Wei-Shun Chang

A Plasmonic Fano Switch

Plasmonic clusters can support Fano resonances, where the line shape characteristics are controlled by cluster geometry. Here we show that clusters with a hemicircular central disk surrounded by a circular ring of closely spaced, coupled nanodisks yield Fano-like and non-Fano-like spectra for orthogonal incident polarization orientations. When this structure is incorporated into an uniquely broadband, liquid crystal device geometry, the entire Fano resonance spectrum can be switched on and off in a voltage-dependent manner. A reversible transition between the Fano-like and non-Fano-like spectra is induced by relatively low (∼6 V) applied voltages, resulting in a complete on/off switching of the transparency window.

Plasmonic nanorod absorbers as orientation sensors

Nanoparticles are actively exploited as biological imaging probes. Of particular interest are gold nanoparticles because of their nonblinking and nonbleaching absorption and scattering properties that arise from the excitation of surface plasmons. Nanoparticles with anisotropic shapes furthermore provide information about the probe orientation and its environment. Here we show how the orientation of single gold nanorods (25 × 73 nm) can be determined from both the transverse and longitudinal surface plasmon resonance by using polarization-sensitive photothermal imaging. By measuring the orientation of the same nanorods separately using scanning electron microscopy, we verified the high accuracy of this plasmon-absorption-based technique. However, care had to be taken when exciting the transverse plasmon absorption using a large numerical aperture objective as out-of-plane plasmon oscillations were also excited then. For the size regime studied here, being able to establish the nanorod orientation from the transverse mode is unique to photothermal imaging and almost impossible with conventional dark-field scattering spectroscopy. This is important because the transverse surface plasmon resonance is mostly insensitive to the medium refractive index and nanorod aspect ratio allowing nanorods of any length to be used as orientation sensors without changing the laser frequency.

Vivid, full-color aluminum plasmonic pixels.

Significance Full-color displays are typically fabricated using a combination of chromatic materials of various types, introduced into an addressable pixel-based electronic device. Here we show that brightly colored, highly vivid pixels, directly suitable for RGB displays, can be fabricated using periodic areas of Al nanorods in each pixel. Both nanorod length and spacing are critically important in achieving strong and spectrally distinct scattering signatures across the visible spectrum. This use of a low-cost, abundant metal for achieving full-spectrum coloration is compatible with complementary metal-oxide semiconductor manufacturing methods and directly applicable to current liquid crystal display technology. 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.

Plasmon Emission Quantum Yield of Single Gold Nanorods as a Function of Aspect Ratio

We report on the one-photon photoluminescence of gold nanorods with different aspect ratios. We measured photoluminescence and scattering spectra from 82 gold nanorods using single-particle spectroscopy. We found that the emission and scattering spectra closely resemble each other independent of the nanorod aspect ratio. We assign the photoluminescence to the radiative decay of the longitudinal surface plasmon generated after fast interconversion from excited electron-hole pairs that were initially created by 532 nm excitation. The emission intensity was converted to the quantum yield and was found to approximately exponentially decrease as the energy difference between the excitation and emission wavelength increased for gold nanorods with plasmon resonances between 600 and 800 nm. We compare this plasmon emission to its molecular analogue, fluorescence.

Using the Plasmon Linewidth To Calculate the Time and Efficiency of Electron Transfer between Gold Nanorods and Graphene

We present a quantitative analysis of the electron transfer between single gold nanorods and monolayer graphene under no electrical bias. Using single-particle dark-field scattering and photoluminescence spectroscopy to access the homogeneous linewidth, we observe broadening of the surface plasmon resonance for gold nanorods on graphene compared to nanorods on a quartz substrate. Because of the absence of spectral plasmon shifts, dielectric interactions between the gold nanorods and graphene are not important and we instead assign the plasmon damping to charge transfer between plasmon-generated hot electrons and the graphene that acts as an efficient acceptor. Analysis of the plasmon linewidth yields an average electron transfer time of 160 ± 30 fs, which is otherwise difficult to measure directly in the time domain with single-particle sensitivity. In comparison to intrinsic hot electron decay and radiative relaxation, we furthermore calculate from the plasmon linewidth that charge transfer between the gold nanorods and the graphene support occurs with an efficiency of ∼10%. Our results are important for future applications of light harvesting with metal nanoparticle plasmons and efficient hot electron acceptors as well as for understanding hot electron transfer in plasmon-assisted chemical reactions.

Electromagnetic Energy Transport in Nanoparticle Chains via Dark Plasmon Modes

Using light to exchange information offers large bandwidths and high speeds, but the miniaturization of optical components is limited by diffraction. Converting light into electron waves in metals allows one to overcome this problem. However, metals are lossy at optical frequencies and large-area fabrication of nanometer-sized structures by conventional top-down methods can be cost-prohibitive. We show electromagnetic energy transport with gold nanoparticles that were assembled into close-packed linear chains. The small interparticle distances enabled strong electromagnetic coupling causing the formation of low-loss subradiant plasmons, which facilitated energy propagation over many micrometers. Electrodynamic calculations confirmed the dark nature of the propagating mode and showed that disorder in the nanoparticle arrangement enhances energy transport, demonstrating the viability of using bottom-up nanoparticle assemblies for ultracompact opto-electronic devices.

Active modulation of nanorod plasmons.

Confining visible light to nanoscale dimensions has become possible with surface plasmons. Many plasmonic elements have already been realized. Nanorods, for example, function as efficient optical antennas. However, active control of the plasmonic response remains a roadblock for building optical analogues of electronic circuits. We present a new approach to modulate the polarized scattering intensities of individual gold nanorods by 100% using liquid crystals with applied voltages as low as 4 V. This novel effect is based on the transition from a homogeneous to a twisted nematic phase of the liquid crystal covering the nanorods. With our method it will be possible to actively control optical antennas as well as other plasmonic elements.

One-Dimensional Coupling of Gold Nanoparticle Plasmons in Self-Assembled Ring Superstructures

Plasmon coupling in ordered metal nanoparticle assemblies leads to tunable collective surface plasmon resonances that strongly depend on the interparticle distance. Here we report on the surface plasmon scattering of polystyrene-functionalized 40 nm gold nanoparticles self-assembled into close-packed rings. Using single particle dark-field scattering spectroscopy, we observed strong near-field coupling between neighboring nanoparticles, which results in red-shifted multipolar plasmon modes highly polarized along the ring circumference. Correlated optical spectroscopy and scanning electron microscopy of individual rings with different diameters revealed that the plasmon coupling is independent of ring curvature and mostly insensitive to the local nanoparticle arrangement. Our results further suggest that a one-dimensional gold nanoparticle assembly yields long-range collective plasmonic properties similar to those of metallic nanowires.

Toward Plasmonic Polymers

We establish the concept of a plasmonic polymer, whose collective optical properties depend on the repeat unit. Experimental and theoretical analyses of the super- and sub- radiant plasmon response of plasmonic polymers comprising repeat units of single nanoparticles or dimers of gold nanoparticles show that (1) the redshift of the lowest energy coupled mode becomes minimal as the chain approaches the infinite chain limit at a length of ∼10 particles, (2) the presence and energy of the modes are sensitive to the geometries of the constituents, that is, repeat unit, but (3) spatial disorder and nanoparticle heterogeneity have only small effects on the super-radiant mode.

A Plethora of Plasmonics from the Laboratory for Nanophotonics at Rice University

The study of the surface plasmons of noble metals has emerged as one of the most rapidly growing and dynamic topics in nanoscience. Key advances in the synthesis of noble metal nanoparticles and nanostructures have resulted in a broad variety of structures whose geometries can be controlled systematically at the nanoscale. Arising from these efforts is a new level of insight and understanding regarding the fundamental properties of localized plasmons supported by these structures, and, in particular, the properties of interacting plasmon systems. This additional insight has led to the design of plasmonic systems that support coherent phenomena, such as Fano resonances. A broad range of applications are emerging for these structures: single- nanoparticle and nanogap chemical sensors, low-loss plasmon waveguides, and active plasmonic devices and detectors. Applications in biomedicine that exploit the strong photothermal response of nanoparticle plasmons have developed and advanced into clinical trials. The Laboratory for Nanophotonics at Rice has been home to many of these advances. Here, we showcase a variety of functional plasmonic materials and nanodevices emerging from our individual and collaborative efforts.