Twin-Boundary Reduced Surface Diffusion on Electrically Stressed Copper Nanowires.

Surface diffusion is intimately correlated with crystal orientation and surface structure. Fast surface diffusion accelerates phase transformation and structural evolution of materials. Here, through in situ transmission electron microscopy observation, we show that a copper nanowire with dense nanoscale coherent twin-boundary (CTB) defects evolves into a zigzag configuration under electric-current driven surface diffusion. The hindrance at the CTB-intercepted concave triple junctions decreases the effective surface diffusivity by almost 1 order of magnitude. The energy barriers for atomic migration at the concave junctions and different faceted surfaces are computed using density functional theory. We proposed that such a stable zigzag surface is shaped not only by the high-diffusivity facets but also by the stalled atomic diffusion at the concave junctions. This finding provides a defect-engineering route to develop robust interconnect materials against electromigration-induced failures for nanoelectronic devices.

Enhanced photolysis stability of Cu2O grown on Cu nanowires with nanoscale twin boundaries.

Cuprous oxide (Cu2O) that has a direct bandgap corresponding to visible-light absorption exhibits versatile functionalities, which are appealing to solar cell, photocatalyst, bio-sensing and water splitting applications. However, photolysis stability has long been a problem for Cu2O under light exposure and a humid environment. Here, we found that the Cu2O layer grown on Cu nanowires (CuNWs) with high-density nanoscale twin boundaries can maintain the integrity of Cu/Cu2O core-shell structure under ambient air conditions for more than one year. The Cu2O on nanotwinned CuNWs also demonstrates much higher stability in humid air and water with light exposure than its counterpart on nanocrystalline CuNWs. The superior photolysis stability of Cu2O is attributed to (1) photoelectrons drained to the Cu core, (2) limited vacancy sources in the Cu2O layer and (3) the suppressed out-diffusion of Cu cations through the oxide layer. It is suggested that the presence of nanoscale twin boundaries modifies the atomic surface structure of the CuNWs and alters the photolysis reaction of Cu2O.

Electrochemical Cycling-Induced Spiky Cu x O/Cu Nanowire Array for Glucose Sensing.

The glucose level is an important biological indicator for diabetes diagnosis. In contrast with costly and unstable enzymatic glucose sensing, oxide-based glucose sensors own the advantages of low fabrication cost, outstanding catalytic ability, and high chemical stability. Here, we fabricate a self-supporting spiky Cu x O/Cu nanowire array structure by electrochemical cycling treatment. The spiky Cu x O/Cu nanowire is identified to be a Cu core passivated by a conformal Cu2O layer with extruded CuO petals, which provides abundant active sites for electrocatalytic reaction in glucose detection. An interruptive potential sweeping experiment is presented to elucidate the growth mechanism of the spiky Cu x O/Cu nanostructure during the potential cycling treatment. The spiky Cu x O/Cu nanowire array electrode exhibits a sensitivity of 1210 ± 124 µA·mM-1·cm-2, a wide linear detection range of 0.01-7 mM, and a short response time (<1 s) for amperometric glucose sensing. The study demonstrates a route to modulate oxide phase, crystal morphology, and electrocatalytic properties of metal/oxide core-shell nanostructures.

Suppression of interdiffusion-induced voiding in oxidation of copper nanowires with twin-modified surface.

Cavitation and hollow structures can be introduced in nanomaterials via the Kirkendall effect in an alloying or reaction system. By introducing dense nanoscale twins into copper nanowires (CuNWs), we change the surface structure and prohibit void formation in oxidation of the nanowires. The nanotwinned CuNW exhibits faceted surfaces of very few atomic steps as well as a very low vacancy generation rate at copper/oxide interfaces. Together they lower the oxidation rate and eliminate void formation at the copper/oxide interface. We propose that the slow reaction rate together with the highly effective vacancy absorption at interfaces leads to a lattice shift in the oxidation reaction. Our findings suggest that the nanoscale Kirkendall effect can be manipulated by controlling the internal and surface crystal defects of nanomaterials.

Twin-mediated epitaxial growth of highly lattice-mismatched Cu/Ag core-shell nanowires.

Lattice-mismatch is an important factor for the heteroepitaxial growth of core-shell nanostructures. A large lattice-mismatch usually leads to a non-coherent interface or a polycrystalline shell layer. In this study, a conformal Ag layer is coated on Cu nanowires with dense nanoscale twin boundaries through a galvanic replacement reaction. Despite a large lattice mismatch between Ag and Cu (∼12.6%), the Ag shell replicates the twinning structure in Cu nanowires and grows epitaxially on the nanotwinned Cu nanowire. A twin-mediated growth mechanism is proposed to explain the epitaxy of high lattice-mismatch bimetallic systems in which the misfit dislocations are accommodated by coherent twin boundaries.