This review focuses on the synthesis, protection, functionalization, and application of magnetic nanoparticles, as well as the magnetic properties of nanostructured systems. Substantial progress in the size and shape control of magnetic nanoparticles has been made by developing methods such as co-precipitation, thermal decomposition and/or reduction, micelle synthesis, and hydrothermal synthesis. A major challenge still is protection against corrosion, and therefore suitable protection strategies will be emphasized, for example, surfactant/polymer coating, silica coating and carbon coating of magnetic nanoparticles or embedding them in a matrix/support. Properly protected magnetic nanoparticles can be used as building blocks for the fabrication of various functional systems, and their application in catalysis and biotechnology will be briefly reviewed. Finally, some future trends and perspectives in these research areas will be outlined.

Magnetic nanoparticles: Synthesis, protection, functionalization, and application

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 nanocrystals has been intensively pursued, not only for their fundamental scientific interest, but also for many technological applications. The synthesis of monodisperse nanocrystals (size variation <5%) is of key importance, because the properties of these nanocrystals depend strongly on their dimensions. For example, the colour sharpness of semiconductor nanocrystal-based optical devices is strongly dependent on the uniformity of the nanocrystals, and monodisperse magnetic nanocrystals are critical for the next-generation multi-terabit magnetic storage media. For these monodisperse nanocrystals to be used, an economical mass-production method needs to be developed. Unfortunately, however, in most syntheses reported so far, only sub-gram quantities of monodisperse nanocrystals were produced. Uniform-sized nanocrystals of CdSe (refs 10,11) and Au (refs 12,13) have been produced using colloidal chemical synthetic procedures. In addition, monodisperse magnetic nanocrystals such as Fe (refs 14,15), Co (refs 16-18), gamma-Fe(2)O(3) (refs 19,20), and Fe(3)O(4) (refs 21,22) have been synthesized by using various synthetic methods. Here, we report on the ultra-large-scale synthesis of monodisperse nanocrystals using inexpensive and non-toxic metal salts as reactants. We were able to synthesize as much as 40 g of monodisperse nanocrystals in a single reaction, without a size-sorting process. Moreover, the particle size could be controlled simply by varying the experimental conditions. The current synthetic procedure is very general and nanocrystals of many transition metal oxides were successfully synthesized using a very similar procedure.

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Ultra-large-scale syntheses of monodisperse nanocrystals.

The development of novel materials is a fundamental focal point of chemical research; and this interest is mandated by advancements in all areas of industry and technology. A good example of the synergism between scientific discovery and technological development is the electronics industry, where discoveries of new semiconducting materials resulted in the evolution from vacuum tubes to diodes and transistors, and eventually to miniature chips. The progression of this technology led to the development * To whom correspondence should be addressed. B.L.C.: (504) 2801385 (phone); (504) 280-3185 (fax); bcushing@uno.edu (e-mail). C.J.O.: (504)280-6846(phone);(504)280-3185(fax);coconnor@uno.edu (e-mail). 3893 Chem. Rev. 2004, 104, 3893−3946

http://depa.fquim.unam.mx/amyd//archivero/FidelmarLechugaSanabria_4940.pdf

Recent advances in the liquid-phase syntheses of inorganic nanoparticles.

Wide-band-gap oxides such as SrTiO3 are shown to be critical tests of theories of Schottky barrier heights based on metal-induced gap states and charge neutrality levels. This theory is reviewed and used to calculate the Schottky barrier heights and band offsets for many important high dielectric constant oxides on Pt and Si. Good agreement with experiment is found for barrier heights. The band offsets for electrons on Si are found to be small for many key oxides such as SrTiO3 and Ta2O5 which limit their utility as gate oxides in future silicon field effect transistors. The calculations are extended to screen other proposed oxides such as BaZrO3. ZrO2, HfO2, La2O3, Y2O3, HfSiO4, and ZrSiO4. Predictions are also given for barrier heights of the ferroelectric oxides Pb1−xZrxTiO3 and SrBi2Ta2O9 which are used in nonvolatile memories.

Band offsets of wide-band-gap oxides and implications for future electronic devices

Shape Control of Thermodynamically Stable Cobalt Nanorods through Organometallic Chemistry

Unprecedented crystalline super-lattices of monodisperse cobalt nanorods.

Magnetic properties of nanoparticle composites, consisting of aligned ferromagnetic nanoparticles embedded in a nonmagnetic matrix, have been determined using a model based on phenomenological approaches. Input materials parameters for this model include the saturation magnetization (Ms), the crystal anisotropy field (Hk), a damping parameter (α) that describes the magnetic losses in the particles, and the conductivity (σ) of the particles; all particles are assumed to have identical properties. Control of the physical characteristics of the composite system—such as the particle size, shape, volume fraction, and orientation—is necessary in order to achieve optimal magnetic properties (e.g., the magnetic permeability) at GHz frequencies. The degree to which the physical attributes need to be controlled has been determined by analysis of the ferromagnetic resonance (FMR) and eddy current losses at varying particle volume fractions. Composites with approximately spherical particles with radii smaller than 10...

Magnetic properties of metallic ferromagnetic nanoparticle composites

Ferroelectric non-volatile memories for low-voltage, low-power applications

In this letter, we report the results for capacitance versus frequency measurements on a set of Ba0.5Sr0.5TiO3 (BST) capacitors with platinum electrodes (Pt) and varying BST film thicknesses. The study shows that Pt/BST interfacial capacitance is independent of frequency whereas the bulk dielectric constant has a power law dependence on frequency. Also, the bulk dielectric constant is observed to decrease whereas the interfacial capacitance increases with increasing temperature. In addition, we report the dependence of dielectric dispersion on BST film thickness and temperature. Calculations are performed which provide insights into the observed dispersion effects.

Peter Zurcher

Papers

Shape Control of Thermodynamically Stable Cobalt Nanorods through Organometallic Chemistry

Unprecedented crystalline super-lattices of monodisperse cobalt nanorods.

Magnetic properties of metallic ferromagnetic nanoparticle composites

Ferroelectric non-volatile memories for low-voltage, low-power applications

Investigation of bulk and interfacial properties of Ba0.5Sr0.5TiO3 thin film capacitors