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The synthesized hyperbranched polyimides obtained from a novel tetra-amine have a treelike randomly branched topology with a branch-on-branch structure, which affords a compact, globular molecule.

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A series of hyperbranched polyimides (HBPIs) were synthesized by reacting a triamine monomer N,N′,N″‐tris(4‐methoxyphenyl)‐N,N′,N″‐tris(4‐phenylamino)−1,3,5‐benzenetriamine with various dianhydrides such as oxydiphthalic dianhydride (ODPA), 3,3′,4,4′‐diphenylsulfonetetracarboxylic dianhydride (DSDA), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), and pyromellitic dianhydride (PMDA). The hyperbranched polyimide (6FHBPI) using 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) as dianhydride monomer was also added into the discussion. All the hyperbranched polyimides exhibited excellent organo‐solubility and high thermal stability. Memory devices with a sandwiched structure of indium tin oxide (ITO)/HBPI/Al were constructed by using these HBPIs as the active layers. All these HBPIs based memory devices exhibited favorable memory performances, with switching voltages between −1.3 V and −2.5 V, ON/OFF current ratios up to 107 and retention times long to 104 s. Tunable memory characteristics from electrical insulator to volatile memory, and then to nonvolatile memory were obtained by adjusting the electron acceptors of these HBPIs. Molecular simulation results suggested that the electron affinity and the dipole moment of these HBPIs were responsible for the conversion of the memory characteristics. With the electron affinity and dipole moment of these HBPIs increasing, the memory characteristics turned from volatile to nonvolatile. The present study suggested that tunable memory performance could be achieved through adjusting the acceptor moieties of the hyperbranched polyimides. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2281–2288

A series of ferrocene‐terminated hyperbranched polyimides (HBPI‐Fcs) were synthesized from a tetra‐amine, bis(4‐(3,5‐bis (4‐amino‐2‐(trifluoromethyl) phenoxy) phenoxy) phenyl) methanon, and various dianhydrides, followed by termination with (4‐amino) phenyl ferrocene. All the HBPI‐Fcs possessed good organo‐solubility and high thermal stability. The devices based on HBPI‐Fcs exhibited bipolar and nonvolatile write‐once‐read‐many times (WORM) memory performance with various threshold voltages and the same ON/OFF current ratio of 104. Moreover, the devices possessed excellent bistability under a constant bias of −1.00 V during a test period of 104 s. The different charge trapping ability of the electron‐accepting moiety endowed the devices with different the threshold voltages. Mechanism analysis showed that the switching behavior was dominated by the charge trapping effect and the charge transfer was well fitted with the space‐current‐limited‐current (SCLC) and ohmic model. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 505–513