Wafer-Scale Programmed Assembly of One-Atom-Thick Crystals.

Crystalline films offer various physical properties based on the modulation of their thicknesses and atomic structures. The layer-by-layer assembly of atomically thin crystals provides a powerful means to arbitrarily design films at the atomic level, which are unattainable with existing growth technologies. However, atomically clean assembly of the materials with high scalability and reproducibility remains challenging. We report programmed crystal assembly of graphene and monolayer hexagonal boron nitride, assisted by van der Waals interactions, to form wafer-scale films of pristine interfaces with near-unity yield. The atomic configurations of the films are tailored with layer-resolved compositions and in-plane crystalline orientations. We demonstrate batch-fabricated tunnel device arrays with modulation of the resistance over orders of magnitude by thickness control of the hexagonal boron nitride barrier with single-atom precision and large-scale, twisted multilayer graphene with programmable electronic band structures and crystal symmetries. Our results constitute an important development in the artificial design of large-scale films.

Programmable Synthesis of Silver Wheels.

The synthesis of sandwich-shaped multinuclear silver complexes with planar penta- and tetranuclear wheel-shaped silver units and a central anion, [Agn(2-HPB)2(A-)](OTf-)n-1, nAgA, n = 4 or 5 and A- = OH- or F- or Cl-, is reported, along with complete spectroscopic and structural characterization. An NMR mechanistic study reveals that silver complexes were formed in the following order: 2Ag → 3AgH2O → 5AgOH → 4AgOH. The central hydroxides in 4AgOH and 5AgOH exhibit exotic physical properties due to the confined environment inside the complex. The size of these silver wheels can be tuned by changing the central anion or extracting/adding one silver atom. This study provides the facile way to synthesize discrete wheel-shaped multinuclear silver complexes and provides valuable insights into the dynamics of the self-assembly process.

Long-Term Chemical Aging of Hybrid Halide Perovskites.

Because the power conversion efficiency (PCE) of hybrid halide perovskite solar cells (PSCs) could exceed 24%, extensive research has been focused on improving their long-term stability for commercialization in the near future. In a previous study, we reported that the addition of a number of ionized iodide (triiodide: I3-) ions during perovskite film formation significantly improved the efficiency of PSCs by reducing deep-level defects in the perovskite layer. Understanding the relationship between the concentration of these defects and the long-term chemical aging of PSCs is important not only for obtaining fundamental insight into the perovskite materials but also for studying the long-term chemical stability of PSCs. Herein we aim to identify the origin of the natural decay in PCE during long-term chemical aging of PSCs in the dark based on formamidinium lead triiodide by comparing the performance of control and low-defect (LD) devices. After aging for 200 days, the change in the PCE of the LD devices (1.3%) was found to be half that of the control devices (2.6%). We investigated this difference using grazing incidence wide-angle X-ray scattering, deep-level transient spectroscopy, scanning photoelectron microscopy, and high-resolution photoemission spectroscopy. The addition of I3- was found to reduce the amounts of hydroxide and Ox in the halide perovskites (HPs), affecting the migration of defects and the structural transformation of the HPs.

Shape transformation and self-alignment of Fe-based nanoparticles.

New types of functional material structures will emerge if the shape and properties are controlled in three-dimensional nanodevices. Possible applications of these would be nanoelectronics and medical systems. Magnetic nanoparticles (MNPs) are especially important in electronics such as magnetic storage, sensors, and spintronics. Also, in those that are used as magnetic resonance imaging contrasts, and tissue specific therapeutic agents, as well as in the labeling and sorting of cells, drug delivery, separation of biochemical products, and in other medical applications. Most of these applications require MNPs to be chemically stable, uniform in size, and controllable in terms of their magnetic properties and shape. In this paper three new functions of iron (Fe)-based nanoparticles are reported: shape transformation, oxidation prevention, and self-alignment. The shape of the Fe nanoparticles could be controlled by changing their oxidation states and properties by using a nanocarbon coating. Full field X-ray microscopy using synchrotron radiation revealed controllable magnetic properties of MNPs at the L3 edge which depended on the oxidation states. Then, inkjet printing was successfully performed to deposit a uniform layer of MNPs by the size.