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.

5.1. Nanoalloys of Group 11 (Cu, Ag, Au) 865 5.1.1. Cu−Ag 866 5.1.2. Cu−Au 867 5.1.3. Ag−Au 870 5.1.4. Cu−Ag−Au 872 5.2. Nanoalloys of Group 10 (Ni, Pd, Pt) 872 5.2.1. Ni−Pd 872 * To whom correspondence should be addressed. Phone: +39010 3536214. Fax:+39010 311066. E-mail: ferrando@fisica.unige.it. † Universita di Genova. ‡ Argonne National Laboratory. § University of Birmingham. | As of October 1, 2007, Chemical Sciences and Engineering Division. Volume 108, Number 3

Nanoalloys: From Theory to Applications of Alloy Clusters and Nanoparticles

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

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Controlling the synthesis and assembly of silver nanostructures for plasmonic applications

When light interacts with a metal nanoparticle (NP), its conduction electrons can be driven by the incident electric field in collective oscillations known as localized surface plasmon resonances (LSPRs). These give rise to a drastic alteration of the incident radiation pattern and to striking effects such as the subwavelength localization of electromagnetic (EM) energy, the formation of high intensity hot spots at the NP surface, or the directional scattering of light out of the structure. LSPRs can also couple to the EM fields emitted by molecules, atoms, or quantum dots placed in the vicinity of the NP, leading in turn to a strong modification of the radiative and nonradiative properties of the emitter. Since LSPRs enable an efficient transfer of EM energy from the near to the far-field of metal NPs and vice versa, we can consider plasmonic nanostructures as nanoantennas, because they operate in a similar way to radio antennas but at higher frequencies. Typically, plasmonic nanoantennas at optical frequencies are made of gold and silver due to their goodmetallic properties and low absorption. Controlling and guiding light has been one of science’s most influential achievements. It affects everyday life in many ways, such as the development of telescopes, microscopes, spectrometers, and optical fibers, to name but a few. These examples exploit the wave nature of light and are based on the reflection, refraction and diffraction of light by optical elements such as mirrors, lenses or gratings. However, the wave nature of light limits the resolution to which an object can be imaged, as well as the size of the transverse cross section of efficient guiding structures to the wavelength dimension. Plasmonic resonances in nanoantennas overcome these constraints, allowing unprecedented control of light-matter interactions within subwavelength volumes (i.e., within the nanoscale at optical frequencies). Such properties have attracted much interest lately, due to the implications they have both in fundamental research and in technological applications. Metal NPs have been used since antiquity. Due to their strong scattering properties in the visible range, they show attractive colors. One of their first applications, dating back to the Roman Empire more than 2000 years ago, was as a colorant for clothing. In art, they were used to stain window glass and ceramics. Obviously, it was not known then that the colorants being used contained metal NPs or that the spectacular colors were due to the excitation of LSPRs. The first reported intentional production of metal NPs dates from 1857, when Faraday synthesized gold colloids. However, at the time there was not much interest in understanding the physics behind the optical properties of colloids due to the impossibility of synthesizing NPs with well-controlled shapes and sizes, as well as the lack of accurate detection techniques. The first theoretical work on the scattering of light by particles smaller than the incident wavelength was carried out by Lord Rayleigh at the end of the 19th century. He analyzed the diffusion of light by diluted gases, and his theory explained physical phenomena such as the blueness of the sky, the redness of the sunset, or the yellow color of the sun. Mie took the next step forward by deriving an analytical solution to Maxwell’s equations to describe the interaction of light with spheres of arbitrary radius and composition. Subsequently, based on the results of Rayleigh and Mie, Gans considered elliptical geometries. He demonstrated that the optical response of metal NPs is

Plasmonic nanoantennas: fundamentals and their use in controlling the radiative properties of nanoemitters.

In the last two decades, plasmon resonance in gold nanoparticles (Au NPs) has been the subject of intense research efforts. Plasmon physics is intriguing and its precise modelling proved to be challenging. In fact, plasmons are highly responsive to a multitude of factors, either intrinsic to the Au NPs or from the environment, and recently the need emerged for the correction of standard electromagnetic approaches with quantum effects. Applications related to plasmon absorption and scattering in Au NPs are impressively numerous, ranging from sensing to photothermal effects to cell imaging. Also, plasmon-enhanced phenomena are highly interesting for multiple purposes, including, for instance, Raman spectroscopy of nearby analytes, catalysis, or sunlight energy conversion. In addition, plasmon excitation is involved in a series of advanced physical processes such as non-linear optics, optical trapping, magneto-plasmonics, and optical activity. Here, we provide the general overview of the field and the background for appropriate modelling of the physical phenomena. Then, we report on the current state of the art and most recent applications of plasmon resonance in Au NPs.

Surface plasmon resonance in gold nanoparticles: a review.

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Cookie‐like Au/NiO Nanoparticles with Optical Gas‐Sensing Properties

An investigation of the finite depth square well model is presented in this article: model features and limitations, concerning size dependent band gap of semiconductor quantum structures, are presented and discussed. Model predictions are compared with large sets of experimental data for III–V, II–VI and lead salt semiconductor quantum dots and quantum wires. Matrix influence on the confinement is studied by modeling experimental results for colloidal CdS, CdSe, CdTe and InP quantum dots. The effect of quantum structure dimensionality is investigated and successfully simulated for colloidal CdSe and InP experimental data and Si first-principle calculations. Finally, model limitations for narrow band gap semiconductors are studied and discussed.

Finite depth square well model: Applicability and limitations

The quest for efficient ways of modulating localized surface plasmon resonance is one of the frontiers in current research in plasmonics; the use of a magnetic field as a source of modulation is among the most promising candidates for active plasmonics. Here we report the observation of magnetoplasmonic modes on colloidal gold nanoparticles detected by means of magnetic circular dichroism (MCD) spectroscopy and provide a model that is able to rationalize and reproduce the experiment with unprecedented qualitative and quantitative accuracy. We believe that the steep slope observed at the plasmon resonance in the MCD spectrum can be very efficient in detecting changes in the refractive index of the surrounding medium, and we give a simple proof of principle of its possible implementation for magnetoplasmonic refractometric sensing.

Circular Magnetoplasmonic Modes in Gold Nanoparticles

Thin films composed of Au nanoparticles dispersed inside a TiO2−NiO mixed oxide matrix are prepared by the sol−gel method, resulting in nanostructured composites with a morphology and crystallinity that depend on synthesis parameters and thermal treatment. Their functional activity as hydrogen sulfide optical sensors is due to Au-localized surface plasmon resonance (SPR) which is reversible. The detection sensitivity is shown to be down to a few parts per million of H2S, and almost no interference in response is observed during simultaneous exposure to CO or H2, resulting in a highly sensitive and selective sensor for hydrogen sulfide detection. For mechanistic studies, experimental evidence using reaction product analysis and thin film surface characterization suggests a direct catalytic oxidation of H2S over the Au−TiO2−NiO nanocomposite film.

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Au Nanoparticles in Nanocrystalline TiO2−NiO Films for SPR-Based, Selective H2S Gas Sensing

Silver, copper, and mixed silver–copper nanocluster‐doped silica thin layers were prepared by the sol‐gel process. Samples were heat treated in different annealing atmospheres (air, argon, or 5%H2–95%N2) in the temperature range 500–1100 °C. Specimens were characterized by optical absorption spectroscopy, Rutherford backscattering spectrometry, x‐ray diffraction, and transmission electron microscopy. Cluster growth and dissolution, as well as migration of metal atoms towards the sample surface, with a subsequent evaporation, were observed to occur at temperatures that depend on the annealing atmosphere. In the mixed silver–copper system, the formation of Ag–Cu phase‐separated clusters was observed.

Giovanni Mattei

Papers

Cookie‐like Au/NiO Nanoparticles with Optical Gas‐Sensing Properties

Finite depth square well model: Applicability and limitations

Circular Magnetoplasmonic Modes in Gold Nanoparticles

Au Nanoparticles in Nanocrystalline TiO2−NiO Films for SPR-Based, Selective H2S Gas Sensing

Annealing behavior of silver, copper, and silver-copper nanoclusters in a silica matrix synthesized by the sol-gel technique