What is Nano?

From greek « nannos » = dwarf

Journal of Nannoplankton research

From latin « nanus » = dwarf

Journal of Nanotechnology
Introduction:
Notion of scale
Tools to observe nano-objects
What changes at the nanoscale ?
Nanotechnologies: main fields of application
Energy
Electronics
Health
Environment
New life styles
Allready for sale
Methods of preparation
Conclusion
 Notion of scale
Nanometer
Micron

nanoworld

Atom Agregate Quantum Nano- Photo- Micro- Chip for Cell Car
of atoms box transistor transistor processor credit phone
card

Technological object
 Vous avez dit nano… 10-9m
Quelques dimensions caractéristiques :

90 nm

Sn/SnOx
Nano…
25-30nm

C60 0,7nm

Nano-objet : solide dont une des dimensions caractéristiques est entre 1 et 100 nm
Nano-structure: structure dont une des dimensions caractéristiques est entre 1 et 100
nm ou résultant de l’assemblage de nano-objets
• A micron:
1 mm = 10-6m 1m = 1 million of microns

Hair : tens of microns

Micron large roughness of the

Lotus leeves

Adhesion: micron large hair and

Van der Waals bonds

2mm
A nanometer : one thousand time smaller than a micron

1 nm = 10-9m = 0.000000001 m in 1m: 1 billion of nanometers

1 Å = 0.1 nm
1 pm = 0.001 nm

C60 0.7nm

DNA 2.5 nm of diameter

Atomic radius : 0.1 to 0.3 nm

Distance between 2 atoms in a molecule or a solid : 0.08 to 0.6 nm

The nanometer is a large unit for chemistry !

 Nano-Objects

© F. Caillaud/CNRS
Photothèque/SAGASCIENCE
Liposomes, vesicles measuring tens
to hundreds of nanometers, make
excellent nanovectors for drugs.
Micelles
 CHO OHC
OHC CHO
OHC CHO
O O O
O CHO
OHC PS P S
O Me N O CHO
OHC O PS MeN
N N Me P O

Polymers et OHC
OHC O
O PS
N
Me N
N
Me N
CH
HC

O O
CH N
CH
N S
O
Me P
N S
O
CHO

CHO
O O N

dendrimers OHC
OHC
OS
O PN
N
Me HC
CH

O S
P S
MeN
HC
N
HC
N
P
Me N S

Me
O
CH

HC
N
Me P O
N
S
O
CHO

CHO
O PN NP O
N HC N S O
O S Me CH O O Me O
P S P CHO
OHC OP O N Me P O N S
NN N S N
Me HC Me N CH
CH N
OS CHO
OHC
S H CH Me O Me
OP N N C O PN O NP O C N N PO
N C N S
O
Me Me HC H
O
P NO
Me O H
H S O CHO
OHC OS N C P O
N
PN C NNP

Carbon OHC
O
S
P N N
O Me C
H
S
O PN
N C
H
O Me
P N
O O

HC
H S O
CH Me
NN O
P
Me O
C N N PO
H S
CHO

O Me HC SO CHO

Nanotubes
OHC N N Me
HC S N N CH Me
S N O P Me S PO N
NP
N O O O CHO
OHC OP CH Me S
O Me S N CH N O
O PN N O
Me HC CH P CHO
OHC CH O N S O
N CH Me
N N Me N Me N
OSP N S P N
Me HC S P PO
OHC O O O O O HC CHO
S O
N N
N HC N Me
OHC S P Me HC CHO
O N CH HC S P O
O N N Me O
OHC S N N N CHO
Me N Me
OP N Me S P
OHC S P O CHO
O SP O
OHC O O O O
CHO
OHC

« A small piece » of a solid (metal or oxyde etc.):

CHO
OHC CHO
CHO CHO

Nanoparticle
 Nanostructures

Nanocrystalline copper, 3 times Resistive strain gauges

more resistant than regular copper
(deforms more easily under strain)

Transistor
80nm large drain obtained by
lithography (University of Aachen)
Tools for observation at the nanoscale
Transmission electron microscope (TEM)

1931
E. Ruska

SEM to
study
surfaces
Observation of populations of
nano-objects.
e.g. Cobalt nanoparticles

High Resolution TEM image of a composite

nanoparticle Sn/SnOx (25-30nm)
 High resolution TEM micrograph of an
individual FePt NP. The image is contrast
enhanced by means of Fourier filtering
(Leibniz Institute for Solid State and Materials
Research Dresden)
Energy Filtered TEM showing silica NPs in
organic coating. Conventional TEM images
show little of no contrast. (C. Simon et al
"Transmission Electron Microscopy Analysis of Hybrid
Coatings", Proc. of the 6th International Congress on
Advanced Coating Technology, Nuremberg 2001)

Rh M4,5 Co L2,3
Co and Rh distributions in 6.1 nm large CoRh nanoparticles evidenced by E-filtered TEM. LCC-
CEMES-CEA
TEM image of a
porous silica

1000-1500 m²/g
Scanning tunneling microscope –STM-

Displacements 1981: Binning et Rohrer,

IBM Zurich
Nobel Prize 1986
Electric
current

Electric
tip (with E. Ruska for inventing
current the first electron
microscope )

Sample

1nm
5nm
Surface of graphite Quantum Corral : image of 48 iron atoms
forming a circle on a copper surface
Atomic force microscope –AFM-

Probe

Image of DNA strands

Image of a membrane with pore

diameter around 20nm
AFM image of SWCNT
http://www.firstnano.com/applications.html
 What changes at the nanoscale ?
Increase in surface/volume and surface/mass ratios

A spoon of nanoparticles may

have the surface of a rugby field

Definition: specific surface (around 100 m2/g)

 Dispersion and surface

- A 1 cm cube has a surface area of 6 cm2

- Slice it into pieces 1mm large, the surface increases up to 60 cm2

- If pieces are 1 μm large, the surface reaches

- If they are as small as 1 nm, the surface reaches

 Surface and reactivity …
…a show

Reaction between potassium permanganate and glycerol

What changes at the nanoscale ?
FCC Octahedron

Apex

Edge Face

Size of the particle

The properties (catalytic, optic, magnetic, transport)

depend on the composition, size, shape of the object;
that’s seldom the case at the macroscopic scale
 Porosity and surface

10 nm

The specific surface area of a 1cm large silica cube is 0.00027 m2 g-1

If you make 10 μm large holes (pores) in it, the specific surface area
reaches tens of m2 g-1

With 4 nm large pores, it reaches 1000 to 1500 m2 g-1

TEM image of a
porous silica

1000-1500 m²/g
 Metal organic frameworks (MOFs)

Fig. 1. Single-crystal x-ray structures of MOF-5 (A), IRMOF-6 (B), and IRMOF-8 (C) illustrated
for a single cube fragment of their respective cubic three-dimensional extended structure.

N L Rosi et al. Science 2003;300:1127-1129

 New electronic properties

Story of St Nicaise,
Cathedral of Soisson
Gold treasure 1600-1200 BC (France), XIIIth AC

a) Gold Nanoparticles
b) Gold rods
d) AgxAu1-x Nanoparticles
e) Different aspect ratios
Materials Today, 2004
 Under visible light

Under UV light

Shell
CdSe Nanoparticles

Core Core
(3nm) (5nm)
 Weak interactions become predominent !

Iron powder
attracted by a
magnet

«Liquid Iron»
Colloidal solutions of
Fe3O4
= Ferrofluid
 Nanotechnology

Nanoscience concerns the study of phenomenon observed in objects,

structures, or systems with sizes of a few nanometers in at least one
direction, and the properties of which are directly related to this size
reduction (meaning that they are different from those of similar objects,
structures or systems of larger size).

Nanotechnology covers all technics allowing fabrication, observation and

measure of these objects, structures and systems.
It also corresponds to any technological development and application of
nanoscience.

Nanoparticle + fonction : Nanomaterial

 Main fields of application

• Energy
• Electronics
• Health
• Environment

The fast development of nanotechnologies is due to their huge

economic impact.

« The smallest is the platform conceived and realised, the more

important are benefits »
Energy
•Photovoltaic cells
(remplacement of silicium-14% yield- by association
of nanocrystals-85% yield-)
•Portable Batteries
(reloading, huge power)
•Thermoelectric materials
(cooling of microprocessors, transformation of heat
into electricity)
•Isolation
(treatment of glass surfaces to stop heat diffusion,
e.g. aerogels)
 •Dihydrogen storage (large specific area)

Neutron-scattering image reveals where dihydrogen molecules (red-green circles) connect to a

metal organic framework (MOF, Chem. Soc. Rev., 2003, 32, 276–288). The ball-and-stick
model of the MOF is superimposed on the neutron image.
Left Image: T. Yildirim/NIST; right image: B. Panella, M. Hirscher, Advanced Materials, 2005,
17(5), 538–541,2005
 Actually
Electronics 250 millions

•Size reduction of electronics components:

The size of transistors decreases by half every 10

months
The cost of an elaboration line doubles every 36
months
10mm
 Electronics
•Size reduction of electronics components:
Prescott (from Intel) processor used in 2006 devices 90nm large,
Size limit was down to 65 nm in 2007
Below 20 nm silicium components aren’t insulating anymore: physics
limitation (qauntum phenomena) to miniaturisation of integrated
circuits with today silicium technology

80nm large drain obtained by

lithography (University of Aachen)

Molecular computer ?
•Increase the speed of data transfer:
Optoelectronics: transmission of a signal, not with an electric current
through copper wires but with light from a QD emitting at a selected wavelength

•Efficiency of light emission (screens, light sources -LED-)

• Increase data storage density

(MRAM, dots)

Disk of Phaistos,
Crète, 2000 BC
 FePt, S. Sun et al.
Science 2000 AC

How to precisely localise, connect, address nano-objects

and repeat these steps at will?
Connections for the futur:
carbon nanotubes
 Health
•Prevent (anti-microbian coatings, filters, monitoring)

Ag nanoparticles 15nm, anti-viral, anti-bacterial

•Diagnostic (monitoring, bioassays -biochips-, imaging -IRM)

•Thérapeutics :
implants, identification of our genetic map
for individual treatment, new delivery
pathways, new medecines, new technics
(e.g.hyperthermia)
Nanostructured surface of a stent preventing the formation of
blood-clots…
Artery
Blood
circulation
blocked
Fat deposits
Metal mesh tube
Blood
circulation
Stent restored
 Environment

Monitoring (detection of pollutants):

 Sensors of reduced dimensions, portables systems, faster

(real time) and better localised detection of today’s
pollutants.

 Monitoring of sub-micrometer particles in the atmosphere;

degradation of nanomaterials, nanostructured composites
etc.
i.e. monitoring of pollutions generated by the development of
nanotechnologies
Miniaturised Sensors
Imprinted circuit

Oxide nanoparticles
Purification of air and water, etc.:
Nanoparticles can be used as catalysts for depolution (e.g. self-cleaning St
Gobain’s window glass doped by TiO2 nanoparticles- AC Sept. 2007; Ecopaint from
Millenium Chemicals )

 Use of catalytic filters : Co3O4,

or Pd, Pt, Rh on Al2O3

Magnetic separation. Ex. of arsenic.

Yavuz, C.T. et al. (2006) Science 314(5801): 964-967

Arsenic easily binds to the surface of Fe3O4

nanoparticles; it can thus be eliminated from
water with a magnet
 Decrease of materials and energy consumption:
Increase the efficiency of fuel combustion (CeO2 nanoparticles)
 Development of renewable sources of energy (e.g. photovoltaics)
 Valorisation of lost heat (development of thermoelectric materials)

Recycling ???
 Decrease of materials and energy consumption:

 Size reduction of the components (e.g. nanoelectronics)

 Molecular electronics: using molecules in place of silicium

based components e.g. diode, transistor…

In 2003, to make a PC (42 millions of transistors), 240 kg of conventional

energy, 22 chemical products, 1500 L water were necessary

And to make molecules ??? Chemists prepare moles of molecules in one

batch ( 1 mole: 6,02.1023 molecules).

1965: Jacques MONOD,

an electronic component weigths 10-2g, an enzyme: 10-17g

?
Nanotechnology = Ecotechnology
 New consumption goods

Reinforced and/or
lighter materials:
transports, construction,
sports etc..
e.g. carbon nanotubes, fullerens or
Sulfur bridge
SiO2 nanoparticles in pare-chocs,
racquets structure or golf clubs

Ceramics nanoparticles in cement,

silica in « green » tires…

(NB: carbon particles (10-100nm) have

Polymers
been introduced in tires since 1917s
for reinforcement) Silica or carbon
black loading
 Smart Materials
 cosmetics : liposomes and micelles to transport nutriments inside cells
(anti-age products); solar screens (TiO2, ZnO…)
e.g. superhydrophobic surfaces
  Self-cleaning glasses, easily washed paints, anti-bacterial coatings
Light Dirt (fat)

CO2
H2O

Window with (right) or without (left) a phtocatalytic coating of TiO2 nanoparticles.

TEM image of the nanoparticles
 New generation of electronics goods: Increased efficiency, faster
communication, increased mobility.
e.g. cameras, cell phones, MP3 players (walkman), flexible screens …
 New generation of pigments

SEM of rutile (titane white)

obtained byt the New Jersey
Zinc Company.

The Kerr collections

Harmony in green and pink:
M. José-Yacaman, et al. Science, 1996 (273) 223
The Music Room by Whistler
Maya ceramics (250-850 AC), technics
used till the 20th century

Iridescent paint
 Already for sale2006:

212 products made world wide have been identified as 'nano'

(the preparation of which requires nanotechnologies or uses
nanomaterials)

Essentially nanoparticles… carbone, Ag, oxides (Ti, Zn, Sn, Ce…),

and silicon based materials.

Main domains: clothes,sports goods, cosmetics, catalysts

 How to make nanocomponents ?

Top-down approach
Bulk material
Ball-milling
bll

Powder

Nanoparticles

Agregates
Evaporation/condensation
Sol-gel and other chemical technics
Chemical Vapor Deposition
Atoms

Bottom-up approach
 Gold nanoparticles

M. Faraday’s method (1857)

How would you know the
purple color indeed
corresponds to
nanoparticles?

Dispersions of nanoparticles
diffuse light !
That’s the so–called Tyndall
effect

Left: solution of the gold precursor

Right: final solution with gold nanoparticles
 Conclusions
Many kinds of nano-objects and nanostructurees

Many applications due to changes of properties at

the nanoscale

New physical properties, new chemical reactivity

Surface, interfaces and weak interactions play a

major role
 The course will focus on nanoparticles
(chemical synthesis, properties and
applications) and their assembly into
nanostructures; when needed some basic
knowledge on soft nano-objects will be
introduced (e.g. micelles, liposomes)