2021, Chen, Chia-Hsiang, Spree, Lukas, Koutsouflakis, Emmanouil, Krylov, Denis S., Liu, Fupin, Brandenburg, Ariane, Velkos, Georgios, Schimmel, Sebastian, Avdoshenko, Stanislav M., Federov, Alexander, Weschke, Eugen, Choueikani, Fadi, Ohresser, Philippe, Dreiser, Jan, Büchner, Bernd, Popov, Alexey A.

Tremendous progress in the development of single molecule magnets (SMMs) raises the question of their device integration. On this route, understanding the properties of low‐dimensional assemblies of SMMs, in particular in contact with electrodes, is a necessary but difficult step. Here, it is shown that fullerene SMM self‐assembled on metal substrate from solution retains magnetic hysteresis up to 10 K. Fullerene‐SMM DySc2N@C80 and Dy2ScN@C80 are derivatized to introduce a thioacetate group, which is used to graft SMMs on gold. Magnetic properties of grafted SMMs are studied by X‐ray magnetic circular dichroism and compared to the films of nonderivatized fullerenes prepared by sublimation. In self‐assembled films, the magnetic moments of the Dy ions are preferentially aligned parallel to the surface, which is different from the disordered orientation of endohedral clusters in nonfunctionalized fullerenes. Whereas chemical derivatization reduces the blocking temperature of magnetization and narrows the hysteresis of Dy2ScN@C80, for DySc2N@C80 equally broad hysteresis is observed as in the fullerene multilayer. Magnetic bistability in the DySc2N@C80 grafted on gold is sustained up to 10 K. This study demonstrates that self‐assembly of fullerene‐SMM derivatives offers a facile solution‐based procedure for the preparation of functional magnetic sub‐monolayers with excellent SMM performance.

2020, Schwabe, Stefan, Niemann, Robert, Backen, Anja, Wolf, Daniel, Damm, Christine, Walter, Tina, Seiner, Hanuš, Heczko, Oleg, Nielsch, Kornelius, Fähler, Sebastian

Martensitic materials show a complex, hierarchical microstructure containing structural domains separated by various types of twin boundaries. Several concepts exist to describe this microstructure on each length scale, however, there is no comprehensive approach bridging the whole range from the nano- up to the macroscopic scale. Here, it is described for a Ni-Mn-based Heusler alloy how this hierarchical microstructure is built from scratch with just one key parameter: the tetragonal distortion of the basic building block at the atomic level. Based on this initial block, five successive levels of nested building blocks are introduced. At each level, a larger building block is formed by twinning the preceding one to minimize the relevant energy contributions locally. This naturally explains the coexistence of different types of twin boundaries. The scale-bridging approach of nested building blocks is compared with experiments in real and reciprocal space. The approach of nested building blocks is versatile as it can be applied to the broad class of functional materials exhibiting diffusionless transformations. © 2020 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH

2021, Yang, Liangtao, Kuo, Liang-Yin, López del Amo, Juan Miguel, Nayak, Prasant Kumar, Mazzio, Katherine A., Maletti, Sebastian, Mikhailova, Daria, Giebeler, Lars, Kaghazchi, Payam, Rojo, Teófilo, Adelhelm, Philipp

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na0.67Mn0.6Ni0.2Li0.2O2 is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g-1 after 100 cycles. In contrast, the Li-free compositions Na0.67Mn0.6Ni0.4O2 and Na0.67Mn0.8Ni0.2O2 show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni3+/Ni4+ and O2-/O2-δ redox processes by DFT, although a small contribution from Mn4+/Mn5+ to the capacity cannot be excluded. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH

2021, Yang, Xiaoqin, Ta, Huy Q., Hu, Huimin, Liu, Shuyuan, Liu, Yu, Bachmatiuk, Alicja, Luo, Jinping, Liu, Lijun, Choi, Jin-Ho, Rummeli, Mark H.

In this study, in situ transmission electron microscopy is performed to study the interaction between single (monomer) and paired (dimer) Sn atoms at graphene edges. The results reveal that a single Sn atom can catalyze both the growth and etching of graphene by the addition and removal of C atoms respectively. Additionally, the frequencies of the energetically favorable configurations of an Sn atom at a graphene edge, calculated using density functional theory calculations, are compared with experimental observations and are found to be in good agreement. The remarkable dynamic processes of binary atoms (dimers) are also investigated and is the first such study to the best of the knowledge. Dimer diffusion along the graphene edges depends on the graphene edge termination. Atom pairs (dimers) involving an armchair configuration tend to diffuse with a synchronized shuffling (step-wise shift) action, while dimer diffusion at zigzag edge terminations show a strong propensity to collapse the dimer with each atom diffusing in opposite directions (monomer formation). Moreover, the data reveals the role of C feedstock availability on the choice a single Sn atom makes in terms of graphene growth or etching. This study advances the understanding single atom catalytic activity at graphene edges. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH

2020, Aftenieva, Olha, Schnepf, Max, Mehlhorn, Börge, König, Tobias A.F.

In nanophotonics, there is a current demand for ultrathin, flexible nanostructures that are simultaneously easily tunable, demonstrate a high contrast, and have a strong response in photoluminescent polarization. In this work, the template-assisted self-assembly of water-dispersed colloidal core–shell quantum dots into 1D light-emitting sub-micrometer gratings on a flexible substrate is demonstrated. Combining such structures with a light-absorbing metallic counterpart by simple stacking at various angles results in a tunable Moiré pattern with strong lateral contrast. Furthermore, a combination with an identical emitter-based grating leads to a chiroptical effect with a remarkably high degree of polarization of 0.72. Such a structure demonstrates direct circular polarized photoluminescence, for the first time, without a need for an additional chiral template as an intermediary. The suggested approach allows for reproducible, large-area manufacturing at reasonable costs and is of potential use for chiroptical sensors, photonic circuit applications, or preventing counterfeit. © 2020 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH

2021, Spree, Lukas, Liu, Fupin, Neu, Volker, Rosenkranz, Marco, Velkos, Georgios, Wang, Yaofeng, Schiemenz, Sandra, Dreiser, Jan, Gargiani, Pierluigi, Valvidares, Manuel, Chen, Chia-Hsiang, Büchner, Bernd, Avdoshenko, Stanislav M., Popov, Alexey A.

The chemical functionalization of fullerene single molecule magnet Tb2@C80(CH2Ph) enables the facile preparation of robust monolayers on graphene and highly oriented pyrolytic graphite from solution without impairing their magnetic properties. Monolayers of endohedral fullerene functionalized with pyrene exhibit magnetic bistability up to a temperature of 28 K. The use of pyrene terminated linker molecules opens the way to devise integration of spin carrying units encapsulated by fullerene cages on graphitic substrates, be it single-molecule magnets or qubit candidates. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH

2021, Zhou, Junhua, Lian, Xueyu, You, Yizhou, Shi, Qitao, Liu, Yu, Yang, Xiaoqin, Liu, Lijun, Wang, Dan, Choi, Jin-Ho, Sun, Jingyu, Yang, Ruizhi, Rummeli, Mark H.

Sn4P3 binary alloy anode has attracted much attention, not only because of the synergistic effect of P and Sn, but also its universal popularity in alkali metal ion batteries (AIBs), including lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), and potassium-ion batteries (PIBs). However, the alkali metal ion (A+) storage and capacity attenuation mechanism of Sn4P3 anodes in AIBs are not well understood. Herein, a combination of ex situ X-ray diffraction, transmission electron microscopy, and density functional theory calculations reveals that the Sn4P3 anode undergoes segregation of Sn and P, followed by the intercalation of A+ in P and then in Sn. In addition, differential electrochemical curves and ex situ XPS results demonstrate that the deep insertion of A+ in P and Sn, especially in P, contributes to the reduction in capacity of AIBs. Serious sodium metal dendrite growth causes further reduction in the capacity of SIBs, while in PIBs it is the unstable solid electrolyte interphase and sluggish dynamics that lead to capacity decay. Not only the failure mechanism, including structural deterioration, unstable SEI, dendrite growth, and sluggish kinetics, but also the modification strategy and systematic analysis method provide theoretical guidance for the development of other alloy-based anode materials. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH

2021, Bandari, Vineeth Kumar, Schmidt, Oliver G.

The development of small machines, once envisioned by Feynman decades ago, has stimulated significant research in materials science, robotics, and computer science. Over the past years, the field of miniaturized robotics has rapidly expanded with many research groups contributing to the numerous challenges inherent to this field. Smart materials have played a particularly important role as they have imparted miniaturized robots with new functionalities and distinct capabilities. However, despite all efforts and many available soft materials and innovative technologies, a fully autonomous system-engineered miniaturized robot (SEMR) of any practical relevance has not been developed yet. In this review, the foundation of SEMRs is discussed and six main areas (structure, motion, sensing, actuation, energy, and intelligence) which require particular efforts to push the frontiers of SEMRs further are identified. During the past decade, miniaturized robotic research has mainly relied on simplicity in design, and fabrication. A careful examination of current SEMRs that are physically, mechanically, and electrically engineered shows that they fall short in many ways concerning miniaturization, full-scale integration, and self-sufficiency. Some of these issues have been identified in this review. Some are inevitably yet to be explored, thus, allowing to set the stage for the next generation of intelligent, and autonomously operating SEMRs.

2021, Dong, Haiyun, Saggau, Christian Niclaas, Zhu, Minshen, Liang, Jie, Duan, Shengkai, Wang, Xiaoyu, Tang, Hongmei, Yin, Yin, Wang, Xiaoxia, Wang, Jiawei, Zhang, Chunhuan, Zhao, Yong Sheng, Ma, Libo, Schmidt, Oliver G.

Metal halide perovskites are promising materials for optoelectronic and photonic applications ranging from photovoltaics to laser devices. However, current perovskite devices are constrained to simple low-dimensional structures suffering from limited design freedom and holding up performance improvement and functionality upgrades. Here, a micro-origami technique is developed to program 3D perovskite microarchitectures toward a new type of microcavity laser. The design flexibility in 3D supports not only outstanding laser performance such as low threshold, tunable output, and high stability but also yields new functionalities like 3D confined mode lasing and directional emission in, for example, laser “array-in-array” systems. The results represent a significant step forward toward programmable microarchitectures that take perovskite optoelectronics and photonics into the 3D era. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH.

2020, Zhu, Minshen, Wang, Xiaojie, Tang, Hongmei, Wang, Jiawei, Hao, Qi, Liu, Lixiang, Li, Yang, Zhang, Kai, Schmidt, Oliver G.

Hydrogels are widely used in flexible aqueous batteries due to their liquid-like ion transportation abilities and solid-like mechanical properties. Their potential applications in flexible and wearable electronics introduce a fundamental challenge: how to lower the freezing point of hydrogels to preserve these merits without sacrificing hydrogels' basic advantages in low cost and high safety. Moreover, zinc as an ideal anode in aqueous batteries suffers from low reversibility because of the formation of insulative byproducts, which is mainly caused by hydrogen evolution via extensive hydration of zinc ions. This, in principle, requires the suppression of hydration, which induces an undesirable increase in the freezing point of hydrogels. Here, it is demonstrated that cooperatively hydrated cations, zinc and lithium ions in hydrogels, are very effective in addressing the above challenges. This simple but unique hydrogel not only enables a 98% capacity retention upon cooling down to −20 °C from room temperature but also allows a near 100% capacity retention with >99.5% Coulombic efficiency over 500 cycles at −20 °C. In addition, the strengthened mechanical properties of the hydrogel under subzero temperatures result in excellent durability under various harsh deformations after the freezing process. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim