Recent Advances of Spatial Self‐Phase Modulation in 2D Materials and Passive Photonic Device Applications

Optical nonlinearity in 2D materials excited by spatial Gaussian laser beam is a novel and peculiar optical phenomenon, which exhibits many novel and interesting applications in optical nonlinear devices. Passive photonic devices, such as optical switches, optical logical gates, photonic diodes, and optical modulators, are the key compositions in the future all‐optical signal‐processing technologies. Passive photonic devices using 2D materials to achieve the device functionality have attracted widespread concern in the past decade. In this Review, an overview of the spatial self‐phase modulation (SSPM) in 2D materials is summarized, including the operating mechanism, optical parameter measurement, and tuning for 2D materials, and applications in photonic devices. Moreover, some current challenges are also proposed to solve, and some possible applications of SSPM method are predicted for the future. Therefore, it is anticipated that this summary can contribute to the application of 2D material‐based spatial effect in all‐optical signal‐processing technologies.     

2D Layered Graphene Oxide Films Integrated with Micro‐Ring Resonators for Enhanced Nonlinear Optics

Layered 2D graphene oxide (GO) films are integrated with micro‐ring resonators (MRRs) to experimentally demonstrate enhanced nonlinear optics. Both uniformly coated (1?5 layers) and patterned (10?50 layers) GO films are integrated on complementary‐metal‐oxide‐semiconductor (CMOS)‐compatible doped silica MRRs using a large‐area, transfer‐free, layer‐by‐layer GO coating method with precise control of the film thickness. The patterned devices further employ photolithography and lift‐off processes to enable precise control of the film placement and coating length. Four‐wave‐mixing (FWM) measurements for different pump powers and resonant wavelengths show a significant improvement in efficiency of ≈7.6 dB for a uniformly coated device with 1 GO layer and ≈10.3 dB for a patterned device with 50 GO layers. The measurements agree well with theory, with the enhancement in FWM efficiency resulting from the high Kerr nonlinearity and low loss of the GO films combined with the strong light–matter interaction within the MRRs. The dependence of GO's third‐order nonlinearity on layer number and pump power is also extracted from the FWM measurements, revealing interesting physical insights about the evolution of the GO films from 2D monolayers to quasi bulk‐like behavior. These results confirm the high nonlinear optical performance of integrated photonic resonators incorporated with 2D layered GO films.     

Hot‐Electron‐Assisted Femtosecond All‐Optical Modulation in Plasmonics

The optical Kerr nonlinearity of plasmonic metals provides enticing prospects for developing reconfigurable and ultracompact all‐optical modulators. In nanostructured metals, the coherent coupling of light energy to plasmon resonances creates a nonequilibrium electron distribution at an elevated electron temperature that gives rise to significant Kerr optical nonlinearities. Although enhanced nonlinear responses of metals facilitate the realization of efficient modulation devices, the intrinsically slow relaxation dynamics of the photoexcited carriers, primarily governed by electron–phonon interactions, impedes ultrafast all‐optical modulation. Here, femtosecond (≈190 fs) all‐optical modulation in plasmonic systems via the activation of relaxation pathways for hot electrons at the interface of metals and electron acceptor materials, following an on‐resonance excitation of subradiant lattice plasmon modes, is demonstrated. Both the relaxation kinetics and the optical nonlinearity can be actively tuned by leveraging the spectral response of the plasmonic design in the linear regime. The findings offer an opportunity to exploit hot‐electron‐induced nonlinearities for design of self‐contained, ultrafast, and low‐power all‐optical modulators based on plasmonic platforms.     

Highly Efficient Organic Solar Cells Consisting of Double Bulk Heterojunction Layers

An organic solar cell (OSCs) containing double bulk heterojunction (BHJ) layers, namely, double‐BHJ OSCs is constructed via stamp transferring of low bandgap BHJ atop of mediate bandgap active layers. Such devices allow a large gain in photocurrent to be obtained due to enhanced photoharvest, without suffering much from the fill factor drop usually seen in thick‐layer‐based devices. Overall, double‐BHJ OSC with optimal ≈50 nm near‐infrared PDPP3T:PC₇₁BM layer atop of ≈200 nm PTB7‐Th:PC₇₁BM BHJ results in high power conversion efficiencies over 12%.     

Kerr Nonlinearity in 2D Graphdiyne for Passive Photonic Diodes

Graphdiyne is a new carbon allotrope comprising sp‐ and sp²‐hybridized carbon atoms arranged in a 2D layered structure. In this contribution, 2D graphdiyne is demonstrated to exhibit a strong light–matter interaction with high stability to achieve a broadband Kerr nonlinear optical response, which is useful for nonreciprocal light propagation in passive photonic diodes. Furthermore, advantage of the unique Kerr nonlinearity of 2D graphdiyne is taken and a nonreciprocal light propagation device is proposed based on the novel similarity comparison method. Graphdiyne has demonstrated a large nonlinear refractive index in the order of ≈10^?5 cm² W^?1, comparing favorably to that of graphene. Based on the strong Kerr nonlinearity of 2D graphdiyne, a nonlinear photonic diode that breaks time‐reversal symmetry is demonstrated to realize the unidirectional excitation of Kerr nonlinearity, which can be regarded as a significant demonstration of a graphdiyne‐based prototypical application in nonlinear photonics and might suggest an important step toward versatile graphdiyne‐based advanced passive photonics devices in the future.     

Surface Plasmon‐Enhanced Photodetection in Few Layer MoS2 Phototransistors with Au Nanostructure Arrays

2D Molybdenum disulfide (MoS₂) is a promising candidate material for high‐speed and flexible optoelectronic devices, but only with low photoresponsivity. Here, a large enhancement of photocurrent response is obtained by coupling few‐layer MoS₂ with Au plasmonic nanostructure arrays. Au nanoparticles or nanoplates placed onto few‐layer MoS₂ surface can enhance the local optical field in the MoS₂ layer, due to the localized surface plasmon (LSP) resonance. After depositing 4 nm thick Au nanoparticles sparsely onto few‐layer MoS₂ phototransistors, a doubled increase in the photocurrent response is observed. The photocurrent of few‐layer MoS₂ phototransistors exhibits a threefold enhancement with periodic Au nanoarrays. The simulated optical field distribution confirms that light can be trapped and enhanced near the Au nanoplates. These findings offer an avenue for practical applications of high performance MoS₂‐based optoelectronic devices or systems in the future.     

Ultrahigh Responsivity UV Photodetector Based on Cu Nanostructure/ZnO QD Hybrid Architectures

Strong near‐surface electromagnetic field formed by collective oscillation of electrons on Cu nanostructure a shows a strong dependence on geometry, offering a promising approach to boost the light absorption of ZnO photoactive layers with enhanced plasmon scattering. Here, a facile way to fabricate UV photodetectors with tunable configuration of the self‐assembled Cu nanostructures on ZnO thin films is reported. The incident lights are effectively confined in ZnO photoactive layers with the existence of the uplayer Cu nanostructures, and the interdiffusion of Cu atoms during fabrication of the Cu nanostructures can improve the carrier transfer in ZnO thin films. The optical properties of the hybrid architectures are successfully tailored over a control of the geometric evolution of the Cu nanostructures, resulting in significantly enhanced photocurrent and responsivity of 2.26 mA and 234 A W^?1 under a UV light illumination of 0.62 mW cm^?2 at 10 V, respectively. The photodetectors also exhibit excellent reproducibility, stability, and UV–visible rejection ratio (R_{370 nm}/R_{500 nm}) of ≈370, offering an approach of high‐performance UV photodetectors for practical applications.     

Solvent effect on the third order optical nonlinearity and optical limiting ability of betanin natural dye extracted from red beet root

We report on the solvent effect on the third order optical nonlinearity of betanin natural dye extracted from red beet root and their third order nonlinear optical (NLO) properties have been studied using a Q-switched Nd:YAG laser at 532 nm. The third order nonlinearity of these samples are dominated by nonlinear absorption, which leads to strong optical limiting and their strength is influenced by the solvent used, suggesting that betanin natural dyes are promising candidate for the development of photonic nonlinear optic devices.     

Water‐Dispersible,Multifunctional, Magnetic,Luminescent Silica‐Encapsulated Composite Nanotubes

A multifunctional one‐dimensional nanostructure incorporating both CdSe quantum dots (QDs) and Fe₃O₄ nanoparticles (NPs) within a SiO₂‐nanotube matrix is successfully synthesized based on the self‐assembly of preformed functional NPs, allowing for control over the size and amount of NPs contained within the composite nanostructures. This specific nanostructure is distinctive because both the favorable photoluminescent and magnetic properties of QD and NP building blocks are incorporated and retained within the final silica‐based composite, thus rendering it susceptible to both magnetic guidance and optical tracking. Moreover, the resulting hydrophilic nanocomposites are found to easily enter into the interiors of HeLa cells without damage, thereby highlighting their capability not only as fluorescent probes but also as possible drug‐delivery vehicles of interest in nanobiotechnology.     

Retina-Inspired Carbon Nitride-Based Photonic Synapses for Selective Detection of UV Light

Photonic synapses combine sensing and processing in a single device, so they are promising candidates to emulate visual perception of a biological retina. However, photonic synapses with wavelength selectivity, which is a key property for visual perception, have not been developed so far. Herein, organic photonic synapses that selectively detect UV rays and process various optical stimuli are presented. The photonic synapses use carbon nitride (C₃N₄) as an UV-responsive floating-gate layer in transistor geometry. C₃N₄ nanodots dominantly absorb UV light; this trait is the basis of UV selectivity in these photonic synapses. The presented devices consume only 18.06 fJ per synaptic event, which is comparable to the energy consumption of biological synapses. Furthermore, in situ modulation of exposure to UV light is demonstrated by integrating the devices with UV transmittance modulators. These smart systems can be further developed to combine detection and dose-calculation to determine how and when to decrease UV transmittance for preventive health care.     

Photonic Reactions Leading to Fluorescence in a Polymeric System Induced by the Photothermal Effect of Magnetite Nanoparticles Using a 780 nm Multiphoton Laser

Recently, polymer‐coated magnetite (Fe₃O₄) nanoparticles (NPs) are extensively studied for applications in therapeutics or diagnostics using photothermal effect. Therefore, it is essential to understand the interactions between Fe₃O₄ NPs and polymers when optical stimuli are applied. Herein, the photonic reactions of Fe₃O₄ NPs and polymer composites upon application of a 780 nm multiphoton laser are analyzed. The photonic reactions produce unique results including fluorescence from conformationally changed polymer and low‐temperature phase transformation of Fe₃O₄ NPs. Typically, π‐conjugated chains are formed, inducing fluorescence through a series of main and side‐chain cleavage reactions of polymers with the aliphatic chain. In addition, fluorescence is detected in the cellular system by photonic reactions between Fe₃O₄ NPs and biomolecules. After multiphoton laser irradiation, light emission is detected near the intracellular Fe₃O₄ NPs, and a stronger intensity is observed in large‐sized NPs.     

Phonon‐Assisted Electro‐Optical Switches and Logic Gates Based on Semiconductor Nanostructures

High‐performance nanostructured electro‐optical switches and logic gates are highly desirable as essential building blocks in integrated photonics. In contrast to silicon‐based optoelectronic devices, with their inherent indirect optical bandgap, weak light‐modulation mechanism, and sophisticated device configuration, direct‐bandgap‐semiconductor nanostructures with attractive electro‐optical properties are promising candidates for the construction of nanoscale optical switches for on‐chip photonic integrations. However, previously reported semiconductor‐nanostructure optical switches suffer from serious drawbacks such as high drive voltage, limited operation spectral range, and low modulation depth. High‐efficiency electro‐optical switches based on single CdS nanobelts with low drive voltage, ultra‐high on/off ratio, and broad operation wavelength range, properties resulting from unique electric‐field‐dependent phonon‐assisted optical transitions, are demonstrated. Furthermore, functional NOT, NOR, and NAND optical logic gates are demonstrated based on these switches. These switches and optical logic gates represent an important step toward integrated photonic circuits.     

A Solution‐Processed Ultrafast Optical Switch Based on a Nanostructured Epsilon‐Near‐Zero Medium

All the optical properties of materials are derived from dielectric function. In spectral region where the dielectric permittivity approaches zero, known as epsilon‐near‐zero (ENZ) region, the propagating light within the material attains a very high phase velocity, and meanwhile the material exhibits strong optical nonlinearity. The interplay between the linear and nonlinear optical response in these materials thus offers unprecedented pathways for all‐optical control and device design. Here the authors demonstrate ultrafast all‐optical modulation based on a typical ENZ material of indium tin oxide (ITO) nanocrystals (NCs), accessed by a wet‐chemistry route. In the ENZ region, the authors find that the optical response in these ITO NCs is associated with a strong nonlinear character, exhibiting sub‐picosecond response time (corresponding to frequencies over 2 THz) and modulation depth up to ≈160%. This large optical nonlinearity benefits from the highly confined geometry in addition to the ENZ enhancement effect of the ITO NCs. Based on these ENZ NCs, the authors successfully demonstrate a fiber optical switch that allows switching of continuous laser wave into femtosecond laser pulses. Combined with facile processibility and tunable optical properties, these solution‐processed ENZ NCs may offer a scalable and printable material solution for dynamic photonic and optoelectronic devices.     

Electro-tunable optical diode based on photonic bandgap liquid-crystal heterojunctions

Manipulation of light is in strong demand in information technologies. Among the wide range of linear and nonlinear optical devices that have been used, growing attention has been paid to photonic crystals that possess a periodic modulation of dielectric function. Among many photonic bandgap (PBG) structures, liquid crystals with periodic structures are very attractive as self-assembled photonic crystals, leading to optical devices such as dye lasers. Here we report a new hetero-PBG structure consisting of an anisotropic nematic layer sandwiched between two cholesteric liquid-crystal layers with different helical pitches. We optically visualized the dispersion relation of this structure, displaying the optical diode performance: that is, the non-reciprocal transmission of circular polarized light at the photonic-bandgap regions. Transmittance spectra with circularly polarized light also reveal the diode performance, which is well simulated in calculations that include an electro-tunable diode effect. Lasing action was also confirmed to show the diode effect with a particular directionality.     

Designed ultrafast optical nonlinearity in a plasmonic nanorod metamaterial enhanced by nonlocality

All-optical signal processing enables modulation and transmission speeds not achievable using electronics alone. However, its practical applications are limited by the inherently weak nonlinear effects that govern photon-photon interactions in conventional materials, particularly at high switching rates. Here, we show that the recently discovered nonlocal optical behaviour of plasmonic nanorod metamaterials enables an enhanced, ultrafast, nonlinear optical response. We observe a large (80%) change of transmission through a subwavelength thick slab of metamaterial subjected to a low control light fluence of 7 mJ cm(-2), with switching frequencies in the terahertz range. We show that both the response time and the nonlinearity can be engineered by appropriate design of the metamaterial nanostructure. The use of nonlocality to enhance the nonlinear optical response of metamaterials, demonstrated here in plasmonic nanorod composites, could lead to ultrafast, low-power all-optical information processing in subwavelength-scale devices.     

Biosynthesis and Characterization of Copper Nanoparticles Using Shewanella oneidensis: Application for Click Chemistry

Copper nanoparticles (Cu‐NPs) have a wide range of applications as heterogeneous catalysts. In this study, a novel green biosynthesis route for producing Cu‐NPs using the metal‐reducing bacterium, Shewanella oneidensis is demonstrated. Thin section transmission electron microscopy shows that the Cu‐NPs are predominantly intracellular and present in a typical size range of 20–40 nm. Serial block‐face scanning electron microscopy demonstrates the Cu‐NPs are well‐dispersed across the 3D structure of the cells. X‐ray absorption near‐edge spectroscopy and extended X‐ray absorption fine‐structure spectroscopy analysis show the nanoparticles are Cu(0), however, atomic resolution images and electron energy loss spectroscopy suggest partial oxidation of the surface layer to Cu₂O upon exposure to air. The catalytic activity of the Cu‐NPs is demonstrated in an archetypal “click chemistry” reaction, generating good yields during azide‐alkyne cycloadditions, most likely catalyzed by the Cu(I) surface layer of the nanoparticles. Furthermore, cytochrome deletion mutants suggest a novel metal reduction system is involved in enzymatic Cu(II) reduction and Cu‐NP synthesis, which is not dependent on the Mtr pathway commonly used to reduce other high oxidation state metals in this bacterium. This work demonstrates a novel, simple, green biosynthesis method for producing efficient copper nanoparticle catalysts.     

Periodical 2D Photonic–Plasmonic Au/TiOx Nanocavity Resonators for Photoelectrochemical Applications

Effective light trapping at the nanoscale is vital for efficient photoelectrochemical (PEC) applications. Photonic and plasmonic resonators are the two most promising approaches for this purpose, and the synergetic combination of these two resonators will tail the propagation lengths of incident light along with field enhancements, and thus presents further enhanced light‐trapping activity. Herein, a new hybrid photonic–plasmonic resonator is proposed through sputtering plasmonic Au nanoparticles (NPs) into the 2D photonic TiO_x nanocavity. Through facile control of the size of Au NPs, the matching of resonant wavelength of plasmonic Au NPs and photonic nanocavities maximize the light‐trapping intensity and thus further improve the PEC performance. Furthermore, for expanding the PEC applications, after functionalization of Au NPs with aptamer as a biomolecular recognition unit, a PEC aptasensor is also proposed and presents the highest sensitivity for antibiotic detection.     

Plasmonic Enhancement in BiVO4 Photonic Crystals for Efficient Water Splitting

Photo‐electrochemical water splitting is a very promising and environmentally friendly route for the conversion of solar energy into hydrogen. However, the solar‐to‐H₂ conversion efficiency is still very low due to rapid bulk recombination of charge carriers. Here, a photonic nano‐architecture is developed to improve charge carrier generation and separation by manipulating and confining light absorption in a visible‐light‐active photoanode constructed from BiVO₄ photonic crystal and plasmonic nanostructures. Synergistic effects of photonic crystal stop bands and plasmonic absorption are observed to operate in this photonic nanostructure. Within the scaffold of an inverse opal photonic crystal, the surface plasmon resonance is significantly enhanced by the photonic Bragg resonance. Nanophotonic photoanodes show AM 1.5 photocurrent densities of 3.1 ± 0.1 mA cm^?2 at 1.23 V versus RHE, which is among the highest for oxide‐based photoanodes and over 4 times higher than the unstructured planar photoanode.     

A Highly Active Star Decahedron Cu Nanocatalyst for Hydrocarbon Production at Low Overpotentials

The electrochemical carbon dioxide reduction reaction (CO₂RR) presents a viable approach to recycle CO₂ gas into low carbon fuels. Thus, the development of highly active catalysts at low overpotential is desired for this reaction. Herein, a high‐yield synthesis of unique star decahedron Cu nanoparticles (SD‐Cu NPs) electrocatalysts, displaying twin boundaries (TBs) and multiple stacking faults, which lead to low overpotentials for methane (CH₄) and high efficiency for ethylene (C₂H₄) production, is reported. Particularly, SD‐Cu NPs show an onset potential for CH₄ production lower by 0.149 V than commercial Cu NPs. More impressively, SD‐Cu NPs demonstrate a faradaic efficiency of 52.43% ± 2.72% for C₂H₄ production at ?0.993 ± 0.0129 V. The results demonstrate that the surface stacking faults and twin defects increase CO binding energy, leading to the enhanced CO₂RR performance on SD‐Cu NPs.     

DNA‐Driven Two‐Layer Core–Satellite Gold Nanostructures for Ultrasensitive MicroRNA Detection in Living Cells

It is a significant challenge to achieve controllable self‐assembly of superstructures for biological applications in living cells. Here, a two‐layer core–satellite assembly is driven by a Y‐DNA, which is designed with three nucleotide chains that hybridized through complementary sequences. The two‐layer core–satellite nanostructure (C₃₀S₅S₁₀ NS) is constructed using 30 nm gold nanoparticles (Au NPs) as the core, 5 nm Au NPs as the first satellite layer, and 10 nm Au NPs as the second satellite layer, resulting in a very strong circular dichroism (CD) and surface‐enhanced Raman scattering. After optimization, the yield is up to 85%, and produces a g‐factor of 0.16 × 10^?2. The hybridization of the target microRNA (miRNA) with the molecular probe causes a significant drop in the CD and Raman signals, and this phenomenon is used to detect the miRNA in living cells. The CD signal has a good linear range of 0.011–20.94 amol ng_RNA^?1 and a limit of detection (LOD) of 0.0051 amol ng_RNA^?1, while Raman signal with the range of 0.052–34.98 amol ng_RNA^?1 and an LOD of 2.81 × 10^?2 amol ng_RNA^?1. This innovative dual‐signal method can be used to quantify biomolecules in living cells, opening the way for ultrasensitive, highly accurate, and reliable diagnoses of clinical diseases.