Tailoring a Lead-Free Organic–Inorganic Halobismuthate for Large Piezoelectric Effect

Molecular piezoelectrics are a potentially disruptive technology, enabling a new generation of self-powered electronics that are flexible, high performing, and inherently low in toxicity. Although significant efforts have been made toward understanding their structural design by targeted manipulation of phase transition behavior, the resulting achievable piezoresponse has remained limited. In this work, we use a low-symmetry, zero-dimensional (0D) inorganic framework alongside a carefully selected 'quasi-spherical' organic cation to manipulate organic-inorganic interactions and thus form the hybrid, piezoelectric material [(CH<sub>3</sub>)<sub>3</sub>NCH<sub>2</sub>I]<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub>. Using variable-temperature single crystal X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy, we demonstrate that this material simultaneously exhibits an order-disorder and displacive symmetry-breaking phase transition. This phase transition is mediated by halogen bonding between the organic and inorganic frameworks and results in a large piezoelectric response, <i>d</i><sub>33</sub> = 161.5 pm/V. This value represents a 4-fold improvement on previously reported halobismuthate piezoelectrics and is comparable to those of commercial inorganic piezoelectrics, thus offering a new pathway toward low-cost, low-toxicity mechanical energy harvesting and actuating devices.

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Publication Details

Journal
Journal of the American Chemical Society
Published
2025-11-25
DOI
https://doi.org/10.1021/jacs.5c15484
Primary Topic
Perovskite Materials and Applications
Type
article
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article

Tailoring a Lead-Free Organic–Inorganic Halobismuthate for Large Piezoelectric Effect

Harry C. Sansom, Khaled Kaja, Shrestha Banerjee, Marina R. Filip et al.
Journal of the American Chemical Society
Perovskite Materials and Applications
article

Tailoring a Lead-Free Organic–Inorganic Halobismuthate for Large Piezoelectric Effect

Harry C. Sansom, Khaled Kaja, Shrestha Banerjee, Marina R. Filip, Robert L. Harniman, Harish Bhaskaran, Esther Y.-H. Hung, Nakita K. Noel, Paolo G. Radaelli, Benjamin M. Gallant, Dominik J. Kubicki, Santanu Saha, Henry James Snaith, Jakob Möbs, Nikolaos Farmakidis, Charles M. Godfrey
article en

Abstract

Molecular piezoelectrics are a potentially disruptive technology, enabling a new generation of self-powered electronics that are flexible, high performing, and inherently low in toxicity. Although significant efforts have been made toward understanding their structural design by targeted manipulation of phase transition behavior, the resulting achievable piezoresponse has remained limited. In this work, we use a low-symmetry, zero-dimensional (0D) inorganic framework alongside a carefully selected 'quasi-spherical' organic cation to manipulate organic-inorganic interactions and thus form the hybrid, piezoelectric material [(CH<sub>3</sub>)<sub>3</sub>NCH<sub>2</sub>I]<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub>. Using variable-temperature single crystal X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy, we demonstrate that this material simultaneously exhibits an order-disorder and displacive symmetry-breaking phase transition. This phase transition is mediated by halogen bonding between the organic and inorganic frameworks and results in a large piezoelectric response, <i>d</i><sub>33</sub> = 161.5 pm/V. This value represents a 4-fold improvement on previously reported halobismuthate piezoelectrics and is comparable to those of commercial inorganic piezoelectrics, thus offering a new pathway toward low-cost, low-toxicity mechanical energy harvesting and actuating devices.

Journal of the American Chemical SocietyVol. 147(49)
Bruker (United States) (US), Justus-Liebig-Universität Gießen (DE), Clarendon College (US), Helmholtz-Zentrum Berlin für Materialien und Energie (DE), University of Bristol (GB), University of Oxford (GB), Applied Nano Surfaces (Sweden) (SE), Bruker (Germany) (DE), Centre Européen de la Céramique (FR), Advanced Materials and Devices (United States) (US), Université de Limoges (FR), University of Birmingham (GB)
Openalex Percentile: Top 63%
Perovskite Materials and Applications
DOIOpen Access PDFOpenAlex
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