Raman study of cations' distribution in Zn _xMg _(12x)Fe _2O _4 nanoparticles

摘要

In a complementary way, Raman and M?ssbauer spectroscopy were successfully employed to assess the cations' distribution among the tetrahedral (A-site) and octahedral (B-site) sites of nonosized ZnxMg _(1-x)Fe _2O _4 (0 B x B 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. M?ssbauer data indicated that as the Zncontent (x) increases in the range 0 B x B 1, the Fe3? ion monotonically increases (decreases) the A-site (B-site) occupancy up to nearly equal values at thehighest end x value. Analysis of the Raman data,however, confirms that the three highest energy modes around 650, 668 and 710 cm-1 are assigned to Zn-O (B-site), Fe-O (A-site) and Mg-O (A-site) vibrations, respectively. Additionally, in agreement with the M?ssbauer data, the Raman data show that as the Zn-content (x) increases in the range 0 B x B 1, the occupancy of A-sites by Mg _2? ions monotonically reduces with concomitant increase of A- and B-sites occupancy by Fe _3? and Zn _2? ions, respectively.Indeed, combination of the two sets of spectroscopic data (Raman and M?ssbauer) provides an effective protocol for assessing the cations' distribution within the crystal structure of nanosized quaternary cubic ferrite samples running for instance from Fe ~3+ _(0:42) Mg ~2+ i-A Zn ~2+ _(0:20)Mg ~2+ _(0:22)Fe ~3+ _(1:58)-B O ~2- _4 at x = 0.2 up toFe ~3+ _(1:0)-A Zn ~2+ _(0:60)Mg ~2+ _(0:40)Fe ~3+ _(1:0)-B O ~2- _4 at x = 0.6.