In-field X-ray and neutron diffraction studies of re-entrant charge-ordering and field induced metastability in La0.175Pr0.45Ca0.375MnO3-δ

Low-temperature high-magnetic field (2 K, 8 T) (LTHM) powder X-ray diffraction (XRD) and time of flight powder neutron diffraction (NPD), low-temperature transmission electron microscopic (TEM), and resistivity and magnetization measurements have been carried out to investigate the re-entrant charge ordering (CO), field induced structural phase transitions, and metastability in phase-separated La_0.175Pr_0.45Ca_0.375MnO_3-δ (LPCMO). Low-temperature TEM and XRD studies reveal that on cooling under zero-field, paramagnetic Pnma phase transforms to P2₁/m CO antiferromagnetic (AFM) insulating phase below ∼233 K. Unlike reported literature, no structural signature of CO AFM P2₁/m to ferromagnetic (FM) Pnma phase-transition during cooling down to 2 K under zero-field was observed. However, the CO phase was found to undergo a re-entrant transition at ∼40 K. Neutron diffraction studies revealed a pseudo CE type spin arrangement of the observed CO phase. The low-temperature resistance, while cooled under zero-field, shows insulator to metal like transition below ∼105 K with minima at ∼25 K. On application of field, the CO P2₁/m phase was found to undergo field-induced transition to FM Pnma phase, which shows irreversibility on field removal below ∼40 K. Zero-field warming XRD and NPD studies reveal that field-induced FM Pnma phase is a metastable phase, which arise due to the arrest of kinetics of the first-order phase transition of FM Pnma to CO-AFM P2₁/m phase, below 40 K. Thus, a strong magneto-structural coupling is observed for this system. A field-temperature (H-T) phase-diagram has been constructed based on the LTHM-XRD, which matches very nicely with the reported H-T phase-diagram constructed based on magnetic measurements. Due to the occurrence of gradual growth of the re-entrant CO phase and the absence of a clear structural signature of phase-separation of CO-AFM P2₁/m and FM Pnma phases, the H-T minima in the phase-diagram of the present LPCMO sample has been attributed to the strengthening of AFM interaction during re-entrant CO transition and not to glass like "dynamic to frozen" transition.