Tuning the structures of two-dimensional cuprous oxide confined on Au(111)

Two-dimensional (2D) cuprous oxide (Cu₂O) nanostructures (NSs) of monolayer thickness were synthesized on Au(111) and characterized using atomic-resolution scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations. The surface and edge structures of 2D Cu₂O were resolved at the atomic level and found to exhibit a graphene-like lattice structure. Cu₂O NSs grew preferentially at the face centered cubic (fcc) domains of Au(111). Depending on the annealing temperature, the shapes and structures of Cu₂O NSs were found to vary from elongated islands with a defective hexagonal lattice (mostly topological 5–7 defects) to triangular NSs with an almost-perfect hexagonal lattice. The edge structures of Cu₂O NSs also varied with the annealing temperature, from predominantly the arm-chair 56 structure at 400 K to almost exclusively the zig-zag structure at 600 K. DFT calculations suggested that the herringbone ridges of Au(111) confined the growth and structure of Cu₂O NSs on Au(111). As such, the arm-chair edges of Cu₂O NSs, which are less stable than the zig-zag edges, could be exposed preferentially at 400 K. Cu₂O NSs developed into the thermodynamically-favored triangular form and exposed zig-zag edges at 600 K, when the Au(111) substrate became mobile. The confined growth of 2D cuprous oxide on Au(111) demonstrated the importance of metal-oxide interactions in tuning the structures of supported 2D oxide NSs.