Publication | Open Access
Principles of melting in hybrid organic–inorganic perovskite and polymorphic ABX <sub>3</sub> structures
34
Citations
36
References
2022
Year
Four novel dicyanamide-containing hybrid organic-inorganic ABX<sub>3</sub> structures are reported, and the thermal behaviour of a series of nine perovskite and non-perovskite [AB(N(CN)<sub>2</sub>)<sub>3</sub>] (A = (C<sub>3</sub>H<sub>7</sub>)<sub>4</sub>N, (C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N, (C<sub>5</sub>H<sub>11</sub>)<sub>4</sub>N; B = Co, Fe, Mn) is analyzed. Structure-property relationships are investigated by varying both A-site organic and B-site transition metal cations. In particular, increasing the size of the A-site cation from (C<sub>3</sub>H<sub>7</sub>)<sub>4</sub>N → (C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N → (C<sub>5</sub>H<sub>11</sub>)<sub>4</sub>N was observed to result in a decrease in <i>T</i> <sub>m</sub> through an increase in Δ<i>S</i> <sub>f</sub>. Consistent trends in <i>T</i> <sub>m</sub> with metal replacement are observed with each A-site cation, with Co < Fe < Mn. The majority of the melts formed were found to recrystallise partially upon cooling, though glasses could be formed through a small degree of organic linker decomposition. Total scattering methods are used to provide a greater understanding of the melting mechanism.
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