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Phonon dynamics of Zn(Mg,Cd)O alloy nanostructures and their phase segregation

In this paper we report phonon dynamics in chemically synthesized Zn1- xMgxO (0\leqx\leq0.07) and Zn1-yCdyO (0\leqy\leq0.03) alloy nanostructures of sizes ~10 nm using non-resonant Raman and Fourier Transformed Infrared Spectroscopy (FTIR). Substitution by Mg makes the unit cell compact while Cd substitution leads to unit cell expansion. On alloying, both A1(LO) and E1(LO) mode of wurtzite ZnO show blue shift for Zn1-xMgxO and red shift for Zn1-yCdyO alloy nanostructures due to mass defect and volume change induced by the impurity atoms. Significant shift has been observed in E1(LO) mode for Zn1-xMgxO (73 cm-1 for x = 0.07) and Zn1-yCdyO (17 cm-1 for y = 0.03) nanostructures. The variation in Zn(Mg,Cd)-O bond length determined from the blue (red) shift of IR bands on alloying with Mg (Cd) is consistent with their respective ionic sizes and the structural changes predicted by X-ray diffraction study. However, on progressive alloying one can detect phase segregation (due to presence of interstitial Mgand Cd ions) in the alloy nanostructures for relatively higher Mg and Cd concentrations. This is confirmed by the gradual absence of the characteristic IR and Raman bands of wurtzite ZnO near 400-600 cm-1 as well as by X-Ray and TEM studies.