Ferroelectricity in a semiconducting all-inorganic halide perovskite

Zhang, Ye; Parsonnet, Eric; Fernández, Abel; Griffin, Sinéad M.; Huyan, Huaixun; Lin, Chenxi; Teng, Lirong; Jin, Jianbo; Barnard, Edward S.; Raja, Archana; Behera, Piush; Pan, Xiaoqing; Ramesh, R.; Yang, Peidong

doi:10.1126/sciadv.abj5881

Cited by 61 publications

(64 citation statements)

References 52 publications

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“…However, for FA, only one C−N bond of it is aligned along the c ‐axis and the other triple‐disordered C−N bond exhibits a C 3 v symmetry around the c ‐axis (Figure S8a). The distortion of the [GeBr 6 ] octahedra increases with the increasing organic cation size (Figure 2 and Table 1), which is accompanied by the change of bond length and angle, as well as the displacement of Ge 2+ along the [111] direction in the unit cell (Tables S6–S9 and Figure S6) [51, 55] . Noted that there are two kinds of Ge−Br bonds (short and long bond) due to the prominent lone pair effect of Ge 2+ .…”

Section: Resultsmentioning

confidence: 98%

“…and the interplay between ionic radius and the tolerance factor. [46][47][48][49][50][51] Chen et al reported a series of hybrid metal halide (C 6 H 5 (CH 2 ) 4 NH 3 ) 4 MX 7 •H 2 O (M = Bi, In, X = Br or I) with SHG responses. [46] Previously, we have reported a series of Ge-based iodide perovskites with excellent SHG properties.…”

Section: Introductionmentioning

confidence: 99%

“…The SHG intensity can also be tuned by Br/Cl solid solutions in CsGe(Br x Cl 1− x ) 3 [52] . CsGeBr 3 was recently reported to be ferroelectric with clear SHG responses [51] . In the bromide‐based system, as the ionic radius decreases from Pb to Ge, the tolerance factor has largely increased for A GeBr 3 ( A =Cs, MA and FA), compared with the Pb‐ and Sn‐based analogues (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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Hybrid Germanium Bromide Perovskites with Tunable Second Harmonic Generation

et al. 2022

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Ge‐based hybrid perovskite materials have demonstrated great potential for second harmonic generation (SHG) due to the geometry and lone‐pair induced non‐centrosymmetric structures. Here, we report a new family of hybrid 3D Ge‐based bromide perovskites AGeBr3, A=CH3NH3 (MA), CH(NH2)2 (FA), Cs and FAGe0.5Sn0.5Br3, crystallizing in polar space groups. These compounds exhibit tunable SHG responses, where MAGeBr3 shows the strongest SHG intensity (5×potassium dihydrogen phosphate, KDP). Structural and theoretical analysis indicate the high SHG efficiency is attributed to the displacement of Ge2+ along [111] direction and the relatively strong interactions between lone pair electrons of Ge2+ and polar MA cations along the c‐axis. This work provides new structural insights for designing and fine‐tuning the SHG properties in hybrid metal halide materials.

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Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Hybrid Germanium Bromide Perovskites with Tunable Second Harmonic Generation

et al. 2022

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Section: Introductionmentioning

confidence: 99%

Hybrid Germanium Bromide Perovskites with Tunable Second Harmonic Generation

et al. 2022

View full text Add to dashboard Cite

Ge-based hybrid perovskite materials have demonstrated great potential for second harmonic generation (SHG) due to the geometry and lone-pair induced non-centrosymmetric structures. Here, we report a new family of hybrid 3D Ge-based bromide perovskites AGeBr 3 , A = CH 3 NH 3 (MA), CH(NH 2 ) 2 (FA), Cs and FAGe 0.5 Sn 0.5 Br 3 , crystallizing in polar space groups. These compounds exhibit tunable SHG responses, where MAGeBr 3 shows the strongest SHG intensity (5 × potassium dihydrogen phosphate, KDP). Structural and theoretical analysis indicate the high SHG efficiency is attributed to the displacement of Ge 2 + along [111] direction and the relatively strong interactions between lone pair electrons of Ge 2 + and polar MA cations along the c-axis. This work provides new structural insights for designing and fine-tuning the SHG properties in hybrid metal halide materials.

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“…A particularly important structure–property relationship discovered in recent studies is related to the stereochemical expression of the 6s 2 lone pair on the Pb 2+ cation, ,− which causes dynamic or static distortion of the local octahedral geometry, as the resulting lone pair occupies one of the coordination sites. The dynamic lone-pair expression is likely responsible for the strong lattice anharmonicities and local polar fluctuations in LHPs, ,− whereas the static manifestation may give rise to inversion symmetry breaking and noncentrosymmetric structuresa prerequisite to properties such as ferroelectricity, even-order nonlinear optical properties, and Rashba–Dresselhaus effect. ,,− …”

Section: Introductionmentioning

confidence: 99%

Stereochemically Active Lone Pairs and Nonlinear Optical Properties of Two-Dimensional Multilayered Tin and Germanium Iodide Perovskites

Guan

et al. 2022

J. Am. Chem. Soc.

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Two-dimensional (2D) metal halide perovskites are promising tunable semiconductors. Previous studies have focused on Pb-based structures, whereas the multilayered Sn-and Ge-based analogues are largely unexplored, even though they potentially exhibit more diverse structural chemistry and properties associated with the more polarizable ns 2 lone-pair electrons. Herein, we report the synthesis and structures of 2D tin iodide perovskites (BA) 2 (A)Sn 2 I 7 , where BA = n-butylammonium and A = methylammonium, formamidinium, dimethylammonium, guanidinium, or acetamidinium, and those of 2D germanium iodide perovskites (BA) 2 (A)Ge 2 I 7 , where A = methylammonium or formamidinium. By comparing these structures along with their Pb counterparts, we establish correlations between the effect of group IV-cation's lonepair stereochemical activity on the perovskite crystal structures and the resulting semiconducting properties such as bandgaps and carrier−phonon interactions and nonlinear optical properties. We find that the strength of carrier−phonon interaction increases with increasing lone-pair activity, leading to a more prominent photoluminescence tail on the low-energy side. Moreover, (BA) 2 (A)Ge 2 I 7 exhibit strong second harmonic generation with second-order nonlinear coefficients of ∼10 pm V −1 that are at least 10 times those of Sn counterparts and 100 times those of Pb counterparts. We also report the third-order two-photon absorption coefficients of (BA) 2 (A)Sn 2 I 7 to be ∼10 cm MW −1 , which are one order of magnitude larger than those of the Pb counterparts and traditional inorganic semiconductors. These results not only highlight the role of lone-pair activity in linking the compositions and physical properties of 2D halide perovskites but also demonstrate 2D tin and germanium iodide perovskites as promising lead-free alternatives for nonlinear optoelectronic devices.

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Ferroelectricity in a semiconducting all-inorganic halide perovskite

Cited by 61 publications

References 52 publications

Hybrid Germanium Bromide Perovskites with Tunable Second Harmonic Generation

Hybrid Germanium Bromide Perovskites with Tunable Second Harmonic Generation

Hybrid Germanium Bromide Perovskites with Tunable Second Harmonic Generation

Stereochemically Active Lone Pairs and Nonlinear Optical Properties of Two-Dimensional Multilayered Tin and Germanium Iodide Perovskites

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