In organic resistive random-access memory (ReRAM) devices, deeply understanding how to control the performance of π-conjugated semiconductors through molecular-shape-engineering is important and highly desirable. Herein, we design a family of N-containing heteroaromatic semiconductors with molecular shapes moving from mono-branched 1Q to di-branched 2Q and tri-branched 3Q. We find that this molecular-shape engineering can induce reliable binary to ternary ReRAM switching, affording a highly enhanced device yield that satisfies the practical requirement. The density functional theory calculation and experimental evidence suggest that the increased multiple paired electroactive nitrogen sites from mono-branched 1Q to tri-branched 3Q are responsible for the multilevel resistance switching, offering stable bidentate coordination with the active metal atoms. This study sheds light on the prospect of N-containing heteroaromatic semiconductors for promising ultrahigh-density data-storage ReRAM application.

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http://dx.doi.org/10.1021/acsami.2c11960DOI Listing

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