Plasmonic Metasurfaces for Simultaneous Thermal Infrared Invisibility and Holographic Illusion

In 1860s, Gustav Kirchhoff proposed his famous law of thermal radiation, setting a fundamental contradiction between the infrared reflection and thermal radiation. Here, for the first time an ultrathin plasmonic metasurface is proposed to simultaneously produce ultralow specular reflection and infrared emission across a broad spectrum and wide incident angle range by combining the low emission nature of metal and the photonic spin–orbit interaction in spatially inhomogeneous structures. As a proof‐of‐concept, a phase gradient metasurface composed of sub‐wavelength metal gratings is designed and experimentally characterized in the infrared atmosphere window of 8–14 µm, demonstrating an ultralow specular reflectivity and infrared emissivity below 0.1. Furthermore, it is demonstrated that infrared illusion could be generated by the metasurface, enabling not only invisibility for thermal and laser detection, but also multifunctionalities for potential applications. This technology is also scalable across a wide range of electromagnetic spectrum and provides a feasible alternative for surface coating.     

Simultaneous Control of Light Polarization and Phase Distributions Using Plasmonic Metasurfaces

Harnessing light for modern photonic applications often involves the control and manipulation of light polarization and phase. Traditional methods require a combination of multiple discrete optical components, each of which contributes to a specific functionality. Here, plasmonic metasurfaces are proposed that accomplish the simultaneous manipulation of polarization and phase of the transmitted light. Arbitrary spatial field distribution of the optical phase and polarization direction can be obtained. The multifunctional metasurfaces are validated by demonstrating a broadband near‐perfect anomalous refraction with controllable linear polarization through introducing a constant phase gradient along the interface. Furthermore, the power of the proposed metasurfaces is demonstrated by generating a radially polarized beam. The new degrees of freedom of metasurfaces facilitate arbitrary manipulation of light and will profoundly affect a wide range of photonic applications.     

Broadband Enhanced Chirality with Tunable Response in Hybrid Plasmonic Helical Metamaterials

Designing broadband enhanced chirality is of strong interest to the emerging fields of chiral chemistry and sensing, or to control the spin orbital momentum of photons in recently introduced nanophotonic chiral quantum and classical optical applications. However, chiral light-matter interactions have an extremely weak nature, are difficult to control and enhance, and cannot be made tunable or broadband. In addition, planar ultrathin nanophotonic structures to achieve strong, broadband, and tunable chirality at the technologically important visible to ultraviolet spectrum still remain elusive. Here, these important problems are tackled by experimentally demonstrating and theoretically verifying spectrally tunable, extremely large, and broadband chiroptical response by nanohelical metamaterials. The reported new designs of all-dielectric and dielectric-metallic (hybrid) plasmonic metamaterials permit the largest and broadest ever measured chiral Kuhn's dissymmetry factor achieved by a large-scale nanophotonic structure. In addition, the strong circular dichroism of the presented bottom-up fabricated optical metamaterials can be tuned by varying their dimensions and proportions between their dielectric and plasmonic helical subsections. The currently demonstrated ultrathin optical metamaterials are expected to provide a substantial boost to the developing field of chiroptics leading to significantly enhanced and broadband chiral light-matter interactions at the nanoscale.     

Tunable Metasurfaces Based on Active Materials

Metasurfaces, planer artificial materials composed of subwavelength unit cells, have shown superior abilities to manipulate the wavefronts of electromagnetic waves. In the last few years, metasurfaces have been a burgeoning field of research, with a large variety of functional devices, including planar lenses, beam deflectors, polarization converters, and metaholograms, being demonstrated. Up to date, the majority of metasurfaces cannot be tuned postfabrication. Yet, the dynamic control of optical properties of metasurfaces is highly desirable for a plethora of applications including free space optical communications, holographic displays, and depth sensing. Recently, much effort has been made to exploit active materials, whose optical properties can be controlled under external stimuli, for the dynamic control of metasurfaces. The tunability enabled by active materials can be attributed to various mechanisms, including but not limited to thermo‐optic effects, free‐carrier effects, and phase transitions. This short review summarizes the recent progress on tunable metasurfaces based on various approaches and analyzes their respective advantages and challenges to be confronted with. A number of potential future directions are also discussed at the end.     

Optical Properties of Hybrid Organic‐Inorganic Materials and their Applications

Research on hybrid inorganic‐organic materials has experienced an explosive growth since the 1980s, with the expansion of soft inorganic chemistry based processes. Indeed, mild synthetic conditions, low processing temperatures provided by “chimie douce” and the versatility of the colloidal state allow for the mixing of the organic and inorganic components at the nanometer scale in virtually any ratio to produce the so called hybrid materials. Today a high degree of control over both composition and nanostructure of these hybrids can be achieved allowing tunable structure‐property relationships. This, in turn, makes it possible to tailor and fine‐tune many properties (mechanical, optical, electronic, thermal, chemical…) in very broad ranges, and to design specific multifunctional systems for applications. In particular, the field of “Hybrid‐Optics” has been very productive not only scientifically but also in terms of applications. Indeed, numerous optical devices based on hybrids are already in, or very close, to the market. This review describes most of the recent advances performed in this field. Emphasis will be given to luminescent, photochromic, NLO and plasmonic properties. As an outlook we show that the controlled coupling between plasmonics and luminescence is opening a land of opportunities in the field of “Hybrid‐Optics”.     

Multistate Tuning of Third Harmonic Generation in Fano-Resonant Hybrid Dielectric Metasurfaces

Hybrid dielectric metasurfaces have emerged as a promising approach to enhancing near field confinement and thus high optical nonlinearity by utilizing low loss dielectric rather than relatively high loss metallic resonators. A wider range of applications can be realized if more design dimensions can be provided from material and fabrication perspectives to allow dynamic control of light. Here, tunable third harmonic generation (THG) via hybrid metasurfaces with phase change material Ge₂Sb₂Te₅ (GST) deposited on top of amorphous silicon metasurfaces is demonstrated. Fano resonance is excited to confine the incident light inside the hybrid metasurfaces, and an experimental quality factor (Q-factor ≈ 125) is achieved at the fundamental pump wavelength around 1210 nm. Not only the switching between a turn-on state of Fano resonance in the amorphous state of GST and a turn-off state in its crystalline state are demonstrated, but also gradual multistate tuning of THG emission at its intermediate states. A high THG conversion efficiency of η = 2.9 × 10⁻⁶% is achieved, which is 32 times more than that of a GST-based Fabry–Pèrot cavity under a similar pump laser power. Experimental results show the potential of exploring GST-based hybrid dielectric metasurfaces for tunable nonlinear optical devices.     

Enhanced Fluorescence Microscopic Imaging by Plasmonic Nanostructures: From a 1D Grating to a 2D Nanohole Array

A two‐dimensional (2D) plasmonic coupling nanostructure for enhanced fluorescence observation using a microscope is presented. The substrate contained periodically assembled nanohole arrays with a pitch of 400 nm and a depth of 25 nm. In comparison with one‐dimensional (1D) gratings, this new substrate presented an excellent surface plasmon coupling ability to illuminate light from all directions. Under an optical microscope, an enhancement in the fluorescence intensity of up to 100 times compared with a plain glass slide was observed. The ability to markedly increase the fluorescence intensity means this technique has great potential for application in biodiagnostics, imaging, sensing, and photovoltaic cells.     

3D Aluminum Hybrid Plasmonic Nanostructures with Large Areas of Dense Hot Spots and Long‐Term Stability

Plasmonic materials possessing dense hot spots with high field enhancement over a large area are highly desirable for ultrasensitive biochemical sensing and efficient solar energy conversion; particularly those based on low‐cost noncoinage metals with high natural abundance are of considerable practical significance. Here, 3D aluminum hybrid nanostructures (3D‐Al‐HNSs) with high density of plasmonic hot spots across a large scale are fabricated via a highly efficient and scalable nonlithographic method, i.e., millisecond‐laser‐direct‐writing in liquid nitrogen. The nanosized alumina interlayer induces intense and dual plasmonic resonance couplings between adjacent Al nanoparticles with bimodal size distribution within each of the hybrid assemblies, leading to remarkably elevated localized electric fields (or hot spots) accessible to the analytes or reactants. The 3D‐stacked nanostructure substantially raises the hot spot density, giving rise to plasmon‐enhanced light harvesting from deep UV to the visible, strong enhancement of Raman signals, and a very low limit of detection outperforming reported Al nanostructures, and even comparable to the noble metals. Combined with the long‐term stability and good reproducibility, the 3D‐Al‐HNSs hold promise as a robust low‐cost plasmonic material for applications in plasmon‐enhanced spectroscopic sensing and light harvesting.     

Rational Assembly of Optoplasmonic Hetero‐nanoparticle Arrays with Tunable Photonic–Plasmonic Resonances

Metallic and dielectric nanoparticles (NPs) have synergistic electromagnetic properties but their positioning into morphologically defined hybrid arrays with novel optical properties still poses significant challenges. A template‐guided self‐assembly strategy is introduced for the positioning of metallic and dielectric NPs at pre‐defined lattice sites. The chemical assembly approach facilitates the fabrication of clusters of metallic NPs with interparticle separations of only a few nanometers in a landscape of dielectric NPs positioned hundreds of nanometers apart. This approach is used to generate two‐dimensional interdigitated arrays of 250 nm diameter TiO₂ NPs and clusters of electromagnetically strongly coupled 60 nm Au NPs. The morphology‐dependent near‐ and far‐field responses of the resulting multiscale optoplasmonic arrays are analyzed in detail. Elastic and inelastic scattering spectroscopy in combination with electromagnetic simulations reveal that optoplasmonic arrays sustain delocalized photonic–plasmonic modes that achieve a cascaded E‐field enhancement in the gap junctions of the Au NP clusters and simultaneously increase the E‐field intensity throughout the entire array.     

Stacking of 2D Materials

2D layered materials have sparked great interest from the perspective of basic physics and applied science in the past few years. Extraordinarily, many novel stacked structures that bring versatile properties and applications can be artificially assembled, as exemplified by vertical van der Waals (vdW) heterostructures, twisted multilayer 2D materials, hybrid dimensional structures, etc. Compared with the ordinary synthesis process, the stacking technique is a powerful strategy to achieve high-quality and freely controlled 2D material stacked structures with atomic accuracy. This review highlights the most advanced stacking techniques involving the preparation, transfer, and stacking of high-quality single crystal 2D materials. Apart from the 2D–2D stacked structures, 2D–0D, 2D–1D, and 2D–3D structures offer a prospective platform for the increasing application of 2D materials. The assembly strategy and physical properties of these stacked structures strongly depend on the factors in the stacking process, including the surface quality, angle control, and sample size. In addition, comparative analysis tables on the techniques involved are also available. The summary of these strategies and techniques will hopefully provide a valuable reference for relevant work.     

2D Organic–Inorganic Hybrid Thin Films for Flexible UV–Visible Photodetectors

Flexible 2D inorganic MoS₂ and organic g‐C₃N₄ hybrid thin film photodetectors with tunable composition and photodetection properties are developed using simple solution processing. The hybrid films fabricated on paper substrate show broadband photodetection suitable for both UV and visible light with good responsivity, detectivity, and reliable and rapid photoswitching characteristics comparable to monolayer devices. This excellent performance is retained even after the films are severely deformed at a bending radius of ≈2 mm for hundreds of cycles. The detailed charge transfer and separation processes at the interface between the 2D materials in the hybrid films are confirmed by femtosecond transient absorption spectroscopy with broadband capability.     

Encapsulation of Nanoparticle Organic Hybrid Materials within Electrospun Hydrophobic Polymer/Ceramic Fibers for Enhanced CO2 Capture

Liquid-like nanoparticle organic hybrid materials (NOHMs) consisting of a silica core with ionically grafted branched polyethyleneimine chains (referred to as NIPEI) are encapsulated within submicron-scale polyacrylonitrile (PAN)/polymer-derived-ceramic electrospun fibers. The addition of a room-temperature curable, liquid-phase organopolysilazane (OPSZ) ceramic precursor to the PAN/NOHM solution enhances the internal dispersion of NOHMs and forms a thin ceramic sheath layer on the fiber exterior, shielding the hydrophilic NIPEI to produce near-superhydrophobic non-woven fiber mats with contact angles exceeding 140°. 60:40 loadings of NOHMs to PAN/OPSZ can be reliably achieved with low OPSZ percentages required, and up to 4:1 NOHM:polymer loadings are possible before losing hydrophobicity. These fibers demonstrate up to ≈2 mmol CO₂ g⁻¹ fiber capture capacities in a pure CO₂ atmosphere through the nonwoven fibrous networks and the permeability of the OPSZ shell. The hybrid fibers additionally show enhanced capture kinetics under pure CO₂ and 400 ppm CO₂ conditions, indicating their promising application as a direct air capture platform.     

Highly Conductive Optical Quality Solution‐Processed Films of 2D Titanium Carbide

MXenes comprise a new class of solution‐dispersable, 2D nanomaterials formed from transition metal carbides and nitrides such as Ti₃C₂. Here, it is shown that 2D Ti₃C₂ can be assembled from aqueous solutions into optical quality, nanometer thin films that, at 6500 S cm^?1, surpass the conductivity of other solution‐processed 2D materials, while simultaneously transmitting >97% of visible light per‐nanometer thickness. It is shown that this high conductivity is due to a metal‐like free‐electron density as well as a high degree of coplanar alignment of individual nanosheets achieved through spincasting. Consequently, the spincast films exhibit conductivity over a macroscopic scale that is comparable to the intrinsic conductivity of the constituent 2D sheets. Additionally, optical characterization over the ultraviolet‐to‐near‐infrared range reveals the onset of free‐electron plasma oscillations above 1130 nm. Ti₃C₂ is therefore a potential building block for plasmonic applications at near‐infrared wavelengths and constitutes the first example of a new class of solution‐processed, carbide‐based 2D optoelectronic materials.     

2D Layered Dipeptide Crystals for Piezoelectric Applications

2D piezoelectric materials such as transition metal dichalcogenides are attracting significant attention because they offer various benefits over bulk piezoelectrics. In this work, the fabrication of layered biomolecular crystals of diphenylalanine (FF) obtained via a co-assembly of l,l - and d,d - enantiomers of FF monomers is reported. Their crystal structure, thermal and chemical stabilities, and piezoelectric properties are investigated. Single crystal X-ray diffraction results show that FF enantiomers are arranged in the form of bilayers consisting of monomers with alternating chirality packed into a tape-like monoclinic structure belonging to a polar space group P2₁. Each bilayer ( ≈ 1.5 nm thick) demonstrates strong out-of-plane piezoelectricity (d₃₃  ≈  20 pm V⁻¹) that is almost an order of magnitude higher than in the archetypical piezoelectric material quartz. The grown crystals demonstrate better thermal and chemical stabilities than self-assembled hexagonal FF nanotubes studied in the past. Piezoelectric bilayers, being held via weak aromatic interaction in the bulk crystals, can be exfoliated by mechanical or chemical methods, thus resulting in a 2D piezoelectric material, which can find various applications in biocompatible and ecologically friendly electromechanical microdevices, such as sensors, actuators, and energy harvesting elements used in implantable and wearable electronics.     

Flexible Protective Film: Ultrahard,Yet Flexible Hybrid Nanocomposite Reinforced by 3D Inorganic Nanoshell Structures

Emerging flexible optoelectronics requires a new type of protective material that is not only hard but also flexible. Organic–inorganic (O–I) hybrid materials have been used as a flexible cover window to increase wear resistance and polymer-like flexibility. However, the hardness of O–I hybrid materials is much lower than that of metals and ceramics due to the low intrinsic hardness of the organic matrix and limited volume fraction of inorganic reinforcement. Herein, a new type of hybrid nanocomposite combining an O–I hybrid material with continuous and ordered 3D inorganic nanoshell as an additional reinforcement is proposed. The 3D alumina nanoshell uniformly embedded in the epoxy-siloxane molecular hybrid (ESMH) enables a rule of mixture without a loss in flexibility. Two types of reinforcements comprising siloxane molecules and 3D alumina shell ensure a metal-like hardness (1.3 GPa), which is significantly higher than that of the typical polymers and polymer nanocomposites. The 3D hybrid nanocomposite films show superb impact resistance due to the 3D alumina nanoshell that effectively suppresses crack propagation. Inch-scale 3D hybrid nanocomposite films also endure 20 000 bending cycles without failure and maintain high transparency (>82.0% at 550 nm) in the visible regions.     

Recent Advances in 2D Rare Earth Materials

2D rare earth (RE) materials have received considerable attention in recent years due to the fascinating luminescence, magnetism, and electric properties originated from RE associated with sharp and various emission peaks, intrinsic 2D ferromagnetism, and incommensurate charge density wave. These materials might open up a new prospect in next-generation lighting, magnetic devices, and phototransistors. Herein, a comprehensive review of 2D RE materials is presented, focusing on their recent progresses. First, the crystal structures of 2D RE materials are discussed. Then, typical synthesis methods such as mechanical exfoliation, molecular beam epitaxy, pulsed laser deposition, and chemical vapor deposition are introduced. Furthermore, various properties in luminescence, magnetism, and electronics are summarized. The recently reported RE-based 2D novel photodetectors are outlined as three constructions: MoS₂/RE, graphene/RE, and perovskite/RE, which show promising applications for both narrow and broad band detection arised from the special absorption windows of different RE elements. Finally, the conclusions and outlook of this area are proposed, such as exploring novel 2D RE compounds, improving stability, and broadening applications.