Microstructure-Dependent Conformal Atomic Layer Deposition on 3D Nanotopography

The capability of atomic layer deposition (ALD) to coat conformally complex 3D nanotopography has been examined by depositing amorphous, polycrystalline, and single-crystal TiO₂ films over SnO₂ nanowires (NWs). Structural characterizations reveal a strong correlation between the surface morphology and the microstructures of ALD films. Conformal growth can only be rigorously achieved in amorphous phase with circular sectors developed at sharp asperities. Morphology evolution convincingly demonstrates the principle of ALD, i.e., sequential and self-limiting surface reactions result in smooth and conformal films. Orientation-dependent growth and surface reconstruction generally lead to nonconformal coating in polycrystalline and single-crystal films. Especially, an octagonal single-crystal TiO₂ shell was derived from a rectangular SnO₂ NW core, which was the consequence of both self-limited growth kinetics and surface reconstruction. Models were proposed to explain the conformality of ALD deposition over 3D nanostructures by taking account of the underlying microstructures. Besides the surface morphologies, the microstructures also have significant consequence to the surface electronic states, characterized by the broad band photoluminescence. The comparison study suggests that ALD process is determined by the interplay of both thermodynamic and kinetic factors

Atomic-scale observation of lithiation reaction front in nanoscale SnO \u3c inf\u3e 2 materials

In the present work, taking advantage of aberration-corrected scanning transmission electron microscopy, we show that the dynamic lithiation process of anode materials can be revealed in an unprecedented resolution. Atomically resolved imaging of the lithiation process in SnO2 nanowires illustrated that the movement, reaction, and generation of b = [1Ì...1Ì...1] mixed dislocations leading the lithiated stripes effectively facilitated lithium-ion insertion into the crystalline interior. The geometric phase analysis and density functional theory simulations indicated that lithium ions initial preference to diffuse along the [001] direction in the {200} planes of SnO2 nanowires introduced the lattice expansion and such dislocation behaviors. At the later stages of lithiation, the Li-induced amorphization of rutile SnO2 and the formation of crystalline Sn and LixSn particles in the Li2O matrix were observed. © 2013 American Chemical Society

Doping Monolayer Graphene with Single Atom Substitutions

Functionalized graphene has been extensively studied with the aim of tailoring properties for gas sensors, superconductors, supercapacitors, nanoelectronics, and spintronics. A bottleneck is the capability to control the carrier type and density by doping. We demonstrate that a two-step process is an efficient way to dope graphene: create vacancies by high-energy atom/ion bombardment and fill these vacancies with desired dopants. Different elements (Pt, Co, and In) have been successfully doped in the single-atom form. The high binding energy of the metal-vacancy complex ensures its stability and is consistent with in situ observation by an aberration-corrected and monochromated transmission electron microscope