摘要
Three organic conjugated small molecules, DTA-DTPZ, Cz-DTPZ, and DTA-me-DTPZ comprising an antiaromatic 5,10-ditolylphenazine (DTPZ) core and electron-donating peripheral substituents with high HOMOs (−4.2 to −4.7 eV) and multiple reversible oxidative potentials are reported. The corresponding films sandwiched between two electrodes show unipolar and switchable hysteresis current-voltage (I-V) characteristics upon voltage sweeping, revealing the prominent features of nonvolatile memristor behaviors. The numerical simulation of the I-V curves suggests that the carriers generated by the oxidized molecules lead to the increment of conductance. However, the accumulated carriers tend to deteriorate the device endurance. The electroactive sites are fully blocked in the dimethylated molecule DTA-me-DTPZ, preventing the irreversible electrochemical reaction, thereby boosting the endurance of the memristor device over 300 cycles. Despite the considerable improvement in endurance, the decrement of on/off ratio from 10 5 to 10 1 after 250 cycles suggests that the excessive charge carriers (radical cations) remains a problem. Thus, a new strategy of doping an electron-deficient material, CN-T2T, into the unipolar active layer was introduced to further improve the device stability. The device containing DTA-me-DTPZ:CNT2T (1:1) blend as the active layer retained the endurance and on/off ratio (∼10 4 ) upon sweeping 300 cycles. The molecular designs and doping strategy demonstrate effective approaches toward more stable metal-free organic conjugated small-molecule memristors.