Rational Design of Non-Centrosymmetric Hybrid Halide Perovskites

Chakraborty, R and Rajput, PK and Anilkumar, GM and Maqbool, S and Das, R and Rahman, A and Mandal, P and Nag, A (2022) Rational Design of Non-Centrosymmetric Hybrid Halide Perovskites. In: Journal of the American Chemical Society, 145 (2). 1378- 1388.

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Abstract

Structural non-centrosymmetry in semiconducting organic-inorganic hybrid halide perovskites can introduce functionalities like anomalous photovoltaics and nonlinear optical properties. Here we introduce a design principle to prepare Pb- and Bi-based two- and one-dimensional hybrid perovskites with polar non-centrosymmetric space groups. The design principle relies on creating dissimilar hydrogen and halogen bonding non-covalent interactions at the organic-inorganic interface. For example, in organic cations like I-(CH2)3-NH2(CH3)+ (MIPA), −CH3 is substituted by −CH2I at one end, and −NH3+ is substituted by −NH2(CH3)+ at the other end. These substitutions of two −H atoms by −I and −CH3 reduce the rotational symmetry of MIPA at both ends, compared to an unsubstituted cation, for example, H3C-(CH2)3-NH3+. Consequently, the dissimilar hydrogen-iodine and iodine-iodine interactions at the organic-inorganic interface of (MIPA)2PbI4 2D perovskites break the local inversion symmetries of Pb-I octahedra. Owing to this non-centrosymmetry, (MIPA)2PbI4 displays visible to infrared tunable nonlinear optical properties with second and third harmonic generation susceptibility values of 5.73 pm V-1 and 3.45 × 10-18 m2 V-2, respectively. Also, the single crystal shows photocurrent on shining visible light at no external bias, exhibiting anomalous photovoltaic effect arising from the structural asymmetry. The design strategy was extended to synthesize four new non-centrosymmetric hybrid perovskite compounds. Among them, one-dimensional (H3N-(CH2)3-NH(CH3)2)BiI5 shows a second harmonic generation susceptibility of 7.3 pm V-1 and a high anomalous photovoltaic open-circuit voltage of 22.6 V

Item Type:	Journal Article
Publication:	Journal of the American Chemical Society
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society.
Department/Centre:	Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited:	03 Feb 2023 04:47
Last Modified:	03 Feb 2023 04:47
URI:	https://eprints.iisc.ac.in/id/eprint/79811

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