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Self-assembled monolayers of thiolates on metals as a form of nanotechnology.

The surface science of titanium dioxide

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.

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

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

Synthesis of monodisperse iron-platinum (FePt) nanoparticles by reduction of platinum acetylacetonate and decomposition of iron pentacarbonyl in the presence of oleic acid and oleyl amine stabilizers is reported. The FePt particle composition is readily controlled, and the size is tunable from 3- to 10-nanometer diameter with a standard deviation of less than 5%. These nanoparticles self-assemble into three-dimensional superlattices. Thermal annealing converts the internal particle structure from a chemically disordered face-centered cubic phase to the chemically ordered face-centered tetragonal phase and transforms the nanoparticle superlattices into ferromagnetic nanocrystal assemblies. These assemblies are chemically and mechanically robust and can support high-density magnetization reversal transitions.

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Monodisperse FePt Nanoparticles and Ferromagnetic FePt Nanocrystal Superlattices

High K/sub u/, uniaxial magnetocrystalline anisotropy, materials are generally attractive for ultrahigh density magnetic recording applications as they allow smaller, thermally stable media grains. Prominent candidates are rare-earth transition metals (Co/sub 5/Sm,...), and tetragonal intermetallic compounds (L1/sub 0/ phases FePt, CoPtY,...), which have 20-40 times higher K/sub u/ than today's hexagonal Co-alloy based media. This allows for about 3 times smaller grain diameters, D, and a potential 10-fold areal density increase (/spl prop/1/D/sup 2/), well beyond the currently projected 40-100 Gbits/in/sup 2/ mark, Realization of such densities will depend on a large number of factors, not all related to solving media microstructure problems, In particular it is at present not known how to record into such media, which may require write fields in the order of 10-100 kOe. Despite this unsolved problem, there is considerable interest in high Ku alternative media, both for longitudinal and perpendicular recording. Activities in this area will be reviewed and data on sputtered and evaporated thin FePt films, with coercivities exceeding 10000 Oe will be presented.

High K/sub u/ materials approach to 100 Gbits/in/sup 2/

We have used oxygen-plasma-assisted molecular-beam epitaxy (OPA-MBE) to grow CoxTi1−xO2 anatase on SrTiO3(001) for x=∼0.01–0.10, and have measured the structural, compositional, and magnetic properties of the resulting films. Whether epitaxial or polycrystalline, these CoxTi1−xO2 films are ferromagnetic semiconductors at and above room temperature. However, the magnetic and structural properties depend critically on the Co distribution, which varies widely with growth conditions. Co is substitutional in the anatase lattice and in the +2 formal oxidation state in ferromagnetic CoxTi1−xO2. The magnetic properties of OPA-MBE grown material are significantly better than those of analogous pulsed laser deposition-grown material.

Epitaxial growth and properties of ferromagnetic co-doped TiO2 anatase

The magnetic domain structure and magnetization curves of chemically ordered epitaxial FePt (001) films with perpendicular magnetic anisotropy are discussed. Films were dc magnetron sputtered from a Fe50Pt50 alloy target onto Pt seeded MgO (001) at substrate temperatures of 550 °C. The thickness of the FePt layers was varied between 18 and 170 nm. Specular and grazing incidence x-ray diffraction measurements confirm the presence of the anisotropic, face centered tetragonal (L10) crystal structure. Long range chemical order parameters of up to 0.95 and small mosaic spread, similar to results reported for FePt (001) films grown by molecular beam epitaxy. For film thicknesses ⩾50 nm in-plane and out-of-plane hysteresis measurements indicate large perpendicular magnetic anisotropies and at the same time low (about 10%) perpendicular remanence. Magnetic force microscopy reveals highly interconnected perpendicular stripe domain patterns. From their characteristic widths, which are strongly dependent on the film...

Perpendicular magnetic anisotropy and magnetic domain structure in sputtered epitaxial FePt (001) L10 films

We show that under certain conditions, highly Co-enriched TiO2 anatase clusters nucleate on epitaxial TiO2 anatase grown on LaAlO3(001) by oxygen plasma assisted molecular beam epitaxy. In the most extreme cases, virtually all incident Co segregates to the clusters, yielding a nanoscale ferromagnetic phase that is not ferromagnetic in homogeneous films of the same Co concentration. The nucleation of this phase simultaneous with continuous epitaxial film growth must be carefully monitored in order to avoid drawing false conclusions about the film structure.

Liesl Folks

Papers

Monodisperse FePt Nanoparticles and Ferromagnetic FePt Nanocrystal Superlattices

High K/sub u/ materials approach to 100 Gbits/in/sup 2/

Epitaxial growth and properties of ferromagnetic co-doped TiO2 anatase

Perpendicular magnetic anisotropy and magnetic domain structure in sputtered epitaxial FePt (001) L10 films

Clusters and magnetism in epitaxial Co-doped TiO2 anatase