Nanomaterials

The family of nanomaterials

Atom clusters, nanoparticles, quantum dots
FePt-Al-O

C60

Thin films
Tunnel spin-valve head

QD in the nucleus of a cell Alkane thiol selfassembly on Au

Nanotubes, rods, belts, spheres

SWCNT

ZnO belt

ZnO tube

TiO2 spheres Co-Pc

Dendrimers, supra molecular structures, biomolecules

dendrimer

catenane

DNA on mica

Nanometer clusters and particles

1. Nanoparticles
Nanoparticles: are the simplest nano-structures.
In principle, any assembly of atoms bonded together with a radius of < 100 nm can be considered a nanoparticle.

These can include:

< 100 nm

Nanoclusters Nanoclusters

Fullerenes
C60

Metal clusters (agglomerates of metal atoms)

Au

Oxide (magnetic) and semiconducting nanoparticles (QD) Fe2O3

QD Ferritin

Large molecules, such as proteins, and supramolecular structures

1.1 Nanoclusters
Free atomic clusters: constituted by no more than a few hundred of atoms (maximum size of a few nm).

Kr clusters

C60

FePt icosahedral cluster

1.1 Nanoclusters
Nanocluster: is a nanometer sized particle made up of equal subunits (condensed hard matter). These subunits can
be atoms of a single element, molecules, combinations of atoms of several elements in subunits of equal stoichiometries (alloys) E.g.: Nan, (Cu3Au)n, (H2O)n, (TiO2)n Molecules have functionality which depends on the inter-positioning of their atoms, whereas the properties of nanoclusters are solely governed by the number of subunits they contain. In general, the physical properties of materials are dependent on the size and are scaleable with the amount of atoms - scaleable size regime - N

1.1 Nanoclusters
Non-scaleable size-regime: Every atom counts!
Nanoclusters their properties vary greatly with every addition or subtraction of an atom

Size does matter!

Small Small is is very very different different !!

1.1 Nanoclusters: geometric structure

Crystal structure of large nanoclusters (>1000 atoms): the same as the bulk structure of the material with somewhat different lattice parameters (clusters are slightly contracted). E.g.: Cu clusters tend to have an FCC structure

Wulff polyhedron

Smaller clusters of metallic atoms have other atomic arrangements which minimize surface energy (and internal energy).

Closed geometric shells

1.1 Nanoclusters: geometric structure

Very many atoms are sitting on the surface of a cluster: large effect of the surface energy. Structural magic numbers: closed geometric shells occur for icosahedral geometry (13, 55, 147, 309, 561). Five-fold symmetry cannot occur in bulk materials! Examples of clusters with icosahedral geometry.

561 Au

Ag icosahedral

W-Au12

1.1 Nanoclusters: geometric structure

Structural magic numbers: occur when an exact amount of
atoms is needed for a specific structure. Usually these species are more abundant than the rest.

tetrahedral Au20

icosahedral Au147

Smaller clusters can be also amorphous-like (disordered), spherical,

5 nm Au

Au55

Ag75

1.1 Nanoclusters: electronic structure

Structural magic numbers affect the formation and abundances of larger clusters and noble gas clusters, whereas for smaller metallic clusters the combined electronic structure of all the atoms is of greater importance. The jellium model It envisions the cluster as a single large atom, where the distribution of ionic cores is replaced by a deformable positive background (jellium density), and only valence electrons are treated explicitly.
Deformable spherical potential well atom
3p6 3s2 2p6 2s2 1s2

cluster
1f14 2s2 1d10 1p6 1s2

Energy levels can be calculated by solving the Schrdinger equation in a similar manner to that for the hydrogen atom.

1.1 Nanoclusters: electronic structure

Experimental abundance spectrum for sodium clusters compared with the ionization potentials calculated by the Clemenger-Nilsson model. In this case, electronic structure rather than geometrical factors governs the stability of the clusters.

W. D. Knight et al., Phys. Rev. Lett. 52 (1984) 2141

The maxima (2, 8, 20) can be associated with the fully filled-up shells in a spherical potential (s, s+p, s+p+d+s). Compare these numbers to the electronic level filling in the periodic table and the related chemical inertness of elements.

1.1 Nanoclusters: electronic structure

When a bulk lattice is formed for larger metallic clusters, the discrete energy levels are grouped tending to form energy bands. However, for small sizes these levels are still very different to the continuous bands of bulk materials.
E E E

size

Many properties of the material are dramatically modified! E.g.: optical and electrical transport properties.

1.1 Nanoclusters: optical properties

In semiconductors the band gap will be increased as particle size is decreased (blue shift in the absorption spectrum of the semiconductor). Energy level separations are also dependent on the size of the clusters, which affects the energies needed for the transitions of electrons to excited states.

The fluorescence spectrum depends on the size!

Fluorescence of cadmium selenide QDs
D. Talapin, University of Hamburg, Physica E 17, 99 (2003)

1.9 6.7 nm

1.1 Nanoclusters: reactivity

Since the electronic structure of nanoclusters depends on size, their ability to react with other species should also depend on size. Reactivity is highly dependent on the electronic
structure, leading to large variations even for sizes differing only by a single atom.

Nanoclusters: higher surface to volume ratio

Higher Higher reactivity reactivity

E.g.: gold nanoclusters are highly reactive if compared to the fairly inert bulk material

1.1 Nanoclusters: melting point

Lindermann (1906): a solid melts if its thermal fluctuations become too large; the solid shakes itself apart.

Melting starts at the surface!

1.1 Nanoclusters: melting temperature

For large gold clusters the melting temperature is reduced as 1/(cluster radius).

Koga et al. PRL92 11507 (2004)

Melting Melting starts starts at at the the surface! surface!

1.1 Nanoclusters: melting temperature

Melting temperature for Na clusters: more complex dependence for smaller sizes.

Solid-to-solid transition between N=400 to 1000

1.1 Nanoclusters: negative heat capacity

Negative heat capacities have been observed in nanoclusters under certain conditions. At the melting + temperature, an increase of the internal energy of Na147 by 1 eV
leads to a decrease in temperature by about 10 K. In large enough systems added energy is converted completely into potential energy, reducing continuously the fraction of its solid phase. The kinetic energy and thus the temperature remain constant. A small system tries to avoid partially molten states and prefers to convert some of its kinetic energy into potential energy instead.

The Thecluster cluster can can become becomecolder, colder, while while its itstotal totalenergy energy increases increases

1.1 Nanoclusters: negative heat capacity

A Amicro-canonical micro-canonical system system can canhave have negative negativeheat heat capacity capacity

H. Haberland et al., PRL86 1191 (2001)

1.1 Nanoclusters: magnetism

The cluster has a net magnetic moment: the interatomic
magnetic interactions can force all the atomic moments to align in one direction with respect to some symmetry axis of the cluster (it will be magnetized).

The Thecluster cluster behaves behaves like likea asmall small magnet magnet

Nanoparticulate materials

1.2 Nanoparticulate materials

Naked nanoparticles: (metallic, oxidized, semiconducting ) in the form of a powder (size between 2-100 nm).

Co 9nm

Fe2O3

Ag nanoprisms

10 nm
7 nm CdSe (QD) Tetrapod of CdSe

1.2 Nanoparticulate materials

Nanoparticles embedded in a matrix: (metallic, oxidized, semiconducting ) in the form of a thin film or a bulk material.
ZnO in Al-O matrix FePt in Al-O matrix

Co in ZrO2 matrix

1.2 Nanoparticulate materials

Nanoparticles in a colloidal suspension: metallic, oxidized, semiconducting Usually they are coated by a surfactant which avoids particle agglomeration.

Length scale: macroscopic

colloid

nanoparticle

Stability?
Surface active agent : Organic compounds containing both hydrophobic and hydrophilic groups.

Sedimentation Agglomeration

small particles (10 nm) surfactant (e.g. oleic acid)

1.2 Nanoparticulate materials

Bulk nanocrystalline materials (nanocomposites): They can be prepared by slow deposition or by consolidation of nanocrystalline powders.
Nanocomposite of CNb nanocrystalls in an amorphous C matrix

Nanocrystalline structure in a copper thin film

1.2.1 Mechanical properties

Bulk materials:
Metals are usually considered to be ductile and malleable. Ceramics are usually considered to be elastically hard and brittle.

Grain sizes move into the nanoscale (simplified view):

Metals get stronger and harder and more brittle. Ceramics become more ductile, loosing elastic hardness

Nanocrystalline materials

One Onecan canimprove improveon on the theproperties propertiesof ofboth both metals metalsand andceramics ceramics towards towardsthe theother other class classof ofmaterials materials

This is, however, a simplification: reality is more complex!

1.2.1 Background: yield strength

The yield strength y: Point in the stress vs. strain curve (strain is
relative elongation) where an external force has lead a permanent deformation of 0.2% after the external pressure is relieved. It is a measure of how much you can draw out a material before it fails for practical purposes.
Metal Yield strength (MPa) Tensile strength (MPa)

Gold Copper Iron Nickel Titanium Molybdenum

---------28 130 138 240 565

130 69 262 480 330 655

The plastic behavior is usually controlled by the motion of dislocations.

1.2.1 Background: Hall-Petch relation

Hall and Petch (1950): they found that y of a polycrystalline metal follows:
K y = 0 + d

where 0 and K are constants depending on the specific material. Explanation: the grain boundaries hinder dislocation motion, thereby making plastic deformation more difficult at small grain sizes. Many polycrystalline metals obey such a relationship over several orders of magnitude in grain size!

1.2.1 Breakdown of Hall-Petch relation

For nanoscale materials:
d 0y

which is obviously not true. Natural lower limit: atom size d 0.2 nm (in this limit the H-P relation is clearly not valid). Critical size: minimum grain size for which at least one dislocation loop must fit into average grain. Hall-Petch relationship breaks down below a critical size!

1.2.1 Reverse Hall-Petch effect

For nanometer grain sizes atomistic simulations of the deformation (molecular dynamics). MDS in nanocrystalline copper
Reverse H-P effect

Flow stress: average stress in the strain interval 7 to 10%

J. Schiotz, Science 301, 1357 (2004)

1.2.1 Reverse Hall-Petch effect

Deformation at the grain scale.
(A) d=49 nm after 10% deformation. (B) additional strain accumulated when deformation is increased from 10% to 11%. (C and D) the same for d=7 nm.

Scale bars: 5 nm

At small sizes: deformation is mainly located at the boundaries

and is mediated by atomic sliding.
J. Schiotz, Science 301, 1357 (2004)

1.2.1 Hall-Petch effect in Cu nanocrystals

Cu of 50 m: y=56 MPa. Cu of 23 nm: y =770 MPa A Atruly trulydramatic dramatic improvement improvement of of strength strength

Mechanical milling in situ consolidation

Good ductility: general rule (metals becoming brittle as the size of

the grain is reduced) is not always true!
Youssef, APL85, 929 (2004)