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.

Nanocrystals are fundamental to modern science and technology. Mastery over the shape of a nanocrystal enables control of its properties and enhancement of its usefulness for a given application. Our aim is to present a comprehensive review of current research activities that center on the shape-controlled synthesis of metal nanocrystals. We begin with a brief introduction to nucleation and growth within the context of metal nanocrystal synthesis, followed by a discussion of the possible shapes that a metal nanocrystal might take under different conditions. We then focus on a variety of experimental parameters that have been explored to manipulate the nucleation and growth of metal nanocrystals in solution-phase syntheses in an effort to generate specific shapes. We then elaborate on these approaches by selecting examples in which there is already reasonable understanding for the observed shape control or at least the protocols have proven to be reproducible and controllable. Finally, we highlight a number of applications that have been enabled and/or enhanced by the shape-controlled synthesis of metal nanocrystals. We conclude this article with personal perspectives on the directions toward which future research in this field might take.

Shape‐Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?

The development of optical gain in chemically synthesized semiconductor nanoparticles (nanocrystal quantum dots) has been intensely studied as the first step toward nanocrystal quantum dot lasers. We examined the competing dynamical processes involved in optical amplification and lasing in nanocrystal quantum dots and found that, despite a highly efficient intrinsic nonradiative Auger recombination, large optical gain can be developed at the wavelength of the emitting transition for close-packed solids of these dots. Narrowband stimulated emission with a pronounced gain threshold at wavelengths tunable with the size of the nanocrystal was observed, as expected from quantum confinement effects. These results unambiguously demonstrate the feasibility of nanocrystal quantum dot lasers.

http://science.sciencemag.org/content/sci/290/5490/314.full.pdf

Optical gain and stimulated emission in nanocrystal quantum dots.

Green synthesis of metal nanoparticles using plants

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

/pdf/controlling-the-synthesis-and-assembly-of-silver-1ktlgomyt6.pdf

Controlling the synthesis and assembly of silver nanostructures for plasmonic applications

Heterostructures based on nitrides of group III elements: technical processes, properties, and light-emitting devices

Cold-cavity 3-D transverse-vertical modes of 850 nm GaAs/AlGaAs vertical-cavity surface-emitting lasers with thick oxide aperture layers were simulated. Single fundamental mode operation at large aperture diameters is achieved by proper positioning of the layer with low Al content and thickness beyond a quarter-wavelength in the top distributed Bragg reflector above the aperture layers. This modification promotes the lateral leakage of the transverse higher-order modes along the oxidized layers and their discrimination due to increased gain thresholds at certain aperture diameters. At high leakage, even the fundamental mode exhibits confined spatially-modulated states due to coupling with the leakage field component.

Leakage-Assisted Transverse Mode Selection in Vertical-Cavity Surface-Emitting Lasers With Thick Large-Diameter Oxide Apertures

Metamorphic modulation-doped InGaAs/InAlAs heterostructures have been MBE-grown on GaAs substrates. The optimization of low-temperature growth conditions for a graded-composition buffer layer made it possible to reduce the amount of structural defects in the active layers of the structure. The electron mobility in the 2D channel of metamorphic structures grown under optimum conditions (8100 cm2/V s at 300 K) noticeably exceeds the values achievable in strained InGaAs/AlGaAs heterostructures on GaAs substrates.

Metamorphic modulation-doped InAlAs/InGaAs/InAlAs heterostructures with high electron mobility grown on gaas substrates

Lateral association of vertically-coupled quantum dots

Hot exciton relaxation is observed in GaAs/AlxGa1−xAs multiple quantum wells. The photolumnescence excitation spectra of the localized exciton emission at low temperatures and excitation densities are composed of narrow equidistant peaks exactly separated by the GaAs LO-phonon energy (36 meV). The relaxation mechanism via LO-phonons is found to be important for localized excitons in multiple quantum wells with GaAs layer thicknesses of about 50 A, where pronounced alloy fluctuations in the barriers provide a strong additional lateral potential which suppresses the dissociation of hot excitons.

Nikolai N. Ledentsov

Papers

Heterostructures based on nitrides of group III elements: technical processes, properties, and light-emitting devices

Leakage-Assisted Transverse Mode Selection in Vertical-Cavity Surface-Emitting Lasers With Thick Large-Diameter Oxide Apertures

Metamorphic modulation-doped InAlAs/InGaAs/InAlAs heterostructures with high electron mobility grown on gaas substrates

Lateral association of vertically-coupled quantum dots

Barrier-disorder induced exciton relaxation via LO-phonons in GaAs/AlxGa1−xAs multiple quantum wells