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.

1. Introduction 20642. Synthesis of Magnetic Nanoparticles 20662.1. Classical Synthesis by Coprecipitation 20662.2. Reactions in Constrained Environments 20682.3. Hydrothermal and High-TemperatureReactions20692.4. Sol-Gel Reactions 20702.5. Polyol Methods 20712.6. Flow Injection Syntheses 20712.7. Electrochemical Methods 20712.8. Aerosol/Vapor Methods 20712.9. Sonolysis 20723. Stabilization of Magnetic Particles 20723.1. Monomeric Stabilizers 20723.1.1. Carboxylates 20733.1.2. Phosphates 20733.2. Inorganic Materials 20733.2.1. Silica 20733.2.2. Gold 20743.3. Polymer Stabilizers 20743.3.1. Dextran 20743.3.2. Polyethylene Glycol (PEG) 20753.3.3. Polyvinyl Alcohol (PVA) 20753.3.4. Alginate 20753.3.5. Chitosan 20753.3.6. Other Polymers 20753.4. Other Strategies for Stabilization 20764. Methods of Vectorization of the Particles 20765. Structural and Physicochemical Characterization 20785.1. Size, Polydispersity, Shape, and SurfaceCharacterization20795.2. Structure of Ferro- or FerrimagneticNanoparticles20805.2.1. Ferro- and Ferrimagnetic Nanoparticles 20805.3. Use of Nanoparticles as Contrast Agents forMRI20825.3.1. High Anisotropy Model 20845.3.2. Small Crystal and Low Anisotropy EnergyLimit20855.3.3. Practical Interests of Magnetic NuclearRelaxation for the Characterization ofSuperparamagnetic Colloid20855.3.4. Relaxation of Agglomerated Systems 20856. Applications 20866.1. MRI: Cellular Labeling, Molecular Imaging(Inﬂammation, Apoptose, etc.)20866.2.

Magnetic Iron Oxide Nanoparticles: Synthesis, Stabilization, Vectorization, Physicochemical Characterizations, and Biological Applications

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 unprecedented ability of nanometallic (that is, plasmonic) structures to concentrate light into deep-subwavelength volumes has propelled their use in a vast array of nanophotonics technologies and research endeavours. Plasmonic light concentrators can elegantly interface diffraction-limited dielectric optical components with nanophotonic structures. Passive and active plasmonic devices provide new pathways to generate, guide, modulate and detect light with structures that are similar in size to state-of-the-art electronic devices. With the ability to produce highly confined optical fields, the conventional rules for light-matter interactions need to be re-examined, and researchers are venturing into new regimes of optical physics. In this review we will discuss the basic concepts behind plasmonics-enabled light concentration and manipulation, make an attempt to capture the wide range of activities and excitement in this area, and speculate on possible future directions.

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Plasmonics for extreme light concentration and manipulation.

1. Introduction 2. Theoretical foundations 3. Propagation and focusing of optical fields 4. Spatial resolution and position accuracy 5. Nanoscale optical microscopy 6. Near-field optical probes 7. Probe-sample distance control 8. Light emission and optical interaction in nanoscale environments 9. Quantum emitters 10. Dipole emission near planar interfaces 11. Photonic crystals and resonators 12. Surface plasmons 13. Forces in confined fields 14. Fluctuation-induced phenomena 15. Theoretical methods in nano-optics Appendices Index.

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Principles of nano-optics

It is known that light can be slowed down in dispersive materials near resonances. Dramatic reduction of the light group velocity-and even bringing light pulses to a complete halt-has been demonstrated recently in various atomic and solid state systems, where the material absorption is cancelled via quantum optical coherent effects. Exploitation of slow light phenomena has potential for applications ranging from all-optical storage to all-optical switching. Existing schemes, however, are restricted to the narrow frequency range of the material resonance, which limits the operation frequency, maximum data rate and storage capacity. Moreover, the implementation of external lasers, low pressures and/or low temperatures prevents miniaturization and hinders practical applications. Here we experimentally demonstrate an over 300-fold reduction of the group velocity on a silicon chip via an ultra-compact photonic integrated circuit using low-loss silicon photonic crystal waveguides that can support an optical mode with a submicrometre cross-section. In addition, we show fast (approximately 100 ns) and efficient (2 mW electric power) active control of the group velocity by localized heating of the photonic crystal waveguide with an integrated micro-heater.

Active control of slow light on a chip with photonic crystal waveguides

Single molecule confocal microscopy is used to study fluorescence intermittency of individual ZnS overcoated CdSe quantum dots (QDs) excited at 488 nm The confocal apparatus permits the distribution of “on” and “off” times (ie, periods of sustained fluorescence emission and darkness) to be measured over an unprecedentedly large dynamic range (109) of probability densities, with nonexponential behavior in τoff over a 105 range in time scales In dramatic contrast, these same τoff distributions in all QDs are described with remarkable simplicity over this 109-fold dynamic range by a simple inverse power law, ie, P(τoff)∝1/τoff1+α Such inverse power law behavior is a clear signature of distributed kinetics, such as predicted for (i) an exponential distribution of trap depths or (ii) a distribution of tunneling distances between QD core/interface states This has important statistical implications for all previous studies of fluorescence intermittency in semiconductor QDs and may have broader implications for other systems such as single polymer molecules

Nonexponential “blinking” kinetics of single CdSe quantum dots: A universal power law behavior

Single molecule confocal microscopy is used to investigate the detailed kinetics of fluorescence intermittency in colloidal II–VI (CdSe) semiconductor quantum dots. Two distinct modes of behavior are observed corresponding to (i) sustained “on” episodes (τon) of rapid laser absorption/fluorescence cycling, followed by (ii) sustained “off” episodes (τoff) where essentially no light is emitted despite continuous laser excitation. Both on-time and off-time probability densities follow an inverse power law, P(τon/off)∝1/τon/offm, over more than seven decades in probability density and five decades in time. Such inverse power law behavior is an unambiguous signature of highly distributed kinetics with rates varying over 105-fold, in contrast with models for switching between “on” and “off” configurations of the system via single rate constant processes. The unprecedented dynamic range of the current data permits several kinetic models of fluorescence intermittency to be evaluated at the single molecule level a...

``On''/``off'' fluorescence intermittency of single semiconductor quantum dots

Monodisperse 4 nm FePt magnetic nanoparticles were synthesized by superhydride reduction of FeCl2 and Pt(acac)2 at high temperature, and thin assemblies of FePt nanoparticles with controlled thickness were formed via polymer mediated self-assembly. Adding superhydride (LiBEt3H) to the phenyl ether solution of FeCl2 and Pt(acac)2 in the presence of oleic acid, oleylamine, and 1,2-hexadecanediol at 200 °C, followed by refluxing at 263 °C, led to monodisperse 4 nm FePt nanoparticles. The initial molar ratio of the metal precursors was retained during the synthesis, and the final FePt composition of the particles was readily tuned. Alternately, adsorbing a layer of polyethylenimine (PEI) and the FePt nanoparticles onto a solid substrate resulted in nanoparticle assemblies with tunable thickness. Chemical analysis of the assemblies revealed that more iron oxide was present in the thinner assemblies annealed at lower temperature or for shorter time. Thermal annealing induced the internal particle structure chan...

Controlled synthesis and assembly of FePt nanoparticles

Phase-change storage is widely used in optical information technologies (DVD, CD-ROM and so on), and recently it has also been considered for non-volatile memory applications. This work reports advances in thermal data recording of phase-change materials. Specifically, we show erasable thermal phase-change recording at a storage density of 3.3 Tb inch(-2), which is three orders of magnitude denser than that currently achievable with commercial optical storage technologies. We demonstrate the concept of a thin-film nanoheater to realize ultra-small heat spots with dimensions of less than 50 nm. Finally, we show in a proof-of-concept demonstration that an individual thin-film heater can write, erase and read the phase of these storage materials at competitive speeds. This work provides important stepping stones for a very-high-density storage or memory technology based on phase-change materials.

Hendrik F. Hamann

Papers

Active control of slow light on a chip with photonic crystal waveguides

Nonexponential “blinking” kinetics of single CdSe quantum dots: A universal power law behavior

``On''/``off'' fluorescence intermittency of single semiconductor quantum dots

Controlled synthesis and assembly of FePt nanoparticles

Ultra-high-density phase-change storage and memory.