The formation energies of Ag-N-codoped (8,0) ZnO SWNT were calculated to evaluate their stability. The formation energy can be expressed as In this equation, E(Ag,N-ZnO) and E(ZnO) are the total energies of ZnO SWNTs with and without the impurity, GSK2118436 chemical structure respectively, and
μ is the chemical potentials of Zn, O, Ag, and N, which depend on the growth conditions. The formation energies are listed in Table 1. The formation energy of Ag-doped ZnO nanotubes is apparently smaller than Ag-doped ZnO nanowires , which indicates that Ag-doped nanotubes is more easily achieved than nanowires. For the configurations with N atoms replacing O atoms, the formation energy increases with the increase of N concentration, Dibutyryl-cAMP mouse indicating that low N concentration is more stable. For the configuration with the same N concentration, the Ag1N2 configuration is more stable than Ag1N5 and Ag1N6 configurations. The formation energies of Ag1N2, Ag1N5, and Ag1N6 are smaller than Ag1N2,3,4 and Ag1N3,4 configurations, which indicates single N atom doping will induce more stable structures than that of more N atoms doped. The Ag-doped (8,0) ZnO www.selleckchem.com/products/Fulvestrant.html nanotube is distorted compared with the undoped one because the Ag-O bond lengths are longer than
the Zn-O bond lengths. For the Ag1N2, Ag1N3,4, and Ag1N2,3,4 configurations, there are bonds between Ag and N atoms. The average bond lengths in these configurations and the bond lengths of Zn atoms and N atoms are displayed in Table 1. Table 1 Bandgap ( E gap ), Zn-N bond lengths ( R Zn-N ), and formation energies ( E f ) of Ag-N-codoped ZnO nanotubes E gap(eV) R Ag-N(Å) R Zn-N(Å) R Ag-O(Å) E f(eV) (8,0) Ag1 1.17 – - 1.868 0.410 (8,0) Ag1N2 1.10 1.853 1.838 1.883 0.523 (8,0) Ag1N3,4 1.20 1.860 1.836 1.893 0.626 (8,0) Ag1N2,3,4 1.25 1.879 1.833 – 0.719 (8,0) Ag1N5 1.15 – 1.842 1.870 0.570 (8,0) Ag1N6 1.17 – 1.846 1.869 0.572 Electronic properties As shown in Figure 2, the further calculation of band structure for bulk wurtzite ZnO shows a direct bandgap
of 0.81 eV, which is in good agreement with the previous calculation , but is smaller than the experimental value. In Figure 2, the valence band maximum (VBM) of the bulk ZnO is predominantly contributed by O 2p character. The conduction band minimum (CBM) basically originates from the Zn 4s states with small see more O 2p states. That is to say, the electronic transition from O 2p states to Zn 4s states is responsible for the optical absorption onset of pure ZnO. For the pure (8,0) ZnO nanotube, the bandgap is 1.0 eV, close to other calculated value of 1.17 eV. The bandgap of ZnO nanotube is larger than the bulk material (0.81 eV) due to the quantum confinement effect. For Ag-doped ZnO nanotube, the bandgap increases to 1.17 eV (shown in Figure 3b), and two impurity levels appear and are located below the Fermi level, which show a donor character.