Effect of Mn doping on the structural and optical properties of ZrO2 thin films prepared by sol–gel method

Abstract Homogeneous and transparent Mn doped ZrO 2 thin films were prepared by sol–gel dip coating method. The films were annealed in air atmosphere at 500 °C. The X-ray diffraction pattern of the undoped ZrO 2 thin film revealed a mixed phase of tetragonal and monoclinic ZrO 2 with preferred orientations along T(111) and M(− 111). Grazing Incidence X-ray Diffraction of Mn doped ZrO 2 thin films reveals the introduction of Mn interstitial in ZrO 2 which stabilize the mixed phase of ZrO 2 into tetragonal phase. Atomic force microscope image shows the addition of catalyst (Mn) which stops isotropic agglomeration of particles, instead of anisotropic agglomeration that occurred resulting in growth of particles in certain direction. Average transmittances of > 70% (in UV–vis region) were observed for all samples. The optical band gap decreased from 5.72 to 4.52 eV with increase in Mn doping concentration. The reduced band gap is due to the introduction of impurity levels in the band gap, by incorporation of the metal ions into the ZrO 2 lattice. The d-electron of Mn (t 2g level) can easily overlap with the ZrO 2 's valence band (VB) because t 2g of Mn is very close to VB of ZrO 2 . This overlap caused a wide VB and consequently decreases the band gap of ZrO 2 . The photoluminescence (PL) spectrum of undoped zirconia thin film exhibits an intense near band edge emission peak at 392.5 nm (3.15 eV) and weak emission peaks at 304 (4.07 eV), 604 nm (2.05 eV) and 766 nm (1.61 eV). Additional PL peaks were observed for Mn doped ZrO 2 located at around 420, 447 (blue), 483 (blue) and 529 (green) nm respectively. These peaks were due to the redox properties of various valence state of Mn in ZrO 2 . The prepared Mn doped ZrO 2 thin films can be applied in optical devices.