Although challenging, assembling and orienting non-spherical nanomaterials into two- and three-dimensional (2D and 3D) ordered arrays can facilitate versatile collective properties by virtue of their shape-dependent properties that cannot be realized with their spherical counterparts. Here, we report on the self-assembly of gold nanorods (AuNRs) into 2D films at the vapor/liquid interface facilitated by grafting them with poly(ethylene glycol) (PEG). Using surface sensitive synchrotron grazing incidence small angle X-ray scattering (GISAXS) and specular X-ray reflectivity (XRR), we show that PEG-AuNRs in aqueous suspensions migrate to the vapor/liquid interface in the presence of salt, forming a uniform monolayer with planar-to-surface orientation. Furthermore, the 2D assembled PEG functionalized AuNRs exhibit short range order into rectangular symmetry with side-by-side and tail-to-tail nearest-neighbor packing. The effect of PEG chain length and salt concentration on the 2D assembly are also reported.
The synthesis of Au@AgAu yolk-shell cuboctahedra nanoparticles formed by galvanic replacement in a seed-mediated method is described. Initially, single-crystal Au seeds are used for the formation of Au@Ag core-shell nanocubes, which serve as the template material for the deposition of an external Au layer. The well-controlled synthesis yields the formation of cuboctahedra nanoparticles with smooth inner and outer Au/Ag surfaces. The deposition/oxidation process is described to understand the formation of cuboctahedra and octahedra nanoparticles. The Au core maintains the initial morphology of the seed and remains static at the center of the yolk-shell because of residual Ag. Structural analysis of the shell indicates intrinsic stacking faults (SFs) near the surface. Energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) compositional analysis show an Au-Ag nonordered alloy forming the shell. The three-dimensional structure of the nanoparticles presented open facets on the [111] as observed by electron tomography SIRT reconstruction over a stack of high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images. The geometrical model was validated by analyzing the direction of streaks in coherent nanobeam diffraction (NBD). The catalytic activity was evaluated using a model reaction based on the reduction of 4-nitrophenol (4-NTP) by NaBH4 in the presence of Au@AgAu yolk-shell nanoparticles.
Abstract2D memristors have demonstrated attractive resistive switching characteristics recently but also suffer from the reliability issue, which limits practical applications. Previous efforts on 2D memristors have primarily focused on exploring new material systems, while damage from the metallization step remains a practical concern for the reliability of 2D memristors. Here, the impact of metallization conditions and the thickness of MoS2 films on the reliability and other device metrics of MoS2‐based memristors is carefully studied. The statistical electrical measurements show that the reliability can be improved to 92% for yield and improved by ≈16× for average DC cycling endurance in the devices by reducing the top electrode (TE) deposition rate and increasing the thickness of MoS2 films. Intriguing convergence of switching voltages and resistance ratio is revealed by the statistical analysis of experimental switching cycles. An “effective switching layer” model compatible with both monolayer and few‐layer MoS2, is proposed to understand the reliability improvement related to the optimization of fabrication configuration and the convergence of switching metrics. The Monte Carlo simulations help illustrate the underlying physics of endurance failure associated with cluster formation and provide additional insight into endurance improvement with device fabrication optimization.
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