Rationalizing the design and implementation of chiral hybrid perovskites

Pietropaolo, Adriana; Mattoni, Alessandro; Pica, Giovanni; Fortino, Mariagrazia; Schifino, Gioacchino; Grancini, Giulia

doi:10.1016/j.chempr.2022.01.014

Cited by 61 publications

(53 citation statements)

References 104 publications

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“…We chose A 2 PbI 4 (X = I) to yield lower band gaps, compared to other halides (X = Cl or Br). For A-site cations, choosing chiral ammonium molecules can result in hybrid perovskites in non-centrosymmetric space groups. − However, enantiomeric pure chiral ammonium cations are often less abundant or expensive due to the challenges in asymmetric synthesis and chiral separation techniques . On the other hand, choosing achiral cations that can introduce non-centrosymmetry and polarity in hybrid perovskite structures, is an important material design challenge.…”

Section: Introductionmentioning

confidence: 99%

Rational Design of Non-Centrosymmetric Hybrid Halide Perovskites

et al. 2023

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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.

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Section: Introductionmentioning

confidence: 99%

Rational Design of Non-Centrosymmetric Hybrid Halide Perovskites

et al. 2023

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“…Among them, chiral semiconductor perovskites are attracting tremendous interest recently for producing strong CPL signals. 8,9 Metal-halide chiral perovskites exhibit many unique optical characteristics of chiral materials and notable optoelectronic properties inherited from the perovskite, such as optical rotation, tunable composition, high quantum efficiency, flexible crystal structure, and so on. 10−13 Notably, metal-halide chiral perovskites can be used efficiently in typical optoelectronic modulations, such as in manipulating the charge, spin, and CP light simultaneously by adjusting the material characters.…”

Section: ■ Introductionmentioning

confidence: 99%

“…At present, the research on CPL-active materials is just in its infancy but is rapidly developing, and many potential materials with chiral structures are emerging. Among them, chiral semiconductor perovskites are attracting tremendous interest recently for producing strong CPL signals. , Metal-halide chiral perovskites exhibit many unique optical characteristics of chiral materials and notable optoelectronic properties inherited from the perovskite, such as optical rotation, tunable composition, high quantum efficiency, flexible crystal structure, and so on. − Notably, metal-halide chiral perovskites can be used efficiently in typical optoelectronic modulations, such as in manipulating the charge, spin, and CP light simultaneously by adjusting the material characters . Specifically, the chiral perovskite materials can act as a spin filter to produce spin-polarized charge carriers based on its induced spin selectivity (CISS) effect, which can be used to develop spin LED and other applications in related fields.…”

Section: Introductionmentioning

confidence: 99%

Solvent Modulation of Chiral Perovskite Films Enables High Circularly Polarized Luminescence Performance from Chiral Perovskite/Quantum Dot Composites

Zhu

Wang

Sun

et al. 2023

ACS Appl. Mater. Interfaces

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Materials with circularly polarized luminescence (CPL) activity are promising in many chiroptoelectronics fields, such as for biological probes, asymmetric photosynthesis, information storage, spintronic devices, and so on. Promoting the value of the dissymmetry factor (g lum) for the CPL-active materials based on chiral perovskite draws increasing attention since a higher g lum value indicates better CPL. In this work, we find that, after being treated with a facile solvent modulation strategy, the chirality of 2D chiral perovskite films has been enhanced a lot, which we attribute to an increased lattice distortion degree. By forming chiral perovskite/quantum dot (QD) composites, the CPL-active material is successfully obtained. The calculated maximum |g lum| of these composites increased over 4 times after solvent modulation treatment (1.53 × 10–3 for the pristine sample of R-DMF and 6.91 × 10–3 for R-NMP) at room temperature. Moreover, the enhancement of the CPL intensity is ascribed to two aspects: one is the generation and transportation of spin-polarized charge carriers from chiral perovskite films to combine in the QD layer, and the other is the solvent modulation strategy to enlarge the lattice distortion of chiral perovskite films. This facile route provides an effective way to construct CPL-active materials. More importantly, this kind of composite material (chiral perovskite film/QD layer) can be easily applied for fabricating circularly polarized light-emitting diode devices for electroluminescence.

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“…For example, chiroptical properties can be transferred to the perovskite structure by the intercalation of chiral cationic organic compounds. 18,[25][26][27][28][29] In the last five years, the interest in chiral Hybrid Organic-Inorganic Perovskites (c-HOIP) has grown, mainly due to their intriguing physical properties including nonlinear optical responses, circular dichroism, ferroelectricity, circularly polarized light absorption and emission and spin dependent transport. [30][31][32] 1D c-HOIPs perovskites combine the advantages of chiral materials and low-dimensional lead halide perovskite structures and hold promise for a wide range of applications in life science, material science and in next-generation optical and spintronic devices.…”

Section: Introductionmentioning

confidence: 99%

“…For example, chiroptical properties can be transferred to the perovskite structure by the intercalation of chiral cationic organic compounds. 18,25–29 In the last five years, the interest in c hiral Hybrid Organic–Inorganic Perovskites ( c -HOIP) has grown, mainly due to their intriguing physical properties including nonlinear optical responses, circular dichroism, ferroelectricity, circularly polarized light absorption and emission and spin dependent transport. 30–32…”

Section: Introductionmentioning

confidence: 99%