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<p>X-ray detection has extensive applications in medical imaging, scientific research, and security inspection. Despite the superior radiation detection properties of lead-based perovskites, including high carrier mobility and superior attenuation efficiency, their toxicity and instability arising from ion migration hinders further development. To address these challenges, a series of halogen-tuned lead-free 3-methylpiperidine bismuth halides, (C<sub>6</sub>H<sub>14</sub>N)<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub>, (C<sub>6</sub>H<sub>14</sub>N)<sub>2</sub>BiBr<sub>5</sub> and (C<sub>6</sub>H<sub>14</sub>N)<sub>2</sub>BiCl<sub>5</sub> (C<sub>6</sub>H<sub>14</sub>N = 3-methylpiperidine) single crystals were grown and systematically characterized. 3-methylpiperidine was selected for its steric effect stabilizing the lattice, and the synergistic tuning through halogen variation enabled a structural transition along with modulation of their properties. Notably, the lateral-structured (C<sub>6</sub>H<sub>14</sub>N)<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub> single-crystal X-ray detector exhibits a sensitivity of 388.05 μC Gy<sup>−1</sup> cm<sup>−2</sup>, a low detection limit of 71.05 nGy s<sup>−1</sup>, and a small dark current drift of 2.16 × 10<sup>–8</sup> nA cm<sup>−1</sup>&#xa0;s<sup>−1</sup>&#xa0;V<sup>−1</sup>. Importantly, this material retains its original morphology after 8&#xa0;months of storage in ambient conditions. Furthermore, flexible X-ray devices fabricated via spin-coating (C<sub>6</sub>H<sub>14</sub>N)<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub> exhibited a favorable X-ray response with a sensitivity of 121.48 μC Gy<sup>−1</sup> cm<sup>−2</sup>, as well as excellent mechanical stability. This work reveals that halogen tuning effectively optimizes the structure and performance of Bi-based perovskites, providing valuable insights for advancing them in X-ray detection applications.</p>

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Halogen (Cl, Br, I) tuning of 3-methylpiperidine bismuth halides for highly sensitive, low-dose, and stable X-ray detection

  • 期刊论文

  • 发表日期：

    2025年12月18日

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  • Huayushuo Zhang,
  • Qian Ma,
  • Pan Gao,
  • Bolong Li,
  • Xiaoxia Yang,
  • Chao Li,
  • Mingming Song,
  • Zhiwei Hou,
  • Xiaomei Jiang

摘要

X-ray detection has extensive applications in medical imaging, scientific research, and security inspection. Despite the superior radiation detection properties of lead-based perovskites, including high carrier mobility and superior attenuation efficiency, their toxicity and instability arising from ion migration hinders further development. To address these challenges, a series of halogen-tuned lead-free 3-methylpiperidine bismuth halides, (C6H14N)3Bi2I9, (C6H14N)2BiBr5 and (C6H14N)2BiCl5 (C6H14N = 3-methylpiperidine) single crystals were grown and systematically characterized. 3-methylpiperidine was selected for its steric effect stabilizing the lattice, and the synergistic tuning through halogen variation enabled a structural transition along with modulation of their properties. Notably, the lateral-structured (C6H14N)3Bi2I9 single-crystal X-ray detector exhibits a sensitivity of 388.05 μC Gy−1 cm−2, a low detection limit of 71.05 nGy s−1, and a small dark current drift of 2.16 × 10–8 nA cm−1 s−1 V−1. Importantly, this material retains its original morphology after 8 months of storage in ambient conditions. Furthermore, flexible X-ray devices fabricated via spin-coating (C6H14N)3Bi2I9 exhibited a favorable X-ray response with a sensitivity of 121.48 μC Gy−1 cm−2, as well as excellent mechanical stability. This work reveals that halogen tuning effectively optimizes the structure and performance of Bi-based perovskites, providing valuable insights for advancing them in X-ray detection applications.