Nanoscale form dictates mesoscale function in plasmonic DNA–nanoparticle superlattices

Abstract

The nanoscale manipulation of matter allows properties to be created in a material that would be difficult or even impossible to achieve in the bulk state. Progress towards such functional nanoscale architectures requires the development of methods to precisely locate nanoscale objects in three dimensions and for the formation of rigorous structure-function relationships across multiple size regimes (beginning from the nanoscale). Here, we use DNA as a programmable ligand to show that two- and three-dimensional mesoscale superlattice crystals with precisely engineered optical properties can be assembled from the bottom up. The superlattices can transition from exhibiting the properties of the constituent plasmonic nanoparticles to adopting the photonic properties defined by the mesoscale crystal (here a rhombic dodecahedron) by controlling the spacing between the gold nanoparticle building blocks. Furthermore, we develop a generally applicable theoretical framework that illustrates how crystal habit can be a design consideration for controlling far-field extinction and light confinement in plasmonic metamaterial superlattices.

Charge Transfer at Hybrid Interfaces: Plasmonics of Aromatic Thiol-Capped Gold Nanoparticles

“…In conjunction with the shape sensitivity, this approach is the basis of plasmonic metamaterials. 15,17,18 Despite these known effects, the role of the ligands themselves on the plasmon resonance of gold nanoparticles has hardly B been investigated in the literature. However, such coupling may pave the way to an emerging field where inorganic nanocrystals could be combined with specific organic molecules in order to design hybrid nanoplasmonic devices.…”

Defect tolerance and the effect of structural inhomogeneity in plasmonic DNA-nanoparticle superlattices

“…These efficient interactions with visible light are due to localized surface plasmon resonances (LSPRs), the collective oscillation of conduction electrons (1). Hierarchical arrangements of plasmonic nanoparticles have become the basis for colorimetric sensors (2,3), subdiffraction limited waveguides (4), visible light metamaterials (5), and nanoscale lasing devices (6,7), and the ability to adjust architecture in such materials has led to a wide variety of structures with tunable and unusual optical properties (8)(9)(10)(11)(12). Many of these technologies leverage the scalability and modularity of bottom-up assembly techniques, which use chemically synthesized colloidal nanoparticles as building blocks (13,14).…”

Optical properties of anisotropic 3D nanoparticles arrays

“…By changing the number of DNA-base pairs, superlattice engineering of different crystalline structures [4] is possible as well as directional crystallization [5,6]. The many applications derived from DNA superlattice engineering include the assembly of superstructures for biological delivery [7], biosensors [8], tuning of the plasmonic response of superlattices [9,10], ordering of Au nanoparticles in one-dimensional arrays [11,12], among others.…”

“…DNA self-assembled superlattices have become a way to design novel metamaterials with a very specific response to electromagnetic fields [6,9,10]. In this paper, we focus on the use of DNA, which has the advantage that the resulting structures are robust to small variations or perturbations [15] and the inter-particle separation can be finely tuned [16].…”