Tuning the Electrical Memory Behavior from Nonvolatile to Volatile in Functional Copolyimides Bearing Varied Fluorene and Pyrene Moieties

摘要

For producing polymer based electronics with good memory behavior, a series of functional copolyimides were designed and synthesized in this work by copolymerizing 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA) with (9,9'-bis(4-aminophenyl)fluorene) (BAPF) and N,N-bis(4-aminophenyl) aminopyrene (DAPAP) diamines. The synthesized copolyimides DSDA/(DAPAP/BAPF) were denoted as coPI-DAPAPx (x = 100, 50, 20, 10, 5, 1, 0), where x% represents the molar fraction of the DAPAP unit in the diamines. Characterization results indicate that the coPI-DAPAPx exhibits tunable electrical switching behaviors from write once read many times (WORM, nonvolatile, coPI-DAPAP100, coPI-DAPAP50, coPI-DAPAP20, coPI-DAPAP10) to the static random access memory (SRAM, volatile, coPI-DAPAP5, coPI-DAPAP1) with the variation of the DAPAP content. Optical and electrochemical characterization show gradually decreasing highest occupied molecular orbital levels and enlarged energy gap with the decrease of the DAPAP moiety, suggesting decreasing charge-transfer effect in the copolyimides, which can account for the observed WORM-SRAM memory conversion. Meanwhile, the charge transfer process was elucidated by quantum chemical calculation at B3LYP/6-31G(d) theory level. This work shows the effect of electron donor content on the memory behavior of polymer electronic materials.