Molecular scale structure and dynamics at an ionic liquid/electrode interface.

After a century of research, the potential-dependent ion distribution at electrode/electrolyte interfaces is still under debate. In particular for solvent-free electrolytes such as room-temperature ionic liquids, classical theories for the electrical double layer are not applicable. Using a combination of in situ high-energy X-ray reflectivity and impedance spectroscopy measurements, we determined this distribution with sub-molecular resolution. We find oscillatory charge density profiles consisting of alternating anion- and cation-enriched layers at both cathodic and anodic potentials. This structure is shown to arise from the same ion-ion correlations dominating the liquid bulk structure.…

Anisotropic carrier diffusion in single MAPbI(3) grains correlates to their twin domains

Polycrystalline thin films and single crystals of hybrid perovskites – a material group successfully used for photovoltaic and optoelectronic applications – reportedly display heterogeneous charge carrier dynamics often attributed to grain boundaries or crystalline strain. Here, we locally resolved the carrier diffusion in large, isolated methylammonium lead iodide (MAPbI3) grains via spatial- and time-resolved photoluminescence microscopy. We found that the anisotropic carrier dynamics directly correlate with the arrangement of ferroelastic twin domains. Comparing diffusion constants parallel and perpendicular to the domains showed carriers diffuse around 50–60% faster along the parallel d…

Anisotropic Charge Carrier Diffusion Correlated to Ferroelastic Twin Domains in MAPbI3 Perovskite

Salt-induced microheterogeneities in binary liquid mixtures

The salt-induced microheterogeneity (MH) formation in binary liquid mixtures is studied by small-angle x-ray scattering (SAXS) and liquid state theory. Previous experiments have shown that this phenomenon occurs for antagonistic salts, whose cations and anions prefer different components of the solvent mixture. However, so far the precise mechanism leading to the characteristic length scale of MHs has remained unclear. Here, it is shown that MHs can be generated by the competition of short-ranged interactions and long-ranged monopole-dipole interactions. The experimental SAXS patterns can be reproduced quantitatively by fitting to the derived correlation functions without assuming any speci…

Interfacial premelting of ice in nano composite materials

Physical chemistry, chemical physics 21, 3734 - 3741 (2019). doi:10.1039/C8CP05604H

The Catalytic Effect of Fluoroalcohol Mixtures Depends on Domain Formation

In the present contribution, we investigated catalytically active mixtures of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and aqueous H2O2 by molecular dynamics simulations. It is clearly observable that the HFIP molecule strongly binds to the H2O2, which is necessary for the desired catalytic reaction to occur. Upon the addition of the substrate cyclooctene to the solution, this interaction is enhanced, which suggests that the catalytic activity is increased by the presence of the hydrocarbon. We could clearly observe the microheterogeneous structure of the mixture, which is the result of the separation of the hydroxyl groups, water, and H2O2 from the fluorinated alkyl moiety in the form of l…

Structure and Dynamics of Confined Liquids: Challenges and Perspectives for the X-ray Surface Forces Apparatus

Preprint of the open access article Weiss, H., Cheng, H.-W., Mars, J., Li, H., Merola, C., Renner, F. U., Honkimäki, V., Valtiner, M., & Mezger, M. (2019). Structure and Dynamics of Confined Liquids: Challenges and Perspectives for the X-ray Surface Forces Apparatus. Langmuir, 35(51), 16679–16692. https://doi.org/10.1021/acs.langmuir.9b01215

Humidity-Induced Grain Boundaries in MAPbI3 Perovskite Films

Methylammonium lead halide perovskites (MAPbI3) are very sensitive to humid environments. We performed in situ scanning force microscopy and in situ X-ray diffraction measurements on MAPbI3 films to track changes in the film morphology and crystal structure upon repeated exposure to a high relative humidity environment (80%). We found that the appearance of monohydrate (MAPbI3·H2O) Bragg reflections coincided with the appearance of additional grain boundaries. Prolonging the exposure time to humidity induced more grain boundaries and steps in the MAPbI3 films, and the peak intensities of the monohydrate MAPbI3·H2O increased. The monohydrate was not stable under dry atmosphere and could be r…

Ferroelastic Fingerprints in Methylammonium Lead Iodide Perovskite

Methylammonium lead iodide (MAPbI3) perovskite shows an outstanding performance in photovoltaic devices. However, certain material properties, especially the possible ferroic behavior, remain unclear. We observed distinct nanoscale periodic domains in the piezoresponse of MAPbI3(Cl) grains. The structure and the orientation of these striped domains indicate ferroelasticity as their origin. By correlating vertical and lateral piezoresponse force microscopy experiments performed at different sample orientations with X-ray diffraction, the preferred domain orientation is suggested to be the a1–a2-phase. The observation of these ferroelastic fingerprints appears to strongly depend on the film t…

Correction: Surface induced smectic order in ionic liquids – an X-ray reflectivity study of [C22C1im]+[NTf2]−

Physical chemistry, chemical physics 20(37), 24494 - 24495 (2018). doi:10.1039/C8CP91851A

Surface induced smectic order in ionic liquids - an X-ray reflectivity study of [C(22)C(1)im](+)[NTf2](-)

Physical chemistry, chemical physics 19(39), 26651 - 26661 (2017). doi:10.1039/C7CP04852A