Nanoscale electrochemical kinetics & dynamics: the challenges and opportunities of single-entity measurements.

The development of nanoscale electrochemistry since the mid-1980s has been predominately coupled with steady-state voltammetric (i-E) methods. This research has been driven by the desire to understand the mechanisms of very fast electrochemical reactions, by electroanalytical measurements in small volumes and unusual media, including in vivo measurements, and by research on correlating electrocatalytic activity, e.g., O2 reduction reaction, with nanoparticle size and structure. Exploration of the behavior of nanoelectrochemical structures (nanoelectrodes, nanoparticles, nanogap cells, etc.) of a characteristic dimension λ using steady-state i-E methods generally relies on the well-known relationship, λ2 ∼ Dt, which relates diffusional lengths to time, t, through the coefficient, D. Decreasing λ, by performing measurements at a nanometric length scales, results in a decrease in the effective timescale of the measurement, and provides a direct means to probe the kinetics of steps associated with very rapid electrochemical reactions. For instance, steady-state voltammetry using a nanogap twin-electrode cell of characteristic width, λ ∼ 10 nm, allows investigations of events occurring at timescales on the order of ∼100 ns. Among many other advantages, decreasing λ also increases spatial resolution in electrochemical imaging, e.g., in scanning electrochemical microscopy, and allows probing of the electric double layer. This Introductory Lecture traces the evolution and driving forces behind the "λ2 ∼ Dt" steady-state approach to nanoscale electrochemistry, beginning in the late 1950s with the introduction of the rotating ring-disk electrode and twin-electrode thin-layer cells, and evolving to current-day investigations using nanoelectrodes, scanning nanocells for imaging, nanopores, and nanoparticles. The recent focus on so-called "single-entity" electrochemistry, in which individual and very short redox events are probed, is a significant departure from the steady-state approach, but provides new opportunities to probe reaction dynamics. The stochastic nature of very fast single-entity events challenges current electrochemical methods and modern electronics, as illustrated using recent experiments from the authors' laboratory.

Spatially Resolved Imaging on Photocarrier Generations and Band Alignments at Perovskite/PbI2 Heterointerfaces of Perovskite Solar Cells by Light-Modulated Scanning Tunneling Microscopy.

The presence of the PbI2 passivation layers at perovskite crystal grains has been found to considerably affect the charge carrier transport behaviors and device performance of perovskite solar cells. This work demonstrates the application of a novel light-modulated scanning tunneling microscopy (LM-STM) technique to reveal the interfacial electronic structures at the heterointerfaces between CH3NH3PbI3 perovskite crystals and PbI2 passivation layers of individual perovskite grains under light illumination. Most importantly, this technique enabled the first observation of spatially resolved mapping images of photoinduced interfacial band bending of valence bands and conduction bands and the photogenerated electron and hole carriers at the heterointerfaces of perovskite crystal grains. By systematically exploring the interfacial electronic structures of individual perovskite grains, enhanced charge separation and reduced back recombination were observed when an optimal design of interfacial PbI2 passivation layers consisting of a thickness less than 20 nm at perovskite crystal grains was applied.

Highly Sensitive Electrical Detection of HIV-1 Virus Based on Scanning Tunneling Microscopy.

A highly sensitive immunosensor based on scanning tunneling microscopy (STM) was developed for the first time to detect living material such as HIV-1 virus by gold (Au) nanoparticle and fragmented antibody complex. Fragmented antibodies were pre-immobilized on the Au surface, then HIV-1 virus like particles (HIV-1 VLPs) and Au-nanoparticle and fragmented antibody complexes were applied to develop sandwich assay. The developed surface morphology and the current profile of fabricated immunosensing element were characterized by Raman spectroscopy and investigated with STM. The power spectrum derived from the current profile was found to be related with concentrations of HIV-1 VLPs. Using the electrical detection method based on current mapping profile of STM, living material such as virus, HIV-1 VLPs, was able to be detected successfully. The proposed technique can be a promising method to construct the highly sensitive and efficient sensor for detecting viruses and other living materials.

Fabrication of Gate-tunable Graphene Devices for Scanning Tunneling Microscopy Studies with Coulomb Impurities.

Owing to its relativistic low-energy charge carriers, the interaction between graphene and various impurities leads to a wealth of new physics and degrees of freedom to control electronic devices. In particular, the behavior of graphene's charge carriers in response to potentials from charged Coulomb impurities is predicted to differ significantly from that of most materials. Scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) can provide detailed information on both the spatial and energy dependence of graphene's electronic structure in the presence of a charged impurity. The design of a hybrid impurity-graphene device, fabricated using controlled deposition of impurities onto a back-gated graphene surface, has enabled several novel methods for controllably tuning graphene's electronic properties. Electrostatic gating enables control of the charge carrier density in graphene and the ability to reversibly tune the charge and/or molecular states of an impurity. This paper outlines the process of fabricating a gate-tunable graphene device decorated with individual Coulomb impurities for combined STM/STS studies. These studies provide valuable insights into the underlying physics, as well as signposts for designing hybrid graphene devices.

The Scanning TMR Microscope for Biosensor Applications.

We present a novel tunnel magnetoresistance (TMR) scanning microscope set-up capable of quantitatively imaging the magnetic stray field patterns of micron-sized elements in 3D. By incorporating an Anderson loop measurement circuit for impedance matching, we are able to detect magnetoresistance changes of as little as 0.006%/Oe. By 3D rastering a mounted TMR sensor over our magnetic barcodes, we are able to characterize the complex domain structures by displaying the real component, the amplitude and the phase of the sensor's impedance. The modular design, incorporating a TMR sensor with an optical microscope, renders this set-up a versatile platform for studying and imaging immobilised magnetic carriers and barcodes currently employed in biosensor platforms, magnetotactic bacteria and other complex magnetic domain structures of micron-sized entities. The quantitative nature of the instrument and its ability to produce vector maps of magnetic stray fields has the potential to provide significant advantages over other commonly used scanning magnetometry techniques.

Fixed-gap tunnel junction for reading DNA nucleotides.

Previous measurements of the electronic conductance of DNA nucleotides or amino acids have used tunnel junctions in which the gap is mechanically adjusted, such as scanning tunneling microscopes or mechanically controllable break junctions. Fixed-junction devices have, at best, detected the passage of whole DNA molecules without yielding chemical information. Here, we report on a layered tunnel junction in which the tunnel gap is defined by a dielectric layer, deposited by atomic layer deposition. Reactive ion etching is used to drill a hole through the layers so that the tunnel junction can be exposed to molecules in solution. When the metal electrodes are functionalized with recognition molecules that capture DNA nucleotides via hydrogen bonds, the identities of the individual nucleotides are revealed by characteristic features of the fluctuating tunnel current associated with single-molecule binding events.

Dynamic behavior of tuning fork shear-force structures in a SNOM system.

Piezoelectric tuning fork shear-force structures are widely used as a distance control unit in a scanning near-field optical microscopy. However, the complex dynamic behavior among the micro-tuning forks (TFs), optical fiber probes, and the probe-surface interactions is still a crucial issue to achieve high-resolution imaging or near-field interaction inspections. Based on nonlinear beam tension-bending vibration theory, vibration equations in both longitudinal and lateral directions have been established when the TF structure and the optical fiber are treated as deformable structures. The relationship of the probe-surface interaction induced by Van der Waals force has been analyzed and the corresponding numerical results used to describe the vibrational behavior of the probe approaching the sample surface are obtained. Meanwhile, the viscous resistance of the liquid film on the sample surface has also been investigated using linear beam-bending vibration theory. Experiments testing the interaction between the probe and the water film on a single crystal silicon wafer have been carried out and the viscous resistance of the water film was estimated using the established equations. Finally, to use the TF-probe structure as a force sensor, the relation between the dynamic response of the TF-probe system and an external force on the probe tip was obtained.

Mapping image potential states on graphene quantum dots.

Free-electron-like image potential states are observed in scanning tunneling spectroscopy on graphene quantum dots on Ir(111) acting as potential wells. The spectrum strongly depends on the size of the nanostructure as well as on the spatial position on top, indicating lateral confinement. Analysis of the substructure of the first state by the spatial mapping of the constant energy local density of states reveals characteristic patterns of confined states. The most pronounced state is not the ground state, but an excited state with a favorable combination of the local density of states and parallel momentum transfer in the tunneling process. Chemical gating tunes the confining potential by changing the local work function. Our experimental determination of this work function allows us to deduce the associated shift of the Dirac point.

Design of a scanning gate microscope for mesoscopic electron systems in a cryogen-free dilution refrigerator.

We report on our design of a scanning gate microscope housed in a cryogen-free dilution refrigerator with a base temperature of 15 mK. The recent increase in efficiency of pulse tube cryocoolers has made cryogen-free systems popular in recent years. However, this new style of cryostat presents challenges for performing scanning probe measurements, mainly as a result of the vibrations introduced by the cryocooler. We demonstrate scanning with root-mean-square vibrations of 0.8 nm at 3 K and 2.1 nm at 15 mK in a 1 kHz bandwidth with our design. Using Coulomb blockade thermometry on a GaAs/AlGaAs gate-defined quantum dot, we demonstrate an electron temperature of 45 mK.

Modulation of nanocavity plasmonic emission by local molecular states of C60 on Au(111).

We investigate the modulation of C60 monolayers on the nanocavity plasmonic (NCP) emission on Au(111) by tunneling electron excitation from a scanning tunneling microscope (STM) tip. STM induced luminescence spectra show not only suppressed emission, but also significant redshift of NCP emission bands on the C60 molecules relative to the bare metal surface. The redshift, together with the bias- and coverage-dependent emission feature, indicates that the C60 molecules act beyond a pure dielectric spacer, their electronic states are heavily involved in the inelastic tunneling process for plasmonic emission. A modified quantum cutoff relation is proposed to explain qualitatively the observed emission feature at both bias polarities. We also demonstrate molecularly resolved optical contrast on the C60 monolayer and discuss the contrast mechanism briefly.

Measuring the elastic properties of living cells through the analysis of current-displacement curves in scanning ion conductance microscopy.

Knowledge of mechanical properties of living cells is essential to understand their physiological and pathological conditions. To measure local cellular elasticity, scanning probe techniques have been increasingly employed. In particular, non-contact scanning ion conductance microscopy (SICM) has been used for this purpose; thanks to the application of a hydrostatic pressure via the SICM pipette. However, the measurement of sample deformations induced by weak pressures at a short distance has not yet been carried out. A direct quantification of the applied pressure has not been also achieved up to now. These two issues are highly relevant, especially when one addresses the investigation of thin cell regions. In this paper, we present an approach to solve these problems based on the use of a setup integrating SICM, atomic force microscopy, and optical microscopy. In particular, we describe how we can directly image the pipette aperture in situ. Additionally, we can measure the force induced by a constant hydrostatic pressure applied via the pipette over the entire probe-sample distance range from a remote point to contact. Then, we demonstrate that the sample deformation induced by an external pressure applied to the pipette can be indirectly and reliably evaluated from the analysis of the current-displacement curves. This method allows us to measure the linear relationship between indentation and applied pressure on uniformly deformable elastomers of known Young's modulus. Finally, we apply the method to murine fibroblasts and we show that it is sensitive to local and temporally induced variations of the cell surface elasticity.

Electrochemical scanning tunneling microscopy.

The electrochemical scanning tunneling microscope was the first tool for the investigation of solid-liquid interfaces that allowed in situ real space imaging of electrode surfaces at the atomic level. Therefore it quickly became an important addition to the repertoire of methods for the determination of the local surface structure as well as the dynamics of reactions and processes taking place at surfaces in an electrolytic environment. In this short overview we present several examples to illustrate the powerful capabilities of the EC-STM, including the observation of clean metal surfaces as well as the adsorption of thin metal layers, specifically adsorbed anions and non-specifically adsorbed organic cations. In several cases the electrode potential has a significant influence on structure and reactivity of the surface that can be explained by the observations made with the EC-STM.

Insulated gold scanning tunneling microscopy probes for recognition tunneling in an aqueous environment.

Chemically functionalized probes are required for tunneling measurements made via chemical contacts ("Recognition Tunneling"). Here, we describe the etching of gold STM probes suitable for chemical functionalization with moieties bearing thiol groups. Insulated with high density polyethylene, these probes may be used in aqueous electrolytes with sub pA leakage currents. The area of the exposed probe surface was characterized via the saturation current in an electroactive solution (0.1 M K(3)Fe(CN)(6)). Twenty five percent of the probes had an exposed region of 10 nm radius or less.

Electron-induced dynamics of heptathioether ß-cyclodextrin molecules.

Variable-temperature scanning tunneling microscopy (STM) and spectroscopy (STS) measurements are performed on heptathioether ß-cyclodextrin (ß-CD) self-assembled monolayers (SAMs) on Au. The ß-CD molecules exhibit very rich dynamical behavior, which is not apparent in ensemble-averaged studies. The dynamics are reflected in the tunneling current-time traces, which are recorded with the STM feedback loop disabled. The dynamics are temperature independent, but increase with increasing tunneling current and sample bias, thus indicating that the conformational changes of the ß-CD molecules are induced by electrons that tunnel inelastically. Even for sample biases as low as 10 mV, well-defined levels are observed in the tunneling current-time traces. These jumps are attributed to the excitations of the molecular vibration of the macrocyclic ß-CD molecule. The results are of great importance for a proper understanding of transport measurements in SAMs.

Electrical conduction of organic ultrathin films evaluated by an independently driven double-tip scanning tunneling microscope.

The electrical transport properties of organic thin films within the micrometer scale have been evaluated by a laboratory-built independently driven double-tip scanning tunneling microscope, operating under ambient conditions. The two tips were used as point contact electrodes, and current in the range from 0.1 pA to 100 nA flowing between the two tips through the material can be detected. We demonstrated two-dimensional contour mapping of the electrical resistance on a poly(3-octylthiophene) thin films as shown below. The obtained contour map clearly provided an image of two-dimensional electrical conductance between two point electrodes on the poly(3-octylthiophene) thin film. The conductivity of the thin film was estimated to be (1-8) × 10(-6) S cm(-1). Future prospects and the desired development of multiprobe STMs are also discussed.

Optical modulation of molecular conductance.

A novel scanning probe microscope stage permits break junction measurements of single molecule conductance while the molecules are illuminated with visible light. We studied a porphyrin-fullerene dyad molecule designed to form a charge separated state on illumination. A significant fraction of illuminated molecules become more conductive, returning to a lower conductance in the dark, suggesting the formation of a long-lived charge separated state on the indium-tin oxide surface. Transient absorption spectra of these molecular layers are consistent with formation of a long-lived charge separated state, a finding with implications for the design of molecular photovoltaic devices.

MEMS-based high speed scanning probe microscopy.

The high speed performance of a scanning probe microscope (SPM) is improved if a microelectromechanical systems (MEMS) device is employed for the out-of-plane scanning motion. We have carried out experiments with MEMS high-speed z-scanners (189 kHz fundamental resonance frequency) in both atomic force microscope and scanning tunneling microscope modes. The experiments show that with the current MEMS z-scanner, lateral tip speeds of 5 mm/s can be achieved with full feedback on surfaces with significant roughness. The improvement in scan speed, obtained with MEMS scanners, increases the possibilities for SPM observations of dynamic processes. Even higher speed MEMS scanners with fundamental resonance frequencies in excess of a megahertz are currently under development.

Characterization of the electrical and optical properties of viologen devices using chlorophyll a as an electron excimer.

This paper uses self-assembled monolayers (SAMs) on an Au(111) substrate to detect the unique characteristics of viologen molecules using scanning tunneling microscopy (STM), and reports the orientation and surface changes of molecules at the nano level in real-time. In particular, the rectification characteristics of the viologen molecule were observed at the molecular level using scanning tunneling spectroscopy (STS). After verifying the rectification characteristics of viologen molecules, an experiment was carried out to demonstrate the possibility of applying viologen to photodiodes and switching devices by forming a thin film of chlorophyll a on the viologen SAMs using the Langmuir-Blodgett (LB) method. This material mimics the photoinduced electron transport phenomenon in the early stage of photosynthesis in living plants. This study demonstrates the applicability of viologen to bioelectronic photodiodes and switching devices based on photo effects by observing the topography, current sensing, and current-voltage (I-V) characteristics using current-sensing atomic force microscopy (CS-AFM) by introducing light to the AFM-tip/chlorophyll a/viologen/Au(111) substrate structure.