Molecular-scale in-operando reconfigurable electronic hardware.

It is challenging to reconfigure devices at molecular length scales. Here we report molecular junctions based on molecular switches that toggle stably and reliably between multiple operations to reconfigure electronic devices at molecular length scales. Rather than static on/off switches that always revert to the same state, our voltage-driven molecular device dynamically switches between high and low conduction states during six consecutive proton-coupled electron transfer steps.

Molecular switching by proton-coupled electron transport drives giant negative differential resistance.

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.

Supramolecular tunnelling junctions with robust high rectification based on assembly effects.

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 () 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, HSCFc-CC-Fc ( = 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 (), the associated maximum (), and the bias at which the is achieved ().

Gradual Change between Coherent and Incoherent Tunneling Regimes Induced by Polarizable Halide Substituents in Molecular Tunnel Junctions.

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)OPhX, X = F, Cl, Br, or I; = 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 = 0 (associated with coherent tunneling) to 257 meV for = 5 with X = Br (associated with incoherent tunneling). Interestingly, this increase in incoherent tunneling rate with polarizability resulted in an improved molecular diode performance.

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.

Upconversion electroluminescence in 2D semiconductors integrated with plasmonic tunnel junctions.

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.

Engineering the Outcoupling Pathways in Plasmonic Tunnel Junctions via Photonic Mode Dispersion for Low-Loss Waveguiding.

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.

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) 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.

Extreme long-lifetime self-assembled monolayer for air-stable molecular junctions.

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.

High performance mechano-optoelectronic molecular switch.

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.

A Method to Investigate the Mechanism of Charge Transport Across Bio-Molecular Junctions with Ferritin.

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 floating on its surface giving this material non-Newtonian properties allowing it to be shaped in to cone-shaped tips or stabilized in microchannels.

Plasmonic phenomena in molecular junctions: principles and applications.

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.

Charge Transport across Proteins inside Proteins: Tunneling across Encapsulin Protein Cages and the Effect of Cargo Proteins.

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.

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.

Temperature-Dependent Coherent Tunneling across Graphene-Ferritin Biomolecular Junctions.

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.

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.

AFM Manipulation of EGaIn Microdroplets to Generate Controlled, On-Demand Contacts on Molecular Self-Assembled Monolayers.

Liquid metal droplets, such as eutectic gallium-indium (EGaIn), are important in many research areas, such as soft electronics, catalysis, and energy storage. Droplet contact on solid surfaces is typically achieved without control over the applied force and without optimizing the wetting properties in different environments (e.g.

Smart Eutectic Gallium-Indium: From Properties to Applications.

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.

Verification and Temperature-Dependent Rectification by HBQ, the Smallest Unimolecular Donor-Acceptor Rectifier.

Five years ago, rectification of electrical current was found in 4'-bromo-3,4-dicyano-2',5'-dimethoxy-[1,1'-biphenyl]-2,5-dione (), a hemibiquinone (which we will call either or HBQ) that has a very small working length (1.1 nm). Monolayers of HBQ on Au were detected by "nanodozing" atomic force microscopy (AFM) and were contacted with two types of top electrodes: either cold Au or eutectic Ga-In.

Phase Matching via Plasmonic Modal Dispersion for Third Harmonic Generation.

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.

Interplay between Interfacial Energy, Contact Mechanics, and Capillary Forces in EGaIn Droplets.

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 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.

Stable Universal 1- and 2-Input Single-Molecule Logic Gates.

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 ) -Fc-(CH ) -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 ) and gate (V ) voltages. Reliable and low-voltage (ǀV ǀ ≤ 80 mV, ǀV 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.

Biomolecular control over local gating in bilayer graphene induced by ferritin.

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.

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.