silver nanoclusters, with varying sizes from 0.9 to 3.0 nm, using the mechanically controllable break junction (MCBJ) technique combined with quantum transport theory. Our charge transport investigations of these single-cluster junctions revealed that the conductance grows with increasing cluster size. The conductance decay constant was determined to be ∼-0.4 nm-1, which is of opposite sign to that of organic molecules. Comparison between experiment and theory reveals that although charge transport through the silver single-cluster junctions occurs via phase-coherent tunneling, this is compensated by a rapid decrease in the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO gap) with size and the increase in the electrode-cluster coupling, which results in their conductance increase up to lengths of ∼3.0 nm. These results demonstrate that such families of nanoclusters provide unique bottom-up building blocks for the fabrication of nanodevices in the sub-5 nm size range.

Benchmark Study of Alkane Molecular Chains

Alkanes serve an important role as benchmark system in molecular electronics. However, a large variation in the conductance values is reported in the literature. To better understand these fluctuations, in this study we measure large molecular data sets (up to 100 000 breaking traces) of a series of alkanes with different lengths and anchoring groups using the mechanically controlled break junction (MCBJ) technique. Employing an unsupervised learning algorithm, we investigate both the time evolution and the distance dependence of the measured traces. For all the molecules considered, we have been able to identify the single-molecule conductance value for the fully stretched molecular configuration. For alkanedithiols, the corresponding extracted β decay constant of 1.05 ± 0.08 per CH2 group agrees well with literature values. In the case of the stronger thiol bonding, additional peaks in the conductance histograms are found, suggesting the formation of molecular junctions containing a single molecule plus additional gold/molecule unit(s). The results shine light on the dispersion in reported conductance values and show that the evolution of the molecule as a function of stretching and time contains crucial information in determining the molecular junction configuration in MCBJs.

Electronic transport through single-molecule oligophenyl-diethynyl junctions with direct gold-carbon bonds formed at low temperature.

We report on the first systematic transport study of alkynyl-ended oligophenyl-diethynyl (OPA) single-molecule junctions with direct Au–C anchoring scheme at low temperature using the mechanically controlled break junction technique. Through quantitative statistical analysis of opening traces, conductance histograms and density functional theory studies, we identified different types of junctions, classified by their conductance and stretching behavior, for OPA molecules between Au electrodes with two to four phenyl rings. We performed inelastic electron tunneling spectroscopy and observed the excitation of Au–C vibrational modes confirming the existence of Au–C bonds at low temperature and compared the stability of molecule junctions upon mechanical stretching. Our findings reveal the huge potential for future functional molecule transport studies at low temperature using alkynyl endgroups.

Atomistic modeling to predict and improve the strength of doped Sn-Cu solder interfaces

Abstract The reliability of solder joints depends upon the strength of the interface where two materials are joined. The strengthening of solder joints has been routinely achieved via doping with other elements, though this is not yet well understood at a fundamental level, and typically accomplished by trial and error. In the present work, we have used atomistic modeling based on density functional theory (DFT) and ab initio molecular dynamics (AIMD) to study the mechanical strength of the Sn-Cu interface under various conditions. We have investigated the cleavage energy (CE) of the Sn-Cu interface, and how it changes with various dopants (Ag, Au, Bi, Cu, Ni, Zn) to determine the benefit (or detriment) to the strength of this simulated solder joint. We have also tested multiple faces of Sn ([001], [100] and [110]) as potential interfaces with Cu. Our simulations show that each of the dopants considered, except for Bi, increases the strength of the interface. In all our constructed Sn-Bi interfaces, a single atomic layer of Sn atoms deposits on the Cu and binds strongly to it. The weakest point of the interface is located between the deposited Sn layer and the remaining bulk Sn. For the undoped [001] Sn-Cu system, the cleavage energy between the Sn and Cu layers is 1.63 J/m2, whereas the cleavage energy between the deposited layer of Sn and the remaining Sn bulk is considerably lower: 0.54 J/m2; this is likely the location of joint failure, and the focus of our investigation. We observed this trend in each interface that we studied. As expected, the strength of the Sn-Cu interface can be modified with dopants; the CE of the weakest point can be increased (strengthening it) by 0.1–0.2 J/m2 when doping it with Ag, Au, Cu, Ni and Zn, though Bi results in a decrease (weakening it) by 0.15 J/m2. As a complementary method for investigating this interface, we have used AIMD to simulate a mechanically controlled break junction (MCBJ) of the solder interface by gradually increasing the separation between the two ends of the simulated junction. The process is continued until the junction completely breaks, yielding an energy vs. distance curve, which provides information about the strength of the solder joint that is similar to a stress-strain curve. We observe that, as the Sn is moved away from the Cu, there is a relatively steady increase in energy until the system begins to separate. From this separation point, the energy curve plateaus as the interaction between the two halves of the system vanishes. The location of the breaking point is in excellent accordance with our CE calculations; there is also a correlation between the CE and the amount of distance that the system must be stretched before reaching the breaking point. Furthermore, we have adapted the MCBJ method in AIMD to simulate shearing of the Sn-Cu interface. In these simulations, as opposed to moving Sn atoms away from the Cu atoms perpendicularly to the interface, we are sliding the Sn atoms laterally across the interface relative to the Cu atoms. The deposited Sn layer remains strongly bonded to the Cu surface, with most of the shearing occurring inside the bulk Sn region. The first principles nature of the methods employed makes them highly transferable and applicable to any chemical composition. These atomistic simulations provide valuable insights that can be used to design stronger solder joints based on physical understanding.

Guiding Students to Understand the Nanoscale Charge Transport by the Mechanically Controllable Break Junction Technique

Fabrication of molecular devices will meet the demands of the miniaturization of traditional electronic devices. Although microfabrication based on the complementary metal-oxide–semiconductor process can fabricate high-quality single-molecule devices, the cost is high, leading to a challenge to provide a hands-on experiment in the teaching practice of charge transport through single-molecule devices. Here, we demonstrate the low cost and simple procedures associated with a mechanically controllable break junction (MCBJ) technique to fabricate single-molecule devices. On the basis of the MCBJ technique, the conductance of gold–gold atomic contacts and single-molecule junctions can be readily characterized. The teaching practice helps students understand charge transport at the single-molecule level, that is, the quantum tunneling mechanisms. Moreover, the MCBJ technique study provides students the opportunity to develop interdisciplinary thinking, which is vital for understanding, designing, and developing single-molecule electronics.

Conductance quantization in atomic-sized gold contacts using a low-cost mechanically controllable break junction setup

The mechanically controllable break junction (MCBJ) experimental setup is one of the main techniques employed in the study of electronic transport properties at the atomic and molecular scales. This work presents the construction of an inexpensive and simple but robust setup that shows the emergence of conductance quantization as a macroscopic gold wire is pulled to atomic dimensions. The homemade device is based on the MCBJ principle and allows repeatedly forming and breaking the metallic contact to perform a statistical analysis of the data extracting the most frequent electron transport structure. The histogram built from conductance measurements, at room temperature in air, show that the quality of the MCBJ equipment developed here is comparable to that of more sophisticated devices used in research laboratories. It is able to resolve up to three conductance peaks associated with gold nanowires reported in the literature. Such an experiment is suggested to be implemented as a powerful pedagogical tool in modern undergraduate physics labs.

Intermolecular Effects on Tunneling through Acenes in Large-Area and Single-Molecule Junctions

This paper describes the conductance of single-molecules and self-assembled monolayers comprising an oligophenyleneethynylene core, functionalized with acenes of increasing length that extend conjugation perpendicular to the path of tunneling electrons. In the Mechanically Controlled Break Junction (MCBJ) experiment, multiple conductance plateaus were identified. The high conductance plateau, which we attribute to the single molecule conformation, shows an increase of conductance as a function of acene length, in good agreement with theoretical predictions. The lower plateau is attributed to multiple molecules bridging the junctions with intermolecular interactions playing a role. In junctions comprising a self-assembled monolayer with eutectic Ga–In top-contacts (EGaIn), the pentacene derivative exhibits unusually low conductance, which we ascribe to the inability of these molecules to pack in a monolayer without introducing significant intermolecular contacts. This hypothesis is supported by the MCBJ data and theoretical calculations showing suppressed conductance through the PC films. These results highlight the role of intermolecular effects and junction geometries in the observed fluctuations of conductance values between single-molecule and ensemble junctions, and the importance of studying molecules in both platforms.

Structure‐Independent Conductance of Thiophene‐Based Single‐Stacking Junctions

AbstractThe experimental investigation of intermolecular charge transport in π‐conjugated materials is challenging. Herein, we describe the investigation of charge transport through intermolecular and intramolecular paths in single‐molecule and single‐stacking thiophene junctions by the mechanically controllable break junction (MCBJ) technique. We found that the ability for intermolecular charge transport through different single‐stacking junctions was approximately independent of the molecular structure, which contrasts with the strong length dependence of conductance in single‐molecule junctions with the same building blocks, and the dominant charge‐transport path of molecules with two anchors transited from an intramolecular to an intermolecular path when the degree of conjugation increased. An increase in conjugation further led to higher binding probability owing to the variation in binding energies, as supported by DFT calculations.

Structure‐Independent Conductance of Thiophene‐Based Single‐Stacking Junctions

The experimental investigation of intermolecular charge transport in π-conjugated materials is challenging. Herein, we describe the investigation of charge transport through intermolecular and intramolecular paths in single-molecule and single-stacking thiophene junctions by the mechanically controllable break junction (MCBJ) technique. We found that the ability for intermolecular charge transport through different single-stacking junctions was approximately independent of the molecular structure, which contrasts with the strong length dependence of conductance in single-molecule junctions with the same building blocks, and the dominant charge-transport path of molecules with two anchors transited from an intramolecular to an intermolecular path when the degree of conjugation increased. An increase in conjugation further led to higher binding probability owing to the variation in binding energies, as supported by DFT calculations.

Electric-Field-Induced Connectivity Switching in Single-Molecule Junctions.

SummaryThe manipulation of molecule-electrode interaction is essential for the fabrication of molecular devices and determines the connectivity from electrodes to molecular components. Although the connectivity of molecular devices could be controlled by molecular design to place anchor groups in different positions of molecule backbones, the reversible switching of such connectivities remains challenging. Here, we develop an electric-field-induced strategy to switch the connectivity of single-molecule junctions reversibly, leading to the manipulation of different connectivities in the same molecular backbone. Our results offer a new concept of single-molecule manipulation and provide a feasible strategy to regulate molecule-electrode interaction.

Evolution of Magnetic Anisotropy of an Organometallic Molecule in a Mechanically Controlled Break Junction: The Roles of Connecting Electrodes

The precise control of local spin states in magnetic organometallic molecules by means of a mechanically controlled break junction (MCBJ) is a cutting edge frontier of single molecule science. For instance, a fine-tuning of the magnetic anisotropy of a Co(tpy–SH)2 molecule has been achieved experimentally by sandwiching the molecule between two electrodes and gradually enlarging their separation. However, an accurate simulation of such a process has remained rather challenging, which is largely due to the complex structure of the composite junction as well as the static electron correlation originating from the nearly degenerate d-orbitals of the cobalt atom. In this work, by employing an embedding method which combines the high-level complete active space self-consistent field (CASSCF) method and a density functional theory (DFT) method, we carefully simulate the evolution of magnetic anisotropy of the Au–Co(tpy–S)2–Au junction during the mechanical stretching process. It is found that the presence of th...

Can One Define the Conductance of Amino Acids?

We studied the electron-transport properties of ten different amino acids and one dimer (di-methionine) using the mechanically controlled break-junction (MCBJ) technique. For methionine and cysteine, additional measurements were performed with the scanning tunneling microscope break-junction (STM-BJ) technique. By means of a statistical clustering technique, we identified several conductance groups for each of the molecules considered. Ab initio calculations revealed that the observed broad conductance distribution stems from the possibility of various binding geometries which can be formed during stretching combined with a multitude of possible conformational changes. The results suggest that it would be helpful to explore different experimental techniques such as recognition tunneling and conditions to help identify the nature of amino-acid-based junctions even further, for example, with the goal to establish a firm platform for their unambiguous recognition by tunneling break-junction experiments.

A reference-free clustering method for the analysis of molecular break-junction measurements

Single-molecule break-junction measurements are intrinsically stochastic in nature, requiring the acquisition of large datasets of “breaking traces” to gain insight into the generic electronic properties of the molecule under study. For example, the most probable conductance value of the molecule is often extracted from the conductance histogram built from these traces. In this letter, we present an unsupervised and reference-free machine learning tool to improve the determination of the conductance of oligo(phenylene ethynylene)dithiol from mechanically controlled break-junction (MCBJ) measurements. Our method allows for the classification of individual breaking traces based on an image recognition technique. Moreover, applying this technique to multiple merged datasets makes it possible to identify common breaking behaviors present across different samples, and therefore to recognize global trends. In particular, we find that the variation in the extracted molecular conductance can be significantly reduced resulting in a more reliable estimation of molecular conductance values from MCBJ datasets. Finally, our approach can be more widely applied to different measurement types which can be converted to two-dimensional images.

Quantum Interference Effects in Charge Transport through Single-Molecule Junctions: Detection, Manipulation, and Application.

Quantum interference effects (QIEs), which offer unique opportunities for the fine-tuning of charge transport through molecular building blocks by constructive or destructive quantum interference, have become an emerging area in single-molecule electronics. Benefiting from the QIEs, charge transport through molecular systems can be controlled through minor structural and environmental variations, which cause various charge transport states to be significantly changed from conductive to insulative states and offer promising applications in future functional single-molecule devices. Although QIEs were predicted by theoreticians more than two decades ago, only since 2011 have the challenges in ultralow conductance detection originating from destructive quantum interference been overcome experimentally. Currently, a series of single-molecule conductance investigations have been carried out experimentally to detect constructive and destructive QIEs in charge transport through various types of molecular junctions by altering molecular patterns and connectivities. Furthermore, the use of QIEs to tune the properties of charge transport through single-molecule junctions using external gating shows vital potential in future molecular electronic devices. The experimental and theoretical investigations of QIEs offer new fundamental understanding of the structural-electronic relationships in molecular devices and materials at the nanoscale. In this Account, we discuss our progress toward the experimental detection, manipulation, and further application of QIEs in charge transport through single-molecule junctions. These experiments were carried out continuously in our previous group at the University of Bern and in our lab at Xiamen University. As a result of the development of mechanically controllable break junction (MCBJ) and scanning tunneling microscope break junction (STM-BJ) techniques, we could detect ultralow charge transport through the cross-conjugated anthraquinone center, which was one of the earliest experimental studies of QIEs. In close cooperation with organic chemists and theoretical physicists, we systematically investigated charge transport through single-molecule junctions originating from QIEs in conjugated centers ranging from simple single benzene to polycyclic aromatic hydrocarbons (PAHs), heteroaromatics, and even complicated metalla-aromatics at room temperature. Then we further investigated the quantitative correlation between molecular structure and quantum interference by altering different molecular patterns and connectivities in homologous series of PAHs and heteroatom systems. Additionally, external chemical and electrochemical gating of single-molecule devices can be used for direct QIE manipulation via not only tuning molecular conjugation but also shifting the electrode Fermi level. Our study further suggested that distinguishable differences in conductance resulting from QIEs offer opportunities to detect photothermal reaction kinetics and to recognize isomers at the single-molecule scale. These investigations demonstrate the universality of QIEs in charge transport through various molecular building blocks. Moreover, effective manipulation of QIEs leads to various novel phenomena and promising applications in molecular electronic devices.

Mechanically controlled quantum interference in graphene break junctions.

The ability to detect and distinguish quantum interference signatures is important for both fundamental research and for the realization of devices such as electron resonators1, interferometers2 and interference-based spin filters3. Consistent with the principles of subwavelength optics, the wave nature of electrons can give rise to various types of interference effects4, such as Fabry-Pérot resonances5, Fano resonances6 and the Aharonov-Bohm effect7. Quantum interference conductance oscillations8 have, indeed, been predicted for multiwall carbon nanotube shuttles and telescopes, and arise from atomic-scale displacements between the inner and outer tubes9,10. Previous theoretical work on graphene bilayers indicates that these systems may display similar interference features as a function of the relative position of the two sheets11,12. Experimental verification is, however, still lacking. Graphene nanoconstrictions represent an ideal model system to study quantum transport phenomena13-15 due to the electronic coherence16 and the transverse confinement of the carriers17. Here, we demonstrate the fabrication of bowtie-shaped nanoconstrictions with mechanically controlled break junctions made from a single layer of graphene. Their electrical conductance displays pronounced oscillations at room temperature, with amplitudes that modulate over an order of magnitude as a function of subnanometre displacements. Surprisingly, the oscillations exhibit a period larger than the graphene lattice constant. Charge-transport calculations show that the periodicity originates from a combination of the quantum interference and lattice commensuration effects of two graphene layers that slide across each other. Our results provide direct experimental observation of a Fabry-Pérot-like interference of electron waves that are partially reflected and/or transmitted at the edges of the graphene bilayer overlap region.