Plasmene Nanosheets Research Articles

Active strain engineering of soft plasmene nanosheets by thermoresponsive hydrogels

Integration of soft plasmene nanosheets with thermoresponsive hydrogel enables omnidirectional strain engineering that leads to the dynamic manipulation of their plasmonic property by programming temperature.

Self-assembled Janus plasmene nanosheets as flexible 2D photocatalysts

A leaf is a free-standing photocatalytic system that can effectively harvest solar energy and convert CO2 and H2O into carbohydrates in a continuous manner without the need for regeneration or tedious product extraction steps. Despite encouraging advances achieved in designing artificial photocatalysts, most of them function in bulk solution or on rigid surfaces. Here, we report on a 2D flexible photocatalytic system based on close packed Janus plasmene nanosheets. One side of the Janus nanosheets is hydrophilic with catalytically active palladium, while the opposite side is hydrophobic with plasmonic nanocrystals. Such a unique design ensures a stable nanostructure on a flexible polymer substrate, preventing dissolution/degradation of plasmonic photocatalysts during chemical conversion in aqueous solutions. Using catalytic reduction of 4-nitrophenol as a model reaction, we demonstrated efficient plasmon-enhanced photochemical conversion on our flexible Janus plasmene. The photocatalytic efficiency could be tuned by adjusting the palladium thickness or types of constituent building blocks or their orientations, indicating the potential for tailor-made catalyst design for desired reactions. Furthermore, the flexible Janus plasmene nanosheets were designed into a small 3D printed artificial tree, which could continuously convert 30 mL of chemicals in 45 minutes.

Orientation-Dependent Soft Plasmonics of Gold Nanobipyramid Plasmene Nanosheets.

In parallel to the burgeoning field of soft electronics, soft plasmonics focuses on the design and fabrication of plasmonic structures supported on elastomers and to understand how their properties respond to mechanical deformations. Here, we report on a partial ligand-stripping strategy to fabricate elastomer-supported gold nanobipyramid (NBP) plasmene nanosheets. Unlike spherelike building blocks, NBP-building blocks display complex orientation-dependent plasmonic responses to external strains. By collecting polarized plasmonic resonance spectra in conjunction with electrostatic eigenmode modeling, we reveal simultaneous changes in interparticle spacing and spatial orientations of NBP building blocks under mechanical strains. Such changes are directly related to initial NBP packing orders. Further analysis of strain sensitivities for various NBP plasmenes indicated that plasmonic spectra of ∼45° oriented samples are mostly susceptible to strain at acute polarized angles. The results presented may enable novel applications in future soft optoelectronic devices in sensing, encryption, and data storage.

Plasmene nanosheets as optical skin strain sensors.

Skin-like optoelectronic sensors can have a wide range of technical applications ranging from wearable/implantable biodiagnostics, human-machine interfaces, and soft robotics to artificial intelligence. The previous focus has been on electrical signal transduction, whether resistive, capacitive, or piezoelectric. Here, we report on "optical skin" strain sensors based on elastomer-supported, highly ordered, and closely packed plasmonic nanocrystal arrays (plasmene). Using gold nanocubes (AuNCs) as a model system, we find that the types of polymeric ligands, interparticle spacing, and AuNC sizes play vital roles in strain-induced plasmonic responses. In particular, brush-forming polystyrene (PS) is a "good" ligand for forming elastic plasmenes which display strain-induced blue shift of high-energy plasmonic peaks with high reversibility upon strain release. Further experimental and simulation studies reveal the transition from isotropic uniform plasmon coupling at a non-strained state to anisotropic plasmon coupling at strained states, due to the AuNC alignment perpendicular to the straining direction. The two-term plasmonic ruler model may predict the primary high-energy peak location. Using the relative shift of the averaged high-energy peak to the coupling peak before straining, a plasmene nanosheet may be used as a strain sensor with the sensitivity depending on its internal structures, such as the constituent AuNC size or inter-particle spacing.

Self-assembly and characterization of 2D plasmene nanosheets

Freestanding plasmonic nanoparticle (NP) superlattice sheets are novel 2D nanomaterials with tailorable properties that enable their use for broad applications in sensing, anticounterfeit measures, ionic gating, nanophotonics and flat lenses. We recently developed a robust, yet general, two-step drying-mediated approach to produce freestanding monolayer, plasmonic NP superlattice sheets, which are typically held together by holey grids with minimal solid support. Within these superlattices, NP building blocks are closely packed and have strong plasmonic coupling interactions; hence, we termed such freestanding materials 'plasmene nanosheets'. Using the desired NP building blocks as starting material, we describe the detailed fabrication protocol, including NP surface functionalization by thiolated polystyrene and the self-assembly of NPs at the air-water interface. We also discuss various characterization approaches for checking the quality and optical properties of the as-obtained plasmene nanosheets: optical microscopy, spectrophotometry, transmission/scanning electron microscopy (TEM/SEM) and atomic force microscopy (AFM). With regard to different constituent building blocks, the key experimental parameters, including NP concentration and volume, are summarized to guide the successful fabrication of specific types of plasmene nanosheets. This protocol, from initial NP synthesis to the final fabrication and characterization, takes ~33.5 h.

Covalent-Cross-Linked Plasmene Nanosheets

Thiol-polystyrene (SH-PS)-capped plasmonic nanoparticles can be fabricated into free-standing, one-nanoparticle-thick superlattice sheets (termed plasmene) based on physical entanglement between ligands, which, however, suffer from irreversible dissociation in organic solvents. To address this issue, we introduce coumarin-based photo-cross-linkable moieties to the SH-PS ligands to stabilize gold nanoparticles. Once cross-linked, the obtained plasmene nanosheets consisting of chemically locked nanoparticles can well maintain structural integrity in organic solvents. Particularly, arising from ligand-swelling-induced enlargement of the interparticle spacing, these plasmene nanosheets show significant optical responses to various solvents in a specific as well as reversible manner, which may offer an excellent material for solvent sensing and dynamic plasmonic display.

Ultrathin Fresnel lens based on plasmene nanosheets

Ultrathin Fresnel lens may revolutionize current optical imaging system, leading to thinner and lighter optoelectronic devices with a myriad of technical applications. To date, evaporated bulk metal films and top-down grown graphene represent viable material choices toward the design of ultrathin Fresnel lenses. Despite recent advances, it is still lack of a scalable fabrication strategy to achieve ultrathin lens with high focusing efficiency. Here, we report a new self-assembled metamaterials-based strategy to design ultrathin Fresnel lens using our recently reported plasmene nanosheets. With comparable thickness, our plasmene-based Fresnel lens offers a much better focusing efficiency than that based on continuous metallic films. This may be attributed to the dual Huygens’ effects from both slits and plasmene-constituent nanoparticle building blocks. Importantly, internal structural features of plasmene can be precisely tuned simply by adjusting sizes and shapes of its constituent building blocks, allowing for maximizing the focusing efficiency at a desired operating wavelength – a capability impossible to achieve with continuous metal films or graphene. Our plasmene-based strategy opens a new route to design tailor-made flat lens with finely tunable internal and overall structural properties, which offers new dimensionalities in controlling light-matter interactions for a myriad of technological applications.

Dual‐Coded Plasmene Nanosheets as Next‐Generation Anticounterfeit Security Labels

Dual‐Coded Plasmene Nanosheets as Next‐Generation Anticounterfeit Security Labels

SERS: Ultrathin Plasmene Nanosheets as Soft and Surface‐Attachable SERS Substrates with High Signal Uniformity (Advanced Optical Materials 7/2015)

SERS: Ultrathin Plasmene Nanosheets as Soft and Surface‐Attachable SERS Substrates with High Signal Uniformity (Advanced Optical Materials 7/2015)

Ultrathin Plasmene Nanosheets as Soft and Surface‐Attachable SERS Substrates with High Signal Uniformity

Ultrathin Plasmene Nanosheets as Soft and Surface‐Attachable SERS Substrates with High Signal Uniformity

Giant plasmene nanosheets, nanoribbons, and origami.

We introduce Plasmene- in analogy to graphene-as free-standing, one-particle-thick, superlattice sheets of nanoparticles ("meta-atoms") from the "plasmonic periodic table", which has implications in many important research disciplines. Here, we report on a general bottom-up self-assembly approach to fabricate giant plasmene nanosheets (i.e., plasmene with nanoscale thickness but with macroscopic lateral dimensions) as thin as ∼40 nm and as wide as ∼3 mm, corresponding to an aspect ratio of ∼75,000. In conjunction with top-down lithography, such robust giant nanosheets could be milled into one-dimensional nanoribbons and folded into three-dimensional origami. Both experimental and theoretical studies reveal that our giant plasmene nanosheets are analogues of graphene from the plasmonic nanoparticle family, simultaneously possessing unique structural features and plasmon propagation functionalities.