An asymmetric 2,3-fluoranthene imide building block for regioregular semiconductors with aggregation-induced emission properties.

For organic semiconductors, the development of electron-deficient building blocks has lagged far behind that of the electron-rich ones. Moreover, it remains a significant challenge to design organic molecules with efficient charge transport and strong solid-state emission simultaneously. Herein, we describe a facile synthetic route toward a new π-acceptor imide building block, namely 2,3-fluoranthene imide, based on which four regioregular small molecules (F1-F4) are synthesized by tuning the imide orientations and the central linkage bridges. All molecules exhibit attractive aggregation-induced emission (AIE) characteristics with strong far-red emission in the powder state, and F3 shows the highest photoluminescence quantum yield of 5.9%. F1 and F3 with a thiophene bridge present an obvious p-type characteristic, while for F3 with an outward imide orientation, the maximum hole mobility from a solution-processed field-effect transistor (FET) device reaches 0.026 cm2 V-1 s-1, being ∼104 times higher than the value of F1 with an inward imide orientation. By using a fluorinated thiophene bridge, the resulting F2 and F4 can be turned into n-type semiconductors, showing an electron mobility of ∼1.43 × 10-4 and ∼3.34 × 10-5 cm2 V-1 s-1, respectively. Our work not only demonstrates that asymmetric 2,3-fluoranthene imide is a promising building block for constructing organic materials with high carrier mobility and strong solid-state emission, but also highlights the importance of regioregular structures in the materials' properties.

Comprehensive Non-volatile Photo-programming Transistor Memory via a Dual-Functional Perovskite-Based Floating Gate.

Photonic transistor memory has received increasing attention as next-generation optoelectronic devices for light fidelity (Li-Fi) application due to the attractive advantages of ultra-speed, high security, and low power consumption. However, most transistor-type photonic memories developed to date still rely on electrical bias for operation, imposing certain limits on data transmission efficiency and energy consumption. In this study, the dual manipulation of "photo-writing" and "photo-erasing" of a novel photonic transistor memory is successfully realized by cleverly utilizing the complementary light absorption between the photoactive material, n-type BPE-PTCDI, in the active channel and the hybrid floating gate, CH3NH3PbBr3/poly(2-vinylpyridine). The fabricated device not only can be operated under the full spectrum but also shows stable switching cycles of photo-writing (PW)-reading (R)-photo-erasing (PE)-reading (R) (PW-R-PE-R) with a high memory ratio of ∼104, and the memory characteristics possess a stable long-term retention of >104 s. Notably, photo-erasing only requires 1 s light illumination. Due to the fully optical functionality, the rigid gate electrode is removed and a novel two-terminal flexible photonic memory is fabricated. The device not only exhibits stable electrical performance after 1000 bending cycles but also manifests a multilevel functional behavior, demonstrating a promising potential for the future development of photoactive electronic devices.

Solution-Processable Anion-doped Conjugated Polymer for Nonvolatile Organic Transistor Memory with Synaptic Behaviors.

Brain-inspired synaptic transistors have been considered as a promising device for next-generation electronics. To mimic the behavior of a biological synapse, both data processing and nonvolatile memory capability are simultaneously required for a single electronic device. In this work, a simple approach to realize a synaptic transistor with improved memory characteristics is demonstrated by doping an ionic additive, tetrabutylammonium perchlorate (TBAP), into an active polymer semiconductor without using any extra charge storage layer. TBAP doping is first revealed to improve the memory window of a derived transistor memory device from 19 to 32 V (∼68% enhancement) with an on/off current ratio over 103 at VG = -10 V. Through morphological analysis and theoretical calculations, it is revealed that the association of anion with polymers enhances the charge retention capability of the polymer and facilitates the interchain interactions to result in improved memory characteristics. More critically, the doped device is shown to successfully mimic the synaptic behaviors, such as paired-pulse facilitation (PPF), excitatory and inhibitory postsynaptic currents, and spike-rate dependent plasticity. Notably, the TBAP-doped device is shown to deliver a PPF index of up to 204% in contrast to the negligible value of an undoped device. This study describes a novel approach to prepare a synaptic transistor by doping conjugated polymers, which can promote the future development of artificial neuromorphic systems.

Two-Dimensional Cs2Pb(SCN)2Br2-Based Photomemory Devices Showing a Photoinduced Recovery Behavior and an Unusual Fully Optically Driven Memory Behavior.

The rapid development of Internet of Things and big data has made the conventional storage devices face the need of reforming. Rather than using electrical pulses to store data in one of two states, photomemory exploiting optical stimulation to store light information emerges as a revolutionary candidate for the optoelectronic community. However, fully optically driven photomemory with fast data transmission speed and outstanding energy saving capability suffers from less exploration. Herein, a transistor-type photomemory using a 2D Cs2Pb(SCN)2Br2/polymer hybrid floating gate is explored and three host polymers, polystyrene, poly(4-vinylphenol), and poly(vinylpyrrolidone) (PVP), are investigated to understand the relationship between polymer matrix selection and memory performance. All devices show a photoinduced recovery memory behavior but with two distinctly different photomemory behaviors. In addition to the demonstration of a regular nonvolatile photomemory showing a high on/off ratio of >106 over 104 s, an unusual fully optically driven memory behavior is intriguingly accomplished in the Cs2Pb(SCN)2Br2/PVP photomemory. Using white light as the driver of programming and a blue laser as the main performer of erasing, this device can be switched between two distinguishable states and possesses acceptable data discriminability, as evidenced by its fully optically driven writing (programing)-reading-erasing-reading switching function that shows an on/off current ratio of 103. This study not only presents the first 2D perovskite-based photomemory but also shows a novel fully optically driven memory that has been rarely reported in the literature.

Stable, color-tunable 2D SCN-based perovskites: revealing the critical influence of an asymmetric pseudo-halide on constituent ions.

Two-dimensional (2D) layered perovskites (An+1BnX3n+1, n = 1, 2, …) have recently attracted significant research interest because of their enhanced ambient stability compared to their conventional 3D counterparts. In addition to the common A-site cation engineering, using an asymmetric pseudo-halide anion, SCN-, in the anion X-site has been recently proven to be another effective approach to constitute 2D perovskites. Among these, 2D (MA)2Pb(SCN)2I2 was the most widely investigated and was considered to be a promising material owing to its good optoelectronic properties; however, its poor stability has aroused concerns in recent researches. In this study, systematical composition engineering of A2Pb(SCN)2X2 (A = FA+, MA+, Cs+ and X = Br-, I-) was conducted. Our results revealed that the linear SCN- anion dictates critical restrictions on the constituent ions of its derived 2D framework (PbX4(SCN)2), which has not yet been extensively discussed. We demonstrated that using a smaller Cs+ cation can afford a more favorable 2D structure compared with the MA+ cation. Cs2Pb(SCN)2I2 was revealed to possess improved stability and photo-response compared to (MA)2Pb(SCN)2I2. Interestingly, Cs2Pb(SCN)2I2 and (MA)2Pb(SCN)2I2 appear to possess distinct electronic band structures. This is indicated by their discrepant photoluminescence spectra, in which the former exhibits a rather intense singlet emission at room temperature in contrast with the latter, which shows a dominant emission associated with triplet or defective states. Furthermore, using a smaller Cs+ cation enables facile replacement of a smaller halide anion. A series of mixed-halide 2D Cs2Pb(SCN)2(I1-xBrx)2 (x = 0, 1/3, 1/2, 2/3, 1) with varying vivid colors was explored by both calculation and experimental efforts to corroborate the enhanced stability when the x value increases. The results revealed in this study might represent a novel discovery of an inherent trait of the 2D SCN-based perovskites and also suggest that the all-inorganic 2D Cs2Pb(SCN)2X2 perovskite system is a promising class of materials with good stability and color-tunability that deserves further exploration.