High Strength Conductive Composites with Plasmonic Nanoparticles Aligned on Aramid Nanofibers

Rapidly evolving fields of biomedical, energy, and (opto)electronic devices bring forward the need for deformable conductors with constantly rising benchmarks for mechanical properties and electronic conductivity. The search for conductors with improved strength and strain have inspired the multiple studies of nanocomposites and amorphous metals. However, finding conductors that defy the boundaries of classical materials and exhibit simultaneously high strength, toughness, and fast charge transport while enabling their scalable production, remains a difficult materials engineering challenge. Here, composites made from aramid nanofibers (ANFs) and gold nanoparticles (Au NPs) that offer a new toolset for engineering high strength flexible conductors are described. ANFs are derived from Kevlar macrofibers and retain their strong mechanical properties and temperature resilience. Au NPs are infiltrated into a porous, free‐standing aramid matrix, becoming aligned on ANFs, which reduces the charge percolation threshold and facilitates charge transport. Further thermal annealing at 300 °C results in the Au‐ANF composites with an electrical conductivity of 1.25 × 10⁴ S cm^?1 combined with a tensile strength of 96 MPa, a Young's modulus of 5.29 GPa, and a toughness of 1.3 MJ m^?3. These parameters exceed those of most of the composite materials, and are comparable to those of amorphous metals but have no volume limitations. The plasmonic optical frequencies characteristic for constituent NPs are present in the composites with ANFs enabling plasmon‐based optoelectronic applications.     

Electrically Oscillating Plasmonic Nanoparticles for Enhanced DNA Vaccination against Hepatitis C Virus

The promise of DNA vaccines is far‐reaching. However, the development of potent immunization methods remains a key challenge for its use in clinical applications. Here, an approach for in vivo DNA vaccination by electrically activated plasmonic Au nanoparticles is reported. The electrical excitation of plasmonic nanoparticles can drive vibrational and dipole‐like oscillations that are able to disrupt nearby cell membranes. In combination with their intrinsic ability to focus and magnify the electric field on the surface of cells, Au nanoparticles allow enhanced cell poration and facilitate the uptake of DNA vaccine. Mice immunized with this approach showed up to 100‐fold higher gene expression compared to control treatments (without nanoparticles) and exhibited significantly increased levels of both antibody and cellular immune responses against a model hepatitis C virus DNA vaccine. This approach can be tuned to establish controlled and targeted delivery of different types of therapeutic molecules into cells and live animals as well.     

Gold Core‐DNA‐Silver Shell Nanoparticles with Intense Plasmonic Chiroptical Activities

The strong plasmonic chiroptical activities of gold core‐DNA‐silver shell nanoparticles (NPs) are reported for the first time, using cytosine‐rich single‐stranded DNA as the template for the guidance of silver shell growth. The anisotropy factor of the optically active NPs at 420 nm reaches 1.93 × 10^?2. Their chiroptical properties are likely induced by the DNA–plasmon interaction and markedly amplified by the strong electromagnetic coupling between the gold core and silver shell.     

Supramolecular Polymeric Fluorescent Nanoparticles Based on Quadruple Hydrogen Bonds

A facile approach for the preparation of supramolecular polymer‐based fluorescent nanoparticles (FNPs) is reported. FNPs with homogeneous shape and size distribution are fabricated from low‐molecular‐weight molecules, and thus, different compositional constituents can be efficiently incorporated via copolymerization. The emission color of the FNPs covers a wide region from blue to near infrared and can be easily tuned using efficient excitation energy transfer. The photoswitchable fluorescent nanoparticles with high on–off fluorescence contrast are also simply prepared by copolymerization of monomers containing a fluorophore and a photochromic unit. Our FNPs are successfully applied in living cell imaging and as fluorescent inks.     

Maskless Preparation of Spatially-Resolved Plasmonic Nanoparticles on Polydimethylsiloxane via In Situ Fluoride-Assisted Synthesis

Here, a fluoride-assisted route for the controlled in-situ synthesis of metal nanoparticles (NPs) (i.e., AgNPs, AuNPs) on polydimethylsiloxane (PDMS) is reported. The size and coverage of the NPs on the PDMS surface are modulated with time and over space during the synthetic process, leveraging the improved yield (10×) and faster kinetics (100×) of NP formation in the presence of F⁻ ions, compared to fluoride-free approaches. This enables the maskless preparation of both linear and step gradients and patterns of NPs in 1D and 2D on the PDMS surface. As an application in flexible plasmonics/photonics, continuous and step-wise spatial modulations of the plasmonic features of PDMS slabs with 1D and 2D AgNP gradients on the surface are demonstrated. An excellent spatially resolved tuning of key optical parameters, namely, optical density from zero to 5 and extinction ratio up to 100 dB, is achieved with AgNP gradients prepared in AgF solution for 12 minutes; the performance are comparable to those of commercial dielectric/interference filters. When used as a rejection filter in optical fluorescence microscopy, the AgNP-PDMS slabs are able to reject the excitation laser at 405 nm and retain the green fluorescence of microbeads (100 µm) used as test cases.     

Efficiency Enhancement of Organic Solar Cells by Using Shape‐Dependent Broadband Plasmonic Absorption in Metallic Nanoparticles

It is been widely reported that plasmonic effects in metallic nanomaterials can enhance light trapping in organix solar cells (OSCs). However, typical nanoparticles (NP) of high quality (i.e., mono‐dispersive) only possess a single resonant absorption peak, which inevitably limits the power conversion efficiency (PCE) enhancement to a narrow spectral range. Broadband plasmonic absorption is obviously highly desirable. In this paper, a combination of Ag nanomaterials of different shapes, including nanoparticles and nanoprisms, is proposed for this purpose. The nanomaterials are synthesized using a simple wet chemical method. Theoretical and experimental studies show that the origin of the observed PCE enhancement is the simultaneous excitation of many plasmonic low‐ and high‐order resonances modes, which are material‐, shape‐, size‐, and polarization‐dependent. Particularly for the Ag nanoprisms studied here, the high‐order resonances result in higher contribution than low‐order resonances to the absorption enhancement of OSCs through an improved overlap with the active material absorption spectrum. With the incorporation of the mixed nanomaterials into the active layer, a wide‐band absorption improvement is demonstrated and the short‐circuit photocurrent density (J_sc) improves by 17.91%. Finally, PCE is enhanced by 19.44% as compared to pre‐optimized control OSCs. These results suggest a new approach to achieve higher overall enhancement through improving broadband absorption.     

Plasmonic Charge Transfers in Large-Scale Metallic and Colloidal Photonic Crystal Slabs

The challenges in plasmonic charge transfer on a large-scale and low losses are systematically investigated by optical designs using 1D-plasmonic lattice structures. These plasmonic lattices are used as couplers to guide the energy in an underneath sub-wavelength titanium dioxide layer, resulting in the photonic crystal slabs. So far, photodetection is possible at energy levels close to the semiconductor bandgap; however, with the observed hybrid plasmonic–photonic modes, other wavelengths over the broad solar spectrum can be easily accessed for energy harvesting. The photo-enhanced current is measured locally with simple two-point contact on the centimeter-squared nanostructure by applying a bias voltage. As lattice couplers, interference lithographically fabricated conventional gold grating provides an advantage in fabrication; this optical concept is extended for the first time toward colloidal self-assembled nanoparticle chains to make the charge injection accessible for large-scale at reasonable costs with possibilities of photodetection by electric field vectors both along and perpendicular to the grating lines. To discuss the bottleneck of unavoidable isolating ligand shell of nanoparticles in contrast to the directly contacted nanobars, polarization-dependent ultrafast characterizations are carried out to study the charge injection processes in femtosecond resolution.     

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.     

Vertical 3D Printed Forest-Inspired Hierarchical Plasmonic Superstructure for Photocatalysis

Efficient light-harvesting is of significant importance to achieve high solar energy utilization efficiency for various solar-driven technologies. Compared with a 2D planar structure, a 3D plasmonic structure can largely increase the light adsorption/interaction areas and also utilizes the plasmonic effect to achieve much higher light utilization efficiency. However, this remains challenging in terms of structural design, reliable manufacturing, and ability to scale up. Herein, inspired by the light absorption strategy of natural forests, a hierarchical plasmonic superstructure is demonstrated composed of vertical TiO₂ pillar arrays (as tree trunks), dense nanorod arrays (as branches), and a large number of plasmonic Au nanoparticles (as leaves). Such a forest-like plasmonic superstructure can effectively absorb light from the surface plasmonic resonance effects of Au nanoparticles and the multiple scattering of light in the hierarchical branched structure. The strong light absorption and abundant photocatalytic active sites help yield a 15-fold higher nitrogen photo-fixation activity than that of the flat TiO₂ films decorated with Au nanoparticles. The study provides an effective strategy to construct 3D plasmonic superstructures with excellent light-harvesting efficiency and high stability and can be readily applied to a range of light-driven applications     

Encapsulation of Noble Metal Nanoparticles through Seeded Emulsion Polymerization as Highly Stable Plasmonic Systems

The implementation of plasmonic nanoparticles in vivo remains hindered by important limitations such as biocompatibility, solubility in biological fluids, and physiological stability. A general and versatile protocol is presented, based on seeded emulsion polymerization, for the controlled encapsulation of gold and silver nanoparticles. This procedure enables the encapsulation of single nanoparticles as well as nanoparticle clusters inside a protecting polymer shell. Specifically, the efficient coating of nanoparticles of both metals is demonstrated, with final dimensions ranging between 50 and 200 nm, i.e., sizes of interest for bio‐applications. Such hybrid nanocomposites display extraordinary stability in high ionic strength and oxidizing environments, along with high cellular uptake, and low cytotoxicity. Overall, the prepared nanostructures are promising candidates for plasmonic applications under biologically relevant conditions.     

Highly Secure Plasmonic Encryption Keys Combined with Upconversion Luminescence Nanocrystals

This study proposes a novel and highly secure encryption technology based on plasmonic‐enhanced upconversion luminescence (UCL). The technology can be realized by a disordered plasmonic nanostructure composed of a transferred metal nanoparticle–UC nanocrystals (UCNC)–metal (tMUM) film using the graphene transfer process, in which the metal nanoparticles that formed on the graphene layer are transferred using Scotch tape. The plasmonic tMUM film strongly enhances the UCL by a factor of 200 mainly because of the excitation of the gap plasmon polaritons. Meanwhile, the UCNCs in direct contact with the metal film result in luminescence quenching caused by a nonradiative process. Herein, a highly secure anti‐counterfeit film is developed, which is very hard to duplicate and cannot be reused, using two conflicting features (i.e., emission enhancement and quenching phenomena). The UCL is strongly amplified only when the first (i.e., a random metal nanoparticle array) and second (i.e., UCNCs on a Ag film) codes are very precisely overlapped as designed, thereby generating the originally designed final code. Therefore, our novel high‐level security device is expected to be easily applied to protect and identify genuine products.     

Degenerately Hydrogen Doped Molybdenum Oxide Nanodisks for Ultrasensitive Plasmonic Biosensing

Plasmonic biosensors based on noble metals generally suffer from low sensitivities if the perturbation of refractive‐index in the ambient is not significant. By contrast, the features of degenerately doped semiconductors offer new dimensions for plasmonic biosensing, by allowing charge‐based detection. Here, this concept is demonstrated in plasmonic hydrogen doped molybdenum oxides (H_xMoO₃), with the morphology of 2D nanodisks, using a representative enzymatic glucose sensing model. Based on the ultrahigh capacity of the molybdenum oxide nanodisks for accommodating H⁺, the plasmon resonance wavelengths of H_xMoO₃ are shifted into visible‐near‐infrared wavelengths. These plasmonic features alter significantly as a function of the intercalated H⁺ concentration. The facile H⁺ deintercalation out of H_xMoO₃ provides an exceptional sensitivity and fast kinetics to charge perturbations during enzymatic oxidation. The optimum sensing response is found at H_1.55MoO₃, achieving a detection limit of 2 × 10^?9m at 410 nm, even when the biosensing platform is adapted into a light‐emitting diode‐photodetector setup. The performance is superior in comparison to all previously reported plasmonic enzymatic glucose sensors, providing a great opportunity in developing high performance biosensors.     

Self‐Assembly of Nanoparticle‐Spiked Pillar Arrays for Plasmonic Biosensing

Plasmonic biosensors have demonstrated superior performance in detecting various biomolecules with high sensitivity through simple assays. Scaled‐up, reproducible chip production with a high density of hotspots in a large area has been technically challenging, limiting the commercialization and clinical translation of these biosensors. A new fabrication method for 3D plasmonic nanostructures with a high density, large volume of hotspots and therefore inherently improved detection capabilities is developed. Specifically, Au nanoparticle‐spiked Au nanopillar arrays are prepared by utilizing enhanced surface diffusion of adsorbed Au atoms on a slippery Au nanopillar arrays through a simple vacuum process. This process enables the direct formation of a high density of spherical Au nanoparticles on the 1 nm‐thick dielectric coated Au nanopillar arrays without high‐temperature annealing, which results in multiple plasmonic coupling, and thereby large effective volume of hotspots in 3D spaces. The plasmonic nanostructures show signal enhancements over 8.3 × 10⁸‐fold for surface‐enhanced Raman spectroscopy and over 2.7 × 10²‐fold for plasmon‐enhanced fluorescence. The 3D plasmonic chip is used to detect avian influenza‐associated antibodies at 100 times higher sensitivity compared with unstructured Au substrates for plasmon‐enhanced fluorescence detection. Such a simple and scalable fabrication of highly sensitive 3D plasmonic nanostructures provides new opportunities to broaden plasmon‐enhanced sensing applications.     

Ultrabroadband Optical Superchirality in a 3D Stacked‐Patch Plasmonic Metamaterial Designed by Two‐Step Glancing Angle Deposition

Low‐cost and large‐scale fabrication of 3D chiral metamaterials is highly desired for potential applications such as nanophotonics devices and chiral biosensors. One of the promising fabrication methods is to use glancing angle deposition (GLAD) of metal on self‐assembled dielectric microsphere array. However, structural handedness varies locally due to long‐range disorder of the array and therefore large‐scale realization of the same handedness is impossible. Here, using symmetry considerations a two‐step GLAD process is proposed to eliminate this longstanding problem. In the proposed scheme, the unavoidable long‐range disorder gives rise to microscale domains of the same handedness but of slightly different structural geometries and ultimately contributes to a broad‐band response. Experimentally, a record‐breaking superchiral response of circular dichroism signal of ≈11° is demonstrated and an average polarization rotation angle of 27° in the visible region on ≈1 cm² sample is observed. Computer‐aided geometric reconstruction with experimental parameters unambiguously reveal the presence of strong structural anisotropy and chirality in the prepared stacked‐patch plasmonic chiral metamaterial; microscopic spectral analyses combined with full‐wave electromagnetic simulations coherently provide deeper insights into the measured circular dichroism and optical activity. The observed chiroptical response can also be flexibly controlled by adjusting the deposition parameters for various potential applications.     

Metallic Nanowire Coupled CsPbBr3 Quantum Dots Plasmonic Nanolaser

Plasmonic nanolasers provide a valuable opportunity for expanding sub-wavelength applications. Due to the potential of on-chip integration, semiconductor nanowire (NW)-based plasmonic nanolasers that support the waveguide mode attract a high level of interest. To date, perovskite quantum dots (QDs) based plasmonic lasers, especially nanolasers that support plasmonic-waveguide mode, are still a challenge and remain unexplored. Here, metallic NW coupled CsPbBr₃ QDs plasmonic-waveguide lasers are reported. By embedding Ag NWs in QDs film, an evolution from amplified spontaneous emission with a full width at half maximum (FWHM) of 6.6 nm to localized surface plasmon resonance (LSPR) supported random lasing is observed. When the pump light is focused on a single Ag NW, a QD-NW coupled plasmonic-waveguide laser with a much narrower emission peak (FWHM = 0.4 nm) is realized on a single Ag NW with the uniform polyvinylpyrrolidone layer. The QDs serve as the gain medium while the Ag NW serves as a resonant cavity and propagating plasmonic lasing modes. Furthermore, by pumping two Ag NWs with different directions, a dual-wavelength lasing switch is realized. The demonstration of metallic NW coupled QDs plasmonic nanolaser would provide an alternative approach for ultrasmall light sources as well as fundamental studies of light matter interactions.     

Human Platelet Membrane Functionalized Microchips with Plasmonic Codes for Cancer Detection

The possibility of functional roles played by platelets in close alliance with cancer cells has inspired the design of new biomimetic systems that exploit platelet–cancer cell interactions. Here, the role of platelets in cancer diagnostics is leveraged to design a microfluidic platform capable of detecting cancer‐derived extracellular vesicles (EVs) from ultrasmall volumes (1 µL) of human plasma samples. Further, the captured EVs are counted by direct optical coding of plasmonic nanoprobes modified with EV‐specific antibodies. Owing to the inherent properties of platelets for multifaceted interaction with cancer cells, the microfluidic chip equipped with a biologically interfaced platelet membrane‐cloaked surface (denoted “PLT‐Chip”) can capture a significantly higher number of EVs from multiple types of cancer cell lines (prostate, lung, bladder, and breast) than the normal cell‐derived EVs. Furthermore, this chip allows the monitoring of the growth of tumor spheroids (100 µm–2.5 mm) and clearly distinguishes the plasma of cancer patients from that of normal healthy controls. This robust, multifaceted, and cancer‐specific binding affinity, coupled with excellent biocompatibility, is a unique feature of platelet membrane‐cloaked surfaces, which therefore represent promising alternatives to antibodies for application in EVs‐based cancer theranostics.     

Plasmonic Nanoneedle Arrays with Enhanced Hot Electron Photodetection for Near-IR Imaging

Hot electron photodetection based on metallic nanostructures is attracting significant attention due to its potential to overcome the limitation of the traditional semiconductor bandgap. To enable efficient hot electron photodetection for practical applications, it is necessary to achieve broadband and perfect light absorption within extremely thin plasmonic nanostructures using cost-effective fabrication techniques. In this study, an ultrahigh optical absorption (up to 97.3% in average across the spectral range of 1200−2400 nm) is demonstrated in the ultrathin plasmonic nanoneedle arrays (NNs) with thickness of 10 nm, based on an all-wet metal-assisted chemical etching process. The efficient hot electron generation, transport, and injection at the nanoscale apex of the nanoneedles facilitate the photodetector to achieve a record low noise equivalent power (NEP) of 4.4 × 10⁻¹² W Hz^−0.5 at the wavelength of 1300 nm. The hot-electron generation and injection process are elucidated through a transport model based on a Monte Carlo approach, which quantitatively matches the experimental data. The photodetector is further integrated into a light imaging system, as a demonstration of the exceptional imaging capabilities at the near-IR regime. The study presents a lithography-free, scalable, and cost-effective approach to enhance hot electron photodetection, with promising prospects for future imaging systems.