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.     

Broadband scattering of the solar spectrum by spherical metal nanoparticles

Metal nanoparticles offer the possibility of improved light trapping in solar cells, but careful design is required to maximise scattering and minimise parasitic absorption across the wavelength range of interest. We present an analysis of the broadband scattering and absorption characteristics of spherical metal nanoparticles, optimized for either crystalline silicon (c‐Si) or amorphous silicon (a‐Si:H) solar cells. A random two‐dimensional array of optimally sized Ag spheres can scatter over 97% of the AM1.5 spectrum from 400 to 1100 nm. Larger particles are required for c‐Si devices than a‐Si:H due to the increased spectral range, with optimum particle sizes ranging from 60 nm for a‐Si:H to 116 nm for c‐Si. Positioning the particles at the rear of the solar cell decreases absorption losses because these principally occur at short wavelengths. Increasing the refractive index of the surrounding medium beyond the optimum value, which is 1.0 for a‐Si:H and 1.6 for c‐Si, shifts absorption to longer wavelengths and decreases scattering at short wavelengths. Ag nanoparticles scatter more of the solar spectrum than Au, Cu or Al nanoparticles. Of these other metals, Al can only be considered for a‐Si:H applications due to high absorption in the near‐infrared, whereas Au and Cu can only be considered for the rear of c‐Si devices due to high absorption in the ultraviolet (UV) and visible. In general, we demonstrate the importance of considering the broadband optical properties of metal nanoparticles for photovoltaic applications. Copyright © 2012 John Wiley & Sons, Ltd.     

Ordered 3D Thin‐Shell Nanolattice Materials with Near‐Unity Refractive Indices

The refractive indices of naturally occurring materials are limited, and there exists an index gap between indices of air and available solid materials. With many photonics and electronics applications, there has been considerable effort in creating artificial materials with optical and dielectric properties similar to air while simultaneously being mechanically stable to bear load. Here, a class of ordered nanolattice materials consisting of periodic thin‐shell structures with near‐unity refractive index and high stiffness is demonstrated. Using a combination of 3D nanolithography and atomic layer deposition, these ordered nanostructured materials have reduced optical scattering and improved mechanical stability compared to existing randomly porous materials. Using ZnO and Al₂O₃ as the building materials, refractive indices from 1.3 down to 1.025 are achieved. The experimental data can be accurately described by Maxwell Garnett effective media theory, which can provide a guide for index design. The demonstrated low‐index, low‐scattering, and high‐stiffness materials can serve as high‐quality optical films in multilayer photonic structures, waveguides, resonators, and ultra‐low‐k dielectrics.     

Nanoparticle Stacks with Graded Refractive Indices Enhance the Omnidirectional Light Harvesting of Solar Cells and the Light Extraction of Light‐Emitting Diodes

In this study, nanoparticles (NPs) of various types and sizes are arranged to enhance both the omnidirectional light harvesting of solar cells and the light extraction of light emitting diodes (LEDs). A graded‐refractive‐index NP stack can minimize reflectance, not only over a broad range of wavelengths but also at different incident angles; the photocurrent of silicon‐based solar cells an also be significantly improved omnidirectionally. In addition, the optical gradient of an NP stack can also enhance the light‐extraction efficiency of LEDs, due to both the graded refractive index and the moderate surface roughness. Large particles having sizes on the same order of the wavelength of the incident light roughen the LED surfaces further and extract light from beyond the critical angle, as supported by three‐dimensional finite‐difference time‐domain simulations. Using this approach, the photoluminescence intensity can be increased by up to sevenfold. The developed technique: arranging sequences of different NPs in graded‐refractive‐index stacks, and considering their ability to scatter light due to their sizes and optical constants, may also significantly improve the performance of various optoelectronic devices.     

Silver‐Nanowire‐Based Interferometric Optical Tweezers for Enhanced Optical Trapping and Binding of Nanoparticles

Light‐induced self‐assembly offers a new route to build mesoscale optical matter arrays from nanoparticles (NPs), yet the low stability of optical matter systems limits the assembly of large‐scale NP arrays. Here it is shown that the interferometric optical fields created by illuminating a single Ag nanowire deposited on a coverslip can enhance the electrodynamic interactions among NPs. The Ag nanowire serves as a plasmonic antenna to shape the incident laser beam and guide the optical assembly of colloidal metal (Ag and Au) and dielectric (polystyrene) NPs in solution. By controlling the laser polarization direction, both the mesoscale interactions among multiple NPs and the near‐field coupling between the NPs and nanowire can be tuned, leading to large‐scale and stable optical matter arrays consisting of up to 60 NPs. These results demonstrate that single Ag nanowires can serve as multifunctional antennas to guide the optical trapping and binding of multiple NPs and provide a new strategy to control electrodynamic interactions using hybrid nanostructures.     

A Generic Synthetic Approach to Large‐Scale Pristine‐Graphene/Metal‐Nanoparticles Hybrids

The homogeneous attachment of metal‐nanoparticles (metal‐NPs) on pristine‐graphene surface to construct pristine‐graphene/metal‐NPs hybrids is highly expected for application in many fields such as transparent electrodes and conductive composites. However, it remains a great challenge since the pristine‐graphene is highly hydrophobic. Here, an environmentally friendly generic synthetic approach to large‐scale pristine‐graphene/metal‐NPs hybrids is presented, by a combinatorial process of exfoliating expanded graphite in N‐methyl pyrrolidone via sonication and centrifugation to achieve the pristine‐graphene, and attaching pre‐synthesized metal‐NPs on the pristine‐graphene in ethanol via van der Waals interactions between the metal‐NPs and the pristine‐graphene. Nanoparticles of different metals (such as Ag, Au, and Pd) with various morphologies (such as sphere, cube, plate, multi‐angle, and spherical‐particle assembling) can be homogeneously attached on the defect‐free pristine‐graphene with controlled packing densities. Both the pristine‐graphene and the metal‐NPs preserve their original intrinsic structures. The as‐synthesized pristine‐graphene/Ag‐NPs hybrids show very high surface‐enhanced Raman scattering activity due to the combined effects of large surface area of the pristine‐graphene to adsorb more target molecules and the electromagnetic enhancement of the Ag‐NPs. This large‐scale synthesis of the pristine‐graphene/metal‐NPs hybrids with tunable shape and packing density of metal‐NPs opens up opportunities for fundamental research and potential applications ranging from devices to transparent electrodes and conductive composites.     

Novel Method of Preparation of Gold‐Nanoparticle‐Doped TiO2 and SiO2 Plasmonic Thin Films: Optical Characterization and Comparison with Maxwell–Garnett Modeling

SiO₂ and TiO₂ thin films with gold nanoparticles (NPs) are of particular interest as photovoltaic materials. A novel method for the preparation of spin‐coated SiO₂–Au and TiO₂–Au nanocomposites is presented. This fast and inexpensive method, which includes three separate stages, is based on the in situ synthesis of both the metal‐oxide matrix and the Au NPs during a baking process at relatively low temperature. It allows the formation of nanocomposite thin films with a higher concentration of Au NPs than other methods. High‐resolution transmission electron microscopy studies revealed a homogeneous distribution of NPs over the film volume along with their narrow size distribution. The optical manifestation of localized surface plasmon resonance was studied in more detail for TiO₂‐based Au‐doped nanocomposite films deposited on glass (in absorption and transmittance) and silicon (in specular reflectance). Maxwell–Garnett effective‐medium theory applied to such metal‐doped nanocomposite films describes the peculiarities of the experimental spectra, including modification of the antireflective properties of bare TiO₂ films deposited on silicon by varying the concentration of metal NPs. The antireflective capabilities of the film are increased after a wet etching process.     

Use of Reversal Nanoimprinting of Nanoparticles to Prepare Flexible Waveguide Sensors Exhibiting Enhanced Scattering of the Surface Plasmon Resonance

A flexible surface plasmon resonance (SPR)‐based scattering waveguide sensor is prepared by directly imprinting hollow gold nanoparticles (NPs) and solid gold NPs onto flexible polycarbonate (PC) plates—without any surface modification—using a modified reversal nanoimprint lithography technology. Controlling the imprinting conditions, including temperature and pressure, allows for the fine adjustment of the depths of the embedded metal NPs and their SPR properties. This patterning approach exhibits a resolution down to the submicrometer level. A 3D finite‐difference time domain simulation is used to examine the optical behavior of light propagating parallel to the air/substrate interface within the near‐field regime. Consistent with the simulations, almost an order of magnitude enhancement in the scattering signal after transferring the metal NPs from the glass mold to the PC substrate is obtained experimentally. The enhanced signal is attributed to the particles' strong scattering of the guiding‐mode waves (within the waveguide) and the evanescent wave (above the waveguide) simultaneously. Finally, the imprinting conditions are optimized to obtain a strongly scattering bio/chemical waveguide sensor.     

光纤Bragg光栅滤波响应的轴向分布特性研究

为揭示光纤Bragg光栅（FBG）的局部滤波特征,研究和分析了滤波响应沿光栅轴向的空间分布规律。从均匀、切趾和啁啾型等基本光纤Bragg光栅（FBG）类型出发,分析了反射带滤波光场沿轴向的分布规律。结果表明,均匀型FBG中,光场反射多集中在前1/2个光栅长度内,呈现非对称性;切趾型FBG中,光场反射在光栅长度内的均匀性...     

Supported Faceted Gold Nanoparticles with Tunable Surface Plasmon Resonance for NIR‐SERS

A novel dry plasma methodology for fabricating directly stabilized substrate‐supported gold nanoparticle (NP) ensembles for near infrared surface enhanced Raman scattering (NIR SERS) is presented. This maskless stepwise growth exploits Au‐sulfide seeds by plasma sulfidization of gold nuclei to produce highly faceted Au NPs with a multiple plasmon resonance that can be tuned from the visible to the near infrared, down to 1400 nm. The role of Au sulfidization in modifying the dynamics of Au NPs and of the corresponding plasmon resonance is discussed. The tunability of the plasmon resonance in a broad range is shown and the effectiveness as substrates for NIR SERS is demonstrated. The SERS response is investigated by using different laser sources operating both in the visible and in the NIR. SERS mapping of the SERS enhancement factor is carried out in order to evaluate their effectiveness, stability, and reproducibility as NIR SERS substrates, also in comparison with gold NPs fabricated by conventional sputtering and with the state‐of‐the‐art in the current literature.     

Physical Unclonable Anticounterfeiting Electrodes Enabled by Spontaneously Formed Plasmonic Core–Shell Nanoparticles for Traceable Electronics

Counterfeit electronics are a growing problem for the electronic information industry worldwide, so developing unbreakable security tags is crucial to ensure the trustworthiness and traceability of electronics. Traditional anticounterfeiting and trace solutions rely on reproducible deterministic processes and additional labels, which can still be copied or faked by counterfeiters. Herein, physical unclonable functions enabled by spontaneously formed plasmonic core–shell nanoparticles on electrodes are proposed to ensure label-free traceable electronics, giving a practical solution to fight against counterfeit electronics. Random hemispherical core–shell nanoparticles are intentionally introduced on the metal electrode of different semiconductors (Si, GaAs, and GaN) from Ni/Au bilayer heterofilms by rapid thermal annealing, which can be integrated with electronics seamlessly, with no negative effect on electrical properties. The position, size, and shape of nanoparticles are random and uncontrollable; the corresponding scattering patterns, intensity, and spectra can work as nanofingerprints of the electrode, proving multidimensional unclonable labels with large encoding capacity suitable for electrodes smaller than several micrometers. It can be further combined with machine vision and artificial intelligence to identify and track electronics automatically and efficiently. The anticounterfeiting electrodes also show good thermal robustness and mechanical stability, opening up a prospect for practical anticounterfeiting of electronics.     

Designer Colloidal Layers of Disordered Plasmonic Nanoparticles for Light Extraction

Basic design rules are disclosed for broadband light‐extraction colloidal films formed with disordered ensembles of plasmonic particles. They are derived through the numerical study of a test‐bed geometry consisting of a low‐refractive index slab in air. Albeit simple, the geometry encompasses many physically effects encountered in real light‐emitting devices, including the pronounced absorption at the peak of the nanoparticles resonance spectrum, the anisotropy of the radiation diagram of nanoparticles in waveguides and unavoidable coherent multiple interferences that ruin the predictive strength of first‐order scattering models. How we can simultaneously take advantage of (1) the shape or size of the individual nanoparticles, (2) their transverse position with respect to the guiding photonic structure, (3) their concentration, and (4) the structural topology of the disorder ensemble are illustrated. Following this approach, a threefold enhancement in the extraction efficiency can be reached as compared to a film without plasmonic particles. It is also predicted that the extraction rapidly saturates and then decreases as the nanoparticle density increases, suggesting that best performance is achieved at low concentrations. Spectrally broad and directionally random far‐field radiation diagrams are additionally reported, which do not suffer from deterministic interferential behaviors observed at particular wavelengths and directionalities with periodic light‐extraction structures.     

Mesostructured Arrays of Nanometer‐spaced Gold Nanoparticles for Ultrahigh Number Density of SERS Hot Spots

A novel one‐trough synthesis via an air‐water interface is demonstrated to provide hexagonally packed arrays of densely spaced metallic nanoparticles (NPs). In the synthesis, a mesostructured polyoxometalate (POM)‐silicatropic template (PSS) is first self‐assembled at the air‐water interface; upon UV irradiation, anion exchange cycles enable the free‐floating PSS film to continuously uptake gold precursors from the solution subphase for diffusion‐controlled and POM‐site‐directed photoreduction inside the silica channels. NPs ≈ 2 nm can hence be homogeneously formed inside the silica‐surfactant channels until saturation. As revealed via X‐ray diffraction, small‐angle X‐ray scattering (SAXS), grazing incidence SAXS, and transmission electron microscopy, the Au NPs directed by the PSS template are arrayed into a 2D hexagonal lattice with inter‐channel spacing of 3.2 nm and a mean along‐channel NP spacing of 2.8 nm. This corresponds to an ultra‐high number density (≈10¹⁹ NPs cm^?3) of narrowly spaced Au NPs in the Au‐NP@PSS composite, leading to 3D densely deployed hot‐spots along and across the mesostructured POM‐silica channels for surface‐enhanced Raman scattering (SERS). Consequently, the Au‐NP@PSS composite exhibits prominent SERS with 4‐mercaptobenzoic acid (4‐MBA) adsorbed onto Au NPs. The best 4‐MBA detection limit is 5 nm , with corresponding SERS enhancement factors above 10⁸.     

Flexible,Large‐Area Covert Polarization Display Based on Ultrathin Lossy Nanocolumns on a Metal Film

Covert polarization displays provide a barrier to the inadvertent viewing of stored optical information. For security and anti‐counterfeiting purposes, access to concealed information without compromising packaging aesthetics is required in certain situations. However, optical conversion with polarized light typically requires sophisticated nanostructures only possible with limited materials, which are not appropriate for application to objects requiring flexibility or conformability, and color selectivity. A flexible, large‐area covert polarization display based on ultrathin lossy nanocolumns with wide color selectivity is presented. Self‐aligned porous nanocolumns (PNCs) fabricated by glancing angle deposition are a facile approach to polarization distinguishable structures. PNCs deposited on metal are designed to switch color in accordance with polarization by ultrathin resonance, which is modeled using the complex effective refractive index. Several combinations of material and thickness are presented to extend color selectivity with the standard red green blue gamut and color palette. As a demonstration, covert polarization display labels are attached to daily objects with curved and wrinkled surfaces, and hidden quick response codes are revealed by polarization adjustment in indoor and outdoor environments. Moreover, a multifunctional water contact detection covert polarization display is demonstrated based on the sensitivity of PNCs to the refractive index of the analyte.     

Plasmonic Electrically Functionalized TiO2 for High‐Performance Organic Solar Cells

Optical effects of the plasmonic structures and the materials effects of the metal nanomaterials have recently been individually studied for enhancing performance of organic solar cells (OSCs). Here, the effects of plasmonically induced carrier generation and enhanced carrier extraction of the carrier transport layer (i.e., plasmonic‐electrical effects) in OSCs are investigated. Enhanced charge extraction in TiO₂ as a highly efficient electron transport layer by the incorporation of metal nanoparticles (NPs) is proposed and demonstrated. Efficient device performance is demonstrated by using Au NPs incorporated TiO₂ at a plasmonic wavelength (560–600 nm), which is far longer than the originally necessary UV light. By optimizing the concentration ratio of the Au NPs in the NP‐TiO₂ composite, the performances of OSCs with various polymer active layers are enhanced and efficiency of 8.74% is reached. An integrated optical and electrical model, which takes into account plasmonic‐induced hot carrier tunneling probability and extraction barrier between TiO₂ and the active layer, is introduced. The enhanced charge extraction under plasmonic illumination is attributed to the strong charge injection of plasmonically excited electrons from NPs into TiO₂. The mechanism favors trap filling in TiO₂, which can lower the effective energy barrier and facilitate carrier transport in OSCs.     

“Ship‐in‐a‐Bottle” Growth of Noble Metal Nanostructures

Noble metal nanostructures are grown inside hollow mesoporous silica microspheres using “ship‐in‐a‐bottle” growth. Small Au seeds are first introduced into the interior of the hollow microspheres. Au nanorods with synthetically tunable longitudinal plasmon wavelengths and Au nanospheres are obtained through seed‐mediated growth within the microspheres. The encapsulated Au nanocrystals are further coated with Pd or Pt shells. The microsphere‐encapsulated bimetallic core/shell nanostructures can function as catalysts. They exhibit high catalytic performance and their stability is superior to that of the corresponding unencapsulated core/shell nanostructures in the catalytic oxidation of o‐phenylenediamine with hydrogen peroxide. Therefore, these hollow microsphere‐encapsulated metal nanostructures are promising as recoverable and efficient catalysts for various liquid‐phase catalytic reactions.     

Near‐Field Enhanced Plasmonic‐Magnetic Bifunctional Nanotubes for Single Cell Bioanalysis

Near‐field enhanced bifunctional plasmonic‐magnetic (PM) nanostructures consisting of silica nanotubes with embedded solid nanomagnets and uniformly dual‐surface‐coated plasmonic Ag nanoparticles (NPs) are rationally synthesized. The solid embedded sections of nanotubes provide single‐molecule sensitivity with an enhancement factor up to 7.2 × 10⁹ for surface‐enhanced Raman scattering (SERS). More than 2× SERS enhancement is observed from the hollow section compared to the solid section of the same nanotube. The substantial SERS enhancement on the hollow section is attributed to the dual‐sided coating of Ag NPs as well as the near‐field optical coupling of Ag NPs across the nanotube walls. Experimentation and modeling are carried out to understand the dependence of SERS enhancement on the NP sizes, junctions, and the near field effects. By tuning the aspect ratio of the embedded nanomagnets, the magnetic anisotropy of nanotubes can be readily controlled to be parallel or vertical to the long directions for nano‐manipulation. Leveraging the bifunctionality, a nanotube is magnetically maneuvered to a single living mammalian cell amidst many and its membrane composition is analyzed via SERS spectroscopy.     

有限元法求解任意折射率分布光纤波导截止波长

本文应用有限元方法,求解了任意径向非均匀折射率分布圆柱对称介质波导中纵向场耦合波动方程定解问题所对应的变分问题,计算了任意径向非均匀折射率分布介质波导的截止波长。阶跃光纤与幂指数折射率分布光纤计算结果与文献结果的比较表明,该方法计算结果精度高且不需要弱导或高斯模场分布等限制要求。然后本文研究了带阶跃环的三角型分段折射率分布光纤归一化截止频率随结构参数变化的规律。     

High‐Temperature Large‐Scale Self‐Assembly of Highly Faceted Monocrystalline Au Metasurfaces

Localized surface plasmon resonance (LSPR) devices based on resonant metallic metasurfaces have shown disruptive potential for many applications including biosensing and photocatalysis. Despite significant progress, highly performing Au plasmonic nanotextures often suffer of suboptimal electric field enhancement, due to damping effects in multicrystalline domains. Fabricating well‐defined Au nanocrystals over large surfaces is very challenging, and usually requires time‐intensive multi‐step processes. Here, presented are first insights on the large‐scale self‐assembly of monocrystalline Au nano‐islands with tunable size and separation, and their application as efficient LSPR surfaces. Highly homogeneous centimeter‐sized Au metasurfaces are fabricated by one‐step deposition and in situ coalescence of hot nanoparticle aerosols into a discontinuous monolayer of highly faceted monocrystals. First insights on the mechanisms driving the high‐temperature synthesis of these highly faceted Au nanotextures are obtained by molecular dynamic and detailed experimental investigation of their growth kinetics. Notably, these metasurfaces demonstrat high‐quality and tunable LSPR, enabling the fabrication of highly performing optical gas molecule sensors detecting down to 3 × 10^?6 variations in refractive index at room temperature. It is believed that these findings provide a rapid, low‐cost nanofabrication tool for the engineering of highly homogenous Au metasurfaces for large‐scale LSPR devices with application ranging from ultrasensitive optical gas sensors to photocatalytic macroreactors.     

光学薄膜减散射特性研究

为了降低光学薄膜的表面散射损耗,依据微粗糙面的一阶微扰理论,在不考虑多重散射效应的情况下,利用电磁场边界条件给出的光学薄膜任一界面粗糙度引起的散射场在入射介质中的表达式,重点讨论了单层光学薄膜实现零散射的条件以及实现减散射的条件,理论研究结果表明:当膜层的光学厚度为/4的偶数倍时,单层薄膜要实现减散射就必须使单层膜的折射率大于基底的折射率,且空气-薄膜界面的微粗糙度必须小于薄膜-基底界面之间的微粗糙度。当膜层的光学厚度为/4的奇数倍时,单层薄膜的折射率小于基底的折射率,且膜层两个界面的粗糙度必须满足特定条件,才能实现减散射的效果。