Publikationen

In this work, an electrochemically formed porous Cu current collector (p-Cu) is utilized for the development of a high-performance binder-free silicon anode. Two electrolyte compositions based on sulfolane (SL) and [BMP][TFSI] ionic liquid (IL) are implemented for silicon deposition. The electrochemical experiments confirm the advantages of applying the p-Cu structure in terms of specific capacity, rate capability, and long-term cycling, where the best electrochemical properties have been observed for the Si deposited from SL electrolyte. The Si-based p-Cu anodes formed in SL display stable 2500 mAh g^-1 reversible capacity during the first 250 cycles and promising capacity retention. Compared to this result, the cycling performance of the same type of material deposited on flat Cu foil (f-Cu) showed significantly reduced capacity (1400 mAh g^-1) and inferior cycling performance. The positive effect can be attributed to the improved mechanical stability of the active material and accelerated ionic transport in the porous structure of the anode. The improved functional properties of the electrochemically deposited Si from SL electrolyte in p-Cu samples compared to those obtained in IL can be ascribed to differences in the chemical composition. While the layers deposited in SL electrolyte involve Si domains incorporated in a matrix containing C and O that offer high mechanical stability, the Si material obtained in IL is additionally influenced by N and F chemical species, resulting from active IL decomposition. These differences in the chemical surrounding of the Si domains are the primary reason for the inferior electrochemical performance of the material deposited from [BMP][TFSI] electrolyte. XPS analysis shows that the initial composition of the as deposited layers, containing a considerable amount of elemental Si, is changed after lithiation and that the electrochemical activity of the anode is governed by switching between the intermediate redox states of Si, where the carbon-oxygen matrix is also involved.

The full transient dielectric-function (DF) tensor of ZnO after UV-laser excitation in the spectral range 1.4-3.6 eV is obtained by measuring an m-plane-oriented ZnO thin film with femtosecond (fs)-time-resolved spectroscopic ellipsometry. From the merits of the method, we can distinguish between changes in the real and the imaginary part of the DF as well as changes in birefringence and dichroism, respectively. We find pump-induced switching from positive to negative birefringence in almost the entire measured spectral range for about 1 ps. Simultaneously, weak dichroism in the spectral range below 3.0 eV hints at contributions of inter-valence-band transitions. Line-shape analysis of the DF above the band gap based on discrete exciton, exciton-continuum, and exciton-phonon-complex contributions shows a maximal dynamic increase in the transient exciton energy by 80 meV. The absorption coefficient below the band gap reveals an exponential line shape attributed to Urbach-rule absorption mediated by exciton-longitudinal-optic-phonon interaction. The transient DF is supported by first-principles calculations for 1020cm^-3 excited electron-hole pairs in ideal bulk ZnO.

We elaborate on the deviation of the Jordan structures of two linear relations that are finite-dimensional perturbations of each other. We compare their number of Jordan chains of length at least n. In the operator case, it was recently proved that the difference of these numbers is independent of n and is at most the defect between the operators. One of the main results of this paper shows that in the case of linear relations this number has to be multiplied by n+1 and that this bound is sharp. The reason for this behavior is the existence of singular chains. We apply our results to one-dimensional perturbations of singular and regular matrix pencils. This is done by representing matrix pencils via linear relations. This technique allows for both proving known results for regular pencils as well as new results for singular ones.

The atomic structure and electronic properties of the InP and Al0.5In0.5P(001) surfaces at the initial stages of oxidation are investigated via density functional theory. Thereby, we focus on the mixed-dimer (2 × 4) surfaces stable for cation-rich preparation conditions. For InP, the top In-P dimer is the most favored adsorption site, while it is the second-layer Al-Al dimer for AlInP. The energetically favored adsorption sites yield group III-O bond-related states in the energy region of the bulk band gap, which may act as recombination centers. Consistently, the In p state density around the conduction edge is found to be reduced upon oxidation.