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The performance of large-area molecular diodes can in rare cases approach the lower limit of commercial semiconductor devices but predictive structure-property design remains difficult as the rectification ratio ( R ) achieved by self-assembled monolayer (SAM) based diodes depends on several intertwined parameters. This paper describes a systematic approach to achieve high rectification in bisferrocenyl-based molecular diodes, HSC n Fc-CC-Fc ( n = 9-15) immobilised on metal surfaces (Ag, Au and Pt). Experiments supported by molecular dynamics simulations show that the molecular length and bottom electrode influence the SAM packing, which affects the breakdown voltage ( V BD ), the associated maximum R ( R max ), and the bias at which the R max is achieved ( V sat,R ). From the electrical characterisation of the most stable Pt-SC n Fc-CC-Fc//GaO x /EGaIn junctions, we found that V BD , V sat,R , and R max all scale linearly with the spacer length of C n , and that R max for all the SAMs consistently exceeds the "Landauer limit" of 10 3 . Our data shows that the robust switching of M-SC n Fc-CC-Fc//GaO x /EGaIn junctions is the result of the combined optimisation of parameters involving the molecular structure, the type of metal substrate, and the applied operating conditions (bias window), to create stable and high-performance junctions.

To develop new types of dynamic molecular devices with atomic-scale control over electronic function, new types of molecular switches are needed with time-dependent switching probabilities. We report such a molecular switch based on proton-coupled electron transfer (PCET) reaction with giant hysteric negative differential resistance (NDR) with peak-to-valley ratios of 120 ± 6.6 and memory on/off ratios of (2.4 ± 0.6) × 10 3 . The switching dynamics probabilities are modulated by bias voltage sweep rate and can also be controlled by pH and relative humidity, confirmed by kinetic isotope effect measurements. The demonstrated dynamical and environment-specific modulation of giant NDR and memory effects provide new opportunities for bioelectronics and artificial neural networks., (© 2024. The Author(s).)

This paper describes a gradual transition of charge transport across molecular junctions from coherent to incoherent tunneling by increasing the number and polarizability of halide substituents of phenyl-terminated aliphatic monolayers of the form S(CH 2 ) 10 OPhX n , X = F, Cl, Br, or I; n = 0, 1, 2, 3, or 5. In contrast to earlier work where incoherent tunneling was induced by introducing redox-active groups or increasing the molecular length, we show that increasing the polarizability, while keeping the organization of the monolayer structure unaltered, results in a gradual change in the mechanism of tunneling of charge carriers where the activation energy increased from 23 meV for n = 0 (associated with coherent tunneling) to 257 meV for n = 5 with X = Br (associated with incoherent tunneling). Interestingly, this increase in incoherent tunneling rate with polarizability resulted in an improved molecular diode performance. Our findings suggest an avenue to improve the electronic function of molecular devices by introducing polarizable atoms.

Plasmon excitation in molecular tunnel junctions is interesting because the plasmonic properties of the device can be, in principle, controlled by varying the chemical structure of the molecules. The plasmon energy of the excited plasmons usually follows the quantum cutoff law, but frequently overbias plasmon energy has been observed, which can be explained by quantum shot noise, multielectron processes, or hot carrier models. So far, clear correlations between molecular structure and the plasmon energy have not been reported. Here, we introduce halogenated molecules (HS(CH 2 ) 12 X, with X = H, F, Cl, Br, or I) with polarizable terminal atoms as the tunnel barriers and demonstrate molecular control over both the excited plasmon intensity and energy for a given applied voltage. As the polarizability of the terminal atom increases, the tunnel barrier height decreases, resulting in an increase in the tunneling current and the plasmon intensity without changing the tunneling barrier width. We also show that the plasmon energy is controlled by the electrostatic potential drop at the molecule-electrode interface, which depends on the polarizability of the terminal atom and the metal electrode material (Ag, Au, or Pt). Our results give new insights in the relation between molecular structure, electronic structure of the molecular junction, and the plasmonic properties which are important for the development of molecular scale plasmonic-electronic devices.

Plasmonic tunnel junctions are a unique electroluminescent system in which light emission occurs via an interplay between tunnelling electrons and plasmonic fields instead of electron-hole recombination as in conventional light-emitting diodes. It was previously shown that placing luminescent molecules in the tunneling pathway of nanoscopic tunnel junctions results in peculiar upconversion electroluminescence where the energy of emitted photons exceeds that of excitation electrons. Here we report the observation of upconversion electroluminescence in macroscopic van der Waals plasmonic tunnel junctions comprising gold and few-layer graphene electrodes separated by a ~2-nm-thick hexagonal boron nitride tunnel barrier and a monolayer semiconductor. We find that the semiconductor ground exciton emission is triggered at excitation electron energies lower than the semiconductor optical gap. Interestingly, this upconversion is reached in devices operating at a low conductance (<10 -6  S) and low power density regime (<10 2  W cm -2 ), defying explanation through existing proposed mechanisms. By examining the scaling relationship between plasmonic and excitonic emission intensities, we elucidate the role of inelastic electron tunnelling dipoles that induce optically forbidden transitions in the few-layer graphene electrode and ultrafast hot carrier transfer across the van der Waals interface., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

In the last two decades, perchlorate salts have been identified as environmental pollutants and recognized as potential substances affecting human health. We describe self-assembled monolayers (SAMs) of novel semiaza-bambus[6]urils (semiaza-BUs) equipped with thioethers or disulfide (dithiolane) functionalities as surface-anchoring groups on gold electrodes. Cyclic voltammetry (CV) with Fe(CN) 6 3-/4- as a redox probe, together with X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and ellipsometry, were employed to characterize the interactions at the interface between the anchoring groups and the metal substrate. Data showed that the anion receptors' packing on the gold strongly depends on the anchoring group. As a result, SAMs of BUs with lipoic amide side chains show a concentration-dependent layer thickness. The BU SAMs are extremely stable on repeated electrochemical potential scans and can selectively recognize perchlorate anions. Our electrochemical impedance spectroscopy (EIS) studies indicated that semiaza-BU equipped with the lipoic amide side chains binds perchlorate (2-100 mM) preferentially over other anions such as F - , Cl - , I - , AcO - , H 2 PO 4 - , HPO 4 2- , SO 4 2- , NO 2 - , NO 3 - , or CO 3 2- . The resistance performance is 10 to 100 times more efficient than SAMs containing all other tested anions., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Outcoupling of plasmonic modes excited by inelastic electron tunneling (IET) across plasmonic tunnel junctions (TJs) has attracted significant attention due to low operating voltages and fast excitation rates. Achieving selectivity among various outcoupling channels, however, remains a challenging task. Employing nanoscale antennas to enhance the local density of optical states (LDOS) associated with specific outcoupling channels partially addressed the problem, along with the integration of conducting 2D materials into TJs, improving the outcoupling to guided modes with particular momentum. The disadvantage of such methods is that they often involve complex fabrication steps and lack fine-tuning options. Here, we propose an alternative approach by modifying the dielectric medium surrounding TJs. By employing a simple multilayer substrate with a specific permittivity combination for the TJs under study, we show that it is possible to optimize mode selectivity in outcoupling to a plasmonic or a photonic-like mode characterized by distinct cutoff behaviors and propagation length. Theoretical and experimental results obtained with a SiO 2 -SiN-glass multilayer substrate demonstrate high relative coupling efficiencies of (62.77 ± 1.74)% and (29.07 ± 0.72)% for plasmonic and photonic-like modes, respectively. The figure-of-merit, which quantifies the tradeoff between mode outcoupling and propagation lengths (tens of μm) for both modes, can reach values as high as 180 and 140. The demonstrated approach allows LDOS engineering and customized TJ device performance, which are seamlessly integrated with standard thin film fabrication protocols. Our experimental device is well-suited for integration with silicon nitride photonics platforms.

The molecular electronic devices based on self-assembled monolayer (SAM) on metal surfaces demonstrate novel electronic functions for device minimization yet are unable to realize in practical applications, due to their instability against oxidation of the sulfur-metal bond. This paper describes an alternative to the thiolate anchoring group to form stable SAMs on gold by selenides anchoring group. Because of the formation of strong selenium-gold bonds, these stable SAMs allow us to incorporate them in molecular tunnel junctions to yield extremely stable junctions for over 200 days. A detailed structural characterization supported by spectroscopy and first-principles modeling shows that the oxidation process is much slower with the selenium-gold bond than the sulfur-gold bond, and the selenium-gold bond is strong enough to avoid bond breaking even when it is eventually oxidized. This proof of concept demonstrates that the extraordinarily stable SAMs derived from selenides are useful for long-lived molecular electronic devices and can possibly become important in many air-stable applications involving SAMs.

Highly-efficient molecular photoswitching occurs ex-situ but not to-date inside electronic devices due to quenching of excited states by background interactions. Here we achieve fully reversible in-situ mechano-optoelectronic switching in self-assembled monolayers (SAMs) of tetraphenylethylene molecules by bending their supporting electrodes to maximize aggregation-induced emission (AIE). We obtain stable, reversible switching across >1600 on/off cycles with large on/off ratio of (3.8 ± 0.1) × 10 3 and 140 ± 10 ms switching time which is 10-100× faster than other approaches. Multimodal characterization shows mechanically-controlled emission with UV-light enhancing the Coulomb interaction between the electrons and holes resulting in giant enhancement of molecular conductance. The best mechano-optoelectronic switching occurs in the most concave architecture that reduces ambient single-molecule conformational entropy creating artificially-tightened supramolecular assemblies. The performance can be further improved to achieve ultra-high switching ratio on the order of 10 5 using tetraphenylethylene derivatives with more AIE-active sites. Our results promise new applications from optimized interplay between mechanical force and optics in soft electronics., (© 2023. Springer Nature Limited.)

Charge transport across proteins can be surprisingly efficient over long distances-so-called long-range tunneling-but it is still unclear as to why and under which conditions (e.g., presence of co-factors, type of cargo) the long-range tunneling regime can be accessed. This paper describes molecular tunneling junctions based on an encapsulin (Enc), which is a large protein cage with a diameter of 24 nm that can be loaded with various types of (small) proteins, also referred to as "cargo". We demonstrate with dynamic light scattering, transmission electron microscopy, and atomic force microscopy that Enc, with and without cargo, can be made stable in solution and immobilized on metal electrodes without aggregation. We investigated the electronic properties of Enc in EGaIn-based tunnel junctions (EGaIn = eutectic alloy of Ga and In that is widely used to contact (bio)molecular monolayers) by measuring the current density for a large range of applied bias of ±2.5 V. The encapsulated cargo has an important effect on the electrical properties of the junctions. The measured current densities are higher for junctions with Enc loaded with redox-active cargo (ferritin-like protein) than those junctions without cargo or redox-inactive cargo (green fluorescent protein). These findings open the door to charge transport studies across complex biomolecular hierarchical structures., Competing Interests: The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analysis, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

Eutectic gallium-indium (EGaIn), a liquid metal with a melting point close to or below room temperature, has attracted extensive attention in recent years due to its excellent properties such as fluidity, high conductivity, thermal conductivity, stretchability, self-healing capability, biocompatibility, and recyclability. These features of EGaIn can be adjusted by changing the experimental condition, and various composite materials with extended properties can be further obtained by mixing EGaIn with other materials. In this review, not only the are unique properties of EGaIn introduced, but also the working principles for the EGaIn-based devices are illustrated and the developments of EGaIn-related techniques are summarized. The applications of EGaIn in various fields, such as flexible electronics (sensors, antennas, electronic circuits), molecular electronics (molecular memory, opto-electronic switches, or reconfigurable junctions), energy catalysis (heat management, motors, generators, batteries), biomedical science (drug delivery, tumor therapy, bioimaging and neural interfaces) are reviewed. Finally, a critical discussion of the main challenges for the development of EGaIn-based techniques are discussed, and the potential applications in new fields are prospected., (© 2022 Wiley-VCH GmbH.)

To investigate the mechanisms of charge transport (CT) across biomolecular tunnel junctions, it is required to make electrical contacts by a non-invasive method that leaves the biomolecules unaltered. Although different methods to form biomolecular junctions are available, here we describe the EGaIn-method because it allows us to readily form electrical contacts to monolayers of biomolecules in ordinary laboratory settings and to probe CT as a function of voltage, temperature, or magnetic field. This method relies on a non-Newtonian liquid-metal ally of Ga and In with a few nm thin layer of GaO x floating on its surface giving this material non-Newtonian properties allowing it to be shaped in to cone-shaped tips or stabilized in microchannels. These EGaIn structures form stable contacts to monolayers making it possible to investigate CT mechanisms across biomolecules in great detail., (© 2023. The Author(s), under exclusive license to Springer Science+Business Media, LLC, part of Springer Nature.)

To realize molecular-scale electrical operations beyond the von Neumann bottleneck, new types of multifunctional switches are needed that mimic self-learning or neuromorphic computing by dynamically toggling between multiple operations that depend on their past. Here, we report a molecule that switches from high to low conductance states with massive negative memristive behaviour that depends on the drive speed and number of past switching events, with all the measurements fully modelled using atomistic and analytical models. This dynamic molecular switch emulates synaptic behavior and Pavlovian learning, all within a 2.4-nm-thick layer that is three orders of magnitude thinner than a neuronal synapse. The dynamic molecular switch provides all the fundamental logic gates necessary for deep learning because of its time-domain and voltage-dependent plasticity. The synapse-mimicking multifunctional dynamic molecular switch represents an adaptable molecular-scale hardware operable in solid-state devices, and opens a pathway to simplify dynamic complex electrical operations encoded within a single ultracompact component., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Understanding the mechanisms of charge transport (CT) across biomolecules in solid-state devices is imperative to realize biomolecular electronic devices in a predictive manner. Although it is well-accepted that biomolecule-electrode interactions play an essential role, it is often overlooked. This paper reveals the prominent role of graphene interfaces with Fe-storing proteins in the net CT across their tunnel junctions. Here, ferritin (AfFtn-AA) is adsorbed on the graphene by noncovalent amine-graphene interactions confirmed with Raman spectroscopy. In contrast to junctions with metal electrodes, graphene has a vanishing density of states toward its intrinsic Fermi level ("Dirac point"), which increases away from the Fermi level. Therefore, the amount of charge carriers is highly sensitive to temperature and electrostatic charging (induced doping), as deduced from a detailed analysis of CT as a function of temperature and iron loading. Remarkably, the temperature dependence can be fully explained within the coherent tunneling regime due to excitation of hot carriers. Graphene is not only demonstrated as an alternative platform to study CT across biomolecular tunnel junctions, but it also opens rich possibilities in employing interface electrostatics in tuning CT behavior.

In biomolecular electronics, the role of structural order in charge transport (CT) is poorly understood. It has been reported that the metal oxide cores of protein cages (e.g., iron oxide and ferrihydrite nanoparticles (NPs) present in ferritin and E2-LFtn, which is E2 protein engineered with an iron-binding sequence) play an important role in the mechanism of CT. At the same time, the NP core also plays a major role in the structural integrity of the proteins. This paper describes the role of structural order in CT across tunnel junctions by comparing three iron-storing proteins. They are (1) DNA binding protein from starved cells (Dps, diameter (∅) = 9 nm); (2) engineered archaeal ferritin (AfFtn-AA, ∅ = 12 nm); and (3) engineered E2 of pyruvate dehydrogenase enzyme complex (E2-LFtn, ∅ = 25 nm). Both holo-Dps and apo-Dps proteins undergo CT by coherent tunneling because their globular architecture and relative structural stability provide a coherent conduction pathway. In contrast, apo-AfFtn-AA forms a disordered structure across which charges have to tunnel incoherently, but holo-AfFtn-AA retains its globular structure and supports coherent tunneling. The large E2-LFtn always forms disordered structures across which charges incoherently tunnel regardless of the presence of the NP core. These findings highlight the importance of structural order in the mechanism of CT across biomolecular tunnel junctions., (© 2022 The Authors. Small published by Wiley-VCH GmbH.)

Molecular junctions are building blocks for constructing future nanoelectronic devices that enable the investigation of a broad range of electronic transport properties within nanoscale regions. Crossing both the nanoscopic and mesoscopic length scales, plasmonics lies at the intersection of the macroscopic photonics and nanoelectronics, owing to their capability of confining light to dimensions far below the diffraction limit. Research activities on plasmonic phenomena in molecular electronics started around 2010, and feedback between plasmons and molecular junctions has increased over the past years. These efforts can provide new insights into the near-field interaction and the corresponding tunability in properties, as well as resultant plasmon-based molecular devices. This Review presents the latest advancements of plasmonic resonances in molecular junctions and details the progress in plasmon excitation and plasmon coupling. We also highlight emerging experimental approaches to unravel the mechanisms behind the various types of light-matter interactions at molecular length scales, where quantum effects come into play. Finally, we discuss the potential of these plasmonic-electronic hybrid systems across various future applications, including sensing, photocatalysis, molecular trapping and active control of molecular switches., (© 2022. Springer Nature Limited.)

Five years ago, rectification of electrical current was found in 4'-bromo-3,4-dicyano-2',5'-dimethoxy-[1,1'-biphenyl]-2,5-dione ( 1 ), a hemibiquinone (which we will call either 1 or HBQ) that has a very small working length (1.1 nm). Monolayers of HBQ on Au TS were detected by "nanodozing" atomic force microscopy (AFM) and were contacted with two types of top electrodes: either cold Au or eutectic Ga-In. Here, we describe cyclic voltammetry of a self-assembled monolayer (SAM) of HBQ and its orientation on a gold substrate with angle-resolved X-ray photoelectron spectroscopy. New measurements of its rectification as a monolayer as a function of bias range and temperature confirm and prove that HBQ is truly the smallest donor-acceptor rectifier and provide some insight into the mechanism of rectification., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The overall effectiveness of nonlinear optical processes along extended nonlinear media highly depends on the fulfillment of the phase-matching condition for pump and generated fields. This is traditionally accomplished by exploiting the birefringence of nonlinear crystals requiring long interaction lengths (cm-scale). For nonbirefringent media and integrated photonic devices, modal phase matching can compensate the index mismatch. Here, the various interacting waves propagate in transverse modes with appropriate phase velocities, but they suffer from a low refractive index contrast and cm-scale interaction lengths. This work harnesses modal phase matching for third-harmonic generation (THG) in plasmonic waveguides using an organic polymer (poly[3-hexylthiophene-2,5-diyl]) as the nonlinear medium. One demonstrates experimentally an effective interaction area as small as ≈ 0.11 µm 2 and the phase-matched modal dispersion results in THG efficiency as high as ≈ 10 -3 W -2 within an effective length scale of ≈ 4.3 µm. THG also shows a strong correlation with the polarization of the incident laser beam, corresponding to the excitation of the antisymmetric plasmonic modes, corroborating that plasmonic modal phase matching is achieved. This large reduction in device area of orders of magnitude is interesting for various applications where space is critical (e.g., device integration or on-chip applications)., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Controllable single-molecule logic operations will enable development of reliable ultra-minimalistic circuit elements for high-density computing but require stable currents from multiple orthogonal inputs in molecular junctions. Utilizing the two unique adjacent conductive molecular orbitals (MOs) of gated Au/S-(CH 2 ) 3 -Fc-(CH 2 ) 9 -S/Au (Fc = ferrocene) single-electron transistors (≈2 nm), a stable single-electron logic calculator (SELC) is presented, which allows real-time modulation of output current as a function of orthogonal input bias (V b ) and gate (V g ) voltages. Reliable and low-voltage (ǀV b ǀ ≤ 80 mV, ǀV g ǀ ≤ 2 V) operations of the SELC depend upon the unambiguous association of current resonances with energy shifts of the MOs (which show an invariable, small energy separation of ≈100 meV) in response to the changes of voltages, which is confirmed by electron-transport calculations. Stable multi-logic operations based on the SELC modulated current conversions between the two resonances and Coulomb blockade regimes are demonstrated via the implementation of all universal 1-input (YES/NOT/PASS&#95;1/PASS&#95;0) and 2-input (AND/XOR/OR/NAND/NOR/INT/XNOR) logic gates., (© 2022 Wiley-VCH GmbH.)

Eutectic gallium-indium (EGaIn) is increasingly employed as an interfacial conductor material in molecular electronics and wearable healthcare devices owing to its ability to be shaped at room temperature, conductivity, and mechanical stability. Despite this emerging usage, the mechanical and physical mechanisms governing EGaIn interactions with surrounding objects─mainly regulated by surface tension and interfacial adhesion─remain poorly understood. Here, using depth-sensing nanoindentation (DSN) on pristine EGaIn/GaO x surfaces, we uncover how changes in EGaIn/substrate interfacial energies regulate the adhesive and contact mechanic behaviors, notably the evolution of EGaIn capillary bridges with distinct capillary geometries and pressures. Varying the interfacial energy by subjecting EGaIn to different chemical environments and by functionalizing the tip with chemically distinct self-assembled monolayers (SAMs), we show that the adhesion forces between EGaIn and the solid substrate can be increased by up to 2 orders of magnitude, resulting in about a 60-fold increase in the elongation of capillary bridges. Our data reveal that by deploying molecular junctions with SAMs of different terminal groups, the trends of charge transport rates, the resistance of monolayers, and the contact interactions between EGaIn and monolayers from electrical characterizations are governed by the interfacial energies as well. This study provides a key understanding into the role of interfacial energy on geometrical characteristics of EGaIn capillary bridges, offering insights toward the fabrication of EGaIn junctions in a controlled fashion.

This work describes the self-assembled monolayers (SAMs) of two ferrocene derivatives with two anchoring groups (at the bottom and at the top of the SAM) deposited on ultraflat template-stripped gold substrates by cyclic voltammetry and analyzed by complementary surface characterization techniques. The SAM of each molecule is deposited by three different protocols: direct deposition (one step), click reaction on the surface (two steps), and reverse click reaction on the surface (two steps). The SAM structure is well studied to determine the SAM orientation, SAM arrangement, and ferrocene position within the SAM. Electron transfer kinetics have also been studied, which agree with the quality of each SAM. With the help of two anchoring groups and click-chemistry active functional groups, we have shown that the two molecules can be deposited by controlling the position of ferrocene at either end. We further investigated the involvement of the triazole five-membered ring in the electron transfer mechanism. We have found that a carbon spacer between ferrocene and triazole improves the SAM packing. This study enhances the understanding of tethering thiol and thiol acetate anchoring groups on gold by a controlled orientation, which may help in the development of functional molecular devices requiring two anchoring groups.

Electrical field-induced charge modulation in graphene-based devices at the nanoscale with ultrahigh density carrier accumulation is important for various practical applications. In bilayer graphene (BLG), inversion symmetry can simply be broken by an external electric field. However, control over charge carrier density at the nanometer scale is a challenging task. We demonstrate local gating of BLG in the nanometer range by adsorption of AfFtnAA (which is a bioengineered ferritin, an iron-storing globular protein with ∅ = 12 nm). Low-temperature electrical transport measurements with field-effect transistors with these AfFtnAA/BLG surfaces show hysteresis with two Dirac peaks. One peak at a gate voltage V BG  = 35 V is associated with pristine BLG, while the second peak at V BG  = 5 V results from local doping by ferritin. This charge trapping at the biomolecular length scale offers a straightforward and non-destructive method to alter the local electronic structure of BLG., Competing Interests: Christian A. Nijhuis is an Editorial advisory board member of iScience., (© 2022 The Author(s).)

Robust processes to fabricate densely packed high-aspect-ratio (HAR) vertical semiconductor nanostructures are important for applications in microelectronics, energy storage and conversion. One of the main challenges in manufacturing these nanostructures is pattern collapse, which is the damage induced by capillary forces from numerous solution-based processes used during their fabrication. Here, using an array of vertical silicon (Si) nanopillars as test structures, we demonstrate that pattern collapse can be greatly reduced by a solution-phase deposition method to coat the nanopillars with self-assembled monolayers (SAMs). As the main cause for pattern collapse is strong adhesion between the nanopillars, we systematically evaluated SAMs with different surface energy components and identified H-bonding between the surfaces to have the largest contribution to the adhesion. The advantage of the solution-phase deposition method is that it can be implemented before any drying step, which causes patterns to collapse. Moreover, after drying, these SAMs can be easily removed using a gentle air-plasma treatment right before the next fabrication step, leaving a clean nanopillar surface behind. Therefore, our approach provides a facile and effective method to prevent the drying-induced pattern collapse in micro- and nanofabrication processes.

To develop methods to generate, manipulate, and detect plasmonic signals by electrical means with complementary metal-oxide-semiconductor (CMOS)-compatible materials is essential to realize on-chip electronic-plasmonic transduction. Here, electrically driven, CMOS-compatible electronic-plasmonic transducers with Al-AlO X -Cu tunnel junctions as the excitation source of surface plasmon polaritons (SPPs) and Si-Cu Schottky diodes as the detector of SPPs, connected via plasmonic strip waveguides of Cu, are demonstrated. Remarkably, the electronic-plasmonic transducers exhibit overall transduction efficiency of 1.85 ± 0.03%, five times higher than previously reported transducers with two tunnel junctions (metal-insulator-metal (MIM)-MIM transducers) where SPPs are detected based on optical rectification. The result establishes a new platform to convert electronic signals to plasmonic signals via electrical means, paving the way toward CMOS-compatible plasmonic components., (© 2021 The Authors. Small published by Wiley-VCH GmbH.)

Deoxyribonucleic acid (DNA) has been hypothesized to act as a molecular wire due to the presence of an extended π-stack between base pairs, but the factors that are detrimental in the mechanism of charge transport (CT) across tunnel junctions with DNA are still unclear. Here we systematically investigate CT across dense DNA monolayers in large-area biomolecular tunnel junctions to determine when intrachain or interchain CT dominates and under which conditions the mechanism of CT becomes thermally activated. In our junctions, double-stranded DNA (dsDNA) is 30-fold more conductive than single-stranded DNA (ssDNA). The main reason for this large change in conductivity is that dsDNA forms ordered monolayers where intrachain tunneling dominates, resulting in high CT rates. By varying the temperature T and the length of the DNA fragments in the junctions, which determines the tunneling distance, we reveal a complex interplay between T , the length of DNA, and structural order on the mechanism of charge transport. Both the increase in the tunneling distance and the decrease in structural order result in a change in the mechanism of CT from coherent tunneling to incoherent tunneling (hopping). Our results highlight the importance of the interplay between structural order, tunneling distance, and temperature on the CT mechanism across DNA in molecular junctions.

Inelastic quantum mechanical tunneling of electrons across plasmonic tunnel junctions can lead to surface plasmon polariton (SPP) and photon emission. So far, the optical properties of such junctions have been controlled by changing the shape, or the type of the material, of the electrodes, primarily with the aim to improve SPP or photon emission efficiencies. Here we show that by tuning the tunneling barrier itself, the efficiency of the inelastic tunneling rates can be improved by a factor of 3. We exploit the anisotropic nature of hexagonal boron nitride (hBN) as the tunneling barrier material in Au//hBN//graphene tunnel junctions where the Au electrode also serves as a plasmonic strip waveguide. As this junction constitutes an optically transparent hBN-graphene heterostructure on a glass substrate, it forms an open plasmonic system where the SPPs are directly coupled to the dedicated strip waveguide and photons outcouple to the far field. We experimentally and analytically show that the photon emission rate per tunneling electron is significantly improved (~ ×3) in Au//hBN//graphene tunnel junction due to the enhancement in the local density of optical states (LDOS) arising from the hBN anisotropy. With the dedicated strip waveguide, SPP outcoupling efficiency is quantified and is found to be ∼ 80% stronger than the radiative outcoupling in Au//hBN//graphene due to the high LDOS of the SPP decay channel associated with the inelastic tunneling. The new insights elucidated here deepen our understanding of plasmonic tunnel junctions beyond the isotropic models with enhanced LDOS., (© 2021. The Author(s).)

Objective: The presence of metallic species around failed implants raises concerns about the stability of titanium alloy (Ti-6Al-4V). Graphene nanocoating on titanium alloy (GN) has promising anti-corrosion properties, but its long-term protective potential and structural stability remains unknown. The objective was to determine GN's anti-corrosion potential and stability over time., Methods: GN and uncoated titanium alloy (Control) were challenged with a highly acidic fluorinated corrosive medium (pH 2.0) for up to 240 days. The samples were periodically tested using potentiodynamic polarization curves, electrochemical impedance spectroscopy and inductively coupled plasma-atomic emission spectroscopy (elemental release). The integrity of samples was determined using Raman spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy and scanning electron microscopy. Statistical analyses were performed with one-sample t-test, paired t-test and one-way ANOVA with Tukey post-hoc test with a pre-set significance level of 5%., Results: There was negligible corrosion and elemental loss on GN. After 240 days of corrosion challenge, the corrosion rate and roughness increased by two and twelve times for the Control whereas remained unchanged for GN. The nanocoating presented remarkably high structural integrity and coverage area (>98%) at all time points tested., Significance: Graphene nanocoating protects titanium alloy from corrosion and dissolution over a long period while maintaining high structural integrity. This coating has promising potential for persistent protection of titanium and potentially other metallic alloys against corrosion., (Copyright © 2021 The Author(s). Published by Elsevier Inc. All rights reserved.)

Titanium implants present 2 major drawbacks-namely, the long time needed for osseointegration and the lack of inherent antimicrobial properties. Surface modifications and coatings to improve biomaterials can lose their integrity and biological potential when exposed to stressful microenvironments. Graphene nanocoating (GN) can be deposited onto actual-size dental and orthopedic implants. It has antiadhesive properties and can enhance bone formation in vivo. However, its ability to maintain structural integrity and quality when challenged by biologically relevant stresses remains largely unknown. GN was produced by chemical vapor deposition and transferred to titanium via a polymer-assisted transfer technique. GN has high inertness and did not increase expression of inflammatory markers by macrophages, even in the presence of lipopolysaccharides. It kept high coverage at the top tercile of tapered dental implant collars after installation and removal from bone substitute and pig maxilla. It also resisted microbiologically influenced corrosion, and it maintained very high coverage area and quality after prolonged exposure to biofilms and their removal by different techniques. Our findings show that GN is unresponsive to harsh and inflammatory environments and that it maintains a promising level of structural integrity on the top tercile of dental implant collars, which is the area highly affected by biofilms during the onset of implant diseases. Our findings open the avenues for the clinical studies required for the use of GN in the development of implants that have higher osteogenic potential and are less prone to implant diseases.

Charge transfer (CT) dynamics across metal-molecule interfaces has important implications for performance and function of molecular electronic devices. CT times, on the order of femtoseconds, can be precisely measured using synchrotron-based core-hole clock (CHC) spectroscopy, but little is known about the impact on CT times of the metal work function and the bond dipole created by metals and the anchoring group. To address this, here we measure CT dynamics across self-assembled monolayers bound by thiolate anchoring groups to Ag, Au, and Pt. The molecules have a terminal ferrocene (Fc) group connected by varying numbers of methylene units to a diphenylacetylene (DPA) wire. CT times measured using CHC with resonant photoemission spectroscopy (RPES) show that conjugated DPA wires conduct electricity faster than aliphatic carbon wires of a similar length. Shorter methylene connectors exhibit increased conjugation between Fc and DPA, facilitating CT by providing greater orbital mixing. We find nearly 10-fold increase in the CT time on Pt compared to Ag due to a larger bond dipole generated by partial electron transfer from the metal-sulfur bond to the carbon-sulfur bond, which creates an electrostatic field that impedes CT from the molecules. By fitting the RPES signal, we distinguish electrons coming from the Fe center and from cyclopentadienyl (Cp) rings. The latter shows faster CT rates because of the delocalized Cp orbitals. Our study demonstrates the fine tuning of CT rates across junctions by careful engineering of several parts of the molecule and the molecule-metal interface., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

This paper describes the transition from the normal to inverted Marcus region in solid-state tunnel junctions consisting of self-assembled monolayers of benzotetrathiafulvalene (BTTF), and how this transition determines the performance of a molecular diode. Temperature-dependent normalized differential conductance analyses indicate the participation of the HOMO (highest occupied molecular orbital) at large negative bias, which follows typical thermally activated hopping behavior associated with the normal Marcus regime. In contrast, hopping involving the HOMO dominates the mechanism of charge transport at positive bias, yet it is nearly activationless indicating the junction operates in the inverted Marcus region. Thus, within the same junction it is possible to switch between Marcus and inverted Marcus regimes by changing the bias polarity. Consequently, the current only decreases with decreasing temperature at negative bias when hopping is "frozen out," but not at positive bias resulting in a 30-fold increase in the molecular rectification efficiency. These results indicate that the charge transport in the inverted Marcus region is readily accessible in junctions with redox molecules in the weak coupling regime and control over different hopping regimes can be used to improve junction performance., (© 2021 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The energy level alignment after the formation of a molecular tunnel junction is often poorly understood because spectroscopy inside junctions is not possible, which hampers the rational design of functional molecular junctions and complicates the interpretation of the data generated by molecular junctions. In molecular junction platforms where the top electrode-molecule interaction is weak; one may argue that the energy level alignment can be deduced from measurements with the molecules supported by the bottom electrode (sometimes referred to as "half junctions"). This approach, however, still relies on a series of assumptions, which are challenging to address experimentally due to difficulties in studying the molecule-top electrode interaction. Herein, we describe top electrode-molecule junctions with a liquid metal alloy top electrode of EGaIn (which stands for eutectic alloy of Ga and In) interacting with well-characterised ferrocene (Fc) moieties. We deposited a ferrocene derivative on films of EGaIn, coated with its native GaOx layer, and studied the energy level alignment with photoelectron spectroscopy. Our results reveal that the electronic interaction between the Fc and GaOx/EGaIn is very weak, resembling physisorption. Therefore, investigations of "half junctions" for this system can provide valuable information regarding the energy level alignment of complete EGaIn junctions. Our results help to improve our understanding of the energy landscape in weakly coupled molecular junctions and aid to the rational design of molecular electronic devices.

We present an efficient strategy to modulate tunnelling in molecular junctions by changing the tunnelling decay coefficient, β, by terminal-atom substitution which avoids altering the molecular backbone. By varying X = H, F, Cl, Br, I in junctions with S(CH 2 ) (10-18) X, current densities (J) increase >4 orders of magnitude, creating molecular conductors via reduction of β from 0.75 to 0.25 Å -1 . Impedance measurements show tripled dielectric constants (ε r ) with X = I, reduced HOMO-LUMO gaps and tunnelling-barrier heights, and 5-times reduced contact resistance. These effects alone cannot explain the large change in β. Density-functional theory shows highly localized, X-dependent potential drops at the S(CH 2 ) n X//electrode interface that modifies the tunnelling barrier shape. Commonly-used tunnelling models neglect localized potential drops and changes in ε r . Here, we demonstrate experimentally that [Formula: see text], suggesting highly-polarizable terminal-atoms act as charge traps and highlighting the need for new charge transport models that account for dielectric effects in molecular tunnelling junctions.

Metal-insulator-metal tunnel junctions (MIM-TJs) can electrically excite surface plasmon polaritons (SPPs) well below the diffraction limit. When inelastically tunneling electrons traverse the tunnel barrier under applied external voltage, a highly confined cavity mode (MIM-SPP) is excited, which further out-couples from the MIM-TJ to photons and single-interface SPPs via multiple pathways. In this work we control the out-coupling pathways of the MIM-SPP mode by engineering the geometry of the MIM-TJ. We fabricated MIM-TJs with tunneling directions oriented vertical or lateral with respect to the directly integrated plasmonic strip waveguides. With control over the tunneling direction, preferential out-coupling of the MIM-SPP mode to SPPs or photons is achieved. Based on the wavevector distribution of the single-interface SPPs or photons in the far-field emission intensity obtained from back focal plane (BFP) imaging, we estimate the out-coupling efficiency of the MIM-SPP mode to multiple out-coupling pathways. We show that in the vertical-MIM-TJs the MIM-SPP mode preferentially out-couples to single-interface SPPs along the strip waveguides while in the lateral-MIM-TJs photon out-coupling to the far-field is more efficient.

Control over the energy level alignment in molecular junctions is notoriously difficult, making it challenging to control basic electronic functions such as the direction of rectification. Therefore, alternative approaches to control electronic functions in molecular junctions are needed. This paper describes switching of the direction of rectification by changing the bottom electrode material M = Ag, Au, or Pt in M-S(CH 2 ) 11 S-BTTF//EGaIn junctions based on self-assembled monolayers incorporating benzotetrathiafulvalene (BTTF) with EGaIn (eutectic alloy of Ga and In) as the top electrode. The stability of the junctions is determined by the choice of the bottom electrode, which, in turn, determines the maximum applied bias window, and the mechanism of rectification is dominated by the energy levels centered on the BTTF units. The energy level alignments of the three junctions are similar because of Fermi level pinning induced by charge transfer at the metal-thiolate interface and by a varying degree of additional charge transfer between BTTF and the metal. Density functional theory calculations show that the amount of electron transfer from M to the lowest unoccupied molecular orbital (LUMO) of BTTF follows the order Ag > Au > Pt. Junctions with Ag electrodes are the least stable and can only withstand an applied bias of ±1.0 V. As a result, no molecular orbitals can fall in the applied bias window, and the junctions do not rectify. The junction stability increases for M = Au, and the highest occupied molecular orbital (HOMO) dominates charge transport at a positive bias resulting in a positive rectification ratio of 83 at ±1.5 V. The junctions are very stable for M = Pt, but now the LUMO dominates charge transport at a negative bias resulting in a negative rectification ratio of 912 at ±2.5 V. Thus, the limitations of Fermi level pinning can be bypassed by a judicious choice of the bottom electrode material, making it possible to access selectively HOMO- or LUMO-based charge transport and, as shown here, associated reversal of rectification.

Redox-active molecular junctions have attracted considerable attention because redox-active molecules provide accessible energy levels enabling electronic function at the molecular length scales, such as, rectification, conductance switching, or molecular transistors. Unlike charge transfer in wet electrochemical environments, it is still challenging to understand how redox-processes proceed in solid-state molecular junctions which lack counterions and solvent molecules to stabilize the charge on the molecules. In this minireview, we first introduce molecular junctions based on redox-active molecules and discuss their properties from both a chemistry and nanoelectronics point of view, and then discuss briefly the mechanisms of charge transport in solid-state redox-junctions followed by examples where redox-molecules generate new electronic function. We conclude with challenges that need to be addressed and interesting future directions from a chemical engineering and molecular design perspectives., (© 2020 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.)

Herein, we report the first room temperature switchable Fe(iii) molecular spin crossover (SCO) tunnel junction. The junction is constructed from [Fe III (qsal-I) 2 ]NTf 2 (qsal-I = 4-iodo-2-[(8-quinolylimino)methyl]phenolate) molecules self-assembled on graphene surfaces with conductance switching of one order of magnitude associated with the high and low spin states of the SCO complex. Normalized conductance analysis of the current-voltage characteristics as a function of temperature reveals that charge transport across the SCO molecule is dominated by coherent tunnelling. Temperature-dependent X-ray absorption spectroscopy and density functional theory confirm the SCO complex retains its SCO functionality on the surface implying that van der Waals molecule-electrode interfaces provide a good trade-off between junction stability while retaining SCO switching capability. These results provide new insights and may aid in the design of other types of molecular devices based on SCO compounds., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Although the dielectric behavior of monolayers is important in a large range of applications, its role in charge transport studies involving molecular junctions is largely ignored. This paper describes a large increase in the relative static dielectric constant (ε r ) by simply increasing the thickness of well-organized monolayers of oligoglycine and oligo(ethylene glycol) from 7 up to 14. The resulting large capacitance of 3.5-5.1 μF/cm 2 is thickness-independent, which is highly attractive for field-effect transistor applications. This increase of ε r results in a linear increase of the thermal activation energy by a factor of 6, which suggests that the mechanism of charge transport gradually changes from coherent to (partially) incoherent tunneling. The comparisons of oligoglycine (which readily forms hydrogen bonds with neighboring molecules) and methyl terminated oligo(ethylene glycol) (which lacks hydrogen bond donors) monolayers, kinetic isotope effects, and relative humidity-dependent measurements all indicate the importance of strong hydrogen bonds involving ionic species and strongly bonded water in the unusual dielectric behavior and the incoherent tunneling mechanism. This partial loss of coherence of the charge carriers can explain the unusually small tunneling decay coefficients across long molecular wires, and the length-dependent increase of ε r of monolayers opens up interesting new applications.

To avoid crosstalk and suppress leakage currents in resistive random access memories (RRAMs), a resistive switch and a current rectifier (diode) are usually combined in series in a one diode-one resistor (1D-1R) RRAM. However, this complicates the design of next-generation RRAM, increases the footprint of devices and increases the operating voltage as the potential drops over two consecutive junctions 1 . Here, we report a molecular tunnel junction based on molecules that provide an unprecedented dual functionality of diode and variable resistor, resulting in a molecular-scale 1D-1R RRAM with a current rectification ratio of 2.5 × 10 4 and resistive on/off ratio of 6.7 × 10 3 , and a low drive voltage of 0.89 V. The switching relies on dimerization of redox units, resulting in hybridization of molecular orbitals accompanied by directional ion migration. This electric-field-driven molecular switch operating in the tunnelling regime enables a class of molecular devices where multiple electronic functions are preprogrammed inside a single molecular layer with a thickness of only 2 nm.

Electronic symmetry breaking by charge disproportionation results in multifaceted changes in the electronic, magnetic and optical properties of a material, triggering ferroelectricity, metal/insulator transition and colossal magnetoresistance. Yet, charge disproportionation lacks technological relevance because it occurs only under specific physical conditions of high or low temperature or high pressure. Here we demonstrate a voltage-triggered charge disproportionation in thin molecular films of a metal-organic complex occurring in ambient conditions. This provides a technologically relevant molecular route for simultaneous realization of a ternary memristor and a binary memcapacitor, scalable down to a device area of 60 nm 2 . Supported by mathematical modelling, our results establish that multiple memristive states can be functionally non-volatile, yet discrete-a combination perceived as theoretically prohibited. Our device could be used as a binary or ternary memristor, a binary memcapacitor or both concomitantly, and unlike the existing 'continuous state' memristors, its discrete states are optimal for high-density, ultra-low-energy digital computing.

Successful integration of proteins in solid-state electronics requires contacting them in a non-invasive fashion, with a solid conducting surface for immobilization as one such contact. The contacts can affect and even dominate the measured electronic transport. Often substrates, substrate treatments, protein immobilization, and device geometries differ between laboratories. Thus the question arises how far results from different laboratories and platforms are comparable and how to distinguish genuine protein electronic transport properties from platform-induced ones. We report a systematic comparison of electronic transport measurements between different laboratories, using all commonly used large-area schemes to contact a set of three proteins of largely different types. Altogether we study eight different combinations of molecular junction configurations, designed so that A geo of junctions varies from 10 5 to 10 -3 μm 2 . Although for the same protein, measured with similar device geometry, results compare reasonably well, there are significant differences in current densities (an intensive variable) between different device geometries. Likely, these originate in the critical contact-protein coupling (∼contact resistance), in addition to the actual number of proteins involved, because the effective junction contact area depends on the nanometric roughness of the electrodes and at times, even the proteins may increase this roughness. On the positive side, our results show that understanding what controls the coupling can make the coupling a design knob. In terms of extensive variables, such as temperature, our comparison unanimously shows the transport to be independent of temperature for all studied configurations and proteins. Our study places coupling and lack of temperature activation as key aspects to be considered in both modeling and practice of protein electronic transport experiments., Competing Interests: The authors declare no competing interests., (© 2020 The Author(s).)

The identification of metal ions and particles in the vicinity of failed implants has raised the concern that biomedical titanium alloys undergo corrosion in healthy and infected tissues. Various surface modifications and coatings have been investigated to prevent the deterioration and biocorrosion of titanium alloys but so far with limited success. Graphene is a cytocompatible atom-thick film made of carbon atoms. It has a very high surface area and can be deposited onto metal objects with complex shapes. As the carbon lattice has a very small pore size, graphene has promising impermeability capacity. Here, we show that graphene coating can effectively protect Ti-6Al-4V from corrosion. Graphene nanocoatings were produced on Ti-6Al-4V grade 5 and 23 discs and subjected to corrosive challenge (0.5M NaCl supplemented with 2-ppm fluoride, pH of 2.0) up to 30 d. The linear polarization resistance curves and electrochemical impedance spectroscopy analysis showed that the graphene-coated samples presented higher corrosion resistance and electrochemical stability at all time points. Moreover, the corrosion rate of the graphene-coated samples was very low and stable (~0.001 mm/y), whereas that of the uncoated controls increased up to 16 and 5 times for grade 5 and 23 (~0.091 mm/y) at the end point, respectively. The surface oxidation, degradation (e.g., crevice defects), and leaching of Ti, Al, and V ions observed in the uncoated controls were prevented by the graphene nanocoating. The Raman mappings confirmed that the graphene nanocoating presented high structural stability and resistance to mechanical stresses and chemical degradation, keeping >99% of coverage after corrosion challenge. Our findings open the avenues for the use of graphene as anticorrosion coatings for metal biomedical alloys and implantable devices.

Surface plasmon polaritons (SPPs) are viable candidates for integration into on-chip nano-circuitry that allow access to high data bandwidths and low energy consumption. Metal-insulator-metal tunneling junctions (MIM-TJs) have recently been shown to excite and detect SPPs electrically; however, experimentally measured efficiencies and outcoupling mechanisms are not fully understood. It is shown that the MIM-TJ cavity SPP mode (MIM-SPP) can outcouple via three pathways to i) photons via scattering of MIM-SPP at the MIM-TJ interfaces, ii) SPPs at the metal-dielectric interfaces (bound-SPPs) by mode coupling through the electrodes, and iii) photons and bound-SPP modes by mode coupling at the MIM-TJ edges. It is also shown that, for Al-AlO x -Cr-Au MIM-TJs on glass, the MIM-SPP mode outcouples efficiently to bound-SPPs through either electrode (pathway 2); this outcoupling pathway can be selectively turned on and off by changing the respective electrode thickness. Outcoupling at the MIM-TJ edges (pathway 3) is efficient and sensitive to the edge topography, whereas most light emission originates from roughness-induced scattering of the MIM-SPP mode (pathway 1). Using an arbitrary roughness profile, it is demonstrated that various roughness facets can raise MIM-SPP outcoupling efficiencies to 0.62%. These results pave the way for understanding the topographical parameters needed to develop CMOS-compatible plasmonic circuitry elements., Competing Interests: The authors declare no conflict of interest., (© 2020 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.)

A major obstacle for transforming large-area molecular junctions into a viable technology is the deposition of a top, metallic contact over the self-assembled monolayer (SAM) without chemically damaging the molecules and preventing an interface-limited charge transport. Often a thin conducting layer is softly deposited over the SAM to protect it during the deposition of the metal electrode which requires conditions under which organic molecules are not stable. We report a new protective layer based on carbon paint which is highly conductive and has metallic-like behavior. Junctions made of SAMs of n -alkanethiolates supported by Au were characterized with both dc and ac techniques, revealing that carbon paint protective layers provide a solution to three well-known challenges in molecular junctions: series resistance of the leads, poor interface conductance, and low effective contact area related to the roughness of the interfaces. Transport is constant with coherent tunneling down to 10 K, indicating the carbon paint does not add spurious thermally activated components. The junctions have both high reproducibility and good stability against bias stressing. Finally, normalized differential conductance analysis of the tunneling characteristics of the junctions as a function of molecular length reveals that the scaling voltage changes with molecular length, indicating a significant voltage drop on the molecules rather than on the molecule-electrode interface. There is a clear inverse dependence of the scaling voltage on length, which we deduced has a tunneling barrier height of close to 2 eV. The paper establishes the reliability of carbon paint protective layers and provides a procedure for discriminating genuine molecular effects from interfacial contributions.

In principle, excitation of surface plasmons by molecular tunnel junctions can be controlled at the molecular level. Stable electrical excitation sources of surface plasmons are therefore desirable. Herein, molecular junctions are reported where tunneling charge carriers excite surface plasmons in the gold bottom electrodes via inelastic tunneling and it is shown that the intermittent light emission (blinking) originates from conformational dynamics of the molecules. The blinking rates, in turn, are controlled by changing the rigidity of the molecular backbone. Power spectral density analysis shows that molecular junctions with flexible aliphatic molecules blink, while junctions with rigid aromatic molecules do not., Competing Interests: The authors declare no conflict of interest., (© 2019 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.)

Predictions about the electrical conductance across molecular junctions based on self-assembled monolayers (SAMs) are often made from the SAM precursor properties. Collective electrostatic effects, however, in a densely packed SAM can override these predictions. We studied, experimentally and theoretically, molecular tunneling junctions based on thiolate SAMs with an aromatic biphenyl backbone and variable, highly polarizable halogen termini X (S-(C 6 H 5 ) 2 X; X = H, F, Cl, Br, or I). We found that the halogen-terminated systems show tunneling rates and dielectric behavior that are independent of X despite the large change in the electronegativity of the terminal atom. Using density functional theory, we show that collective electrostatic effects result in modulations of the electrostatic potential that are strongly confined spatially along the direction of charge transport, thereby rendering the role of the halogen atoms insignificant for SAMs with conjugated backbones.

Directional excitation of surface plasmon polaritons (SPPs) by electrical means is important for the integration of plasmonics with molecular electronics or steering signals toward other components. We report electrically driven SPP sources based on quantum mechanical tunneling across molecular double-barrier junctions, where the tunneling pathway is defined by the molecules' chemical structure as well as by their tilt angle with respect to the surface normal. Self-assembled monolayers of S(CH 2 ) n BPh (BPh = biphenyl, n = 1-7) on Au, where the alkyl chain and the BPh units define two distinct tunnel barriers in series, were used to demonstrate and control the geometrical effects. The tilt angle of the BPh unit with respect to the surface normal depends on the value of n, and is 45° when n is even and 23° when n is odd. The tilt angle of the alkyl chain is fixed at 30° and independent of n . For values of n = 1-3, SPPs are directionally launched via directional tunneling through the BPh units. For values of n > 3, tunneling along the alkyl chain dominates the SPP excitation. Molecular level control of directionally launching SPPs is achieved without requiring additional on-chip optical elements, such as antennas, or external elements, such as light sources. Using the molecular tunneling junctions, we provide the first direct experimental demonstration of molecular double-barrier tunneling junctions.

This paper describes how the intensive (tunneling decay coefficient β and rectification ratio R) and extensive (current density J) properties of Ag-S(CH 2 ) n-1 CH 3 //GaO x /EGaIn junctions ( n = 10, 14, 18) and molecular diodes of the form of Ag-S(CH 2 ) 11 Fc//GaO x /EGaIn depend on A geo , the contact area between the self-assembled monolayer and the cone-shaped EGaIn tip. Large junctions with A geo ≥ 1000 μm 2 are unreliable and defects, such as pinholes, dominate the charge transport characteristics. For S(CH 2 ) 11 Fc SAMs, R decreases from 130 to unity with increasing A geo due to an increase in the leakage current (the current flowing across the junction at reverse bias when the diodes block current flow). The value of β decreases from 1.00 ± 0.06 n -1 to 0.70 ± 0.03 n -1 with increasing A geo which also indicates that large junctions suffer from defects. Small junctions with A geo ≤ 300 μm 2 are not stable due to the high surface tension of the bulk EGaIn resulting in unstable EGaIn tips. In addition, the contact area for such small junctions is dominated by the rough tip apex reducing the effective contact area and reproducibility significantly. The contact area of very large junctions is dominated by the relatively smooth side walls of the tips. Our findings show that there is an optimum range for the value of A geo between 300-500 μm 2 where the electrical properties of the junctions are dominated by molecular effects. In this range of A geo , the value of J (defined by I/ A geo where I is the measured current) increases with A geo until it plateaus for junctions with A geo > 1000 μm 2 in agreement with recently reported findings by the Whitesides group. In this regime reproducible measurements of J can be obtained provided A geo is kept constant.