Although gold is the subject of one of the most ancient themes of investigation in science, its renaissance now leads to an exponentially increasing number of publications, especially in the context of emerging nanoscience and nanotechnology with nanoparticles and self-assembled monolayers (SAMs). We will limit the present review to gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles, and they present fascinating aspects such as their assembly of multiple types involving materials science, the behavior of the individual particles, size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology. Their promises are in these fields as well as in the bottom-up approach of nanotechnology, and they will be key materials and building block in the 21st century. Whereas the extraction of gold started in the 5th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that “soluble” gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass 293 Chem. Rev. 2004, 104, 293−346

Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

Surface plasmons are waves that propagate along the surface of a conductor. By altering the structure of a metal's surface, the properties of surface plasmons--in particular their interaction with light--can be tailored, which offers the potential for developing new types of photonic device. This could lead to miniaturized photonic circuits with length scales that are much smaller than those currently achieved. Surface plasmons are being explored for their potential in subwavelength optics, data storage, light generation, microscopy and bio-photonics.

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Surface plasmon subwavelength optics

The emerging field of plasmonics has yielded methods for guiding and localizing light at the nanoscale, well below the scale of the wavelength of light in free space. Now plasmonics researchers are turning their attention to photovoltaics, where design approaches based on plasmonics can be used to improve absorption in photovoltaic devices, permitting a considerable reduction in the physical thickness of solar photovoltaic absorber layers, and yielding new options for solar-cell design. In this review, we survey recent advances at the intersection of plasmonics and photovoltaics and offer an outlook on the future of solar cells based on these principles.

Plasmonics for improved photovoltaic devices

Fundamentals of Plasmonics.- Electromagnetics of Metals.- Surface Plasmon Polaritons at Metal / Insulator Interfaces.- Excitation of Surface Plasmon Polaritons at Planar Interfaces.- Imaging Surface Plasmon Polariton Propagation.- Localized Surface Plasmons.- Electromagnetic Surface Modes at Low Frequencies.- Applications.- Plasmon Waveguides.- Transmission of Radiation Through Apertures and Films.- Enhancement of Emissive Processes and Nonlinearities.- Spectroscopy and Sensing.- Metamaterials and Imaging with Surface Plasmon Polaritons.- Concluding Remarks.

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Plasmonics: Fundamentals and Applications

The interest in nanoscale materials stems from the fact that new properties are acquired at this length scale and, equally important, that these properties * To whom correspondence should be addressed. Phone, 404-8940292; fax, 404-894-0294; e-mail, mostafa.el-sayed@ chemistry.gatech.edu. † Case Western Reserve UniversitysMillis 2258. ‡ Phone, 216-368-5918; fax, 216-368-3006; e-mail, burda@case.edu. § Georgia Institute of Technology. 1025 Chem. Rev. 2005, 105, 1025−1102

Chemistry and properties of nanocrystals of different shapes.

Achieving control of light-material interactions for photonic device applications at nanoscale dimensions will require structures that guide electromagnetic energy with a lateral mode confinement below the diffraction limit of light. This cannot be achieved by using conventional waveguides or photonic crystals. It has been suggested that electromagnetic energy can be guided below the diffraction limit along chains of closely spaced metal nanoparticles that convert the optical mode into non-radiating surface plasmons. A variety of methods such as electron beam lithography and self-assembly have been used to construct metal nanoparticle plasmon waveguides. However, all investigations of the optical properties of these waveguides have so far been confined to collective excitations and direct experimental evidence for energy transport along plasmon waveguides has proved elusive. Here we present observations of electromagnetic energy transport from a localized subwavelength source to a localized detector over distances of about 0.5 μm in plasmon waveguides consisting of closely spaced silver rods. The waveguides are excited by the tip of a near-field scanning optical microscope, and energy transport is probed by using fluorescent nanospheres.

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Local detection of electromagnetic energy transport below the diffraction limit in metal nanoparticle plasmon waveguides.

The further integration of optical devices will require the fabrication of waveguides for electromagnetic energy below the diffraction limit of light. We investigate the possibility of using arrays of closely spaced metal nanoparticles for this purpose. Coupling between adjacent particles sets up coupled plasmon modes that give rise to coherent propagation of energy along the array. A point dipole analysis predicts group velocities of energy transport that exceed 0.1c along straight arrays and shows that energy transmission and switching through chain networks such as corners (see Figure) and tee structures is possible at high efficiencies. Radiation losses into the far field are expected to be negligible due to the near-field nature of the coupling, and resistive heating leads to transmission losses of about 6 dB/lm for gold and silver particles. We analyze macroscopic analogues operating in the microwave regime consisting of closely spaced metal rods by experiments and full field electrodynamic simulations. The guiding structures show a high confinement of the electromagnetic energy and allow for highly variable geometries and switching. Also, we have fabricated gold nanoparticle arrays using electron beam lithography and atomic force microscopy manipulation. These plasmon waveguides and switches could be the smallest devices with optical functionality.

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Plasmonics—A Route to Nanoscale Optical Devices

Hydroxylamine-seeding of colloidal gold particles has been used to fabricate gold nanostructures on a SiO2 substrate. Gold nanoparticles (15 nm diameter) were randomly deposited on a SiO2 surface that had been modified with aminopropyltrimethoxysilane (APTS). The nanoparticles were then manipulated using a scanning force microscope (SFM) tip to produce 1-D templates for gold deposition. We demonstrate the utility of this approach by fabricating a gold nanowire by using 13 nanoparticles as a template. The junction between joined (coated) particles was examined by mechanical manipulation, and homogeneous deposition was shown to form stable structures. This approach was also used to fabricate nanostructures in a small gap between two gold electrodes. Particles were pushed into the gap, and then gold deposition was used to “connect” the particles and electrodes. Although the particular structure tested was not electrically connected to the electrode, we suggest that this approach will be useful in tackling th...

Fabrication of Nanostructures by Hydroxylamine Seeding of Gold Nanoparticle Templates

Designed fabrication of nanostructures requires progress on a number of fronts in research and development. The ability to synthesize, deposit, and position nanometer scale materials is important for the development of this technology. We report here on studies of deposition and manipulation of electrochemically prepared, micelle-capped Au nanorods deposited on silicon dioxide (SiO2) surfaces. A thiol-terminated silane (3-mercaptopropylmethyldimethoxysilane, MPMDMS) was used as an active interface for gold nanorod assembly. A scanning force microscope (SFM) was used to image and manipulate individual Au nanorods. It was found that mechanical movement of the rods depends on the location of the pushing point along the rod.

Sheffer Meltzer

Papers

Local detection of electromagnetic energy transport below the diffraction limit in metal nanoparticle plasmon waveguides.

Plasmonics—A Route to Nanoscale Optical Devices

Fabrication of Nanostructures by Hydroxylamine Seeding of Gold Nanoparticle Templates

Imaging and manipulation of gold nanorods with an atomic force microscope

Plasmonics—A Route to Nanoscale Optical Devices (Advanced Materials, 2001, 13, 1501)