Huge Photo-Stability Enhancement in Bismuth Doped Methylammonium Lead Iodide Hybrid Perovskites by Light Induced Transformation

Abstract

The doping strategy of hybrid perovskites is being extensively explored not only for higher efficiency but also to overcome issues in photovoltaic materials such as self-degradation pathways in an ambient atmosphere or under visible irradiation. Here, BiI3 is introduced in the synthesis of MAPbI3 films (MA: CH3–NH3+) to stabilize the material. Around 25% of nominal Bi3+ is accommodated in the perovskite structure, producing a shrinking of the unit cell and a small increase of the band gap. The presence of empty Bi gap states quenches the 770 nm red interband emission and results in a near-infrared emission at 1100 nm. However, high enough visible irradiation density induces a progressive segregation of Bi3+ out of the perovskite lattice and promotes the re-emergence of the red emission. This emission is blue-shifted, and its intensity increases strongly with time until it reaches a saturation value which remains stable in the transformed films for extremely high power densities, around 1000 times higher than for undoped samples. We propose that the underlying processes include the formation of BiI3 and BiOI, probably at the surface of the crystals, hampering the usual decomposition pathways into PbI2 and PbOx for undoped MAPbI3. These results provide a new path for obtaining highly stable materials which would allow an additional boost of hybrid perovskite-based optoelectronics.