An ultrawide field-of-view pinhole compound eye using hemispherical nanowire array for robot vision.

Garnering inspiration from biological compound eyes, artificial vision systems boasting a vivid range of diverse visual functional traits have come to the fore recently. However, most of these artificial systems rely on transformable electronics, which suffer from the complexity and constrained geometry of global deformation, as well as potential mismatches between optical and detector units. Here, we present a unique pinhole compound eye that combines a three-dimensionally printed honeycomb optical structure with a hemispherical, all-solid-state, high-density perovskite nanowire photodetector array. The lens-free pinhole structure can be designed and fabricated with an arbitrary layout to match the underlying image sensor. Optical simulations and imaging results matched well with each other and substantiated the key characteristics and capabilities of our system, which include an ultrawide field of view, accurate target positioning, and motion tracking function. We further demonstrate the potential of our unique compound eye for advanced robotic vision by successfully completing a moving target tracking mission.

Full-color fiber light-emitting diodes based on perovskite quantum wires.

Fiber light-emitting diodes (Fi-LEDs), which can be used for wearable lighting and display devices, are one of the key components for fiber/textile electronics. However, there exist a number of impediments to overcome on device fabrication with fiber-like substrates, as well as on device encapsulations. Here, we uniformly grew all-inorganic perovskite quantum wire arrays by filling high-density alumina nanopores on the surface of Al fibers with a dip-coating process. With a two-step evaporation method to coat a surrounding transporting layer and semitransparent electrode, we successfully fabricated full-color Fi-LEDs with emission peaks at 625 nanometers (red), 512 nanometers (green), and 490 nanometers (sky-blue), respectively. Intriguingly, additional polydimethylsiloxane packaging helps instill the mechanical bendability, stretchability, and waterproof feature of Fi-LEDs. The plasticity of Al fiber also allows the one-dimensional architecture Fi-LED to be shaped and constructed for two-dimensional or even three-dimensional architectures, opening up a new vista for advanced lighting with unconventional formfactors.

Improving the Operational Lifetime of Metal-Halide Perovskite Light-Emitting Diodes with Dimension Control and Ligand Engineering.

Perovskite light-emitting diodes (LEDs) have emerged as one of the most propitious candidates for next-generation lighting and displays, with the highest external quantum efficiency (EQE) of perovskite LEDs already surpassing the 20% milestone. However, the further development of perovskite LEDs primarily relies on addressing operational instability issues. This Perspective examines some of the key factors that impact the lifetime of perovskite LED devices and some representative reports on recent advancements aimed at improving the lifetime. Our analysis underscores the significance of "nano" strategies in achieving long-term stable perovskite LEDs. Significant efforts must be directed toward proper device encapsulation, perovskite material passivation, interfacial treatment to address environment-induced material instability, bias-induced phase separation, and ion migration issues.

Geometric Shape Recognition with an Ultra-High Density Perovskite Nanowire Array-Based Artificial Vision System.

Artificial vision systems (AVS) have potential applications in visual prosthetics and artificially intelligent robotics, and they require a preprocessor and a processor to mimic human vision. Halide perovskite (HP) is a promising preprocessor and processor due to its excellent photoresponse, ubiquitous charge migration pathways, and innate hysteresis. However, the material instability associated with HP thin films hinders their utilization in physical AVSs. Herein, we have developed ultrahigh-density arrays of robust HP nanowires (NWs) rooted in a porous alumina membrane (PAM) as the active layer for an AVS. The NW devices exhibit gradual photocurrent change, responding to changes in light pulse duration, intensity, and number, and allow contrast enhancement of visual inputs with a device lifetime of over 5 months. The NW-based processor possesses temporally stable conductance states with retention >105 s and jitter <10%. The physical AVS demonstrated 100% accuracy in recognizing different shapes, establishing HP as a reliable material for neuromorphic vision systems.

High-efficiency, flexible and large-area red/green/blue all-inorganic metal halide perovskite quantum wires-based light-emitting diodes.

Metal halide perovskites have shown great promise as a potential candidate for next-generation solid state lighting and display technologies. However, a generic organic ligand-free and antisolvent-free solution method to fabricate highly efficient full-color perovskite light-emitting diodes has not been realized. Herein, by utilizing porous alumina membranes with ultra-small pore size as templates, we have successfully fabricated crystalline all-inorganic perovskite quantum wire arrays with ultrahigh density and excellent uniformity, using a generic organic ligand-free and anti-solvent-free solution method. The quantum confinement effect, in conjunction with the high light out-coupling efficiency, results in high photoluminescence quantum yield for blue, sky-blue, green and pure-red perovskite quantum wires arrays. Consequently, blue, sky-blue, green and pure-red LED devices with spectrally stable electroluminescence have been successfully fabricated, demonstrating external quantum efficiencies of 12.41%, 16.49%, 26.09% and 9.97%, respectively, after introducing a dual-functional small molecule, which serves as surface passivation and hole transporting layer, and a halide vacancy healing agent.

A neuromorphic bionic eye with filter-free color vision using hemispherical perovskite nanowire array retina.

Spherical geometry, adaptive optics, and highly dense network of neurons bridging the eye with the visual cortex, are the primary features of human eyes which enable wide field-of-view (FoV), low aberration, excellent adaptivity, and preprocessing of perceived visual information. Therefore, fabricating spherical artificial eyes has garnered enormous scientific interest. However, fusing color vision, in-device preprocessing and optical adaptivity into spherical artificial eyes has always been a tremendous challenge. Herein, we demonstrate a bionic eye comprising tunable liquid crystal optics, and a hemispherical neuromorphic retina with filter-free color vision, enabled by wavelength dependent bidirectional synaptic photo-response in a metal-oxide nanotube/perovskite nanowire hybrid structure. Moreover, by tuning the color selectivity with bias, the device can reconstruct full color images. This work demonstrates a unique approach to address the color vision and optical adaptivity issues associated with artificial eyes that can bring them to a new level approaching their biological counterparts.

Neuromorphic-computing-based adaptive learning using ion dynamics in flexible energy storage devices.

High-accuracy neuromorphic devices with adaptive weight adjustment are crucial for high-performance computing. However, limited studies have been conducted on achieving selective and linear synaptic weight updates without changing electrical pulses. Herein, we propose high-accuracy and self-adaptive artificial synapses based on tunable and flexible MXene energy storage devices. These synapses can be adjusted adaptively depending on the stored weight value to mitigate time and energy loss resulting from recalculation. The resistance can be used to effectively regulate the accumulation and dissipation of ions in single devices, without changing the external pulse stimulation or preprogramming, to ensure selective and linear synaptic weight updates. The feasibility of the proposed neural network based on the synapses of flexible energy devices was investigated through training and machine learning. The results indicated that the device achieved a recognition accuracy of ∼95% for various neural network calculation tasks such as numeric classification.

Three-Dimensional Nanopillar Arrays-Based Efficient and Flexible Perovskite Solar Cells with Enhanced Stability.

Perovskite nanopillars (PNPs) are propitious candidates for solar irradiation harvesting and are potential alternatives to thin films in flexible photovoltaics. To realize efficient daily energy output, photovoltaics must absorb sunlight over a broad range of incident angles and wavelengths congruent with the solar spectrum. Herein, we report highly periodic three-dimensional (3D) PNP-based flexible photovoltaics possessing a core-shell structure. The vertically aligned PNP arrays demonstrate up to 95.70% and 75.10% absorption at peak and under an incident angle of 60°. The efficient absorption and the orthogonal carrier collection facilitate an external quantum efficiency of 84.0%-89.18% for broadband wavelength. PNPs have been successfully implemented in flexible solar cells. The porous alumina membrane protects PNPs against water and oxygen intrusion and thereby imparts robustness to photovoltaic devices. Meanwhile, the excellent tolerance to mechanical stress/strain enables our unique PNP-based device to provide efficient solar-to-electricity conversion while undergoing mechanical bending.

Image processing with a multi-level ultra-fast three dimensionally integrated perovskite nanowire array.

Besides its ubiquitous applications in optoelectronics, halide-perovskites (HPs) have also carved a niche in the domain of resistive switching memories (Re-RAMs). However owing to the material and electrical instability challenges faced by HP thin-films, rarely perovskite Re-RAMs are used to experimentally demonstrate data processing which is a fundamental requirement for neuromorphic applications. Here, for the first time, lead-free, ultrahigh density HP nanowire (NW) array Re-RAM has been utilized to demonstrate image processing via design of convolutional kernels. The devices exhibited superior switching characteristics including a high endurance of 5 × 106 cycles, an ultra-fast erasing and writing speed of 900 ps and 2 ns, respectively, and a retention time >5 × 104 s for the resistances. The work is bolstered by an in-depth mechanistic study and first-principles simulations which provide evidence of electrochemical metallization triggering the switching. Employing the robust multi-level switching behaviour, image processing functions of embossing, outlining and sharpening were successfully implemented.

Strongly Quantum-Confined Perovskite Nanowire Arrays for Color-Tunable Blue-Light-Emitting Diodes.

Color tunability of perovskite light-emitting diodes (PeLEDs) by mixed halide compositional engineering is one of the primary intriguing characteristics of PeLEDs. However, mixed halide PeLEDs are often susceptible to color red-shifting caused by halide ion segregation. In this work, strongly quantum-confined perovskite nanowires (QPNWs) made of CsPbBr3 are grown in nanoporous anodic alumina templates using a closed space sublimation process. By tuning the pore size with atomic layer deposition, QPNWs with a diameter of 6.6 to 2.8 nm have been successfully obtained, with continuous tunable photoluminescence emission color from green (512 nm) to pure blue (467 nm). To better understand the photophysics of QPNWs, carrier dynamics and the benefit of alumina passivation are studied and discussed in detail. Eventually, PeLEDs using various diameters of CsPbBr3 QPNWs are successfully fabricated with cyan color (492 nm) PeLEDs, achieving a record high 7.1% external quantum efficiency (EQE) for all CsPbBr3-based cyan color PeLEDs. Sky blue (481 nm) and pure blue (467 nm) PeLEDs have also been successfully demonstrated, respectively. The work here demonstrates a different approach to achieve quantum-confined one-dimensional perovskite structures and color-tunable PeLEDs, particularly blue PeLEDs.

Vertical Heterogeneous Integration of Metal Halide Perovskite Quantum-Wires/Nanowires for Flexible Narrowband Photodetectors.

Charge collection narrowing (CCN) has been reported to be an efficient strategy to achieve optical filter-free narrowband photodetection (NPD) with metal halide perovskite (MHP) single crystals. However, the necessity of utilizing thick crystals in CCN limits their applications in large scale, flexible, self-driven, and high-performance optoelectronics. Here, for the first time, we fabricate vertically integrated MHP quantum wire/nanowire (QW/NW) array based photodetectors in nanoengineered porous alumina membranes (PAMs) showing self-driven broadband photodetection (BPD) and NPD capability simultaneously. Two cutoff detection edges of the NPDs are located at around 770 and 730 nm, with a full-width at half-maxima (fwhm) of around 40 nm. The optical bandgap difference between the NWs and the QWs, in conjunction with the high carrier recombination rate in QWs, contributes to the intriguing NPD performance. Thanks to the excellent mechanical flexibility of the PAMs, a flexible NPD is demonstrated with respectable performance. Our work here opens a new pathway to design and engineer a nanostructured MHP for novel color selective and full color sensing devices.

Three-dimensional perovskite nanowire array-based ultrafast resistive RAM with ultralong data retention.

Resistive random access memories (Re-RAMs) have transpired as a foremost candidate among emerging nonvolatile memory technologies with a potential to bridge the gap between the traditional volatile and fast dynamic RAMs and the nonvolatile and slow FLASH memories. Here, we report electrochemical metallization (ECM) Re-RAMs based on high-density three-dimensional halide perovskite nanowires (NWs) array as the switching layer clubbed between silver and aluminum contacts. NW Re-RAMs made of three types of methyl ammonium lead halide perovskites (MAPbX3; X = Cl, Br, I) have been explored. A trade-off between device switching speed and retention time was intriguingly found. Ultrafast switching speed (200 ps) for monocrystalline MAPbI3 and ~7 × 109 s ultralong extrapolated retention time for polycrystalline MAPbCl3 NW devices were obtained. Further, first-principles calculation revealed that Ag diffusion energy barrier increases when lattice size shrinks from MAPbI3 to MAPbCl3, culminating in the trade-off between the device switching speed and retention time.

Down-Scalable and Ultra-fast Memristors with Ultra-high Density Three-Dimensional Arrays of Perovskite Quantum Wires.

With strikingly high speed, data retention ability and storage density, resistive RAMs have emerged as a forerunning nonvolatile memory. Here we developed a Re-RAM with ultra-high density array of monocrystalline perovskite quantum wires (QWs) as the switching matrix with a metallic silver conducting pathway. The devices demonstrated high ON/OFF ratio of ∼107 and ultra-fast switching speed of ∼100 ps which is among the fastest in literature. The devices also possess long retention time of over 2 years and record high endurance of ∼6 × 106 cycles for all perovskite Re-RAMs reported. As a concept proof, we have also successfully demonstrated a flexible Re-RAM crossbar array device with a metal-semiconductor-insulator-metal design for sneaky path mitigation, which can store information with long retention. Aggressive downscaling to ∼14 nm lateral dimension produced an ultra-small cell effectively having 76.5 nm2 area for single bit storage. Furthermore, the devices also exhibited unique optical programmability among the low resistance states.

Wireless Self-Powered High-Performance Integrated Nanostructured-Gas-Sensor Network for Future Smart Homes.

The accelerated evolution of communication platforms including Internet of Things (IoT) and the fifth generation (5G) wireless communication network makes it possible to build intelligent gas sensor networks for real-time monitoring chemical safety and personal health. However, this application scenario requires a challenging combination of characteristics of gas sensors including small formfactor, low cost, ultralow power consumption, superior sensitivity, and high intelligence. Herein, self-powered integrated nanostructured-gas-sensor (SINGOR) systems and a wirelessly connected SINGOR network are demonstrated here. The room-temperature operated SINGOR system can be self-driven by indoor light with a Si solar cell, and it features ultrahigh sensitivity to H2, formaldehyde, toluene, and acetone with the record low limits of detection (LOD) of 10, 2, 1, and 1 ppb, respectively. Each SINGOR consisting of an array of nanostructured sensors has the capability of gas pattern recognition and classification. Furthermore, multiple SINGOR systems are wirelessly connected as a sensor network, which has successfully demonstrated flammable gas leakage detection and alarm function. They can also achieve gas leakage localization with satisfactory precision when deployed in one single room. These successes promote the development of using nanostructured-gas-sensor network for wide range applications including smart home/building and future smart city.

Optically tunable ultra-fast resistive switching in lead-free methyl-ammonium bismuth iodide perovskite films.

Resistive RAMs (Re-RAMs) have come to the fore as a rising star among the next generation non-volatile memories with fast operational speed, excellent endurance and prolonged data retention capabilities. Re-RAMs are being profusely used as storage and processing modules in neuromorphic hardware and high frequency switches in radio-frequency (RF) circuits. Owing to its intrinsic hysteresis and abundance of charge migration pathways, lead halide perovskites have emerged as a promising switching medium in Re-RAMs besides their ubiquitous usage in optoelectronic devices. Here, we adopted a lead-free eco-friendly methyl-ammonium bismuth iodide (MA3Bi2I9) perovskite (prepared by solvent-free engineering) as the switching medium sandwiched between copper (Cu) and indium doped tin oxide (ITO) electrodes. The devices exhibited a 104 high ON/OFF ratio that provided a large window for the multi-bit data storage in a single cell with good accuracy. Robust endurance of 1730 cycles and good data retention ability of >3 × 105 s were also observed. Careful switching speed measurements showed the devices can operate with an ultra-fast speed of 10 ns for writing and erasing respectively. The devices responded to light illumination and the prolonged retention of the opto-electrically tuned resistance states paved the way for image memorization.

A biomimetic eye with a hemispherical perovskite nanowire array retina.

Human eyes possess exceptional image-sensing characteristics such as an extremely wide field of view, high resolution and sensitivity with low aberration1. Biomimetic eyes with such characteristics are highly desirable, especially in robotics and visual prostheses. However, the spherical shape and the retina of the biological eye pose an enormous fabrication challenge for biomimetic devices2,3. Here we present an electrochemical eye with a hemispherical retina made of a high-density array of nanowires mimicking the photoreceptors on a human retina. The device design has a high degree of structural similarity to a human eye with the potential to achieve high imaging resolution when individual nanowires are electrically addressed. Additionally, we demonstrate the image-sensing function of our biomimetic device by reconstructing the optical patterns projected onto the device. This work may lead to biomimetic photosensing devices that could find use in a wide spectrum of technological applications.

Three-Dimensional Perovskite Nanophotonic Wire Array-Based Light-Emitting Diodes with Significantly Improved Efficiency and Stability.

Hybrid perovskites have emerged as promising candidates for highly efficient light-emitting diodes in the past few years due to their excellent crystallinity, high color purity, wide-range bandgap tunability, and solution processability. However, the reported device external quantum efficiency has not reached the level on par with that of conventional inorganic and organic light-emitting diodes. Moreover, device stability still needs substantial improvement. In this work, we demonstrate the fabrication of perovskite nanophotonic wire array-based light-emitting diodes with a capillary-effect-assisted template method. Compared with the planar control device, the nanostructured device demonstrates 45% improvement of external quantum efficiency from 11% to 16% owing to substantial enhancement on device light extraction efficiency verified by optical modeling. Intriguingly, it is also discovered that the nanostructured device possesses 3.89 times lifetime compared to the planar control device, due to effective template passivation. The results here have clearly shown that with a proper photonic device structure design, both the device performance and lifetime can be significantly improved.

Increasing Photoluminescence Quantum Yield by Nanophotonic Design of Quantum-Confined Halide Perovskite Nanowire Arrays.

High-photoluminescence quantum yield (PLQY) is required to reach optimal performance in solar cells, lasers, and light-emitting diodes (LEDs). Typically, PLQY can be increased by improving the material quality to reduce the nonradiative recombination rate. It is in principle equally effective to improve the optical design by nanostructuring a material to increase light out-coupling efficiency (OCE) and introduce quantum confinement, both of which can increase the radiative recombination rate. However, increased surface recombination typically minimizes nanostructure gains in PLQY. Here a template-guided vapor phase growth of CH3NH3PbI3 (MAPbI3) nanowire (NW) arrays with unprecedented control of NW diameter from the bulk (250 nm) to the quantum confined regime (5.7 nm) is demonstrated, while simultaneously providing a low surface recombination velocity of 18 cm s-1. This enables a 56-fold increase in the internal PLQY, from 0.81% to 45.1%, and a 2.3-fold increase in OCEy to increase the external PLQY by a factor of 130, from 0.33% up to 42.6%, exclusively using nanophotonic design.

Efficient metal halide perovskite light-emitting diodes with significantly improved light extraction on nanophotonic substrates.

Metal halide perovskite has emerged as a promising material for light-emitting diodes. In the past, the performance of devices has been improved mainly by optimizing the active and charge injection layers. However, the large refractive index difference among different materials limits the overall light extraction. Herein, we fabricate efficient methylammonium lead bromide light-emitting diodes on nanophotonic substrates with an optimal device external quantum efficiency of 17.5% which is around twice of the record for the planar device based on this material system. Furthermore, optical modelling shows that a high light extraction efficiency of 73.6% can be achieved as a result of a two-step light extraction process involving nanodome light couplers and nanowire optical antennas on the nanophotonic substrate. These results suggest that utilization of nanophotonic structures can be an effective approach to achieve high performance perovskite light-emitting diodes.

Significantly improved black phase stability of FAPbI3 nanowires via spatially confined vapor phase growth in nanoporous templates.

The formamidinium lead iodide (FAPbI3) perovskite has attracted immense research interest as it has much improved stability than methylammonium lead iodide (MAPbI3) while still maintaining excellent optoelectronic properties. Compared to MAPbI3, FAPbI3 has shown an elevated decomposition temperature and a slower decomposition process and therefore it is considered as a more promising candidate for future high-efficiency and reliable optoelectronic devices. However, these excellent optoelectronic properties only exist in the alpha phase and this phase will spontaneously transform into an undesired delta phase with much poorer optoelectronic properties regardless of the environment. This is the main challenge for the application of the FAPbI3 perovskite. Herein, we report a novel strategy to stabilize the cubic black phase of FAPbI3 by using nanoengineering templates. Without further treatment, the black phase can be held over 7 months under ambient conditions and 8 days in an extreme environment with a Relative Humidity (RH) of 97%. A systematic study further reveals that this great improvement can be attributed to the spatial confinement in anodized alumina membrane (AAM) nanochannels, which prohibits the unwanted α-to-δ phase transition by restricting the expansion of NWs in the ab plane, and the excellent passivation against water molecule invasion. Meanwhile, we also demonstrate the potency of these NWs in practical applications by configuring them into photodetectors, which have shown reasonable response and excellent device stability.