X-ray study of anisotropically shaped metal halide perovskite nanoparticles in tubular pores

Recently, we have reported that metal halide perovskite nanoparticles formed in nanoporous alumina and silicon thin films exhibit blue shifted photoluminescence due to spatial confinement, thus allowing for color tuning of the emission by varying the pore size. While perovskite nanoparticles grown in nanoporous alumina films have been integrated into LEDs, similar approaches have failed with silicon. Here, we report the results of investigating the structure of the alumina pore system and the perovskite crystallites forming within. We use two x-ray diffraction techniques, namely, small-angle x-ray scattering (SAXS) and high-energy microbeam wide-angle x-ray scattering (WAXS). SAXS reveals that the alumina pore system diffracts like regularly arranged tubes with the average diameter and nearest neighbor distance of 12 nm and 20 nm, respectively. High-energy microbeam WAXS shows that perovskite nanoparticles within the nanoporous alumina have a distinctly anisotropic shape with the average particle length along and perpendicular to the pore axis of 26 nm and 13 nm, respectively. In contrast, no shape anisotropy has been detected for nanoparticles inside the silicon pores in a previous study. This suggests that utilizing nanoporous alumina has a twofold advantage. First, the tubular alumina pores, spanning the entire insulating film, offer percolated paths for the perovskite to fill. Second, the elongation of the nanoparticles in the tubular alumina pores can be expected to aid device performance as the length of the nanoparticles approaches the active layer thickness (ca. 40 nm) of LEDs, while the small diameter of the crystallites accounts for the observed blue shifted emission.