Michael Zäch

Gold, Platinum, and Aluminum Nanodisk Plasmons: Material Independence, Subradiance, and Damping Mechanisms

Localized surface plasmon resonances (LSPR) are collective electronic excitations in metallic nanoparticles. The LSPR spectral peak position, as a function of nanoparticle size and material, is known to depend primarily on dynamic depolarization and electron structure related effects. The former gives rise to the well-known spectral red shift with increasing nanoparticle size. A corresponding understanding of the LSPR spectral line width for a wide range of nanoparticle sizes and different metals does, however, not exist. In this work, the radiative and nonradiative damping contributions to the LSPR line width over a broad nanoparticle size range (40-500 nm) for a selection of three metals with fundamentally different bulk dielectric properties (Au, Pt, and Al) are explored experimentally and theoretically. Excellent agreement was obtained between the observed experimental trends and the predictions based on electrostatic spheroid theory (MLWA), and the obtained results were successfully related to the specific band structure of the respective metal. Moreover, for the first time, a clear transition from a radiation damping dominated to a quenched radiation damping regime (subradiance) in large nanoparticles was observed and probed by varying the electron density through appropriate material choice. To minimize inhomogeneous broadening (commonly present in ensemble-based spectroscopic measurements), a novel, electron-beam lithography (EBL)-based nanofabrication method was developed. The method generates large-area 2D patterns of randomly distributed nanodisks with well-defined size and shape, narrow size distribution, and tunable (minimum) interparticle distance. In order to minimize particle-particle coupling effects, sparse patterns with a large interparticle distance (center-to-center ≥6 particle diameters) were considered.

Electromagnetic coupling of light into a silicon solar cell by nanodisk plasmons

Photocurrents of silicon pn junctions patterned with arrays of elliptical Au nanodisks were experimentally and theoretically investigated near the particle plasmon resonance wavelengths, for varying light polarizations and angles of incidence. At plasmon resonance wavelengths, overall backscattering and dissipation were strongly enhanced compared to an unpatterned junction, resulting in lower photocurrents. In contrast, enhanced photocurrents were observed for wavelengths slightly off resonance. Measurements and finite element calculations show that the photocurrent changes occur via plasmon-induced far field effects, rather than by near field enhancement close to the particles. The far field effects are strongly dependent on the particle proximity and coupling to the Si substrate.

Enhanced charge carrier generation in dye sensitized solar cells by nanoparticle plasmons

An interesting possibility to improve the conversion and cost efficiencies of photovoltaic solar cells is to exploit the large optical cross sections of localized (nanoparticle) surface plasmon resonances (LSPRs). We have investigated this prospect for dye sensitized solar cells. Photoconductivity measurements were performed on flat TiO2 films, sensitized by a combination of dye molecules and arrays of nanofabricated elliptical gold disks. An enhanced dye charge carrier generation rate was found and shown to derive from the LSPR contribution by means of the polarization dependent resonance frequency in the anisotropic, aligned gold disks.

Solar hydrogen production with semiconductor metal oxides: new directions in experiment and theory

An overview of a collaborative experimental and theoretical effort toward efficient hydrogen production via photoelectrochemical splitting of water into di-hydrogen and di-oxygen is presented here. We present state-of-the-art experimental studies using hematite and TiO(2) functionalized with gold nanoparticles as photoanode materials, and theoretical studies on electro and photo-catalysis of water on a range of metal oxide semiconductor materials, including recently developed implementation of self-interaction corrected energy functionals.

A multifaceted approach to hydrogen storage

The widespread adoption of hydrogen as an energy carrier could bring significant benefits, but only if a number of currently intractable problems can be overcome. Not the least of these is the problem of storage, particularly when aimed at use onboard light-vehicles. The aim of this overview is to look in depth at a number of areas linked by the recently concluded HYDROGEN research network, representing an intentionally multi-faceted selection with the goal of advancing the field on a number of fronts simultaneously. For the general reader we provide a concise outline of the main approaches to storing hydrogen before moving on to detailed reviews of recent research in the solid chemical storage of hydrogen, and so provide an entry point for the interested reader on these diverse topics. The subjects covered include: the mechanisms of Ti catalysis in alanates; the kinetics of the borohydrides and the resulting limitations; novel transition metal catalysts for use with complex hydrides; less common borohydrides; protic-hydridic stores; metal ammines and novel approaches to nano-confined metal hydrides.

Combined QCM-D and EIS study of supported lipid bilayer formation and interaction with pore-forming peptides.

A novel set-up combining the quartz crystal microbalance with dissipation monitoring technique (QCM-D) and electrochemical impedance spectroscopy (EIS) under flow conditions was successfully used to follow supported lipid bilayer (SLB) formation on SiO(2). This study demonstrates the simultaneous detection, in real time, of both the electrical and the structural properties of the SLB. The combination of the two techniques provided novel insights regarding the mechanism of SLB formation: we found indications for an annealing process of the lipid alkyl chains after the mass corresponding to complete bilayer coverage had been deposited. Moreover, the interaction of the SLB with the pore-forming toxin, gramicidin D (grD) was studied for grD concentrations ranging from 0.05 to 40 mg L(-1). Membrane properties were altered depending on the toxin concentration. For low grD concentrations, the electrical properties of the SLB changed upon insertion of active ion channels. For higher concentrations, the QCM-D data showed dramatic changes in the viscoelastic properties of the membrane while the EIS spectra did not change. AFM confirmed significant structural changes of the membrane at higher grD concentrations. Thus, the application of combined QCM-D and EIS detection provides complementary information about the system under study. This information will be particularly important for the continued detailed investigation of interactions at model membrane surfaces.

Vesicle Adsorption and Phospholipid Bilayer Formation on Topographically and Chemically Nanostructured Surfaces

We have investigated the influence of combined nanoscale topography and surface chemistry on lipid vesicle adsorption and supported bilayer formation on well-controlled model surfaces. To this end, we utilized colloidal lithography to nanofabricate pitted Au-SiO(2) surfaces, where the top surface and the walls of the pits consisted of silicon dioxide whereas the bottom of the pits was made of gold. The diameter and height of the pits were fixed at 107 and 25 nm, respectively. Using the quartz crystal microbalance with dissipation monitoring (QCM-D) technique and atomic force microscopy (AFM), we monitored the processes occurring upon exposure of these nanostructured surfaces to a solution of extruded unilamellar 1-palmitolyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) vesicles with a nominal diameter of 100 nm. To scrutinize the influence of surface chemistry, we studied two cases: (1) the bare gold surface at the bottom of the pits and (2) the gold passivated by biotinamidocaproyl-labeled bovine serum albumin (BBSA) prior to vesicle exposure. As in our previous work on pitted silicon dioxide surfaces, we found that the pit edges promote bilayer formation on the SiO(2) surface for the vesicle size used here in both cases. Whereas in the first case we observed a slow, continuous adsorption of intact vesicles onto the gold surface at the bottom of the pits, the presence of BBSA in the second case prevented the adsorption of intact vesicles into the pits. Instead, our experimental results, together with free energy calculations for various potential membrane configurations, indicate the formation of a continuous, supported lipid bilayer that spans across the pits. These results are significantly important for various biotechnology applications utilizing patterned lipid bilayers and highlight the power of the combined QCM-D/AFM approach to study the mechanism of lipid bilayer formation on nanostructured surfaces.

Influence of nanotopography on phospholipid bilayer formation on silicon dioxide

We have investigated the effect of well-defined nanoscale topography on the 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) lipid vesicle adsorption and supported phospholipid bilayer (SPB) formation on SiO2 surfaces using a quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). Unilamellar lipid vesicles with two different sizes, 30 and 100 nm, were adsorbed on pitted surfaces with two different pit diameters, 110 and 190 nm, as produced by colloidal lithography, and the behavior was compared to results obtained on flat surfaces. In all cases, complete bilayer formation was observed after a critical coverage of adsorbed vesicles had been reached. However, the kinetics of the vesicle-to-bilayer transformation, including the critical coverage, was significantly altered by surface topography for both vesicle sizes. Surface topography hampered the overall bilayer formation kinetics for the smaller vesicles, but promoted SPB formation for the larger vesicles. Depending on vesicle size, we propose two modifications of the precursor-mediated vesicle-to-bilayer transformation mechanism used to describe supported lipid bilayer formation on the corresponding flat surface. Our results may have important implications for various lipid-membrane-based applications using rough or topographically structured surfaces.

Thermodynamic and kinetic supercooling of liquid in a wedge pore.

Cyclohexane allowed to capillary condense from vapor in an annular wedge pore of mica in a surface force apparatus (SFA) remains liquid down to at least 14 K below the bulk melting-point T(m). This is an example of supercooling of a liquid due to confinement, like melting-point depression in porous media. In the wedge pore, however, the supercooled liquid is in equilibrium with vapor, and the amount of liquid (and thereby the radius of curvature r of the liquid-vapor interface) depends on the surface tension gamma(LV) of the liquid, not the interfacial tension between the solid and liquid. At coexistence r is inversely proportional to the temperature depression DeltaT below T(m), in accordance with a recently proposed model [P. Barber, T. Asakawa, and H. K. Christenson, J. Phys. Chem. C 111, 2141 (2007)]. We have now extended this model to include effects due to the temperature dependence of both the surface tension and the enthalpy of melting. The predictions of the improved model have been quantitatively verified in experiments using both a Mark IV SFA and an extended surface force apparatus (eSFA). The three-layer interferometer formed by the two opposing, backsilvered mica surfaces in a SFA was analyzed by conventional means (Mark IV) and by fast spectral correlation of up to 40 fringes (eSFA). We discuss the absence of freezing in the outermost region of the wedge pore down to 14 K below T(m) and attribute it to nonequilibrium (kinetic) supercooling, whereas the inner region of the condensate is thermodynamically supercooled.

Bioreducible insulin-loaded nanoparticles and their interaction with model lipid membranes

To improve design processes in the field of nanomedicine, in vitro characterization of nanoparticles with systematically varied properties is of great importance. In this study, surface sensitive analytical techniques were used to evaluate the responsiveness of nano-sized drug-loaded polyelectrolyte complexes when adsorbed to model lipid membranes. Two bioreducible poly(amidoamine)s (PAAs) containing multiple disulfide linkages in the polymer backbone (SS-PAAs) were synthesized and used to form three types of nanocomplexes by self-assembly with human insulin, used as a negatively charged model protein at neutral pH. The resulting nanoparticles collapsed on top of negatively charged model membranes upon adsorption, without disrupting the membrane integrity. These structural rearrangements may occur at a cell surface which would prevent uptake of intact nanoparticles. By the addition of glutathione, the disulfide linkages in the polymer backbone of the SS-PAAs were reduced, resulting in fragmentation of the polymer and dissociation of the adsorbed nanoparticles from the membrane. A decrease in ambient pH also resulted in destabilization of the nanoparticles and desorption from the membrane. These mimics of intracellular environments suggest dissociation of the drug formulation, a process that releases the protein drug load, when the nanocomplexes reaches the interior of a cell.