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Published on: March 19, 2017
Odd-Even Alkyl Chain Effect of Aromatic Monoammoniums on the Interlayer Architecture and Stability of
Yang Liu1, Jianfei Fu1, Qingyong Tian2
1Ningbo Key Laboratory of Electronic Materials and Equipment, School of Materials and Energy Engineering, NingboTech University, Ningbo, China.
Abstract:
Ruddlesden-Popper (RP) 2D perovskites with organic bilayers attract great interest for optoelectronics owing to their high stability and tunable functionality. However, the relationship between the interlayer architecture, molecular configuration of aromatic cations, and resulting stability remains poorly understood. Herein, we systematically investigate phenyl alkylammonium-based RP 2D perovskites with varying alkyl chain lengths (─(CH2)mNH3 + with m = 1-4) of organic cations. We find that odd-carbon cations (m = 1, 3) preferentially form type-I 2D perovskites featuring interdigitated organic cations, which induces substantial inorganic distortion and lower octahedral symmetry to the C1 point group. Even-carbon cations (m = 2, 4) favor type-II 2D perovskites with well-defined interlayer gaps, wherein the alkylammonium groups rotate to optimize registry with the inorganic sublattice, minimizing distortion and yielding higher-symmetry D2 h octahedra. Furthermore, we demonstrate that intrinsic structural stability of RP 2D perovskites is primarily governed by π-π packing within the organic layer, whereas air stability of the thin films is determined by surface hydrophobicity. The type-II films exhibit higher hydrophobicity, conferring enhanced stability under ambient conditions compared to type-I films. These findings establish odd-even alkyl chain parity as a design principle for tailoring structurally diverse yet stable RP 2D perovskites.
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