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NANOSTRUCTURAL PROPERTIES MASTER IN NANOSCIENCE April 2008 Lourdes del Valle Carrandi
Introduction
Metallic nanostructures have been a subject of considerable interest in recent years. The field of metallic nanostructures is now more popularly called plasmonics, since the major manifestation produced by optical excitations is the collective oscillation of electrons, which are localized along the interface. Hence, this wave is called a surface plasmon wave. Metal nanostructures and nanoparticles have found applications in a wide variety of areas: catalysis, optics, optoelectronics, information storage, biological and chemical sensing, and surface-enhanced Raman scattering. By tailoring the size and shape of metal nanoparticles, one can tune their intrinsic properties.
http://webs.uvigo.es/coloides/nano/research.html
Turkevich, P. C. Stevenson, J. Hillie. A study of the nucleation and growth processes in the synthesis of colloidal gold. Discussions of the Faraday Society. 1951, 11, 55-75.. OF THE FARADAY SOCIETY(11): 55 (1951)
Shape-Controlled Synthesis of Gold and Silver Nanoparticles Yugang SUN, Younan XIA. SCIENCE 13 December 2002: Vol. 298. no. 5601, pp. 2176 - 2179
Liz-Marzn and coworkers have reported the ability of N,N-dimethylformamide (DMF) to reduce Ag+ ions, so that stable spherical Ag nanoparticles can be synthesized using PVP as a stabilizer (larger PVP concentrations, star-like, multipod nanoparticles).
I. Pastoriza-Santos, L.M. Liz-Marzn, Formation of PVP-Protected Metal Nanoparticles in DMF Langmuir 2002, 18,2888-2894.
Response-resonance
The light absorption by metallic nanoparticles is described by coherent oscillation of the electrons, which is induced by interaction with the electromagnetic field. These oscillations produce surface plasmon waves. The specific wavelengths of light absorption producing plasmon oscillations are called surface plasmon bands or simply plasmon bands. The electric field of the incoming radiation induces the formation of a dipole in the nanoparticle. A restoring force in the nanoparticle tries to compensate for this, resulting in a unique resonance wavelength.
The oscillation wavelength depends on a number of factors, among which particle size and shape, as well as the nature of the surrounding medium, are the most important. For nonspherical particles, such as rods, the resonance wavelength depends also on the orientation of the electric field.
Response-resonance
For metallic nanoparticles significantly smaller than the wavelength of light, light absorption is within a narrow wavelength range. The wavelength of the absorption peak maximum due to the surface plasmon absorption band is dependent on the size and the shape of the nanocrystals, as well as on the dielectric environment surrounding the particles. For extremely small particles (less than 25 nm for gold), the shift of the surface plasmon band peak position is rather small. For larger nanoparticles (more than 25 nm for gold), the surface plasmon peak shows a red-shift.
Response-resonance
For a nanorod-shaped metallic nanoparticle, the plasmon band splits into two bands corresponding to oscillation of the free electrons along (longitudinal) and perpendicular (transverse) to the long axis of the rod. The longitudinal oscillation is very sensitive to the aspect ratio of the particles.
Henglein, A., J. Phys. Chem. (1993) 97, 5457 Nanophotonics. Prasad, Paras N. Hoboken, New Jersey : Wiley-Interscience, 2004
Response-resonance
Metal nanoellipsoids possess 3 plasmon resonances corresponding to the oscillation of electrons along the 3 axes of the NP. The resonance wavelength depends on the orientation of the electric field relative to the particle. Changing the axes length, the plasmon resonance frequencies of the nanoellipsoid can be tuned systematically.
Surface Plasmons on Metal Nanoparticles: The Influence of Shape and Physical Environment Cecilia Noguez J. Phys. Chem. C 2007, 111, 3806-3819
Response-resonance
To understand the influence of morphology, the SPRs for polyhedral NP have been recently studied. A general relationship between the SPRs and the morphology of each NP was established in terms of their vertices and faces. In summary, it was found that as the truncation increases:
(i) the main resonance is always blue-shifted. (ii) the SPRs at smaller wavelength are closer to the dominant mode, so they can be hidden. (iii) the width of the main SPRs increases.
Influence of morphology on the optical properties of metal nanoparticles Journal of computational and theoretical nanoscience. A. L. Gonzlez and Cecilia Noguez. Volume: 4 Issue: 2 Pages 231-238 Pulishes: Mar 2007
Response-resonance
The optical response of complex nanostructures can often be understood in terms of the coupling of plasmons in simpler components that make up the structure. Extinction measurements have shown that the plasmon resonance of gold nanorings, fabricated using lithographic techniques and latex sphere templates, is strongly redshifted as compared to the response of a disk with the same size. The calculations show that this redshift is due to increased coupling between plasmons on the inner and outer edges of the nanorings.
Optical Properties of Gold Nanorings. J. Aizpurua, P. Hanarp, D. S. Sutherland, M. Kll, Garnett W. Bryant, and F. J. Garca de Abajo. Physical Review Letters. VOLUME 90, NUMBER 5. 7 FEBRUARY 2003
Response-resonance
The presence of sharp edges or tips has been shown to increase electricfield enhancement, which is important for applications involving metal nanoparticles as sensors. It is also found that the corners induce more surface plasmons in a wider energy range.
The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric Environment K. Lance Kelly, Eduardo Coronado, Lin Lin Zhao, and George C. Schatz J. Phys. Chem. B 2003, 107, 668-677
High-yield synthesis and optical response of gold nanostars Pandian Senthil Kumar, Isabel Pastoriza-Santos, Benito Rodrguez-Gonzlez, F. Javier Garca de Abajo and Luis M Liz-Marzn Nanotechnology 19 (2008)
Conclusions
Metal-NP plasmonics promises to have significant impact on fastly developing technologies. Applications currently being developed include: nanoscale optical and infrared sensing, microscopy, and spectroscopy (the metal NPs effectively act as nanoantennas to enhance signal emission). Metal NPs can act as nanoantennas to collect and localize energy input. Critical uses in medicine, for example to locally and selectively heat and kill cancerous tumors, are already being developed. Nanoscale optical communication along pathways defined by assemblies of coupled NPs, is also being explored as one approach to push electronic and optical technologies down to the nanoscale.
Gold nanoparticles dont stick as well to noncancerous cells. The results can be seen with a simple microscope. Mostafa El-Sayed. Georgia Tech
Bibliography
Nanophotonics. Prasad, Paras N. Hoboken, New Jersey : Wiley-Interscience, 2004. Nanoparticles : from theory to application. Schmid, Gnter Weinheim, Germany: Wiley-VCH, 2004. Nano-optics. Kawata, Satoshi, Ohtsu, Motoichi, Irie, Masahiro. Berlin: Springer, 2002. Nanometals: formation and color. Luis M. Liz-Marzn. Review Feature. Materials Today. February 2004. Metal-Nanoparticle Plasmonics. Matthew Pelton, Javier Aizpurua, and Garnett Bryant. Laser & Photonics Reviews. 2008.
Gold nanostars (digitally coloured electron microscopy images) on a background of real colour spots produced by interaction of visible light with nanoparticles of various shapes.