Plasmons in different shapes

NANOSTRUCTURAL PROPERTIES MASTER IN NANOSCIENCE April 2008 Lourdes del Valle Carrandi

Plasmons in different shapes

Introduction Synthesis of metallic nanoparticles Response-resonance Conclusions Bibliography

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.

Synthesis of metallic nanoparticles

Two approaches: -TOP-DOWN Lithography -BOTTOM-UP Colloidal synthesis

Synthesis of metallic nanoparticles

TOP-DOWN Lithography Electron-beam-lithography (EBL): An electronbeam resist is first deposited on a substrate, and is then exposed by scanning a focused electron beam over the surface. Development of the resist removes the exposed portions. A metal layer is then deposited on the sample, and the remaining resist is subsequently dissolved in a solvent, so that the metal deposited on the unpatterned part of the samples is removed. Despite the sophistication and flexibility of these techniques, difficulties remain in obtaining high-quality metal nanostructures (sharp corners and nanometer-scale interparticle spacings) needed for exploitation of plasmon effects. To achieve greater control over the atomic-scale structure of metal NPs, the complementary technique of colloidal synthesis must be considered.
Optical properties of two interacting gold nanoparticles W. Rechberger, A. Hohenau, A. Leitner, J. R. Krenn, B. Lamprecht and F. R. Aussenegg Optics CommunicationsVolume 220, Issues 1-3, 1 May 2003, Pages 137-141

Synthesis of metallic nanoparticles

BOTTOM-UP Colloidal synthesis

http://webs.uvigo.es/coloides/nano/research.html

Synthesis of metallic nanoparticles

This technique of synthesis is inspired by Faradays two-phase system but developed by Schiffrin and coworkers. It uses the thiol ligands that strongly bind gold due to the soft character of both Au and S. AuCl4- is transferred from water to toluene using tetraoctylammonium bromide as the phase-transfer reagent and reduced by NaBH4 in the presence a thiol. Depending on the ratio of the Au salt and capping agent (thiol), the particle size can be tuned to between ~1 nm and ~10 nm.
Faraday, M. Experimental Relations of Gold (and other Metals) to Light. Philos. Trans. 1857, 147, 145-181. Synthesis of Thiol-Derivatized Gold Nanoparticles in a Two-PhaseLiquid-LiquidSystem. M. Brust, M. Walker, D. Bethell, D. J. Schiffrin, R. J. Whyman J. Chem. Soc., Chem. Commun.1994, 801-802.

Synthesis of metallic nanoparticles

The most popular method of preparing Au nanospheres dispersed in water is the reduction of HAuCl4 in a boiling sodium citrate solution. The formation of uniform Au nanoparticles is revealed by a deep wine red color observed after ~10 minutes. The average particle diameter can be tuned over quite a wide range (~10-100 nm) by varying the concentration ratio between the Au salt and sodium citrate (less citrate leads to larger nanoparticles). The same procedure can be used to reduce an Ag salt, but particle size control is very limited. Citrate reduction has also been applied to the production of Pt colloids of smaller particle sizes (2-4 nm), which can be grown further by hydrogen treatment. Standard citrate reduction introduced by Turkevich:

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)

Synthesis of metallic nanoparticles

In the polyol process, AgNO3 is reduced at high temperature by ethylene glycol, which also serves as the solvent. The use of polyvinylpyrrolidone (PVP) as a capping agent leads to highly non-spherical silver particles, such as singlecrystal nanocubes. The dimensions of Ag nanoparticles can be controlled varying the experimental conditions (temperature, ratio of Ag salt and PVP, etc.).

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.

Nanophotonics. Prasad, Paras N. Hoboken, New Jersey : Wiley-Interscience, 2004

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 stick to cancer cells and make them shine.

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.