Orbital-order phase transition in Pr1−xCaxMnO3 probed by photovoltaics

A new phase diagram of $Pr_{1-x}Ca_xMnO_3$ for x $\le$ 0.3 is derived that suggests a necessary revaluation of the phase diagram of other manganites in that doping region. Rather than an orbital ordered phase reaching up to high temperatures 850 K for x=0.1 and 950 K for x=0, we propose a loss of spontaneous order already near room temperature. Above this temperature, the phase is characterized by a finite orbital polarization and octahedral tilt pattern. The tilt pattern couples to the Jahn-Teller distortion and thus induces a remaining orbital order, which persists up to high temperatures, where the tilt order is lost as well. This explains the experimental observation of orbital order up to high temperatures. Anomalies at a temperature 220-260 K have been observed in epitaxial thin films of doping x=0.1 for photovoltaic effect, electric transport, magnetisation, optical and ultrafast transient pump probe studies. The onset of the polaron photovoltaic effect and the increase of the hot polaron relaxation time below $T_{OO}$ suggest a change in the orbital order. Finite-temperature simulations based on a tight-binding model with carefully adjusted parameters from first-principles calculations exhibit an orbital-order phase transition at $T_{OO} \approx$ 300 K for x=0.1. This is consistent with the experimental observation of a change in temperature dependent lattice parameter for bulk samples of the same doping at 300 K for x=0.1 and 350 K for x=0, typical for a second order phase transition.