Scientific publications

The present work proposes the use of a TiO2 electrode coupled to a one-dimensional photonic crystal (1DPC), all formed by the sequential deposition of nanocolumnar thin films by physical vapor oblique angle deposition (PV-OAD), to enhance the optical and electrical performance of DSCs while transparency is preserved. We demonstrate that this approach allows building an architecture combining a non-dispersive 3 µm of TiO2 electrode and 1 µm TiO2-SiO2 1DPC, both columnar, in a single-step process. The incorporation of the photonic structure is responsible for a rise of 30% in photovoltaic efficiency, as compared with a transparent cell with a single TiO2 electrode. Detailed analysis of the spectral dependence of the photocurrent demonstrates that the 1DPC improves light harvesting efficiency by both back reflection and optical cavity modes confinement within the TiO2 films, thus increasing the overall performance of the cell.

Four new praseodymium alkoxo and amido compounds ([Pr3(µ3-OtBu)2(µ2-OtBu)3(OtBu)4(HOtBu)2] (1), [Pr{OC(tBu)3}3(THF)] (2), [PrCl{N(SiMe3)2}2(THF)]2 (3), and [PrCl{OC(tBu)3}2(THF)]2 (4)) were synthesized and structurally characterized by single-crystal X-ray diffraction analysis. Application of these compounds in solvothermal synthesis of praseodymium oxide/hydroxide nanostructures showed their templating influence on the morphology and phase composition of the resulting solid-state materials. Differential reactivity of the chosen alkoxide ligands toward water and the different arrangements of metal-oxygen units in the studied precursor compounds strongly influenced the kinetics of hydrolysis and cross-condensation reactions as manifested in the morphological changes and phase composition of the final products. Thermal decomposition studies of 1- 4 confirmed their conversion into the corresponding oxide phases. Activation of compounds 1, 2, and 4 by either a base or a stoichiometric amount of water showed the distinct influence of their chemical configuration on the obtained nanopowders: whereas 1 solely produced nanorods of Pr(OH)3, 2 predominantly formed a mixture of rod-shaped and spherical particles. The solvothermal decomposition of 4 resulted in Pr(OH)2Cl or PrOCl due to the presence of Cl ligands in the molecular precursor. The resultant materials were thoroughly characterized to demonstrate the relationship between precursor chemistry and the processing parameters that are clearly manifested in the morphology and phase of the final ceramics.

A novel synthesis of a nanostructured cell adhesive surface is investigated for future stent developments. One-dimensional (1D) Al2O3 nanostructures were prepared by chemical vapor deposition of a single source precursor. Afterwards, recombinant filamentous bacteriophages which display a short binding motif with a cell adhesive peptide (RGD) on p3 and p8 proteins were immobilized on these 1D Al2O3 nanostructures by a simple dip-coating process to study the cellular response of human endothelial EA hy.926. While the cell density decreased on as-deposited 1D Al2O3 nanostructures, we observed enhanced cell proliferation and cell-cell interaction on recombinant phage overcoated 1D Al2O3 nanostructures. The recombinant phage overcoating also supports an isotropic cell spreading rather than elongated cell morphology as we observed on as-deposited Al2O3 1D nanostructures.

Polypropylene (PP)-based nanocomposites compounded by a twin-screw extruder and injection molded into plates those were then joined by linear vibration welding. The mechanical performances of the welds and bulk materials were examined. While the incorporation of rigid particles slightly improves the impact strength of the bulk PP, the mechanical properties of the welds decrease with increasing nanoparticle contents. The best weld quality is obtained at low weld pressure without nanoparticles. The fracture surfaces and microstructure of the welds showed that the reduced weld quality is caused by the orientation of nanofillers parallel to the weld plane, the destruction of interphase between fillers and matrix, and the reduction of molten-film thickness by incorporation of nanoparticles.

1D Al/Al2O3 nanostructures have been synthesized by chemical vapour deposition (CVD) of the molecular precursor [tBuOAlH2]2. The deposited nanostructures grow chaotically on the substrate forming a layer with a high porosity (80%). Depending on the deposition time, diverse nanostructured surfaces with different distribution densities were achieved. A three-dimensional (3D) reconstruction has been evaluated for every nanostructure density using the Focus Ion Beam (FIB) tomography technique and reconstruction software tools. Several structural parameters such as porosity, Euler number, geometrical tortuosity and aspect ratio have been quantified through the analysis with specified software of the reconstructions. Additionally roughness of the prepared surfaces has been characterized at micro- and nanoscale using profilometry and AFM techniques, respectively. While high aspects ratio around 20-30 indicates a strong anisotropy in the structure, high porosity values (around 80%) is observed as a consequence of highly tangled geometry of such 1D nanostructures. 1D nanostructures have tube or wire-like shapes with diameters below 100 nm and lengths of several micrometers. There are various methods to fabricate such ultrafine structures. The growth out of a chemical synthesis is the most elegant and simplest approach for fabrication of these ultra-small wires. Some of these methods are known as wet chemical syntheses since the material fabrication takes place within a solution. The chemical synthesis may also be carried out in the gas phase. Chemical Vapour Deposition (CVD) is such a chemical method, which leads to the fabrication of solid materials through accumulation of the vapour phase chemical species on a solid substrate. In this work, we have used a special CVD process to fabricate the nano-wires. The obtained wires have core-shell geometry. The inner core is made of aluminium and the outer surrounding shell is made of aluminium oxide. These ultrafine and extremely long wires form an assembly, which is similar to a bundle of spaghettis. It is difficult to analyse their shape, assembly, voids and other structural properties easily, just by looking from the top-view using a high-resolution electron microscopy. This microscopic method can give extremely high-resolution images (more than 500,000 times magnification) to analyse any fine detail. On the other hand, the gathered information is limited only to the planar 2D surface of the material. To get 3D information, we cut several slices perpendicular to the surface of the nano-wire assembly by edging and analysed every slice in terms of their morphology (destructing process). Afterwards, all these 2D projection images are brought together in order to get a reconstructed 3D image. This method allows observing every fine detail in the assembly just by rotating 3D image along any axis of interest.

Polyvinylpyrrolidone (PVP) is presented as a "greener" alternative to commonly used supercapacitor binders, namely polyvinylidenedifluoride (PVDF) or polytetrafluoroethylene (PTFE). The key advantages of using PVP are that it is non-toxic and soluble in ethanol and it can be used to spray coat or drain cast activated carbon (AC) electrodes directly on a current collector such as aluminum foil – in contrast to PTFE that requires rolling or PVDF that requires toxic N-methylpyrrolidone (NMP). The electrodes with the best mechanical stability incorporated 3.5 mass% of 1.300.000 g mol−1 PVP. Compared to PTFE or PVDF, the resulting pore volume was significantly higher and the specific surface area significantly larger when using PVP (normalized to the amount of AC). A good electrochemical performance was observed in organic electrolytes for AC–PVP electrodes: 112 or 97 F g−1 at 0.1 A g−1 in 1 M TEA–BF4 in propylene carbonate or acetonitrile, respectively. The performance stability was comparable to PTFE-bound electrodes when adjusting the maximum cell voltage to 2.5 V while preserving the manufacturing features of PVDF–AC films. (Electro)chemical stability is shown by electrochemical testing and infrared vibrational spectroscopy for propylene carbonate and acetonitrile.

The thermal conductivity of supercapacitor film electrodes composed of activated carbon (AC), AC with 15 mass% multi-walled carbon nanotubes (MWCNTs), AC with 15 mass% onion-like carbon (OLC), and only OLC, all mixed with polymer binder (polytetrafluoroethylene), has been measured. This was done for dry electrodes and after the electrodes have been saturated with an organic electrolyte (1 M tetraethylammonium-tetrafluoroborate in acetonitrile, TEA-BF4). The thermal conductivity data was implemented in a simple model of generation and transport of heat in a cylindrical cell supercapacitor systems. Dry electrodes showed a thermal conductivity in the range of 0.09-0.19 W K-1 m-1 and the electrodes soaked with an organic electrolyte yielded values for the thermal conductivity between 0.42 and 0.47 W K-1 m-1. It was seen that the values related strongly to the porosity of the carbon electrode materials. Modeling of the internal temperature profiles of a supercapacitor under conditions corresponding to extreme cycling demonstrated that only a moderate temperature gradient of several degrees Celsius can be expected and which depends on the ohmic resistance of the cell as well as the wetting of the electrode materials.

Room temperature ionic liquids (RTIL) are an emerging class of electrolytes enabling high cell voltages and, in return, high energy density of advanced supercapacitors. Yet, the low temperature behavior, including freezing and thawing, is little understood when confined in the narrow space of nanopores. This study shows that RTILs may show a tremendously different thermal behavior when comparing bulk with nanoconfined properties as a result of the increased surface energy of carbon pore walls. In particular, continuous increase in viscosity is accompanied with slowed-down charge/discharge kinetics during in-situ electrochemical characterization. Freezing reversibly collapses the energy storage ability – while thawing fully restores the initial energy density of the material. For the first time, a different thermal behavior in positively and negatively polarized electrodes is demonstrated. This leads to different freezing and melting points in the two electrodes. Compared to bulk, RTIL in the confinement of electrically charged nanopores, shows the unique behavior of being highly affine for supercooling; that is, the electrode freezing during heating.

The goal of our study is to better understand the design parameters of bioinspired dry adhesives inspired by geckos. For this, we fabricated single macroscopic pillars of 400µm diameter with different aspect ratios and different tip shapes, i.e. flat tips, spherical tips with different radii, and mushroom tips with different diameters. Tilt angle dependent adhesion measurements showed that although the tip shape of the pillars strongly influences the pull-off force, the pull-off strength is similar for flat and mushroom shaped tips. We found no tilt angle dependency of adhesion for spherical tip structures, and, except for high tilt angle and low preload experiments, no tilt angle effect for mushroom tip pillars. For flat tip pillars we found a strong influence of tilt angle on adhesion, which decreased linearly with increasing aspect ratio. The experiments show that for the tested aspect ratios between 1 and 5, a linear decrease of tilt angle dependency is found. The results of our studies will help to design bioinspired adhesives for application on smooth and rough surfaces.

Abstract Correlative fluorescence microscopy combined with scanning transmission electron microscopy (STEM) of cells fully immersed in liquid is a new methodology with many application areas. Proteins, in live cells immobilized on microchips, are labeled with fluorescent quantum dot nanoparticles. In this protocol, the epidermal growth factor receptor (EGFR) is labeled. The cells are fixed after a selected labeling time, for example, 5 min as needed to form EGFR dimers. The microchip with cells is then imaged with fluorescence microscopy. Thereafter, STEM can be accomplished in two ways. The microchip with the labeled cells and one microchip with a spacer are assembled into a special microfluidic device and imaged with dedicated high-voltage STEM. Alternatively, thin edges of cells can be studied with environmental scanning electron microscopy with a STEM detector, by placing a microchip with cells in a cooled wet environment.