Jiahao Geng, Donghao Ma, Meng Xu, Zhihui Gao, Long Zhou, Zixuan Jia, Mengyao Liu, Zhiyu Zheng, Wei Zheng, Huaiyu Zhang, Xinkai Peng, Chen Li, Dou Zhao, Wanqi Jie, Yadong Xu
Pure-organic semiconductors have attracted broad interest in tissue-equivalent and biocompatible X-ray sensors, while their low-dose X-ray imaging capability still suffers from poor charge transport properties. Here, we report a dimensionality tailoring method to enhance hole transport in pure-organic semiconductors, enabling highly stable and low-dose X-ray detection and imaging without toxic elements such as Pb or Hg. By substituting the -CN group in 4-hydroxycyanobenzene (4HCB, HO-C6H4-CN) with a -COOCH3 group, we transform the two-dimensional (2D) structure into a three-dimensional (3D) 4-methyl hydroxybenzoate (4MHB, HO-C6H4-COOCH3) crystal featuring enhanced intermolecular π-π stacking. This structural reconfiguration yields a high hole mobility of 19.91 cm2 V−1 s−1 and an ultralow dark current drift of 1.14 × 10−10 nA cm−1 s−1 V−1 at 100 V mm−1. The superior charge transport facilitated by stronger π-π interactions enables stable X-ray detection with a detection limit as low as 4.22 nGyair s−1 and high-resolution imaging at 1.6 lp mm−1 under low-dose irradiation (58.76 μGyair s−1). This work demonstrates a molecular tailoring strategy to modulate the structural dimensionality and the charge transport path of pure-organic semiconductors, advancing tissue-equivalence and biocompatible X-ray imagers toward high-resolution and low-dose operation. The charge transport properties of organic semiconductors limit their low-dose X-ray imaging capability. Here, authors report 3D 4-methyl hydroxybenzoate for enhanced π-π stacking, achieving stable X-ray detection with detection limit of 4.22 nGyair s−1 and high-resolution imaging at 1.6 lp mm−1.