Role of Central Atom on the Pressure Response of 2D Perovskites Containing a Long Alkyl Chain (Decylammonium, DA): DA2PbI4 and DA2GeI4

The application of an external pressure on Metal Halide Perovskite (MHPs) has become a fascinating way of tuning their optical properties, achieving also novel features. Here, the pressure response of 2D MHPs including a long alkyl chain made of ten carbon atoms, namely decylammonium (DA), has been investigated as a function of the central atom in DA2PbI4 and DA2GeI4. The two systems share a common trend in the phase stability, displaying a transition from an orthorhombic to a monoclinic phase around 2 GPa, followed by a phase separation in two monoclinic phases characterized by different c-axis. The optical properties show rather different behavior due to the presence of Pb or Ge. DA2PbI4 shows a progressive red shift of the band gap from 2.28 eV at ambient conditions, to 1.64 eV at 11.5 GPa, with a narrow PL emission composed by two components, with the second one appearing in concomitance with the phase separation and significantly shifted to lower energy. On the other hand, DA2GeI4, changes from a non-PL system at ambient pressure, to a clear broadband emitter centered around 730 nm (FWHM ~ 170 nm), with a large stoke shift, and an intensity maximum at about 3.7 GPa. This work sheds light on the structural stability of 2D perovskites characterized by extended alkyl chains, to date limited to four carbon atoms, and shows the pressure-induced emergence of broad emission in a novel lead-free perovskite, DA2GeI4. The evidence of wide emission by a moderate pressure in a germanium-based 2D MHP represents a novel result which may open the design, by chemical pressure, of efficient wide or even white lead-free emitters.