Nanoclusters

What are Nanoclusters?

From a few atoms to several thousand atoms y High fraction of atoms on the surface y This gives them properties different from bulk material properties. y Properties of nanoclusters are solely guided by the number of subunits they contain.
y
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Magic Numbers
High mass spectral abundances that occur for certain cluster sizes which represent special electronic or geometric configurations. For clusters of noble gas atoms and, generally, for large clusters (n > 100), the magic numbers are determined by geometric considerations and not by the filling of electronic shells. Structural magic numbers affect the formation and abundancies of larger clusters. In case of smaller clusters the combined electronic structure of all the atoms is of greater importance. For simple free-electron systems, such as alkali metal and the main group metal (IIIIA) clusters,the magic numbers are often observed to follow the jellium-shell model

Jellium Model
In this model, the valence electrons are highly delocalized and occupy spatially delocalized orbitals. y There are nZ such electrons in an A_n cluster of valence Z (Z = 1 for Na, 2 for Mg, 3 for Al). The delocalized orbitals are classified according to their angular momentum as S, P, D, F, . . . orbitals, just as in isolated atoms. y Similar to the stability of atoms with filled atomic shells, clusters whose total number of valence electrons fill an electronic shell are especially stable. y Therefore, the magic numbers observed as peaks in the abundance spectra (for example, for Na at n = 8, 20, 40,
y

58, 92) correspond to major electronic shell closings.

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OPTICAL PROPERTIES
In

semiconductors the band gap will be increased as cluster size is decreased a blue shift in the absorption spectrum of the semiconductor.

Individual energy levels and separations are also dependent on the size of the clusters, which therefore affect the energies needed for the transitions of electrons to excited states. Clusters of different sizes will therefore have different absorption spectra and hence different colors

Magnetic properties
In a cluster the magnetic moment of each atom will interact with the moments of the other atoms y all the moments align in one direction with respect to some symmetry axis of the cluster the cluster will have a net magnetic moment.
y

As cluster size decreases it therefore becomes easier for them to exhibit ferromagnetic behaviour. y Even clusters made up of nonmagnetic atoms can have a net magnetic moment. For instance rhenium clusters show a pronounced increase in their magnetic moment when they contain less than 20 atoms y For clusters with less than 15 atoms these moments are fairly large.
y
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System
y

Cluster
Ferromagnetic Superparamagnetic Superparamagnetic Ferromagnetic

Bulk
Paramagnetic Ferromagnetic Ferromagnetic Paramagnetic

Na, K Fe, Co, Ni Gd,Tb Rh, Pd

Magnetic Moment vs. Cluster Size

y y y

The total magnetic moment of an atom is the zangular momentum added to the spin of the atom . Increased dimensionality the atomic coordination number. In 3d metals, this increase in coordination number causes an overlapping of the 3d orbitals, those primarily responsible for the magnetic moment of the atom. overlapping causes energy band structures to arise which tend to deplete the overall magnetic moment per atom of the material. The extreme case of this is the bulk material which has the lowest magnetic moment per atom and the highest orbital overlap.
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A Few Types of Nanoclusters

Van der Waals Nanoclusters
Binding energy: < 0.3 eV / atom y Balance between induced dipole force and quantum closed shell interaction y Noble gases form icosahedral Van der Waals clusters
y

Figure above from: Alonso, J. A., Structure and Properties of Atomic Nanoclusters, 2005

Ionic Nanoclusters
Bond Strength: 2-4 eV / atom  Tend to form boxes

NaCl Cluster

Graph above from: Martin, T. P., Physics Reports, 273 (1996) 199

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Metal Nanoclusters Metal clusters have complicated bonding that varies from metal to metal y Due to this variation the bond strength varies from around 0.5 eV to 3 eV per atom
y

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Transition metal nanoclusters

different types of magic numbers based upon an icosahedral and/or closely packed type structures have been observed. y metal-insulator transition in Hg clusters is the famous example: y Hg is metallic for larger clusters, while it is insulating for smaller clusters, owing to the change in the bonding mechanism from a metallic-type to a Van der Waals, being ascribed to the obvious quantum-size effect of the discrete electronic levels .
y
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Nanocluster Production
y

In principle physical methods for producing clusters is the initial vaporization of atoms from a bulk target.

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Laser Vaporization
Metal Nanoclusters Produced By Laser Vaporization

Figure above from: Billas et al., J. Magn. Magn. Mater. 168 (1997) 64

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The technique involves focusing a laser beam onto a metal sample. Metal atoms evaporate and are cooled with a flow of inert gas. As they cool the atoms combine into nanoclusters of varying sizes. They are then expanded through a nozzle into a vacuum to further cool them. Their sizes can be measured using a time-offlight mass spectrometer

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Plasma-GasPlasma-Gas-Condensation Technique

PGC cluster source is a combination of sputtering vaporization and gas-condensation techniques Versatile to vaporize transition metals and refractive elements enable to control the cluster size by adjusting the sputter yield, the gas pressure and the volume of the cluster growth region The metal vapor is generated by a dc magnetron sputtering. A continuous Ar gas stream was injected through the 0.3-mm gap between the shield cover and the target in order to avoid the accumulation of formed particles, which induce the abnormal discharge. He gas was also introduced into the sputtering chamber from the backside of the source.The cluster beam was extracted through the nozzle of 5 mm in diameter by differential 16 pumping.

Liquid nitrogen

Shield cover

He gas Ar gas cooling water

Magnets

Sputtering target
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NANOCLUSTER APPLICATIONS
Low energy deposition When nanoclusters are deposited at low energies, they generally retain some memory of their initial shape. This is useful in the manufacturing of complex nanometer sized structures (e.g. quantum dots

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HighHigh-energy deposition
At higher deposition energies the usefulness of cluster beams is at its fullest. Irradiation with high energy cluster ions can be used for instance in the manufacturing of high standard thin films, for y shallow implantation of cluster material and surface cleaning.
y

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Fluorescent Metallic Nanoclusters

y

Development of fluorescent noble-metal nanoclusters Au,Ag(similar to semiconductor quantum dots) have allowed researchers to manipulate their surface chemistry for biological application. High-quality nanoclusters are also more biocompatible and stable against photobleaching compared with organic dyes. These novel optical properties render the fluorescent noble-metal nanoclusters ideal fluorophores for multicolor and multiplexing applications. low toxicity as well as its ultra fine size.

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Nanoelectronic device applications

y

Electronic properties of metallic nanoclusters on semiconductor surfaces exploited in nanoelectronics. Current area of research is nanometerscale single-electron devices.

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Gold Nanoclusters For Drug Delivery and Imaging of Cancer Cells

Gold nanoclusters (GNCs) impregnated onto reduced graphene oxide (RGO) nanosheets cross swiftly across HepG2 hepatocarcinoma cell membranes to alter proteins and DNA and transport anticancer molecular drugs, such as doxorubicin (DOX).

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Nanomedicine
y

Gold nanoclusters (Au NCs) are potential antimicrobial agents for antibiotic-resistant bacteria and broad labeling agents for pathogenic bacteria. Generation of functional Au NCs by using lysozyme as the sequester and the reducing agent for Au precursors at 40C lysozymeAu NCs with desirable fluorescence feature can be employed as broad-band labeling agents for pathogenic bacteria. LysozymeAu NCs can be used to effectively inhibit the cell growth of notorious antibiotic-resistant bacteria.
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Thanks
Presented By:
Abhay Sachdev Ishita Matai Pallavi Gupta M.Tech Nanotechnology (Biotech Group)

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