Rainer Hock

Formation of CuInSe2 by the annealing of stacked elemental layers—analysis by in situ high-energy powder diffraction

Phases and phase transitions in three binary systems, Cu–Se, In–Se, Cu–In and in the ternary and quaternary systems Cu–In–Se (Ga) were investigated by in situ high energy powder diffraction in a temperature range from 25 to 550 °C. Results for the binary systems are compared to the known equilibrium phase diagrams of Cu–In, Cu–Se and In–Se. Above 225 °C Cu–In and Cu–Se follow the equilibrium phase diagrams. For In–Se significant deviations from the equilibrium diagram are observed. The results on binary systems yielded the basis for the qualitative phase analysis of the phase sequences observed in the CuInSe2 precursors during thermal anneal. On ternary and quaternary systems Cu–In–Se–(Ga) the reaction path to the formation of CuInSe2 could be determined in real time. Deviations of phase sequences from the equilibrium phase diagrams are attributed to the digression from the chemical rather than the thermal equilibrium. CuInSe2 finally crystallises from the direct precursors Cu2Se (Cu2−xSe, respectively) and InSe within a melt rich in selenium. The influence of gallium and sodium on the phase sequences and the resulting formation of CuInSe2 are discussed. Both, Na and Ga promote the crystallisation of Cu2Se, the direct precursor phase for CuInSe2. A comparison of the crystallographic structures of Cu2Se and InSe shows that epitaxial growth of InSe (0001) on Cu2Se (111) lattice planes is feasible. Based upon the experimental and crystallographic analysis a qualitative model for CuInSe2 crystallisation from the precursors in the melt is developed.

Brightly Luminescent and Color-Tunable Formamidinium Lead Halide Perovskite FAPbX3 (X = Cl, Br, I) Colloidal Nanocrystals

In the past few years, hybrid organic-inorganic and all-inorganic metal halide perovskite nanocrystals have become one of the most interesting materials for optoelectronic applications. Here, we report a facile and rapid room temperature synthesis of 15-25 nm formamidinium CH(NH2)2PbX3 (X = Cl, Br, I, or mixed Cl/Br and Br/I) colloidal nanocrystals by ligand-assisted reprecipitation (LARP). The cubic and platelet-like nanocrystals with their emission in the range of 415-740 nm, full width at half-maximum (fwhm) of 20-44 nm, and radiative lifetimes of 5-166 ns enable band gap tuning by halide composition as well as by their thickness tailoring; they have a high photoluminescence quantum yield (up to 85%), colloidal and thermodynamic stability. Combined with surface modification that prevents degradation by water, this nanocrystalline material is an ideal candidate for optoelectronic devices and applications. In addition, optoelectronic measurements verify that the photodetector based on FAPbI3 nanocrystals paves the way for perovskite quantum dot photovoltaics.

Storage of X-ray photons in a crystal resonator

The temporal structure and high brilliance of the X-ray beams produced by third-generation synchrotrons open up new possibilities in time-dependent diffraction and spectroscopy, where timescales down to the sub-nanosecond regime can now be accessed. These beam properties are such that one can envisage the development of the X-ray equivalent of optical components, such as photon delay lines and resonators, that have proved indispensable in a wide range of experiments—for example, pump-probe and multiple-interaction experiments—and (through shaping the temporal structure and repetition rate of the beams) time-dependent measurements in crystallography, physics, biology and chemistry. Optical resonators, such as those used in lasers, are available at wavelengths from the visible to soft X-rays. Equivalent components for hard X-rays have been discussed for more than thirty years, but have yet to be realized. Here we report the storage of hard X-ray photons (energy 15.817 keV) in a crystal resonator formed by two plates of crystalline silicon. The photons are stored for as many as 14 back-and-forth cycles within the resonator, each cycle separated by one nanosecond.

Intergrown niobian rutile phases with Sc- and W-rich ferrocolumbite: An electron-microprobe and Rietveld study

Abstract A pegmatite from Diethensdorf, Saxonian Granulite Massif, Germany, contains fine-grained aggregates of at least three different varieties of niobian rutile and a (W, Sc)-rich ferrocolumbite. In addition, rutile 1 occurs as larger grains. Electron microprobe analyses of niobian rutile gave compositions close to the general formula (Fe,Mn)x(Nb,Ta)2xTi3-3xO6, with Nb and Fe contents decreasing in the order rutile 1 → rutile 2 → rutile 3 and Ti increasing accordingly. The substitution of (Ti,Sn) by Fe + (Nb,Ta) is 35-32 at% in rutile 1, 28-26 at% in rutile 2, and 24-19 at% in rutile 3. The intergrown ferrocolumbite has Ta/(Nb + Ta) ratios of <0.10 and Mn/(Fe + Mn) ratios <0.25, and shows unusually high contents of Sc2O3 and WO3 (up to 4.0 and 8.8 wt%, respectively). Powder X-ray diffraction (XRD) analysis with Guinier and Bragg-Brentano methods identified at least three rutile phases (herein termed A, B, and C) with cell volumes decreasing with the Nb (+ Ta, W) contents. Nb/Ti ratios of rutiles estimated from Rietveld refinements roughly conform to the results of electron microprobe analysis. The cation distribution in the ferrocolumbite was refined on the basis of a two-scatterer model at sites 8d and 4c in space group Pbcn, leading to ordering of the heavy atoms on site 8d. Textural evidence suggests that the fine-grained intergrowths of ferrocolumbite + rutile 2 + rutile 3 (+ rutile 1) were formed by exsolution from a precursor phase that most probably was not rutile 1.

Gallium-rich Pd–Ga phases as supported liquid metal catalysts

A strategy to develop improved catalysts is to create systems that merge the advantages of heterogeneous and molecular catalysis. One such system involves supported liquid-phase catalysts, which feature a molecularly defined, catalytically active liquid film/droplet layer adsorbed on a porous solid support. In the past decade, this concept has also been extended to supported ionic liquid-phase catalysts. Here we develop this idea further and describe supported catalytically active liquid metal solutions (SCALMS). We report a liquid mixture of gallium and palladium deposited on porous glass that forms an active catalyst for alkane dehydrogenation that is resistant to coke formation and is thus highly stable. X-ray diffraction and X-ray photoelectron spectroscopy, supported by theoretical calculations, confirm the liquid state of the catalytic phase under the reaction conditions. Unlike traditional heterogeneous catalysts, the supported liquid metal reported here is highly dynamic and catalysis does not proceed at the surface of the metal nanoparticles, but presumably at homogeneously distributed metal atoms at the surface of a liquid metallic phase.

A comprehensive study on the mechanism behind formation and depletion of Cu2ZnSnS4 (CZTS) phases

High efficiency kesterite based solar cells have vigorously raised the research interests in this material. The challenge lies in understanding the formation and co-existence of more than 10 possible by-products during and after the synthesis of Cu2ZnSnS4 (CZTS) and their various different structural and electronic defects. The present contribution shows an in-depth study on the stages of formation and depletion of nanoparticulate CZTS. Employing a hot injection synthesis method, we give direct experimental evidence of the co-existence of cubic, tetragonal and defected CZTS structures and different by-products as a function of time and temperature. SEM, (HR)TEM, XRD, EDX, ICP-OES, Raman spectroscopy and UV-Vis-NIR spectroscopy have been used in order to better evaluate and interpret data for crystal structures and compositions. The obtained understanding on the formation of different phases suggests 250 °C as the most favourable synthesis temperature. Based on our study, general strategies can be developed for controlling the amount of formed phases, the by-products and the defects in kesterite and other similar multicomponent nanoparticles as well as in bulk systems.

Photoinduced degradation of methylammonium lead triiodide perovskite semiconductors

Photoinduced degradation is a critical obstacle for the real application of novel semiconductors for photovoltaic applications. In this paper, the photoinduced degradation of CH3NH3PbI3 in a vacuum and air (relative humidity 40%) is analyzed by ex situ and advanced in situ technologies. Without light illumination, CH3NH3PbI3 films slowly degrade under vacuum and air within 24 hours. However, we find that CH3NH3PbI3 converts to metallic lead (Pb0) when exposed to vacuum and light illumination. Further, a series of lead salts (e.g. PbO, Pb(OH)2 and PbCO3) are formed when CH3NH3PbI3 is degraded under environmental conditions, i.e. under the combination of light, oxygen and moisture. Photoinduced degradation is found to be determined by the environmental atmosphere as CH3NH3PbI3 films remain very stable under nitrogen conditions. The results from vacuum conditions underpin that the high volatility of the organic component (CH3NH3I) is in conflict with reaching excellent intrinsic stability due to its role in creating ion vacancies. The degradation in air suggests that both oxygen and water contribute to the fast photodecomposition of CH3NH3PbI3 into lead salts rather than water alone. Given these basic yet fundamental understandings, the design of hydrophobic capping layers becomes one prerequisite towards long-term stable perovskite-based devices.

Ligand-assisted thickness tailoring of highly luminescent colloidal CH3NH3PbX3 (X = Br and I) perovskite nanoplatelets

Quantum size-confined CH3NH3PbX3 (X = Br and I) perovskite nanoplatelets with remarkably high photoluminescence quantum yield (up to 90%) were synthesized by ligand-assisted re-precipitation. Thickness-tunability was realized by varying the oleylamine and oleic acid ligand ratio. This method allows tailoring the nanoplatelet thickness by adjusting the number of unit cell monolayers. Broadly tunable emission wavelengths (450-730 nm) are achieved via the pronounced quantum size effect without anion-halide mixing.

Low-Temperature Solution-Processed Kesterite Solar Cell Based on in Situ Deposition of Ultrathin Absorber Layer

The production of high-performance, solution-processed kesterite Cu2ZnSn(Sx,Se1-x)4 (CZTSSe) solar cells typically relies on high-temperature crystallization processes in chalcogen-containing atmosphere and often on the use of environmentally harmful solvents, which could hinder the widespread adoption of this technology. We report a method for processing selenium free Cu2ZnSnS4 (CZTS) solar cells based on a short annealing step at temperatures as low as 350 °C using a molecular based precursor, fully avoiding highly toxic solvents and high-temperature sulfurization. We show that a simple device structure consisting of ITO/CZTS/CdS/Al and comprising an extremely thin absorber layer (∼110 nm) achieves a current density of 8.6 mA/cm(2). Over the course of 400 days under ambient conditions encapsulated devices retain close to 100% of their original efficiency. Using impedance spectroscopy and photoinduced charge carrier extraction by linearly increasing voltage (photo-CELIV), we demonstrate that reduced charge carrier mobility is one limiting parameter of low-temperature CZTS photovoltaics. These results may inform less energy demanding strategies for the production of CZTS optoelectronic layers compatible with large-scale processing techniques.

Lattice-plane curvature and small-angle grain boundaries in SiC bulk crystals

SiC crystals grown by the physical vapour transport process along the [001] direction show a curvature of the crystal growth front in correspondence with the shape of the isotherms. A large radius for the curvature of the isotherms enhances the formation of an extended facet. Under the facet, the lattice planes are flat with a high crystal quality as expressed by rocking-curve half widths of 0.022°. In the non-faceted region, the lattice planes become bent, following the shape of the isotherms with a radius of typically 0.5 to 0.8 m and an increased rocking-curve half width of 0.3°. A reduction of the growth rate from 300 μm h -1 to 70 μm h -1 does not affect this behaviour significantly. The lattice-plane curvature and the development of the facet are predominantly affected by the shape of the isotherms. For crystals grown in the [015] direction, the lattice planes adjust only in a one-dimensional manner to the isotherms. In all cases, the lattice-plane curvature results from the formation of a high density of small-angle grain boundaries. They are generated by the condensation of dislocations with Burgers vectors in the ab plane.