Plasmonic Superstructures Research Articles

Plasmonic Copper‐Ruthenium Superstructure for Efficient Photothermal Conversion and Plastic Recycling

AbstractPlasmonic superstructures offer broad prospects in photothermal catalysis, yet their controllable synthesis remains a challenge. Here, a controlled synthesis method for Cu‐Ru plasmonic superstructures via a one‐step polyol reduction process is presented, where Cu nanoparticles serve as the core, while the shell is formed from Ru nanoclusters. Through a comprehensive investigation of the growth mechanism, precise control over the composition and size of the superstructures is achieved. Finite‐difference time‐domain simulations and photothermal conversion experiments demonstrated that the optimized Cu3Ru1 superstructures possess strong light absorption capabilities and efficient photothermal conversion performance. These properties are effectively utilized in the photothermal recycling of waste polyethylene and polyethylene terephthalate, marking a significant advance in employing Cu‐based plasmonic materials for sustainable catalytic technology.

Antielectric Potential Synthesis of Plasmonic Au-Ag Multidimensional Dimers Array for High-Resolution Encrypted Information.

Plasmonic superstructures hold great potential in encrypted information chips but are still unsatisfactory in terms of resolution and maneuverability because of the limited fabrication strategies. Here, we develop an antielectric potential method in which the interfacial energy from the modification of 5-amino-2-mercapto benzimidazole (AMBI) ligand is used to overcome the electric resistance between the Au nanospheres (NSs) and substrate, thereby realizing the in situ growth of a Au-Ag heterodimers array in large scale. The morphology, number, and size of Ag domains on Au units can be controlled well by modulating the reaction kinetics and thermodynamics. Experiments and theoretical simulations reveal that patterned 3D Au-2D Ag and 3D Au-3D Ag dimer arrays with line widths of 400 nm exhibit cerulean and cyan colors, respectively, and achieve fine color modulation and ultrahigh information resolution. This work not only develops a facile strategy for fabricating patterned plasmonic superstructures but also pushes the plasmon-based high-resolution encrypted information chip into more complex applications.

Dichroic Engineering from Invisible to Full Colors Using Plasmonics

AbstractPlasmonic nanoparticles serve as nonfading pigments for vibrant outdoor glasses and smart windows, offering vivid colors under sunlight with exceptional spatial resolution. However, simultaneously achieving the desired plasmonic coloration in both reflection and transmission with a full‐color gamut remains a formidable challenge, especially when using a single fabrication method. Here, a facile physical triple co‐deposition method to construct scalable plasmonic superstructures, optimal for dichroic color engineering is demonstrated. A key feature of such all‐in‐one plasmonic superstructures lies in extensive color performance in transmission and reflection modes, spanning from transparent invisibility to vivid full colors across the wavelength range of over 600 nm. This exceptional coloration fidelity stems from their 3D‐stacked nanocomposite where plasmonic nanoparticles incorporate a random but uniform distribution within a glass matrix. Wafer‐scale rich and dynamic color images useful for colorful data storage and steganography, as demonstrated through layer‐by‐layer color painting with combinatorial plasmonic superstructures are shown.

Supra-Photothermal CO2 Methanation over Greenhouse-Like Plasmonic Superstructures of Ultrasmall Cobalt Nanoparticles.

Improving the solar-to-thermal energy conversion efficiency of photothermal nanomaterials at no expense of other physicochemical properties, e.g., the catalytic reactivity of metal nanoparticles, is highly desired for diverse applications but remains a big challenge. Herein, a synergistic strategy is developed for enhanced photothermal conversion by a greenhouse-like plasmonic superstructure of 4 nm cobalt nanoparticles while maintaining their intrinsic catalytic reactivity. The silica shell plays a key role in retaining the plasmonic superstructures for efficient use of the full solar spectrum, and reducing the heat loss of cobalt nanoparticles via the nano-greenhouse effect. The optimized plasmonic superstructure catalyst exhibits supra-photothermal CO2 methanation performance with a record-high rate of 2.3 mol gCo -1 h-1 , close to 100% CH4 selectivity, and desirable catalytic stability. This work reveals the great potential of nanoscale greenhouse effect in enhancing photothermal conversions through the combination with conventional promoting strategies, shedding light on the design of efficient photothermal nanomaterials for demanding applications.

Percolated Plasmonic Superlattices of Nanospheres with 1 nm-Level Gap as High-Index Metamaterials.

Nanophotonics relies on precise control of refractive index (RI) which can be designed with metamaterials. Plasmonic superstructures of nanoparticles (NPs) can suggest a versatile way of tuning RI. However, the plasmonic effects in the superstructures demand 1 nm-level exquisite control over the interparticle gap, which is challenging in a sub-wavelength NPs. Thus far, a large-area demonstration has been mostly discouraged. Here, heteroligand AuNPs are prepared, which are stable in oil but become Janus particles at the oil-water interface, called "adaptive Janus particles." NPs are bound at the interface and assembled into 2D arrays over square centimeters as toluene evaporates, which distinctively exhibits the RI tunability. In visible and NIR light, the 2D superstructures exhibit the highest-ever RI (≈7.8) with varying the size and interparticle gap of NPs, which is successfully explained by a plasmonic percolation model. Furthermore, fully solution-processable 2D plasmonic superstructures are proved to be advantageous in flexible photonic devices such as distributed Bragg reflectors.

DNA Programmable Self-Assembly of Planar, Thin-Layered Chiral Nanoparticle Superstructures with Complex Two-Dimensional Patterns.

Planar, thin-layered chiral plasmonic superstructures with complex two-dimensional (2D) patterns, namely, double-layered binary stars (bi-stars) and pinwheels, were realized through DNA programmable 2D supramolecular self-assembly of gold nanorods (AuNRs). The chirality of the chiral superstructures was defined by a finite number of AuNR pairs as enantiomeric motifs, and their sizes (∼240 nm) were precisely defined by the underlying DNA template. These planar, thin-layered chiral nanoparticle superstructures exhibited prescribed shapes and sizes at the dried state on the substrate surface and are characteristic of giant anisotropy of chiroptical responses, with enhanced g-factors from the axial incident excitation as compared to the in-plane excitation. This work will inspire possibilities for the construction of 2D chiral materials, for example, chiral metasurfaces, for the on-chip manipulation of chiral light-matter interactions via programmable self-assembly of nanoparticles.

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

AbstractEfficient 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

Constructing chiral gold nanorod oligomers using a spatially separated sergeants-and-soldiers effect.

A sergeants-and-soldiers (S&S) effect is very useful to the fabrication of supramolecular chirality. This strategy has not yet been explored in the construction of chiral plasmonic superstructures. Herein, we demonstrate a spatially separated S&S effect in fabricating plasmonic superstructures and modulating their chiroptical responses. Specifically, chiral cysteine (Cys) molecules, acting as sergeants, are sandwiched between a gold nanorod (AuNR) core and a Au shell via AuNR-templated Au overgrowth. Cationic surfactants, CTAB (cetyltrimethylammonium bromide) or CPC (cetylpyridinium chloride), are modified on the AuNR@Cys@Au shell surface, thus spatially separating from the chiral sergeants. During the assembly process, the surfactants act as soldiers which could transfer and amplify the local chirality induced by the adsorbed chiral molecules from the plasmonic monomers to the oligomers. Huge PCD signals could be achieved in the plasmonic oligomers by finely tuning chiral sergeants and achiral soldiers, indicating the feasibility of the S&S effect in fabricating chiral plasmonic superstructures.

Bicontinuous microemulsion as confined reaction media for the synthesis of plasmonic silver self-assembled hierarchical superstructures

Plasmonic superstructures may concentrate hot spots both on the external surface and within the inner gaps of the assembly. However, these materials are usually obtained by two-steps procedures from synthesis of plasmonic nanoparticles to their 3D assembly. The interconnected nano-network of water and oil channels in a bicontinuous microemulsion (BμE) may act as a preorganized reaction system giving reticulated materials. In this work, a silver hierarchical superstructure (HSS-AgCt) was obtained in the water channels of a BµE in a one-pot procedure. The characterization of the morphology and crystalline structure revealed that this superstructure is composed of silver nanoparticles embedded in polymeric silver citrate forming a 3D mesh of interconnected fibers with mean width of 30 nm. The aging of HSS-AgCt in the BμE allowed the degradation of the citrate fibers giving rise to interconnected spherical silver nanoparticles (HSS-Ag) of 8 nm as measured from TEM images. Rhodamine 6-G was detected by SERS up to 10–12 M with an analytical enhancement factor of 109 for both materials using a 633 nm laser operating at 0.85 mW (5% of the nominal power). These results introduce a novel route to obtain highly sensitive SERS substrates in one-pot procedures by using BμE as a nanoreactor and template.

PolyA-based DNA bonds with programmable bond length and bond energy

DNA-functionalized Au nanoparticles (AuNPs) have been intensively exploited as programmable atom equivalents (PAEs) for the self-assembly of molecule-like structures. However, it remains challenging to build hierarchical PAE assemblies via discrete DNA bonds at different levels. Here, we report a strategy to program DNA bond length and bond energy on PAEs using DNA encoders carrying consecutive adenines (polyA). On AuNPs, we built three types of DNA motifs with different topologic configurations, which can form bonds for PAE self-assembly. By small-angle X-ray scattering (SAXS) analysis, we found that the bond length and flexibility between the coupled PAEs can be tuned by programming the bond structure. We also found that these bonds show different bond energies and thus differ, depending on their topologic configuration, leading to different PAE assembly efficiencies. We demonstrated that the bonds at different levels can be arranged in different directions on one nanoparticle, leading to asymmetric PAEs that allow ionic strength-controlled hierarchical assembly of multiparticle structures. This programmable bonding system may provide a new route for building complex plasmonic superstructures.

Cobalt Plasmonic Superstructures Enable Almost 100% Broadband Photon Efficient CO2 Photocatalysis.

The efficiency of heterogeneous photocatalysis for converting solar to chemical energy is low on a per photon basis mainly because of the difficulty of capturing and utilizing light across the entire solar spectral wavelength range. This challenge is addressed herein with a plasmonic superstructure, fashioned as an array of nanoscale needles comprising cobalt nanocrystals assembled within a sheath of porous silica grown on a fluorine tin oxide substrate. This plasmonic superstructure can strongly absorb sunlight through different mechanisms including enhanced plasmonic excitation by the hybridization of Co nanoparticles in close proximity, as well as inter- and intra-band transitions. With nearly 100% sunlight harvesting ability, it drives the photothermal hydrogenation of carbon dioxide with a 20-fold rate increase from the silica-supported cobalt catalyst. The present work bridges the gap between strong light-absorbing plasmonic superstructures with photothermal CO2 catalysis toward the complete utilization of the solar energy.

Quantitative Surface-Enhanced Raman Spectroscopy Analysis through 3D Superlattice Arrays of Au Nanoframes with Attomolar Detection.

This paper reports a methodology for synthesizing and ordering gold nanoframes into three-dimensional (3D) arrays with a controlled thickness, leading to homogeneous plasmonic superstructures, with which quantitative analysis via surface-enhanced Raman spectroscopy (SERS) has been successfully demonstrated. Because this preparation method allows for systematic control of nanoframe film thickness and the resulting 3D plasmonic superstructure, which exhibits a unique nanoporous network of hot-spots, detection limits down to 10-18 M, corresponding to ≈6000 molecules, have been measured. Compared to analogous solid nanoparticle superstructures, the nanoframe superstructures with their unique nanoporous architecture effectively dissipate the heat inevitably generated by laser excitation during measurement, effectively suppressing the formation of carbonaceous materials and therefore their accompanying fluorescence interference, especially important for low concentration detection.

Extending Surface-Enhanced Raman Spectroscopy to Liquids Using Shell-Isolated Plasmonic Superstructures.

Invited for the cover of this issue is the group of Bert M. Weckhuysen at Utrecht University. The image on the cover shows SHIPS, shell-isolated plasmonic superstructures, detecting the presence of picomoles Rhodamine 6G in an aqueous solution using shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). Read the full text of the article at 10.1002/chem.2019032004.

Extending Surface-Enhanced Raman Spectroscopy to Liquids Using Shell-Isolated Plasmonic Superstructures.

Plasmonic superstructures (PS) based on Au/SiO2 were prepared for Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy (SHINERS) in liquid phase applications. These superstructures are composed of functionalized SiO2 spheres with plasmonic Au nanoparticles (NPs) on their surface. Functionalization was performed with (3-aminopropyl)trimethoxysilane, (3-mercaptopropyl)trimethoxysilane and poly(ethylene-imine) (PEI). Of these three, PEI-functionalized spheres showed the highest adsorption density of Au NPs in TEM, UV/Vis and dynamic light scattering (DLS) experiments. Upon decreasing the Au NP/SiO2 sphere size ratio, an increase in adsorption density was also observed. To optimize plasmonic activity, 61 nm Au NPs were adsorbed onto 900 nm SiO2 -PEI spheres and these PS were coated with an ultrathin layer (1-2 nm) of SiO2 to obtain Shell-Isolated Plasmonic Superstructures (SHIPS), preventing direct contact between Au NPs and the liquid medium. Zeta potential measurements, TEM and SHINERS showed that SiO2 coating was successful. The detection limit for SHINERS using SHIPS and a 638 nm laser was around 10-12 m of Rhodamine (10-15 m for uncoated PS), all with acquisition settings suitable for catalysis applications.

Chiral Plasmonic Nanocrystals for Generation of Hot Electrons: Toward Polarization-Sensitive Photochemistry.

The use of biomaterials, with techniques such as DNA-directed assembly or biodirected synthesis, can surpass top-down fabrication techniques in creating plasmonic superstructures in terms of spatial resolution, range of functionality, and fabrication speed. In particular, by enabling a very precise placement of nanoparticles in a bioassembled complex or through the controlled biodirected shaping of single nanoparticles, plasmonic nanocrystals can show remarkably strong circular dichroism (CD) signals. We show that chiral bioplasmonic assemblies and single nanocrystals can enable polarization-sensitive photochemistry based on the generation of energetic (hot) electrons. It is now established that hot plasmonic electrons can induce surface photochemistry or even reshape plasmonic nanocrystals. We show that merging chiral plasmonic nanocrystal systems and the hot-election generation effect offers unique possibilities in photochemistry, such as polarization-sensitive photochemistry promoting nonchiral molecular reactions, chiral photoinduced growth of a colloid at the atomic level, and chiral photochemical destruction of chiral nanocrystals. In contrast, for chiral molecular systems, the equivalent of the described effects is challenging to observe because molecular species typically exhibit very small CD signals. Moreover, we compare our findings with traditional chiral photochemistry at the molecular level, identifying new, different regimes for chiral photochemistry with possibilities that are unique for plasmonic colloidal systems. In this study, we bring together the concept of hot-electron generation and the field of chiral colloidal plasmonics. Using chiral plasmonic nanorod complexes as a model system, we demonstrate remarkably strong CD in both optical extinction and generation rates of hot electrons. Studying the regime of steady-state excitation, we discuss the influence of geometrical and material parameters on the chiral effects involved in the generation of hot electrons. Optical chirality and the chiral hot-electron response in the nanorod dimers result from complex interparticle interactions, which can appear in the weak coupling regime or in the form of Rabi splitting. Regarding practical applications, our study suggests interesting opportunities in polarization-sensitive photochemistry, in chiral recognition or separation, and in promoting chiral crystal growth at the nanoscale.

Colloid-Interface-Assisted Laser Irradiation of Nanocrystals Superlattices to be Scalable Plasmonic Superstructures with Novel Activities.

High-efficient charge and energy transfer between nanocrystals (NCs) in a bottom-up assembly are hard to achieve, resulting in an obstacle in application. Instead of the ligands exchange strategies, the advantage of a continuous laser is taken with optimal wavelength and power to irradiate the film-scale NCs superlattices at solid-liquid interfaces. Owing to the Au-based NCs' surface plasmon resonance (SPR) effect, the gentle laser irradiation leads the Au NCs or Au@CdS core/shell NCs to attach each other with controlled pattern at the interfaces between solid NCs phase and liquid ethanol/ethylene glycol. A continuous wave 532 nm laser (6.68-13.37 W cm-2 ), to control Au-based superlattices, is used to form the monolayer with uniformly reduced interparticle distance followed by welded superstructures. Considering the size effect to Au NCs' melting, when decreasing the Au NCs size to ≈5 nm, stronger welding nanostructures are obtained with diverse unprecedented shapes which cannot be achieved by normal colloidal synthesis. With the help of facile scale-up and formation at solid-liquid interfaces, and a good connection of crystalline between NCs, the obtained plasmonic superstructured films that could be facilely transferred onto different substrates exhibit broad SPR absorption in the visible and near-infrared regime, enhanced electric conductivities, and wide applications as surface enhanced Raman scattering (SERS)-active substrates.

Plasmon resonance coupling phenomena in self-assembled colloidal monolayers

Colloidal self-assembly merges the flexibility provided by (wet-chemical) colloid synthesis and the structural diversity offered by self-assembly. Using plasmonic nanocrystals as colloidal building blocks, this enables the fabrication of plasmonic superstructures that show optical response superior to the individual colloid properties. In this review, we highlight recent examples of colloidal monolayers featuring coupled plasmonic resonances. Depending on the average inter-particle distance and the structure of such monolayers, the discussed examples show either near-field or radiative coupling signatures depending on the critical interference length scale of the localized resonances. In addition, templated assembly is highlighted as a pathway for the preparation of monolayers that show anisotropic optical coupling. The collected works not only reflect the recent state of the art in plasmonic resonance engineering in self-assembled monolayers, but also point to future directions relevant for their use in nanophotonic applications such as plasmonic lasing.

Optical tuning by the self-assembly and disassembly of chain-like plasmonic superstructures

Optical tuning by the self-assembly and disassembly of chain-like plasmonic superstructures

Spiral Patterning of Au Nanoparticles on Au Nanorod Surface to Form Chiral AuNR@AuNP Helical Superstructures Templated by DNA Origami

Plasmonic motifs with precise surface recognition sites are crucial for assembling defined nanostructures with novel functionalities and properties. In this work, a unique and effective strategy is successfully developed to pattern DNA recognition sites in a helical arrangement around a gold nanorod (AuNR), and a new set of heterogeneous AuNR@AuNP plasmonic helices is fabricated by attaching complementary-DNA-modified gold nanoparticles (AuNPs) to the predesigned sites on the AuNR surface. AuNR is first assembled to one side of a bifacial rectangular DNA origami, where eight groups of capture strands are selectively patterned on the other side. The subsequently added link strands make the rectangular DNA origami roll up around the AuNR into a tubular shape, therefore giving birth to a chiral patterning of DNA recognition sites on the surface of AuNR. Following the hybridization with the AuNPs capped with the complementary strands to the capture strands on the DNA origami, left-handed and right-handed AuNR@AuNP helical superstructures are precisely formed by tuning the pattern of the recognition sites on the AuNR surface. Our strategy of nanoparticle surface patterning innovatively realizes hierarchical self-assembly of plasmonic superstructures with tunable chiroptical responses, and will certainly broaden the horizon of bottom-up construction of other functional nanoarchitectures with growing complexity.

Synthesis of micro-sized shell-isolated 3D plasmonic superstructures for in situ single-particle SERS monitoring.

A single-particle SERS system enabling real-time and in situ observation of Au-catalyzed reactions has been developed. Both the catalytic activity and the SERS effect are coupled into a single bi-functional 3D superstructure comprising Au nanosatellites self-assembled onto a shell-insulated Ag microflower core, which eliminates the interference from photocatalysis.