The organic-based memristive devices are widely studied as a next-generation electronics for eco-friendly wearable applications, thanks to materials` flexibility and biocompatibility. However, poor operational reliability and stability of the devices remain a critical challenge. Here, the study demonstrates a crystalline organohalide, Dabconium ammonium triiodide (DABCO-NH4-I3, DABCO is 1,4-diazabicyclo[2.2.2] octonium)-based memristive device with exceptionally high reliability and endurance. Owing to the low dielectric constant and anisotropic hexagonal crystal structure consisting of hydrogen bonds with a high bandgap, the DABCO-NH4-I3-based conductive bridging random access memory device demonstrates millivolt-scale operating voltages with a remarkably high on/off ratio of ≈109, capable of multi-level storage. The relatively higher thermal conductivity of the crystalline organohalide (1.06Wm-1K-1), compared to most of organic materials (0.1-0.5Wm-1K-1), is found to be beneficial to suppress intense heat accumulation generated by Joule heating effect during device operation. With the facilitated dissipation of the generated heat, the simple planar heterojunction structured device shows remarkably endurable resistive switching over 103 cycles of program-erase at both room temperature and 85 °C with high switching reliability. This study introduced a new class of materials that can overcome the limitations of existing organic materials for high-performance next-generation organic electronic devices.
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