Showing papers by "Mark W. Knight published in 2014"

Aluminum for Plasmonics

Abstract: Unlike silver and gold, aluminum has material properties that enable strong plasmon resonances spanning much of the visible region of the spectrum and into the ultraviolet. This extended response, combined with its natural abundance, low cost, and amenability to manufacturing processes, makes aluminum a highly promising material for commercial applications. Fabricating Al-based nanostructures whose optical properties correspond with theoretical predictions, however, can be a challenge. In this work, the Al plasmon resonance is observed to be remarkably sensitive to the presence of oxide within the metal. For Al nanodisks, we observe that the energy of the plasmon resonance is determined by, and serves as an optical reporter of, the percentage of oxide present within the Al. This understanding paves the way toward the use of aluminum as a low-cost plasmonic material with properties and potential applications similar to those of the coinage metals.

Au Nanomatryoshkas as Efficient Near-Infrared Photothermal Transducers for Cancer Treatment: Benchmarking against Nanoshells

Abstract: Au nanoparticles with plasmon resonances in the near-infrared (NIR) region of the spectrum efficiently convert light into heat, a property useful for the photothermal ablation of cancerous tumors subsequent to nanoparticle uptake at the tumor site. A critical aspect of this process is nanoparticle size, which influences both tumor uptake and photothermal efficiency. Here, we report a direct comparative study of ∼90 nm diameter Au nanomatryoshkas (Au/SiO2/Au) and ∼150 nm diameter Au nanoshells for photothermal therapeutic efficacy in highly aggressive triple negative breast cancer (TNBC) tumors in mice. Au nanomatryoshkas are strong light absorbers with 77% absorption efficiency, while the nanoshells are weaker absorbers with only 15% absorption efficiency. After an intravenous injection of Au nanomatryoshkas followed by a single NIR laser dose of 2 W/cm2 for 5 min, 83% of the TNBC tumor-bearing mice appeared healthy and tumor free >60 days later, while only 33% of mice treated with nanoshells survived the...

Vivid, full-color aluminum plasmonic pixels

Abstract: Aluminum is abundant, low in cost, compatible with complementary metal-oxide semiconductor manufacturing methods, and capable of supporting tunable plasmon resonance structures that span the entire visible spectrum. However, the use of Al for color displays has been limited by its intrinsically broad spectral features. Here we show that vivid, highly polarized, and broadly tunable color pixels can be produced from periodic patterns of oriented Al nanorods. Whereas the nanorod longitudinal plasmon resonance is largely responsible for pixel color, far-field diffractive coupling is used to narrow the plasmon linewidth, enabling monochromatic coloration and significantly enhancing the far-field scattering intensity of the individual nanorod elements. The bright coloration can be observed with p-polarized white light excitation, consistent with the use of this approach in display devices. The resulting color pixels are constructed with a simple design, are compatible with scalable fabrication methods, and provide contrast ratios exceeding 100:1.

Fluorescence Enhancement of Molecules Inside a Gold Nanomatryoshka

Abstract: Metallic nanoparticles exhibiting plasmonic Fano resonances can provide large enhancements of their internal electric near field. Here we show that nanomatryoshkas, nanoparticles consisting of an Au core, an interstitial nanoscale SiO2 layer, and an Au shell layer, can selectively provide either a strong enhancement or a quenching of the spontaneous emission of fluorophores dispersed within their internal dielectric layer. This behavior can be understood by taking into account the near-field enhancement induced by the Fano resonance of the nanomatryoshka, which is responsible for enhanced absorption of the fluorophores incorporated into the nanocomplex. The combination of compact size and enhanced light emission with internal encapsulation of the fluorophores for increased biocompatibility suggests outstanding potential for this type of nanoparticle complex in biomedical applications.

The Surprising in Vivo Instability of Near-IR-Absorbing Hollow Au–Ag Nanoshells

Abstract: Photothermal ablation based on resonant illumination of near-infrared-absorbing noble metal nanoparticles that have accumulated in tumors is a highly promising cancer therapy, currently in multiple clinical trials. A crucial aspect of this therapy is the nanoparticle size for optimal tumor uptake. A class of nanoparticles known as hollow Au (or Au–Ag) nanoshells (HGNS) is appealing because near-IR resonances are achievable in this system with diameters less than 100 nm. However, in this study, we report a surprising finding that in vivo HGNS are unstable, fragmenting with the Au and the remnants of the sacrificial Ag core accumulating differently in various organs. We synthesized 43, 62, and 82 nm diameter HGNS through a galvanic replacement reaction, with nanoparticles of all sizes showing virtually identical NIR resonances at ∼800 nm. A theoretical model indicated that alloying, residual Ag in the nanoparticle core, nanoparticle porosity, and surface defects all contribute to the presence of the plasmon...

Thermoplasmonics: quantifying plasmonic heating in single nanowires.

Abstract: Plasmonic absorption of light can lead to significant local heating in metallic nanostructures, an effect that defines the subfield of thermoplasmonics and has been leveraged in diverse applications from biomedical technology to optoelectronics. Quantitatively characterizing the resulting local temperature increase can be very challenging in isolated nanostructures. By measuring the optically induced change in resistance of metal nanowires with a transverse plasmon mode, we quantitatively determine the temperature increase in single nanostructures with the dependence on incident polarization clearly revealing the plasmonic heating mechanism. Computational modeling explains the resonant and nonresonant contributions to the optical heating and the dominant pathways for thermal transport. These results, obtained by combining electronic and optical measurements, place a bound on the role of optical heating in prior experiments and suggest design guidelines for engineered structures meant to leverage such effects.

Three-Dimensional Plasmonic Nanoclusters

Abstract: Assembling nanoparticles into well-defined structures is an important way to create and tailor the optical properties of materials. Most advances in metamaterials research to date have been based on structures fabricated in two-dimensional planar geometries. Here, we show an efficient method for assembling noble metal nanoparticles into stable, three-dimensional (3-D) clusters, whose optical properties can be highly sensitive or remarkably independent of cluster orientation, depending on particle number and cluster geometry. Some of the clusters, such as tetrahedra and icosahedra, could serve as the optical kernels for metafluids, imparting metamaterial optical properties into disordered media such as liquids, glasses, or plastics, free from the requirement of nanostructure orientation.

Thermoplasmonics: Quantifying plasmonic heating in single nanowires

Abstract: Plasmonic absorption of light can lead to significant local heating in metallic nanostructures, an effect that defines the sub-field of thermoplasmonics and has been leveraged in diverse applications from biomedical technology to optoelectronics. Quantitatively characterizing the resulting local temperature increase can be very challenging in isolated nanostructures. By measuring the optically-induced change in resistance of metal nanowires with a transverse plasmon mode, we quantitatively determine the temperature increase in single nanostructures, with the dependence on incident polarization clearly revealing the plasmonic heating mechanism. Computational modeling explains the resonant and nonresonant contributions to the optical heating and the dominant pathways for thermal transport. These results, obtained by combining electronic and optical measurements, place a bound on the role of optical heating in prior experiments, and suggest design guidelines for engineered structures meant to leverage such effects.