Plasmonic Nanowire‐Enhanced Upconversion Luminescence for Anticounterfeit Devices

A novel, efficient, cost‐effective, and high‐level security performance anticounterfeit device achieved by plasmonic‐enhanced upconversion luminescence (UCL) is demonstrated. The plasmonic architecture consists of the randomly dispersed Ag nanowires (AgNWs) network, upconversion nanoparticles (UCNPs) monolayer, and metal film, in which the UCL is enhanced by a few tens, compared to reference sample, becuase the plasmonic modes lead to the concentration of the incident near infrared (NIR) light in the UCNPs monolayer. In the configuration, both the localized surface plasmons (LSPs) around the metallic nanostructures and gap plasmon polaritons (GPPs) confined in the UCNPs monolayer, significantly contribute to the UCL enhancement. The UCL enhancement mechanism resulting from enhanced NIR absorption, boosted internal quantum process, and formation of strong plasmonic hot spots in the plasmonic architecture is analyzed theoretically and numerically. More interestingly, a proof‐of‐concept anticounterfeit device using the plasmonic‐enhanced UCL is proposed, through which a nonreusable and high‐level cost‐effective security device protecting the genuine products is realized.     

A Multi‐Functional Highly Efficient Upconversion Luminescent Film with an Array of Dielectric Microbeads Decorated with Metal Nanoparticles

Upconversion nanoparticles (UCNPs) have been integrated with photonic platforms to overcome the intrinsically low quantum efficiency limit of upconversion luminescence (UCL). However, platforms based on thin films lack transferability and flexibility, which hinders their broader and more practical application. A plasmonic structure is developed that works as a multi‐functional platform for flexible, transparent, and washable near‐infrared (NIR)‐to‐visible UCL films with ultra‐strong UCL intensity. The platform consists of dielectric microbeads decorated with plasmonic metal nanoparticles on an insulator/metal substrate. Distinct improvements in NIR confinement, visible light extraction, and boosted plasmonic effects for upconversion are observed. With weak NIR excitation, the UCL intensity is higher by three orders of magnitude relative to the reference platform. When the microbeads are organized in a square lattice array, the functionality of the platform can be expanded to wearable and washable UCL films. The platform can be transferred to transparent, flexible, and foldable films and still emit strong UCL with a wide viewing angle.     

Graphene as an Electron Shuttle for Silver Deoxidation: Removing a Key Barrier to Plasmonics and Metamaterials for SERS in the Visible

The role of graphene in enabling deoxidation of silver nanostructures, thereby contributing to enhance plasmonic properties and to improve the temporal stability of graphene/silver hybrids for both general plasmonic and meta‐materials applications, as well as for surface enhanced Raman scattering (SERS) substrates, is demonstrated. The chemical mechanism occurring at the graphene–silver oxide interface is based on the reduction of silver oxide triggered by graphene that acts as a shuttle of electrons and as a kind of catalyst in the deoxidation. A mechanism is formulated, combining elements of electron transfer, role of defects in graphene, and electrochemical potentials of graphene, silver, and oxygen. Therefore, the formulated model represents a step forward from the simple view of graphene as barrier to oxygen diffusion proposed so far in literature. Single layer graphene grown by chemical vapor deposition is transferred onto silver thin films, a periodic silver fishnet structure fabricated by nanoimprint lithography, and onto silver nanoparticle ensembles supporting a localized surface plasmon resonance in the visible range. Through the study of these nanostructured graphene/Ag hybrids, the effectiveness of graphene in preventing and reducing oxidation of silver plasmonic structures, keeping silver in a metallic state over months at air exposure, is demonstrated. The enhanced and stable plasmonic properties of the silver‐fishnet/graphene hybrids are evaluated through their SERS response for detecting benzyl mercaptane.     

Symmetric and Asymmetric Decoration of Graphene: Bimetal‐Graphene Sandwiches

Low‐dimensional carbon materials, i.e., graphene and its functionalization with a number of semiconductor or conductor materials, such as noble metal nanostructures, have primary importance for their potential exploitation as electro‐active materials, i.e., as new generation catalysts. Here, low‐cost, solution chemistry‐based, two‐step functionalization of an individual, free‐standing, chemical vapor‐deposited graphene monolayer is reported, with noble metal (Au, Pt, Pd) nanoparticles to build up two‐side decorated graphene‐based metal nanoclusters. Either the same metal (symmetric decoration) or different metals (asymmetric decoration) are used for the preparation of bimetal graphene sandwiches, which are adsorbed at the liquid/liquid (organic/water) interface. The successful fabrication of such dual‐decorated graphene‐based metal nanocomposites is confirmed using various microscopic techniques (scanning electron and atomic force microscopies) and several spectroscopic methods (x‐ray photoelectron, energy dispersive x‐ray, mapping mode Raman spectroscopy, and electron energy loss spectroscopy). Taken together, it is inferred from these techniques that the location of deposited metal nanoparticles is on opposite sides of the graphene.     

Controlling Red Color–Based Multicolor Upconversion through Selective Photon Blocking

Photon upconversion multiplexing has attracted increasing interest in recent years; however, realizing the red color–based multicolor‐tunable output in upconversion nanoparticles (UCNPs) at a fixed composition remains a huge challenge. Here, a novel and versatile approach to fine‐control upconversion luminescence (UCL) colors from UCNPs through selectively confining specific excitation energy by the photon blocking effect is reported. Four types of dual‐color switchable UCNPs capable of emitting red‐blue and red‐green emissions are successfully designed following this strategy, and their UCL performance shows a multiwavelength (808/980/1550 nm) excitable feature that is well sustained in a wide range of excitation power density. The use of the photon blocking effect further enables the dynamically switchable red‐green‐blue UCL with 808/980 nm excitations. These findings provide a general method to achieve multicolor‐tunable UCL at a single nanoparticle level. Moreover, the UCNPs with red‐based multicolor emissions in this work enriches the upconversion system and should have potential applications in display, anti‐counterfeiting, and bioimaging.     

Non‐Covalent Functionalization of Graphene Using Self‐Assembly of Alkane‐Amines

A simple, versatile method for non‐covalent functionalization of graphene based on solution‐phase assembly of alkane‐amine layers is presented. Second‐order Møller–Plesset (MP2) perturbation theory on a cluster model (methylamine on pyrene) yields a binding energy of ≈220 meV for the amine–graphene interaction, which is strong enough to enable formation of a stable aminodecane layer at room temperature. Atomistic molecular dynamics simulations on an assembly of 1‐aminodecane molecules indicate that a self‐assembled monolayer can form, with the alkane chains oriented perpendicular to the graphene basal plane. The calculated monolayer height (≈1.7 nm) is in good agreement with atomic force microscopy data acquired for graphene functionalized with 1‐aminodecane, which yield a continuous layer with mean thickness ≈1.7 nm, albeit with some island defects. Raman data also confirm that self‐assembly of alkane‐amines is a non‐covalent process, i.e., it does not perturb the sp² hybridization of the graphene. Passivation and adsorbate n‐doping of graphene field‐effect devices using 1‐aminodecane, as well as high‐density binding of plasmonic metal nanoparticles and seeded atomic layer deposition of inorganic dielectrics using 1,10‐diaminodecane are also reported.     

Large Upconversion Enhancement in the “Islands” Au–Ag Alloy/NaYF4: Yb3+, Tm3+/Er3+ Composite Films,and Fingerprint Identification

The surface plasmon (SP) modulation is a promised way to highly improve the strength of upconversion luminescence (UCL) and expand its applications. In this work, the “islands” Au–Ag alloy film is prepared by an organic removal template method and explored to improve the UCL of NaYF₄: Yb3+, Tm³⁺/Er³⁺. After the optimization of Au–Ag molar ratio (Au_1.25–Ag_0.625) and the size of NaYF₄ nanoparticles (NPs, ≈7 nm), an optimum enhancement as high as 180 folds is obtained (by reflection measurement) for the overall UCL intensity of Tm³⁺. Systematic studies indicate that the UCL enhancement factor (EF) increases with the increased size of metal NPs and the increase of diffuse reflection, with the decreased size of NaYF₄ NPs, with the decreased power density of excitation light and with improving order of multiphoton populating. The total decay rate varies only ranging of about 20% while EF changes significantly. All the facts above indicate that the UCL enhancement mainly originates from coupling of SP with the excitation electromagnetic field. Furthermore, the fingerprint identification based on SP‐enhanced UCL is realized in the metal/UC system, which provides a novel insight for the application of the metal/UC device.     

Polymer Brush Guided Formation of Conformal,Plasmonic Nanoparticle‐Based Electrodes for Microwire Solar Cells

This report explores the use of sacrificial thin polymer films prepared by surface‐initiated polymerization as a template for the fabrication of highly conformal metal nanoparticle solar cell electrodes. As a first proof‐of‐principle, the use of this method is demonstrated to prepare top electrodes on planar and microwire‐based silicon solar cell devices. These metal nanoparticle films are dual functional in that they not only mediate charge transport, but also enhance light capture due to the plasmonic scattering properties of the nanoparticles. Solar cells with a conformal silver nanoparticle‐based electrode layer show short circuit currents that are 46% higher as compared to those exhibit by devices coated with standard indium tin oxide as the electrode. It is anticipated that this methodology will contribute to novel electrode concepts in the next generation solar cells.     

Smart Metal–Polymer Bionanocomposites as Omnidirectional Plasmonic Black Absorber Formed by Nanofluid Filtration

The first smart plasmonic absorber based on metal‐polymer bionanocomposites performing via conformational changes of the biological functional agent, i.e., a protein, is introduced. Such a progress is done through bridging the gaps between nanofluid filtration, plasmonics, and bioswitching. Initially, a biofunctionalized nanofibrous membrane is developed that could filter out metal nanoparticles (<100 nm) from an aqueous stream with a high separation efficiency (97%). This approach brings about a breakthrough in applicability of the macroporous nanofibrous membranes for rejection of suspended nanosolids and extends the application area beyond microfiltration (MF) to ultrafiltration (UF). This operative filtration in the next step leads to a novel synthesis route for plasmonic materials as formation of a smart free‐standing metal–polymer bionanocomposite able to act as an omnidirectional black absorber.     

Plasmonic Enhancement or Energy Transfer? On the Luminescence of Gold‐, Silver‐, and Lanthanide‐Doped Silicate Glasses and Its Potential for Light‐Emitting Devices

With the technique of synchrotron X‐ray activation, molecule‐like, non‐plasmonic gold and silver particles in soda‐lime silicate glasses can be generated. The luminescence energy transfer between these species and lanthanide(III) ions is studied. As a result, a significant lanthanide luminescence enhancement by a factor of up to 250 under non‐resonant UV excitation is observed. The absence of a distinct gold and silver plasmon resonance absorption, respectively, the missing nanoparticle signals in previous SAXS and TEM experiments, the unaltered luminescence lifetime of the lanthanide ions compared to the non‐enhanced case, and an excitation maximum at 300–350 nm (equivalent to the absorption range of small noble metal particles) indicate unambiguously that the observed enhancement is due to a classical energy transfer between small noble metal particles and lanthanide ions, and not to a plasmonic field enhancement effect. It is proposed that very small, molecule‐like noble metal particles (such as dimers, trimers, and tetramers) first absorb the excitation light, undergo a singlet‐triplet intersystem crossing, and finally transfer the energy to an excited multiplet state of adjacent lanthanide(III) ions. X‐ray lithographic microstructuring and excitation with a commercial UV LED show the potential of the activated glass samples as bright light‐emitting devices with tunable emission colors.     

Plasmon‐Enhanced Blue Upconversion Luminescence by Indium Nanocrystals

Numerous endeavors have been undertaken to gain enhanced upconversion luminescence via surface plasmon resonance (SPR) generated by specially designed nanostructures of noble metals (e.g., Au, Ag). However, the SPR response of these metals is usually weak in the ultraviolet (UV) region because of their intrinsic electronic configurations; thus, only green and red upconversion emissions can undergo significant plasmonic enhancement yet without selectivity, while an efficient approach to selectively enhancing the blue upconversion luminescence has been lacking. Herein, by integrating the pronounced UV SPR of silica‐coated indium nanocrystals (InNCs) with blue‐emission upconversion nanoparticles (UCNPs) of NaYbF₄:Tm, an up to tenfold selective luminescence enhancement at 450 nm is obtained upon 980 nm laser excitation. Precise manipulation of the silica shell thickness suggests an optimal working distance of 3 nm between InNCs and UCNPs. This study has, for the first time, realized selective blue upconversion luminescence enhancement by using an inexpensive, non‐noble metal material, which will not only enrich the fundamental investigations of SPR‐enhanced upconversion emission, but also widen the applications of blue light‐emitting nanomaterials, for example, in therapeutics.     

Plasmonic Dual‐Enhancement and Precise Color Tuning of Gold Nanorod@SiO2 Coupled Core–Shell–Shell Upconversion Nanocrystals

The last decade has witnessed the remarkable research progress of lanthanide‐doped upconversion nanocrystals (UCNCs) at the forefront of promising applications. However, the future development and application of UCNCs are constrained greatly by their underlying shortcomings such as significant nonradiative processes, low quantum efficiency, and single emission colors. Here a hybrid plasmonic upconversion nanostructure consisting of a GNR@SiO₂ coupled with NaGdF₄:Yb³⁺,Nd³⁺@NaGdF₄:Yb³⁺,Er³⁺@NaGdF₄ core–shell–shell UCNCs is rationally designed and fabricated, which exhibits strongly enhanced UC fluorescence (up to 20 folds) and flexibly tunable UC colors. The experimental findings show that controlling the SiO₂ spacer thickness enables readily manipulating the intensity ratio of the Er³⁺ red, green, and blue emissions, thereby allowing us to achieve the emission color tuning from pale yellow to green upon excitation at 808 nm. Electrodynamic simulations reveal that the tunable UC colors are due to the interplay of plasmon‐mediated simultaneous excitation and emission enhancements in the Er³⁺ green emission yet only excitation enhancement in the blue and red emissions. The results not only provide an upfront experimental design for constructing hybrid plasmonic UC nanostructures with high efficiency and color tunability, but also deepen the understanding of the interaction mechanism between the Er³⁺ emissions and plasmon resonances in such complex hybrid nanostructure.     

Removing the Obstacle of Dye‐Sensitized Upconversion Luminescence in Aqueous Phase to Achieve High‐Contrast Deep Imaging In Vivo

Although upconversion nanoparticles (UCNPs) have drawn increasing attention for their unique photophysical characteristics, they suffer from a bottleneck of low luminescence efficiency due to the poor absorption coefficient of Ln³⁺. Dye sensitization has provided thousands‐fold enhancement of upconversion luminescence (UCL) in organic solvents because of the remarkably improved light absorption ability, but the sensitization of UCL in aqueous phase is only less than 20 folds by far, with unknown restrictive factors. Herein, the aggregation‐caused quenching (ACQ) of dyes is revealed as the most important reason limiting dye sensitization in aqueous phase, and the problem is circumvented through delicately modulating the physical properties of dyes and their assembly manner with UCNPs. By further alleviating energy back transfer (EBT) from Ln³⁺ to dyes, more than 600‐fold enhancement of UCL is achieved in aqueous phase. The as‐obtained dyes modified UCNPs show good biocompatibility and high signal contrast when applied for deep in vivo imaging.     

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.     

Controllable Fabrication of Transparent Macroporous Graphene Thin Films and Versatile Applications as a Conducting Platform

Graphene sheets have been demonstrated to be the building blocks for various assembly structures, which eventually determine the macroscopic properties of graphene materials. As a new assembly structure, transparent macroporous graphene thin films (MGTFs) are not readily prepared due to the restacking tendency of graphene sheets during processing. Here, an ice crystal‐induced phase separation process is proposed for preparation of transparent MGTFs. The ice crystal‐induced phase separation process exhibits several unique features, including efficient prevention of graphene oxide restacking, easy control on the transparency of the MGTFs, and wide applicability to substrates. It is shown that the MGTFs can be used as porous scaffold with high conductivity for electrochemical deposition of various semiconductors and rare metal nanoparticles such as CdSe, ZnO, and Pt, as well as successive deposition of different materials. Notably, the macroporous structures bestow the MGTFs and the nanoparticle‐decorated MGTFs (i.e., Pt@MGTF and CdSe@MGTF) enhanced performance as electrode for oxygen reduction reaction and photoelectrochemical H₂ generation.     

Robust Fabrication of Nonstick,Noncorrosive, Conductive Graphene‐Coated Liquid Metal Droplets for Droplet‐Based,Floating Electrodes

Nontoxic liquid metals (conductive materials in a liquid state at room temperature) are an emerging class of materials for applications ranging from soft electronics and robotics to medical therapy and energy devices. Their sticky and corrosive properties, however, are becoming more of a critical concern for circuits and devices containing other metals as these are easily destroyed or contaminated by the liquid metals. Herein, a feasible method for fabricating highly conductive graphene‐coated liquid metal (GLM) droplets is reported and their application as nonstick, noncorrosive, movable, soft contacts for electrical circuits is demonstrated. The as‐prepared GLM droplets consist of a liquid‐phase soft core of liquid metal and a slippery outer layer of graphene sheets. These structures address the issue of simultaneous control of the wettability and conductivity of a soft electronic contact by combining extraordinary properties, i.e., nonstick, noncorrosive, yet exhibiting high electronic conductivity while in contact with metal substrates, e.g., Au, Cu, Ag, and Ni. As proof‐of‐concept, the as‐prepared GLM droplets are demonstrated as floating electrodes for movable, recyclable electronic soft contacts in electrical circuits.     

Highly Aligned Plasmonic Gold Nanorods in a DNA Matrix

Since the Lycurgus Cup was made in the 4th century, metal nanoparticles have attracted much interest due to the characteristics of the plasmonic and metamaterials that show beautiful colors. Despite these fascinating properties, the practical use is limited because it is difficult to control the orientation of the plasmonic nanoparticles. Here, highly aligned plasmonic gold nanorods are obtained using self‐assembled DNA material. Simple mechanical shearing results in long‐range DNA–gold nanorod arrays which show parallel, perpendicular, and zigzag configurations due to the competition between the shear force and DNA elasticity. The resulting surface plasmonic resonance properties of the aligned DNA–gold nanorods film show highly polarization‐dependent behavior in a large area, which is critical for optical and photonic applications. This simple way to form anisotropic plasmonic films can be used for plasmonic nanoparticles in potential applications such as displays and sensors.     

Direct Optical Fabrication of Fluorescent,Multilevel 3D Nanostructures for Highly Efficient Chemosensing Platforms

Development of fast and intuitive detection techniques for explosive vapors is highly desired for security applications. Among those techniques, fluorescence quenching has advantages in terms of portability and maintenance cost compared to electrically driven platforms. One of the challenging issues is the restricted sensitivity (i.e., low initial quenching and quenching saturation) caused by hindered diffusion of gaseous analytes inside a dense, solid film, and resulting limited surface area, where the target molecules are reacting. Here, multilevel 3D porous nanostructures are introduced, which possess strong fluorescence and enhanced sensing abilities, produced by a rapid and scalable lithographic technique. The cyanostilbene fluorophore with low‐absorption around patterning wavelengths (≈355 nm) is newly designed to be incorporated into transparent photopolymer. The emission color and intensity of the composite films under excitation can be precisely controlled by adjusting the concentration of fluorophore based on intermolecular effects. The patterned, monolithic film with low‐volume fraction (<40%) offers efficient diffusion paths inside a film and a large number of reaction sites for detecting gaseous analytes, enabling fast fluorescence quenching at an early stage (≈7.5 times higher than the solid film at 30 s) and fully suppressed fluorescence without quenching saturation, which cannot be achieved by conventional solid films.     

Nanoparticle‐enhanced light trapping in thin‐film silicon solar cells

A systematic investigation of the nanoparticle‐enhanced light trapping in thin‐film silicon solar cells is reported. The nanoparticles are fabricated by annealing a thin Ag film on the cell surface. An optimisation roadmap for the plasmon‐enhanced light‐trapping scheme for self‐assembled Ag metal nanoparticles is presented, including a comparison of rear‐located and front‐located nanoparticles, an optimisation of the precursor Ag film thickness, an investigation on different conditions of the nanoparticle dielectric environment and a combination of nanoparticles with other supplementary back‐surface reflectors. Significant photocurrent enhancements have been achieved because of high scattering and coupling efficiency of the Ag nanoparticles into the silicon device. For the optimum light‐trapping scheme, a short‐circuit current enhancement of 27% due to Ag nanoparticles is achieved, increasing to 44% for a “nanoparticle/magnesium fluoride/diffuse paint” back‐surface reflector structure. This is 6% higher compared with our previously reported plasmonic short‐circuit current enhancement of 38%. Copyright © 2011 John Wiley & Sons, Ltd.     

Penetration (intercalation) of copper atoms under a graphene layer on iridium (111)

The mechanisms of intercalation of a graphene layer (a two-dimensional graphite film) on a metal (iridium, the (111) face) with copper atoms are studied. It is shown that, in the rather narrow temperature range 1100–1200 K, a thin copper film deposited onto the graphene surface at room temperature totally breaks down, and the atoms transfer to the intercalated state, i.e., become arranged between the graphene layer and the substrate. The nature of the asymmetry of intercalation and backward escape of atoms with high ionization potentials is discussed. Due to the asymmetry, the graphene layer plays the role of a trap for such particles.