Doping-Induced Surface and Grain Boundary Effects in Ni-Rich Layered Cathode Materials.

In this work, the effects of dopant size and oxidation state on the structure and electrochemical performance of LiNi0.8Co0.1Mn0.1O2 (NCM811) are investigated. It is shown that doping with boron (B) which has a small ionic radius and an oxidation state of 3+, leads to the formation of a boron oxide-containing surface coating (probably Li3BO3), mainly on the outer surface of the secondary particles. Due to this effect, boron only slightly affects the size of the primary particle and the initial capacity, but significantly improves the capacity retention. On the other hand, the dopant ruthenium (Ru) with a larger ionic radius and a higher oxidation state of 5+ can be stabilized within the secondary particles and does not experience a segregation to the outer agglomerate surface. However, the Ru dopant preferentially occupies incoherent grain boundary sites, resulting in smaller primary particle size and initial capacity than for the B-doped and pristine NCM811. This work demonstrates that a small percentage of dopant (2 mol%) cannot significantly affect bulk properties, but it can strongly influence the surface and/or grain boundary properties of microstructure and thus the overall performance of cathode materials.

Selective Area Epitaxy of Quasi-1-Dimensional Topological Nanostructures and Networks.

Quasi-one-dimensional (1D) topological insulators hold the potential of forming the basis of novel devices in spintronics and quantum computing. While exposure to ambient conditions and conventional fabrication processes are an obstacle to their technological integration, ultra-high vacuum lithography techniques, such as selective area epitaxy (SAE), provide all the necessary ingredients for their refinement into scalable device architectures. In this work, high-quality SAE of quasi-1D topological insulators on templated Si substrates is demonstrated. After identifying the narrow temperature window for selectivity, the flexibility and scalability of this approach is revealed. Compared to planar growth of macroscopic thin films, selectively grown regions are observed to experience enhanced growth rates in the nanostructured templates. Based on these results, a growth model is deduced, which relates device geometry to effective growth rates. After validating the model experimentally for various three-dimensional topological insulators (3D TIs), the crystal quality of selectively grown nanostructures is optimized by tuning the effective growth rates to 5 nm/h. The high quality of selectively grown nanostructures is confirmed through detailed structural characterization via atomically resolved scanning transmission electron microscopy (STEM).