Georg Hähner

Near edge X-ray absorption fine structure spectroscopy as a tool to probe electronic and structural properties of thin organic films and liquids

Synchrotron-based spectroscopic techniques have contributed significantly to a better understanding of the properties of materials on the macroscopic and microscopic scale over the last decades. They can be applied to samples from a diversity of fields, including Biology, Life Sciences, Chemistry and Materials. One of these techniques is Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy, revealing electronic structure and information on the orientation of adsorbed molecules. The present article describes the basics of the technique and the progress it has made over the last three decades, and summarizes some of its more recent developments and applications. This tutorial review article should be accessible for novices to the field from Physics, Chemistry, Biology, Materials, and the Life Sciences, interested in thin organic films and liquid systems.

Investigation of the pore formation in anodic aluminium oxide

The mechanism accounting for the self-organization of nanoscale pores during anodic oxidation of aluminium is studied. Microstructural studies support the equifield strength model, which can be used to explain the formation of the hemispherical electrolyte/oxide and oxide/metal interfaces, uniform thickness of the oxide layer, as well as self-adjustment of the pore size and pore ordering. The fundamentals of the model are the electric field enhanced oxide dissolution rate and oxygen anion migration rate. The most important factor for determining the porosity of anodic alumina films with both ordered and disordered pores is the relative dissociation rate of water. The relationships between the porosity and anodization conditions, such as voltage, current density, and electric field strength, are also estimated.

Simultaneous determination of density and viscosity of liquids based on resonance curves of uncalibrated microcantilevers

The response of magnetically driven noncalibrated atomic force microscope cantilevers was measured in water/ethanol mixtures. Data recorded in pure water and in pure ethanol were used independently to extract parameters characteristic of the resonance behavior of the system. These parameters were then employed to determine the viscosity and density values of the mixtures. The values obtained are within ∼5% of those published in the literature. The procedure presented allows small volumes (approximately microliters) of liquids to be investigated and does not require any knowledge of the spring constant or the geometry of the microcantilever.

Replicative generation of metal microstructures by template-directed electrometallization

Copper structures were produced by electrochemical deposition onto patterned self-assembled monolayers (SAMS) of thiols adsorbed on polycrystalline gold substrates and subsequent transfer to an insulating substrate. Selective metal deposition was achieved by use of thiols which differ in their electrochemical blocking properties, namely hexadecane thiol [CH3(CH2)15SH] and ω-(4′-methyl-biphenyl-4-yl)-methanethiol (CH3–C6H4–C6H4–CH2–SH). Besides control of the blocking properties, the SAM served to minimize adhesion between the metal deposit and the substrate, thus, allowing the transfer of the metal pattern. Since the process is replicative, it represents a very simple and fast route to generating metal patterns.

RUBBING AND SCRUBBING

The “rubbing and scrubbing department” was how David Tabors friction, lubrication and wear laboratory was described by certain uncharitable colleagues at the Cavendish Laboratory in Cambridge, England, some 40 years ago. The tables have turned. Tribology, as Tabor named his discipline (from the Greek tribos, meaning “rubbing”), has become respectable—even positively modish—in physics departments worldwide. And Tabor, having become the revered elder statesman of this flourishing field, is often accorded a place in reference of even the most hardcore tribo‐physics papers.

Orientation and order in microcontact-printed, self-assembled monolayers of alkanethiols on gold investigated with near edge x-ray absorption fine structure spectroscopy

Near edge x-ray absorption fine structure spectroscopy (NEXAFS) was used to investigate contact-printed (CP), self-assembled monolayers (SAMs) of alkanethiols on gold. We studied the influence on order and orientation of the alkyl chains of both the chain length of the thiols and the concentration of the inking solution that was used for stamping. The results are compared to those for monolayers prepared by the conventional technique of immersing the substrate into solution. Our study shows that the CP process, when performed with a sufficiently concentrated solution of the thiol, can result in monolayers indistinguishable from those established by immersion into solution, independent of the thiol chain length. For lower concentrations, however, CP monolayers show a significant deviation from well-ordered films and have to be classified as mainly disordered. As with SAMs prepared from solution, shorter chains (dodecanethiol) lead to a lower degree of order compared to longer ones (hexadecanethiol), which ...

Mass determination and sensitivity based on resonance frequency changes of the higher flexural modes of cantilever sensors

Micro- and nanocantilevers are increasingly employed as mass sensors. Most studies consider the first flexural mode and adsorbed masses that are either discretely attached or homogeneously distributed along the entire length of the cantilever. We derive general expressions that allow for the determination of the total attached mass with any mass distribution along the cantilever length and all flexural modes. The expressions are valid for all cantilevers whose flexural deflection can be described by a one-dimensional function. This approach includes the most common types of microcantilevers, namely, rectangular, picket, and V-shaped. The theoretical results are compared with experimental data up to the fourth flexural mode obtained from thermal noise spectra of rectangular and V-shaped cantilevers.

Temperature dependence of viscosity and density of viscous liquids determined from thermal noise spectra of uncalibrated atomic force microscope cantilevers

We demonstrate that the thermal response of uncalibrated atomic force microscope cantilevers can be used to extract the density and the viscosity of viscous liquids with good accuracy. Temperature dependent thermal noise spectra were measured in water/poly(ethylene glycol) mixtures. Empirical parameters characteristic of the resonance behavior of the system were extracted from data recorded for one of the solutions at room temperature. These parameters were then employed to determine both viscosity and density values of the solutions simultaneously at different temperatures. In addition, activation energies for viscous flow were determined from the viscosity values obtained. The method presented is both fast and reliable and has the potential to be applied in connection with microfluidic systems, making macroscopic amounts of liquid and separate measurements with a viscometer and a densimeter redundant.

Calibration of the normal spring constant of microcantilevers in a parallel fluid flow.

We demonstrate a novel approach to determine the normal spring constant of microcantilevers. The cantilevers are placed parallel to a fluid flow thus establishing one of the walls of the flow channel. Resonance frequencies are recorded depending on the velocity of the fluid. The pressure gradient resulting from the flow causes the resonance frequency to change. This change can be exploited to deduce the cantilever spring constant with high precision. The method we present can be performed in situ and does not involve any contact of the cantilever with a surface thus having great potential for the calibration of modified probes and for being incorporated in microfluidic systems. In case the spring constant is known, the setup can also be employed to determine the velocity of fluid flows and the flow rate with high precision and up to high speeds.

Dynamic spring constants for higher flexural modes of cantilever plates with applications to atomic force microscopy

In atomic force microscopy (AFM) a sharp tip fixed close to the free end of a cantilever beam interacts with a surface. The interaction can be described by a point-mass model of an equivalent oscillator with a single spring located at the position of the tip. However, other spring constants have to be used to describe the oscillation behavior correctly if forces are acting on the cantilever over an extended lateral range. A point-mass model is then no longer valid. In the present study we derive expressions for the spring constants of cantilevers that can interact with any part of their plan view area along the beam and for all flexural modes. The equations describe the oscillation behavior in the corresponding mass model and are based on the eigenfrequencies and modal shapes of the free cantilever. The results are of high practical relevance, for example if an AFM is operated in a higher flexural mode, if the tip is not located at the free end of the cantilever beam, or if the external conservative forces affecting cantilever movement are not restricted to a single point. The limitations of the approach are discussed.