Abstract
Diluted magnetic semiconductors (DMSs) doped glasses are attractive to magneto-optical and nonlinear applications due to the sp-d exchange interaction between semiconductor carriers and magnetic ions in glass matrix. This paper reports the synthesis, characterization and doping of ZnO, Zn0.96Mn0.04O and Zn0.6Cu0.4O in heavy metal oxides homogeneous matrix. Mn2+ and Mn3+ co-existed in Zn0.96Mn0.04O while only Cu+ existed in Zn0.6Cu0.4O which occupied or entered into the interstitial of Zn2+ sites, resulting the increase of lattice spacing and newly Raman vibration mode at 526.9 cm−1 and 571 cm−1. Due to the large incorporation concentration of Cu, Zn0.6Cu0.4O presented ZnO and Cu2O crystallites. Due to the s–d and p–d exchange interactions of doped ions, Zn0.96Mn0.04O and Zn0.6Cu0.4O showed decreased energy band gap, characteristic transition of Mn2+, Mn3+ and Cu+ ions and ferromagnetic magnetization.The influence of DMSs to the homogeneity, color and structure of heavy metal oxide glasses is apparent. Zn0.96Mn0.04O doping caused slightly crystallization of cubic Bi2O3. FT-IR displayed the network former role of ZnO as ZnO4 units and the modification of Mn2+, Mn3+, and Cu+, Cu2+ to the frame units of PbO4, BiO3, BiO6, BO3 in glass. DMSs doped glasses all exhibited red-shift of cutoff wavelength, shrinkage of energy band gap, electron transition and luminescence of Mn and Cu ions. The third order nonlinear absorption coefficient and refractive index were calculated and increased due to the enhancement of polarizability by the doping ions. even though Zn0.96Mn0.04O and Zn0.6Cu0.4O doped glasses showed superfine structures in EPR spectra, all glasses displayed diamagnetic behavior and the Zn0.6Cu0.4O doped glass showed the highest magnetization and Verdet constant (0.2524 min/G.cm at 500 nm wavelength) which is attractive for photonics, nonlinearity and Faraday rotation applications.
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