Cation distribution and particle size effect on Raman spectrum of CoFe2O4

Mössbauer and Raman spectroscopic studies were carried out on CoFe₂O₄ particles synthesized with size ranging from 6 to 500 nm (bulk). Cation distribution studies were carried out on the high temperature and room temperature phases of the microcrystalline CoFe₂O₄ by Mössbauer and Raman spectroscopic methods. The high temperature phase of CoFe₂O₄ showed a decreased inversion parameter of 0.69 as compared to the value of the room temperature phase of 0.95, indicating that the structure gradually transforms towards a normal spinel. Corresponding Raman spectra for these two phases of CoFe₂O₄ showed a change in relative peak intensity of the vibrational mode at 695 cm⁻¹(A_1g(1)) to 624 cm⁻¹ (A_1g(2)). The relative peak intensity ratio, I_v between the A_1g(1) and A_1g(2) vibrational mode was decreasing with lowering of inversion parameter of the CoFe₂O₄ spinel system. A variation of laser power on the sample surface was reflected in the cation distribution in ferrite phase. Superparamagnetic, single domain CoFe₂O₄ particles (6 nm) showed a 20 cm⁻¹ red shift and broadening of phonon modes when compared to the macro-crystalline CoFe₂O₄ (500 nm). Variation of Raman shift with particle size was studied by considering the bond polarization model. Raman spectroscopic studies clearly indicate the variation in the cation distribution in nano-sized particles and distribution tending to a normal spinel structural configuration.