Synthesis and properties of Zn(Cu–Mn)O dilute magnetic semiconductor thin films by chemical spray pyrolysis technique

Abstract

The Mn–Cu co-doped ZnO thin films with Zn1–2xCuxMnxO (x=0.05) composition were synthesized by precursor solution spray pyrolysis at ≤300°C in the highly crystalline c-axis oriented wurtzite structural form. X-ray diffraction studies show absence of binary oxide phases and substitutional doping of Mn and Cu in ZnO. The chemical environment of the dopant ions probed by the XPS analysis of the binding energy shifts and structure of the Cu and Mn XPS peaks show that Mn2+ and Cu2+ occupy Zn2+ sites in the ZnO lattice with Mn ions having bonding with lattice and interstitial O2− ions. The lowering of the optical band gap energy from undoped ZnO films at ∼3.22eV to 3.16eV shows doping by Mn and Cu in ZnO gives rise to band gap bowing in Zn0.90Cu0.05Mn0.05O thin films. The magnetization studies of the Zn0.90Cu0.05Mn0.05O films analyzed at 2K and 300K using squid magnetometer show ferromagnetic behavior with magnetization value of 5×10−5emu and saturation magnetization at ∼15kOe at 300K. The observance of the ferromagnetism at room temperature is attributed to the mixed valence state of Mn in ZnO akin to the Mn3O4 spinel phase and the interstitial oxygen defects.