2D Graphene Oxide Films Expand Functionality of Photonic Chips.

On-chip integration of two-dimensional (2D) materials with unique structures and properties endow integrated devices with new functionalities and improved performance. With high flexibility in ways to modify its properties and compatibility with integrated platforms, graphene oxide (GO) is an exceptionally attractive 2D material for hybrid integrated photonic chips. Here, we demonstrate novel functionalities beyond the capability of photonic integrated circuits, by harnessing unique property changes induced by photo-thermal effects in 2D GO films. These include all-optical control and tuning, optical power limiting, and non-reciprocal light transmission. The 2D layered GO films are integrated onto photonic chips with precise control of their thickness and size. Benefitting from the broadband optical response of 2D GO films, all three functionalities feature a very wide operational optical bandwidth. By fitting the experimental results with theory, we analyze the changes in GO film properties induced by the photo-thermal effects, revealing interesting insights about the physics of 2D GO films. These results highlight the versatility of 2D GO films in implementing new functions for integrated photonic devices for a wide range of applications. This article is protected by copyright. All rights reserved.

Regulating Surface Defects to Achieve More Positive Light Soaking Effect in Perovskite Solar Cells.

The dynamic defect tolerance under light soaking is a crucial aspect of halide perovskites. However, the underlying physics of light soaking remains elusive and is subject to debate, exhibiting both positive and negative effects. In this investigation, we demonstrated that surface defects in perovskite films significantly impact the performance and stability of perovskite solar cells, closely correlated with light soaking behaviors. Removing the top surface layer through adhesive tape, the surface defect density noticeably decreases, leading to enhanced photoluminescence (PL) efficiency, prolonged carrier lifetime, and higher conductivity. Consequently, the power conversion efficiency (PCE) of solar cells improves from 17.70% to 20.5%. Furthermore, we confirmed a positive correlation between surface defects and the light soaking effect. Perovskite films with low surface defects surprisingly exhibit a 3-fold increase in PL intensity and an 85% increase in carrier lifetime under 500 s of continuous illumination at an intensity of 100 mW/cm2. Beyond the conventional strategy of suppressing defect trapping, we propose increasing the capability of dynamic defect tolerance as an effective strategy to enhance the optoelectronic properties and performance of perovskite solar cells.

Can thick metal-halide perovskite single crystals have narrower optical bandgaps with near-infrared absorption?

Metal-halide perovskite (MHP) single crystals are emerging as potential competitors to their polycrystalline thin-film counterparts. These materials have shown the specific feature of extended absorbance towards the near-infrared (NIR) region, which promises further extension of their applications in the field of photovoltaics and photodetectors. This notable expansion of absorbance has been explained by the narrower effective optical bandgap of MHP single crystals promoted by their large thickness over several micrometres to millimetres. Herein, the attributes of the material's thickness and the measurement technique used to estimate these characteristics are discussed to elucidate the actual origins of the extended absorbance of MHP single crystals. Contrary to the general belief of the narrower bandgap of the MHP single crystals, we demonstrate that the extended NIR absorption in the MHP single crystals mainly originates from the combination of unique below-bandgap absorption of MHPs, the thickness of single crystals, and the technical limitation of the spectrophotometer, with the key attributes of (i) significantly large thickness of the MHP single crystals by suppressing the transmitted light and (ii) the detector's limited dynamic range. Combining the theoretical and experimental characterizations, we clarify the significant role of the large thickness together with the limited sensitivity of the detector in promoting the well-known red shift of the absorption onset of the MHP single crystals. The observations evidently show that in some special circumstances, the acquired absorption spectrum cannot reliably represent the optical bandgap of MHP materials. This highlights some misinterpretations in the estimation of the narrower optical bandgap of the MHP single crystals from conventional optical methods, while the optical bandgap is an inherent property independent of the thickness. The proposed broad applications of the MHP single crystals are dictated by their fascinating properties, and therefore, a deep insight into these features should be considered besides device applications, because much of their property-function relationships are still ambiguous and a subject of debate.

Synergy of Dendrites-Impeded Atomic Clusters Dissociation and Side Reactions Suppressed Inert Interface Protection for Ultrastable Zn Anode.

The sluggish ions-transfer and inhomogeneous ions-nucleation induce the formation of randomly oriented dendrites on Zn anode, while the chemical instability at anode-electrolyte interface triggers detrimental side reactions. Herein, this report in situ designs a multifunctional hybrid interphase of Bi/Bi2O3, for the first time resulting in a novel synergistic regulation mechanism involving: (i) chemically inert interface protection mechanism suppresses side reactions; and more fantastically, (ii) innovative thermodynamically favorable Zn atomic clusters dissociation mechanism impedes dendrites formation. Assisted by collaborative modulation behavior, the Zn@Bi/Bi2O3 symmetry cell delivers an ultrahigh cumulative plating capacity of 1.88 Ah cm-2 at 5 mA cm-2 and ultralong lifetimes of 300 h even at high current density and depth of discharge (10 mA cm-2, DODZn: 60%). Furthermore, under a low electrolyte-to-capacity ratio (E/C: 45 µL mAh-1) and negative-to-positive capacity ratio (N/P: 6.3), Zn@Bi/Bi2O3||MnO2 full-cell exhibits a superior capacity retention of 86.7% after 500 cycles at 1 A g-1, which outperforms most existing interphases. The scaled-up Zn@Bi/Bi2O3||MnO2 battery module (6 V, 1 Ah), combined with the photovoltaic panel, presents excellent renewable-energy storage ability and long output lifetime (12 h). This work provides a fantastic synergistic mechanism to achieve the ultrastable Zn anode and can be greatly promised to apply it into other metal-based batteries.

Leaping Supercapacitor Performance via a Flash-Enabled Graphene Photothermal Coating.

Elevating the working temperature delivers a simple and universal approach to enhance the energy storage performances of supercapacitors owing to the fundamental improvements in ion transportation kinetics. Among all heating methods, introducing green and sustainable photothermal heating on supercapacitors (SCs) is highly desired yet remains an open challenge, especially for developing an efficient and universal photothermal heating strategy that can be generally applied to arbitrary SC devices. Flash-enabled graphene (FG) absorbers are produced through a simple and facile flash reduction process, which can be coated on the surface of any SC devices to lift their working temperature via a photothermal effect, thus, improving their overall performance, including both power and energy densities. With the systematic temperature-dependent investigation and the in-depth numerical simulation of SC performances, an evident enhancement in capacitance up to 65% can be achieved in photothermally enhanced SC coin cell devices with FG photo-absorbers. This simple, practical, and universal enhancement strategy provides a novel insight into boosting SC performances without bringing complexity in electrode fabrication/optimization. Also, it sheds light on the highly efficient utilization of green and renewable photothermal energies for broad application scenarios, especially for energy storage devices.

Monolithic 2D Perovskites Enabled Artificial Photonic Synapses for Neuromorphic Vision Sensors.

Neuromorphic visual sensors (NVS) based on photonic synapses hold a significant promise to emulate the human visual system. However, current photonic synapses rely on exquisite engineering of the complex heterogeneous interface to realize learning and memory functions, resulting in high fabrication cost, reduced reliability, high energy consumption and uncompact architecture, severely limiting the up-scaled manufacture, and on-chip integration. Here a photo-memory fundamental based on ion-exciton coupling is innovated to simplify synaptic structure and minimize energy consumption. Due to the intrinsic organic/inorganic interface within the crystal, the photodetector based on monolithic 2D perovskite exhibits a persistent photocurrent lasting about 90 s, enabling versatile synaptic functions. The electrical power consumption per synaptic event is estimated to be≈1.45 × 10-16 J, one order of magnitude lower than that in a natural biological system. Proof-of-concept image preprocessing using the neuromorphic vision sensors enabled by photonic synapse demonstrates 4 times enhancement of classification accuracy. Furthermore, getting rid of the artificial neural network, an expectation-based thresholding model is put forward to mimic the human visual system for facial recognition. This conceptual device unveils a new mechanism to simplify synaptic structure, promising the transformation of the NVS and fostering the emergence of next generation neural networks.

Enhancing Green Ammonia Electrosynthesis Through Tuning Sn Vacancies in Sn-Based MXene/MAX Hybrids.

Renewable energy driven N2 electroreduction with air as nitrogen source holds great promise for realizing scalable green ammonia production. However, relevant out-lab research is still in its infancy. Herein, a novel Sn-based MXene/MAX hybrid with abundant Sn vacancies, Sn@Ti2CTX/Ti2SnC-V, was synthesized by controlled etching Sn@Ti2SnC MAX phase and demonstrated as an efficient electrocatalyst for electrocatalytic N2 reduction. Due to the synergistic effect of MXene/MAX heterostructure, the existence of Sn vacancies and the highly dispersed Sn active sites, the obtained Sn@Ti2CTX/Ti2SnC-V exhibits an optimal NH3 yield of 28.4 µg h-1 mgcat-1 with an excellent FE of 15.57% at - 0.4 V versus reversible hydrogen electrode in 0.1 M Na2SO4, as well as an ultra-long durability. Noticeably, this catalyst represents a satisfactory NH3 yield rate of 10.53 µg h-1 mg-1 in the home-made simulation device, where commercial electrochemical photovoltaic cell was employed as power source, air and ultrapure water as feed stock. The as-proposed strategy represents great potential toward ammonia production in terms of financial cost according to the systematic technical economic analysis. This work is of significance for large-scale green ammonia production.

Carbonized polymer dots derived from metformin and L-arginine for tumor cell membrane- and mitochondria-dual targeting therapy.

Metformin has demonstrated antitumor potential in clinical studies; however, achieving optimal antitumor effects requires administering an extremely safe medication dose. To enhance the efficacy and reduce dosage requirements, we propose the creation of large-molecule drugs through the combination of small-molecule drugs. In this study, we developed novel polymer dots, referred to as MA-dots, with sizes of approximately 5 nm, featuring dual targeting capabilities for tumor cell membranes and mitochondria. MA-dots were synthesized using metformin and L-arginine via a rapid microwave-assisted method. Notably, the resulting MA-dots (with a half maximal inhibitory concentration (IC50) of 93.60 µg mL-1) exhibited more than a 12-fold increase in antitumor activity compared to the raw metformin material (IC50 = 1159.00 µg mL-1) over a 24-hour period. In addition, our MA-dots outperformed most metformin-derived nanodrugs in terms of antitumor efficacy. Furthermore, oral gavage treatment with MA-dots led to the suppression of A549 (lung cancer cell lines) tumor growth in vivo. Mechanistic investigations revealed that MA-dots bound to the large neutral amino acid transporter 1 (LAT1) proteins, which are overexpressed in malignant tumor cell membranes. Moreover, these MA-dots accumulated within the mitochondria, leading to increased production of reactive oxygen species (ROS), mitochondrial damage, and disruption of energy metabolism by modulating the 5'-adenosine monophosphate-activated protein kinase (AMPK)/mammalian target of rapamycin (mTOR) pathway in tumor cells. This cascade of events triggers cell-cycle arrest and apoptosis. In summary, this study presented a rapid method for fabricating a novel nanoderivative, MA-dots, capable of both tumor targeting and exerting tumor-suppressive effects.

Effective Suppressing Phase Segregation of Mixed-Halide Perovskite by Glassy Metal-Organic Frameworks.

Lead mixed-halide perovskites offer tunable bandgaps for optoelectronic applications, but illumination-induced phase segregation can quickly lead to changes in their crystal structure, bandgaps, and optoelectronic properties, especially for the Br-I mixed system because CsPbI3 tends to form a non-perovskite phase under ambient conditions. These behaviors can impact their performance in practical applications. By embedding such mixed-halide perovskites in a glassy metal-organic framework, a family of stable nanocomposites with tunable emission is created. Combining cathodoluminescence with elemental mapping under a transmission electron microscope, this research identifies a direct relationship between the halide composition and emission energy at the nanoscale. The composite effectively inhibits halide ion migration, and consequently, phase segregation even under high-energy illumination. The detailed mechanism, studied using a combination of spectroscopic characterizations and theoretical modeling, shows that the interfacial binding, instead of the nanoconfinement effect, is the main contributor to the inhibition of phase segregation. These findings pave the way to suppress the phase segregation in mixed-halide perovskites toward stable and high-performance optoelectronics.

Fabrication and Characterization of 2D Layered Perovskites with a Gradient Band Gap.

Vertical gradient band-gap heterostructures of two-dimensional (2D) layered perovskites have attracted considerable research interest due to their superior optoelectronic properties and demonstrated potential for use in optical devices. However, its fabrication has been challenging. In this investigation, 2D Ruddlesden-Popper mixed halide perovskite single crystals with a vertical gradient band gap were synthesized by using a solid-state halide diffusion process. X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements after diffusion confirm that the crystalline and morphology remain intact. The transmittance and photoluminescence (PL) spectra show the formation of a vertical gradient band gap that is ascribed to gradient halide distribution through halide intermixing. The mixed halide crystal exhibits high stability with completely suppressed phase segregation in the time-dependent PL measurement. The time-resolved photoluminescence (TRPL) spectra prove that the mixed halide sample has an enhanced carrier transport due to the Förster resonance energy transfer (FRET) effect. Besides, the halide diffusion behavior is found to be different from the previously proposed "layer-by-layer" diffusion model in exfoliated crystals. The gradient band-gap structure is critical for various applications in which vertical carrier transport is demanded.

Metal-Free 2D/2D van der Waals Heterojunction Based on Covalent Organic Frameworks for Highly Efficient Solar Energy Catalysis.

Covalent organic frameworks (COFs) have emerged as a kind of rising star materials in photocatalysis. However, their photocatalytic activities are restricted by the high photogenerated electron-hole pairs recombination rate. Herein, a novel metal-free 2D/2D van der Waals heterojunction, composed of a two-dimensional (2D) COF with ketoenamine linkage (TpPa-1-COF) and 2D defective hexagonal boron nitride (h-BN), is successfully constructed through in situ solvothermal method. Benefitting from the presence of VDW heterojunction, larger contact area and intimate electronic coupling can be formed between the interface of TpPa-1-COF and defective h-BN, which make contributions to promoting charge carriers separation. The introduced defects can also endow the h-BN with porous structure, thus providing more reactive sites. Moreover, the TpPa-1-COF will undergo a structural transformation after being integrated with defective h-BN, which can enlarge the gap between the conduction band position of the h-BN and TpPa-1-COF, and suppress electron backflow, corroborated by experimental and density functional theory calculations results. Accordingly, the resulting porous h-BN/TpPa-1-COF metal-free VDW heterojunction displays outstanding solar energy catalytic activity for water splitting without co-catalysts, and the H2 evolution rate can reach up to 3.15 mmol g-1 h-1, which is about 67 times greater than that of pristine TpPa-1-COF, also surpassing that of state-of-the-art metal-free-based photocatalysts reported to date. In particular, it is the first work for constructing COFs-based heterojunctions with the help of h-BN, which may provide new avenue for designing highly efficient metal-free-based photocatalysts for H2 evolution.

2†µm cylindrical vector beam generation from a c-cut Tm:CaYAlO4 crystal resonator.

Different from the traditional ideal column symmetry cavities, we directly generated the cylindrical vector pulsed beams in the folded six-mirror cavity by employing a c-cut Tm:CaYAlO4 (Tm:CYA) crystal and SESAM. By adjusting the distance between the curved cavity mirror (M4) and the SESAM, both the radially polarized beam and azimuthally polarized beam are generated around 1962 nm and the two vectorial modes can be freely switched in the resonator. Further increased the pump power to 7 W, the stable radially polarized Q-switched mode-locked (QML) cylindrical vector beams were also obtained with an output power of 55 mW, the sub-pulse repetition rate of 120.42 MHz, pulse duration of ∼0.5 ns and the beam quality factor M2 of ∼2.9. To our knowledge, this is the first report of radially and azimuthally polarized beams in the 2 µm wavelength solid-state resonator.

Graphene oxide for photonics, electronics and optoelectronics.

Graphene oxide (GO) was initially developed to emulate graphene, but it was soon recognized as a functional material in its own right, addressing an application space that is not accessible to graphene and other carbon materials. Over the past decade, research on GO has made tremendous advances in material synthesis and property tailoring. These, in turn, have led to rapid progress in GO-based photonics, electronics and optoelectronics, paving the way for technological breakthroughs with exceptional performance. In this Review, we provide an overview of the optical, electrical and optoelectronic properties of GO and reduced GO on the basis of their chemical structures and fabrication approaches, together with their applications in key technologies such as solar energy harvesting, energy storage, medical diagnosis, image display and optical communications. We also discuss the challenges of this field, together with exciting opportunities for future technological advances.

Third-Order Optical Nonlinearities of 2D Materials at Telecommunications Wavelengths.

All-optical signal processing based on nonlinear optical devices is promising for ultrafast information processing in optical communication systems. Recent advances in two-dimensional (2D) layered materials with unique structures and distinctive properties have opened up new avenues for nonlinear optics and the fabrication of related devices with high performance. This paper reviews the recent advances in research on third-order optical nonlinearities of 2D materials, focusing on all-optical processing applications in the optical telecommunications band near 1550 nm. First, we provide an overview of the material properties of different 2D materials. Next, we review different methods for characterizing the third-order optical nonlinearities of 2D materials, including the Z-scan technique, third-harmonic generation (THG) measurement, and hybrid device characterization, together with a summary of the measured n2 values in the telecommunications band. Finally, the current challenges and future perspectives are discussed.

Design of a dynamic multi-topological charge graphene orbital angular momentum metalens.

Traditional OAM generation devices are bulky and can generally only create OAM with one specific topological charge. Although metasurface-based devices have overcome the volume limitations, no tunable metasurface-based OAM generators have been demonstrated to date. Here, a dynamically tunable multi-topological charge OAM generator based on an ultrathin integrable graphene metalens is demonstrated by simulation using the detour phase technique and spatial multiplexing. Different topological charges can be designed on different focal planes. Stretching the OAM graphene metalens allows the focal plane and the topological values to be changed dynamically. This design method paves an innovative route toward miniaturization and integrating OAM beam-type photonic devices for practical applications.

Microwave Synthesis of Pt Clusters on Black TiO2 with Abundant Oxygen Vacancies for Efficient Acidic Electrocatalytic Hydrogen Evolution.

Oxygen vacancies-enriched black TiO2 is one promising support for enhancing hydrogen evolution reaction (HER). Herein, oxygen vacancies enriched black TiO2 supported sub-nanometer Pt clusters (Pt/TiO2 -OV ) with metal support interactions is designed through solvent-free microwave and following low-temperature electroless approach for the first time. High-temperature and strong reductants are not required and then can avoid the aggregation of decorated Pt species. Experimental and theoretical calculation verify that the created oxygen vacancies and Pt clusters exhibit synergistic effects for optimizing the reaction kinetics. Based on it, Pt/TiO2 -OV presents remarkable electrocatalytic performance with 18 mV to achieve 10 mA cm-2 coupled with small Tafel slope of 12 mV dec-1 . This work provides quick synthetic strategy for preparing black titanium dioxide based nanomaterials.

Graphene Metamaterial 3D Conformal Coating for Enhanced Light Harvesting.

Silicon (Si) photovoltaic devices present possible avenues for overcoming global energy and environmental challenges. The high reflection and surface recombination losses caused by the Si interface and its nanofabrication process are the main hurdles for pursuing a high energy conversion efficiency. However, recent advances have demonstrated great success in improving device performance via proper Si interface modification with the optical and electrical features of two-dimensional (2D) materials. Firmly integrating large-area 2D materials with 3D Si nanostructures with no gap in between, which is essential for optimizing device performance, has rarely been achieved by any technique due to the complex 3D morphology of the nanostructures. Here we propose the concept of a 3D conformal coating of graphene metamaterials, in which the 2D graphene layers perfectly adapt to the 3D Si curvatures, leading to a universal 20% optical reflection decrease and a 60% surface passivation improvement. In a further application of this metamaterial 3D conformal coating methodology to standard Si solar cells, an overall 23% enhancement of the solar energy conversion efficiency is achieved. The 3D conformal coating strategy could be readily extended to various optoelectronic and semiconductor device systems with peculiar performance, offering a pathway for highly efficient energy-harvesting and storage solutions.

Metallic-Bonded Pt-Co for Atomically Dispersed Pt in the Co4N Matrix as an Efficient Electrocatalyst for Hydrogen Generation.

Exploiting highly efficient electrocatalysts toward hydrogen evolution reaction (HER) has a significant role in the mass production of hydrogen energy through water electrolysis. Herein, ginkgo leaf-like Co4N coupled with trace Pt with metallic bond Pt-Co on nickel foam via solvothermal, tannic acid treated, and nitridation procedures for HER (T-Pt-Co4N) is developed. It only requires low overpotentials of 31 mV and 27 mV to achieve 10 mA cm-2 in alkaline and neutral electrolytes, respectively, surpassing the benchmark Pt/C and previously reported values. Moreover, it presents excellent long-term stability in the studied media and also can drive overall water splitting under the assistance of sustainable energies. The specific nanostructure favors the acceleration of the electrocatalytic process by exposing abundant active sites and providing numerous mass transport channels during the catalytic process. Moreover, experimental and theoretical calculation demonstrate that the atomic Pt coordinates with Co to form metallic bond Pt-Co also act as crucial role to boost the electrocatalytic performance by optimizing the reaction kinetics for HER.

Tunable Multicolor Fluorescence of Perovskite-Based Composites for Optical Steganography and Light-Emitting Devices.

Multicolor fluorescence of mixed halide perovskites enormously enables their applications in photonics and optoelectronics. However, it remains an arduous task to obtain multicolor emissions from perovskites containing single halogen to avoid phase segregation. Herein, a fluorescent composite containing Eu-based metal-organic frameworks (MOFs), 0D Cs4PbBr6, and 3D CsPbBr3 is synthesized. Under excitations at 365 nm and 254 nm, the pristine composite emits blue (B) and red (R) fluorescence, which are ascribed to radiative defects within Cs4PbBr6 and 5D0→7FJ transitions of Eu3+, respectively. Interestingly, after light soaking in the ambient environment, the blue fluorescence gradually converts into green (G) emission due to the defect repairing and 0D-3D phase conversion. This permanent and unique photochromic effect enables anticounterfeiting and microsteganography with increased security through a micropatterning technique. Moreover, the RGB luminescence is highly stable after encapsulation by a transparent polymer layer. Thus, trichromatic light-emitting modules are fabricated by using the fluorescent composites as color-converting layers, which almost fully cover the standard color gamut. Therefore, this work innovates a strategy for construction of tunable multicolor luminescence by manipulating the radiative defects and structural dimensionality.

Photo-Thermal Tuning of Graphene Oxide Coated Integrated Optical Waveguides.

We experimentally investigate power-sensitive photo-thermal tuning (PTT) of two-dimensional (2D) graphene oxide (GO) films coated on integrated optical waveguides. We measure the light power thresholds for reversible and permanent GO reduction in silicon nitride (SiN) waveguides integrated with one and two layers of GO. For the device with one layer of GO, the power threshold for reversible and permanent GO reduction are ~20 and ~22 dBm, respectively. For the device with two layers of GO, the corresponding results are ~13 and ~18 dBm, respectively. Raman spectra at different positions of a hybrid waveguide with permanently reduced GO are characterized, verifying the inhomogeneous GO reduction along the direction of light propagation through the waveguide. The differences between the PTT induced by a continuous-wave laser and a pulsed laser are also compared, confirming that the PTT mainly depend on the average input power. These results reveal interesting features for 2D GO films coated on integrated optical waveguides, which are of fundamental importance for the control and engineering of GO's properties in hybrid integrated photonic devices.