ABSTRACT
In this work, we apply polarized Raman spectroscopy for study of internal vibrations of the 3-cyanopyridinium cation in the halide post-perovskite (3cp)PbBr3 (3cp = 3-CN-C5H5NH+). For a single cation, the vibrational frequencies and intensities of the Raman signal were calculated using the density functional theory. Selection rules were established for vibrations of cations in the crystal. These rules together with modeling results were used to identify the internal vibrations of the cation in the Raman spectrum of the crystal. Narrow and isolated internal vibrations of cations could be used as spectators of the crystalline environment.
ABSTRACT
Halide perovskites and their low-dimensional analogs are promising semiconductor materials for solar cells, LEDs, lasers, detectors and other applications in the area of photonics. The most informative optical property of semiconductor photonics materials is the absorption spectrum enabling observation of the fundamental absorption edge, exciton structure, defect-related bands, etc. Traditionally, in the study of halide perovskites, this spectrum is obtained by absorption spectroscopy of thin films or diffuse reflectance spectroscopy of powders. The first method is applicable only to compounds with the developed thin film deposition technology, and in the second case, a large absorption coefficient narrows the observations down to the sample transparency region. In this paper, we suggest the diffuse reflectance spectroscopy with dilution as a method for obtaining the full-range absorption spectrum from halide perovskite powders, and demonstrate its application to practically important cases.
ABSTRACT
We investigate vibrations of the pyridinium cation PyH+ = C5H5NH+ in one-dimensional lead halide perovskites PyPbX3 and pyridinium halide salts PyHX (X- = I-, Br-), combining infrared absorption and Raman scattering methods at room temperature. Internal vibrations of the cation were assigned based on density functional theory modeling. Some of the vibrational bands are sensitive to perovskite or the salt environment in the solid state, while halide substitution has only a minor effect on them. These findings have been confirmed by 1H, 13C and 207Pb solid-state nuclear magnetic resonance (NMR) experiments. Narrower vibrational bands in perovskites indicate less disorder in these materials. The splitting of NH-group vibrational bands in perovskites can be rationalized the presence of nonequivalent crystal sites for cations or by more exotic phenomena such as quantum tunneling transition between two molecular orientations. We have shown how organic cations in hybrid organic-inorganic crystals could be used as spectators of the crystalline environment that affects their internal vibrations.
