Publikationen von Dr. Rüdiger Schmidt-Grund

Artificial leaves could be the breakthrough technology to overcome the limitations of storage and mobility through the synthesis of chemical fuels from sunlight, which will be an essential component of a sustainable future energy system. However, the realization of efficient solar-driven artificial leaf structures requires integrated specialized materials such as semiconductor absorbers, catalysts, interfacial passivation, and contact layers. To date, no competitive system has emerged due to a lack of scientific understanding, knowledge-based design rules, and scalable engineering strategies. Here, we will discuss competitive artificial leaf devices for water splitting, focusing on multi-absorber structures to achieve solar-to-hydrogen conversion efficiencies exceeding 15%. A key challenge is integrating photovoltaic and electrochemical functionalities in a single device. Additionally, optimal electrocatalysts for intermittent operation at photocurrent densities of 10-20 mA cm^-2 must be immobilized on the absorbers with specifically designed interfacial passivation and contact layers, so-called buried junctions. This minimizes voltage and current losses and prevents corrosive side reactions. Key challenges include understanding elementary steps, identifying suitable materials, and developing synthesis and processing techniques for all integrated components. This is crucial for efficient, robust, and scalable devices. Here, we discuss and report on corresponding research efforts to produce green hydrogen with unassisted solar-driven (photo-)electrochemical devices. This article is protected by copyright. All rights reserved.

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 present a systematic study of the magnetic properties of ZnFe2O4 thin films fabricated by pulsed laser deposition at low and high oxygen partial pressure and annealed in oxygen and argon atmosphere, respectively. The as-grown films show strong magnetization, closely related to a non-equilibrium distribution of defects, namely, Fe cations among tetrahedral and octahedral lattice sites. While the concentration of tetrahedral Fe cations declines after argon treatment at 250 ˚C, the magnetic response is enhanced by the formation of oxygen vacancies, evident by the increase in near-infrared absorption due to the Fe2+-Fe3+ exchange. After annealing at temperatures above 300 ˚C, the weakened magnetic response is related to a decline in disorder with a partial recrystallization toward a less defective spinel configuration.

A global-search method which applies the concept of genetic algorithm (GA) with gradient-based optimizer is proposed for the problem of experimental data analysis from spectroscopic ellipsometry on thin films. The method is applied to evaluate the data obtained for samples with different structure complexity, starting with transparent monolayers (SiO2, HfO2) on a substrate, through absorbing film (diamond-like carbon) and multilayer structures. We demonstrate that by using this method we are able to find material parameters even for limited a priori knowledge about the sample properties, where classical methods fail.