Black Phosphorus Quantum Dots Functionalized with Photochromic Poly(vinylspiropyran)-Grafted Polydopamine for Transient Digital-Type Memristors

Abstract The covalent functionalization of black phosphorus quantum dots (BPQDs) with organic species or polymers will inevitably change or damage their electronic structure and intrinsic structure. To address this problem and explore the application of BPQDs in transient digital-type memristors, a polydopamine (PDA) thin film is first synthesized in situ onto the surface of BPQDs to produce a donor–acceptor-type BPQDs@PDA composite that is directly used to react with 2-bromoisobutyryl bromide to give BPQDs@PDA-Br. By using BPQDs@PDA-Br as an atom transfer radical polymerization agent, a large number of polyvinylspiropyran (PSP) chains are in situ grown from the PDA surface to yield BPQDs@PDA-PSP. Upon ultraviolet (UV)–visible light illumination, the 2 isomers of the spiropyran (ring-closed spiropyran form and ring-opened merocyanine) in the PSP moieties will interconvert into each other rapidly. As expected, the as-fabricated indium tin oxide (ITO)/BPQDs@PDA-PSP/ITO device exhibits typical nonvolatile digital-type memristive performance under visible irradiation, with a small turn-on voltage of −1.52 V, a turn-off voltage of +1.16 V, and an ON/OFF ratio current ratio of 1.02 × 104. Upon UV illumination, the information stored in the device is quickly and completely erased within 6 s. By utilizing a simple memristor-based convolutional neural network, one can easily realize handwritten digit recognition. After 10 epochs of training, numeral recognition accuracy can reach up to 96.21%.