非中心对称杂化卤化物钙钛矿的合理设计,Journal of the American Chemical Society

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非中心对称杂化卤化物钙钛矿的合理设计
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2023-01-03 , DOI: 10.1021/jacs.2c12034
Rayan Chakraborty ₁ , Parikshit Kumar Rajput ₁ , Gokul M Anilkumar ₂ , Shabnum Maqbool ₁ , Ranjan Das ₃ , Atikur Rahman ₂ , Pankaj Mandal ₁ , Angshuman Nag ₁

Affiliation

半导体有机-无机杂化卤化物钙钛矿中的结构非中心对称性可以引入反常光伏和非线性光学特性等功能。在这里，我们介绍了一种设计原则，以制备具有极性非中心对称空间群的 Pb 和 Bi 基二维和一维杂化钙钛矿。设计原理依赖于在有机-无机界面上产生不同的氢键和卤键非共价相互作用。例如，在 I–(CH ₂ ) ₃ –NH ₂ (CH ₃ ) ⁺ (MIPA) 等有机阳离子中，-CH ₃的一端被-CH ₂ I 取代，-NH ₃⁺被-NH 取代₂ (CH ₃ ) ⁺在另一端。_{与未取代的阳离子（例如 H 3} C–(CH ₂ ) ₃ –NH ₃^{+ ）相比，–I 和 –CH}₃对两个 -H 原子的这些取代减少了 MIPA 在两端的旋转对称性。_{因此，在 (MIPA) 2} PbI ₄ 2D 钙钛矿的有机-无机界面处不同的氢-碘和碘-碘相互作用打破了 Pb-I 八面体的局部反转对称性。由于这种非中心对称性，(MIPA) ₂ PbI ₄显示可见到红外可调谐非线性光学特性，二次和三次谐波产生的磁化率值分别为 5.73 pm V ^–1和 3.45 × 10 ^–18 m ² V ^–2。此外，在没有外部偏压的情况下，单晶在照射可见光时显示出光电流，表现出由结构不对称引起的反常光伏效应。扩展设计策略以合成四种新的非中心对称杂化钙钛矿化合物。其中，一维(H ₃ N–(CH ₂ ) ₃ –NH(CH ₃ ) ₂ )BiI ₅的二次谐波产生磁化率为7.3 pm V^–1和 22.6 V 的高异常光伏开路电压。

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Rational Design of Non-Centrosymmetric Hybrid Halide Perovskites

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.

更新日期：2023-01-03

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