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

• Published in: Journal of nanoparticle research : an interdisciplinary forum for nanoscale science and technology Vol. 14; no. 4; p. 1
• Main Authors: Da Silva, S W, Nakagomi, F, Silva, M S, Franco, A, Garg, V K, Oliveira, A C, Morais, P C
• Format: Journal Article
• Language: English
• Published: Dordrecht Springer Nature B.V 01-03-2012
• Subjects: Cations; Ions; Nanoparticles; Zinc
• DOI: 10.1007/s11051-012-0798-4
• EISSN: 1572-896X
• ISSN: 1388-0764

In a complementary way, Raman and Mössbauer 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 ≤ x ≤ 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. Mössbauer data indicated that as the Zn-content (x) increases in the range 0 ≤ x ≤ 1, the Fe^sup 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^sup -1^ are assigned to Zn-O (B-site), Fe-O (A-site) and Mg-O (A-site) vibrations, respectively. Additionally, in agreement with the Mössbauer data, the Raman data show that as the Zn-content (x) increases in the range 0 ≤ x ≤ 1, the occupancy of A-sites by Mg^sup 2+^ ions monotonically reduces with concomitant increase of A- and B-sites occupancy by Fe^sup 3+^ and Zn^sup 2+^ ions, respectively. Indeed, combination of the two sets of spectroscopic data (Raman and Mössbauer) 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.[PUBLICATION ABSTRACT]