Tailoring Wavelength-Adaptive Visual Neuroplasticity Transitions of Synaptic Transistors Comprising Rod-Coil Block Copolymers for Dual-Mode Photoswitchable Learning/Forgetting Neural Functions.

The vision-inspired artificial neural network based on optical synapses has drawn a tremendous amount of attention for emulating biological senses. Although photoexcitation-induced synaptic functionalities have been widely studied, optical habituation via the photoinhibitory pathway is yet to be demonstrated for sophisticated biomimetic visual adaptive systems. Here, the first optical neuromorphic block copolymer (BCP) phototransistor is demonstrated as an all-optical operation responding to various wavelengths, fulfilling photoassisted dynamic learning/forgetting cycles via optical potentiation without gate bias. The polyfluorene BCPs were precisely designed to enable wavelength-adaptive responses, benefiting from interfacial semiconductor/electret morphology and the crystallinity/electron affinity of the BCPs. Notably, this is the first work to simultaneously exhibit fully light-controlled short- and long-term memory based on organic material systems. The device presents a high current contrast above 100-fold and long-term retention over 104 s. As a proof-of-concept for neural networks, a 6 × 6 array of photosynapses performed outstanding visual pattern learning/forgetting with high accuracy. This study exploits the design strategy of a conjugated BCP electret to unleash the full potential of wavelength-adaptive visual neuroplasticity transitions. It provides an effective architecture for designing high-performance and high-storage capacity required applications in next-generation neuromorphic systems.

Molecular template growth of organic heterojunctions to tailor visual neuroplasticity for high performance phototransistors with ultralow energy consumption.

The optical and charge transport properties of organic semiconductors are strongly influenced by their morphology and molecular structures. Here we report the influence of a molecular template strategy on anisotropic control via weak epitaxial growth of a semiconducting channel for a dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT)/para-sexiphenyl (p-6P) heterojunction. The aim is to improve charge transport and trapping, to enable tailoring of visual neuroplasticity. The proposed phototransistor devices, comprising a molecular heterojunction with optimized molecular template thickness, exhibited an excellent memory ratio (ION/IOFF) and retention characteristics in response to light stimulation, owing to the enhanced orientation/packing of DNTT molecules and a favorable match between the LUMO/HOMO levels of p-6P and DNTT. The best performing heterojunction exhibits visual synaptic functionalities, including an extremely high pair-pulse facilitation index of ∼206%, ultralow energy consumption of 0.54 fJ, and zero-gate operation, under ultrashort pulse light stimulation to mimic human-like sensing, computing, and memory functions. An array of heterojunction photosynapses possess a high degree of visual pattern recognition and learning, to mimic the neuroplasticity of human brain activities through a rehearsal learning process. This study provides a guide to the design of molecular heterojunctions for tailoring high-performance photonic memory and synapses for neuromorphic computing and artificial intelligence systems.

Fully Photoswitchable Phototransistor Memory Comprising Perovskite Quantum Dot-Based Hybrid Nanocomposites as a Photoresponsive Floating Gate.

Tremendous research efforts have been dedicated into the field of photoresponsive nonvolatile memory devices owing to their advantages of fast transmitting speed, low latency, and power-saving property that are suitable for replacing current electrical-driven electronics. However, the reported memory devices still rely on the assistance of gate bias to program them, and a real fully photoswitchable transistor memory is still rare. Herein, we report a phototransistor memory device comprising polymer/perovskite quantum dot (QD) hybrid nanocomposites as a photoresponsive floating gate. The perovskite QDs offer an effective discreteness with an excellent photoresponse that are suitable for photogate application. In addition, a series of ultraviolet (UV)-sensitive insulating polymer hosts were designed to investigate the effect of UV light on the memory behavior. We found that a fully photoswitchable memory device was fulfilled by using the independent and sequential photoexcitation between a UV-sensitive polymer host and a visible light-sensitive QD photogates, which produced decent photoresponse, memory switchability, and highly stable memory retention with a memory ratio of 104 over 104 s. This study not only unraveled the mystery in the fully photoswitchable functionality of nonvolatile memory but also enlightened their potential in the next-generation electronics for light-fidelity application.

Fast Photoresponsive Phototransistor Memory Using Star-Shaped Conjugated Rod-Coil Molecules as a Floating Gate.

With the explosive growth in data generation, photomemory capable of multibit data storage is highly desired to enhance the capacity of storage media. To improve the performance of phototransistor memory, an organic-molecule-based electret with an elaborate nanostructure is of great importance because it can enable multibit data storage in a memory device with high stability. In this study, a series of star-shaped rod-coil molecules consisting of perylenediimide (PDI) and biobased solanesol were synthesized in two-armed (PDI-Sol2), four-armed (PDI-Sol4), and six-armed (PDI-Sol6) architectures. Their molecular architecture-morphology relationships were investigated, and phototransistor memory was fabricated and characterized to evaluate the structure-performance relationship of these rod-coil molecules. Accordingly, the memory devices were enabled by photowriting with panchromatic light (405-650 nm) and electrical erasing using a gate bias. The PDI-Sol4-based memory device showed high memory ratios of 10 000 over 10 000 s and a rapid multilevel photoresponse of 50 ms. This achievement is related to the favorable energy-level alignment, isolated nanostructure, and face-on orientation of PDI-Sol4, which eliminated the charge tunneling barrier. The results of this study provide a new strategy for tailoring nanostructures in organic-molecule-based electrets by using a star-shaped rod-coil architecture for high-performance phototransistor memory.

Low-Energy-Consumption and Electret-Free Photosynaptic Transistor Utilizing Poly(3-hexylthiophene)-Based Conjugated Block Copolymers.

Neuromorphic computation possesses the advantages of self-learning, highly parallel computation, and low energy consumption, and is of great promise to overcome the bottleneck of von Neumann computation. In this work, a series of poly(3-hexylthiophene) (P3HT)-based block copolymers (BCPs) with different coil segments, including polystyrene, poly(2-vinylpyridine) (P2VP), poly(2-vinylnaphthalene), and poly(butyl acrylate), are utilized in photosynaptic transistor to emulate paired-pulse facilitation, spike time/rate-dependent plasticity, short/long-term neuroplasticity, and learning-forgetting-relearning processes. P3HT serves as a carrier transport channel and a photogate, while the insulating coils with electrophilic groups are for charge trapping and preservation. Three main factors are unveiled to govern the properties of these P3HT-based BCPs: i) rigidity of the insulating coil, ii) energy levels between the constituent polymers, and iii) electrophilicity of the insulating coil. Accordingly, P3HT-b-P2VP-based photosynaptic transistor with a sought-after BCP combination demonstrates long-term memory behavior with current contrast up to 105 , short-term memory behavior with high paired-pulse facilitation ratio of 1.38, and an ultralow energy consumption of 0.56 fJ at an operating voltage of -0.0003 V. As far as it is known, this is the first work to utilize conjugated BCPs in an electret-free photosynaptic transistor showing great potential to the artificial intelligence technology.

Stretchable OFET Memories: Tuning the Morphology and the Charge-Trapping Ability of Conjugated Block Copolymers through Soft Segment Branching.

The mechanical properties and structural design flexibility of charge-trapping polymer electrets have led to their widespread use in organic field-effect transistor (OFET) memories. For example, in the electrets of polyfluorene-based conjugated/insulating block copolymers (BCPs), the confined fiberlike polyfluorene nanostructures in the insulating polymer matrix act as effective hole-trapping sites, leading to controllable memory performance through the design of BCPs. However, few studies have reported intrinsically stretchable charge-trapping materials and their memory device applications, and a practical method to correlate the thin-film morphology of BCP electrets with their charge-trapping ability has not yet been developed. In this study, a series of new conjugated/insulating BCPs, poly(9,9-di-n-hexyl-2,7-fluorene)-block-poly(δ-decanolactone)s (PF-b-PDLx, x = 1-3), as stretchable hole-trapping materials are reported. The linear and branched PDL blocks with comparable molecular weights were used to investigate the effect of polymer architecture on morphology and device performance. Moreover, the coverage area of the polyfluorene nanofibers on the BCP films was extracted from atomic force microscopy images, which can be correlated with the trapping density of the polymer electrets. The branched PDL segments not only improve stretchability but also tailor crystallinity and phase separation of the BCPs, thus increasing their charge-trapping ability. The OFET memory device with PF-b-PDL3 as the electret layer exhibited the largest memory window (102 V) and could retain its performance at up to 100% strain. This research highlights the importance of the BCP design for developing stretchable charge-trapping materials.

Nano-Micro Dimensional Structures of Fiber-Shaped Luminous Halide Perovskite Composites for Photonic and Optoelectronic Applications.

Perovskite nanomaterials have been revealed as highly luminescent structures regarding their dimensional confinement. In particular, their promising potential lies behind remarkable luminescent properties, including color tunability, high photoluminescence quantum yield, and the narrow emission band of halide perovskite (HP) nanostructures for optoelectronic and photonic applications such as lightning and displaying operations. However, HP nanomaterials possess such drawbacks, including oxygen, moisture, temperature, or UV lights, which limit their practical applications. Recently, HP-containing polymer composite fibers have gained much attention owing to the spatial distribution and alignment of HPs with high mechanical strength and ambient stability in addition to their remarkable optical properties comparable to that of nanocrystals. In this review, the fabrication methods for preparing nano-microdimensional HP composite fiber structures are described. Various advantages of the luminescent composite nanofibers are also described, followed by their applications for photonic and optoelectronic devices including sensors, polarizers, waveguides, lasers, light-down converters, light-emitting diode operations, etc. Finally, future directions and remaining challenges of HP-based nanofibers are presented.

Improving the Performance and Stability of Perovskite Light-Emitting Diodes by a Polymeric Nanothick Interlayer-Assisted Grain Control Process.

CsPbBr3 is a promising light-emitting material due to its wet solution processability, high photoluminescence quantum yield (PLQY), narrow color spectrum, and cost-effectiveness. Despite such advantages, the morphological defects, unsatisfactory carrier injection, and stability issues retard its widespread applications in light-emitting devices (LEDs). In this work, we demonstrated a facile and cost-effective method to improve the morphology, efficiency, and stability of the CsPbBr3 emissive layer using a dual polymeric encapsulation governed by an interface-assisted grain control process (IAGCP). An eco-friendly low-cost hydrophilic polymer poly(vinylpyrrolidone) (PVP) was blended into the CsPbBr3 precursor solution, which endows the prepared film with a better surface coverage with a smoothened surface. Furthermore, it is revealed that inserting a thin PVP nanothick interlayer at the poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)/emissive layer interface further promotes the film quality and the performance of the derived LED. It is mainly attributed to three major consequences: (i) reduced grain size of the emissive layer, which facilitates charge recombination, (ii) reduced current leakage due to the enhanced electron-blocking effect, and (iii) improved color purity and air stability owing to better defect passivation. As a result, the optimized composite emissive film can retain the luminescence properties even on exposure to ambient conditions for 80 days and ∼62% of its initial PL intensity can be preserved after 30 days of storage without any encapsulation.

Stretchable and Ambient Stable Perovskite/Polymer Luminous Hybrid Nanofibers of Multicolor Fiber Mats and Their White LED Applications.

We report the fabrication and optical/mechanical properties of perovskite/thermoplastic polyurethane (TPU)-based multicolor luminescent core-shell nanofibers and their large-scale fiber mats. One-step coaxial perovskite/TPU nanofibers had a high photoluminescence quantum yield value exceeding 23.3%, surpassing that of its uniaxial counterpart, due to the homogeneous distribution of perovskite nanoparticles (NPs) by the confinement of the TPU shell. The fabricated core-shell nanofibers exhibited a high mechanical endurance owing to the well elastic properties of TPU and maintained the luminescence intensity even under a 100% stretched state after 1000 stretching-relaxing cycles. By taking advantage of the hydrophobic nature of TPU, the ambient and moisture stability of the fabricated fibers were enhanced up to 1 month. Besides, large-area stretchable nanofibers with a dimension of 15 cm × 30 cm exhibiting various visible-light emission peaks were fabricated by changing the composition of perovskite NPs. Moreover, a large-scale luminescent and stretchable fiber mat was successfully fabricated by electrospinning. Furthermore, the white-light emission from the fabricated fibers and mats was achieved by incorporating orange-light-emitting poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] into the TPU shell and coupling the turquoise blue-light-emitting perovskite NPs in the core site. Finally, the integrity of the perovskite-based TPU fibers was realized by fabricating a light-emitting diode (LED) device containing the orange-light-emitting fibers embedded in the polyfluorene emissive layer. This work demonstrated an effective way to prepare stable and stretchable luminous nanofibers and the integration of such nanofibers into LED devices, which could facilitate the future development of wearable electronic devices.

Influence of polymeric electrets on the performance of derived hybrid perovskite-based photo-memory devices.

Organic-inorganic hybrid perovskite has become one of the most important photoactive materials owing to its intense light-harvesting property as well as its facile solution processability. Besides its photovoltaic applications, a novel photo-programmed transistor memory was recently developed based on the device architecture of a floating-gate transistor memory using a polymer/perovskite blend as the gate dielectric with the non-volatile memory characteristics of decent light response, applicable On/Off current ratio, and long retention time. In this study, we further clarify the influence of polymer matrix selection on the photo-response and memory properties of derived hybrid perovskite-based photo-memory devices. Four different host polymers, polystyrene (PS), poly(4-vinylphenol) (PVPh), poly(methyl methacrylate) (PMMA), and poly(methacrylic acid) (PMAA), were systematically investigated for comparison herein. This revealed that dissimilar chemical interactions existed between the host polymers and perovskite, resulting in the distinct memory behavior of the derived photo-memory devices, attributable to the different morphologies of the hybrid dielectric layers and the different sizes of the distributed perovskite nanoparticles (NPs). The photo-response behavior and the resultant On/Off current ratio increased as the size of the embedded perovskite NPs decreased, due to the enhanced photo-induced charge transfer across the dielectric/pentacene interface, benefiting from the better confinement effect of perovskite NPs in the polymer matrix. These results demonstrate the influence of perovskite NP aggregation at the dielectric/pentacene interface on the resultant memory behavior of the newly developed photo-memory device.

Uniform Luminous Perovskite Nanofibers with Color-Tunability and Improved Stability Prepared by One-Step Core/Shell Electrospinning.

A one-step core/shell electrospinning technique is exploited to fabricate uniform luminous perovskite-based nanofibers, wherein the perovskite and the polymer are respectively employed in the core and the outer shell. Such a coaxial electrospinning technique enables the in situ formation of perovskite nanocrystals, exempting the needs of presynthesis of perovskite quantum dots or post-treatments. It is demonstrated that not only the luminous electrospun nanofibers can possess color-tunability by simply tuning the perovskite composition, but also the grain size of the formed perovskite nanocrystals is largely affected by the perovskite precursor stoichiometry and the polymer solution concentration. Consequently, the optimized perovskite electrospun nanofiber yields a high photoluminescence quantum yield of 30.9%, significantly surpassing the value of its thin-film counterpart. Moreover, owing to the hydrophobic characteristic of shell polymer, the prepared perovskite nanofiber is endowed with a high resistance to air and water. Its photoluminescence intensity remains constant while stored under ambient environment with a relative humidity of 85% over a month and retains intensity higher than 50% of its initial intensity while immersed in water for 48 h. More intriguingly, a white light-emitting perovskite-based nanofiber is successfully fabricated by pairing the orange light-emitting compositional perovskite with a blue light-emitting conjugated polymer.