Single Junctions Research Articles

Molecular Heat Engines: Quantum Coherence Effects

Recent developments in nanoscale experimental techniques made it possible to utilize single molecule junctions as devices for electronics and energy transfer with quantum coherence playing an important role in their thermoelectric characteristics. Theoretical studies on the efficiency of nanoscale devices usually employ rate (Pauli) equations, which do not account for quantum coherence. Therefore, the question whether quantum coherence could improve the efficiency of a molecular device cannot be fully addressed within such considerations. Here, we employ a nonequilibrium Green function approach to study the effects of quantum coherence and dephasing on the thermoelectric performance of molecular heat engines. Within a generic bichromophoric donor-bridge-acceptor junction model, we show that quantum coherence may increase efficiency compared to quasi-classical (rate equation) predictions and that pure dephasing and dissipation destroy this effect.

Novel Junction-specific and Quantifiable In Situ Detection of AR-V7 and its Clinical Correlates in Metastatic Castration-resistant Prostate Cancer

BackgroundAndrogen receptor splice variant 7 (AR-V7) has been implicated in resistance to abiraterone and enzalutamide treatment in men with metastatic castration-resistant prostate cancer (mCRPC). Tissue- or cell-based in situ detection of AR-V7, however, has been limited by lack of specificity. ObjectiveTo address current limitations in precision measurement of AR-V7 by developing a novel junction-specific AR-V7 RNA in situ hybridization (RISH) assay compatible with automated quantification. Design, setting, and participantsWe designed a RISH method to visualize single splice junctions in cells and tissue. Using the validated assay for junction-specific detection of the full-length AR (AR-FL) and AR-V7, we generated quantitative data, blinded to clinical data, for 63 prostate tumor biopsies. Outcome measurements and statistical analysisWe evaluated clinical correlates of AR-FL/AR-V7 measurements, including association with prostate-specific antigen progression-free survival (PSA-PFS) and clinical and radiographic progression-free survival (PFS), in a subset of patients starting treatment with abiraterone or enzalutamide following biopsy. Results and limitationsQuantitative AR-FL/AR-V7 data were generated from 56 of the 63 (88.9%) biopsy specimens examined, of which 44 were mCRPC biopsies. Positive AR-V7 signals were detected in 34.1% (15/44) mCRPC specimens, all of which also co-expressed AR-FL. The median AR-V7/AR-FL ratio was 11.9% (range 2.7–30.3%). Positive detection of AR-V7 was correlated with indicators of high disease burden at baseline. Among the 25 CRPC biopsies collected before treatment with abiraterone or enzalutamide, positive AR-V7 detection, but not higher AR-FL, was significantly associated with shorter PSA-PFS (hazard ratio 2.789, 95% confidence interval 1.12–6.95; p=0.0081). ConclusionsWe report for the first time a RISH method for highly specific and quantifiable detection of splice junctions, allowing further characterization of AR-V7 and its clinical significance. Patient summaryHigher AR-V7 levels detected and quantified using a novel method were associated with poorer response to abiraterone or enzalutamide in prostate cancer.

Transport gap renormalization at a metal-molecule interface using DFT-NEGF and spin unrestricted calculations.

A method is presented for predicting one-particle energies for a molecule in a junction with one metal electrode, using density functional theory methods. In contrast to previous studies, in which restricted spin configurations were analyzed, we take spin polarization into account. Furthermore, in addition to junctions in which the molecule is weakly coupled, our method is also capable of describing junctions in which the molecule is chemisorbed to the metal contact. We implemented a fully self-consistent scissor operator to correct the highest occupied molecular orbital-lowest unoccupied molecular orbital gap in transport calculations for single molecule junctions. We present results for various systems and compare our results with those obtained by other groups.

Inhomogeneous broadening of the conductance histograms for molecular junctions

We demonstrate that the notched-wire mechanically controllable break junction technique can be exploited for the study of single molecule junctions. We have developed a protocol for deposition of thiol-coupled molecules onto Au electrodes from solution. We find surprisingly sharp conductance historgrams at low temperatures, which suggest that the commonly observed large width of the peaks in conductance historgams is the result of inhomogeneous broadening.

Single molecule electrochemistry in nanoscale junctions

Summary A number of techniques give the ability to tether single molecules between metallic electrodes and to measure their electrical properties. Such techniques can be deployed across a wide range of environments, but importantly for electrochemists they can be applied in electrolytes and with full electrochemical control of both contacting electrodes. This article discusses how such techniques have emerged as powerful tools for analyzing charge transport in single molecule junctions at electrode|electrolyte interfaces and gives outlooks for the future development of this field of single molecule electrochemistry in nanoscale junctions.

Nematodynamics and structures in junctions of cylindrical micropores

ABSTRACTWe explore equilibrium structures and flow-driven deformations of nematic liquid crystals confined to 3D junctions of cylindrical micropores with homeotropic surface anchoring. The topological state of the nematic ordering field in such basic unit of porous networks is controlled by nematic orientation profiles in individual pores, anchoring frustration along the edges of joining pores and coupling to the material flow field. We numerically investigate formation of the flow-aligned configurations in single cylindrical pores and pore junctions. Depending on the arrangement of inlet and outlet flows in the junction, we demonstrate existence of numerous stationary nematic configurations, characterised by specific bulk defects and surface disclinations along joining edges. Observed bulk defects are nonsingular escaped structures, disclinations in the form of loops or disclination lines pinned to the joining edges of the pores. Furthermore, we show examples of defect dynamics during the flow-induced topological transformations.

Electrical characterization of C28 fullerene junctions formed with group 1B metal electrodes

We present an atomistic theory of electronic transport through single molecular junctions based on smallest stable fullerene molecule, C28. The electronic properties of single molecular junctions critically depend on the nature of electrode material. The two probe device is modeled by constraining C28 between two semi-infinite metal electrodes, from group 1B of periodic table, copper, silver and gold. We have highlighted the correlated phenomena of resonant conduction and current driven dynamics in molecular junctions using extendend Huckel theory in combination with non equilibrium Green’s function framework. We conclude strong dependence of conductance on transmissions, which leads to oscillating conductance spectrum. An interesting interplay between conducting channels and different degrees of spatial localization and delocalization of molecular orbitals is evinced. The physical origin of current and conductance of so-formed C28 molecular junctions is discussed in detail by analysing their density of states, transmission spectra, molecular orbital analysis, rectification ratio and molecular projected self consistent Hamiltonian eigen states at different operating voltages ranging from -2V to +2V.

Quantum-confined Stark effect in band-inverted junctions

Topological phases of matter are often characterized by interface states, which were already known to occur at the boundary of a band-inverted junction in semiconductor heterostructures. In IV-VI compounds such interface states are properly described by a two-band model, predicting the appearance of a Dirac cone in single junctions. We study the quantum-confined Stark effect of interface states due to an electric field perpendicular to a band-inverted junction. We find a closed expression to obtain the interface dispersion relation at any field strength and show that the Dirac cone widens under an applied bias. Thus, the Fermi velocity can be substantially lowered even at moderate fields, paving the way for tunable band-engineered devices based on band-inverted junctions.

Magnetic and electric control of spin- and valley-polarized transport across tunnel junctions on monolayer WSe2

The recent experimental realization of high-quality ${\mathrm{WSe}}_{2}$ leads to the possibility of an efficient manipulation of its spin and valley degrees of freedom. Its electronic properties comprise a huge spin-orbit coupling, a direct band gap, and a strong anisotropic lifting of the degeneracy of the valley degree of freedom in a magnetic field. We evaluate its band structure and study ballistic electron transport through single and double junctions (or barriers) on monolayer ${\mathrm{WSe}}_{2}$ in the presence of spin ${M}_{s}$ and valley ${M}_{v}$ Zeeman fields and of an electric potential $U$. The conductance versus the field ${M}_{s}$ or ${M}_{v}$ decreases in a fluctuating manner. For a single junction, the spin ${P}_{s}$ and valley ${P}_{v}$ polarizations rise with $M={M}_{v}=2{M}_{s}$, reach a value of more than $55%$, and become perfect above $U\ensuremath{\approx}45$ meV while for a double junction this change can occur for $U\ensuremath{\ge}50$ meV and $M\ensuremath{\ge}5$ meV. In certain regions of the $(M,U)$ plane ${P}_{v}$ becomes perfect. The conductance ${g}_{c}$, its spin-up and spin-down components, and both polarizations oscillate with the barrier width $d$. The ability to isolate various carrier degrees of freedom in ${\mathrm{WSe}}_{2}$ may render it a promising candidate for new spintronic and valleytronic devices.

Properties of Fe(Se, Te) Bicrystal Grain Boundary Junctions, SQUIDs, and Nanostrips

We have fabricated and characterized single junctions, dc Superconducting Quantum Interference Devices (SQUIDs), and nanostrips made by Fe(Te, Se) superconductive thin films. SrTiO 3 bicrystal substrates with different misorientation angles have been used for the fabrication of Josephson junctions and SQUIDs. Nanostrips have been realized growing thin films on CaF 2 substrates. The interaction between fluxons and antifluxons has been taken into account for the evaluation of the pinning energy values.

Advance of Mechanically Controllable Break Junction for Molecular Electronics.

Molecular electronics stands for the ultimate size of functional elements, keeping up with an unstoppable trend over the past few decades. As a vital component of molecular electronics, single molecular junctions have attracted significant attention from research groups all over the world. Due to its pronounced superiority, the mechanically controllable break junctions (MCBJ) technique has been widely applied to characterize the dynamic performance of single molecular junctions. This review presents a system analysis for single-molecule junctions and offers an overview of four test-beds for single-molecule junctions, thus offering more insight into the mechanisms of electron transport. We mainly focus on the development of state-of-the-art mechanically controlled break junctions. The three-terminal gated MCBJ approaches are introduced to manipulate the electron transport of molecules, and MCBJs are combined with characterization techniques. Additionally, applications of MCBJs and remarkable properties of single molecules are addressed. Finally, the challenges and perspective for the mechanically controllable break junctions technique are provided.

Quantum interference and heteroaromaticity of para- and meta-linked bridged biphenyl units in single molecular conductance measurements

Is there a correlation between the (hetero)aromaticity of the core of a molecule and its conductance in a single molecular junction? To address this question, which is of fundamental interest in molecular electronics, oligo(arylene-ethynylene) (OAE) molecular wires have been synthesized with core units comprising dibenzothiophene, carbazole, dibenzofuran and fluorene. The biphenyl core has been studied for comparison. Two isomeric series have been obtained with 4-ethynylpyridine units linked to the core either at para-para positions (para series 1–5) or meta-meta positions (meta series 6–10). A combined experimental and computational study, using mechanically controlled break junction measurements and density functional theory calculations, demonstrates consistently higher conductance in the para series compared to the meta series: this is in agreement with increased conjugation of the π–system in the para series. Within the para series conductance increases in the order of decreasing heteroaromaticity (dibenzothiophene < carbazole < dibenzofuran). However, the sequence is very different in the meta series, where dibenzothiophene ≈ dibenzofuran < carbazole. Excellent agreement between theoretical and experimental conductance values is obtained. Our study establishes that both quantum interference and heteroaromaticity in the molecular core units play important and inter-related roles in determining the conductance of single molecular junctions.

Controlling the Conductance of a Graphene-Molecule Nanojunction by Proton Transfer.

The possibility of using single molecule junctions as components of nanoelectronic devices has motivated intensive experimental and theoretical research on the underlying transport mechanism in these systems. In this Letter, we investigate from a theoretical perspective intramolecular proton transfer reactions as a mechanism for controlling the conductance state of graphene-based molecular junctions. Employing a methodology that combines first-principles electronic structure methods with transport approaches, we show that the proton transfer reaction proceeds via a stepwise mechanism, giving rise to several tautomers with different conductance states. The analysis reveals that the relative stability of the tautomers as well as the energy barrier for their interconversion can be controlled by means of an external electrostatic field, which provides a mechanism for switching the nanojunction.

Exceptionally Small Statistical Variations in the Transport Properties of Metal-Molecule-Metal Junctions Composed of 80 Oligophenylene Dithiol Molecules.

Strong stochastic fluctuations witnessed as very broad resistance (R) histograms with widths comparable to or even larger than the most probable values characterize many measurements in the field of molecular electronics, particularly those measurements based on single molecule junctions at room temperature. Here we show that molecular junctions containing 80 oligophenylene dithiol molecules (OPDn, 1 ≤ n ≤ 4) connected in parallel display small relative statistical deviations-δR/R ≈ 25% after only ∼200 independent measurements-and we analyze the sources of these deviations quantitatively. The junctions are made by conducting probe atomic force microscopy (CP-AFM) in which an Au-coated tip contacts a self-assembled monolayer (SAM) of OPDs on Au. Using contact mechanics and direct measurements of the molecular surface coverage, the tip radius, tip-SAM adhesion force (F), and sample elastic modulus (E), we find that the tip-SAM contact area is approximately 25 nm2, corresponding to about 80 molecules in the junction. Supplementing this information with I-V data and an analytic transport model, we are able to quantitatively describe the sources of deviations δR in R: namely, δN (deviations in the number of molecules in the junction), δε (deviations in energetic position of the dominant molecular orbital), and δΓ (deviations in molecule-electrode coupling). Our main results are (1) direct determination of N; (2) demonstration that δN/N for CP-AFM junctions is remarkably small (≤2%) and that the largest contributions to δR are δε and δΓ; (3) demonstration that δR/R after only ∼200 measurements is substantially smaller than most reports based on >1000 measurements for single molecule break junctions. Overall, these results highlight the excellent reproducibility of junctions composed of tens of parallel molecules, which may be important for continued efforts to build robust molecular devices.

Zeeman- and electric-field control of spin- and valley-polarized transport through biased magnetic junctions on WSe2

The electronic properties of WSe2 comprise a huge spin-orbit coupling, a wide direct band gap, and especially a strong anisotropic lifting of the degeneracy of the valley degree of freedom in a magnetic field. We study ballistic electron transport through single or double junctions on monolayer WSe2 in the presence of spin Ms and valley Mv Zeeman fields and of an electric potential U. The conductance vs. the field Ms or Mv decreases in a fluctuating manner. For a single junction the spin Ps and valley Pv polarizations rise with , reach a value of more than 70%, and become perfect above while for a double junction this change can occur for and . Pv increases with U and both polarizations oscillate with the junction width. The results may render WSe2 a promising candidate for new spintronic and valleytronic devices.

Fast sensitive amplifier for two-probe conductance measurements in single molecule break junctions.

We demonstrate an amplifier based on the Wheatstone bridge designed specifically for use in single molecule break junctions. This amplifier exhibits superior performance due to its large bandwidth, flat frequency response, and high sensitivity. The amplifier is capable of measuring conductance values from 102 to 10-6G0 (G0 = 2e2/h), while maintaining a bandwidth in excess of 20 kHz, and shows remarkable resolution in the molecular conductance regime of 10-2 to 10-5 G0.

Perspective: Thermal and thermoelectric transport in molecular junctions

With the advent of molecular electronics, tremendous attention has been paid towards understanding the structure-function relationship of molecular junctions. Understanding how heat is transported, dissipated, and converted into electricity in molecular junctions is of great importance for designing thermally robust molecular circuits and high-performance energy conversion devices. Further, the study of thermal and thermoelectric phenomena in molecular junctions provides novel insights into the limits of applicability of classical laws. Here, we present a review of the computational and experimental progress made in probing thermoelectric effects, thermal conduction, heat dissipation, and local heating/cooling in self-assembled monolayer and single molecule junctions. We also discuss some outstanding challenges and potential future directions.

Modeling single molecule junction mechanics as a probe of interface bonding

Using the atomic force microscope based break junction approach, applicable to metal point contacts and single molecule junctions, measurements can be repeated thousands of times resulting in rich data sets characterizing the properties of an ensemble of nanoscale junction structures. This paper focuses on the relationship between the measured force extension characteristics including bond rupture and the properties of the interface bonds in the junction. A set of exemplary model junction structures has been analyzed using density functional theory based calculations to simulate the adiabatic potential surface that governs the junction elongation. The junction structures include representative molecules that bond to the electrodes through amine, methylsulfide, and pyridine links. The force extension characteristics are shown to be most effectively analyzed in a scaled form with maximum sustainable force and the distance between the force zero and force maximum as scale factors. Widely used, two parameter models for chemical bond potential energy versus bond length are found to be nearly identical in scaled form. Furthermore, they fit well to the present calculations of N–Au and S–Au donor-acceptor bonds, provided no other degrees of freedom are allowed to relax. Examination of the reduced problem of a single interface, but including relaxation of atoms proximal to the interface bond, shows that a single-bond potential form renormalized by an effective harmonic potential in series fits well to the calculated results. This allows relatively accurate extraction of the interface bond energy. Analysis of full junction models shows cooperative effects that go beyond the mechanical series inclusion of the second bond in the junction, the spectator bond that does not rupture. Calculations for a series of diaminoalkanes as a function of molecule length indicate that the most important cooperative effect is due to the interactions between the dipoles induced by the donor-acceptor bond formation at the junction interfaces. The force extension characteristic of longer molecules such as diaminooctane, where the dipole interaction effects drop to a negligible level, accurately fit to the renormalized single-bond potential form. The results suggest that measured force extension characteristics for single molecule junctions could be analyzed with a modified potential form that accounts for the energy stored in deformable mechanical components in series.

Large-Area, Ensemble Molecular Electronics: Motivation and Challenges.

We review charge transport across molecular monolayers, which is central to molecular electronics (MolEl), using large-area junctions (NmJ). We strive to provide a wide conceptual overview of three main subtopics. First, a broad introduction places NmJ in perspective to related fields of research and to single-molecule junctions (1mJ) in addition to a brief historical account. As charge transport presents an ultrasensitive probe for the electronic perfection of interfaces, in the second part ways to form both the monolayer and the contacts are described to construct reliable, defect-free interfaces. The last part is dedicated to understanding and analyses of current-voltage (I-V) traces across molecular junctions. Notwithstanding the original motivation of MolEl, I-V traces are often not very sensitive to molecular details and then provide a poor probe for chemical information. Instead, we focus on how to analyze the net electrical performance of molecular junctions, from a functional device perspective. Finally, we point to creation of a built-in electric field as a key to achieve functionality, including nonlinear current-voltage characteristics that originate in the molecules or their contacts to the electrodes. This review is complemented by a another review that covers metal-molecule-semiconductor junctions and their unique hybrid effects.

Field-induced inversion of resonant tunneling currents through single molecule junctions and the directional photo-electric effect

It has been known for several decades that the electric current through tunneling junctions is affected by irradiation. In particular, photon-assisted currents by asymmetric irradiation of the two leads was demonstrated and studied extensively in tunneling junctions of different compositions and for different radiation wavelengths. In this work, this phenomenon is revisited in the context of single molecule junctions. Restricting the theoretical discussion to adiabatic periodic driving of one lead with respect to the other within a non-interacting electron formulation, the main features of specific molecules are encoded in the discrete electronic energy levels. The detailed level structure of the molecule is shown to yield new effects in the presence of asymmetric driving of the leads. In particular, when the field-free tunneling process is dominated by a single electronic level, the electric current can be suppressed to zero or flow against the direction of an applied static bias. In the presence of a second electronic level, a directional photo-electric effect is predicted, where not only the magnitude but also the direction of the steady state electric current through the tunneling junction can be changed by a monotonous increase of the field intensity. These effects are analyzed and explained by outlying the relevant theory, using analytic expressions in the wide-band limit, as well as numerical simulations beyond this limit.