Properties of individual nanoparticles

(Poole, Ch.4)
• Nanoparticles: 106 atoms or less.
• Define nanoparticle (nanostructure):
Radius No. of atoms
Bulk m to mm > 106
Microparticles m (=1000 nm)
Nanoparticles 1 – 1000 nm 104 (for
10nm)
Molecules 1-10 nm 10 (for 1 nm)
• Unique properties.
• Their properties differ from those same atoms bonded
together to form bulk materials.

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• More atoms are on the surface.

• Physical properties of materials can be characterized by some

critical length: A thermal diffusion length or scattering length, for
example.
• Electrical conductivity: Depends on the distance the electrons
travel between collisions. (mean free path).

• Nanotechnology in oldern days: Ancient paintings, Stained

glass, Small colloid particles in photographic plates, Water at
ambient temperature consists of clusters of hydrogen bonded
molecules, Kajal.

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Metal nanoclusters:
 Evaporation of metal atoms.
 Burst of He gas.

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 Clusters of 7 and 10 atoms are more stable.

No. of atoms in particles

 Magic numbers

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 Ionization energy of
atoms as a function of Z.
Maximum for inert gas
atoms 2He, 10Ne, 18Ar
because their outer most
orbits are filled. More
energy is required to
remove electrons from
filled orbits than unfilled
orbits.
 Ionization energy of
sodium nanoparticles.
Peaks are observed for
particles having 2 and 8
atoms.
 These numbers are known
as magic numbers. 5
 Jellium model:
 Considers clusters of
atoms as a large atom
(super atom).
 Spherically symmetric
potential well to
represent the electron
with spherical +ve
charge distribution.
 The hydrogen like atom
is assumed to solve
Schrodinger equation.
 Electronic magic
numbers are 2, 18 and
40 for the clusters.
 In atoms, shells K, L, M,
etc.

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Geometric structure:
 Bulk Au(gold) and Al have fcc structure.

 Gold 3-5 nm particles have icosahedral structure.

 Al particles <5nm have different structures.
 Al clusters have 13 atoms:
 This is a magic number (all fcc, hcp and icos have 13 atoms)
 Number of bonds is maximized.
 Number of atoms on the surface is minimized.
 Molecular orbital calculations predict lower energy for icosahedral structure.

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 Electronic properties of Al13 cluster:
 Binding energy of Al13 is less than in bulk.
 Al13 has an unpaired electron in the outer shell.
 Addition of an electron to form Al13(–) closes the shell with a
significant increase in binding energy.

 Properties such as vibration, structure, stability, reactivity,

electrical conductivity differ.
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Indium nanoparticles:
 At 6.5 nm dia – 6000 atoms – fc tetragonal.
 At 5nm – fcc  c/a=1.

Diameter of nanoparticles (nm)

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 Boron nanoparticles:
Different structures.

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Electronic structure:
 Energy bands form when atoms form a solid.
 Metal: Top band (conduction) is not totally filled.
 Semiconductor: Valence band is nearly filled. Conduction
band is not filled. Band gap is present.
 When a metal particle is reduced in size:
 Density of states in conduction band changes dramatically.
 Energy levels become discrete.
 Number of energy levels is equal to number of atoms.
 If the energy levels have more spacing than kT, then a gap
opens up.

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 In nanoparticles, the energy levels are similar to molecules
having bonding and antibonding levels (eg. H2 molecule –
singlet/triplet states).
 Eventually a size is reached where the surfaces of the particles
are separated by distances which are of the order of the
wavelength of electrons.
 Modeled like a particle in a box problem in quantum mechanics
– Quantum size effect.

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 Colour of a material depends on the energy level separation.
 Particles of different sizes will have different colours.

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 One method of studying the electronic structure of
nanoparticles is UV photoelectron spectroscopy.
 An incident UV photon removes electrons from their outer
valence levels of atoms. The electrons are counted and
energy measured.
 Peaks correspond to
separation of energy levels.

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Reactivity:
 Since the electronic structure depends on the particle size, the
ability of the particle to react with other species should depend
on particle size.
 This is important for designing catalytic agents.

 The reactivity of various gases can be studied using the

apparatus shown in Fig.4.2 (described in 1st lecture).

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 Mass spectra of Al
particles before and
after introduction of
oxygen gas:
 Intensity of Al13 and Al23
increased.
 Certain peaks (12, 14 Mass/charge of nanoparticle
and 20) disappeared.
 Reaction rates for
peaks other than Al13
and Al23 are higher.
 Al13– and Al23– are
more stable.
Mass/charge of nanoparticle

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 Reaction rate of iron with hydrogen.
 Particles with 10 atoms are more reactive.

Number of atoms in nanoparticle

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Fluctuations:

 Surface atoms are less restricted in their ability to vibrate than

those in the interior.
 They are able to make larger excursions from their
equilibrium positions.
 They can also move on the surface.

 This can lead to changes in structure with time.

 Fluctuation induced structural changes occur.

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Magnetic clusters:
 Magnetic moment of nanoparticles is generally less than that of
bulk.
 Superparamagnetism.
 Rhenium nanoparticles:
 Rhenium – nonmagnetic atom.
 Pronounced increase in net magnetic moment when the
particles have less than 20 atoms.

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Nano to bulk transition:
 In some particles with less than 100 atoms, removing an
electron from cluster differs from work function of bulk.
 Particles of gold containing above 1000 atoms have same
melting point as bulk.
 Average separation
of Cu atoms in Cu
nanoparticles
approach bulk value
when clusters have
more than 100
atoms.
 Thus, the nano to
bulk transition
depends on the
property being
measured. 22
Semiconducting nanoparticles

Optical properties:
 A significant shift in the optical absorption spectra towards the
blue (blue shift) as the particle size is reduced.
 In bulk semiconductors: A bound electron-hole pair known as
exciton can be produced.
 i.e An electron excited from valence band to conduction
band can be bound to the hole due to Coulombic attraction.
 This exciton can move through the lattice.
 The exciton can be modeled as a hydrogen-like atom.
 Light induced transitions between these levels produce series
of optical absorption peaks.

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 Cu2O optical absorption spectrum:

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 Weak confinement:
 Particle radius is larger than the radius of exciton.
 Blue shift observed.

 Strong confinement:
 Radius of particle is smaller.
 Motion of hole and electron become independent.
 Exciton does not exist.
 The hole and electron will have their own set of energy
levels.
 Here is also blue shift, but new set of absorption lines
emerge.

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 CdSe nanoparticles:
 The absorption peaks are due to excitons. Blue shift
observed.
 These peaks shift to higher energies for 20Å.

Optical absorption

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Photofragmentation:

 Nanoparticles of Si and Ge can undergo fragmentation when

subjected to light from Nd:YAG laser.
 Certain size fragments are more likely to dissociate than
others.
 Some fissions are:
Si12 + h  Si6 + Si6
Si20 + h  Si10 + Si10

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Coulombic explosion:
 Multiple ionization of a particle:
 Rapid high energy dissociation or explosion.
 Fragment velocities are very high.
 Electrostatic repulsion > binding energy.
 Clusters of inert gases are larger because of the weak van
der Waals forces.

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 Photoionization of deuterium particles:
 Nuclear fusion for femtosecond (10–15 s) laser.
 Fragment energies upto 1 MeV.
 This energy of the fragments is sufficient for nuclear fusion
when the fragments collide.
D + D  3He + neutron

 This reaction releases a neutron energy of 2.54 MeV.

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Rare gas and Molecular clusters:

Inert gas particles:

 Xenon clusters are formed by adiabatic expansion of a

supersonic jet of the gas through a small orifice into a vacuum.
 Van der Waals force is responsible for the binding of the
particles.
 Magic numbers are observed: 13, 19, 25, 55, 71, 87, 147 for
xenon.
 Since the inert gas atoms have filled electronic shells, their
magic numbers are structural magic numbers.

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 Eventhough these atoms have filled shells, because of the
movement of the electrons about the atoms, they can have an
instantaneous electric dipole moment P1.
 This dipole produces an electric field 2P1/R3 at another atom
at a distance R away.
 Thus, the first atom induces a dipole moment P2 on the
second atom, 2P1/R3. Here  is electronic polarizability.
 Thus the two inert gas atoms will have an attractive potential
2 P1 P2 4P12
U ( R)  3
 6
R R
 This is known as van der Waals potential. It is effective at
relatively large separation of atoms.

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 The repulsive potential when the two atoms come very close
together has the form B/R12.
 Thus the overall interaction potential is given by
B C
U ( R)  12  6
R R
 This is known as Lennard-Jones potential. This is used to
calculate the structure of inert gas clusters.
 The equilibrium distance for which the potential is a minimum,
1
B 6
Rmin  
C 

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Superfluid clusters:
 Supersonic free-jet expansion of He gas.
• Clusters of 4He and 3He atoms form.
• Magic numbers are: 7, 10, 14, 23, 30 for 4He.
7, 10, 14, 21, 30 for 3He.

 Superfluidity in He clusters having 64 and 128 atoms.

 Atomic electronic levels are filled by fermions (electrons):
 Having half integral spin.
 Particles lose their atomic nature and they behave as Bosons.
 Having integer spins.

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 At T=0: Fermions obey Pauli’s exclusion principle,
i.e. no two fermions will have the same set of quantum
numbers.
 All Bosons occupy the same lowest level. This is known as
Bose-Einstein condensation.
 When this occurs, the wavelength of each boson is the same
and all the waves are in phase.

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When boson condensation occurs in liquid 4He at T=2.2 K,
called lambda point ( point), the liquid He becomes superfluid
and its viscosity drops to zero.
The transition to superfluid state at 2.2 K is marked by a
discontinuity in specific heat known as lambda transition.
For He cluster of 64 atoms, the superfluid transition is observed
at a lower temperature than bulk liquid of He atoms.

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Molecular clusters:

Individual molecules can form clusters: eg. H2O molecule.

Water does not consist of isolated water molecules, rather it has

hydrogen bonded molecules.

At RT, 80% water molecules are bonded into clusters. As the
temperature increases, the clusters dissociate into isolated H2O
molecules.

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Other examples: (NH3)n+, (CO2)44, (C4H8)30

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