When each atom counts: the world of nanoclusters

The ancient properties of nanoclusters.

Lycurgus Cup- 4th century.

The ruby color is due to gold nanoparticles of different sizes embedded in a silica glass matrix.

What is a nanocluster?

Atom
Bulk

Nanocluster
105

Bulk

Nanocrystal

104
103
Cluster

10

Nanoscale
10
Virus

Microscale
cells
bacteria transistors field emitters

20 50 1

SETs

enzymes

102 101
Molecule

GMR layers molecules quantum dots

atoms

100 Number of atoms

0.1 Diameter (nm)

100 Ns/N (%)

0.1

10

100 1000 10000 nm physics@UniTS

The structure at the nanoscale: magic clusters

Planar ring Au6
C60 Buckminsterfullerene

Pentagonal bipyramid Si7

Fivefold icosahedron Al13

Cage-like structure CdSe34

NANOCLUSTERS on solid surfaces

Self-assembly of highly ordered nanoclusters monolayer 6 indium atoms on Silicon

C60 molecular crystals

Bimetallic Core-shell nanoclusters

Self-organized 3D superlattice of clusters 100 nm

physics@UniTS

The electronic structure at the nanoscale: magic clusters

SuperATOMS
Energy
Super - rare gas atom

Very large

Super- alkali atom

Number of interacting metal atoms

alkali-like electron

Small metal clusters

Large metal clusters

Bulk metal
P. Cheshnovsky, PRL 64, 1234 (1990) H. Handschuh, JCP 102, 6406 (1995)

Energy Level Diagram: Quantum Size Effects

MOLECULE LUMO

NANOPARTICLE

BULK SEMICONDUCTOR

Energy

CB
Eg HOMO Eg Eg

VB

Among the experimental techniques

High-Resolution Core Level Spectroscopy

X-ray Photoelectron Diffraction

Q
20 40 60 80

Au4f7/2

Nanoparticles: Quantum Size Effects

Quantum size effects: Noble metals, Semiconductors, Oxides.
Eg of PbS nanoparticle vs particle size

Engineer Eg over a wide spectral range:

IR to UV.

Semiconductor Q Dots: II-VI: CdS, CdTe, CdSe, PbS, ZnSe

Wang et al. J. Chem. Phys. 87, 12 (1987).

PbS: Eg:0.41 eV (300K, 15 nm)

2.34 eV. (300K, 1.3 nm)

Nanoparticles: Quantum Size Effects

CdSe quantum dots

Semiconducting CdSe nanodots: Illumination with a single light source Emission shifts to higher energy with decreasing particle size.

Metallic Au nanodots:
Fluorescence shifts to longer (lower energy) with increasing nanocluster size.

J.L. West and N. Halas, Ann. Rev. BioMed. Eng. 5, 285 (2003).

Au Nanoclusters

J. Zheng et al, Phys. Rev. Lett. 93, 077402 (2004).

Methods of Synthesis
RF Plasma Chemical Methods Thermolysis Pulsed Laser

The experimental set-up for size-selected clusters production

Cluster source Target Rotary Motor Quadrupole deflector Laser beam Nd:Yag Laser

He pulse valve

Expansion Lens system nozzle Quadrupole mass Thermalization spectrometer chamber

Lens system for focussing and soft-landing Analysis chamber

RF Plasma

Illustration of apparatus for the synthesis of nanoparticles using an RF-produced plasma

Thermolysis

Apparatus used to make metal nanoparticles by thermally decomposing solids consisting of metal cations and molecular anions, or metal organic solids.

Pulsed Laser Method

Apparatus to make silver nanoparticles using a pulsed laser beam that creates hot spots on the surface of a rotating disk.

Magnetic Nanoclusters

Nanocluster Quick Introduction

From a few atoms to several thousand atoms High fraction of atoms on the surface Different elements form different bonds and different nanocluster structures

A Few Types of Nanoclusters

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

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

A Few Types of Nanoclusters

Van der Waals Nanoclusters
The drops at 148 and 309 atoms correspond to completed icosahedra.

Figure above from: Echt, O., et al., J. Chem. Soc. Faraday Trans., 86 (1990) 2411

A Few Types of Nanoclusters

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

A Few Types of Nanoclusters

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

Laser Vaporization
Metal Nanoclusters Produced By Laser Vaporization

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

Stern-Gerlach Apparatus

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

Description of magnetic particles

A series of electron microscope pictures of gold les containing approximately 460 atom taken at various times showing fluctuation-induced changes in the structure.

Stern-Gerlach Experiment

Stern-Gerlach experiment is used to measure the magnetic moments of nanoparticles. A beam of metal clusters from a source is sent between the poles of permanent magnets shaped to produce a uniform gradient DC magnetic field, which produces a net force on the magnetic dipole moments of the clusters. There by deflecting the beam. The magnetic moment can be determined by the extent of the deflection, which is measured on a photographic plate or fluorescent screen.

Band Structure Evolution

Increasing Coordination Number

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

Magnetic Moment vs. Cluster Size

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

Magnetic Moment vs. Temperature

Co

Ni

Fe

Graphs from: Billas, M. L., A. Chatelain, and W. A. de Heer, Science 265 (1994) 1682

Superparamagnetism
Magnetization Loops of Fe Nanoclusters

Graph from: Jackson, T. J., et al., J. Phys.: Condens. Matter, 12 (2000) 1399

Nanoclusters applications: properties and applications

OPTICAL Anti-reflection coatings. Tailored refractive index of surfaces. THERMAL Enhance heat transfer from solar collectors to storage tanks. Improve efficiency of coolants in transformers .

ELECTRONIC High performance and smaller components, e,g, capacitors for small consumer devices such as mobile phones. Displays that are cheaper, larger, brighter and more efficient. High conductivity materials. MAGNETIC Increased density storage media. Nanomagnetic particles to create improved detail and contrast in MRI images. BIOMEDICAL Antibacterial silver coatings on wound dressings. Sensors for disease detection (quantum dots). Programmed release drug delivery systems.

MECHANICAL Improved wear resistance. New anti-corrosion properties. New structural materials, composites, stronger and lighter.

ENERGY High energy density and more durable batteries. Hydrogen storage applications using metal nanoclusters. Electrocatalysts for high efficiency fuel cells. Renewable energy, ultra high performance solar cells. Catalysts for combustion engines to improve efficiency.

Nanoclusters: inspiration and opportunity for science, not just for artists !

and

Summary
Metal nanoclusters of an element behave differently than bulk matter of the same element. d-orbital overlap reduces magnetic moment per atom. Metal nanoclusters exhibit magnetic shell phenomenon Metal nanoclusters do not lose their magnetization as quickly above the Curie temp. Metal nanoclusters exhibit superparamagnetic behavior. Superparamagnetism provides a theoretical minimum size per bit in magnetic moment based memory systems.