Compositional variation in hybrid organic-inorganic lead halide perovskites : kinetically- versus thermodynamically-controlled synthesis
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The formation and study of partial solid solutions in Az1-xFAxPbBr3, using reportedly similar sized cations azetidinium (Az+) and formamidinium (FA+), was explored via mechanosynthesis and precipitation synthesis. The composition and lattice parameters of samples from both syntheses were analyzed by 1H NMR and Rietveld refinement of powder X-ray diffraction. A clear mismatch in the composition of the perovskite was found between the precipitated samples and the corresponding solutions. Such a mismatch was not observed for samples obtained via mechanosynthesis. The discrepancy suggests products are kinetically-controlled during precipitation, compared to thermodynamically controlled mechanosynthesis. Furthermore, the cell volume as a function of composition in both hexagonal, 6H (Az-rich) and cubic, 3C (FA-rich) perovskite solid solutions suggests that FA+ is actually smaller than Az+, contradicting the literature. In the 3C (Az-poor) solid solutions, the extent of Az1-xFAxPbBr3 is unexpectedly smaller than in the corresponding methylammonium (MA+) system, Az1-xMAxPbBr3, which suggests that the extent of solid solution formation in these halide perovskites is predominantly dependent on the average A-cation size while the size mismatch plays a lesser role in comparison to oxides.
Tian , J , Zysman-Colman , E & Morrison , F D 2021 , ' Compositional variation in hybrid organic-inorganic lead halide perovskites : kinetically- versus thermodynamically-controlled synthesis ' , Chemistry of Materials , vol. 33 , no. 10 , pp. 3650-3659 . https://doi.org/10.1021/acs.chemmater.1c00470
Chemistry of Materials
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DescriptionAuthors thank the Chinese Scholarship Council and the University of St Andrews for Ph.D. Studentship support (to JT, CSC No. 201603780020).
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