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.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 457-461 |
| Number of pages | 5 |
| Journal | Proceedings of the National Academy of Sciences of the United States of America |
| Volume | 114 |
| Issue number | 3 |
| DOIs | |
| State | Published - Jan 17 2017 |
Funding
Materials synthesis work was supported by Air Force Office of Scientific Research Award FA9550-12-1-0280 and Asian Office of Aerospace Research and Development Award FA2386-13-1-4124. It is also based upon work supported as part of the Non-equilibrium Energy Research Center and the Center for Bio-Inspired Energy Science, Energy Frontier Research Centers funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under Awards DE-SC0000989 and DE-SC0000989-0002. The theory work was supported by National Science Foundation (NSF) Grant CHE-1465045. This work made use of the Electron Probe Instrumentation Center, Keck-II, and/or Scanned Probe Imaging and Development facility(ies) of Northwestern University's NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the Materials Research Science and Engineering Center program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. Small-angle X-ray scattering (SAXS) experiments were carried out at the Dupont-Northwestern- Dow Collaborative Access Team beam line at the Advanced Photon Source (APS), Argonne National Laboratory, and use of the APS was supported by the DOE (DE-AC02-06CH11357). J.C.K. acknowledges the Department of Defense for a National Defense Science and Engineering Graduate Fellowship. L.S. is grateful for a Ryan Fellowship from IIN. N.P.S. acknowledges support as an Alfred P. Sloan Research Fellow.
Keywords
- Anisotropic 3Dmicrocavity
- DNA programmable assembly
- Directional emission
- Fluorescence enhancement
- Nanoparticle surface plasmon
ASJC Scopus subject areas
- General