3D Plasmonic Nanostructures Research Articles

Laser‐Printed Plasmonic Metasurface Supporting Bound States in the Continuum Enhances and Shapes Infrared Spontaneous Emission of Coupled HgTe Quantum Dots

AbstractIn order to advance the development of quantum emitter‐based devices, it is essential to enhance light‐matter interactions through coupling between semiconductor quantum dots with high quality factor resonators. Here, efficient tuning of the emission properties of HgTe quantum dots in the infrared spectral region is demonstrated by coupling them to a plasmonic metasurface that supports bound states in the continuum. The plasmonic metasurface, composed of an array of gold nanobumps, is fabricated using single‐step direct laser printing, opening up new opportunities for creating exclusive 3D plasmonic nanostructures and advanced photonic devices in the infrared region. A 12‐fold enhancement of the photoluminescence in the 900–1700 nm range is observed under optimal coupling conditions. By tuning the geometry of the plasmonic arrays, controllable shaping of the emission spectra is achieved, selectively enhancing specific wavelength ranges across the emission spectrum. The observed enhancement and shaping of the emission are attributed to the Purcell effect, as corroborated by systematic measurements of radiative lifetimes and optical simulations based on the numerical solution of Maxwell's equations. Moreover, coupling of the HgTe photoluminescence to high quality factor modes of the metasurface improves emission directivity, concentrating output within an ≈20° angle.

Large-scale assembly of geometrically diverse metal nanoparticles-based 3D plasmonic DNA nanostructures for SERS detection of PNK in cancer cells

The organization of geometrically diverse metal nanoparticles into a core/satellite structure at a large scale is a promising strategy for improve SERS performance due to hot spots localized enrichment and signal increase. However, due to the lack of extensional frames and strong electrostatic repulsion between plasma NPs, the fabrication of such 3D architectures with a high-density periodic hotspot in the focus volume has proven exceedingly difficult. Herein, we demonstrate a facile large-scale assembly of geometrically diverse metal nanoparticles strategy for constructing spatially extended 3D plasmonic nanostructures resembling “signal towers” based on RCA-mediated periodic organization of gold nanospheres (GNS) surrounding gold nanorods (GNRs). Using cancer cell T4 PNK as a model, a padlock probe with 5′- hydroxyl (P-circle) was designed as the T4 PNK substrate. The center Au nanorod was coated with P1 and served as a “pedestal” to allow substantial loading of P-circle after target phosphorylation to initiate the rolling ring amplification reaction (RCA). The resultant DNA nanowire serves as an “antenna” to successively lock numerous Raman reporter P2 (Cy3-P2-SH) through base pairing at regular intervals. Finally, the 3D plasma DNA nanostructures that resemble “signal towers” could be obtained by placing a large number of GNS with a strong affinity for Au–S. The proposed 3D SERS sensor exhibited a sensitivity of LOD as low as 0.274 mU/mL, which was attributed to a substantial electromagnetic field enhancement at the inter-nanoparticle gaps between the adjacent pedestal and antenna. Moreover, by exploiting the synergistic effect of the periodically extended DNA scaffold generated by RCA amplification and the co-assembly of thiol ligand, the loaded GNS can be extended to three-dimensional space, forming a high-density periodic hotspot in the focal volume, thereby ensuring high enhancement and high reproducibility of Raman signals. In addition, this method can be used to quantify T4 PNK in HeLa cells, demonstrating its applicability in diagnosing and estimating PNK-related diseases in complex fluids.

3D Plasmonic Nanostructure-Based Polarized ECL Sensor for Exosome Detection in Tumor Microenvironment.

Exosomes of cancer cells play an important role in the proliferation, adhesion, and migration of tumors. Especially, exosomes in the tumor microenvironment can reflect the proliferation of tumors directly, thus serving as ideal referenced markers of the possibility and grade of malignancy in neoplasms. However, the sensitive and accurate detection of exosomes remains challenging. In this work, a novel three-dimensional (3D) plasmonic nanostructure was constructed for exosomal miRNA detection. It combined the advantages of Au nanostar monolayer and Ag nanowire monolayer to provide multiple hot spots. Moreover, Au nanostar monolayer changed the isotropic electrochemiluminescence (ECL) into polarized emission. The Ag nanowire monolayer worked as waveguides for the light direction. As a result, the polarized resolution and intensity of ECL signal were improved. The polarized ECL emission was significantly increased by 47.1 times. This high-resolution polarized ECL sensor was used for detecting exosomal miRNA-146b-5p in the thyroid tumor microenvironment. This sensor showed the linear range from 1 fM to 1 nM with a detection limit of 0.3 fM. The satisfactory results indicated the developed 3D plasmonic nanostructure-based ECL sensor had great potential in biosensing and clinical diagnosis.

Fabrication of core shell Au@Ag supraparticles with 3D hotspots via evaporation self-assembly for sensitive surface enhanced Raman scattering detection

Three-dimensional (3D) plasmonic nanostructures exhibit excellent surface-enhanced Raman scattering (SERS) performance for detecting trace analytes. Nevertheless, fabrication of 3D plasmonic SERS substrates with non-close packed structures via simple evaporation assembly still remains a challenge. Here, we successfully prepared 3D supraparticles in millimeter scale via a simple evaporation assembly of highly concentrated core-shell Au@Ag nanoparticles (NPs) on hydrophobic surface. The formation of supraparticles could account for hydrophobic condensation effect, the huge numbers of spherical NPs, and unique core shell structure of Au@Ag NPs. Such supraparticle was consisting of more than 104 of Au@Ag NPs where nanogaps among NPs created plenty of 3D “hotspots”. The supraparticles with non-close packed structure is benefit for the diffusion of more targets into the hotspots, leading to enhanced interactions that contribute to a higher sensitivity. It was demonstrated that supraparticles could provide great enhancement for SERS behavior, which was eight folds higher than that of Au@Ag NPs assembled 3D multilayered structures. In addition, supraparticles with excellent sensitivity and high reproducibility were successfully applied in the detection of pesticide and antibiotics both in organic and aqueous solvents. This work provides a new way for the fabrication of 3D plasmonic nanostructures with highly sensitive and reproducible SERS performance.

Soft Plasmene Helical Nanostructures

AbstractPlasmene is recently defined as 2D arrays of plasmonic nanoparticles, which could be fabricated by the bottom‐up self‐assembly approach and demonstrated a wide range of applications in sensing, energy harvesting, nanophotonics and encryption. Herein, this work further demonstrates a 3D helical plasmonic nanostructures that can be fabricated from 2D plasmene nanosheet. Inspired by chocolate curls‐making process, a micro‐spatula‐based strategy is developed to selectively scrape substrate‐supported plasmene to free space, which spontaneously folds the plasmene nanosheet into various complex helical nanostructures with controlled dimensions. 3D nanospirals can also be obtained by focus ion beam (FIB)‐based lithography on free‐standing plasmene. Helical plasmene structures are robust, exhibiting elastic mechanical properties and chiral optical response. This methodology represents a versatile fabrication route combining both bottom‐up and top‐down approaches to create soft plasmonic helical structures for potential applications in next‐generation flexible nanophotonic devices.

Rapid and flexible construction of inverted silicon architectures with nanogaps as high-performance SERS substrates

Three-dimensional (3D) plasmonic nanostructures act as excellent surface-enhanced Raman spectroscopy (SERS) substrates for detecting trace analytes. Nevertheless, an efficient 3D architecture and the optimal fabrication route remain to be uncovered to further raise the performance of 3D SERS substrates and expand application horizons. This work reports a cost-effective and flexible route to fabricate 3D inverted silicon (Si) architectures with nanogaps that are difficult to achieve by conventional lithography towards SERS applications. Finite-difference time-domain simulations demonstrated that the distribution of electrical field depended significantly on the architecture and layout of inverted pyramids. Several parameters including volume ratio of HF/HNO3 mixtures, indentation force and etching time were evaluated to determine optimal fabrication process of inverted Si architecture. Based on an electrochemical dissolution model and molecular dynamic simulations, the rapid selective etching can be ascribed to nanocrystals in amorphous Si (a-Si) regions, and distorted Si beneath a-Si layer. SERS detection illustrated an impressive sensitivity and excellent reproducibility, and the practical applicability of as-prepared SERS substrates was demonstrated by detecting malachite green residues from different water environments as well as fish tissues and scales. The proposed selective etching provides a brand-new route for manufacturing high-performance 3D architecture substrates for SERS applications.

Nonlinear light amplification via 3D plasmonic nanocavities.

Plasmonic nanocavities offer prospects for the amplification of inherently weak nonlinear responses at subwavelength scales. However, constructing these nanocavities with tunable modal volumes and reduced optical losses remains an open challenge in the development of nonlinear nanophotonics. Herein, we design and fabricate three-dimensional (3D) metal-dielectric-metal (MDM) plasmonic nanocavities that are capable of amplifying second-harmonic lights by up to three orders of magnitude with respect to dielectric-metal counterparts. In combination with experimental estimations of quantitative contributions of constituent parts in proposed 3D MDM designs, we further theoretically disclose the mechanism governing this signal amplification. We discover that this phenomenon can be attributed to the plasmon hybridization of both dipolar plasmon resonances and gap cavity resonances, such that an energy exchange channel can be attained and helps expand modal volumes while maintaining strong field localizations. Our results may advance the understanding of efficient nonlinear harmonic generations in 3D plasmonic nanostructures.

Solid-state thermal dewetted silver nanoparticles onto electrochemically grown self-standing vertically aligned ZnO nanorods for three-dimensional plasmonic nanostructures

Three dimensional (3D) plasmonic nanostructures composed of silver nanoparticles decorated ZnO NRs arrays, have been fabricated by a process combining the electrochemical growth of ZnO NRs and further formation of Ag nanoparticles by the solid-state thermal dewetting (SSD) process. The effect of SSD parameters on the morphological, structural and optical properties of the Ag NPs decorated ZnO NRs arrays has been investigated. It is possible to tune the bandgap of the Ag NPs@ZnO nanorods array 3D plasmonic nanostructure by tailoring the Ag nanoparticle sizes, allowing light manipulation at the nanoscale. The silver nanoparticles attached to the ZnO NRs arrays experienced surface plasmonic coupling effect, causing enhancement in the room temperature photoluminescence (PL) UV emission and quenching the corresponding visible light one. An enhancement in the near band edge emission PL intensity of ZnO to the deep level emission PL intensity ratio after Ag NPs decoration of the ZnO nanostructures corresponding to ca. 11 folds has been observed, indicating that the defect emission is obviously suppressed.

Fabrication optimization and application of 3D hybrid SERS substrates.

Three-dimensional (3D) plasmonic nanostructures with nanoparticles that can be tuned have got a lot of attention in surface-enhanced Raman scattering (SERS) due to the unique 3D plasmonic coupling. Here, two nanoparticles, gold nanosphere (AuNS) and gold nanooctahedra (AuNO), were used to construct 3D hybrid SERS substrates to investigate the effect of nanoparticle spatial position on the SERS performance of the 3D nanostructure and to obtain 3D substrates with high SERS activity. And more hybrid combination possibilities were tested to explore the variation trend of hot spots generated when the nanoparticles were near. First, two-dimensional (2D) planar substrates were prepared using the air–liquid interface-assisted self-assembly method, to examine the effect of nanoparticle size on SERS performance. Then, 3D hybrid SERS substrates were further prepared layer by layer to discuss the effect of different combination methods within three layers on SERS performance. The optimized 3D hybrid substrate with the sandwich structure of AuNS/AuNO/AuNS performed the strongest SERS enhancement effect, whose intensity was 4.1 and 1.9 times that of AuNS/AuNS/AuNS and AuNO/AuNO/AuNO, respectively, and had good reproducibility (relative standard deviation (RSD) of 1.08%). Furthermore, the thiram molecular result showed that the prepared AuNS/AuNO/AuNS had good linear relationship (R2 of 0.991) and good molecule detection sensitivity (the minimum detection volume of thiram is 100 ppb), which demonstrated the great potential of the 3D hybrid SERS substrates in practical analysis.

Self-Assembled 3D Nanosplit Rings for Plasmon-Enhanced Optofluidic Sensing.

Plasmonic sensors are commonly defined on two-dimensional (2D) surfaces with an enhanced electromagnetic field only near the surface, which requires precise positioning of the targeted molecules within hotspots. To address this challenge, we realize segmented nanocylinders that incorporate plasmonic (1-50 nm) gaps within three-dimensional (3D) nanostructures (nanocylinders) using electron irradiation triggered self-assembly. The 3D structures allow desired plasmonic patterns on their inner cylindrical walls forming the nanofluidic channels. The nanocylinders bridge nanoplasmonics and nanofluidics by achieving electromagnetic field enhancement and fluid confinement simultaneously. This hybrid system enables rapid diffusion of targeted species to the larger spatial hotspots in the 3D plasmonic structures, leading to enhanced interactions that contribute to a higher sensitivity. This concept has been demonstrated by characterizing an optical response of the 3D plasmonic nanostructures using surface-enhanced Raman spectroscopy (SERS), which shows enhancement over a 22 times higher intensity for hemoglobin fingerprints with nanocylinders compared to 2D nanostructures.

Abnormal dewetting of Ag layer on three-dimensional ITO branches to form spatial plasmonic nanoparticles for organic solar cells

Three-dimensional (3D) plasmonic structures have attracted great attention because abnormal wetting behavior of plasmonic nanoparticles (NPs) on 3D nanostructure can enhance the localized surface plasmons (LSPs). However, previous 3D plasmonic nanostructures inherently had weak plasmonic light absorption, low electrical conductivity, and optical transmittance. Here, we fabricated a novel 3D plasmonic nanostructure composed of Ag NPs as the metal for strong LSPs and 3D nano-branched indium tin oxide (ITO BRs) as a transparent and conductive framework. The Ag NPs formed on the ITO BRs have a more dewetted behavior than those formed on the ITO films. We experimentally investigated the reasons for the dewetting behavior of Ag NPs concerning the geometry of ITO BRs. The spherical Ag NPs are spatially separated and have high density, thereby resulting in strong LSPs. Finite-domain time-difference simulation evidenced that spatially-separated, high-density and spherical Ag NPs formed on ITO BRs dramatically boost the localized electric field in the active layer of organic solar cells (OSCs). Photocurrent of PTB7:PCBM OSCs with the ITO BRs/Ag NPs increased by 14%.

Optimizing the SERS Performance of 3D Substrates through Tunable 3D Plasmonic Coupling toward Label-Free Liver Cancer Cell Classification

Three-dimensional (3D) plasmonic nanostructures are emerging as excellent surface-enhanced Raman spectroscopy (SERS) substrates for chemical and biomedical applications. However, the correlation of 3D (including both in-plane and out-of-plane) plasmonic coupling with the SERS properties to deepen the understanding of 3D SERS substrates remains a challenge. Here, we perform correlation studies of 3D plasmonic coupling and SERS properties of the 3D hierarchical SERS substrates by tuning the multiscale structural elements. The effects of zero-dimensional (0D; the size of the building blocks), one-dimensional (1D; the thickness of the 3D substrates), and two-dimensional (2D; the composition of individual monolayers) structural elements on 3D plasmonic coupling are studied by performing UV-vis-near-infrared (NIR) spectroscopy and measuring SERS performance. It shows that both the extinction spectra and SERS enhancement are tuned at the 3D structural level. It is demonstrated that the plasmonic resonance wavelength (PRW) stemming from the 3D plasmonic coupling correlates with the SERS averaged surface enhancement factor (ASEF) and is improved by more than tenfold at the optimum 3D nanostructure. The optimized substrate is used to quantitatively analyze two small biological molecules. Moreover, as a proof-of-concept study, the substrate is first applied to differentiate between living liver normal and cancer cells with a high prediction accuracy through the spectral features of the cell membranes and the metabolites secreted outside the cells. We expect that the tuning of plasmonic coupling at the 3D level can open up new routes to design high-performance SERS substrates for wide applications.

Effects of electric field coupling on the circular dichroism of composite nanostructures

Chirality has substantial applications in the fields of medicine, biology, and physics. Previous studies of strong chiral responses mostly involved complex 3D plasmonic nanostructures. In this study, we demonstrate a planar plasmonic composite nanostructure to achieve large circular dichroism (CD) effect by tuning the coupling effect. By introducing a rectangular block to an L-shaped nanostructure, the resonance wavelength at different handed circular polarization incidences is separated. At the same time, the resonance of the composite nanostructure is observable for one circularly polarized light excitation but subdued for another circularly polarized light excitation, leading to a large CD effect. In addition, the CD effects of composite nanostructures are strongly dependent on the structural parameters. These results could provide a novel approach to tune resonance wavelengths and achieve larger CD effects.

Encapsulation of 3D plasmonic nanostructures with ultrathin hydrogel skin for rapid and direct detection of toxic small molecules in complex fluids.

Nanogap-rich 3D plasmonic nanostructures provide enhanced molecular Raman fingerprints in a nondestructive and label-free manner. However, the molecular detection of small target molecules in complex fluids is challenging due to nonspecific protein adsorption, which prevents access of the target molecules. Therefore, the molecular detection for complex mixtures usually requires a tedious and time-consuming pretreatment of samples. Herein, we report the encapsulation of 3D plasmonic nanostructures with an ultrathin hydrogel skin for the rapid and direct detection of small molecules in complex mixtures. To demonstrate the proof of concept, we directly detect pesticide dissolved in milk without pretreatment. This detection is enabled by the selective permeation of target molecules into the 3D mesh of the hydrogel skin and the adsorption onto plasmonic hotspots, accompanied by the rejection of large adhesive proteins and colloids. The high sensitivity of nanogap-rich plasmonic nanostructures in a conjunction with the molecular selection of the hydrogel skin enables the fast and reliable detection of tricyclazole in whole milk with a limit of detection as low as 10 ppb within 1 h. We believe that this plasmonic platform is highly adaptable for in situ and on-site detection of small molecules in various complex mixtures including foods, biological fluids, and environmental fluids.

Controllable 3D plasmonic nanostructures for high-quantum-efficiency UV photodetectors based on 2D and 0D materials

3D Au nanostructure/anodic aluminum oxide (AAO) matrix plasmonic architectures with strong plasmonic coupling for spatial light utilization are reported.

Enhanced thermal effect of plasmonic nanostructures confined in discoidal porous silicon particles.

The design of plasmonic nanostructures could have many exciting applications since it enhances or provides valuable control over efficient energy conversion. A three-dimensional (3D) space is a realistic hotspot matrix harvesting a wide conversion that has been shown in zero-dimensional nanoparticles, one-dimensional linear structures, or two-dimensional films. A novel 3D plasmonic nanostructure platform consisting of plasmonic metal nanoparticles in discoidal porous silicon particles is used in this study. Plasmonic gold nanoparticles are anchored inside the discoidal porous silicon (DPS) particles by in situ reduction synthesis. The novel plasmonic nanostructures can tailor the plasmon band and overcome the instability of photothermal materials. The “trapping well” for the anchored nanoparticles in 3D space can result in a huge change of plasmonic band of metal nanoparticles to the near-IR region in a novel 3D geometry. A multifunctional scaffold, Au–DPS particle, composed of doxorubicin conjugated to poly-(l-glutamic acid) (pDOX), was developed for combinatorial chemo-photothermal cancer therapy. The therapeutic efficacy was examined in treatment of the A549 cell line under near-IR laser irradiation. The highly efficient photothermal conversion can also be demonstrated in the laser desorption/ionization time-of-flight mass spectrometry detection analysis. The limit of detection was obviously improved in the detection of angiotensin II, P14R, and ACTH fragments 18-39 peptides. Overall, we envision that Au–DPS particles may be used in ultrasensitive theranostics in the future.

A review of 2D and 3D plasmonic nanostructure array patterns: fabrication, light management and sensing applications

Abstract This review article discusses progress in surface plasmon resonance (SPR) of two-dimensional (2D) and three-dimensional (3D) chip-based nanostructure array patterns. Recent advancements in fabrication techniques for nano-arrays have endowed researchers with tools to explore a material’s plasmonic optical properties. In this review, fabrication techniques including electron-beam lithography, focused-ion lithography, dip-pen lithography, laser interference lithography, nanosphere lithography, nanoimprint lithography, and anodic aluminum oxide (AAO) template-based lithography are introduced and discussed. Nano-arrays have gained increased attention because of their optical property dependency (light-matter interactions) on size, shape, and periodicity. In particular, nano-array architectures can be tailored to produce and tune plasmonic modes such as localized surface plasmon resonance (LSPR), surface plasmon polariton (SPP), extraordinary transmission, surface lattice resonance (SLR), Fano resonance, plasmonic whispering-gallery modes (WGMs), and plasmonic gap mode. Thus, light management (absorption, scattering, transmission, and guided wave propagation), as well as electromagnetic (EM) field enhancement, can be controlled by rational design and fabrication of plasmonic nano-arrays. Because of their optical properties, these plasmonic modes can be utilized for designing plasmonic sensors and surface-enhanced Raman scattering (SERS) sensors.

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

AbstractPlasmonic 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.

Gas-phase deposited plasmonic nanoparticles supported on 3D-graphene/nickel foam for highly SERS detection

In this work, we proposed a novel three-dimensional (3D) plasmonic nanostructure based on porous graphene/nickel foam (GNF) and gas-phase deposited Ag nanoparticles (NPs). Ag NPs with high density were directly deposited on the surface of 3D GNF by performing a novel cluster beam deposition approach. In comparison with traditional Ag substrate (SiO2/Ag), such hot-spots enriched 3D nanostructure showed extremely high electromagnetic field enhancement under incident light irradiation which could be used as a sensitive chemical sensor based on surface enhanced Raman scattering (SERS). The experimental results demonstrated that the proposed nanostructure showed superior SERS performance in terms of Raman signal reproducibility and sensitivity for the probe molecules. 3D full-wave simulation showed that the enhanced SERS performance in this 3D hierarchical plasmonic nanostructure was mainly obtained from the hot-spots between Ag NPs and the near-field coupling between Ag NPs and GNF scaffolds. This work can provide a novel assembled SERS substrate as a SERS-based chemical sensor in practical applications.

The numerical scheme of the discrete sources method to analyze 3D plasmonic nanostructures accounting for the non-local effect

We present an extension of the discrete sources method for solving the time-harmonic Maxwell equations accounting for the non-local effect. The developed numerical scheme coupling the non-local hydrodynamic Drude model and the generalized non-local optical response model is described in detail. Numerical results computed for a single non-spherical particle and a linear dimer are presented. Our results demonstrate that the discrete sources method can be efficiently used to model the non-local effect in a wide range of 3D scattering problems.