Tuning Overbias Plasmon Energy and Intensity in Molecular Plasmonic Tunneling Junctions by Atomic Polarizability.

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(CH2)12X, 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.

Selective Perchlorate Sensing Using Electrochemical Impedance Spectroscopy with Self-Assembled Monolayers of semiaza-Bambusurils.

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- , H2 PO4 - , HPO4 2- , SO4 2- , NO2 - , NO3 - , or CO3 2- . The resistance performance is 10 to 100 times more efficient than SAMs containing all other tested anions.

Dynamic molecular switches with hysteretic negative differential conductance emulating synaptic behaviour.

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.

CMOS-Compatible Electronic-Plasmonic Transducers Based on Plasmonic Tunnel Junctions and Schottky Diodes.

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-AlOX -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.

The Role of Structural Order in the Mechanism of Charge Transport across Tunnel Junctions with Various Iron-Storing Proteins.

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.

Improving Orientation, Packing Density, and Molecular Arrangement in Self-Assembled Monolayers of Bianchoring Ferrocene-Triazole Derivatives by "Click" Chemistry.

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.

Role of Order in the Mechanism of Charge Transport across Single-Stranded and Double-Stranded DNA Monolayers in Tunnel Junctions.

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.

Electric-field-driven dual-functional molecular switches in tunnel junctions.

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 junctions1. 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 × 104 and resistive on/off ratio of 6.7 × 103, 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.

Geometric control over surface plasmon polariton out-coupling pathways in metal-insulator-metal tunnel 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.

The energy level alignment of the ferrocene-EGaIn interface studied with photoelectron spectroscopy.

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.

Protective Layers Based on Carbon Paint To Yield High-Quality Large-Area Molecular Junctions with Low Contact Resistance.

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.

Directional Excitation of Surface Plasmon Polaritons via Molecular Through-Bond Tunneling across Double-Barrier Tunnel Junctions.

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(CH2)nBPh (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.

Control over Near-Ballistic Electron Transport through Formation of Parallel Pathways in a Single-Molecule Wire.

This paper reports highly efficient coherent tunneling in single-molecule wires of oligo-ferrocenes with one to three Fc units. The Fc units were directly coupled to the electrodes, i.e., without chemical anchoring groups between the Fc units and the terminal electrodes. We found that a single Fc unit readily interacts with the metal electrodes of an STM break junction (STM = scanning tunneling microscope) and that the zero-voltage bias conductance of an individual Fc molecular junction increased 5-fold, up to 80% of the conductance quantum G0 (77.4 µS), when the length of the molecular wire was increased from one to three connected Fc units. Our compendium of experimental evidence combined with nonequilibrium Green function calculations contemplate a plausible scenario to explain the exceedingly high measured conductance based on the electrode/molecule contact via multiple Fc units. The oligo-Fc backbone is initially connected through all Fc units, and, as one of the junction electrodes is pulled away, each Fc unit is sequentially disconnected from one of the junction terminals, resulting in several distinct conductance features proportional to the number of Fc units in the backbone. The conductance values are independent of the applied temperature (-10 to 85 °C), which indicates that the mechanism of charge transport is coherent tunneling for all measured configurations. These measurements show the direct Fc-electrode coupling provides highly efficient molecular conduits with very low barrier for electron tunneling and whose conductivity can be modulated near the ballistic regime through the number of Fc units able to bridge and the energy position of the frontier molecular orbital.

Robust resistive memory devices using solution-processable metal-coordinated azo aromatics.

Non-volatile memories will play a decisive role in the next generation of digital technology. Flash memories are currently the key player in the field, yet they fail to meet the commercial demands of scalability and endurance. Resistive memory devices, and in particular memories based on low-cost, solution-processable and chemically tunable organic materials, are promising alternatives explored by the industry. However, to date, they have been lacking the performance and mechanistic understanding required for commercial translation. Here we report a resistive memory device based on a spin-coated active layer of a transition-metal complex, which shows high reproducibility (∼350 devices), fast switching (≤30 ns), excellent endurance (∼1012 cycles), stability (>106 s) and scalability (down to ∼60 nm2). In situ Raman and ultraviolet-visible spectroscopy alongside spectroelectrochemistry and quantum chemical calculations demonstrate that the redox state of the ligands determines the switching states of the device whereas the counterions control the hysteresis. This insight may accelerate the technological deployment of organic resistive memories.

Corrigendum: Robust resistive memory devices using solution-processable metal-coordinated azo aromatics.

This corrects the article DOI: 10.1038/nmat5009.

Influence of the donor unit on the rectification ratio in tunnel junctions based on donor-acceptor SAMs using PTM units as acceptors.

Dyads formed by an electron donor unit (D) covalently linked to an electron acceptor (A) by an organic bridge are promising materials as molecular rectifiers. Very recently, we have reported the charge transport measurements across self-assembled monolayers (SAMs) of two D-A systems consisting of the ferrocene (Fc) electron-donor linked to a polychlorotriphenylmethane (PTM) electron-acceptor in its non-radical (SAM 1) and radical (SAM 2) forms. Interestingly, we observed that the non-radical SAM 1 showed rectification behavior of 2 orders of magnitude higher than its radical analogue dyad 2. In order to study the influence of the donor unit on the transport properties, we report herein the synthesis and characterization of two new D-A SAMs in which the electron-donor Fc unit is replaced by a tetrathiafulvalene (TTF) moiety linked to the PTM unit in its non-radical (SAM 3) and radical (SAM 4) forms. The observed decrease in the rectification ratio and increased current density for TTF-PTM based SAMs 3 and 4 in comparison to Fc-PTM based SAMs 1 and 2 are explained, supported by theoretical calculations, by significant changes in the electronic and supramolecular structures.

Tuning the Rectification Ratio by Changing the Electronic Nature (Open-Shell and Closed-Shell) in Donor-Acceptor Self-Assembled Monolayers.

This Communication describes the mechanism of charge transport across self-assembled monolayers (SAMs) of two donor-acceptor systems consisting of a polychlorotriphenylmethyl (PTM) electron-acceptor moiety linked to an electron-donor ferrocene (Fc) unit supported by ultraflat template-stripped Au and contacted by a eutectic alloy of gallium and indium top contacts. The electronic and supramolecular structures of these SAMs were well characterized. The PTM unit can be switched between the nonradical and radical forms, which influences the rectification behavior of the junction. Junctions with nonradical units rectify currents via the highest occupied molecular orbital (HOMO) with a rectification ratio R = 99, but junctions with radical units have a new accessible state, a single-unoccupied molecular orbital (SUMO), which turns rectification off and drops R to 6.

Even the Odd Numbers Help: Failure Modes of SAM-Based Tunnel Junctions Probed via Odd-Even Effects Revealed in Synchrotrons and Supercomputers.

This Account describes a body of research in atomic level design, synthesis, physicochemical characterization, and macroscopic electrical testing of molecular devices made from ferrocene-functionalized alkanethiol molecules, which are molecular diodes, with the aim to identify, and resolve, the failure modes that cause leakage currents. The mismatch in size between the ferrocene headgroup and alkane rod makes waxlike highly dynamic self-assembled monolayers (SAMs) on coinage metals that show remarkable atomic-scale sensitivity in their electrical properties. Our results make clear that molecular tunnel junction devices provide an excellent testbed to probe the electronic and supramolecular structures of SAMs on inorganic substrates. Contacting these SAMs to a eutectic "EGaIn" alloy top-electrode, we designed highly stable long-lived molecular switches of the form electrode-SAM-electrode with robust rectification ratios of up to 3 orders of magnitude. The graphic that accompanies this conspectus displays a computed SAM packing structure, illustrating the lollipop shape of the molecules that gives dynamic SAM supramolecular structures and also the molecule-electrode van der Waals (vdW) contacts that must be controlled to form good SAM-based devices. In this Account, we first trace the evolution of SAM-based electronic devices and rationalize their operation using energy level diagrams. We describe the measurement of device properties using near edge X-ray absorption fine structure spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy complemented by molecular dynamics and electronic structure calculations together with large numbers of electrical measurements. We discuss how data obtained from these combined experimental/simulation codesign studies demonstrate control over the supramolecular and electronic structure of the devices, tuning odd-even effects to optimize inherent packing tendencies of the molecules in order to minimize leakage currents in the junctions. It is now possible, but still very costly to create atomically smooth electrodes and we discuss progress toward masking electrode imperfections using cooperative molecule-electrode contacts that are only accessible by dynamic SAM structures. Finally, the unique ability of SAM devices to achieve simultaneously high and atom-sensitive electrical switching is summarized and discussed. While putting these structures to work as real world electronic devices remains very challenging, we speculate on the scientific and technological advances that are required to further improve electronic and supramolecular structure, toward the creation of high yields of long-lived molecular devices with (very) large, reproducible rectification ratios.

Molecular Coatings for Stabilizing Silver and Gold Nanocubes under Electron Beam Irradiation.

We study the degradation process of closely spaced silver and gold nanocubes under high-energy electron beam irradiation using transmission electron microscopy (TEM). The high aspect ratio gaps between silver and gold nanocubes degraded in many cases as a result of protrusion and filament formation during electron beam irradiation. We demonstrate that the molecular coating of the nanoparticles can act as a protective barrier to minimize electron-beam-induced damage on passivated gold and silver nanoparticles.

Supramolecular vs Electronic Structure: The Effect of the Tilt Angle of the Active Group in the Performance of a Molecular Diode.

It is important to understand how the supramolecular structure of molecular junctions affects their performance. Such studies are challenging because it is difficult to separate electronic effects from supramolecular structural effects because both depend on each other. Here we show that by changing the connector group that connects the active component (a ferrocene unit) of a molecular diode to the backbone (an alkyl chain), both the electronic and supramolecular structures of the junctions are modified. The connector group determines the tilt angle of the Fc unit which in turn affects the packing structure of the molecular diodes. In this case, the supramolecular structure dominates over the electronic structure of the molecular diodes, and junctions with loosely packed SAMs result in poorly performing molecular diodes, while stiff, densely packed SAMs result in well-performing molecular diodes.