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Charge states of atoms can be investigated with scanning tunneling microscopy, but this method requires a conducting substrate. We investigated the charge-switching of individual adsorbed gold and silver atoms (adatoms) on ultrathin NaCl films on Cu(111) using a qPlus tuning fork atomic force microscope (AFM) operated at 5 kelvin with oscillation amplitudes in the subangstrom regime. Charging of a gold atom by one electron charge increases the force on the AFM tip by a few piconewtons. Moreover, the local contact potential difference is shifted depending on the sign of the charge and allows the discrimination of positively charged, neutral, and negatively charged atoms. The combination of single-electron charge sensitivity and atomic lateral resolution should foster investigations of molecular electronics, photonics, catalysis, and solar photoconversion.

Conduction electrons interact with lattice vibrations, leading to coupled electron-phonon states. This effect is of fundamental importance in understanding electron transport and energy relaxation in nanoscale systems. We report quantitative results on the electron-phonon coupling strength in CdSe quantum dots (QDs) and rods, obtained by low-temperature scanning tunneling microscopy. We resolve the polaron eigenstates arising from coupling of the electrons to longitudinal optical phonons. The electron-phonon coupling strength is dependent on the electron orbital symmetry, the number of added electrons, and the size and dielectric environment of the QD.

We use scanning tunnelling microscopy (STM) to controllably contact individual CdSe quantum dots (QDs) in a multilayer array to study electrical contacts to a model QD solid. The probability of electron injection into the QD array depends strongly on the symmetry of the QD wave functions and their response to the local electric field. Quantitative spectroscopy of the QD energy levels is possible if the potential distribution in the STM tip-QD array-substrate system is taken into account.

Metal nanoparticles coated with an organic monolayer, so-called monolayer protected clusters (MPCs), can show quantised charging at room temperature due to their sub-attofarad capacitance arising from the core size and the nature of the protecting monolayer. In this tutorial review, we examine the factors affecting the energetics of MPC charging. In the first section, the underlying physics of quantised charging is outlined and we give an overview of the various methods that can be used to measure single electron transfer to nanoparticles. In the subsequent sections, we discuss how electrochemical measurements can be used to give information on the quantised charging of freely diffusing and films of immobilised MPCs. The predictions of models used to determine MPC capacitance are compared with experimental data from the literature.

A synthesis strategy to obtain monodisperse hexanethiolate-protected Au38 clusters based on their resistance to etching upon exposure to a hyperexcess of thiol is reported. The reduction time in the standard Brust-Schiffrin two-phase synthesis was optimized such that Au38 were the only clusters that were fully passivated by the thiol monolayer which leaves larger particles vulnerable to etching by excess thiol. The isolated Au38 was characterized by mass spectrometry, thermogravimetric analysis, optical spectroscopy, and electrochemical techniques giving Au38(SC6)22 as the molecular formula for the cluster. These ultrasmall Au clusters behave analogously to molecules with a wide energy gap between occupied (HOMO) and unoccupied levels (LUMO) and undergo single-electron charging at room temperature in electrochemical experiments. Electrochemistry provides an elegant means to study the electronic structure and the chemical stability of the clusters at different charge states. We used cyclic voltammetry and scanning electrochemical microscopy to unequivocally demonstrate that Au38 can be reversibly oxidized to charge states z = +1 or +2; however, reduction to z = -1 leads to desorption of the protecting thiolate monolayer. Although this reductive desorption of thiol from the cluster surface is superficially analogous to electrochemical desorption of planar self-assembled monolayers (SAMs) from macroscopic electrodes, the molecular details of the process are likely to be complicated based on the current view that the thiolate monolayer in clusters is in fact composed of polymeric Au-S complexes.

The electronic local density of states (LDOS) of single PbSe quantum dots (QDs) and QD molecules is explored using low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS). Both individual PbSe QDs and molecular aggregates of PbSe QDs (dimers, trimers, etc.) are mechanically stabilized in a two-dimensional superlattice of wide band gap CdSe QDs acting as an inert matrix. The LDOS measured at individual QDs dispersed in the matrix is identical to that of single isolated QDs chemically linked to a substrate. We investigate the degree of quantum mechanical coupling between the PbSe QDs in molecular aggregates by comparing the LDOS measured at each site in the aggregates to that of an individual PbSe QD. We observe a variable broadening of the resonances indicating a spatially dependent degree of electron delocalization in the molecular aggregates.

The bistability in the position of the two hydrogen atoms in the inner cavity of single free-base naphthalocyanine molecules constitutes a two-level system that was manipulated and probed by low-temperature scanning tunneling microscopy. When adsorbed on an ultrathin insulating film, the molecules can be switched in a controlled fashion between the two states by excitation induced by the inelastic tunneling current. The tautomerization reaction can be probed by resonant tunneling through the molecule and is expressed as considerable changes in the conductivity of the molecule. We also demonstrated a coupling of the switching process so that the charge injection in one molecule induced tautomerization in an adjacent molecule.

Molecules, supramolecular structures and semiconductor nanocrystals are increasingly used as the active components in prototype opto-electrical devices with miniaturized dimensions and novel functions. Therefore, there is a strong need to measure the electronic structure of such single, individual nano-objects. Here, we explore the potential of scanning tunnelling spectroscopy to obtain quantitative information on the energy levels and Coulomb interactions of semiconductor quantum dots. We discuss the conditions under which shell-tunnelling, shell-filling and bipolar spectroscopy can be performed, and illustrate this with spectra acquired on individual CdSe and PbSe quantum dots. We conclude that quantitative information on the energy levels and Coulomb interactions can be obtained if the physics of the tip/quantum dot/substrate double-barrier tunnel junction is well understood.

The optoelectronic properties of semiconductor quantum-dot (QD) solids depend on the electronic structure of the building blocks and their interactions. Disorder may affect the coupling on a local scale. We have measured the density of states of 2D arrays of PbSe QDs site by site using scanning tunneling spectroscopy. It markedly differs from that of isolated QDs due to electronic coupling in the array. We observe strong local variations in the coupling strength with two prototypical cases: delocalization of the conduction electrons only, and full coupling with both hole and electron delocalization over the QD sites in the array.

Stable dispersions of molecularlike aggregates of CdTe quantum dots are prepared by chemical cross-linking. Cryo-TEM images confirm the presence of cross-linked quantum dots and show that the size of the small aggregates can be controlled by the amount of cross-linker added. Optical measurements reveal two types of interdot interactions within these quantum-dot molecules: exciton energy transfer and electronic coupling. Quantitative information on the energy transfer rates in quantum-dot molecules is obtained by photoluminescence lifetime measurements. The degree of electronic coupling is dependent on the size of the quantum dots, which is supported by quantum mechanical calculations.

The kinetics of electron transfer between individual gold nanocrystals and a solution redox species is quantified. The observed rate is dependent on the extent of electronic coupling between nanocrystals in the monolayer indicating the effect of Coulomb blockade on electrochemical kinetics.

The quintessence of the hot-injection method, a synthesis route for monodisperse, highly luminescent semiconductor nanocrystals, is reviewed. The separate stages of nucleation and growth of the nanocrystals are discussed in the framework of classical nucleation theory and an equilibrium model proposed by Debye. We also review the numerous adaptations of the original synthesis that currently provide colloidal nanocrystals with well-defined, size-dependent optical, electrical, and magnetic properties. The availability of these remarkable materials is one of the most promising developments in nanoscience and nanotechnology.

A novel channel flow configuration was developed and utilized for studying the poly(styrenesulfonate)-cetylpyridinium ion interaction kinetics. The surfactant solution was continuously injected into a flow of polyelectrolyte solution, and the extent of the association reaction was probed at an ion-selective detector electrode. The system was modeled within an analytical approximation, which was tested by a finite-element simulation of the full convective mass transport problem including the homogeneous complexation reaction. The results show that association kinetics can be resolved and that the initial steps of the reaction are not influenced by intermolecular interactions between the bound surfactants. The presented methodology is general, and further development should enable the study of complex cooperative kinetics of surfactant-polyelectrolyte systems.

The density-of-states function of individual colloidal PbSe nanocrystals varying in diameter between 3 and 7 nm is measured by resonant tunneling spectroscopy. It is in semiquantitative agreement with tight-binding calculations, but the energy separation between electron (hole) levels of S and P symmetry is systematically smaller than predicted by the theory. These results provide an explanation for the second and third excitonic optical transitions, which have been debated for a long time.

The Ti/TiO2/Au junction forms the basis of a promising new type of photovoltaic cell, provided that a light-harvesting antenna layer can be deposited on the thin gold film. We report that the electrical diode characteristics of the TiO2/Au Schottky barrier deteriorate by deposition of a hydrophobic quantum dot film, Merbromin dye adsorption, or electron-hole photogeneration in TiO2 under inert conditions. In the presence of oxygen and water vapor, the Schottky barrier characteristics and high photovoltage are recovered. The strong influence of the TiO2 surface chemistry on the (photo)electrical characteristics of the solar cell is discussed on the basis of an existing microscopic model.

This article reports the use of the scanning electrochemical microscope (SECM) to investigate the electronic properties of Langmuir monolayers of alkane thiol protected gold nanocrystals (NCs). A substantial increase in monolayer conductivity upon mechanical compression of the Au NC monolayer is reported for the first time. This may be the room temperature signature of the insulator to metal transition previously reported for comparable silver NC monolayers. Factors influencing the conductivity of the monolayer NC array are discussed.

A new modification of the channel flow dissolution method is introduced together with the theoretical basis to extract the solubility and mass transfer parameters from the dissolution experiments. Correlation of drug dissolution profiles in the channel flow apparatus was evaluated with respect to USP basket and intrinsic dissolution methods at pH 1.2 or 6.8. Acetylsalicylic acid (ASA) was studied as a pure drug substance and as three simple tablet compositions with microcrystalline cellulose (MCC) and/or lactose as excipients. The channel flow measurements of 100% ASA tablets correlated well with the results of intrinsic dissolution tests. In the channel flow method as well as in the USP basket method the release of ASA was fastest from the tablet compositions containing lactose, while the slowest dissolution rate was observed with the composition containing MCC as the only excipient. As presumed, the dissolution rate of the weak acid was decreased as the pH of the medium was lowered, which was clearly confirmed also by the three dissolution methods. MCC forms matrix tablets and in the USP basket method the dissolution profiles followed square root of time kinetics indicating that diffusion was the rate-controlling step of ASA dissolution. Also the channel flow results indicated that the dissolution of ASA was controlled by mass transfer. The swelling behaviour of the tablets is different in the channel flow method as compared to the basket method: only one tablet surface is exposed to the dissolution medium in the channel flow system. The contact between the tablet surface and the dissolution medium is more similar between the channel flow and intrinsic dissolution methods.

The first observation of 15 voltammetric quantized charging peaks for a solution of hexanethiol-capped gold nanoparticles (so-called monolayer protected clusters MPCs) at room temperature is reported where the variation in peak spacing with increasing charge stored in the metal core is discussed in terms of MPC capacitance.

Solutions of monodisperse monolayer-protected clusters (MPCs) of gold can be used as multivalent redox mediators in electrochemical experiments due to their quantized double-layer charging properties. We demonstrate their use in scanning electrochemical microscopy (SECM) experiments wherein the species of interest (up to 2-electron reduction or 4-electron oxidation from the native charge-state of the MPCs) is generated at the tip electrode, providing a simple means to adjust the driving force of the electron transfer (ET). Approach curves to perfectly insulating (Teflon) and conducting (Pt) substrates are obtained. Subsequently, heterogeneous ET between MPCs in 1,2-dichloroethane and an aqueous redox couple (Ce(IV), Fe(CN)63-/4-, Ru(NH3)63+, and Ru(CN)64-) is probed with both feedback and potentiometric mode of SECM operation. Depending on the charge-state of the MPCs, they can accept/donate charge heterogeneously at the liquid-liquid interface. However, this reaction is very slow in contrast to ET involving MPCs at the metal-electrolyte interface.

The potential of ring-disk ultramicroelectrodes (RD UMEs) as probes for scanning electrochemical microscopy (SECM) was investigated both theoretically and experimentally. In particular, the disk-generation/ring-collection (DG/RC) mode of operation was considered. In this case, the interaction of two species with the substrate under investigation can be followed simultaneously from single tip current-distance measurement (approach curve) to the substrate. Theoretical approach curves for DG/RC were calculated by numerical methods. Such approach curves to both insulating and conducting substrates indicate a strong tip response dependence on the ring radius while the response was relatively insensitive to ring thickness and overall tip radius. The RD tip was characterized by fitting experimental approach curves recorded at insulating and conducting substrates to simulated curves for a given tip geometry. DG/RC SECM was then applied to investigate the partitioning of iodine across a liquid-liquid interface.