Porous Fractals of MAPbI3 Perovskite : Characterization of Crystal Grain Formation by Irreversible Diffusion-Limited Aggregation

• Isopropanol solution based methylammonium lead triiodide (MAPbI3) is studied during the crystallization process. The crystal growth starts in an unstable suspension far from equilibrium by forming different dendritic patterns and terminates with aggregation of stable cubic crystalline grains into fractal clusters. Using transmission electron microscopy (TEM), the time evolution of a newly mixed suspension was studied over a period of two weeks at room temperature and a sequence of the morphological changes was observed. The crystallization process started with single dendritic growth exhibiting branches at 90 degrees angles to one another. After 4 hours, a multi-dendritic growth pattern and a transformation into small crystalline quantum dots were observed. After a week, clusters of crystal grains were formed into a fractal pattern and these patterns appear to be stable also during the second week. Electron and x-ray diffraction revealed the crystallinity of the quantum dots and the clusters of micrometer-sized crystals. Scanning transmission electron microscope (STEM) together with energy dispersive X-ray spectroscopy (EDS) showed that newly formed large grains, from a one hour old solution, displayed a core-shell structure with higher percentage of Pb atoms as compared to iodine at the surface. In the inner core of the grains the percentage of iodine was slightly higher. The electron diffraction (ED) scan over the newly formed grains revealed a polycrystalline surface whereas the inner part had a single crystal pattern. The same solution, now one-week-old, contained grains with only single crystal patterns in the ED scan and showed no core-shell character or polycrystalline surface. The measured percentage of iodine atoms compared to lead was 2:1 throughout the cross section, which is a quantitative value within the measurement. It can be concluded from these measurements that the suspension approaches higher crystallinity of the perovskite grains in an irreversible process, where the perovskite grains are insoluble in isopropanol. The perovskite material has also been characterized with scanning electron microscopy (SEM) and photoluminescence (PL) mapping where both techniques showed a very porous crystalline material. The PL mapping revealed two peaks at 730 and 760 nm for a thin film spin coated from a newly mixed solution, while a film deposited from a one week old solution showed three peaks, the last one at 830 nm. Because of the high crystallinity, it is suggested that all three peaks are due to band-to-band transitions and not due to localized states. These data will be analyzed further; however, the results contain information of the content of quantum dots versus larger crystals, as well as displaying emission intensity variations at different positions of the grains. The purpose with this project is to understand these phenomena of crystal growth. A new mesoporous perovskite material has been designed for optoelectronic purposes.

Nyckelord

Engineering Science with specialization in Solid State Physics

Teknisk fysik med inriktning mot fasta tillståndets fysik

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