Enhanced Plasmonic Trapping and Fluorescent Emission of Nitrogen-Vacancy Nanodiamonds Using a High-Efficiency Nanofocusing Device.

Fluorescent nanodiamonds (FNDs) with nitrogen-vacancy centers are pivotal for advancing quantum photonics and imaging through deterministic quantum state manipulation. However, deterministic integration of quantum emitters into photonic devices remains a challenge due to the need for high coupling efficiency and Purcell enhancement. We report a deterministic FND-integrated nanofocusing device achieved by assembling FNDs at a plasmonic waveguide tip through plasmonic-enhanced optical trapping. This technique not only increases the emission rate by 58.6 times compared to isolated FNDs but also preferentially directs radiation into the waveguide at a rate 5.3 times higher than that into free space, achieving an exceptional figure-of-merit of ∼3000 for efficient energy transfer. Our findings represent a significant step toward deterministic integration in quantum imaging and communication, opening new avenues for quantum technology advancements.

Synchronizing Efficient Purification of VOCs in Durable Solar Water Evaporation over a Highly Stable Cu/W18O49@Graphene Material.

Solar-driven clean water production is challenged by VOCs (volatile organic compounds), which pose health risks in distilled water. Herein, we developed a Cu/W18O49@Graphene photothermal-photocatalytic material addressing VOCs contamination. Plasmonic coupling between Cu and W18O49 enhances light absorption, and 1-2 layers of graphene encapsulation protects oxygen vacancies within W18O49 while facilitating hot electron extraction, effectively mitigating their ultrafast relaxation. Density functional theory calculations revealed enhanced VOCs adsorption on graphene. These synergies address oxygen vacancy decay in W18O49 and provide more active sites for gas-liquid-solid triphase photocatalytic reactions. Integrated with a three-dimensional floating evaporator substrate, the optimized Cu/W18O49@Graphene material achieved an effective water evaporation rate of 1.41 kg m-2 h-1 (efficiency of 88.6%), exceptional stability (>120 h), and remarkable 99% phenol removal under 1 sun irradiation (1 kW m-2). This work provides a promising solution to mitigate VOCs contamination in solar-driven water evaporation.

Advancing COVID-19 Diagnosis: Enhancement in SERS-PCR with 30-nm Au Nanoparticle-Internalized Nanodimpled Substrates.

Real-time polymerase chain reaction (RT-PCR) with fluorescence detection is the gold standard for diagnosing coronavirus disease 2019 (COVID-19) However, the fluorescence detection in RT-PCR requires multiple amplification steps when the initial deoxyribonucleic acid (DNA) concentration is low. Therefore, this study has developed a highly sensitive surface-enhanced Raman scattering-based PCR (SERS-PCR) assay platform using the gold nanoparticle (AuNP)-internalized gold nanodimpled substrate (AuNDS) plasmonic platform. By comparing different sizes of AuNPs, it is observed that using 30 nm AuNPs improves the detection limit by approximately ten times compared to 70 nm AuNPs. Finite-difference time-domain (FDTD) simulations show that multiple hotspots are formed between AuNPs and the cavity surface and between AuNPs when 30 nm AuNPs are internalized in the cavity, generating a strong electric field. With this 30 nm AuNPs-AuNDS SERS platform, the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) ribonucleic acid (RNA)-dependent RNA polymerase (RdRp) can be detected in only six amplification cycles, significantly improving over the 25 cycles required for RT-PCR. These findings pave the way for an amplification-free molecular diagnostic system based on SERS.

Single-Step Plasmonic Dimer Printing by Gold Nanorod Splitting with Light.

Optical printing is a flexible strategy to precisely pattern plasmonic nanoparticles for the realization of nanophotonic devices. However, the generation of strongly coupled plasmonic dimers by sequential particle printing can be a challenge. Here, we report an approach to generate and pattern dimer nanoantennas in a single step by optical splitting of individual gold nanorods with laser light. We show that the two particles that constitute the dimer can be separated by sub-nanometer distances. The nanorod splitting process is explained by a combination of plasmonic heating, surface tension, optical forces, and inhomogeneous hydrodynamic pressure introduced by a focused laser beam. This realization of optical dimer formation and printing from a single nanorod provides a means for dimer patterning with high accuracy for nanophotonic applications.

Reversible Modulation of Plasmonic Coupling of Gold Nanoparticles Confined within Swellable Polymer Colloidal Spheres.

Dynamic optical modulation in response to stimuli provides exciting opportunities for designing novel sensing, actuating, and authentication devices. Here, we demonstrate that the reversible swelling and deswelling of crosslinked polymer colloidal spheres in response to pH and temperature changes can be utilized to drive the assembly and disassembly of the embedded gold nanoparticles (AuNPs), inducing their plasmonic coupling and decoupling and, correspondingly, color changes. The multi-responsive colloids are created by depositing a monolayer of AuNPs on the surface of resorcinol-formaldehyde (RF) nanospheres, then overcoating them with an additional RF layer, followed by a seeded growth process to enlarge the AuNPs and reduce their interparticle separation to induce significant plasmonic coupling. This configuration facilitates dynamic modulation of plasmonic coupling through the reversible swelling/deswelling of the polymer spheres in response to pH and temperature changes. The rapid and repeatable transitions between coupled and decoupled plasmonic states of AuNPs enable reversible color switching when the polymer spheres are in colloidal form or embedded in hydrogel substrates. Furthermore, leveraging the photothermal effect and stimuli-responsive plasmonic coupling of the embedded AuNPs enables the construction of hybrid hydrogel films featuring switchable anticounterfeiting patterns, showcasing the versatility and potential of this multi-stimuli-responsive plasmonic system.

Modulating the Charge Transfer Plasmon in Bridged Au Core-Satellite Homometallic Nanostructures.

The localized surface plasmon resonance (LSPR) is one of the important properties for noble metal nanoparticles. Tuning the LSPR on demand thus has attracted tremendous interest. Beyond the size and shape control, manipulating intraparticle coupling is an effective way to tailor their LSPR. The charge transfer plasmon (CTP) is the most important mode of conductive coupling between subunits linked by conductive bridges that are well studied for structures prepared on substrates by lithography method. However, the colloidal synthesis of CTP structure remains a great challenge. This work reports the colloidal synthesis of extraordinary bridged Au core-satellite structures by exploiting the buffer effect of polydopamine shell on Au core for Au atom diffusion, in which the Au bridge is well controlled in terms of width and length. Benefiting from the tunable Au bridges, the resonance energy of the CTP can be readily controlled. As a result, the LSPR absorptions of the core-satellite structures are continuously tuned within the NIR spectral range (from 900 to >1300 nm), demonstrating their great potentials for ultrafast nano-optics and biomedical applications.

Effective plasmonic spectroscopic amplifiers for hyper-Raman scattering process.

In an asymmetric Au cubic trimer, influence of the rotation angle (θ) and side length (w) on both plasmonic coupling features and corresponding enhancement factor of hyper-Raman scattering (HRS) process have been investigated comprehensively under the illumination of a longitudinally polarized light. The finite-difference time-domain (FDTD) electrodynamic simulation tool has been employed to calculate the optical cross-section and associated nearfield intensity of the irradiated coupled resonators. Asθincreases, the polarization state that dominates the coupling phenomenon is gradually switched from facing sides into facing edges which results in (1) a dramatic change in the spectral response of the trimer and (2) a significant improvement in the nearfield intensity that is directly related to the improvement of HRS signal. Breaking size symmetry of the cubic trimer provides a novel approach to reach the desired spectral response that permits such trimer to be used as an active substrate for HRS procedures. After optimizing both the orientation angle and size of the interacting plasmonic characters forming of the trimer, the enhancement factor of HRS process can reach a value never reported before as high as 1 × 1021.

Phase imaging of transition from classical to quantum plasmonic couplings between a metal nanoparticle and a metal surface.

When a metal nanoparticle is brought near to a metal surface within electron tunneling distance (∼1 nm), classical electromagnetic coupling between the nanoparticle and the metal is expected to transition to quantum coupling. We show that this transition can be observed as a drastic phase change in the surface plasmon resonance (SPR) images of the gold nanoparticles. We study the transition by controlling the distance between the nanoparticles and electrode surface, modeling the impact of the transition on the SPR image in terms of a phase shift and demonstrating detection of microRNA based on the transition from classical to quantum coupling. The work shows that the quantum coupling can be directly visualized in SPR, and the extremely sensitive dependence of the transition on distance leads to a biosensing principle with SPR.

Thickness-Sensing Sandwiched Plasmonic Biosensors Enable Label-Free Naked-Eye Antibody Quantification.

Clinical serology assays for detecting the antibodies of the virus are time-consuming, are less sensitive/selective, or rely on sophisticated detection instruments. Here, we develop a sandwiched plasmonic biosensor (SPB) for supersensitive thickness-sensing via utilizing the distance-dependent electromagnetic coupling in sandwiched plasmonic nanostructures. SPBs quantitatively amplify the thickness changes on the nanoscale range (sensitivity: ∼2% nm-1) into macroscopically visible signals, thereby enabling the rapid, label-free, and naked-eye detection of targeted biomolecular species (via the thickness change caused by immunobinding events). As a proof of concept, this assay affords a broad dynamic range (7 orders of magnitude) and a low LOD (∼0.3 pM), allowing for the extremely accurate SARS-CoV-2 antibody quantification (sensitivity/specificity: 100%/∼99%, with a portable optical fiber device). This strategy is suitable for high-throughput multiplexed detection and smartphone-based sensing at the point-of-care, which can be expanded for various sensing applications beyond the fields of viral infections and vaccination.

Spacer Matters: All-Peptide-Based Ligand for Promoting Interfacial Proteolysis and Plasmonic Coupling.

Plasmonic coupling via nanoparticle assembly is a popular signal-generation method in bioanalytical sensors. Here, we customized an all-peptide-based ligand that carries an anchoring group, polyproline spacer, biomolecular recognition, and zwitterionic domains for functionalizing gold nanoparticles (AuNPs) as a colorimetric enzyme sensor. Our results underscore the importance of the polyproline module, which enables the SARS-CoV-2 main protease (Mpro) to recognize the peptidic ligand on nanosurfaces for subsequent plasmonic coupling via Coulombic interactions. AuNP aggregation is favored by the lowered surface potential due to enzymatic unveiling of the zwitterionic module. Therefore, this system provides a naked-eye measure for Mpro. No proteolysis occurs on AuNPs modified with a control ligand lacking a spacer domain. Overall, this all-peptide-based ligand does not require complex molecular conjugations and hence offers a simple and promising route for plasmonic sensing other proteases.

Adhesive surface-enhanced Raman scattering Cu-Au nanoassembly for the sensitive analysis of particulate matter.

Surface-enhanced Raman scattering (SERS) has been used in atmospheric aerosol detection as it enables the high-resolution analysis of particulate matter. However, its use in the detection of historical samples without damaging the sampling membrane while achieving effective transfer and the high-sensitivity analysis of particulate matter from sample films remains challenging. In this study, a new type of SERS tape was developed, consisting of Au nanoparticles (NPs) on an adhesive double-sided Cu film (DCu). The enhanced electromagnetic field generated by the coupled resonance of the local surface plasmon resonances of AuNPs and DCu led to an enhanced SERS signal with an experimental enhancement factor of 107. The AuNPs were semi-embedded and distributed on the substrate, and the viscous DCu layer was exposed, enabling particle transfer. The substrates exhibited good uniformity and favorable reproducibility with relative standard deviations of 13.53% and 9.74% respectively, and the substrates could be stored for 180 days with no signs of signal weakening. The application of the substrates was demonstrated by the extraction and detection of malachite green and ammonium salt particulate matter. The results demonstrated that SERS substrates based on AuNPs and DCu are highly promising in real-world environmental particle monitoring and detection.

Anisotropic metallic heterotrimer systems for an ultrahigh plasmonic-based improvement of hyper-Raman scattering signal.

An anisotropic metallic trimer is proposed as an active plasmonic substrate for an ultrahigh enhancement in the spectroscopic signal of the hyper-Raman scattering (HRS) process. The suggested three-particle system is composed from non-aligned asymmetric nanoparticles of a cubic shape. The interacting resonators are made of gold material and illuminated by a longitudinally polarized light. The non-alignment condition in the heterotrimer is achieved by shifting the intermediate cube transversely away from the interparticle axis. Optical cross-section, nearfield distribution and charge density are calculated by using the finite-difference time-domain electrodynamic simulation tool. The enhancement factor of the HRS is calculated theoretically from the nearfield intensity associated with the resonance phenomenon of the considered trimer. The extinction profile of the illuminated system exhibits the excitation of two plasmonic modes. A superradiant mode observed in the longer wavelength region which resulted from the in-phase coupling between the plasmonic modes excited in each one of the three resonators. The second mode is a subradiant band emerged from the interference between bright and dark modes. The resonance wavelength of these two modes matches the excitation one and the second-order Stockes condition, respectively. After optimizing the value of both the transverse shift and the gap spacing, the enhancement factor of the HRS can reach as high as a value never reported before of 1 × 1018.

Metallic spherical heterotrimer systems for plasmonic-based improvement in hyper-Raman scattering.

A unique combination between structural parameters of collinearly arranged spherical particles is proposed as an effective plasmonic substrate for ultrahigh enhancement in hyper-Raman scattering signals. The suggested spherical trimer systems are mainly composed from two identical nanoparticle separated by a third alike shape resonator of different size. All the interacting plasmonic element are made from gold, arranged in 1D array and illuminated by a longitudinally polarized light. The optical properties, spatial distribution of nearfields and the surface charge densities were calculated numerically by FDTD tool. The enhancement factor of the hyper-Raman scattering, and the associated Raman shift were calculated theoretically from the optical response of the trimer. The extinction spectra of the heterotrimers demonstrate the excitation of two plasmonic modes, the first coupled band excited at a longer wavelength and is attributed to the in-phase coupling between the dipole moments induced in each of the three spherical resonators, the other hybrid mode observed in the shorter wavelength region and is resulted from the coupling between the dark mode excited in the intermediate particle and the bright band monitored in the bordered particles. The nearfields associated with the excitation of the two plasmonic modes are strongly localized and highly enhanced at the same intercoupling regions (hot spots) which optically match the excitation wavelength and the second-order stock condition. Through careful selecting of the relative size of the coupled nanoparticles and their coupling separation, the enhancement factor of hyper-Raman scattering signal can reach as high as 1 × 1013.

Collective multipole oscillations direct the plasmonic coupling at the nanojunction interfaces.

We present a systematic study of the effect of higher-multipolar order plasmon modes on the spectral response and plasmonic coupling of silver nanoparticle dimers at nanojunction separation and introduce a coupling mechanism. The most prominent plasmonic band within the extinction spectra of coupled resonators is the dipolar coupling band. A detailed calculation of the plasmonic coupling between equivalent particles suggests that the coupling is not limited to the overlap between the main bands of individual particles but can also be affected by the contribution of the higher-order modes in the multipolar region. This requires an appropriate description of the mechanism that goes beyond the general coupling phenomenon introduced as the plasmonic ruler equation in 2007. In the present work, we found that the plasmonic coupling of nearby Ag nanocubes does not only depend on the plasmonic properties of the main band. The results suggest the decay length of the higher-order plasmon mode is more sensitive to changes in the magnitude of the interparticle axis and is a function of the gap size. For cubic particles, the contribution of the higher-order modes becomes significant due to the high density of oscillating dipoles localized on the corners. This gives rise to changes in the decay length of the plasmonic ruler equation. For spherical particles, as the size of the particle increases (i.e., ≥80 nm), the number of dipoles increases, which results in higher dipole-multipole interactions. This exhibits a strong impact on the plasmonic coupling, even at long separation distances (20 nm).

Quantifiable Effect of Interparticle Plasmonic Coupling on Sensitivity and Tuning Range for Wavelength-Mode LSPR Fiber Sensor Fabricated by Simple Immobilization Method.

Herein a gold nanosphere (AuNS)-coated wavelength-mode localized surface plasmon resonance (LSPR) fiber sensor was fabricated by a simple and time-saving electrostatic self-assembly method using poly(allylamine hydrochloride). Based on the localized enhanced coupling effect between AuNSs, the LSPR spectrums of the AuNS monolayer with good dispersity and high density exhibited a favourable capability for refractive index (RI) measurement. Based on the results obtained from the optimization for AuNS distribution, sensing length, and RI range, the best RI sensitivity of the fiber modified by 100 nm AuNS reached up to about 2975 nm/RIU, with the surrounding RI range from 1.3322 to 1.3664. Using an 80 nm AuNS-modified fiber sensor, the RI sensitivity of 3953 nm/RIU was achieved, with the RI range increased from 1.3744 to 1.3911. The effect of sensing length to RI sensitivity was proven to be negligible. Furthermore, the linear relationship between the RI sensitivity and plasma resonance frequency of the bulk metal, which was dependent on the interparticle plasmon coupling effect, was quantified. Additionally, the resonance peak was tuned from 539.18 nm to 820.48 nm by different sizes of AuNSs-coated fiber sensors at a RI of 1.3322, which means the spectrum was extended from VIS to NIR. It has enormous potential in hypersensitive biochemistry detection at VIS and NIR ranges.

Visualization of Plasmonic Couplings Using Ultrafast Electron Microscopy.

Hybrids of graphene and metal plasmonic nanostructures are promising building blocks for applications in optoelectronics, surface-enhanced scattering, biosensing, and quantum information. An understanding of the coupling mechanism in these hybrid systems is of vital importance to its applications. Previous efforts in this field mainly focused on spectroscopic studies of strong coupling within the hybrids with no spatial resolution. Here we report direct imaging of the local plasmonic coupling between single Au nanocapsules and graphene step edges at the nanometer scale by photon-induced near-field electron microscopy in an ultrafast electron microscope for the first time. The proximity of a step in the graphene to the nanocapsule causes asymmetric surface charge density at the ends of the nanocapsules. Computational electromagnetic simulations confirm the experimental observations. The results reported here indicate that this hybrid system could be used to manipulate the localized electromagnetic field on the nanoscale, enabling promising future plasmonic devices.

Transverse and longitudinal coupling of LSPPs in isolated triangular Al-SiO2-Al hybrid nanoplates for generation of local electromagnetic fields with enhanced intensity and increased decay time.

Achieving a large enhancement of local electromagnetic fields in the ultraviolet waveband is desirable for some applications such as surface-enhanced Raman scattering and surface-enhanced fluorescence. In addition, it is more significant for some applications such as plasmon-enhanced harmonic generation to enhance the intensity of local electromagnetic fields and increase their decay time at the same time. In this paper, using the finite-difference time-domain method, we numerically demonstrate that using the linearly polarized light with a wavelength of 325 nm as the illumination light, an isolated triangular Al-SiO2-Al hybrid nanoplate with optimized geometric parameters can produce a local electric field enhanced by a factor of about 108 at one of its top apexes, and produce two local electric fields enhanced by a factor of about 150 at two transverse dielectric/metal interfaces of one of its longitudinal side edges. Moreover, we also numerically demonstrate that the decay time of enhanced local electric fields produced by the isolated triangular Al-SiO2-Al hybrid nanoplate is about 1.6 times as large as that of enhanced local electric fields produced by an isolated triangular Al nanoplate. These unique properties of the isolated triangular Al-SiO2-Al hybrid nanoplate arise because of both the transverse coupling and the longitudinal coupling of localized surface plasmon polaritons in this structure. Our findings make triangular Al-SiO2-Al hybrid nanoplates very promising for application in many fields such as surface-enhanced Raman scattering and plasmon-enhanced harmonic generation.

Self-assembly of Janus Dumbbell Nanocrystals and Their Enhanced Surface Plasmon Resonance.

Self-assembly is a critical process that can greatly expand the existing structures and lead to new functionality of nanoparticle systems. Multicomponent superstructures self-assembled from nanocrystals have shown promise as multifunctional materials for various applications. Despite recent progress in assembly of homogeneous nanocrystals, synthesis and self-assembly of Janus nanocrystals with contrasting surface chemistry remains a significant challenge. Herein, we designed a novel Janus nanocrystal platform to control the self-assembly of nanoparticles in aqueous solutions by balancing the hydrophobic and hydrophilic moieties. A series of superstructures have been assembled by systematically varying the Janus balance and assembly conditions. Janus Au-Fe3O4 dumbbell nanocrystals (<20 nm) were synthesized with the hydrophobic ligands coated on the Au lobe and negatively charged hydrophilic ligands coated on the Fe3O4 lobe. We systematically fine-tune the lobe size ratio, surface coating, external conditions, and even additional growth of Au nanocrystal domains on the Au lobe of dumbbell nanoparticles (Au-Au-Fe3O4) to harvest self-assembly structures including clusters, chains, vesicles, and capsules. It was discovered that in all these assemblies the hydrophobic Au lobes preferred to stay together. In addition, these superstructures clearly demonstrated different levels of enhanced surface plasmon resonance that is directly correlated with the Au coupling in the assembly structure. The strong interparticle plasmonic coupling displayed a red-shift in surface plasmon resonance, with larger structures formed by Au-Au-Fe3O4 assembly extending into the near-infrared region. Self-assembly of Janus dumbbell nanocrystals can also be reversible under different pH values. The biphasic Janus dumbbell nanocrystals offer a platform for studying the novel interparticle coupling and open up opportunities in applications including sensing, disease diagnoses, and therapy.

Electrically Controlled Nano and Micro Actuation in Memristive Switching Devices with On-Chip Gas Encapsulation.

Nanoactuators are a key component for developing nanomachinery. Here, an electrically driven device yielding actuation stresses exceeding 1 MPa withintegrated optical readout is demonstrated. 10 nm thick Al2 O3 electrolyte films are sandwiched between graphene and Au electrodes. These allow reversible room-temperature solid-state redox reactions, producing Al metal and O2 gas in a memristive-type switching device. The resulting high-pressure oxygen micro-fuel reservoirs are encapsulated under the graphene, swelling to heights of up to 1 µm, which can be dynamically tracked by plasmonic rulers. Unlike standard memristors where the memristive redox reaction occurs in single or few conductive filaments, the mechanical deformation forces the creation of new filaments over the whole area of the inflated film. The resulting on-off resistance ratios reach 108 in some cycles. The synchronization of nanoactuation and memristive switching in these devices is compatible with large-scale fabrication and has potential for precise and electrically monitored actuation technology.

Deterministic Coupling of Quantum Emitters in 2D Materials to Plasmonic Nanocavity Arrays.

Quantum emitters in two-dimensional materials are promising candidates for studies of light-matter interaction and next generation, integrated on-chip quantum nanophotonics. However, the realization of integrated nanophotonic systems requires the coupling of emitters to optical cavities and resonators. In this work, we demonstrate hybrid systems in which quantum emitters in 2D hexagonal boron nitride (hBN) are deterministically coupled to high-quality plasmonic nanocavity arrays. The plasmonic nanoparticle arrays offer a high-quality, low-loss cavity in the same spectral range as the quantum emitters in hBN. The coupled emitters exhibit enhanced emission rates and reduced fluorescence lifetimes, consistent with Purcell enhancement in the weak coupling regime. Our results provide the foundation for a versatile approach for achieving scalable, integrated hybrid systems based on low-loss plasmonic nanoparticle arrays and 2D materials.