The interaction of light with free electrons in a gold or silver nanostructure can give rise to collective excitations commonly known as surface plasmons. Plasmons provide a powerful means of confining light to metal/dielectric interfaces, which in turn can generate intense local electromagnetic fields and significantly amplify the signal derived from analytical techniques that rely on light, such as Raman scattering. With plasmons, photonic signals can be manipulated on the nanoscale, enabling integration with electronics (which is now moving into the nano regime). However, to benefit from their interesting plasmonic properties, metal structures of controlled shape (and size) must be fabricated on the nanoscale. This issue of MRS Bulletin examines how gold and silver nanostructures can be prepared with controllable shapes to tailor their surface plasmon resonances and highlights some of the unique applications that result, including enhancement of electromagnetic fields, optical imaging, light transmission, colorimetric sensing, and nanoscale waveguiding.

One-dimensional metallic nanostructures such as nanorods and nanowires are of tremendous interest for electronic, sensing, and catalytic applications. Shape anisotropy introduces new optical properties in gold and silver nanoparticles, such as longitudinal plasmon resonance bands in the visible and near-IR portion of the spectrum. Different approaches employed for the shape-controlled synthesis of silver and gold nanocrystals include chemical, electrochemical, and physical methods. The chemical route for the synthesis of nanorods and nanowires, in which metal salts are reduced in an aqueous solution, is one of the most widely used methods. This route commonly employs a surfactant as the directing agent to introduce asymmetry in the nanocrystal shape. Variation in the concentration of precursor salt and the surfactant, the nature of the surfactant, the nature and concentration of reducing agents, the presence of external salts, and the pH of the reaction solution all affect nanocrystal shape, dimension, and yield. The size and shape of the nanocrystals affect the position of the plasmon bands, which in turn has been widely used in surface-enhanced spectroscopies that include both Raman and fluorescence. The aqueous, surfactant-directed route also promises the synthesis of more complex nanostructures with additional desirable properties.

This article provides a brief account of solution-phase methods that generate silver and gold nanostructures with well-controlled shapes. It is organized into five sections: The first section discusses the nucleation and formation of seeds from which nanostructures grow. The next two sections explain how seeds with fairly isotropic shapes can grow anisotropically into distinct morphologies. Polyol synthesis is selected as an example to illustrate this concept. Specifically, we discuss the growth of silver nanocubes (with and without truncated corners), nanowires, and triangular nanoplates. In the fourth section, we show that silver nanostructures can be transformed into hollow gold nanostructures through a galvanic replacement reaction. Examples include nanoboxes, nanocages, nanotubes (both single- and multi-walled), and nanorattles. The fifth section briefly outlines a potential medical application for gold nanocages.We conclude with some perspectives on areas for future work.

Nanoshells, concentric nanoparticles consisting of a dielectric core and a metallic shell, are simple spherical nanostructures with unique, geometrically tunable optical resonances. As with all metallic nanostructures, their optical properties are controlled by the collective electronic resonance, or plasmon resonance, of the constituent metal, typically silver or gold. In striking contrast to the resonant properties of solid metallic nanostructures, which exhibit only a weak tunability with size or aspect ratio, the optical resonance of a nanoshell is extraordinarily sensitive to the inner and outer dimensions of the metallic shell layer. The underlying reason for this lies beyond classical electromagnetic theory, where plasmon-resonant nanoparticles follow a mesoscale analogue of molecular orbital theory, hybridizing in precisely the same manner as the individual atomic wave functions in simple molecules. This plasmon hybridization picture provides an essential “design rule” for metallic nanostructures that can allow us to effectively predict their optical resonant properties. Such a systematic control of the far-field optical resonances of metallic nanostructures is accomplished simultaneously with control of the field at the surface of the nanostructure. The nanoshell geometry is ideal for tuning and optimizing the near-field response as a stand-alone surface-enhanced Raman spectroscopy (SERS) nanosensor substrate and as a surface-plasmon-resonant nanosensor.Tuning the plasmon resonance of nanoshells into the near-infrared region of the spectrum has enabled a variety of biomedical applications that exploit the strong optical contrast available with nanoshells in a spectral region where blood and tissue are optimally transparent.

Localized surface plasmon resonance (LSPR) excitation in silver and gold nanoparticles produces strong extinction and scattering spectra that in recent years have been used for important sensing and spectroscopy applications. This article describes the fabrication, characterization, and computational electrodynamics of plasmonic materials that take advantage of this concept.Two applications of these plasmonic materials are presented: (1) the development of an ultrasensitive nanoscale optical biosensor based on LSPR wavelength-shift spectroscopy and (2) the use of plasmon-sampled and wavelength-scanned surface-enhanced Raman excitation spectroscopy (SERES) to provide new insight into the electromagnetic-field enhancement mechanism.

Nanoscale materials are beginning to have an impact in the field of molecular diagnostics. In particular, gold nanoparticles surface-functionalized with DNA have garnered much recent interest. Due to the unusual optical and catalytic properties of gold nanoparticle labels, several distinct advantages for assay readout have been realized. This review focuses on the progress made in our group over the past seven years in the development of particle surface chemistry and ultrasensitive protein and nucleic acid assays based upon DNA-functionalized gold nanoparticles. For DNA targets, experiments demonstrate that assays based upon gold nanoparticle labels have enhanced target specificity and in certain cases the sensitivity of polymerase chain reaction (PCR), without the need for target amplification. For protein targets, similar experiments demonstrate that assays based upon gold nanoparticles are up to one million times more sensitive than conventional protein detection methods. Recent data using human samples demonstrate the utility of such assays.

The transmission of light through a hole was thought to be very weak when all of the lateral dimensions of the hole were much smaller than the wavelength of the light.The discovery of enhanced transmission has changed this view, raising fundamental questions and leading to many practical applications ranging from photonics to chemical sensing. A key feature of the transmission process is the activation of surface plasmons. In this article, we review the present understanding of this phenomenon and illustrate its potential through several examples of applications in different fields.

Since the development of the light microscope in the 16th century, optical device size and performance have been limited by diffraction. Optoelectronic devices of today are much bigger than the smallest electronic devices for this reason. Achieving control of light—material interactions for photonic device applications at the nanoscale requires structures that guide electromagnetic energy with subwavelength-scale mode confinement. By converting the optical mode into nonradiating surface plasmons, electromagnetic energy can be guided in structures with lateral dimensions of less than 10% of the free-space wavelength. A variety of methods—including electron-beam lithography and self-assembly—have been used to construct both particle and planar plasmon waveguides. Recent experimental studies have confirmed the strongly coupled collective plasmonic modes of metallic nanostructures. In plasmon waveguides consisting of closely spaced silver rods, electromagnetic energy transport over distances of 0.5 m has been observed. Moreover, numerical simulations suggest the possibility of multi-centimeter plasmon propagation in thin metallic stripes. Thus, there appears to be no fundamental scaling limit to the size and density of photonic devices, and ongoing work is aimed at identifying important device performance criteria in the subwavelength size regime. Ultimately, it may be possible to design an entire class of subwavelength-scale optoelectronic components (waveguides, sources, detectors, modulators) that could form the building blocks of an optical device technology—a technology scalable to molecular dimensions, with potential imaging, spectroscopy, and interconnection applications in computing, communications, and chemical/biological detection.