Alexander Birkel

Highly efficient and stable dye-sensitized solar cells based on SnO2 nanocrystals prepared by microwave-assisted synthesis

Highly efficient dye-sensitized solar cells (DSSCs) with excellent long-term stability were fabricated based on tin(IV) oxide (SnO2) nanocrystals with tunable morphologies and band energy levels. The nanocrystals were prepared by a facile, fast, and energy-saving microwave-assisted solvothermal reaction. Through variation of the precursor base used during nanocrystal synthesis control over morphology was achieved—precursor metal cations are known to have a strong influence on the growth process of SnO2 nanostructures. A simple and economic way to prepare semiconducting pastes for photoanodes was devised. The photovoltaic performance of dye-sensitized solar cells based on SnO2 photoanodes was investigated. A very high power conversion efficiency of up to 3.2%, based on very high Voc and comparable Jsc and FF [under 1 Sun condition (AM 1.5, 100 mW cm−2, with shading masks)] was achieved, reporting the highest efficiency value for the cells based on unmodified SnO2 nanocrystals so far. In order to elucidate the efficient cell behavior, electrochemical properties such as the charge transport in the photoanodes as well as SnO2/electrolyte interfacial properties were investigated. Uncharacteristically for DSSCs, all devices tested in the present study show an unusual long-term stability under ambient conditions over several weeks.

Average and Local Structural Origins of the Optical Properties of the Nitride Phosphor La3–xCexSi6N11 (0 < x ≤ 3)

Structural intricacies of the orange-red nitride phosphor system La(3-x)Ce(x)Si6N11 (0 < x ≤ 3) have been elucidated using a combination of state-of-the art tools, in order to understand the origins of the exceptional optical properties of this important solid-state lighting material. In addition, the optical properties of the end-member (x = 3) compound, Ce3Si6N11, are described for the first time. A combination of synchrotron powder X-ray diffraction and neutron scattering is employed to establish site preferences and the rigid nature of the structure, which is characterized by a high Debye temperature. The high Debye temperature is also corroborated from ab initio electronic structure calculations. Solid-state (29)Si nuclear magnetic resonance, including paramagnetic shifts of (29)Si spectra, are employed in conjunction with low-temperature electron spin resonance studies to probes of the local environments of Ce ions. Detailed wavelength-, time-, and temperature-dependent luminescence properties of the solid solution are presented. Temperature-dependent quantum yield measurements demonstrate the remarkable thermal robustness of luminescence of La2.82Ce0.18Si6N11, which shows little sign of thermal quenching, even at temperatures as high as 500 K. This robustness is attributed to the highly rigid lattice. Luminescence decay measurements indicate very short decay times (close to 40 ns). The fast decay is suggested to prevent strong self-quenching of luminescence, allowing even the end-member compound Ce3Si6N11 to display bright luminescence.

Interaction of Alkaline Metal Cations with Oxidic Surfaces: Effect on the Morphology of SnO2 Nanoparticles

Reaction pathways to SnO(2) nanomaterials through the hydrolysis of hydrated tin tetrachloride precursors were investigated. The products were prepared solvothermally starting from hydrated tin tetrachloride and various (e.g., alkali) hydroxides. The influence of the precursor base on the final morphology of the nanomaterials was studied. X-ray powder diffraction (XRD) data indicated the formation of rutile-type SnO(2). Transmission electron microscopy (TEM) studies revealed different morphologies that were formed with different precursor base cations. Data from molecular dynamics (MD) simulations provide theoretical evidence that the adsorption of the cations of the precursor base to the faces of the growing SnO(2) nanocrystals is crucial for the morphology of the nanostructures.

The interplay of crystallization kinetics and morphology during the formation of SnO2 nanorods: snapshots of the crystallization from fast microwave reactions

A microwave-assisted reaction pathway to rutile SnO2nanorods was investigated. The microwave-treatment significantly reduces the reaction time compared to standard hydro-/solvothermal techniques. By moving the overall process into a shorter time slot, the growth and crystal formation during the reaction could be monitored via snapshots by trapping the intermediates through quenching. To gain a better insight into the template-free growth of one-dimensional (1D) nanostructures, a parameter-dependent (various temperatures/pressures and times were investigated) study was carried out. For all materials, the phase purity and crystallite sizes were determined by X-ray powder diffraction (XRD). The growth-orientation and terminating crystal faces of the reaction intermediates were determined using (HR)-TEM measurements. A growth mechanism was proposed. The optical properties were studied by means of Raman and infrared spectroscopy.

Electrodeposition of ZnO nanorods on opaline replica as hierarchically structured systems

We present a new method to prepare hierarchical structures by using ZnO replica and ZnO-coated PMMA opals as electrodes in an electrodeposition process of ZnO nanorods. Depending on the approach the nanorods can be either grown exclusively on top of the replica or inside the replica structures. Therefore two types of systems are accessible: 3D photonic crystals with a hierarchically structured surface consisting of nanorods and macroporous ZnO structures with an increased surface area.