Raman study of cations' distribution in Zn sub(x) Mg sub(1-x)Fe sub(2)O sub(4) nanoparticles

In a complementary way, Raman and Mossbauer spectroscopy were successfully employed to assess the cations' distribution among the tetrahedral (A-site) and octahedral (B-site) sites of nonosized Zn sub(x) Mg sub(1-x)Fe sub(2)O sub(4) (0 less than or equal to x less than or equal to 1) cubic ferrite structure, synthesized by combustion reaction method. Nanoparticles with little change in size distributions, in the 40 nm (x = 0.0) up to 42 nm (x = 1.0) were obtained. Mossbauer data indicated that as the Zn-content (x) increases in the range 0 less than or equal to x less than or equal to 1, the Fe super(3+) ion monotonically increases (decreases) the A-site (B-site) occupancy up to nearly equal values at the highest end x value. Analysis of the Raman data, however, confirms that the three highest energy modes around 650, 668 and 710 cm super(-1) are assigned to Zn-O (B-site), Fe-O (A-site) and Mg-O (A-site) vibrations, respectively. Additionally, in agreement with the Mossbauer data, the Raman data show that as the Zn-content (x) increases in the range 0 less than or equal to x less than or equal to 1, the occupancy of A-sites by Mg super(2+) ions monotonically reduces with concomitant increase of A- and B-sites occupancy by Fe super(3+) and Zn super(2+) ions, respectively. Indeed, combination of the two sets of spectroscopic data (Raman and Mossbauer) provides an effective protocol for assessing the cations' distribution within the crystal structure of nanosized quaternary cubic ferrite samples running for instance from $$ \left[ {{\text{Fe}}_{0.42}3 + } {\text{Mg}}_{0.58}2 + } } \right]A} \left[ {{\text{Zn}}_{0.20}2 + } {\text{Mg}}_{0.22}2 + } {\text{Fe}}_{1.58}3 + } } \right]B} O_{4}2 - } $$ at x = 0.2 up to $$ \left[ {{\text{Fe}}_{1.0}3 + } } \right]A} \left[ {{\text{Zn}}_{0.60}2 + } {\text{Mg}}_{0.40}2 + } {\text{Fe}}_{1.0}3 + } } \right]B} {\text{O}}_{4}2 - } $$ at x = 0.6.