Journal of Materials Science, Vol.54, No.3, 2001-2015, 2019
Phase-change behavior of hot-pressed methylammonium lead bromide hybrid perovskites
The investigation of hot-pressed methylammonium lead bromide (MAPbBr3) is reported. The as-prepared materials consisted of microcrystallites (30-500 lm size) with a non-centrosymmetric pseudo-cubic tetragonal crystalline structure (P4 mm space group). The thermal analysis under air showed a thermal stability of MAPbBr3 perovskite till T = 250 C and a broad endothermic event at T = 371 C (melting point of solid PbBr2). Under increasing pressure at room temperature, the MA-Pb-Br system retained the pseudo-cubic tetragonal structure, the optical adsorption spectra displayed a strong absorption edge between 570 and 572 nm, and the Tauc plots revealed a direct semiconducting behavior with band energy gaps around 2.20(+/- 0.01) eV. The steady-state emission (PL) photoluminescence spectra (excitation wavelengths kexc = 380 nm) showed an emission band at * 574 nm. With increase in the temperature (under constant pressure and treatment time), the MA-Pb-Br system turned into the higher cubic symmetry (space group Pm 3m), the absorption edges shifted to 571-575 nm, and at T = 120 C, the absorbance profile begins to increase at higher wavelengths ([600 nm). By increasing the pressure at constant temperature, the perovskite adopted the cubic structure and a slight decrease in the energy band gap (2.17 eV for T = 150 C and P = 15 MPa) was recorded. With increase in the hot-pressing time at T = 150 C and P = 20 MPa, the optical absorption edges remained at * 575 nm; however, the decrease in the absorbance can indicate a degradation of the materials. The changes in the emission mechanism(s) of the hot-pressed materials can be related to the observed change in the crystalline structure and morphology.