Cu-Doping Induced Structural Transformation and Magnetocaloric Enhancement in CoCr₂O₄ Nanoparticles

This study systematically investigates the impact of Cu²⁺ doping on the structural, magnetic, and magnetocaloric properties of Cu_xCo_1-xCr₂O₄ nanoparticles synthesized via a solution combustion method. Cu incorporation up to x = 20% induces a progressive structural transformation from a cubic spinel to a trigonal corundum phase, as confirmed by X-ray diffraction and Raman spectroscopy. The doping process also leads to increased particle size, improved crystallinity, and reduced agglomeration. Magnetic measurements reveal a transition from hard to soft ferrimagnetic behavior with increasing Cu content, accompanied by a notable rise in the Curie temperature from 97.7 K (x = 0) to 140.2 K (x = 20%). The magnetocaloric effect (MCE) is significantly enhanced at higher doping levels, with the 20% Cu-doped sample exhibiting a maximum magnetic entropy change (-ΔS_M) of 2.015 J/kg-K and a relative cooling power (RCP) of 58.87 J/kg under a 60 kOe field. Arrott plot analysis confirms that the magnetic phase transitions remain second-order in nature across all compositions. These results demonstrate that Cu doping is an effective strategy for tuning the magnetostructural response of CoCr₂O₄ nanoparticles, making them promising candidates for low-temperature magnetic refrigeration applications.