Effect of Co and Mg doping at Cu site on structural, magnetic and dielectric properties of α–Cu 2 V 2 O 7

We have studied the effect of doping of both magnetic (Co) and nonmagnetic (Mg) ions at the Cu site on phase transition in polycrystalline α–Cu 2 V 2 O 7 through structural, magnetic, and electrical measurements. X-ray diffraction reveals that Mg doping triggers an onset of α - to β -phase structural transition in Cu 2− x Mg x V 2 O 7 above a critical Mg concentration x c = 0.15, and both the phases coexist up to x = 0.25. Cu 2 V 2 O 7 possesses a non-centrosymmetric crystal structure and antiferromagnetic ordering along with a non-collinear spin structure in the α phase, originated from the microscopic Dzyaloshinskii–Moriya interaction between the neighboring Cu spins. Accordingly, a weak ferromagnetic (FM) behavior has been observed up to x = 0.25. However, beyond this concentration, Cu 2− x Mg x V 2 O 7 exhibits complex magnetic properties. A clear dielectric anomaly is observed in α–Cu 2− x Mg x V 2 O 7 around the magnetic transition temperature, which loses its prominence with the increase in Mg doping. The analysis of experimental data shows that the magnetoelectric coupling is nonlinear, which is in agreement with the Landau theory of continuous phase transitions. Co doping, on the other hand, initiates a sharp α to β phase transition around the same critical concentration x c = 0.15 in Cu 2− x Co x V 2 O 7 but the FM behavior is very weak and can be detected only up to x = 0.10. We have drawn the magnetic phase diagram which indicates that the rate of suppression in transition temperature is the same for both types of doping, magnetic (Co) and nonmagnetic (Zn/Mg).