cours 1 introduction nano

8/7/2019 Cours 1 Introduction Nano

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What is Nano?

From greek nannos = dwarfJournal of Nannoplankton research

From latin nanus = dwarfJournal of Nanotechnology


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Introduction:

Notion of scale

Tools to observe nano-objectsWhat changes at the nanoscale ?

Nanotechnologies: main fields of application

Energy

ElectronicsHealth

Environment

New life styles

Allready for sale

Methods of preparation

Conclusion


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Notion of scale

Technological object

MicronNanometer

nanoworld

CarCellphone

Chip forcreditcard

Micro-processor

Photo-transistor

Nano-transistor

Quantumbox

Agregateof atoms

Atom


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90 nm

Quelques dimensions caractristiques :

Vous avez dit nano 10-9m

C60 0,7nm

Sn/SnOxNano

25-30nm

Nano-objet : solide dont une des dimensions caractristiques est entre 1 et 100 nmNano-structure: structure dont une des dimensions caractristiques est entre 1 et 100nm ou rsultant de lassemblage de nano-objets


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A micron:

1 mm = 10-6m 1m = 1 million of microns

Micron large roughness of the

Lotus leeves

Hair : tens of microns

Adhesion: micron large hair andVan der Waals bonds

2mm


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A nanometer : one thousand time smaller than a micron

1 nm = 10-9m = 0.000000001 m in 1m: 1 billion of nanometers1 = 0.1 nm1 pm = 0.001 nm

Atomic radius : 0.1 to 0.3 nmDistance between 2 atoms in a molecule or a solid : 0.08 to 0.6 nm

The nanometer is a large unit for chemistry !

C60 0.7nm

DNA 2.5 nm of diameter


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F. Caillaud/CNRSPhotothque/SAGASCIENCELiposomes, vesicles measuring tensto hundreds of nanometers, makeexcellent nanovectors for drugs.Micelles

Nano-Objects


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Polymers etdendrimers

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

CarbonNanotubes


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Nanostructures

Transistor80nm large drain obtained bylithography (University of Aachen)

Nanocrystalline copper, 3 timesmore resistant than regular copper(deforms more easily under strain)

Resistive strain gauges


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1931

E. Ruska

Transmission electron microscope (TEM)

Tools for observation at the nanoscale

SEM tostudy

surfaces


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High Resolution TEM image of a compositenanoparticle Sn/SnOx (25-30nm)

Observation of populations ofnano-objects.e.g. Cobalt nanoparticles


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High resolution TEM micrograph of anindividual FePt NP. The image is contrastenhanced by means of Fourier filtering(Leibniz Institute for Solid State and Materials

Research Dresden)

Energy Filtered TEM showing silica NPs inorganic coating. Conventional TEM imagesshow 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


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TEM image of aporous silica

1000-1500 m/g


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Quantum Corral : image of 48 iron atoms

forming a circle on a copper surface

Surface of graphite5nm

1nm

1981: Binning et Rohrer,IBM Zurich

Nobel Prize 1986(with E. Ruska for inventingthe first electronmicroscope )

Scanning tunneling microscope STM-

Electric

current

Displacements

Electriccurrent

tip

Sample


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Image of a membrane with porediameter around 20nm

Image of DNA strands

AFM image of SWCNThttp://www.firstnano.com/applications.html

Atomic force microscope AFM-

Probe
http://images.google.com/imgres?imgurl=http://www.cpmoh.cnrs.fr/html/UserFiles/Image/nanomecanique-interfaces/Single%20wall%20carbon%20nanotube.GIF&imgrefurl=http://www.cpmoh.cnrs.fr/backend.php3&h=907&w=1043&sz=118&hl=fr&start=15&um=1&tbnid=F0Vz0RwST9Y0UM:&tbnh=130&tbnw=150&prev=/images?q=carbon+nanotube&svnum=10&um=1&hl=fr&rlz=1T4SUNA_fr___FR213&sa=N


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A spoon of nanoparticles mayhave the surface of a rugby field

What changes at the nanoscale ?Increase in surface/volume and surface/mass ratios

Definition: specific surface (around 100 m2/g)


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- 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 m large, the surface reaches

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

Dispersion and surface


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Reaction between potassium permanganate and glycerol

Surface and reactivity

a show


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The properties (catalytic, optic, magnetic, transport)

depend on the composition, size, shape of the object;thats seldom the case at the macroscopic scale

What changes at the nanoscale ?FCC Octahedron

Apex

Edge Face

Size of the particle


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

If you make 10 m 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

Porosity and surface

10 nm


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TEM image of aporous silica

1000-1500 m/g


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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

Metal organic frameworks (MOFs)


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a) Gold Nanoparticlesb) Gold rodsd) AgxAu1-x Nanoparticlese) Different aspect ratiosMaterials Today, 2004

Gold treasure 1600-1200 BC

Story of St Nicaise,Cathedral of Soisson(France), XIIIth AC

New electronic properties


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Under visible light

Under UV light

Shell

Core(3nm)

Core(5nm)

CdSe Nanoparticles


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Weak interactions become predominent !

Liquid IronColloidal solutions of

Fe3O4

= Ferrofluid

Iron powderattracted by a

magnet
http://www.supermagnete.ch/fre/bigpic.php?pic=1524.jpg&article_id=M-22http://www.supermagnete.ch/fre/bigpic.php?pic=1485.jpg&article_id=M-22


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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


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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


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Energy

Photovoltaic cells

(remplacement of silicium-14% yield- by associationof nanocrystals-85% yield-)

Portable Batteries

(reloading, huge power)

Thermoelectric materials(cooling of microprocessors, transformation of heatinto electricity)

Isolation

(treatment of glass surfaces to stop heat diffusion,e.g. aerogels)


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Dihydrogen storage (large specific area)

Neutron-scattering image reveals where dihydrogen molecules (red-green circles) connect to ametal organic framework (MOF, Chem. Soc. Rev., 2003, 32, 276288). The ball-and-stickmodel 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), 538541,2005


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The size of transistors decreases by half every 10months

Size reduction of electronics components:

The cost of an elaboration line doubles every 36

months

Electronics

10mm

Actually250 millions


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Size reduction of electronics components:Prescott (from Intel) processor used in 2006 devices 90nm large,Size limit was down to 65 nm in 2007Below 20 nm silicium components arent insulating anymore: physics

limitation (qauntum phenomena) to miniaturisation of integratedcircuits with today silicium technology

80nm large drain obtained bylithography (University of Aachen)

Molecular computer ?

Electronics


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FePt, S. Sun et al.Science 2000 AC

How to precisely localise, connect, address nano-objectsand repeatthese steps at will?


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Connections for the futur:carbon nanotubes


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Health

Prevent (anti-microbian coatings, filters, monitoring)

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


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

Thrapeutics :

implants, identification of our genetic mapfor individual treatment, new deliverypathways, new medecines, new technics(e.g.hyperthermia)


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Nanostructured surface of a stent preventing the formation ofblood-clots

Metal mesh tube

BloodcirculationrestoredStent

Bloodcirculationblocked

Fat deposits

Artery


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Environment

Monitoring (detection of pollutants):

Sensors of reduced dimensions, portables systems, faster

(real time) and better localised detection oftodayspollutants.

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


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Imprinted circuit

Miniaturised Sensors

Oxide nanoparticles


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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 ???


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

Molecular electronics: using molecules in place of siliciumbased components e.g. diode, transistor

In 2003, to make a PC (42 millions of transistors), 240 kg of conventionalenergy, 22 chemical products, 1500 L water were necessary

And to make molecules ??? Chemists prepare moles of molecules in onebatch ( 1 mole: 6,02.1023 molecules).

Nanotechnology = Ecotechnology

?

1965: Jacques MONOD,an electronic component weigths 10-2g, an enzyme: 10-17g

Decrease of materials and energy consumption:


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New consumption goods

Reinforced and/orlighter materials:transports, construction,sports etc..

e.g. carbon nanotubes, fullerens orSiO2 nanoparticles in pare-chocs,racquets structure or golf clubs

Ceramics nanoparticles in cement,silica in green tires

(NB: carbon particles (10-100nm) havebeen introduced in tires since 1917sfor reinforcement)

Sulfur bridge

Polymers

Silica or carbonblack loading


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Smart Materials

e.g. superhydrophobic surfaces

cosmetics : liposomes and micelles to transport nutriments inside cells

(anti-age products); solar screens (TiO2, ZnO)


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Dirt (fat)

CO2

H2O

Light

Self-cleaning glasses, easily washed paints, anti-bacterial coatings

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


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New generation of electronics goods: Increased efficiency, fastercommunication, increased mobility.e.g. cameras, cell phones, MP3 players (walkman), flexible screens


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New generation of pigments

M. Jos-Yacaman, et al. Science, 1996 (273) 223

The Kerr collections

Maya ceramics (250-850 AC), technics

used till the 20th century

Harmony in green and pink:

The Music Room by Whistler

SEM of rutile (titane white)

obtained byt the New Jersey

Zinc Company.

Iridescent paint


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Already for sale2006:

212 products made world wide have been identified as 'nano'(the preparation of which requires nanotechnologies or usesnanomaterials)

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

and silicon based materials.

Main domains: clothes,sports goods, cosmetics, catalysts


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How to make nanocomponents ?

Powder

Bulk material

Nanoparticles

Agregates

Atoms

Top-down approach

Bottom-up approach

bllBall-milling

Evaporation/condensationSol-gel and other chemical technics

Chemical Vapor Deposition


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M. Faradays method (1857)

Gold nanoparticles


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How would you know thepurple color indeed

corresponds tonanoparticles?

Dispersions of nanoparticlesdiffuse light !Thats the socalled Tyndalleffect

Left: solution of the gold precursorRight: final solution with gold nanoparticles


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Conclusions

Many kinds of nano-objects and nanostructurees

Many applications due to changes of properties atthe nanoscale

New physical properties, new chemical reactivity

Surface, interfaces and weak interactions play amajor role


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The course will focus on nanoparticles(chemical synthesis, properties and

applications) and their assembly into

nanostructures; when needed some basicknowledge on soft nano-objects will beintroduced (e.g. micelles, liposomes)

cours 1 introduction nano

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