Rizia Bardhan

Self-Assembled Plasmonic Nanoparticle Clusters

Optical Nanoengineering Optics and electronics operate at very different length scales. Surface plasmons are light-induced electronic excitations that are being pursued as a route to bridge the length scales and bring the processing speed offered by optical communication down to the size scales of electronic chip circuitry. Now, Fan et al. (p. 1135) describe the self-assembly of nanoscale dielectric particles coated with gold. Functionalization of the gold surface with polymer ligands allowed controlled production of clusters of nanoparticles. The optical properties of the self-assembled nanostructures depended on the number of components within the cluster and each structure could be selected for its unique optical properties. Such a bottom-up approach should help in fabricating designed optical circuits on the nanoscale. A hierarchy of nanoscale optical structures is created from nanoparticles that have metal shells and dielectric cores. The self-assembly of colloids is an alternative to top-down processing that enables the fabrication of nanostructures. We show that self-assembled clusters of metal-dielectric spheres are the basis for nanophotonic structures. By tailoring the number and position of spheres in close-packed clusters, plasmon modes exhibiting strong magnetic and Fano-like resonances emerge. The use of identical spheres simplifies cluster assembly and facilitates the fabrication of highly symmetric structures. Dielectric spacers are used to tailor the interparticle spacing in these clusters to be approximately 2 nanometers. These types of chemically synthesized nanoparticle clusters can be generalized to other two- and three-dimensional structures and can serve as building blocks for new metamaterials.

Fluorescence enhancement by Au nanostructures: nanoshells and nanorods.

Metallic nanoparticles influence the quantum yield and lifetime of adjacent fluorophores in a manner dependent on the properties of the nanostructure. Here we directly compare the fluorescence enhancement of the near-infrared fluorophore IR800 by Au nanoshells (NSs) and Au nanorods (NRs), where human serum albumin (HSA) serves as a spacer layer between the nanoparticle and the fluorophore. Our measurements reveal that the quantum yield of IR800 is enhanced from approximately 7% as an isolated fluorophore to 86% in a NSs-HSA-IR800 complex and 74% in a NRs-HSA-IR800 complex. This dramatic increase in fluorescence shows tremendous potential for contrast enhancement in fluorescence-based bioimaging.

Air-stable magnesium nanocomposites provide rapid and high-capacity hydrogen storage without using heavy-metal catalysts

Hydrogen is a promising alternative energy carrier that can potentially facilitate the transition from fossil fuels to sources of clean energy because of its prominent advantages such as high energy density (142 MJ kg(-1); ref. 1), great variety of potential sources (for example water, biomass, organic matter), light weight, and low environmental impact (water is the sole combustion product). However, there remains a challenge to produce a material capable of simultaneously optimizing two conflicting criteria--absorbing hydrogen strongly enough to form a stable thermodynamic state, but weakly enough to release it on-demand with a small temperature rise. Many materials under development, including metal-organic frameworks, nanoporous polymers, and other carbon-based materials, physisorb only a small amount of hydrogen (typically 1-2 wt%) at room temperature. Metal hydrides were traditionally thought to be unsuitable materials because of their high bond formation enthalpies (for example MgH(2) has a ΔHf~75 kJ mol(-1)), thus requiring unacceptably high release temperatures resulting in low energy efficiency. However, recent theoretical calculations and metal-catalysed thin-film studies have shown that microstructuring of these materials can enhance the kinetics by decreasing diffusion path lengths for hydrogen and decreasing the required thickness of the poorly permeable hydride layer that forms during absorption. Here, we report the synthesis of an air-stable composite material that consists of metallic Mg nanocrystals (NCs) in a gas-barrier polymer matrix that enables both the storage of a high density of hydrogen (up to 6 wt% of Mg, 4 wt% for the composite) and rapid kinetics (loading in <30 min at 200 °C). Moreover, nanostructuring of the Mg provides rapid storage kinetics without using expensive heavy-metal catalysts.

Optically- and thermally-responsive programmable materials based on carbon nanotube-hydrogel polymer composites

A simple approach is described to fabricate reversible, thermally- and optically responsive actuators utilizing composites of poly(N-isopropylacrylamide) (pNIPAM) loaded with single-walled carbon nanotubes. With nanotube loading at concentrations of 0.75 mg/mL, we demonstrate up to 5 times enhancement to the thermal response time of the nanotube-pNIPAM hydrogel actuators caused by the enhanced mass transport of water molecules. Additionally, we demonstrate the ability to obtain ultrafast near-infrared optical response in nanotube-pNIPAM hydrogels under laser excitation enabled by the strong absorption properties of nanotubes. The work opens the framework to design complex and programmable self-folding materials, such as cubes and flowers, with advanced built-in features, including tunable response time as determined by the nanotube loading.

Fano-like Interference in Self-Assembled Plasmonic Quadrumer Clusters

Assemblies of strongly interacting metallic nanoparticles are the basis for plasmonic nanostructure engineering. We demonstrate that clusters of four identical spherical particles self-assembled into a close-packed asymmetric quadrumer support strong Fano-like interference. This feature is highly sensitive to the polarization of the incident electric field due to orientation-dependent coupling between particles in the cluster. This structure demonstrates how careful design of self-assembled colloidal systems can lead to the creation of new plasmonic modes and the enabling of interference effects in plasmonic systems.

Fanoshells: Nanoparticles with Built-in Fano Resonances

A nanoparticle consisting of a dielectric (SiO(2)) and metallic (Au) shell layer surrounding a solid Au nanoparticle core can be designed with its superradiant and subradiant plasmon modes overlapping in energy, resulting in a Fano resonance in its optical response. Synthesis of this nanoparticle around an asymmetric core yields a structure that possesses additional Fano resonances as revealed by single particle dark field microspectroscopy. A mass-and-spring coupled oscillator model provides an excellent description of the plasmon interactions and resultant optical response of this nanoparticle.

Nanoshells Made Easy: Improving Au Layer Growth on Nanoparticle Surfaces

The growth of a continuous, uniform Au layer on a dielectric nanoparticle is the critical step in the synthesis of nanoparticles such as nanoshells or nanorice, giving rise to their unique geometry-dependent plasmon resonant properties. Here, we report a novel, streamlined method for Au layer metallization on prepared nanoparticle surfaces using carbon monoxide as the reducing agent. This approach consistently yields plasmonic nanoparticles with highly regular shell layers and is immune to variations in precursor or reagent preparation. Single particle spectroscopy combined with scanning electron microscopy reveal that thinner, more uniform shell layers with correspondingly red-shifted optical resonances are achievable with this approach.

Tracking of multimodal therapeutic nanocomplexes targeting breast cancer in vivo.

Nanoparticle-based therapeutics with local delivery and external electromagnetic field modulation holds extraordinary promise for soft-tissue cancers such as breast cancer; however, knowledge of the distribution and fate of nanoparticles in vivo is crucial for clinical translation. Here we demonstrate that multiple diagnostic capabilities can be introduced in photothermal therapeutic nanocomplexes by simultaneously enhancing both near-infrared fluorescence and magnetic resonance imaging (MRI). We track nanocomplexes in vivo, examining the influence of HER2 antibody targeting on nanocomplex distribution over 72 h. This approach provides valuable, detailed information regarding the distribution and fate of complex nanoparticles designed for specific diagnostic and therapeutic functions.

Metallic nanoshells with semiconductor cores: optical characteristics modified by core medium properties.

It is well-known that the geometry of a nanoshell controls the resonance frequencies of its plasmon modes; however, the properties of the core material also strongly influence its optical properties. Here we report the synthesis of Au nanoshells with semiconductor cores of cuprous oxide and examine their optical characteristics. This material system allows us to systematically examine the role of core material on nanoshell optical properties, comparing Cu(2)O core nanoshells (ε(c) ∼ 7) to lower core dielectric constant SiO(2) core nanoshells (ε(c) = 2) and higher dielectric constant mixed valency iron oxide nanoshells (ε(c) = 12). Increasing the core dielectric constant increases nanoparticle absorption efficiency, reduces plasmon line width, and modifies plasmon energies. Modifying the core medium provides an additional means of tailoring both the near- and far-field optical properties in this unique nanoparticle system.

Light trapping in mesoporous solar cells with plasmonic nanostructures

Plasmon resonances in metal nanostructures have been extensively harnessed for light trapping in mesoporous solar cells (MSCs), including dye-sensitized solar cells (DSSCs) and recently in perovskite solar cells (PSCs). By altering the geometry, dimension, and composition of metal nanostructures, their optical characteristics can be tuned to either overlap with the sensitizer absorption and enhance light harvesting, or absorb light at a wavelength complementary to the sensitizer enabling broadband solar light capture in MSCs. In this comprehensive review, we discuss the mechanisms of plasmonic enhancement in MSCs including far-field coupling of scattered light, near-field coupling of localized electromagnetic fields, hot electron transfer, and plasmon resonant energy transfer. We then summarize the progress in plasmon enhanced DSSCs in the past decade and decouple the impact of metal nanostructure shape, size, composition, and surface coatings on the overall efficiency. Further, we also discuss the recent advances in plasmon-enhanced perovskite solar cells. Distinct from other published reviews, we discuss the significance of femtosecond spectroscopies to probe the fundamental underpinnings of plasmon enhanced phenomena and understand the mechanisms that give rise to energy transfer between metal nanoparticles and solar materials. The review concludes with a discussion on the challenges in plasmonic device fabrication, and the promise of low-loss semiconductor nanocrystals for plasmonic enhancement in MSCs that facilitate light capture in the infrared.