Synthesis, Crystal and Electronic Structures, and Optical Properties of (CH3NH3)2CdX4 (X = Cl, Br, I)

We report the synthesis, crystal and electronic structures, as well as optical properties of the hybrid organic-inorganic compounds MA 2 CdX 4 (MA = CH 3 NH 3 ; X = Cl, Br, I). MA 2 CdI 4 is a new compound, whereas, for MA 2 CdCl 4 and MA 2 CdBr 4 , structural investigations have already been conducted but electronic structures and optical properties are reported here for the first time. Single crystals were grown through slow evaporation of MA 2 CdX 4 solutions with optimized conditions yielding mm-sized colorless (X = Cl, Br) and pale yellow (X = I) crystals. Single crystal and variable temperature powder X-ray diffraction measurements suggest that MA 2 CdCl 4 forms a 2D layered perovskite structure and has two structural transitions at 283 and 173 K. In contrast, MA 2 CdBr 4 and MA 2 CdI 4 adopt 0D K 2 SO 4 -derived crystal structures based on isolated CdX 4 etrahedra and show no phase transitions down to 20 K. The contrasting crystal structures and chemical compositions in the MA 2 CdX 4 family impact their air stabilities, investigated for the first time in this work; MA 2 CdCl 4 is air-stable, whereas MA 2 CdBr 4 and MA 2 CdI 4 partially decompose when left in air. Optical absorption measurements suggest that MA 2 CdX 4 have large optical band gaps above 3.9 eV. Room temperature photoluminescence spectra of MA 2 CdX 4 yield broad peaks in the 375-955 nm range with full width at half-maximum values up to 208 nm. These PL peaks are tentatively assigned to self-trapped excitons in MA 2 CdX 4 following the crystal and electronic structure considerations. The bands around the Fermi level have small dispersions, which is indicative of high charge localization with significant exciton binding energies in MA 2 CdX 4 . On the basis of our combined experimental and computational results, MA 2 CdX 4 and related compounds may be of interest for white-light-emitting phosphors and scintillator applications.