Impact of nanostructuring on the magnetic and magnetocaloric properties of microscale phase-separated La5/8-yPryCa3/8MnO3 manganites

Bulk manganites of the form La5/8-yPryCa3/8MnO3 (LPCMO) exhibit a complex phase diagram due to coexisting charge-ordered antiferromagnetic (CO/AFM), charge-disordered paramagnetic (PM), and ferromagnetic (FM) phases. Because phase separation in LPCMO occurs on the microscale, reducing particle size to below this characteristic length is expected to have a strong impact on the magnetic properties of the system. Through a comparative study of the magnetic and magnetocaloric properties of single-crystalline (bulk) and nanocrystalline LPCMO (y = 3/8) we show that the AFM, CO, and FM transitions seen in the single crystal can also be observed in the large particle sizes (400 and 150 nm), while only a single PM to FM transition is found for the small particles (55 nm). Magnetic and magnetocaloric measurements reveal that decreasing particle size affects the balance of competing phases in LPCMO and narrows the range of fields over which PM, FM, and CO phases coexist. The FM volume fraction increases with size reduction, until CO is suppressed below some critical size, similar to 100 nm. With size reduction, the saturation magnetization and field sensitivity first increase as long-range CO is inhibited, then decrease as surface effects become increasingly important. The trend that the FM phase is stabilized on the nanoscale is contrasted with the stabilization of the charge-disordered PM phase occurring on the microscale, demonstrating that in terms of the characteristic phase separation length, a few microns and several hundred nanometers represent very different regimes in LPCMO.