Optoelectronic Synapses and Photodetectors Based on Organic Semiconductor/Halide Perovskite Heterojunctions: Materials,Devices, and Applications

Both photodetectors (PDs) and optoelectronic synaptic devices (OSDs) are optoelectronic devices converting light signals into electrical responses. Optoelectronic devices based on organic semiconductors and halide perovskites have aroused tremendous research interest owing to their exceptional optical/electrical characteristics and low-cost processability. The heterojunction formed between organic semiconductors and halide perovskites can modify the exciton dissociation/recombination efficiency and modulate the charge-trapping effect. Consequently, organic semiconductor/halide perovskite heterojunctions can endow PDs and OSDs with high photo responsivity and the ability to simulate synaptic functions respectively, making them appropriate for the development of energy-efficient artificial visual systems with sensory and recognition functions. This article summarizes the recent advances in this research field. The physical/chemical properties and preparation methods of organic semiconductor/halide perovskite heterojunctions are briefly introduced. Then the development of PDs and OSDs based on organic semiconductor/halide perovskite heterojunctions, as well as their innovative applications, are systematically presented. Finally, some prospective challenges and probable strategies for the future development of optoelectronic devices based on organic semiconductor/halide perovskite heterojunctions are discussed.     

Fine-Tuning Alkyl Chains on Quinoxaline Nonfullerene Acceptors Enables High-Efficiency Ternary Organic Solar Cells with Optimizing Molecular Stacking and Reducing Energy Loss

Material design of guest acceptor is always a big challenge for improving the efficiency of ternary organic solar cells (OSCs). Here, a pair of isomeric nonfullerene acceptors based on quinoxaline core, Qx–p-C₇H₈O and Qx–m-C₇H₈O, is designed and synthesized. By moving the alkoxy chain attached on side phenyl from meta-position to para-position, both π–π stacking distance and crystallinity are enhanced simultaneously. They obtain the uplifted lowest unoccupied molecular orbital level. Compared to Qx–m-C₇H₈O, Qx–p-C₇H₈O exhibits wider absorption spectrum and higher extinction coefficient. Using D18-Cl:N3 as host materials, the addition of guest acceptor Qx–p-C₇H₈O significantly improves the power conversion efficiency (PCE) from 17.61% to 18.49% because of higher open-circuit voltage (0.875 V) and short-circuit current density (27.85 mA cm⁻²). This can be attributed to the faster exciton dissociation, more balanced carrier mobility, fine fiber morphology, and lower energy loss in the ternary devices. However, Qx–m-C₇H₈O-based ternary device achieves relatively low PCE of 17.17% because this device shows extremely low electron mobility. The results indicate that molecular stacking, film morphology, etc., can be effectively modulated by fine-tuning the side chains of guest materials, which may be an effective design rule for further improving the PCE of OSCs.     

Inorganic Filler Enhanced Formation of Stable Inorganic-Rich Solid Electrolyte Interphase for High Performance Lithium Metal Batteries

Lithium metal (LM) is a promising anode material for next generation lithium ion based electrochemical energy storage devices. Critical issues of unstable solid electrolyte interphases (SEIs) and dendrite growth however still impede its practical applications. Herein, a composite gel polymer electrolyte (GPE), formed through in situ polymerization of pentaerythritol tetraacrylate with fumed silica fillers, is developed to achieve high performance lithium metal batteries (LMBs). As evidenced theoretically and experimentally, the presence of SiO₂ not only accelerates Li⁺ transport but also regulates Li⁺ solvation sheath structures, thus facilitating fast kinetics and formation of stable LiF-rich interphase and achieving uniform Li depositions to suppress Li dendrite growth. The composite GPE-based Li||Cu half-cells and Li||Li symmetrical cells display high Coulombic efficiency (CE) of 90.3% after 450 cycles and maintain stability over 960 h at 3 mA cm⁻² and 3 mAh cm⁻², respectively. In addition, Li||LiFePO₄ full-cells with a LM anode of limited Li supply of 4 mAh cm⁻² achieve capacity retention of 68.5% after 700 cycles at 0.5 C (1 C = 170 mA g⁻¹). Especially, when further applied in anode-free LMBs, the carbon cloth||LiFePO₄ full-cell exhibits excellent cycling stability with an average CE of 99.94% and capacity retention of 90.3% at the 160th cycle at 0.5 C.     

Dispersion-Enabled Symmetry Switching of Photonic Angular-Momentum Coupling

Photonic spin-orbit interactions describe the interactions between spin angular momentum and orbital angular momentum of photons, which play essential roles in subwavelength optics. However, the influence of frequency dispersion on photonic angular-momentum coupling is rarely studied. Here, by elaborately designing the contribution of the geometric phase and waveguide propagation phase, the dispersion-enabled symmetry switching of photonic angular-momentum coupling is experimentally demonstrated. This notion may induce many exotic phenomena and be found in enormous applications, such as the spin-Hall effect, optical calculation, and wavelength division multiplexing systems. As a proof-of-concept demonstration, two metadevices, a multi-channel vectorial vortex beam generator and a phase-only hologram, are applied to experimentally display optical double convolution, which may offer additional degrees of freedom to accelerate computing and a miniaturization configuration for optical convolution without collimation operation. These results may provide a new opportunity for complex vector optical field manipulation and calculation, optical information coding, light-matter interaction manipulation, and optical communication.     

Mo-Modified ZnIn2S4@NiTiO3 S-Scheme Heterojunction with Enhanced Interfacial Electric Field for Efficient Visible-Light-Driven Hydrogen Evolution

Designing and developing visible-light-responsive materials for solar to chemical energy is an efficient and promising approach to green and sustainable carbon-neutral energy systems. Herein, a facile in situ growth hydrothermal strategy using Mo-modified ZnIn₂S₄ (Mo-ZIS) nanosheets coupled with NiTiO₃ (NTO) microrods to synthesize multifunctional Mo-modified ZIS wrapped NTO microrods (Mo-ZIS@NTO) photocatalyst with enhanced interfacial electric field (IEF) effect and typical S-scheme heterojunction is reported. Mo-ZIS@NTO catalyst possesses wide-spectrum light absorption properties, excellent visible light-to-thermal energy effect, electron mobility, charges transfer, and strong IEF and exhibits excellent solar-to-chemical energy conversion for efficient visible-light-driven photocatalytic hydrogen evolution. Notably, the engineered Mo_1.4-ZIS@NTO catalyst exhibits superior performance with H₂ evolution rate of up to 14.06 mmol g⁻¹ h^{− 1} and the apparent quantum efficiency of 44.1% at 420 nm. The scientific explorations provide an in-depth understanding of microstructure, S-scheme heterojunction, enhanced IEF, Mo-dopant facilitation effect. Moreover, the theoretical simulations verify the critical role of Mo element in promoting the adsorption and activation of H₂O molecules, modulating the H adsorption behavior on active S sites, and thus accelerating the overall catalytic efficiency. The photocatalytic hydrogen evolution mechanism via S-scheme heterojunction with adjustable IEF regulation over Mo_1.4-ZIS@NTO is also demonstrated.     

Main-Chain Nematic Side-Chain Smectic Composite Liquid Crystalline Elastomers

A composite liquid crystalline elastomer is designed, combining main-chain and side-chain mesogenic polymers in the network, and resulting in micro-phase separated regions of nematic and smectic ordering in the macroscopically homogeneous elastomer. A range of different fractions of the components is explored, from fully nematic main-chain system, across to fully smectic side-chain elastomer. Thermal phase transitions of both phases coexisting in the material are detected by calorimetry, and the nematic/smectic structure investigated by X-ray scattering. The tensile stress–strain data reveal the key effect of such a multi-phase composite, where the nematic fraction adds ductility while the smectic fraction increases the modulus and mechanical stiffness. Varying the composition, the authors are able to optimize the mechanical properties of this material type.     

MXene Functionalized,Highly Breathable and Sensitive Pressure Sensors with Multi-Layered Porous Structure

Breathable, flexible, and highly sensitive pressure sensors have drawn increasing attention due to their potential in wearable electronics for body-motion monitoring, human-machine interfaces, etc. However, current pressure sensors are usually assembled with polymer substrates or encapsulation layers, thus causing discomfort during wearing (i.e., low air/vapor permeability, mechanical mismatch) and restricting their applications. A breathable and flexible pressure sensor is reported with nonwoven fabrics as both the electrode (printed with MXene interdigitated electrode) and sensing (coated with MXene/silver nanowires) layers via a scalable screen-printing approach. Benefiting from the multi-layered porous structure, the sensor demonstrates good air permeability with high sensitivity (770.86–1434.89 kPa⁻¹), a wide sensing range (0–100 kPa), fast response/recovery time (70/81 ms), and low detection limit (≈1 Pa). Particularly, this sensor can detect full-scale human motion (i.e., small-scale pulse beating and large-scale walking/running) with high sensitivity, excellent cycling stability, and puncture resistance. Additionally, the sensing layer of the pressure sensor also displays superior sensitivity to humidity changes, which is verified by successfully monitoring human breathing and spoken words while wearing a sensor-embedded mask. Given the outstanding features, this breathable sensor shows promise in the wearable electronic field for body health monitoring, sports activity detection, and disease diagnosis.     

Mitigating Surface Deficiencies of Perovskite Single Crystals Enables Efficient Solar Cells with Enhanced Moisture and Reverse-Bias Stability

Metal halide perovskite single crystals are promising for diverse optoelectronic applications due to their outstanding properties. In comparison to the bulk, the crystal surface suffers from high defect density and is moisture sensitive; however, surface modification strategies of perovskite single crystals are relatively deficient. Herein, solar cells based on methylammonium lead triiodide (MAPbI₃) thin single crystals are selected as a prototype to improve single-crystal perovskite devices by surface modification. The surface trap passivation and protection against moisture of MAPbI₃ thin single crystals are achieved by one bifunctional molecule 3-mercaptopropyl(dimethoxy)methylsilane (MDMS). The sulfur atom of MDMS can coordinate with bare Pb²⁺ of MAPbI₃ single crystals to reduce surface defect density and nonradiative recombination. As a result, the modified devices show a remarkable efficiency of 22.2%, which is the highest value for single-crystal MAPbI₃ solar cells. Moreover, MDMS modification mitigates surface ion migration, leading to enhanced reverse-bias stability. Finally, the cross-link of silane molecules forms a protective layer on the crystal surface, which results in enhanced moisture stability of both materials and devices. This work provides an effective way for surface modification of perovskite single crystals, which is important for improving the performance of single-crystal perovskite solar cells, photodetectors, X-ray detectors, etc.     

On-chip Diamond MEMS Magnetic Sensing through Multifunctionalized Magnetostrictive Thin Film

Electrically integrable, high-sensitivity, and high-reliability magnetic sensors are not yet realized at high temperatures (500 °C). In this study, an integrated on-chip single-crystal diamond (SCD) micro-electromechanical system (MEMS) magnetic transducer is demonstrated by coupling SCD with a large magnetostrictive FeGa film. The FeGa film is multifunctionalized to actuate the resonator, self-sense the external magnetic field, and electrically readout the resonance signal. The on-chip SCD MEMS transducer shows a high sensitivity of 3.2 Hz mT⁻¹ from room temperature to 500 °C and a low noise level of 9.45 nT Hz^−1/2 up to 300 °C. The minimum fluctuation of the resonance frequency is 1.9 × 10⁻⁶ at room temperature and 2.3 × 10⁻⁶ at 300 °C. An SCD MEMS resonator array with parallel electric readout is subsequently achieved, thus providing a basis for the development of magnetic image sensors. The present study facilitates the development of highly integrated on-chip MEMS resonator transducers with high performance and high thermal stability.     

A Hybrid Strategy-Based Ultra-Narrow Stretchable Microelectrodes with Cell-Level Resolution

Stretchable ultra-narrow (e.g., 10 µm in width) microelectrodes are crucial for the electrophysiological monitoring of single cells providing the fundamental understanding to the working mechanism of neuro network or other electrically functional cells. Current fabrication strategies either focus on the preparation of normal stretchable electrodes with hundreds of micrometers or millimeters in width by using inorganic conductive materials or develop conductive organic polymer gel for ultra-narrow electrodes which suffer from low stretchability and instability for long-term implantation, therefore, it is still highly desirable to explore bio-interfacial ultra-narrow stretchable inorganic electrodes. Herein, a hybrid strategy is reported to prepare ultra-narrow multi-channel stretchable microelectrodes without using photolithography or laser-assisting etching. A 10 µm × 10 µm monitoring window is fabricated with enhanced interfacial impedance by the special rough surface. The stretchability achieves to 120% for this 10 µm-width stretchable electrode. Supported by these superior properties, it is demonstrated that the stretchable microelectrodes can detect electrophysiological signals of single cells in vitro and collect electrophysiological signals more precisely in vivo. The reported strategy will open up the accessible preparation of the fine-size stretchable microelectrode. It will significantly improve the resolution of monitoring and stimulation of inorganic stretchable electrodes.