Surface-Doped Quasi-2D Chiral Organic Single Crystals for Chiroptical Sensing
Xiaobo Shang, Inho Song, Jeong Hyeon Lee, Wanuk Choi, Jaeyong Ahn, Hiroyoshi Ohtsu, Jin Chul Kim, Jin Young Koo, Sang Kyu Kwak, Joon Hak Oh
Abstract
Chiral organic optoelectronics using circularly polarized light (CPL) as the key element in the photonic signal has recently emerged as a next-generation photonic technology. However, it remains challenging to simultaneously achieve high polarization selectivity and superior optoelectronic performance. Supramolecular two-dimensional (2D) chiral organic single crystals may be good candidates for this purpose due to their defect-free nature, molecular diversity, and morphologies. Here, quasi-2D single crystals of chiral perylene diimides with parallelogram and triangle/hexagon morphologies have been selectively fabricated via self-assembly using different cosolvent systems. These materials exhibit amplified circular dichroism (CD) spectral signals, due to their molecular packing modes and supramolecular chirality. Through molecular surface n-doping using hydrazine, chiral single crystals exhibit electron mobility surpassing 1.0 cm2 V–1 s–1, which is one of the highest among chiral organic semiconductors, and excellent optoelectronic functions. Theoretical calculations reveal that the radical anions formed by n-doping increase the electron affinity and/or reduce the energy gap, thus facilitating electron transport. More importantly, the doped organic chiral crystals selectively discriminate CPL handedness with a high anisotropy factor of photoresponsivity (∼0.12). These results demonstrate that surface-doped quasi-2D chiral organic single crystals are highly promising for chiral optoelectronics.