2021, Ta, Huy Q., Mendes, Rafael G., Liu, Yu, Yang, Xiaoqin, Luo, Jingping, Bachmatiuk, Alicja, Gemming, Thomas, Zeng, Mengqi, Fu, Lei, Liu, Lijun, Rümmeli, Mark H.

In recent years, two-dimensional (2D) materials have attracted a lot of research interest as they exhibit several fascinating properties. However, outside of 2D materials derived from van der Waals layered bulk materials only a few other such materials are realized, and it remains difficult to confirm their 2D freestanding structure. Despite that, many metals are predicted to exist as 2D systems. In this review, the authors summarize the recent progress made in the synthesis and characterization of these 2D metals, so called metallenes, and their oxide forms, metallene oxides as free standing 2D structures formed in situ through the use of transmission electron microscopy (TEM) and scanning TEM (STEM) to synthesize these materials. Two primary approaches for forming freestanding monoatomic metallic membranes are identified. In the first, graphene pores as a means to suspend the metallene or metallene oxide and in the second, electron-beam sputtering for the selective etching of metal alloys or thick complex initial materials is employed to obtain freestanding single-atom-thick 2D metal. The data show a growing number of 2D metals/metallenes and 2D metal/ metallene oxides having been confirmed and point to a bright future for further discoveries of these 2D materials.

2023, Tcakaev, Abdul‐Vakhab, Rubrecht, Bastian, Facio, Jorge I., Zabolotnyy, Volodymyr B., Corredor, Laura T., Folkers, Laura C., Kochetkova, Ekaterina, Peixoto, Thiago R. F., Kagerer, Philipp, Heinze, Simon, Bentmann, Hendrik, Green, Robert J., Gargiani, Pierluigi, Valvidares, Manuel, Weschke, Eugen, Haverkort, Maurits W., Reinert, Friedrich, van den Brink, Jeroen, Büchner, Bernd, Wolter, Anja U. B., Isaeva, Anna, Hinkov, Vladimir

The recent realizations of the quantum anomalous Hall effect (QAHE) in MnBi2Te4 and MnBi4Te7 benchmark the (MnBi2Te4)(Bi2Te3)n family as a promising hotbed for further QAHE improvements. The family owes its potential to its ferromagnetically (FM) ordered MnBi2Te4 septuple layers (SLs). However, the QAHE realization is complicated in MnBi2Te4 and MnBi4Te7 due to the substantial antiferromagnetic (AFM) coupling between the SLs. An FM state, advantageous for the QAHE, can be stabilized by interlacing the SLs with an increasing number n of Bi2Te3 quintuple layers (QLs). However, the mechanisms driving the FM state and the number of necessary QLs are not understood, and the surface magnetism remains obscure. Here, robust FM properties in MnBi6Te10 (n = 2) with Tc ≈ 12 K are demonstrated and their origin is established in the Mn/Bi intermixing phenomenon by a combined experimental and theoretical study. The measurements reveal a magnetically intact surface with a large magnetic moment, and with FM properties similar to the bulk. This investigation thus consolidates the MnBi6Te10 system as perspective for the QAHE at elevated temperatures.

2022, Ćwik, Jacek, Koshkid’ko, Yurii, Nenkov, Konstantin, Tereshina-Chitrova, Evgenia, Małecka, Małgorzata, Weise, Bruno, Kowalska, Karolina

To date, significant efforts have been put into searching for materials with advanced magnetocaloric properties which show promise as refrigerants and permit realization of efficient cooling. The present study, by an example of Ho1−xErxNi2, develops the concept of magnetocaloric efficiency in the rare-earth Laves-phase compounds. Based on the magneto-thermodynamic properties, their potentiality as components of magnetocaloric composites is illustrated. The determined regularities in the behaviour of the heat capacity, magnetic entropy change, and adiabatic temperature change of the system substantiate reaching high magnetocaloric potentials in a desired temperature range. For the Ho1−xErxNi2 solid solutions, we simulate optimal molar ratios and construct the composites used in magnetic refrigerators performing an Ericsson cycle at low temperatures. The tailored magnetocaloric characteristics are designed and efficient procedures for their manufacturing are developed. Our calculations based on the real empirical data are very promising and open avenue to further experimental studies. Systems showing large magnetocaloric effect (MCE) at low temperatures are of importance due to their potential utilization in refrigeration for gas liquefaction.

2015, Katukuri, Vamshi M., Nishimoto, Satoshi, Rousochatzakis, Ioannis, Stoll, Hermann, van den Brink, Jeroen, Hozoi, Liviu

With large spin-orbit coupling, the electron configuration in d-metal oxides is prone to highly anisotropic exchange interactions and exotic magnetic properties. In 5d5 iridates, given the existing variety of crystal structures, the magnetic anisotropy can be tuned from antisymmetric to symmetric Kitaev-type, with interaction strengths that outsize the isotropic terms. By many-body electronic-structure calculations we here address the nature of the magnetic exchange and the intriguing spin-glass behavior of Li2RhO3, a 4d5 honeycomb oxide. For pristine crystals without Rh-Li site inversion, we predict a dimerized ground state as in the isostructural 5d5 iridate Li2IrO3, with triplet spin dimers effectively placed on a frustrated triangular lattice. With Rh-Li anti-site disorder, we explain the observed spin-glass phase as a superposition of different, nearly degenerate symmetry-broken configurations.

2022, Grebenko, Artem K., Krasnikov, Dmitry V., Bubis, Anton V., Stolyarov, Vasily S., Vyalikh, Denis V., Makarova, Anna A., Fedorov, Alexander, Aitkulova, Aisuluu, Alekseeva, Alena A., Gilshtein, Evgeniia, Bedran, Zakhar, Shmakov, Alexander N., Alyabyeva, Liudmila, Mozhchil, Rais N., Ionov, Andrey M., Gorshunov, Boris P., Laasonen, Kari, Podzorov, Vitaly, Nasibulin, Albert G.

Following the game-changing high-pressure CO (HiPco) process that established the first facile route toward large-scale production of single-walled carbon nanotubes, CO synthesis of cm-sized graphene crystals of ultra-high purity grown during tens of minutes is proposed. The Boudouard reaction serves for the first time to produce individual monolayer structures on the surface of a metal catalyst, thereby providing a chemical vapor deposition technique free from molecular and atomic hydrogen as well as vacuum conditions. This approach facilitates inhibition of the graphene nucleation from the CO/CO2 mixture and maintains a high growth rate of graphene seeds reaching large-scale monocrystals. Unique features of the Boudouard reaction coupled with CO-driven catalyst engineering ensure not only suppression of the second layer growth but also provide a simple and reliable technique for surface cleaning. Aside from being a novel carbon source, carbon monoxide ensures peculiar modification of catalyst and in general opens avenues for breakthrough graphene-catalyst composite production.

2022, Zhao, Wei, Sun, Tingting, Zheng, Yiwei, Zhang, Qihao, Huang, Aibin, Wang, Lianjun, Jiang, Wan

Development of ionic thermoelectric (iTE) materials is of immense interest for efficient heat-to-electricity conversion due to their giant ionic Seebeck coefficient (Si), but challenges remain in terms of relatively small Si at low humidity, poor stretchability, and ambiguous interaction mechanism in ionogels. Herein, a novel ionogel is reported consisting of polyethylene oxide (PEO), polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), and 1-ethyl-3-methylimidazolium acetate (Emim:OAC). By delicately designing the interactions between ions and polymers, the migration of anions is restricted due to their strong binding with the hydroxyl groups of polymers, while the transport of cations is facilitated through segmental motions due to the increased amorphous regions, thereby leading to enlarged diffusion difference between the cations and anions. Moreover, the plasticizing effect of P123 and Emim:OAC can increase the elongation at break. As a consequence, the ionogel exhibits excellent properties including high Si (18 mV K−1 at relative humidity of 60%), good ionic conductivity (1.1 mS cm−1), superior stretchability (787%), and high stability (over 80% retention after 600 h). These findings show a promising strategy to obtain multifunctional iTE materials by engineering the intermolecular interactions and demonstrate the great potential of ionogels for harvesting low-grade heat in human-comfortable humidity environments.

2022, Fomin, Vladimir M., Rezaev, Roman O., Dobrovolskiy, Oleksandr V.

Extending of nanostructures into the third dimension has become a major research avenue in condensed-matter physics, because of geometry- and topology-induced phenomena. In this regard, superconductor 3D nanoarchitectures feature magnetic field inhomogeneity, non-trivial topology of Meissner currents and complex dynamics of topological defects. Here, we investigate theoretically topological transitions in the dynamics of vortices and slips of the phase of the order parameter in open superconductor nanotubes under a modulated transport current. Relying upon the time-dependent Ginzburg–Landau equation, we reveal two distinct voltage regimes when (i) a dominant part of the tube is in either the normal or superconducting state and (ii) a complex interplay between vortices, phase-slip regions and screening currents determines a rich FFT voltage spectrum. Our findings unveil novel dynamical states in superconductor open nanotubes, such as paraxial and azimuthal phase-slip regions, their branching and coexistence with vortices, and allow for control of these states by superimposed dc and ac current stimuli.

2022, Borrmann, Fabian, Tsuda, Takuya, Guskova, Olga, Kiriy, Nataliya, Hoffmann, Cedric, Neusser, David, Ludwigs, Sabine, Lappan, Uwe, Simon, Frank, Geisler, Martin, Debnath, Bipasha, Krupskaya, Yulia, Al‐Hussein, Mahmoud, Kiriy, Anton

The understanding and applications of electron-conducting π-conjugated polymers with naphtalene diimide (NDI) blocks show remarkable progress in recent years. Such polymers demonstrate a facilitated n-doping due to the strong electron deficiency of the main polymer chain and the presence of the positively charged side groups stabilizing a negative charge of the n-doped backbone. Here, the n-type conducting NDI polymer with enhanced stability of its n-doped states for prospective “in-water” applications is developed. A combined experimental–theoretical approach is used to identify critical features and parameters that control the doping and electron transport process. The facilitated polymer reduction ability and the thermodynamic stability in water are confirmed by electrochemical measurements and doping studies. This material also demonstrates a high conductivity of 10−2 S cm−1 under ambient conditions and 10−1 S cm−1 in vacuum. The modeling explains the stabilizing effects for various dopants. The simulations show a significant doping-induced “collapse” of the positively charged side chains on the core bearing a partial negative charge. This explains a decrease in the lamellar spacing observed in experiments. This study fundamentally enables a novel pathway for achieving both thermodynamic stability of the n-doped states in water and the high electron conductivity of polymers.

2022, Heckel, Sandra, Bilsing, Clemens, Wittmann, Martin, Gemming, Thomas, Büttner, Lars, Czarske, Jürgen, Simmchen, Juliane

Catalytic microswimmers that move by a phoretic mechanism in response to a self-induced chemical gradient are often obtained by the design of spherical janus microparticles, which suffer from multi-step fabrication and low yields. Approaches that circumvent laborious multi-step fabrication include the exploitation of the possibility of nonuniform catalytic activity along the surface of irregular particle shapes, local excitation or intrinsic asymmetry. Unfortunately, the effects on the generation of motion remain poorly understood. In this work, single crystalline BiVO4 microswimmers are presented that rely on a strict inherent asymmetry of charge-carrier distribution under illumination. The origin of the asymmetrical flow pattern is elucidated because of the high spatial resolution of measured flow fields around pinned BiVO4 colloids. As a result the flow from oxidative to reductive particle sides is confirmed. Distribution of oxidation and reduction reactions suggests a dominant self-electrophoretic motion mechanism with a source quadrupole as the origin of the induced flows. It is shown that the symmetry of the flow fields is broken by self-shadowing of the particles and synthetic surface defects that impact the photocatalytic activity of the microswimmers. The results demonstrate the complexity of symmetry breaking in nonspherical microswimmers and emphasize the role of self-shadowing for photocatalytic microswimmers. The findings are leading the way toward understanding of propulsion mechanisms of phoretic colloids of various shapes.

2023, Changizi, Rasa, Zaefferer, Stefan, Ziegler, Christian, Romaka, Vitaliy, Lotsch, Bettina V., Scheu, Christina

Due to the novel properties of both 2D materials and rare-earth elements, developing 2D rare-earth nanomaterials has a growing interest in research. To produce the most efficient rare-earth nanosheets, it is essential to find out the correlation between chemical composition, atomic structure and luminescent properties of individual sheets. In this study, 2D nanosheets exfoliated from Pr3+-doped KCa2Nb3O10 particles with different Pr concentrations were investigated. Energy dispersive X-ray spectroscopy analysis indicates that the nanosheets contain Ca, Nb and O and a varying Pr content between 0.9 and 1.8 at%. K was completely removed after exfoliation. The crystal structure is monoclinic as in the bulk. The thinnest nanosheets are 3 nm corresponding to one triple perovskite-type layer with Nb on the B sites and Ca on the A sites, surrounded by charge compensating TBA+ molecules. Thicker nanosheets of 12 nm thickness (and above) were observed too by transmission electron microscopy with the same chemical composition. This indicates that several perovskite-type triple layers remain stacked similar to the bulk. Luminescent properties of individual 2D nanosheets were studied using a cathodoluminescence spectrometer revealing additional transitions in the visible region in comparison to the spectra of different bulk phases.