Theory of highly excited semiconductor nanostructures including Auger coupling: exciton-bi-exciton mixing in CdSe nanocrystals

We present a theory of highly excited interacting carriers confined in a semiconductor nanostructure, incorporating Auger coupling between excited states with different number of excitations. The Coulomb matrix elements connecting exciton, bi-exciton and tri-exciton complexes are derived and an intuitive picture of breaking neutral multi-exction complexes into positively and negatively charged multi-exciton complexes is given. The general approach is illustrated by analyzing the coupling of biexciton and exciton in CdSe spherical nanocrystals. The electron and hole states are computed using atomistic $sp^3d^5s^*$ tight binding Hamiltonian including an effective crystal field splitting and surface passivation. For each number of electron-hole pairs the many-body spectrum is computed in the configuration-interaction approach. The low-energy correlated biexciton levels are broken into charged complexes: a hole and a negatively charged trion and an electron and a positively charged trion. Out of a highly excited exciton spectrum a subspace coupled to bi-exciton levels via Auger processes is identified. The interaction between correlated bi-exciton and exciton states is treated using exact diagonalization techniques. This allows to extract the spectral function of the biexciton and relate its characteristic width and amplitude to the characteristic amplitude and timescale of the coherent time evolution of the coupled system. It is shown that this process can be described by the Fermi's Golden Rule only if a fast relaxation of the excitonic subsystem is accounted for.Comment: 9 figure

Epitaxial Metal Halide Perovskites by Inkjet‐Printing on Various Substrates

Metal‐halide‐perovskites revolutionized the field of thin‐film semiconductor technology, due to their favorable optoelectronic properties and facile solution processing. Further improvements of perovskite thin‐film devices require structural coherence on the atomic scale. Such perfection is achieved by epitaxial growth, a method that is based on the use of high‐end deposition chambers. Here epitaxial growth is enabled via a ≈1000 times cheaper device, a single nozzle inkjet printer. By printing, single‐crystal micro‐ and nanostructure arrays and crystalline coherent thin films are obtained on selected substrates. The hetero‐epitaxial structures of methylammonium PbBr3 grown on lattice matching substrates exhibit similar luminescence as bulk single crystals, but the crystals phase transitions are shifted to lower temperatures, indicating a structural stabilization due to interfacial lattice anchoring by the substrates. Thus, the inkjet‐printing of metal‐halide perovskites provides improved material characteristics in a highly economical way, as a future cheap competitor to the high‐end semiconductor growth technologies.DFG, 404984854, Bleifreie Perovksite für die RöntgendetektionDFG, 399073171, GRK 2495: Energiekonvertierungssysteme: von Materialien zu Bauteile

Guidelines for reliable urea detection in electrocatalysis

Electrochemical urea synthesis offers a promising green alternative to fossil fuel-based approaches to support the increasing global demand for nitrogen fertilizers. Unfortunately, the conventional urea detection methods produce inconsistent and unreliable results, hindering progress in this field. Both false positives and negatives can be observed depending on environmental factors and interfering chemicals. In this regard, we propose new rigorous 13C NMR and LC-MS protocols for accurate urea detection to analyze catalyst activity in an accessible and reproducible manner

Fine structure and size dependence of exciton and biexciton optical spectra in CdSe nanocrystals

Theory of electronic and optical properties of exciton and biexciton complexes confined in CdSe spherical nanocrystals is presented. The electron and hole states are computed using atomistic sp3d5s* tight binding Hamiltonian including an effective crystal field splitting, spin-orbit interactions, and model surface passivation. The optically excited states are expanded in electron-hole configurations and the many-body spectrum is computed in the configuration-interaction approach. Results demonstrate that the low-energy electron spectrum is organized in shells (s , p, . . .), while the valence hole spectrum is composed of four low-lying, doubly degenerate states separated from the rest by a gap. As a result, the biexciton and exciton spectrum is composed of a manifold of closely lying states, resulting in a fine structure of exciton and biexciton spectra. The quasidegenerate nature of the hole spectrum results in a correlated biexciton state, which makes it slowly convergent with basis size. We carry out a systematic study of the exciton and biexciton emission spectra as a function of the nanocrystal diameter and find that the interplay of repulsion between constituent excitons and correlation effects results in a change of the sign of biexciton binding energy from negative to positive at a critical nanocrystal size.Peer reviewed: YesNRC publication: Ye

In situ cathode-electrolyte interphase enables high cycling stability of Co-free Li-rich layered cathodes

Despite the extensive research in Li-rich layered oxides (LLOs), which are promising candidates for high-energy density cathodes, their cycle life still cannot meet the real-world application requirements. The poor cycle performance arises from the electrolyte decomposition at high voltage, resulting in damage and subsequent surface-initiated conversion of the cathode from layered to spinel phase. This problem is even more challenging for Co-free LLO cathodes. Here, we report a one-pot synthesis of in situ carbonate-coated nanostructured Co-free LLO (Li2CO3@LLO) through a polyol-assisted method. This inorganic coating suppresses oxygen release, provides good Li–ion transport, and protects the cathode from adverse reactions with the electrolyte. The obtained material exhibits excellent long-term stability, with 76% capacity retention after 1000 cycles at a 0.2 C rate without any Co addition, demonstrating a path forward for using LLOs as a next-generation Li–ion battery cathode