Christine H. Moran

Controlling the synthesis and assembly of silver nanostructures for plasmonic applications.

Coinage metals, such as Au, Ag, and Cu, have been important materials throughout history.1 While in ancient cultures they were admired primarily for their ability to reflect light, their applications have become far more sophisticated with our increased understanding and control of the atomic world. Today, these metals are widely used in electronics, catalysis, and as structural materials, but when they are fashioned into structures with nanometer-sized dimensions, they also become enablers for a completely different set of applications that involve light. These new applications go far beyond merely reflecting light, and have renewed our interest in maneuvering the interactions between metals and light in a field known as plasmonics.2–6 In plasmonics, the metal nanostructures can serve as antennas to convert light into localized electric fields (E-fields) or as waveguides to route light to desired locations with nanometer precision. These applications are made possible through a strong interaction between incident light and free electrons in the nanostructures. With a tight control over the nanostructures in terms of size and shape, light can be effectively manipulated and controlled with unprecedented accuracy.3,7 While many new technologies stand to be realized from plasmonics, with notable examples including superlenses,8 invisible cloaks,9 and quantum computing,10,11 conventional technologies like microprocessors and photovoltaic devices could also be made significantly faster and more efficient with the integration of plasmonic nanostructures.12–15 Of the metals, Ag has probably played the most important role in the development of plasmonics, and its unique properties make it well-suited for most of the next-generation plasmonic technologies.16–18 1.1. What is Plasmonics? Plasmonics is related to the localization, guiding, and manipulation of electromagnetic waves beyond the diffraction limit and down to the nanometer length scale.4,6 The key component of plasmonics is a metal, because it supports surface plasmon polariton modes (indicated as surface plasmons or SPs throughout this review), which are electromagnetic waves coupled to the collective oscillations of free electrons in the metal. While there are a rich variety of plasmonic metal nanostructures, they can be differentiated based on the plasmonic modes they support: localized surface plasmons (LSPs) or propagating surface plasmons (PSPs).5,19 In LSPs, the time-varying electric field associated with the light (Eo) exerts a force on the gas of negatively charged electrons in the conduction band of the metal and drives them to oscillate collectively. At a certain excitation frequency (w), this oscillation will be in resonance with the incident light, resulting in a strong oscillation of the surface electrons, commonly known as a localized surface plasmon resonance (LSPR) mode.20 This phenomenon is illustrated in Figure 1A. Structures that support LSPRs experience a uniform Eo when excited by light as their dimensions are much smaller than the wavelength of the light. Figure 1 Schematic illustration of the two types of plasmonic nanostructures discussed in this article as excited by the electric field (Eo) of incident light with wavevector (k). In (A) the nanostructure is smaller than the wavelength of light and the free electrons ... In contrast, PSPs are supported by structures that have at least one dimension that approaches the excitation wavelength, as shown in Figure 1B.4 In this case, the Eo is not uniform across the structure and other effects must be considered. In such a structure, like a nanowire for example, SPs propagate back and forth between the ends of the structure. This can be described as a Fabry-Perot resonator with resonance condition l=nλsp, where l is the length of the nanowire, n is an integer, and λsp is the wavelength of the PSP mode.21,22 Reflection from the ends of the structure must also be considered, which can change the phase and resonant length. Propagation lengths can be in the tens of micrometers (for nanowires) and the PSP waves can be manipulated by controlling the geometrical parameters of the structure.23

Seed-Mediated Synthesis of Ag Nanocubes with Controllable Edge Lengths in the Range of 30−200 nm and Comparison of Their Optical Properties

Silver nanocubes with edge lengths controllable in the range of 30-200 nm were synthesized using an approach based on seeded growth. The keys to the success of this synthesis are the use of single-crystal Ag seeds to direct the growth and the use of AgNO(3) as a precursor to elemental Ag, where the byproduct HNO(3) can block both the homogeneous nucleation and evolution of single-crystal seeds into twinned nanoparticles. Either spherical (in the shape of a cuboctahedron) or cubic seeds could be employed for this growth process. The edge length of the resultant Ag nanocubes can be readily controlled by varying the amount of Ag seeds used, the amount of AgNO(3) added, or both. For the first time, we could obtain Ag nanocubes with uniform edge lengths controllable in the range of 30-200 nm and then compare their localized surface plasmon resonance and surface-enhanced Raman scattering properties.

Generation of Hot Spots with Silver Nanocubes for Single-Molecule Detection by Surface-Enhanced Raman Scattering

This paper presents a simple strategy for the formation of surface-enhanced Raman scattering (SERS) hot spots, or regions with extraordinary large electric-field enhancements, by depositing a silver nanocube on a metal substrate. Our experimental and theoretical results show that hot spots form at the corners of a nanocube in contact with the substrate and the hot spots derived from a single silver nanocube are capable of detecting SERS from a single molecule. By varying the electrical property of the substrate, and the distance between the nanoparticle and the substrate, we show that the substrate can dramatically affect the SERS from a supported nanoparticle. In addition, by comparing the SERS for nanocubes and nanospheres of similar sizes, we show that this effect is also sensitive to the shape of the supported nanoparticle, and enhancement factors of 9.7×106 and 2.1×108 were obtained for a nanosphere and a nanocube on a metal substrate, respectively. This new approach requires minimum fabrication efforts and offers great simplicity for the formation of robust and fully accessible hot spots, providing an effective SERS platform for single-molecule detection.

Synthesis of Ag Nanobars in the Presence of Single-Crystal Seeds and a Bromide Compound, and Their Surface-Enhanced Raman Scattering (SERS) Properties

This Article describes the synthesis of Ag nanobars with different aspect ratios using a seed-mediated method and evaluation of their use for surface-enhanced Raman scattering (SERS). The formation of Ag nanobars was found to critically depend on the introduction of a bromide compound into the reaction system, with ionic salts being more effective than covalent molecules. We examined single-crystal seeds with both spherical and cubic shapes and found that Ag nanobars grown from spherical seeds had much higher aspect ratios than those grown from cubic seeds. The typical product of a synthesis contained nanocrystals with three different morphologies: nanocubes, nanobars with a square cross section, and nanobars with a rectangular cross section. Their formation can be attributed to the difference in growth rates along the three orthogonal <100> directions. The SERS enhancement factor of the Ag nanobar was found to depend on its aspect ratio, its orientation relative to the laser polarization, and the wavelength of excitation.

Facile Synthesis of Gold Nanorice Enclosed by High- Index Facets and Its Application for CO Oxidation

A facile method for generating Au nanorice enclosed by high-index facets in high purity. The nanorice shows much higher catalytic activity for CO oxidation than multiply twinned particles of Au enclosed by {111} facets at temperatures below 300 °C.

Using well-defined Ag nanocubes as substrates to quantify the spatial resolution and penetration depth of surface-enhanced Raman scattering imaging

The multiplexing capability and high sensitivity of surface-enhanced Raman scattering (SERS) make this new imaging modality particularly attractive for rapid diagnosis. With 100 nm Ag nanocubes serving as the substrate, this work quantitatively evaluated, for the first time, some of the fundamental parameters of SERS imaging such as blur, spatial resolution and penetration depth. Our results imply that SERS is a high-resolution imaging technique with a blur value of 0.5 μm that is lower than many traditional modalities such as mammography. The spatial resolution was measured to be 1.1 μm, suggesting that SERS images could be collected effectively by adjusting the imaging step size to the same length scale, or no more than 2 μm. The major drawback of SERS imaging is its penetration depth, which is limited by the scattering and absorption of tissues. We demonstrated that enhancement of signal caused by aggregation of multiple nanoparticles could help overcome this potential road-block to in vivo imaging.

Improving correlated SERS measurements with scanning electron microscopy: an assessment of the problem arising from the deposition of amorphous carbon

For surface-enhanced Raman scattering (SERS) substrates with nonspherical symmetry, it is critical to correlate spectroscopy measurements with imaging by scanning electron microscopy (SEM). However, the deposition of carbon resulting from e-beam exposure during SEM imaging contaminates the surface of nanoparticles, potentially preventing their further functionalization with Raman probe molecules. In addition, the deposited carbon leads to unwanted background SERS signals. In this study, we systematically investigated the deposition of carbon during SEM imaging and examined how it affects the functionalization of nanoparticles with probe molecules and impacts the detection of SERS signals. Significantly, we found that the carbon could be removed or replaced from the surface of Ag nanoparticles through chemical or physical means, rendering the nanoparticles the capability for correlated SEM/SERS studies.