Flat-surface-assisted and self-regulated oxidation resistance of Cu(111).

Oxidation can deteriorate the properties of copper that are critical for its use, particularly in the semiconductor industry and electro-optics applications1-7. This has prompted numerous studies exploring copper oxidation and possible passivation strategies8. In situ observations have, for example, shown that oxidation involves stepped surfaces: Cu2O growth occurs on flat surfaces as a result of Cu adatoms detaching from steps and diffusing across terraces9-11. But even though this mechanism explains why single-crystalline copper is more resistant to oxidation than polycrystalline copper, the fact that flat copper surfaces can be free of oxidation has not been explored further. Here we report the fabrication of copper thin films that are semi-permanently oxidation resistant because they consist of flat surfaces with only occasional mono-atomic steps. First-principles calculations confirm that mono-atomic step edges are as impervious to oxygen as flat surfaces and that surface adsorption of O atoms is suppressed once an oxygen face-centred cubic (fcc) surface site coverage of 50% has been reached. These combined effects explain the exceptional oxidation resistance of ultraflat Cu surfaces.

Hole-Carrier-Dominant Transport in 2D Single-Crystal Copper.

In 2D noble metals like copper, the carrier scattering at grain boundaries has obscured the intrinsic nature of electronic transport. However, it is demonstrated that the intrinsic nature of transport by hole carriers in 2D copper can be revealed by growing thin films without grain boundaries. As even a slight deviation from the twin boundary is perceived as grain boundaries by electrons, it is only through the thorough elimination of grain boundaries that the hidden hole-like attribute of 2D single-crystal copper can be unmasked. Two types of Fermi surfaces, a large hexagonal Fermi surface centered at the zone center and the triangular Fermi surface around the zone corner, tightly matching to the calculated Fermi surface topology, confirmed by angle-resolved photoemission spectroscopy (ARPES) measurements and vivid nonlinear Hall effects of the 2D single-crystal copper account for the presence of hole carriers experimentally. This breakthrough suggests the potential to manipulate the majority carrier polarity in metals by means of grain boundary engineering in a 2D geometry.

Self-Oxidation Resistance of the Curved Surface of Achromatic Copper.

Copper surfaces that exhibit a wide range of achromatic colors while still metallic have not been studied, despite advancements in antireflection coatings. A series of achromatic copper films grown with [111] preferred orientation by depositing 3D porous nanostructures is introduced via coherent/incoherent atomic sputtering epitaxy. The porous copper nanostructures self-regulate the giant oxidation resistance by constructing a curved surface that generates a series of monoatomic steps, followed by shrinkage of the lattice spacing of one or two surface layers. First-principles calculations confirm that these structural components cooperatively increase the energy barrier against oxygen penetration. The achromaticity of the single-crystalline porous copper films is systematically tuned by geometrical parameters such as pore size distribution and 3D linkage. The optimized achromatic copper films with high oxidation resistance show an unusual switching effect between superhydrophilicity and superhydrophobicity. The tailored 3D porous nanostructures can be a candidate material for numerous applications, such as antireflection coatings, microfluidic devices, droplet tweezers, and reversible wettability switches.

Coherent consolidation of trillions of nucleations for mono-atom step-level flat surfaces.

Constructing a mono-atom step-level ultra-flat material surface is challenging, especially for thin films, because it is prohibitively difficult for trillions of clusters to coherently merge. Even though a rough metal surface, as well as the scattering of carriers at grain boundaries, limits electron transport and obscures their intrinsic properties, the importance of the flat surface has not been emphasised sufficiently. In this study, we describe in detail the initial growth of copper thin films required for mono-atom step-level flat surfaces (MSFSs). Deposition using atomic sputtering epitaxy leads to the coherent merging of trillions of islands into a coplanar layer, eventually forming an MSFS, for which the key factor is suggested to be the individual deposition of single atoms. Theoretical calculations support that single sputtered atoms ensure the formation of highly aligned nanodroplets and help them to merge into a coplanar layer. The realisation of the ultra-flat surfaces is expected to greatly assist efforts to improve quantum behaviour by increasing the coherency of electrons.

Abnormally High-Lithium Storage in Pure Crystalline C60 Nanoparticles.

Li+ intercalates into a pure face-centered-cubic (fcc) C60 structure instead of being adsorbed on a single C60 molecule. This hinders the excess storage of Li ions in Li-ion batteries, thereby limiting their applications. However, the associated electrochemical processes and mechanisms have not been investigated owing to the low electrochemical reactivity and poor crystallinity of the C60 powder. Herein, a facile method for synthesizing pure fcc C60 nanoparticles with uniform morphology and superior electrochemical performance in both half- and full-cells is demonstrated using a 1 m LiPF6 solution in ethylene carbonate/diethyl carbonate (1:1 vol%) with 10% fluoroethylene carbonate. The specific capacity of the C60 nanoparticles during the second discharge reaches ≈750 mAh g-1 at 0.1 A g-1 , approximately twice that of graphite. Moreover, by applying in situ X-ray diffraction, high-resolution transmission electron microscopy, and first-principles calculations, an abnormally high Li storage in a crystalline C60 structure is proposed based on the vacant sites among the C60 molecules, Li clusters at different sites, and structural changes during the discharge/charge process. The fcc of C60 transforms tetragonal via orthorhombic Lix C60 and back to the cubic phase during discharge. The presented results will facilitate the development of novel fullerene-based anode materials for Li-ion batteries.

Color of Copper/Copper Oxide.

Stochastic inhomogeneous oxidation is an inherent characteristic of copper (Cu), often hindering color tuning and bandgap engineering of oxides. Coherent control of the interface between metal and metal oxide remains unresolved. Coherent propagation of an oxidation front in single-crystal Cu thin film is demonstrated to achieve a full-color spectrum for Cu by precisely controlling its oxide-layer thickness. Grain-boundary-free and atomically flat films prepared by atomic-sputtering epitaxy allow tailoring of the oxide layer with an abrupt interface via heat treatment with a suppressed temperature gradient. Color tuning of nearly full-color red/green/blue indices is realized by precise control of the oxide-layer thickness; the samples cover ≈50.4% of the standard red/green/blue color space. The color of copper/copper oxide is realized by the reconstruction of the quantitative yield color from the oxide "pigment" (complex dielectric functions of Cu2 O) and light-layer interference (reflectance spectra obtained from the Fresnel equations) to produce structural color. Furthermore, laser-oxide lithography is demonstrated with micrometer-scale linewidth and depth through local phase transformation to oxides embedded in the metal, providing spacing necessary for semiconducting transport and optoelectronics functionality.

Improving the precision of Hall effect measurements using a single-crystal copper probe.

The circuitry and components of a Hall measurement kit were replaced with single-crystal copper (SCC) wires and parts prepared by a novel wire fabrication process. This process preserved the grain-free structure of SCC grown by the Czochralski method. The new kit was used to determine, with greatly improved precision, the electrical coefficients such as carrier density and mobility, establish the reproducibility of the measured values, and define the semiconductor type. The observed reduction in electrical signal losses and distortion has been attributed to grain boundary elimination.