Tailoring the efficiency of fluorescent emission via plasmon-exciton coupling requires structure control on a nanometer length scale using a high-yield fabrication route not achievable with current lithographic techniques. These systems can be fabricated using a bottom-up approach if problems of colloidal stability and low yield can be addressed. We report progress on this pathway with the assembly of quantum dots (emitter) on gold nanorods (plasmonic units) with precisely controlled spacing, quantum dot/nanorod ratio, and long-term colloidal stability, which enables the purification and encapsulation of the assembled architecture in a protective silica shell. Overall, such controllability with nanometer precision allows one to synthesize stable, complex architectures at large volume in a rational and controllable manner. The assembled architectures demonstrate photoluminescent enhancement (5×) useful for applications ranging from biological sensing to advanced optical communication.

The phenomenon of plasmon-induced transparency holds immense potential for high sensitivity sensors and optical information processing due to the extreme dispersion and slowing of light within a narrow spectral window. Unfortunately plasmonic metamaterials demonstrating this effect has been restricted to infrared and greater wavelengths due to requisite precision in structure fabrication. Here we report a novel metamaterial synthesized by bottom-up self-assembly of gold nanorods. The small dimensions (≤ 50/20 nm, length/diameter), atomically smooth surfaces, and nanometer resolution enable the first demonstration of plasmon-induced transparency at visible wavelengths. The slow-down factors within the reduced symmetry heterodimer cluster are comparable to longer wavelength counterparts. The inherent spectral tunability and facile large-scale integration afforded by self-assembled metamaterials will open a new paradigm for physically realizable on-chip photonic device designs.

The future integration of plasmonic nanoparticles, such as gold nanorods (Au NRs), into applications requires the ability to tune the components of their optical properties to optimize performance for the underlying technology. Verifying techniques that model the resonance energy and associated extinction, scattering, and absorption cross sections necessitate experimental data from series of Au NRs where structural features are independently tuned. Here, the extinction cross section and scattering efficiency are presented for Au NR series with high compositional and structural purity where effective volume, aspect ratio, length, and diameter are independently varied by factors of 25, 3, 2, and 4, respectively. The extinction cross sections quantitatively agree with prior calculations, confirming that the volume of the rod is the dominant factor. Comparisons of the scattering efficiency however are less precise, with both quantitative and qualitative differences between the role of rod volume and aspect ratio. Such extensive experimental data sets provide a critical platform to improve quantitative structure−property correlations, and thus enable design optimization of plasmonic nanoparticles for emerging applications.

Metal nanoparticle assemblies are promising materials for nanophotonic applications due to novel linear and nonlinear optical properties arising from their plasmon modes. However, scalable fabrication approaches that provide both precision nano- and macroarchitectures, and performance commensurate with design and model predictions, have been limiting. Herein, we demonstrate controlled and efficient nanofocusing of the fundamental and second harmonic frequencies of incident linearly and circularly polarized light using reduced symmetry gold nanoparticle dimers formed by surface-directed assembly of colloidal nanoparticles. Large ordered arrays (>100) of these C∞v heterodimers (ratio of radii R1/R2 = 150 nm/50 nm = 3; gap distance l = 1 ± 0.5 nm) exhibit second harmonic generation and structure-dependent chiro-optic activity with the circular dichroism ratio of individual heterodimers varying less than 20% across the array, demonstrating precision and uniformity at a large scale. These nonlinear optical properties were mediated by interparticle plasmon coupling. Additionally, the versatility of the fabrication is demonstrated on a variety of substrates including flexible polymers. Numerical simulations guide architecture design as well as validating the experimental results, thus confirming the ability to optimize second harmonic yield and induce chiro-optical responses for compact sensors, optical modulators, and tunable light sources by rational design and fabrication of the nanostructures.

A non-fullerene all small molecule solar cell constructed with a new diketopyrrolopyrrole-based acceptor shows an efficiency of 9.14% and energy loss of 0.54 eV.