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

The luminescence properties of a GaN/Al0.1Ga0.9N double heterostructure grown by vapor-phase deposition from organometallic compounds are studied. When luminescence is observed from the end, the radiation intensity shows a sharply defined threshold dependence on the pump density. The threshold excitation density at T=77 K was ∼40 kW/cm2 and the wavelength of the stimulated emission was λ=357 nm. The long-wavelength shift of the emission line at high pump densities may be attributed to renormalization of the band gap caused by many-particle interactions in the electron-hole plasma.

Characteristics of stimulated emission from an optically pumped GaN/AlGaN double heterostructure

Electronic and optical properties of ensembles of quantum dots with various energies of activation from the ground-state level to the continuous-spectrum region were studied theoretically and experimentally with the InGaN quantum dots as an example. It is shown that, depending on the activation energy, both the quasi-equilibrium statistic of charge carriers at the levels of quantum dots and nonequilibrium statistic at room temperature are possible. In the latter case, the position of the maximum in the emission spectrum is governed by the value of the demarcation transition: the quantum dots with the transition energy higher than this value feature the quasi-equilibrium population of charge carriers, while the quantum dots with the transition energy lower than the demarcation-transition energy feature the nonequilibrium population. A model based on kinetic equations was used in the theoretical analysis. The key parameters determining the statistic are the parameters of thermal ejection of charge carriers; these parameters depend exponentially on the activation energy. It is shown experimentally that the use of stimulated phase decomposition makes it possible to appreciably increase the activation energy. In this case, the thermal-activation time is found to be much longer than the recombination time for an electron-hole pair, which suppresses the redistribution of charge carriers between the quantum dots and gives rise to the nonequilibrium population. The effect of nonequilibrium population on the luminescent properties of the structures with quantum dots is studied in detail.

Nonequilibrium population of charge carriers in structures with InGaN deep quantum dots

It is shown that in order to achieve lasing in structures with CdSe submonolayers inserted in a ZnSe matrix, no additional optical confinement of the active region using thick wide-gap layers is required. The high oscillator strength of the excitons trapped at CdSe islands modulates the permittivity and thus produces a natural exciton-induced waveguiding effect.

Lasing in submonolayer CdSe structures in a ZnSe matrix without external optical confinement

We report on the modeling of 850-nm (Al,Ga)As/GaAs vertical cavity surface-emitting lasers (VCSELs), where the electrical and optical confinement is realized by impurity-induced intermixing. The 3-D simulations of electromagnetic fields are performed by the finite-element method using full vector Maxwell’s equations. An example of a transverse junction VCSEL with Zn-induced intermixing of the areas surrounding the quantum well region is compared with the case of a VCSEL, where the optical modes are confined by selective oxidation of the Al-rich GaAlAs aperture layers. We show that Zn-induced intermixing results in a high efficiency of the leakage of the VCSEL aperture-confined modes into the surrounding intermixed area. Furthermore, there is a strong mode selectivity through the leakage loss between the fundamental and excited transverse modes of the optical cavity. This enables potential realization of a single transverse mode VCSEL at the aperture diameters of 10 $\mu \text{m}$ or above and consequently the realization of high-power single-mode VCSELs. Optimum mode selectivity is realized once the impurity intermixing profile proceeds down to the depth of about 2.6 $\mu \text{m}$ into the bottom distributed Bragg reflector below the quantum well region. Leakage of the optical modes into the intermixed area is accompanied by the evolution of narrow tilted lobes in the far-field emission spectra (at $\sim 60^{\circ }$ tilt angles for the design considered). This effect is similar to the one previously observed in oxide-confined leaky VCSELs and originates from the laterally propagating optical modes outside the non-intermixed aperture region. Where necessary, by applying such phenomenon, a phase-coupled array can be configured. We believe that such single-mode VCSELs may become extremely important in 3-D sensing, printing, and laser illumination. Furthermore, LIDARs with an option of beam steering without moving parts can be realized in 2-D phase-coupled arrays.

Design Considerations for Single-Mode Vertical-Cavity Surface-Emitting Lasers With Impurity-Induced Intermixing

The results of studies of hole energy states in vertically coupled quantum dots in InAs-GaAs p-n heterostructures by deep-level transient spectroscopy are reported. Spectra were recorded at different reverse-bias voltages. Levels related to bonding and antibonding s and p states of vertically coupled quantum dots were revealed. The energies of these states significantly depend on an external electric field applied to a heterostructure. This dependence was attributed to the quantum-dimensional Stark effect for the hole states of vertically coupled quantum dots. In addition to this, it was found that the energy of thermal activation of carriers from vertically coupled quantum dots depends on the conditions of isochronous annealing that was carried out both with the reverse bias switched-on and switched-off and both in the presence and absence of illumination. These changes, as in the case of isolated quantum dots, are typical of a bistable electrostatic dipole formed by carriers, localized in a coupled quantum dot, and ionized lattice point defects. The built-in electric field of this dipole reduces the energy barrier for the carriers in the coupled quantum dot. The investigated structures with vertically coupled quantum dots were grown using molecular-beam epitaxy taking account of self-assembling effects.

Nikolai N. Ledentsov

Papers

Characteristics of stimulated emission from an optically pumped GaN/AlGaN double heterostructure

Nonequilibrium population of charge carriers in structures with InGaN deep quantum dots

Lasing in submonolayer CdSe structures in a ZnSe matrix without external optical confinement

Design Considerations for Single-Mode Vertical-Cavity Surface-Emitting Lasers With Impurity-Induced Intermixing

Stark effect in vertically coupled quantum dots in InAs-GaAs heterostructures