Tuning ferromagnetism and spin state in La$_{(1-x)}$$A_x$CoO$_3$ ($A=$ Sr, Ca) nanoparticles

Abstract: We use the x-ray diffraction, magnetic susceptibility, isothermal magnetization, and photoelectron spectroscopy to study the structural, magnetic and electronic properties of La${(1-x)}$$A_x$CoO$_3$ ($A=$ Sr, Ca; $x=$ 0 -- 0.2) nanoparticles. The Rietveld refinements of room temperature powder x-ray diffraction data confirm the single phase and the rhombohedral crystal structure with R$\bar{3}$C space group. We find drastic changes in the magnetic properties and spin-states with Sr/Ca substitution (hole doping). For $x=$ 0 sample, the magnetic measurements show a ferromagnetic transition at T${\rm C}$$\approx$85 K, which shifted significantly to higher temperatures with hole doping; simultaneously a significant increase in the spontaneous magnetic moment has been observed. Whereas, the coercive field H${\rm C}$ values are 7, 4.4 and 13.2~kOe for $x=$ 0, 0.2 (Sr), and 0.2(Ca) samples. Furthermore, the FC magnetization shows a ferromagnetic Brillouin function like behavior at low temperatures for Ca samples. We demonstrate that the Sr/Ca substitution increases the population of IS (Co$^{3+}$) and LS (Co$^{4+}$) states and tune the ferromagnetism in nanoparticles via double-exchange interactions between Co$^{3+}$-- Co$^{4+}$. Our results suggest an important role of hole carriers and nano-size effect in controlling the spin-state and magnetism in La${(1-x)}$$A_x$CoO$_3$ nanoparticles.