Directional emission from dye-functionalized plasmonic DNA superlattice microcavities

Abstract

Three-dimensional plasmonic superlattice microcavities, made from programmable atom equivalents comprising gold nanoparticles functionalized with DNA, are used as a testbed to study directional light emission. DNA-guided nanoparticle colloidal crystallization allows for the formation of micrometer-scale single-crystal bodycentered cubic gold nanoparticle superlattices, with dye molecules coupled to the DNA strands that link the particles together, in the form of a rhombic dodecahedron. Encapsulation in silica allows one to create robust architectures with the plasmonically active particles and dye molecules fixed in space. At the micrometer scale, the anisotropic rhombic dodecahedron crystal habit couples with photonic modes to give directional light emission. At the nanoscale, the interaction between the dye dipoles and surface plasmons can be finely tuned by coupling the dye molecules to specific sites of the DNA particle-linker strands, thereby modulating dye-nanoparticle distance (three different positions are studied). The ability to control dye position with subnanometer precision allows one to systematically tune plasmon-excition interaction strength and decay lifetime, the results of which have been supported by electrodynamics calculations that span length scales from nanometers to micrometers. The unique ability to control surface plasmon/ exciton interactions within such superlattice microcavities will catalyze studies involving quantum optics, plasmon laser physics, strong coupling, and nonlinear phenomena.DNA programmable assembly | directional emission | anisotropic 3D microcavity | nanoparticle surface plasmon | fluorescence enhancement M icrocavities are important photonic architectures that can be used to couple dipole emitters with optical modes and enhance light-matter interactions typically with long cavity lifetimes (high Q factors). They have been used to understand phenomena in cavity quantum electrodynamics (1, 2), and to enable molecular sensing (3) and lasing (4) technologies. In recent years, researchers have developed strategies for incorporating plasmonic nanostructures into microcavity structures to enhance light-matter interactions via strong light confinement (small mode volume, V), resulting in materials that are capable of plasmon lasing (5-7). These plasmonic microcavities exploit two different aspects of the architectures simultaneously: guided optical modes that resonate or scatter light (via the microcavity geometry) and near-field-driven optical confinement (via the metallic nanostructure). Such hybrid photonic structures are desirable because they can lead to high Q factors and strong light confinement within a single architecture, significantly enhancing light-matter interactions by a large cavity figure of merit, Q/V. However, most of the plasmonic microcavities have been limited to 1D or 2D microcavity geometries and plasmonic mode confinement (7) (metallic nanostructures) due to limitations in fabrication methods (6,8). Importantly, 3D counterparts of these 1D and 2D a...

Optics of exciton-plasmon nanomaterials

“…[55,158,[188][189][190][191][192][193][194][195][196][197][198][199][200][201][202] as well as cavity modes. [178,[203][204][205][206][207][208][209][210] For recent reviews see Refs. [108,175] and [211].…”

Programmable Atom Equivalents: Atomic Crystallization as a Framework for Synthesizing Nanoparticle Superlattices

“…In addition to a stronger understanding of the dynamics of individual building blocks, a second major goal for PAE superstructure control is the ability to arbitrarily control PAE crystallite habit (size and shape). Recently, single‐crystal PAE architectures have been used as individual optical devices in geometrically sensitive applications, reliant on their well‐defined, thermodynamic Wulff polyhedron structure . Furthermore, theoretical work indicates that AuNP superlattices of precisely defined shapes exhibit unique optical responses .…”

Progress and Opportunities in Soft Photonics and Biologically Inspired Optics

“…Very recently, this success in structural DNA nanotechnology has been translated to the fabrication of optical metamaterials. DNA‐based metamaterials can mainly be classified into two groups: 1) materials formed by programmable 3D crystallization of DNA oligomer‐coated metallic NPs and 2) structures generated by assembly of metallic NP onto DNA origami pegboards . These two approaches will be discussed below.…”

“…The term “soft photonics” refers primarily to the realization of photonic systems from various individual components such as gratings, photonic crystals, plasmonic structures, microlenses, and metamaterials, which are formed fully or partially from a broad range of soft materials. These materials include fluids, DNA assemblies, hydrogels, flexible and stretchable elastomers, photo‐reconfigurable polymers, biological components, and colloidal suspensions . They are processed using suitable soft matter processing strategies, including self‐assembly, reaction–diffusion processes, nanoimprinting/transfer printing,…”

“…The use of DNA complementary binding, directed colloidal self‐assembly, programed buckling of elastomers, and reconfigurable microfluidic channels and emulsion droplets has enabled the realization of sophisticated adaptive, stimuli‐responsive, and even autonomously reconfigurable micro‐ and nanophotonic structures. We anticipate that significant potential scientific, economic, and social benefits will arise from broadening our materials' palette to include soft solids and fluids in the effort to design the next generation of photonic systems that are mechanically compliant, dynamically conformal, sensitive to mechanical, chemical, or optical cues, and capable of homeostasis to ensure adequate function in a broad range of conditions.…”