Two series of well-defined brush polymers bearing a triazole moiety on each bristle were prepared from the click chemistry reactions of a poly(glycidyl azide) (PG) and a poly(4-azidomethylstyrene) (PS) with alkyne derivatives. The thin-film morphologies and properties, especially electrical memory performances, of these triazole-containing brush polymers were investigated in detail. The brush polymers with a triazole ring substituted with an alkyl or alkylenylphenyl group in the bristle exhibited only dielectric characteristics. By contrast, the other brush polymers bearing a triazole ring substituted with phenyl or its derivatives with a longer π-conjugation length in the bristle demonstrated excellent unipolar permanent memory behaviors with low power consumption, high ON/OFF current ratios and high stability and reliability under ambient air conditions. Furthermore, their memory type could be tuned to p-or n-type by the incorporation of an electron-donating or -accepting group into the phenyl unit linked to the triazole moiety. Overall, this study presents the first demonstration of the azide-alkyne click chemistry synthesis of triazole moieties with substituent(s) that exhibit a resonance effect; this approach is a very powerful synthetic route to develop electrical memory polymers suitable for the low-cost mass production of high-performance, polarity-free programmable memory devices.
The fully π-conjugated donor-acceptor hybrid polymers Fl-TPA, Fl-TPA-TCNE, and Fl-TPA-TCNQ, which are composed of fluorene (Fl), triphenylamine (TPA), dimethylphenylamine, alkyne, alkyne-tetracyanoethylene (TCNE) adduct, and alkyne-7,7,8,8-tetracyanoquinodimethane (TCNQ) adduct, were synthesized. These polymers are completely amorphous in the solid film state and thermally stable up to 291-409 °C. Their molecular orbital levels and band gaps vary with their compositions. The TCNE and TCNQ units, despite their electron-acceptor characteristics, were found to enhance the π-conjugation lengths of Fl-TPA-TCNE and Fl-TPA-TCNQ (i.e., to produce red shifts in their absorption spectra and significant reductions in their band gaps). These changes are reflected in the electrical digital memory behavior of the polymers. Moreover, the TCNE and TCNQ units were found to diversify the digital memory modes and to widen the active polymer layer thickness window. In devices with aluminum top and bottom electrodes, the Fl-TPA polymer exhibits stable unipolar permanent memory behavior with high reliability. The Fl-TPA-TCNE and Fl-TPA-TCNQ devices exhibit stable unipolar permanent memory behavior as well as dynamic random access memory behavior with excellent reliability. These polymer devices were found to operate by either hole injection or hole injection along with electron injection, depending on the polymer composition. Overall, this study demonstrated that the incorporation of π-conjugated cyano moieties, which control both the π-conjugation length and electron-accepting power, is a sound approach for the design and synthesis of high-performance digital memory polymers. The TCNE and TCNQ polymers synthesized in this study are highly suitable active materials for the low-cost mass production of high-performance, polarity-free, programmable, volatile, and permanent memory devices that can be operated with very low power consumption, high ON/OFF current ratios, and high reliability.
Poly(N‐(1‐hexylheptyl)‐N′‐(12‐oxydodecyl)perylene‐3,4,9,10‐tetracarboxyldiimide acrylate) (PAcPDI), a perylene diimide (PDI) containing brush polymer, is synthesized, revealing good solubility in organic solvents, excellent thermal stability up to around 340 °C, and two melting transitions over 130−220 °C. The self‐assembly and n‐type memory characteristics of PAcPDI in nanoscale thin films are quantitatively investigated. As‐cast films of PAcPDI are completely amorphous and the PDI units nevertheless formed π–π stacks favorably. However, the PAcPDI molecules can self‐assemble via thermal annealing, developing a well‐ordered horizontal lamellar structure with monomorphic or polymorphic monoclinic PDI crystals. The formation of monomorphic or polymorphic monoclinic crystals is attributed to various π–π stack modes of the PDI units, and is shown to be dependent on the film thickness. The differences in the thin film morphologies are directly reflected into the electrical memory behavior. The thermally annealed films demonstrate high‐performance n‐type unipolar volatile memory behavior within the thickness range of 12−31 nm. The as‐cast films show n‐type unipolar nonvolatile or volatile memory behavior in the range of 12−53 nm. The memory mode of PAcPDI films can be tuned by changing either the morphology or the film thickness.
Two series of crystalline−amorphous brush diblock copolymers bearing electroactive moieties were newly synthesized by sequential anionic ring-opening copolymerizations of glycidyl derivatives and subsequent selective postfunctionalizations; their homopolymers and analogues were additionally synthesized. Self-assembly structural details and electrical memory behaviors of these polymers in nanoscale thin films were investigated. The diblock copolymers revealed complex hierarchical self-assembly structures depending on the compositions. The self-assembly structure and orientation of the crystalline block chains were severely affected by the geometrical confinement (i.e., size and shape) stemming from microphase separation. Such film morphologies were found to significantly influence the electrical properties; they exhibited electrical properties from p-type permanent memory behavior to dielectric-like behavior. The memory behaviors were governed by the trap-limited space charge limited conduction mechanism combined with ohmic conduction and the hopping paths composed of the electroactive moieties distributed locally.
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