Air-Stable Self-Driven UV Photodetectors on Controllable Lead-Free CsCu2I3 Microwire Arrays.

The rapid evolution of the Internet of Things has engendered increased requirements for low-cost, self-powered UV photodetectors. Herein, high-performance self-driven UV photodetectors are fabricated by designing asymmetric metal-semiconductor-metal structures on the high-quality large-area CsCu2I3 microwire arrays. The asymmetrical depletion region doubles the photocurrent and response speed compared to the symmetric structure device, leading to a high responsivity of 233 mA/W to 355 nm radiation. Notably, at 0 V bias, the asymmetric device produces an open-circuit voltage of 356 mV and drives to a short-circuit current of 372 pA; meanwhile, the switch ratio (Iph/Idark) reaches up to 103, indicating its excellent potential for detecting weak light. Furthermore, the device maintains stable responses throughout 10000 UV-light switch cycles, with negligible degradation even after 90-day storage in air. Our work establishes that CsCu2I3 is a good candidate for self-powered UV detection and thoroughly demonstrates its potential as a passive device.

Perovskite single-pixel detector for dual-color metasurface imaging recognition in complex environment.

Highly efficient multi-dimensional data storage and extraction are two primary ends for the design and fabrication of emerging optical materials. Although metasurfaces show great potential in information storage due to their modulation for different degrees of freedom of light, a compact and efficient detector for relevant multi-dimensional data retrieval is still a challenge, especially in complex environments. Here, we demonstrate a multi-dimensional image storage and retrieval process by using a dual-color metasurface and a double-layer integrated perovskite single-pixel detector (DIP-SPD). Benefitting from the photoelectric response characteristics of the FAPbBr2.4I0.6 and FAPbI3 films and their stacked structure, our filter-free DIP-SPD can accurately reconstruct different colorful images stored in a metasurface within a single-round measurement, even in complex environments with scattering media or strong background noise. Our work not only provides a compact, filter-free, and noise-robust detector for colorful image extraction in a metasurface, but also paves the way for color imaging application of perovskite-like bandgap tunable materials.

Multifunctional Organic-Inorganic Hybrid Perovskite Microcrystalline Engineering and Electromagnetic Response Switching Multi-Band Devices.

High-efficiency electromagnetic (EM) functional materials are the core building block of high-performance EM absorbers and devices, and they are indispensable in various fields ranging from industrial manufacture to daily life, or even from national defense security to space exploration. Searching for high-efficiency EM functional materials and realizing high-performance EM devices remain great challenges. Herein, a simple solution-process is developed to rapidly grow gram-scale organic-inorganic (MAPbX3 , X = Cl, Br, I) perovskite microcrystals. They exhibit excellent EM response in multi bands covering microwaves, visible light, and X-rays. Among them, outstanding microwave absorption performance with multiple absorption bands can be achieved, and their intrinsic EM properties can be tuned by adjusting polar group. An ultra-wideband bandpass filter with high suppression level of -71.8 dB in the stopband in the GHz band, self-powered photodetectors with tunable broadband or narrowband photoresponse in the visible-light band, and a self-powered X-ray detector with high sensitivity of 3560 µC Gyair -1  cm-2  in the X-ray band are designed and realized by precisely regulating the physical features of perovskite and designing a novel planar device structure. These findings open a door toward developing high-efficiency EM functional materials for realizing high-performance EM absorbers and devices.

Photosensitive Dielectric 2D Perovskite Based Photodetector for Dual Wavelength Demultiplexing.

Stacked 2D perovskites provide more possibilities for next generation photodetector with more new features. Compared with its excellent optoelectronic properties, the good dielectric performance of metal halide perovskite rarely comes into notice. Here, a bifunctional perovskite based photovoltaic detector capable of two wavelength demultiplexing is demonstrated. In the Black Phosphorus/Perovskite/MoS2 structured photodetector, the comprehensive utilization of the photosensitive and dielectric properties of 2D perovskite allows the device to work in different modes. The device shows normal continuous photoresponse under 405 nm, while it shows a transient spike response to visible light with longer wavelengths. The linear dynamic range, rise/decay time, and self-powered responsivity under 405 nm can reach 100, 38 µs/50 µs, and 17.7 mA W-1 , respectively. It is demonstrated that the transient spike photocurrent with long wavelength exposure is related to the illumination intensity and can coexist with normal photoresponse. Two waveband-dependent signals can be identified and used to reflect more information simultaneously. This work provides a new strategy for multispectral detection and demultiplexing, which can be used to improve data transfer rates and encrypted communications. This work mode can inspire more multispectral photodetectors with different stacked 2D materials, especially to the optoelectronic application of the wide bandgap, high dielectric photosensitive materials.

Ultraviolet photodetector based on RbCu2I3microwire.

Copper-based halide perovskites have shown great potential in lighting and photodetection due to their excellent photoelectric properties, good stability and lead-free nature. However, as an important piece of copper-based perovskites, the synthesis and application of RbCu2I3have never been reported. Here, we demonstrate the synthesis of high-quality RbCu2I3microwires (MWs) by a fast-cooling hot saturated solution method. The prepared MWs exhibit an orthorhombic structure with a smooth surface. Optical measurements show the RbCu2I3MWs have a sharp ultraviolet absorption edge with 3.63 eV optical band gap and ultra-large stokes shift (300 nm) in photoluminescence. The subsequent photodetector based on a single RbCu2I3MW shows excellent ultraviolet detection performance. Under the 340 nm illumination, the device shows a specific detectivity of 5.0 × 109Jones and a responsivity of 380 mA·W-1. The synthesis method and physical properties of RbCu2I3could be a guide to the future optoelectronic application of the new material.

Enhanced Optoelectronic Performance Induced by Ion Migration in Lead-Free CsCu2I3 Single-Crystal Microrods.

Lead-free perovskite has attracted great attention in realizing high-performance optoelectronic devices due to their excellent atmospheric stability and nontoxic characteristics. Although a pronounced ion migration effect has been observed in this new class of materials, its potential in enhancing the overall device performance is yet to be fully explored. In this work, we studied the effect of ion migrations on the carrier transport behavior and found that the recoverable migration process can contribute to enhancing the on/off ratio in a lead-free CsCu2I3 single-crystal microrod-based photodetector. In detail, we synthesized CsCu2I3 single-crystal microrods via an in-plane self-assembly supersaturated crystallization approach. These microrods with well-defined morphologies were then used to construct ultraviolet (UV)-band photodetectors, which outperform most reported lead-free perovskite photodetectors based on individual single crystals. Simultaneously, ion migration can result in asymmetric band bending in the two-terminal device, as confirmed by surface potential profiling with Kelvin probe force microscopy (KPFM). Such an effect can be harnessed to increase the on/off ratio by almost an order of magnitude. Furthermore, the lead-free CsCu2I3 single crystal exhibits excellent thermal and air stabilities. These findings demonstrate that the CsCu2I3 single-crystal microrods can be used in stable and efficient photodetection, and the ion migration effect can potentially be utilized for improving the optoelectronic performance of lead-free devices.

Extraordinarily Stable Aqueous Electrochromic Battery Based on Li4Ti5O12 and Hybrid Al3+/Zn2+ Electrolyte.

Aqueous electrochromic battery (ECB) is a multifunctional technology that shows great potential in various applications including energy-saving buildings and wearable batteries with visible energy levels. However, owing to the mismatch between traditional electrochromic materials and the electrolyte, aqueous ECBs generally exhibit poor cycling stability which bottlenecks their practical commercialization. Herein, we present an ultrastable electrochromic system composed of lithium titanate (Li4Ti5O12, LTO) electrode and Al3+/Zn2+ hybrid electrolyte. The fully compatible system exhibits excellent redox reaction reversibility, thus leading to extremely high cycling stabilities in optical contrast (12 500 cycles with unnoticeable degradation) and energy storage (4000 cycles with 82.6% retention of capacity), superior electrochromic performances including high optical contrast (∼74.73%) and fast responses (4.35 s/7.65 s for bleaching/coloring), as well as excellent discharge areal capacity of 151.94 mAh m-2. The extraordinary cycling stability can be attributed to the robust [TiO6] octahedral frameworks which remain chemically active even upon the gradual substitution of Li+ with Al3+ in LTO over multiple operation cycles. The high-performance electrochromic system demonstrated here not only makes the commercialization of low-cost, high-safety aqueous-based electrochromic devices possible but also provides potential design guidance for LTO-related materials used in aqueous-based energy storage devices.

Observation and Suppression of Stacking Interface States in Sandwich-Structured Quantum Dot Light-Emitting Diodes.

Interfacial quality of functional layers plays an important role in the carrier transport of sandwich-structured devices. Although the suppression of interface states is crucial to the overall device performance, our understanding on their formation and annihilation mechanism via direct characterization is still quite limited. Here, we present a thorough study on the interface states present in the electron transport layer (ETL) of blue quantum dot (QD) light-emitting diodes (QLEDs). A ZnO/ZnMgO bilayer ETL is adopted to enhance the electron injection into blue QDs. By probing the ETL band structure with photoelectron spectroscopy, we discover that substantial band bending exists at the ZnO/ZnMgO interface, elucidating the presence of a high density of interface states which hinder electron transport. By inserting a ZnO@ZMO interlayer composed of mixed ZnO and ZnMgO nanoparticles, the band bending and thus the interface states are observed to reduce significantly. We attribute this to the hybrid surface properties of ZnO@ZMO, which can annihilate the surface states of both the ZnO and ZnMgO layers. The introduction of a bridging layer has led to ∼40% enhancement in the power efficiency of blue QLEDs and noticeable performance boosts in green and red QLEDs. The findings here demonstrate a direct observation of interface states via detailed band structure studies and outline a potential pathway for eliminating these states for better performances in sandwich-structured devices.

Efficiency Improvement of Quantum Dot Light-Emitting Diodes via Thermal Damage Suppression with HATCN.

With many advantages including superior color saturation and efficiency, quantum dot light-emitting diodes (QLEDs) are considered a promising candidate for the next-generation displays. Emission uniformity over the entire device area is a critical factor to the overall performance and reliability of QLEDs. In this work, we performed a thorough study on the origin of dark spots commonly observed in operating QLEDs and developed a strategy to eliminate these defects. Using advanced cross section fabrication and imaging techniques, we discovered the occurrence of voids in the organic hole transport layer and directly correlated them to the observed emission nonuniformity. Further investigations revealed that these voids are thermal damages induced during the subsequent thermal deposition of other functional layers and can act as leakage paths in the device. By inserting a thermo-tolerant 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HATCN) interlayer with an optimized thickness, the thermally induced dark spots can be completely suppressed, leading to a current efficiency increase by 18%. We further demonstrated that such a thermal passivation strategy can work universally for various types of organic layers with low thermal stability. Our findings here provide important guidance in enhancing the performances and reliability of QLEDs and also other sandwich-structured devices via the passivation of heat-sensitive layers.

Phosphorescent Carbon-Nanodots-Assisted Förster Resonant Energy Transfer for Achieving Red Afterglow in an Aqueous Solution.

Water-soluble red afterglow imaging agents based on ecofriendly nanomaterials have potential application in time-gated afterglow bioimaging due to their larger penetration depth and nondurable excitation. Herein, red afterglow imaging agents consisted of Rhodamine B (RhB) and carbon nanodots (CNDs) have been designed and demonstrated. In these agents, CNDs act as energy donors, and RhB acts as an energy acceptor. Both of them are confined into a hydrophilic silica shell to form a CNDs-RhB@silica nanocomposite. The phosphorescence emission spectrum of the CNDs and the absorption spectrum of the RhB match well, and efficient energy transfer from the CNDs to the RhB via Förster resonant energy transfer process can be achieved, with a transfer efficiency can reach 99.2%. Thus, the as-prepared nanocomposite can emit a red afterglow in aqueous solution, and the afterglow spectrum of CNDs-RhB@silica nanocomposite can extend to the first near-infrared window (NIR-I). The luminescence lifetime and afterglow quantum yield (QY) of the CNDs-RhB@silica can reach 0.91 s and 3.56%, respectively, which are the best results in red afterglow region. Time-gated in vivo afterglow imaging has been demonstrated by using the CNDs-RhB@silica as afterglow agents.

Stable and Efficient Blue-Emitting CsPbBr3 Nanoplatelets with Potassium Bromide Surface Passivation.

Colloidal all-inorganic perovskites nanocrystals (NCs) have emerged as a promising material for display and lighting due to their excellent optical properties. However, blue emissive NCs usually suffer from low photoluminescence quantum yields (PLQYs) and poor stability, rendering them the bottleneck for full-color all-perovskite optoelectronic applications. Herein, a facile approach is reported to enhance the emission efficiency and stability of blue emissive perovskite nano-structures via surface passivation with potassium bromide. By adding potassium oleate and excess PbBr2 to the perovskite precursor solutions, potassium bromide-passivated (KBr-passivated) blue-emitting (≈450 nm) CsPbBr3 nanoplatelets (NPLs) is successfully synthesized with a respectably high PLQY of 87%. In sharp contrast to most reported perovskite NPLs, no shifting in emission wavelength is observed in these passivated NPLs even after prolonged exposures to intense irradiations and elevated temperature, clearly revealing their excellent photo- and thermal-stabilities. The enhancements are attributed to the formation of K-Br bonding on the surface which suppresses ion migration and formation of Br-vacancies, thus improving both the PL emission and stability of CsPbBr3 NPLs. Furthermore, all-perovskite white light-emitting diodes (WLEDs) are successfully constructed, suggesting that the proposed KBr-passivated strategy can promote the development of the perovskite family for a wider range of optoelectronic applications.

Multi-Phase Heterostructure of CoNiP/Cox P for Enhanced Hydrogen Evolution Under Alkaline and Seawater Conditions by Promoting H2 O Dissociation.

Hydrogen evolution reaction (HER) is a key step for electrochemical energy conversion and storage. Developing well defined nanostructures as noble-metal-free electrocatalysts for HER is promising for the application of hydrogen technology. Herein, it is reported that 3D porous hierarchical CoNiP/Cox P multi-phase heterostructure on Ni foam via an electrodeposition method followed by phosphorization exhibits ultra-highly catalytic activity for HER. The optimized CoNiP/Cox P multi-phase heterostructure achieves an excellent HER performance with an ultralow overpotential of 36 mV at 10 mA cm-2 , superior to commercial Pt/C. Importantly, the multi-phase heterostructure shows exceptional stability as confirmed by the long-term potential cycles (30,000 cycles) and extended electrocatalysis (up to 500 h) in alkaline solution and natural seawater. Experimental characterizations and DFT calculations demonstrate that the strong electronic interaction at the heterointerface of CoNiP/CoP is achieved via the electron transfer from CoNiP to the heterointerface, which directly promotes the dissociation of water at heterointerface and desorption of hydrogen on CoNiP. These findings may provide deep understanding on the HER mechanism of heterostructure electrocatalysts and guidance on the design of earth-abundant, cost-effective electrocatalysts with superior HER activity for practical applications.

Shape-control growth of 2D-In2Se3 with out-of-plane ferroelectricity by chemical vapor deposition.

For potential applications in ferroelectric switching and piezoelectric nano-generator devices, the promising ferroelectric properties of two dimensional (2D) layered In2Se3 attracted much attention. In the present study, 2D In2Se3 flakes down to monolayers are grown by the chemical vapor deposition (CVD) technique on a mica substrate with their structural, optical and ferroelectric properties being studied. The effect of growth parameters (time of growth and Ar flow rate) on the shape and size of the deposited flakes was studied. The optical microscopy study revealed that the flake changed from a circular shape to a sharp face triangle as the Ar flow rate and growth time increased. Raman spectroscopy and high-resolution scanning transmission electron microscopy (HR-STEM) studies revealed that the flakes were of α and ß phases, each of which has a hexagonal crystal structure. Strong second harmonic generation (SHG) was observed from α-In2Se3, demonstrating its non-centrosymmetric structure. The piezo-force microscopic (PFM) study showed the presence of out of plane (OOP) ferroelectricity with no in plane (IP) ferroelectricity in CVD grown α-In2Se3 indicating its vertically confined piezoresponse, which was tuned by the applied electric bias and the flake thickness. The present result of shape-controlled growth of In2Se3 with OOP ferroelectricity would open new pathways in the field of 2D ferroelectric switching devices.

Aliphatic Group-Tethered Iridium Complex as a Theranostic Agent against Malignant Melanoma Metastasis.

Malignant melanoma is a very aggressive form of skin cancer, with a low long-term survival rate. Developing multifunctional theranostic agents to simultaneously track and inhibit the activity of tumor targets is a potential strategy for combating melanoma metastasis. S100B expression is directly correlated with the degree of malignant metastatic melanoma and is overexpressed in the majority of malignant melanoma patients. Herein, the Ir(III) complex 7 was identified as a potent theranostic agent with nanomolar potency against S100B and selectivity over related substrates. Complex 7 exhibited desirable photophysical properties including a large Stokes shift and high photostability, while its long emission lifetime enabled its luminescence signal to be discriminated from a highly autofluorescent background by use of time-resolved emission spectroscopy. Importantly, complex 7 showed strong colocalization with S100B protein in melanoma cells with a stable signal up to at least 12 h, revealing its potential as a cellular probe for S100B. Moreover, complex 7 impeded the interaction between S100B and the C-terminus of p53 in the cytoplasm, thereby restoring the binding of p53 to its target promoters. Finally, complex 7 suppressed tumor growth and restrained lung metastases in vivo in two separate melanoma mouse models. To our knowledge, complex 7 is the first reported theranostic agent for simultaneously monitoring S100B and suppressing malignant melanoma metastasis in vivo via targeting S100B protein.

Homogeneous Core/Shell NiMoO4@NiMoO4 and Activated Carbon for High Performance Asymmetric Supercapacitor.

Here, we report the extraordinary electrochemical energy storage capability of NiMoO4@NiMoO4 homogeneous hierarchical nanosheet-on-nanowire arrays (SOWAs), synthesized on nickel substrate by a two-stage hydrothermal process. Comparatively speaking, the SOWAs electrode displays superior electrochemical performances over the pure NiMoO4 nanowire arrays. Such improvements can be ascribed to the characteristic homogeneous hierarchical structure, which not only effectively increases the active surface areas for fast charge transfer, but also reduces the electrode resistance significantly by eliminating the potential barrier at the nanowire/nanosheet junction, an issue usually seen in other reported heterogeneous architectures. We further evaluate the performances of the SOWAs by constructing an asymmetric hybrid supercapacitor (ASC) with the SOWAs and activated carbon (AC). The optimized ASC shows excellent electrochemical performances with 47.2 Wh/kg in energy density of 1.38 kW/kg at 0-1.2 V. Moreover, the specific capacity retention can be as high as 91.4% after 4000 cycles, illustrating the remarkable cycling stability of the NiMoO4@NiMoO4//AC ASC device. Our results show that this unique NiMoO4@NiMoO4 SOWA has great prospects for future energy storage applications.

Tailoring the Photoluminescence Excitation Dependence of the Carbon Dots via an Alkali Treatment.

Carbon dots (CDs) have shown great potential in various applications including biomedicines and optoelectronics. However, the origin of their photoluminescence excitation dependence (PL-ED) still remains uncertain, and this can limit the full exploit of their wonderful optical properties. Here we studied the mechanism for the PL-ED of solvothermally synthesized CDs using an alkali treatment. As-synthesized CDs were found to agglomerate and exhibited multicolor emissions with strong PL-ED. The alkali treatment can effectively break down the clusters into individual CDs via the hydrolysis of the amide and ester bonds that link the CDs together. This process effectively narrowed the emission line width and suppressed the observed PL-ED. The understanding of the excitation dependence mechanism here outlined a novel strategy for tailoring of the PL-ED of CDs via a synergy of chemical and physical processes, thus enhancing the versatility of CDs for a broader spectrum of applications.

Mixed Two-Dimensional Organic-Inorganic Halide Perovskites for Highly Efficient and Stable Photovoltaic Application.

Solar cells made of hybrid organic-inorganic perovskite (HOIP) materials have attracted ever-increasing attention due to their high efficiency and easy fabrication. However, issues regarding their poor stability remain a challenge for practical applications. Engineering the composition and structure of HOIP can effectively enhance the thermal stability and improve the power conversion efficiency (PCE). In this work, mixed two-dimensional (2D) HOIPs are systematically investigated for solar-power harvesting using first-principles calculations. We find that their electronic properties depend strongly on the mixed atoms (Cs, Rb, Ge and Pb) and the formation energy is related to the HOIP's composition, where the atoms are more easily mixed in SnI-2D-HOIPs due to low formation energy at the same composition ratio. We further show that optimal solar energy harvesting can be achieved on the solar cells composed of mixed SnI-2D-HOIPs because of reduced bandgaps, enhanced mobility and improved stability. Importantly, we find that the mixed atoms (Cs, Rb, Ge and Pb) with the appropriate composition ratios can effectively enhance the solar-to-power efficiency and show greatly improved resistance to moisture. The findings demonstrate that mixed 2D-HOIPs can replace the bulk HOIPs or pure 2D-HOIPs for applications into solar cells with high efficiency and stability.

Black-colored ZnO nanowires with enhanced photocatalytic hydrogen evolution.

Black-colored ZnO nanowires have been prepared in a metal-organic chemical vapor deposition system by employing a relatively low growth temperature and oxygen-deficient conditions. X-ray photoelectron spectroscopy reveals the incorporation of carbon into the nanowires. The photocatalytic hydrogen evolution activity of the black-colored ZnO nanowires is over 2.5 times larger than that of the pristine ZnO nanowires under simulated solar illumination conditions, and the enhanced photocatalytic activity can be attributed to the higher absorption of visible light by the black color and better carrier separation at the ZnO/carbon interface.

Transparent ultraviolet photovoltaic cells.

Photovoltaic cells have been fabricated from p-GaN/MgO/n-ZnO structures. The photovoltaic cells are transparent to visible light and can transform ultraviolet irradiation into electrical signals. The efficiency of the photovoltaic cells is 0.025% under simulated AM 1.5 illumination conditions, while it can reach 0.46% under UV illumination. By connecting several such photovoltaic cells in a series, light-emitting devices can be lighting. The photovoltaic cells reported in this Letter may promise the applications in glass of buildings to prevent UV irradiation and produce power for household appliances in the future.

[Optical Properties Investigation of p-Type ZnO Film Based on Doping by Diffusion].

The main purpose of this paper is to investigate the optical properties of p-type ZnO film based on P doping. ZnO film was grown by Atomic layer deposition (ALD) on InP subsrate in this experiment, and phosphorus diffused into ZnO lattice by annealing treatment at different temperature (500, 700 °C). The optical properties of samples were investigated by photoluminescence (PL) spectroscopy, which indicated that the annealing temperature is the important factor influencing the phosphorus diffusion doping. The low-temperature PL spectra of the sample which annealed at 700 °C for 1 h exhibited acceptor related emission peaks located at 3.351, 3.311, 3.246 and 3.177 eV, which were attributed to A °X, FA, DAP and DA-1LO, respectively. The acceptor binding energy is estimated to be about 122 meV, which is agreed with the theoretic values in phosphorus-doped ZnO films. In this paper, through thermal diffusion method to realize the p-type doped ZnO thin films, it solved the main problems which limited the development of ZnO based optoelectronic devices, and has an important significance for the development of the ZnO semiconductor materials and ZnO based photoelectric device.