SCIENTIA SINICA Chimica, Volume 49, Issue 3: 556-563(2019) https://doi.org/10.1360/N032018-00221

Interface-controlled two-dimensional cuprous oxide structures

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  • ReceivedOct 9, 2018
  • AcceptedNov 22, 2018
  • PublishedJan 17, 2019


The synthesis, structures and properties of two-dimensional oxides have great fundamental significance and application potentials for the fields of catalysis, electronic devices and superconductors. In this article, the growth and synthesis of two-dimensional cuprous oxide were investigated on the surfaces of Ag(111) and Cu(111) single crystals. The structures of these two-dimensional cuprous oxides were characterized at the atomic scale using scanning tunneling microscopy in ultrahigh vacuum (UHV). On Ag(111), two-dimensional cuprous oxide nanostructures exhibit an ordered honeycomb structure with the lattice distance between six-membered rings at ~6.0 Å and the stoichiometry of Cu3O2. The hexagonal lattice of Cu3O2 also contains a small amount of “5-7” defect structure. In comparison, two-dimensional cuprous oxide nanostructures on Cu(111) also exhibit the stoichiometry of Cu3O2, but their surfaces are dominated by the large number of “5-7” defect structure. As a result, their surface lattice does not display the long-range order. Two-dimensional Cu3O2 nanostructures on Ag(111), as well as their zig-zag edges, could remain stable in 10−6 mbar O2 at 400 K or in UHV at 700 K. Under similar oxidation conditions, the Cu3O2 structure without long-range order would grow on Cu(111), due to the continuous oxidation of the exposed Cu surface. The oxidation of the Cu3O2 structure on Cu(111) eventually leads to the formation of the ordered “44”- or “29”-cuprous oxide structure. The comparison of the structure and stability of two-dimensional cuprous oxide on Ag(111) and Cu(111) thus demonstrated that the properties of two-dimensional cuprous oxide could be determined by the interfacial interaction. Our study provides not only a method for the preparation of model catalysts for the interfaces between metal and cuprous oxide, but also a pathway for further exploration of the physical and chemical properties of two-dimensional cuprous oxides.

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  • Figure 1

    The surface of Ag(111) after depositing Cu in 1.5×10−7 mbar O2 at room temperature (RT). (a) STM image of the clean Ag(111) surface. (b) STM image of the Ag(111) surface after depositing Cu for 1.5 min in O2. (c) The surface of (b) after the following deposition of Cu for 2 min in O2. (d) High-resolution STM image and the apparent height of three dimensional islands on Ag(111). Scanning parameters: (a, b) Vs=1.0 V, I=0.1 nA; (c, d) Vs=−1.1 V, I=0.1 nA (color online).

  • Figure 2

    Cuprous oxide structures on Ag(111) prepared by vapor deposition of Cu atoms in O2 at cryogenic temperatures. (a) and (d) correspond to the sample surfaces prepared by depositing Cu in 1.5×10−7 mbar O2 for 40 and 80 s, respectively, while Ag(111) was held at ~120 K. (b) and (e) are STM images of the surfaces (a) and (d) after the annealing at 350 K in UHV. (c) and (f) give atomic resolution STM images of the cuprous oxides in (b) and (e). The Cu lattice of the cuprous oxide exhibits the triangle-stacking kagomé structure. The monolayer cuprous oxide displays an O–Cu–O trilayer structure with the Cu plane in between the upper O (OU) and lower O (OL) planes, similar to that of the Cu2O(111) surface (g). But, unlike the Cu2O(111) surface (g), the monolayer cuprous oxide (h) does not have dangling Cu atoms in the center of the hexagonal ring. The oxide surface contains also “5-7” defects and the corresponding structural model is displayed in (h). Blue, pink and yellow balls represent Cu atoms, O atoms in upper layer and in lower layer, respectively. Yellow and red shaded areas mark the five- and seven-membered rings. (i) The structural model of the zig-zag edges of cuprous oxides. Scanning parameters: (a) Vs=1.9 V, I=0.1 nA; (b) Vs=−3.0 V, I=5.0 nA; (c) Vs=0.2 V, I=1.1 nA; (d) Vs=0.5 V, I=0.2 nA; (e, f) Vs=−2.0 V, I=0.1 nA (color online).

  • Figure 3

    The growth of cuprous oxide structure on Cu(111). (a) STM image of the Cu(111) surface after depositing Cu in 1.5×10−7 mbar O2 at RT. The apparent height of the two dimensional island marked by the white dash line is plotted in (b). (c, d) STM images of cuprous oxide structures on Cu(111) prepared by depositing Cu onto Cu(111) in 1.5×10−7 mbar O2 at ~120 K, which is followed by the annealing at 400 K in UHV. (e, f) STM images of cuprous oxide structures on Cu(111) prepared by directly oxidizing Cu(111) in 5×10−7 mbar O2 at 400 K. (d) and (f) give atomic resolution STM images of cuprous oxide structures obtained by the above two growth methods. Scanning parameters: (a) Vs=−2.5 V, I=17 pA; (c) and (d) Vs=−2.0 V, I=74 pA; (e) Vs=−1.4 V, I=86 pA; (f) Vs=−1.0 V, I=0.3 nA (color online).

  • Figure 4

    Structural stability of cuprous oxide on Ag(111) and Cu(111) in UHV and the O2 atmosphere. (a, b) STM images of cuprous oxides on Au(111) after the annealing at 600 and 700 K in UHV. (c) High-resolution STM image of the cuprous oxide surface in (b). (d) STM image of the surface of cuprous oxides on Ag(111) after the annealing in 5×10−6 mbar O2 at 400 K. (e, f) STM images of the surfaces of cuprous oxides on Cu(111) after the annealing in 5×10−7 mbar O2 (e) and 2×10−6 mbar O2 (f) at 400 K, respectively. Scanning parameters: (a) Vs=2.1 V, I=45 pA; (b) Vs=2.3 V, I=70 pA; (c) Vs=1.1 V, I=0.1 nA; (d) Vs=−1.2 V, I=0.1 nA; (e) Vs=−1.2 V, I=0.3 nA; (f) Vs=−0.2 V, I=0.2 nA (color online).

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