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- ItemAmorphous-Like Ultralow Thermal Transport in Crystalline Argyrodite Cu7PS6(Weinheim : Wiley-VCH, 2024) Shen, Xingchen; Ouyang, Niuchang; Huang, Yuling; Tung, Yung‐Hsiang; Yang, Chun‐Chuen; Faizan, Muhammad; Perez, Nicolas; He, Ran; Sotnikov, Andrei; Willa, Kristin; Wang, Chen; Chen, Yue; Guilmeau, EmmanuelDue to their amorphous-like ultralow lattice thermal conductivity both below and above the superionic phase transition, crystalline Cu- and Ag-based superionic argyrodites have garnered widespread attention as promising thermoelectric materials. However, despite their intriguing properties, quantifying their lattice thermal conductivities and a comprehensive understanding of the microscopic dynamics that drive these extraordinary properties are still lacking. Here, an integrated experimental and theoretical approach is adopted to reveal the presence of Cu-dominated low-energy optical phonons in the Cu-based argyrodite Cu7PS6. These phonons yield strong acoustic-optical phonon scattering through avoided crossing, enabling ultralow lattice thermal conductivity. The Unified Theory of thermal transport is employed to analyze heat conduction and successfully reproduce the experimental amorphous-like ultralow lattice thermal conductivities, ranging from 0.43 to 0.58 W m−1 K−1, in the temperature range of 100–400 K. The study reveals that the amorphous-like ultralow thermal conductivity of Cu7PS6 stems from a significantly dominant wave-like conduction mechanism. Moreover, the simulations elucidate the wave-like thermal transport mainly results from the contribution of Cu-associated low-energy overlapping optical phonons. This study highlights the crucial role of low-energy and overlapping optical modes in facilitating amorphous-like ultralow thermal transport, providing a thorough understanding of the underlying complex dynamics of argyrodites.
- ItemNd─Nd Bond in Ih and D5h Cage Isomers of Nd2@C80 Stabilized by Electrophilic CF3 Addition(Weinheim : Wiley-VCH, 2023) Yang, Wei; Velkos, Georgios; Rosenkranz, Marco; Schiemenz, Sandra; Liu, Fupin; Popov, Alexey A.Synthesis of molecular compounds with metal–metal bonds between 4f elements is recognized as one of the fascinating milestones in lanthanide metallochemistry. The main focus of such studies is on heavy lanthanides due to the interest in their magnetism, while bonding between light lanthanides remains unexplored. In this work, the Nd─Nd bonding in Nd-dimetallofullerenes as a case study of metal–metal bonding between early lanthanides is demonstrated. Combined experimental and computational study proves that pristine Nd2@C80 has an open shell structure with a single electron occupying the Nd─Nd bonding orbital. Nd2@C80 is stabilized by a one-electron reduction and further by the electrophilic CF3 addition to [Nd2@C80]−. Single-crystal X-ray diffraction reveals the formation of two Nd2@C80(CF3) isomers with D5h-C80 and Ih-C80 carbon cages, both featuring a single-electron Nd─Nd bond with the length of 3.78–3.79 Å. The mutual influence of the exohedral CF3 group and endohedral metal dimer in determining the molecular structure of the adducts is analyzed. Unlike Tb or Dy analogs, which are strong single-molecule magnets with high blocking temperature of magnetization, the slow relaxation of magnetization in Nd2@Ih-C80(CF3) is detectable via out-of-phase magnetic susceptibility only below 3 K and in the presence of magnetic field.
- ItemElucidating Structure Formation in Highly Oriented Triple Cation Perovskite Films(Weinheim : Wiley-VCH, 2023) Telschow, Oscar; Scheffczyk, Niels; Hinderhofer, Alexander; Merten, Lena; Kneschaurek, Ekaterina; Bertram, Florian; Zhou, Qi; Löffler, Markus; Schreiber, Frank; Paulus, Fabian; Vaynzof, YanaMetal halide perovskites are an emerging class of crystalline semiconductors of great interest for application in optoelectronics. Their properties are dictated not only by their composition, but also by their crystalline structure and microstructure. While significant efforts are dedicated to the development of strategies for microstructural control, significantly less is known about the processes that govern the formation of their crystalline structure in thin films, in particular in the context of crystalline orientation. This work investigates the formation of highly oriented triple cation perovskite films fabricated by utilizing a range of alcohols as an antisolvent. Examining the film formation by in situ grazing-incidence wide-angle X-ray scattering reveals the presence of a short-lived highly oriented crystalline intermediate, which is identified as FAI-PbI2-xDMSO. The intermediate phase templates the crystallization of the perovskite layer, resulting in highly oriented perovskite layers. The formation of this dimethylsulfoxide (DMSO) containing intermediate is triggered by the selective removal of N,N-dimethylformamide (DMF) when alcohols are used as an antisolvent, consequently leading to differing degrees of orientation depending on the antisolvent properties. Finally, this work demonstrates that photovoltaic devices fabricated from the highly oriented films, are superior to those with a random polycrystalline structure in terms of both performance and stability.
- ItemIs there more than one stickiness criterion?(Berlin ; Heidelberg : Springer, 2022) Wang, Anle; Müser, Martin H.Adhesion between an elastic body and a smooth, rigid substrate can lead to large tensile stresses between them. However, most macroscopic objects are microscopically rough, which strongly suppresses adhesion. A fierce debate has unfolded recently as to whether local or global parameters determine the crossover between small and large adhesion. Here, we report simulations revealing that the dependence of the pull-off force Fn on the surface energy γ does not only have two regimes of high and low adhesion but up to four regimes. They are related to contacts, which at the moment of rupture consist of (i) the last individual Hertzian-shaped contact, in which is linear in γ, (ii) a last meso-scale, individual patches with super-linear scaling, (iii) many isolated contact patches with extremely strong scaling, and (iv) a dominating largest contact patch, for which the pull-off stress is no longer negligible compared to the maximum, microscopic pull-off stress. Regime (iii) can be seen as a transition domain. It is located near the point where the surface energy is half the elastic energy per unit area in conformal contact. A criterion for the transition between regimes (i) and (ii) appears difficult to grasp. [Figure not available: see fulltext.].
- ItemInfluence of structural depth of laser-patterned steel surfaces on the solid lubricity of carbon nanoparticle coatings(Berlin ; Heidelberg : Springer, 2022) Maclucas, Timothy; Daut, Lukas; Grützmacher, Philipp; Guitar, Maria Agustina; Presser, Volker; Gachot, Carsten; Suarez, Sebastian; Mücklich, FrankCarbon nanoparticle coatings on laser-patterned stainless-steel surfaces present a solid lubrication system where the pattern’s recessions act as lubricant-retaining reservoirs. This study investigates the influence of the structural depth of line patterns coated with multi-walled carbon nanotubes (CNTs) and carbon onions (COs) on their respective potential to reduce friction and wear. Direct laser interference patterning (DLIP) with a pulse duration of 12 ps is used to create line patterns with three different structural depths at a periodicity of 3.5 µm on AISI 304 steel platelets. Subsequently, electrophoretic deposition (EPD) is applied to form homogeneous carbon nanoparticle coatings on the patterned platelets. Tribological ball-on-disc experiments are conducted on the as-described surfaces with an alumina counter body at a load of 100 mN. The results show that the shallower the coated structure, the lower its coefficient of friction (COF), regardless of the particle type. Thereby, with a minimum of just below 0.20, CNTs reach lower COF values than COs over most of the testing period. The resulting wear tracks are characterized by scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. During friction testing, the CNTs remain in contact, and the immediate proximity, whereas the CO coating is largely removed. Regardless of structural depth, no oxidation occurs on CNT-coated surfaces, whereas minor oxidation is detected on CO-coated wear tracks. [Figure not available: see fulltext.].
- ItemProbing magnetic properties at the nanoscale: in-situ Hall measurements in a TEM([London] : Macmillan Publishers Limited, 2023) Pohl, Darius; Lee, Yejin; Kriegner, Dominik; Beckert, Sebastian; Schneider, Sebastian; Rellinghaus, Bernd; Thomas, AndyWe report on advanced in-situ magneto-transport measurements in a transmission electron microscope. The approach allows for concurrent magnetic imaging and high resolution structural and chemical characterization of the same sample. Proof-of-principle in-situ Hall measurements on presumably undemanding nickel thin films supported by micromagnetic simulations reveal that in samples with non-trivial structures and/or compositions, detailed knowledge of the latter is indispensable for a thorough understanding and reliable interpretation of the magneto-transport data. The proposed in-situ approach is thus expected to contribute to a better understanding of the Hall signatures in more complex magnetic textures.
- ItemBioactive glass–ceramics containing fluorapatite, xonotlite, cuspidine and wollastonite form apatite faster than their corresponding glasses([London] : Macmillan Publishers Limited, 2024) Kirste, Gloria; Contreras Jaimes, Altair; de Pablos-Martín, Araceli; de Souza e Silva, Juliana Martins; Massera, Jonathan; Hill, Robert G.; Brauer, Delia S.Crystallisation of bioactive glasses has been claimed to negatively affect the ion release from bioactive glasses. Here, we compare ion release and mineralisation in Tris–HCl buffer solution for a series of glass–ceramics and their parent glasses in the system SiO2–CaO–P2O5–CaF2. Time-resolved X-ray diffraction analysis of glass–ceramic degradation, including quantification of crystal fractions by full pattern refinement, show that the glass–ceramics precipitated apatite faster than the corresponding glasses, in agreement with faster ion release from the glass–ceramics. Imaging by transmission electron microscopy and X-ray nano-computed tomography suggest that this accelerated degradation may be caused by the presence of nano-sized channels along the internal crystal/glassy matrix interfaces. In addition, the presence of crystalline fluorapatite in the glass–ceramics facilitated apatite nucleation and crystallisation during immersion. These results suggest that the popular view of bioactive glass crystallisation being a disadvantage for degradation, apatite formation and, subsequently, bioactivity may depend on the actual system study and, thus, has to be reconsidered.