Tetragonal CH3NH3PbI3 Is Ferroelectric

Abstract

Halide perovskite (HaP) semiconductors are revolutionizing photovoltaic (PV) solar energy conversion by showing remarkable performance of solar cells made with esp. tetragonal methylammonium lead tri-iodide (MAPbI3). In particular, the low voltage loss of these cells implies a remarkably low recombination rate of photogenerated carriers. It was suggested that low recombination can be due to spatial separation of electrons and holes, a possibility if MAPbI3 is a semiconducting ferroelectric, which, however, requires clear experimental evidence. As a first step we show that, in operando, MAPbI3 (unlike MAPbBr3) is pyroelectric, which implies it can be ferroelectric. The next step, proving it is (not) ferroelectric, is challenging, because of the material s relatively high electrical conductance (a consequence of an optical band gap suitable for PV conversion!) and low stability under high applied bias voltage. This excludes normal measurements of a ferroelectric hysteresis loop to prove ferroelctricity s hallmark for switchable polarization. By adopting an approach suitable for electrically leaky materials as MAPbI3, we show here ferroelectric hysteresis from well-characterized single crystals at low temperature (still within the tetragonal phase, which is the room temperature stable phase). Using chemical etching, we also image polar domains, the structural fingerprint for ferroelectricity, periodically stacked along the polar axis of the crystal, which, as predicted by theory, scale with the overall crystal size. We also succeeded in detecting clear second-harmonic generation, direct evidence for the material s non-centrosymmetry. We note that the material s ferroelectric nature, can, but not obviously need to be important in a PV cell, operating around room temperature.