The structural and optical properties of the ZnO, Al-doped ZnO, Ga-doped ZnO, and In-doped ZnO nanorods were investigated using field-emission scanning electron microscopy, X-ray diffraction, photoluminescence (PL) and ultraviolet-visible spectroscopy. All the nanorods grew with good alignment on the ZnO seed layers and the ZnO nanorod dimensions could be controlled by the addition of the various dopants. For instance, the diameter of the nanorods decreased with increasing atomic number of the dopants. The ratio between the nearband-edge emission (NBE) and the deep-level emission (DLE) intensities (I NBE /I DLE ) obtained by PL gradually decreased because the DLE intensity from the nanorods gradually increased with increase in the atomic number of the dopants. We found that the dopants affected the structural and optical properties of the ZnO nanorods including their dimensions, lattice constants, residual stresses, bond lengths, PL properties, transmittance values, optical band gaps, and Urbach energies.
Boron-doped ZnO (BZO) nanorods were grown on quartz substrates using hydrothermal synthesis, and the temperature-dependence of their photoluminescence (PL) was measured in order to investigate the origins of their PL properties. In the UV range, near-band-edge emission (NBE) was observed from 3.1 to 3.4 eV; this was attributed to various transitions including recombination of free excitons and their longitudinal optical (LO) phonon replicas, and donor-acceptor pair (DAP) recombination, depending on the local lattice configuration and the presence of defects. At a temperature of 12 K, the NBE produces seven peaks at 3.386, 3.368, 3.337, 3.296, 3.258, 3.184, and 3.106 eV. These peaks are, respectively, assigned to free excitons (FX), neutral-donor bound excitons (D o X), and the first LO phonon replicas of D o X, DAP, DAP-1LO, DAP-2LO, and DAP-3LO. The peak position of the FX and DAP were also fitted to Varshni's empirical formula for the variation in the band gap energy with temperature. The activation energy of FX was about ~70 meV, while that of DAP was about ~38 meV. We also discuss the low temperature PL near 2.251 eV, related to structural defects.
The photoluminescence (PT) properties of Al-doped ZnO thin films grown by the sol-gel dip-coating method have been investigated. At 12 K, nine distinct PL peaks were observed at 2. 037, 2.592, 2.832, 3.027, 3.177, 3.216, 3.260, 3.303, and 3.354 eV. The deep-level emissions (2.037, 2.592, 2.832, and 3.027 eV) were attributed to native defects. The near-band-edge (NBE) emission peaks at 3. 354, 3.303, 3.260, 3.216, and 3.177 eV were attributed to the emission of the neutral-donor-bound excitons (D 0 X), two-electron satellite (TES), free-to-neutral-acceptors (e,A 0 ), donor-acceptor pairs (DAP), and second-order longitudinal optical (2LO) phonon replicas of the TES (TES-2LO), respectively. According to Haynes' empirical rule, we calculated the energy of a free exciton (FX) to be 3.374 eV. The thermal activation energy for D 0 X in the nanocrystalline ZnO thin film was found to be ~25 meV, corresponding to the thermal dissociation energy required for D 0 X transitions.
Hydrothermally grown ZnO nanorods were doped with various concentrations of Sn, ranging from 0 to 2.5 at%. Scanning electron microscopy (SEM), X-ray diffractometer (XRD), ultraviolet (UV)-visible spectroscopy, and Photoluminescence (PL) measurements were used to determine the effect of Sn doping on the structural and optical properties. In the SEM images, the nanorods have hexagonal wurtzite structure and the diameter of the nanorods increases with an increase in the Sn content. The optical parameters of the Sn-doped ZnO (SZO) nanorods such as the absorption coefficients, optical bandgaps, Urbach energies, refractive indices, dispersion parameters, dielectric constants, and optical conductivities were determined from the transmittance and reflectance results. In the PL spectra, the intensity of the NBE peak in the UV region decreases and is blue-shifted with an increase in the Sn content, while the DLE peaks of the nanorods in the visible region shift toward the low-energy region with the introduction of Sn.
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