An Integrated, Exchangeable Three-Electrode Electrochemical Setup for AFM-Based Scanning Electrochemical Microscopy.

Scanning electrochemical microscopy (SECM) is a versatile scanning probe technique that allows monitoring of a plethora of electrochemical reactions on a highly resolved local scale. SECM in combination with atomic force microscopy (AFM) is particularly well suited to acquire electrochemical data correlated to sample topography, elasticity, and adhesion, respectively. The resolution achievable in SECM depends critically on the properties of the probe acting as an electrochemical sensor, i.e., the working electrode, which is scanned over the sample. Hence, the development of SECM probes received much attention in recent years. However, for the operation and performance of SECM, the fluid cell and the three-electrode setup are also of paramount importance. These two aspects received much less attention so far. Here, we present a novel approach to the universal implementation of a three-electrode setup for SECM in practically any fluid cell. The integration of all three electrodes (working, counter, and reference) near the cantilever provides many advantages, such as the usage of conventional AFM fluid cells also for SECM or enables the measurement in liquid drops. Moreover, the other electrodes become easily exchangeable as they are combined with the cantilever substrate. Thereby, the handling is improved significantly. We demonstrated that high-resolution SECM, i.e., resolving features smaller than 250 nm in the electrochemical signal, could be achieved with the new setup and that the electrochemical performance was equivalent to the one obtained with macroscopic electrodes.

Atomic force microscopy with nanoelectrode tips for high resolution electrochemical, nanoadhesion and nanoelectrical imaging.

Multimodal nano-imaging in electrochemical environments is important across many areas of science and technology. Here, scanning electrochemical microscopy (SECM) using an atomic force microscope (AFM) platform with a nanoelectrode probe is reported. In combination with PeakForce tapping AFM mode, the simultaneous characterization of surface topography, quantitative nanomechanics, nanoelectronic properties, and electrochemical activity is demonstrated. The nanoelectrode probe is coated with dielectric materials and has an exposed conical Pt tip apex of ∼200 nm in height and of ∼25 nm in end-tip radius. These characteristic dimensions permit sub-100 nm spatial resolution for electrochemical imaging. With this nanoelectrode probe we have extended AFM-based nanoelectrical measurements to liquid environments. Experimental data and numerical simulations are used to understand the response of the nanoelectrode probe. With PeakForce SECM, we successfully characterized a surface defect on a highly-oriented pyrolytic graphite electrode showing correlated topographical, electrochemical and nanomechanical information at the highest AFM-SECM resolution. The SECM nanoelectrode also enabled the measurement of heterogeneous electrical conductivity of electrode surfaces in liquid. These studies extend the basic understanding of heterogeneity on graphite/graphene surfaces for electrochemical applications.

Controlled Exfoliation of Layered Silicate Heterostructures into Bilayers and Their Conversion into Giant Janus Platelets.

Ordered heterostructures of layered materials where interlayers with different reactivities strictly alternate in stacks offer predetermined slippage planes that provide a precise route for the preparation of bilayer materials. We use this route for the synthesis of a novel type of reinforced layered silicate bilayer that is 15 % stiffer than the corresponding monolayer. Furthermore, we will demonstrate that triggering cleavage of bilayers by osmotic swelling gives access to a generic toolbox for an asymmetrical modification of the two vis-à-vis standing basal planes of monolayers. Only two simple steps applying arbitrary commercial polycations are needed to obtain such Janus-type monolayers. The generic synthesis route will be applicable to many other layered compounds capable of osmotic swelling, rendering this approach interesting for a variety of materials and applications.

Stability of Charge Distributions in Electret Films on the nm-Scale.

Electret materials find use in various applications, such as microphones or filter media. In recent years, electrets have been used also increasingly on the micrometer scale, for example, in MEMS or for nano-xerography. However, for these applications, it becomes more important to prepare defined charge structures with sub-micrometer features. On the macroscopic level, the technique of isothermal potential decay at elevated temperatures has been developed to study aging effects and charge retention capabilities in electret materials. Here, we extend this technique to the nm-level by means of AFM-based methods, such as contact charging by AFM and the Kelvin probe force microscopy. Defined charge distributions in polyetherimide (PEI) ULTEM 1000 thin-film electrets have been studied for the first time with a high lateral resolution on the nanometer scale. We found a linear correlation between externally applied contact charging potential on the AFM-tip and the resulting relative surface potential on the PEI film. Charge decay at elevated temperatures is independent from the length scale. The same time dependence as for macroscopic, homogenously charged films could be established. We observe a potential decay only at an elevated temperature of 120 °C and no significant lateral charge transport. Thus, we propose a thermally enhanced charge carrier release from surface traps and a subsequent charge migration to the back electrode as the dominant mechanism. This finding is in-line with the observation that potential decay can be reduced also on the nm-level by pre-annealing the film slightly below the glass transition temperature. In contrast to many polymeric or inorganic electrets, no lateral charge migration is observed. Therefore, the charge patterns are preserved for PEI ULTEM 1000 thin-film electrets, which makes it a good candidate as electret for applications in MEMS or similar applications.

Functionalized DNA-spider silk nanohydrogels for controlled protein binding and release.

Hydrogels are excellent scaffolds to accommodate sensitive enzymes in a protective environment. However, the lack of suitable immobilization techniques on substrates and the lack of selectivity to anchor a biocatalyst are major drawbacks preventing the use of hydrogels in bioanalytical devices. Here, nanofilm coatings on surfaces were made of a recombinant spider silk protein (rssp) to induce rssp self-assembly and thus the formation of fibril-based nanohydrogels. To functionalize spider silk nanohydrogels for bioselective binding of proteins, two different antithrombin aptamers were chemically conjugated with the rssp, thereby integrating the target-binding function into the nanohydrogel network. Human thrombin was selected as a sensitive model target, in which the structural integrity determines its activity. The chosen aptamers, which bind various exosites of thrombin, enabled selective and cooperative embedding of the protein into the nanohydrogels. The change of the aptamer secondary structure using complementary DNA sequences led to the release of active thrombin and confirmed the addressable functionalization of spider silk nanohydrogels.

Monolayers of poly-L-lysine on mica--Electrokinetic characteristics.

Physicochemical properties of poly-l-lysine and its monolayers on mica were thoroughly investigated by dynamic light scattering, electrokinetic methods and atomic force microscopy. The hydrodynamic diameter of PLL was equal to 25.5 nm within a wide range of pH and ionic strength. The electrophoretic measurements revealed that the molecules are positively charged for pH<10.5. By exploiting the electrophoretic mobility data, theelectrokinetic charge on the PLL molecules and their zeta potential were calculated. PLL monolayers of controlled coverage were deposited on mica under diffusion-controlled conditions by varying PLL bulk concentration and adsorption time. The electrokinetic characteristics of the monolayers were acquired in situ via streaming potential measurements. These studies allowed to uniquely determine the zeta potential of the monolayers as a function of pH and ionic strength. In this way the isoelectric point of the monolayers can be determined in a more convenient way compared to bulk measurements disturbed by the PLL molecule interactions. The stability of the monolayers under flow conditions was quantitatively evaluated via streaming potential measurements. The adsorption constant and the binding energy depth of PLL molecules were determined for different ionic strengths. These parameters indicate that the PLL monolayers remain stable over prolonged times.