Origin of the electron spin resonance signal in the manganites: from polarons to phase separation

In the manganites L_1?xM_xMnO₃ (L = La, Nd, Pr, …; M = Sr, Ba, Ca, …), the doping concentration introduces a mixed valence (Mn³⁺, Mn⁴⁺) which governs the magnetic and electric properties of the compound. Mn³⁺ (S = 2) is scarcely observed in electron spin resonance (ESR). In contrast, Mn⁴⁺ (S = 3/2), is a good ESR probe. However, X-band measurements show an enhanced Mn⁴⁺ susceptibility, which is the signature of some kind of coupling of the Mn⁴⁺ ions with the Mn³⁺ ions, but its exact nature is still controversial. We present multifrequency ESR experiments (9–385 GHz) obtained on different systems (La_1?δMnO₃, La_1?xMnO₃, La_1?xCa_xMnO₃, and Nd_1?xCa_xMnO₃) in the low-concentration range (0 <x< 0.33). In the paramagnetic regime, the Mn³⁺ spectrum cannot be observed because of fast relaxation. The signal arises from polarons, whose size, temperature and magnetic field dependences vary with M andx. The single line observed in the metallic compound evolves towards a double-peak structure visible at high frequency in La_0.97MnO₃. Its evolution with temperature below the magnetic transition reveals the presence of manganese ions in a different magnetic environment, i.e., phase separation. The magnetic order of the separated phase is not ferromagnetic. It is a more complex order, which depends substantially on the nature of the cation M.