Nano Materials

Nanomaterials
Claude TEMPLIER
Universit de Poitiers France
Ali-Reza AKBARI
Sahand University of Technology Iran
Liudvikas PRANEVICIUS
Vytauto Didiojo universitetas Lithuania
Outlines
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What is at nanoscale in nanomaterials?

The nanoworld Nanograins and nanoclusters Current applications The role of surfaces and interfaces
Classification of nanomaterials

Definitions Nanostructures Nanostructurized materials Nanocomposites
The physical properties of nanoclusters and nanomaterials

The morphology The lattice parameter The phase changes The electronic properties The magnetic properties The optical properties
The mechanical properties of nanomaterials

Elasticity, plasticity, dislocations, hardening, twinning, toughness, The role of grain boundaries Hardness, Ductility , Toughness of nanomaterials
Outlines
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Modeling: the backbone of nanotechnology research

Introduction Ab-initio methods Molecular dynamics Classical and kinetic Monte-Carlo
Elaboration of nanomaterials

The bottom-up approach The top-down approach
Methods of investigation of nanomaterials

Interaction with matter Transmission Electron Microscopy X Ray Diffraction Atomic Force Microscopy Nanohardness
Study of the nanocomposite TiN-Ni

Objective Elaboration Structure Mechanical properties
What is at nanoscale in nanomaterials?: The nanoworld
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Classification of the nanomaterials The physical properties of nanoclusters The mechanical properties of nanomaterials Modeling: the backbone of nanotechnology research Methods of investigation of nanomaterials Study of the nanocomposite TiN-Ni
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Material: Transformed matter to allow this matter to ensure a given

function. Material is functional matter.

Nano ?
The prefix nano comes from the Greek and means very small.

1 nm =10-9 m 500000 smaller than a pen line, 50000 smaller than a hair, 100 smaller than the DNA molecule, ~2 Cu atoms on Cu.
DNA

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What is at nanoscale in nanomaterials ?
nanoscale
What is at nanoscale in nanomaterials?: Nanoclusters and nanograins
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The nanoworld Nanoclusters and nanograins Current applications The role of surfaces and interfaces

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Material: Material is functional matter.
Grains in polycrystals
Usually, crystalline materials are in the micrometric range, even being made of atoms with a nanometric size. This micrometric range refers to the size of the grains in polycrystals.
50 m
Grains in bulk gold
How many atoms in a 10 m gold grain ? 2.5 1014 atoms assuming a spherical shape

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Nanoclusters
Nanoclusters
Deposition of atoms or molecules on a clean surface at low temperature. The size ranges from 0.1 nm to a few nanometers.
Self organization Specific properties
Molecular engineering

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Nanoclusters
Array of 25 Fe atoms dots

Laboratory of Nanostructures at Surfaces, EPFL
0.3ML MgO/Ag(100)
270nm x 200nm, T=50K Laboratoire de Physique des Surfaces , EPFL

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Nanoclusters
Silver dendrite grown at 130 K on a platinum (111) surface

Laboratory of Nanoscale Science Max-Planck-Institute for Solid State
C42H28 (Rubrena)/Au(111)
60nm x 60nm, T=5K Laboratoire de Physique des Surfaces , EPFL
20 nm
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From nanoclusters to nanomaterials

1D: nanotubes 2D: multilayers 3D: embedded clusters
SEM pictures of carbon nanotubes
diameters in the range 1-10 nm

(b)
Multilayers of Fe-Pt-C on Si with a period of a few nm.

D. Babonneau, LMP, Poitiers
HRTEM of embedded silver clusters in (a) C and (b) BN.
D. Babonneau, LMP, Poitiers

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From nanoclusters to nanomaterials

3D: nanograins in thin films
TEM cross-sectional image and SAED pattern of 300nm FePt thin film
10nm FePt thin film
Nanomaterials: at least one dimension at the nanometric range
What is at nanoscale in nanomaterials?: Current applications
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What is at nanoscale in nanomaterials?: Current applications: Thinking small
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Past
Cutting tools and wear resistant coatings
Present
Biosensors, transducers and detectors Functional designer fluids Propellants, nozzles & valves
Future
Nano optical, nanoelectronics and nanopower sources High-end flexible displays Nano-bio materials as artificial organs
Pigments in paints Pharmaceuticals & drugs Nanoscale particles and thin films in electronic devices Jewelry, optical and semiconductor wafer polishing
Flame retardant additives Drug delivery, biomagnetic separation and wound healing
NEMS based devices
Faster switches and ultra sensitive sensors
Current applications of nanotechnology and time line for anticipated advances.
What is at nanoscale in nanomaterials?: Current applications, Thinking small
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Nanotube field-effect transistor
Transistors are the basic building blocks of integrated circuits. IBM has successfully fabricated and tested nanotube transistors using individual multi-wall or single-wall nanotubes as the channel of a field-effect transistor (FET).
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Nanotubes for neural networks

A. Microscopic images of neuron bridging an array of carbon nanotubes thereby creating neural networks.
The nanotube coating consists of a pristine carbon nanotube film, which is grown using a chemical vapor deposition process. Dissociated cortical cells from 1-dayold Charles River rats were plated for several days onto patterned quartz or oxidized silicon substrates at a density of 1103 cells/mm2. The bar represents 100 mm.
B. Increased magnification of one nanotube pad

Neurons are generally confined to the nanotubes surface except where neurons extend to adjacent nanotube pads. Bar represents 10 mm.
Annual Review of Physical Chemistry Vol. 55: 613-649 (Volume publication date June 2004) First published online as a Review in Advance on February 26, 2004
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Tools
Nowadays surface engineered materials are developed so as to tailor desired material properties for a specific application: A large variety of functional properties can be optimized for the bulk material and surface by applying an appropriate coating. The incorporation of nanomaterials in surface coatings can provide longterm abrasion resistance without significantly effecting optical clarity, gloss, color or physical properties.
NanoDur Aluminum Oxide is designed for coatings where transparency is of utmost importance. NanoDur Aluminum Oxide is especially suited for incorporation into coating systems, greatly enhancing abrasion resistance with minimal effects on clarity, gloss and physical properties of the coatings.

http://www.foresight.org/Nanomedicine/
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Nanomedicine
Nanomedicine is the application of nanotechnology (the engineering of tiny machines) to the prevention and treatment of disease in the human body. This discipline is in its infancy. It has the potential to change medical science dramatically in the 21st century. Diagnose illness: to monitor or to report on the internal chemistry of the body. Nanodevices: to dispense drugs or hormones as needed in people with chronic imbalance or deficiency states.
This image shows an hypothetical device, attached to a red blood cell and releasing its payload molecules. Copyright 2002 Rutgers University Bio-Nano Project.
Nanosurgeons
Nanoscale Biological Engineering and Transport Group/Cornell University, Copyright Cornell University
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Paint, ink
In paint and coatings nanomaterials fulfil decorative needs (e.g. color and gloss), functional purposes (e.g. conductivity, microbial inactivation) and improve protection (e.g. scratch resistance, UV stability) of paints and coatings. In particular nano-size metal-oxides, such as TiO2 and ZnO or Alumina, Ceria and Silica and nano-size pigments find application in new paint and coating formulations.
When matter is reduced in size it changes its characteristics, such as color and interaction with other matter such as chemical reactivity. The change in the characteristics is caused by the change of the electronic properties. Nano-meter sized molecules penetrate into the smallest inclusions in painted metal, fiberglass, wood and ceramic, protecting them from harsh elements. Nanomaterials exhibit uncommon characteristics like superior scratch resistance, clarity, UV protection, hydrophobicity and adhesion. Ultra-scratch resistant self-cleaning effect

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Nano inclusions
Metallic nanoinclusions in a dielectric matrix affect its optical properties. A part of the visible spectra is absorbed due to surface plasmon. A plasmon is a collective oscillation of electric charges submitted to an electromagnetic wave. It appears in gaseous plasma as well as in metals like silver, gold and copper. If the electrons from the metal are confined in a very small inclusion, resonance takes place with a characteristic frequency which depends on the nature and the geometry of the inclusion. If the corresponding wavelength is between 400 and 800 nm, it produces a color like a pigment. This technology has been used during the roman era. Gold and silver were added to glasses. The Lycurgus cup is from the 4th century AD and was probably carved in Rome. It appears RED by reflexion and GREEN by transmission.
http://www.cambridge2000.com/gallery Labors of the Months (Norwich, England, ca. 1480).
The ruby color is probably due to embedded gold nanoparticles.
What is at nanoscale in nanomaterials?: Current applications, Thinking small Deodorant/Antiperspirant Shaving/Depilatory Products Foot Powder Oral care
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Nanomaterials can impart antibacterial and anti-odour functionality on human skin in powder, gel, stick or spray underarm products. It has also antimicrobial and antiirritant properties.
NanoGard zinc oxide or silver doped zinc oxide appear to be naturals for this application. It can provide effective odour and bacterial control while maintaining clarity in silky-smooth, non-sticky formulations. The anti-irritant properties of zinc oxide are an added benefit! Silver doped zinc oxide may offer an enhancement in odor fighting antibacterial properties.

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Quantum dots
Inorganic nanostructures measuring only a few nanometers (quantum dots) have unique optical properties.
Material properties change dramatically because quantum effects arise from the confinement of electrons and "holes" in the material (a hole is the absence of an electron; the hole behaves as though it were a positively charged particle). Size changes other material properties such as the electrical and nonlinear optical properties of a material, making them very different from those of the material's bulk form. If a dot is excited, the smaller the dot, the higher the energy and intensity of its emitted light. These very small, semiconducting quantum dots are gateways to an enormous array of possible applications and new technologies.
What is at nanoscale in nanomaterials?: The role of surfaces and interfaces
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Crystal structure and dense planes

The crystal structure is a unique arrangement of atoms in a crystal. It is composed of a unit cell with a set of atoms at each vertex. This is periodically repeated in 3D in a lattice. The various possible structures are defined by their symmetries. These symmetries and structure play a role in determining many of its properties.
The denser planes for a fcc structure
Vicinal surfaces

A vicinal surface is a surface that makes a small angle with a dense plane (from 0 to ~15). Due to the crystalline structure, this surface is no longer a plane and exhibits terraces and steps. The length L of the terraces is such that L~h where h is the height of the steps.
A (788) vicinal surface, close to the (111) plane.
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surface
The atoms on the surface play a dominant role for the physical and chemical properties that are controlled by surface exchanges Contrary to classical materials, the proportion of atoms on the surface of the nanoclusters becomes non negligible.
Total number of atoms
Percentage of surface atoms
13 55 147 309 561 1415
92 % 76 % 63 % 52 % 45 % 35%
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Surface, interfaces
Ratio of atoms on the surface

1,2 2,5E+05
Nanoclusters: a high surface-to-volume ratio.

ratio Ns/N
2,0E+05
1,5E+05 0,6 1,0E+05 0,4 5,0E+04
0,2
0
0 2 4 6 8 10
0,0E+00
Nanomaterials: a high volume of atoms in grain boundaries and triple junctions.

100
Atoms in Grain Boundaries (%)
radius of the cluster (nm)
80 60 40 20 0 1 10
Grain Size (nm)
1 nm 0.5 nm
100
Number of atoms
0,8
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The surface energy

in J.m-2 is the work needed to increase the surface by dS. In this transformation, the atomic surface concentration is kept constant. If the surface is increased while keeping the same number of atoms (the concentration is decreased), the work needed to increase the surface by dS is now: dW = ij dS where ij is the stress tensor.
ij = ij + u ij
dW = dS
where
u ij
is the strain tensor.
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The surface energy

To create a surface needs an energy dW. This energy depends on the orientation of the surface. The surface energy depends on the number of cut bonds between nearest neighbor and next nearest neighbor interactions.
Square lattice
tan =
m q
m=0 and q=1 for the plane. m=1 and q=3 for the plane.
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The surface energy

The number of nearest neighbor cut bonds:

N1= 1 and N1= 4 N1= q+m N2= 2 and N2= 6 N2= 2q
The number of next nearest neighbor cut bonds:

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The surface energy

It is clear that the creation of a dense surface cut less bonds per unit surface than the creation of a less dense surface. Thus, the surface energy of a given surface is higher than the surface energy of the denser surface.
An higher surface energy
The lowest surface energy
What is at nanoscale in nanomaterials?: summary
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The nanoworld
It ranges from 1 nm to ~100 nm. Nanomaterials have at least one dimension in the nanometric range.
Nanoscience has already many applications:

Electronics, Mechanics, Optics Biomedicine
One simple obvious characteristic of the nanomaterials is related to their surfaces or interfaces.

A large percentage of atoms are on the surface or in grain boundaries. 2000 atoms in a 2nm gold cluster, ~50% on the surface. The surface energy is the work needed to create a surface. The lowest values corresponds to the denser surfaces. The size of the nanograins is a parameter that should be included into classical description of bulk materials when they are for nanomaterials.
Classification of nanomaterials: Definitions

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Definitions Elementary building units Nanostructurized materials Nanocomposites

The physical properties of nanomaterials The mechanical properties of nanomaterials Modeling: the backbone of nanotechnology research Elaboration of nanomaterials Methods of investigation of nanomaterials Study of the nanocomposite TiN-Ni
Classification of nanomaterials: Definitions
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Nanostructures (NSs)

A structure with a d at least less or equal to a critical one dc. ddc100 nm. The value of dc is dictated by a critical characteristic of some physical phenomena (free path length of electrons, phonons, length of de Broglie wave, length of
external electromagnetic and acoustical waves, correlation length, penetration length, diffusion length) giving rise to the size effects.
Nanostructures (NSs) are characterized by a form and a dimensionality k.
Nanostructured Materials (NSMs)

Low dimensional materials comprising of building units of a submicron or nanoscale size at least in one direction and exhibiting size effects. Nanostructured materials are characterized by a form, form a dimensionality and by a composition. composition Nanocomposite materials (two or more component materials) cover a vast range of ceramic, metallic and ceramometallic materials in the form of bulk materials and thin films.
Nanocomposites (NCMs)
Classification of nanomaterials: Elementary building units

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Definitions
Nanostructures

Nanostructurized materials Nanocomposites

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The elementary blocks

All NSs can be built from elementary units (blocks) having low dimensionality 0D, 0D 1D, 1D and 2D. 2D The 3D units are excluded because they can't be used to build low dimensional NSs except 3D matrix. 3D structures can be considered as NSMs if they involve the 0D, 1D, 2D NSs (Gleiters classification of NSMs).
The 0D units (3 dimensions in the nanometric range)

Molecules, clusters, fullerenes, rings, metcarbs (metal carbides), particles, powders, grains...
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The 1D units (2 dimensions in the nanometric range)

Nanotubes, fibers, filaments, whiskers, spirals, belts, springs, columns, needles, pillars, helicoids, wires, ribbons
100 nm
Nanowires and nanoribbons of GaN S. Biswas et al, Mat. Res. Bull 42, 2007 Ta and CdSe Nanopillars, CM Zhou et al, Thin Sol. Films 515 (2006) L.K. Teh et al., Thin Solid Films 515 (2007)
The 2D units (1 dimension

in the nanometric range) Layers
ZNO nanoneedles, R. Wahab et al, Applied Surf. Science 2007
nc-Si/a-SiO2 superlattices, D.J. Lockwood, Journal of Crystal Growth 237239 (2002) 1898
Classification of nanomaterials: Nanostructurized materials
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Definitions Nanostructures
Nanostructurized materials
Nanocomposites

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The Gleiters classification

Two types of parameters: chemical composition: monophase or multiphase dimensionality or shape: layered, rod and equiaxed 12 different structural categories.
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The kDlmn classification

(V.V. Pokropivny, V.V. Skorokhod, Materials Science and Engineering C xx (2006) xxxxxx)
Fullerenes and nanotubes are not taken into account in the Gleiters classification A new classification: kDlmn where

k is the dimensionality l, m, n are the dimensionality of the building units.

kl,m,n, and k,l,m,n = 0,1,2,3.
It follows from these conditions that restricted number (36) of NSs classes exists, namely:

3 sorts of elementary units (0D, 1D, 2D), 9 single classes of kDl type built of 1 sort units, 19 binary classes of kDlm type built of 2 sort units, restricting the classification by 5 main ternary structures of kDlmn type built of 3 sort units.
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The 0Dlm structures
The 1Dlm structures

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The 2Dlmn structures

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The 3Dlmn structures
Classification of nanomaterials: Nanocomposite Materials
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What is at nanoscale in nanomaterials? Classification of nanomaterials

Definitions Elementary building units Nanostructurized materials Nanocomposites

Classification of nanomaterials: Nanocomposite Materials
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Nanocomposites (NCMs)

Nanocomposites can be classified according to their structures. Two main groups of nanocomposites are distinguished:
microcrystal matrix (micro-nano type), in which nanometer sized particles or inclusions

(spherical, fiber-like, plate-like) of a second phase are dispersed in the intergranular regions or in both the inter/intra granular spaces of matrix grains.
Micro-nano inter-type
Micro-nano intera-type
Micro-nano inter-intera-type
nanocrystal matrix nanocomposites.

nano-nano type: nanocrystalline phases or amorphous inclusions in a nanocrystalline matrix. nano-fiber type: dispersion of nano sized fibers in a nanocrystalline matrix. nano-nanolayer type: nanocrystalline grains in a nanolayer of a second phase.
Nano-fiber type Nano-nanolayer type
Nano-nano type
The physical properties of nanoclusters: the morphology

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What is at nanoscale in nanomaterials? Classification of nanomaterials The physical properties of nanoclusters


The mechanical properties of nanomaterials Modeling: the backbone of nanotechnology research Elaboration of nanomaterials Methods of investigation of nanomaterials Study of the nanocomposite TiN-Ni
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The plot

The plot curve is obtained by plotting the surface energy as a function of the angles and in polar coordinates. The plot curves are often obtained using the interactions with the nearest and next nearest neighbors.
The plot curve of a squared structure using the nearest neighbor interactions
The plot curve of a squared structure using the next nearest neighbor interactions
The shape of a cluster is obtained by minimizing the surface energy at constant volume.
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The Wulff construction

To minimize the energy requires to use the Euler Lagrange theorem. It has a rather simple geometrical solution. The Wulff diagram is the pedal curve of the plot.
For a parabola, the pedal point is the focus and the pedal curve is a line.
X T
WIKIPEDIA: Pedal curve of a circle. Take a curve C and a fixed point P (called the pedal point). On any tangential line T there is a unique point X which is either P or forms with P a line perpendicular to T. The pedal curve is the set of all X for which T is a tangent of the curve.
The Wulff construction of a squared structure using the nearest neighbor interactions
The Wulff construction of a squared structure using the next nearest neighbor interactions
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The Wulff formula (example of an hexagonal crystal)

The formula is obtained by minimizing the surface energy at constant volume.
E = i E i (Vc V0 ) where is the Lagrange multiplicator.

i
E = 26
a2 3
h + 6
4ah 3
a (2h.2 3 a 2 V0 )
E = 4 3 a 2 h + 8 3 ah a (4 3 a 2 h V0 )
Minimizing E with respect to a and h gives:
E = 8 3 a h + 8 3 h a 8 3 ah = 0 a
Using (3) in (1) gives
(1)
E = 8 3 a a 4 3 a 2 = 0 h
(2)
2 a a
(3)
a = h a h
This result does not depend on the cluster shape:
i = Cte hi
CuSO4

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The morphology of clusters

The surface energy depends on the orientation of the surface. The equilibrium shape is unique. For a liquid, is constant and the equilibrium shape is a sphere in the absence of gravity. For a solid, the total surface energy is Es = i dS.i
i
The lowest energy is obtained for a polyhedra such that the distance from the center to the faces are proportional to their surface energy. i
hi
= C te
The equilibrium shape for nanoclusters with size larger than 10 nm is the thermodynamic equilibrium shape. For the smaller size, the i are not constant and depend on the number of atoms on the edge.

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The morphology of clusters: example of fcc materials

The smallest clusters have an icosahedral shape with the (111) face as the main faces, in order to decrease the energy.
An icosahedron is not an accepted equilibrium shape in crystallography since it has a 5 order symmetry. The quasicrystals are another exception.
As the cluster grows, it transforms to truncated octahedron with (111) and (100) faces.

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The equilibrium shape of supported clusters

There is an interaction between the cluster and the substrate. This interaction is described using an energy of adhesion Eadh. The equilibrium shape is a truncated Wulff polyhedra.
h s E adh = hi i
If Eadh=0, then hs=0. If Eadh is very large compare to the i, the deposited material cluster perfectly wets the substrate and it becomes a film.
Usually, the substrate and the supported material have not the same lattice parameter and it leads to strain energy that should be taken into account to calculate the equilibrium shape.
5.8 ML of Ge on Si (001) at 550C Appl. Phys. Letters 74, 994 (1999)
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The equilibrium shape of supported clusters: Pd on MgO

It is a truncated octahedra. It has (111) and (100) facets.
a. b.
A view perpendicular to <110> direction HRTEM. The distance between the (200) planes is 0.2 nm.
Scheme of a Pd cluster
hs=h1-h2
Graoui et al, Surf. Sci 417, 350, 1998
h s = 0.55 h1
h s E adh = hi i
gives
Eadh(111/100 MgO)=0.90 J.m-2
In agreement with the calculations: Eadh(111/100 MgO)=0.85 J.m-2
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The shape of embedded clusters: Xe bubbles in Aluminium

The radius is about 1 nm. The clusters exhibit (111) and (100) facets. They can move and coalesce. When two clusters coalesce, the resulting cluster rearrange its surface to minimize the energy.
With the courtesy of S.E. Donnelly, Salford University
The physical properties of nanoclusters: the lattice parameter
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What is at nanoscale in nanomaterials? Classification of the nanomaterials The physical properties of nanoclusters


The physical properties of nanoclusters: the lattice parameter The lattice parameter change
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For a liquid sphere, the internal pressure is given by Laplace law:
Pint = Pext +
2 r
For a solid, is replaced by the strain tensor . For a solid sphere of radius r and material with a constant value of , the strain tensor is:
=+
d dS / S
The atomic volume is compressibility is .
a3,
the total volume is
n.a3
and the
1 dV V dP
dP =
2 r
It leads to a decrease of the lattice parameter as the size of the particles increases (r-1 power law): law
a 2 = a 3r
Cu clusters The slope of the line gives the surface stress (3.35 GPa) and the pressure exerted on the nanocluster is terrific: 6.7 GPa. Apai et al, Phys. Rev. Lettres 43, 165, 1979
The physical properties of nanoclusters: the lattice parameter The lattice parameter change: limitations
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The previous results are deduced from thermodynamics, i.e. when the numbers of particles in the studied system is very large. Is thermodynamic still valid for nanoclusters?
Answer to this question:

It is possible to numerically model the evolution of the lattice parameter using, not thermodynamics, but directly the interactions between particles, described by particular potentials. The previous power law ( R-1) is valid till R=4 a0 where a0 is the bulk lattice parameter. At lower size, the deviation is mainly due to the fact that the surface energy is no longer constant (more atoms on the edges).
Swaminarayan et al, Surf. Sci. 306, 367, 1994
The physical properties of nanoclusters: the lattice parameter The equilibrium shape of supported clusters: Pd on MgO

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Due to the difference in lattice parameters between MgO and bulk Pd, it exists a strain energy. This strain energy is responsible for a gradient of the lattice parameter in the Pd cluster. The accommodation depth depends on the size of the cluster.
The 5 nm Pd cluster has 12 atomic planes. The plane closer to the MgO substrate has a period equal to the MgO (100) planes (0.21 nm). The period of bulk Pd (0.195 nm) is reached for the third plane. The 1.2 nm Pd cluster possesses 4 planes. The period stays about the same as the MgO period.
5 nm Giorgo et al, Phil. Mag. B 67, 773, 1993
1.2 nm
The physical properties of nanoclusters: The phase changes
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What is at nanoscale in nanomaterials? Classification of the nanomaterials The physical properties of nanoclusters


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The physical properties of nanomaterials depend on the grain size. Two types of effects:
Dimensional or confinement effect (the affected parameters evolutes non monotonously and exhibits extremes) Surface effects that are described using the surface energy, as already mentioned. This surface energy evolutes monotonously and can be used in the frame of a thermodynamic point of view.
The size of nanoclusters influences:

the shape, the lattice parameter, and also the crystalline structure.

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Example of the Barium titanate BaTiO3

a ferroelectric ceramic material It has four phases as a solid: cubic, tetragonal, orthorhombic, and rhombohedric crystal structure.
Tetragonal BaTiO3
Grains (powder) of BaTiO3

If d>dc (80 nm), the structure is tetragonal. The ratio c/a decreases with the cluster size but the volume ca2 is constant. If d<dc, the structure is cubic and the lattice parameter increases as the size decreases. decreases
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Example of nickel
Bulk Ni is fcc, however, it has a metastable hcp phase. Ni clusters have an hcp structure if the cluster diameter is less than 4 nm.
Example of zirconia ZrO2

Bulk zirconia is monoclinic at low temperature and becomes tetragonal at temperature higher than ~1100 C. Nanocrystals of zirconia (10nm) are tetragonal at room temperature. If the cluster size is 7 nm, the transition from monoclinic to tetragonal occurs at 175 K.
The size effect on the phase transition is a common characteristic of nanoclusters

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Elemental explanation using thermodynamics

The phase transitions at constant pressure P and temperature T are described using the free enthalpy G. H = E + PV and G=H-TS where E is the energy, H is the enthalpy and S the entropy.

A stable equilibrium is obtained if G is minimal (dG=0)
For nanomaterials, since the surface energy plays an important role, it is necessary to add the additional parameter D (diameter) or the curvature 2/D together with P and T. Therefore, the free enthalpy becomes G*=G-(4/D)V and the stable state corresponds to dG*=0. For a given (P, T) state, a phase transition occurs at a critical size Dc. It is equivalent to say that the critical temperature Tc of the phase transition depends on the size of the nanoclusters. nanoclusters Tc=f(P, D, , ) where and are the interfacial energies of the two phases.

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From a thermodynamical point of view, the size of the particles becomes a new intensive parameter, similarly to pressure and temperature. Tc=f(P, D, , ) Application to the tetragonal cubic phase transition of BaTiO3.
P. Labastie, F. Calvo, chapter 2, Les Nanosciences 2, Ed. Belin 2006

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If the interfacial energies , plays a role, the temperature of transition should depend on the state of the interface. A comparison of two types of BaTiO3 grains demonstrates the role of these energies.

Powder interface solid-gas Ceramic interface solid-solid.
Application to the tetragonal cubic phase transition of BaTiO3.
For given grain size and temperature, the stabilized phase depends on the nature of the interface. The changes of the transition temperature with the grain size are rather high for the solid-gas interface. They are smaller for the interface solid-solid, where the interface energy is smaller. Ref 13 in chapter 2, Les Nanosciences 2, Ed. Belin 2006

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The solid liquid transition

Thermodynamics of nanosystems differs from the thermodynamics of macroscopic systems, where the number of particles tends to infinity. In statistical mechanics, the partition function Z describes the statistical properties of a system in thermodynamic equilibrium. Most of the thermodynamic variables of the system, such as the total energy, free energy, entropy, and pressure, can be expressed in terms of the partition function or its derivatives. There are actually several different types of partition functions, each corresponding to different types of statistical ensemble (or, equivalently, different types of free energy.)
The microcanonical ensemble: the system has no exchange with the environment and its energy is constant. All states are equiprobable. The canonical ensemble: the number of particles is constant and the system can exchange energy with the environment (at a constant temperature). The grand canonical ensemble: the system can exchange both heat and particles with the environment, at fixed temperature, volume, and chemical potential.
Ref 13 in chapter 2, Les Nanosciences 2, Ed. Belin 2006

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The solid liquid transition

Macroscopic level: The amount of energy in the form of heat released or absorbed by a substance during a phase change is the enthalpy of transformation (often called the Latent Heat L). Microscopic level The amplitude of vibration of atoms around their equilibrium position increases with temperature. f is the ratio of this amplitude and the distance between first neighbors. For the single crystalline solids, the solid liquid transition occurs if f=7% (it means that the first neighbor distance varies by 14%.
P. Labastie, F. Calvo, chapter 2, Les Nanosciences 2, Ed. Belin 2006

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Transition in a nanomaterial
The temperature of the solid liquid transition decreases as the size of the particles is reduced. Classical approach
A Laplace term is added to a GibbsDuheim equation.
Tf (r ) 2 = Tf () s L r
Buffat et al, Phys. Rev A 13, 2287, 1976
Where: Tf(r) is the temperature of transition of the particle of radius r, Tf() is the temperature of transition of the bulk material, s is the density of the bulk material, L is the enthalpy of transformation of the bulk material, is a parameter which depends on the surface tensions S and
L of the bulk solid and liquid material.
Assuming an equilibrium between the solid particles, the liquid and the vapor, it gives:
T (r ) 2 = 1 f Tf () s L(r ) rS
2 S 3 S L ( ) L
Where Lis the density of the liquid and rS the radius of the solid particles. It is in good agreement with the experimental values (solid line).

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It is experimentally observed that the transition occurs in an interval of temperature, contrary to the bulk. As the size is reduced, the temperature of transition decreases, as well as the enthalpy of transition Hm.
Solid liquid transition of Sn nanoclusters.

Guo et al, phys; Rev. Letters 77, 99 1996.

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Assuming that the particles are either entirely liquid or entirely solid allows to express the enthalpy of transition as a function of the radius of the particles:
3 L( ) L ( r ) = ( S L ) + r S L
Tf ( ) Tf ( r )
(c P, L (T) c P,S (T) dT
Where: Tf(r) is the temperature of transition of the particle of radius r, Tf() is the temperature of transition of the bulk material, s and L are the densities of solid and liquid bulk material, L is the enthalpy of transformation of the bulk material, L(r) is the enthalpy of a particle of radius r.
S and L are the surface tensions of the bulk solid and liquid material.

The variation from the bulk value of the enthalpy of transition increases as the radius is decreased. This is in rather good agreement with the experimental results (solid line).
Solid liquid transition of Sn nanoclusters.
Guo et al, phys; Rev. Letters 77, 99 1996.

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In small particles, the transition occurs in a range of temperature T. It has an intrinsic origin which results of the nanometric size.

Assuming a constant value of the enthalpy of formation and of the temperature of transition. If N is the number of atoms in a particles, the probability for this particle to have an energy E at the temperature T is given by the Einstein equation: TS( E ) E
p( E, T ) =
Where Z(T) is the partition function and S(E) is the entropy.
kT
Z( T )
Ei kT

ss ans es are the entropy and energy per atom in a solid particle. sl and el are the entropy and the energy per atom in a liquid particle.
Z( T ) = e
i
L being the enthalpy of formation per atom and Tf the temperature of transition, it means that sl=ss+L/Tf and el = es +L . Therefore, the ratio of the probability to get a solid or liquid particle with an energy E at a temperature T is:
pl e = NTs Ne = e s s ps ( ) kT e
NTs l Nel ) kT
N L T ( s s + s s ) e s L e s kT Tf
=e
N Tl L kT Tf
NL 1 1 k Tf T =e

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the ratio of the probability to get a solid or liquid particle with an energy E at a temperature T exhibits a huge variation on an interval T such that T=Tf T with:
NL 1 1 pl k Tf T =e
ps
Tf2 T k NL
For a Sn particles with 20000 atoms, i.e. a size of 5.3 nm, it gives T= 0.03K using L= 4 10-21 J/at. If the particle contains only 20 atoms, then T= 30K. In this size range, the evolution of the temperature of fusion and of the enthalpy of transition are no longer monotonous. Complementary interpretations of T:

What is the meaning of fusion of a 20 sized cluster? More than half of the atoms are on the surface and classical thermodynamics is no longer valid. The stabilization of particular sizes could be due to a sort of quantum confinement.
Solid liquid transition of Na nanoclusters.
Schmidt et al, Phys. Rev. Letters 90, 103401, 2003
The physical properties of nanoclusters: The electronic properties
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The need of quantum mechanics

The electronic properties of solids (energy levels, types of bonds between atoms, energy bands, energy gap, Fermi level) are of primary importance. The thermal, magnetic and optical properties of solids result from their electronic state. The best description of the electronic properties is obtained using quantum mechanics, although classical descriptions can be used for macroscopic solids. The basic steps of quantum mechanics studies for solids

The Schrdingers equation. The energy levels and atomic orbitals for the hydrogen atom. Atoms with n electrons. Bonds between atoms, hybridization of atomic orbitals. Energy bands in solids.

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The Schrdingers equation

The probability to get the particle at location r at time t is given by (r,t) *(r,t) dV where (r,t) is the wavefunction, *(r,t) the complex conjugate and dV=r2 sin dr d d. Nowadays, the possible states are described using a ket vector In> in the Hilbert space. The conjugate is the bra vector <nI such that <nIn>=1. Therefore, the energy is a measurable quantity which is an eigenvalue of the operator Hamiltonien , known as the observable corresponding to the energy of the particle.
Other observables are of primary importance to get the modern shape of the Schrdingers equation:

is the observable position. is the observable momentum.
2 p d (t) = H ( t ) + V ( r , t ) ( t ) = i h n ( t ) n n n 2m dt
The non-relativist time-dependent Schrdingers equation.

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The solution of the Schrdingers equation

The solution of the time-dependent Schrdingers equation can be written as
n ( t ) = n e
En t h
The time-independent Schrdingers equation is:

H n 2 p ) n = E n n = n + V(r 2m
=E H n n n

With
= ih where is the gradient operator. p
V(r) is the potential energy operator.
The previous equation can be solved (quite rigorously) for the atom of hydrogen.

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The solution of the Schrdingers equation for the atom of hydrogen

The potential energy is the interaction potential between the proton and the electron.
V(r ) = 1 e2 4 0 r
The states In> can be described using quantic numbers n, l and ml and can be written as In,l,ml>.
n is the principal quantum number (n = 1, 2, 3, 4 ...). It is an eigenvalue that denotes for

the average distance between the electron and the nucleus (i.e. the electron shell).
l is the orbital quantum number (l = 0, 1 ... n1). It corresponds to the eigenvalues l(l+1) of the operator L2 where L is the orbital angular momentum operator. The quantic number l specifies the shape of an atomic orbital and strongly influences chemical bonds and bond angles.

l=0 is called an s orbital. l=1 is called a p orbital. l=2 is called a d orbital.
ml is the orbital magnetic quantum number (ml = l , l +1 ... 0 ... l 1, l ). It is the eigenvalue of Lz, the z component of the orbital angular momentum operator.

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The solution of the Schrdingers equation for the atom of hydrogen

The eigenvalues E are expressed as a function of the quantum number n.

E(r ) = E0 n2 1 me e2 with E 0 = 2h 2 (40 ) 2
The wavefunctions or eigenstates In, l, ml> have the form:

I1,0,0> I2,1,0> I3,2,0> I4,3,0>
n , l , m l (r, , = R n , l (r ) Ylm l (, )
where Yl l (, ) are the spherical harmonics.
m

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The solution of the Schrdingers equation for hydrogen

The Stern and Gerlach experiment has shown that an additional intrinsic angular momentum of the electron must be introduced to describe the electronic states of atoms.

This intrinsic angular momentum is called the spin. The total angular momentum is J=L+S. The spin of an electron is . The eigenvalues of the operator S2 are s(s+1). Sz is the component of the spin operator on Z axis. Its eigenvalues are ms such that
(ms= s , s +1 ... 0 ... s 1, s ).

For an electron, ms =. The eigenstates can be written as In , l, ml, s , ms> or In , l, ml, , ms> for hydrogen.
ms=+
ms=-

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Atoms with N electrons

There are many interactions:

Electrostatic interactions between electrons and the nucleus, Electrostatic interactions between electrons, Magnetic interactions between spin of electrons and orbital motion of electrons (coupling of L and S), Magnetic interactions between the nucleus and the electrons
The Hartree-Fock approximation (a mean field theory) is used to solve the Schrdinger equation. It gives that the eigenstates cannot be described by the same set of quantum numbers. Pauli exclusion principle: principle two identical fermions (electrons are fermions) cannot occupy the same quantum state simultaneously. It leads to the Hunds rules for the distribution of electrons on the energy levels.

S 1s 2s 2p6 3s 3p4 Si 1s 2s 2p6 3s 3p2

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Atomic bonding
Covalent bonding

Sharing of one or more electrons between two atoms, The external energy shell of each atoms becomes saturated Example: CH4
Ionic bonding

Atoms looses or gains electrons to complete the external energy shell, They become ions. Example: NaCl
Polar covalent bond

Due to the difference in electro negativity, the molecule is electrically polarized (Example: HCl)
Metallic bond
Sharing of electrons between all atoms, interactions between ions and electrons. Example: sodium
Low intensity bonds

In many molecules with covalent bonds, the distribution of charges is not homogenous and it leads to a weak permanent electrical dipole. The interactions between these dipoles are the origin of Van der Waals bond as well as the Hydrogen bond (a bridge between polar molecules).

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Hybridization
The atoms combine their atomic orbitals to form new hybrid orbitals, so that the total energy is decreased. The sp3 hybridization (diamond)
The sp2 hybridization (graphite)
From the graphite to the fullerenes
From the fullerenes to the nanotubes

http://lesnanotubes.ibelgique.com/

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Electrons in solids, the energy bands

J.S. Blakemore, solid state physics, Saunders Comp. 1974
In an isolated atoms, the electrons are moving in the potential distributed on quantified energy levels, according to the Pauli principle. In solids, the distance between atoms is low and the electrons orbitals interact. It leads to a broadening of the energy levels and to energy bands.

The inner-core electrons form narrow bands called internal bands. The electrons from the external shells or valence shells form the valence bands. The conduction bands corresponds to the excitated states of the electrons.
In Les matriaux , JP Bailon, Montral, 2000

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Electrons in solids, the energy bands, the Fermi level

The energy gap Eg is the difference between the upper value of the valence band and the lower value of the conduction band. In solids with covalent and ionic bondings, Eg is large. Eg=1.12 eV for Si. In most metals, the energy gap is equal to zero as the conduction band and the valence band overlap. The Fermi level or Fermi energy is the maximum energy for the electrons at 0K. It plays an important role in physics as the physical properties of materials are mainly governed by the electrons that have an energy larger than this energy. EF value is a few eV.


The Fermi function gives the probability to occupy a state of energy E. For metals, its value ranges from 3 to 7 eV. The population of electrons n(E)*p(E) depends upon the product of the Fermi function and the electron density of states.
p( E ) = 1+
EE F exp kT

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Electrons in solids, the energy bands, the Fermi level

The Fermi level for insulators as Si semiconductors is halfway between the valence band and the conduction band. The valence band is completely filled and the sizable energy gap (1.12 eV for Si) prevents any conduction by electrons passing in the conduction band. For intrinsic semiconductors, the Fermi level is halfway between the valence and conduction bands separated by a narrow energy gap (0.66 eV for Ge). Although no conduction occurs at 0 K, at higher temperatures a finite number of electrons can reach the conduction band and provide some current. In doped semiconductors, extra energy levels are added. In conductors, the Fermi level is in the overlap region and electrons are present in the conduction band.

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Electrons in crystalline solids, the Brillouin zones

In crystalline solids, the electrons are moving in a periodic potential due to the nucleus and other electrons. This potential has the periodicity of the array. The Bloch's Theorem states that the wavefunctions have the same periodicity.
rr r r i k.r k ( r ) = u k ( r ) exp
r r r u k ( r ) = u k ( r + T)
J.S. Blakemore, solid state physics, Saunders Comp. 1974
The periodicity in the reciprocal space allows to define shells which have the dimension of the reciprocal lattice. The discontinuity of E(k) at k=G, where G is a vector of the reciprocal lattice, explains the apparition of forbidden bands.

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And in nanomaterials ?
Nanoparticles are a connection between isolated atoms and condensed matter. Their electronic structure are deduced from computational methods starting from the electronic Hamiltonian and using several assumptions.
N Z Z n Za 1 H el ( R a , ri ) = ( i )+ a b 2 i < j ri r j i a ri R a N
Metallic nanoclusters
The confinement of the valence electrons, which are almost free electrons in a quasi spherical finite volume leads to the quantification of their energy, similarly to the energy of nucleons in nucleus. The liquid droplet model, where the nucleus is described as a fluid constituted of nucleons confined in a finite volume by the Strong interactions . It leads to discrete values of the energies of nucleons.

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Structure of nucleus

The nuclear droplet has an electrical charge and a surface. The binding energy per nucleon (the work required to put the nucleon outside the nucleus) depends on the mass number. The nucleus is stabilized when the A=2 Z. Z
P. Morel, Physique quantique, Hermann, Paris 1969

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Structure of metallic clusters

In a Na cluster beam, cluster with magic numbers N=8, 20, 40, 58 are favored. Following the nucleus nomenclature, the shell model assume that all electrons in a given shell have the same radial quantum number n and angular momentum numbers l. A shell can contain 2 (2l+1) electrons. When the electrons in a cluster exactly fill an energy level, it gives a closed shell cluster. The closed shell clusters have a lower energy. It means that it is relatively more costly to add one more atom to a closed shell than to an open shell cluster. Extended theoretical models (ab initio methods) improve the electronic description.
K.H. Meiwes-Broer, Metal clusters at surface, Springer 2000

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Quantum dots
In a quantum dot crystal, the energy gap is size dependent and can be altered to produce a range of energies between the valence and conduction band. Modeling using quantum mechanics gives that the gap of a quantum dot is enlarged. In solids, energy levels in a band are separated by such small amount of energy that for some processes, they may be treated as if they were continuous. It works well for semiconductor crystals with large numbers of atoms and physical dimensions much greater than the exciton Bohr radius (a few nm, depending on the material). In nanoclusters, the energy levels are well separated and the addition or subtraction of one atom or electron of the nanocrystal measurably change the electronic properties. It is the case of semiconductor crystals with a small number of atoms and physical dimensions on the order of 10 nanometers. When a semiconductor crystal has discrete states, it can be defined as a quantum dot. Quantum dots have useful, interesting and tunable properties.

Exciton Bohr radius: the natural physical separation in a crystal between an electron in the conduction band and the hole it leaves behind in the valence band. The size of this radius controls how large a crystal must be before its energy bands can be treated as continuous.

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Quantum well
A few nm thick multilayers with different energy gaps. The material with the narrowest width constitute a potential well quite infinite in the layers plane and with nanometric size in the perpendicular direction (GaAs/Alx Ga1x As). It leads to narrower emission bands and it is used for laser diode.
The discrete values of the energies can be tuned adjusting the dimension L. If the confinement layers are without impurities, the mobility of electrons is high and these nanomaterials can be used as high frequency devices. If the two layers have a periodicity L = L1+ L2, it leads to new Brillouin zones and eventually new forbidden bands. It is the origin of the gap engineering in microelectronics.
P. Costa, Nanomatriaux, Proprits et applications Techniques de lingnieur

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Metallic nanoclusters in an insulator

The resistivity of such materials depends on the volumic concentration of the metallic material and the evolution changes as percolation occurs. For x >x0 , conducting path exist within the composite material and it has a metallic response with a low resistivity (about 106 .m) which increases with temperature. For x < x0 , the conduction proceeds by jumps or tunneling effect within the insulator. The resistivity is drastically higher and it decreases with temperature.
Abeles et al, Phys. Rev. Lett. vol. 35, p. 247 (1975).
The physical properties of nanoclusters: The magnetic properties
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Magnetism of solids
The magnetic momentum of an atom has two contributions:

The magnetic orbital momentum ml=B l where B is the Bohr magneton and l is the orbital momentum. l =0, 1, 2 and 3 for the electron shells s, p, d and f. The spin magnetic momentum for an electron is ms=-2B S where S is the spin quantum number which has the value 1/2. eh
B =
2m
= 9.274 10 24 J.K 1
The quantum description of magnetism

It results from the partial filling of the energy levels. The manner in which electrons are assigned to various quantum states within a partially filled subshell is determined by the Pauli principle and the Hunds rule. A magnetic atom has some unpaired electrons and therefore a non-vanishing permanent magnetic momentum. It results also from the coupling between electrons from the various atoms. Magnetic properties of a solid are described by a magnetization M per unit volume.
M = B (L + 2S) = g B J

g =1+
J (J + 1) + S(S + 1 L(L + 1) 2J ( J + 1)
J=L+S is the total angular momentum and g is the Lande splitting factor. The magnetic momentum associated with the nucleus can be neglected (except when looking at the hyperfine structure). eh N = = 5.051 10 27 J.K 1 2M p

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The different types of magnetism

The most interesting forms of magnetism are the strong forms which arise in solids having a permanent magnetization. Diamagnetism:

For material in which all electrons are in paired states, there is zero magnetic momentum. momentum If a magnetic field H is applied, the response is the appearance of a magnetization per unit volume M such that M=dia H (assuming a linear response). dia is the diamagnetic susceptibility. According to Lentz law, dia is negative. All materials exhibits diamagnetism but, since dia is low, it it is hindered by the other type of magnetism. Copper is a diamagnetic material and dia= - 9.5 10-3.

Paramagnetism:

Atoms in paramagnetic materials have a permanent magnetic momentum M randomly oriented. In the absence of external magnetic field, the macroscopic magnetization M is equal to zero. When a magnetic field is applied, it induces a preferential orientation and M=m H. m depends on temperature (proportional to 1/T in the weak field approximation). Aluminium is a paramagnetic material with m = 2.2 10-3 at 300K.

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Ferromagnetism
Ferromagnetic materials exhibit permanent magnetization (below a temperature known as the Curie point, point 1043 K for Fe, 627K for Ni, 1388K for Co) which involves the cooperative alignment of permanent atomic moments. The two conditions for a material to be ferromagnetic are:

Atoms have a magnetic momentum. An internal interaction between the spins tends to align these spins through an exchange field BE called the Weiss field. BE can be as large as 103 T. The range of these interactions is a few interatomic distances, up to 11-2 nm in rare earth elements.

Using a mean field approximation, the exchange field is BE= M. The interaction energy between two atoms 1 and 2 can be written as E=-2I S1S2 where I is an exchange integral (corresponding to the overlapping of the 3d orbitals) and S1 and S2 are the spins of the two atoms. Quantum mechanic shows that the exchange integral I is a negative quantity for a small distance between neighboring magnetic atoms. This makes parallel spins energetically unfavorable. However, when this distance is larger than a critical distance (about three times the nearest neighbor distance), I becomes positive (Fe, Co and Ni are ferromagnetic but not Cr). Elements which are paramagnetic can form ferromagnetic alloys (Cu-Mn, Cu-Mn-Sn, Mn-Sb) J.S. Blakemore, solid state physics, Saunders Comp. 1974

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From the KITTEL

Ferromagnetism and Weiss domains

If all magnetic moments of the atoms in a magnetic material where aligned, the magnetic energy would be very large. When it is divided into domains, it lowers the total energy. Thus, a ferromagnetic solid can appear non magnetized on a macroscopic scale. The number of domains and the shapes and relationships between domains are determined by the crystal directions in which spin alignment can occur and by the requirement that energy is a minimum. Domain size is typically 1 m.
MFM image of nitrided ASS 316L, C. Tromas, LMP, Poitiers

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Ferromagnetism and Weiss domains

Each domain is separated from neighboring domains by a domain wall called Bloch wall. The thickness of a Bloch wall is about 300 nm for a soft material (easy magnetization) and
5 nm for a hard material (resistance to magnetization).
The Bloch wall width can be defined by =I1/2K-1/2 where I is an exchange integral and K an anisotropy constant. The exchange length is =I1/2/M where M is the magnetization.

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Ferromagnetism and coercive field

When an external field H is applied, Bloch walls move in a manner that enlarges domains in which the magnetization M is close to the direction of this field. The resulting field B=0 (H+M) increases till a saturation value which involves wall movements (low applied field) and domain rotation (high applied field). The motion of Bloch walls is partly reversible if the applied field is decreased and a remanent magnetization is observed.
The magnetization goes to zero if an opposite field Hc is applied. Hc is called the coercive field
(Hc=2K/Ms where Ms is the magnetization at saturation).
Magnetic anisotropy of Fe, Co and Ni is low and the Bloch walls easily move. These elements are soft materials. materials The rare earth materials (Nd2Fe14B) are hard since their anisotropy is large, giving a high coercive field. An alternation between positive and negative applied fields produces the Hysteresis loop. loop

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Antiferromagnetism
There is no display of gross magnetization because neighboring atoms displays anti-parallels spins. The two directions originate from two magnetic sub-lattices that oppose the magnetization from each other. The antiferromagnetism breaks at a temperature called the Nel temperature. Example: MnO. The moments on a (111) plane are anti-parallels to the moments of the adjacent (111) planes.
Ferrimagnetism

The two groups of sub-lattices have unequal magnetic moments. There is a spontaneous magnetization at low temperature given by the difference between the magnetization of the two sub-lattices. Example: Ferrite Fe2O3.

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Magnetism in nanomaterials
Since the domain size is typically 1 m, it is assumed that the nanoclusters are single domain and complications due to domain structure can be ignored. When the system size is of the order of magnitude of and , the formation of domain walls requires too much energy. Thus, the magnetization remains in the single domain state. The magnetization reverse by uniform rotation.
At smallest size below and , one must take into account the band structure and its modifications at the particles boundaries. When the size is so small that one must consider individual atoms, tunneling effects take place.
K.H. Meiwes-Broer, Metal clusters at surface, Springer 2000

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Magnetism in nanomaterials
The magnetization is larger in nanoclusters. For example, M=2.08 B in Co nanoclusters and 1.72 B in bulk Co.
Due to the lowest number of atoms in nanoclusters, the band width is smaller and favor the jump of electrons from one band to another one, thus enhancing magnetization. However, the interatomic distance is sometimes reduced and the magnetization can be reduced.
Paramagnetic materials become ferromagnetic.

Bulk rhodium (32 atoms) is not magnetic while nanoclusters of Rh have a magnetization M=1 B. This is attributed to the shrinkage of the d band.
Soft ferromagnetic materials become harder

Nanoclusters are more anisotropic. The rotation of the magnetic moments occurs in an entire grain, much lower than the width of the Bloch wall of the bulk soft material. It needs more energy and the coercive field is larger. Nanomaterials better withstand changes of magnetization.
The physical properties of nanoclusters: The optical properties
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Photoluminescence of semiconductors

This has been introduced in the electronic properties of nanomaterials. Photoluminescence corresponds to the annihilation of an electron-hole pair. It corresponds to light emission in the visible range of wavelenght. For nanomaterials, this is shift towards higher frequencies blue (lower wavelength). This is due to the confinement effect when at least one dimension of the material becomes nanometric (quantum well). Photoluminescence is used in optoelectronics to develop optical connections rather than electrical connections and to produce light-emitting diodes (LEDs).

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Absorption bands in insulators.

The interaction between an electromagnetic wave and an insulator (polarization) polarization can be described using the dielectric constant which depends on the frequency of the wave. The dielectric constant is complex, which gives a refractive index nr and an absorption index ni.
The Drudes model allows finding the expression of the electric susceptibility as a function of the frequency of the applied electric field. It gives a satisfactory description of the evolution of the permittivity in the frequency interval extending from infrareds to soft X-rays.
r = 1 + 2 p
2 ( '0 2 ) + j
Where 0 and are constants depending on the insulator.

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Absorption bands (filter for solar protection).

4.E+16 -1 (rad.s ) 3.E+16
The dispersion curve for an insulator
=ck
The study of the imaginary part shows that there is a forbidden band for propagation, which corresponds to absorption. Insulators have a large forbidden band width which corresponds to ultraviolet absorption. When their size is decreased towards the nanometric range, the absorption peaks are shifted towards the high frequencies. For 20 nm TiO2 nanograins, the absorption band starts at 0=310 nm; it allows reducing the UVB and keeping the UVA, which is suitable for solar protection.
2.E+16
Forbidden band
1.E+16
1.E+13 0.0E+00
5.0E+07
1.0E+08
1.5E+08
k (m )
-1

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Optical properties of metallic clusters in a matrix

The effects depend on the size of the clusters and on the wavelength of the light.
When the interaction between the electromagnetic wave and the material can be described by the polarization of the electron cloud, plasmons are created (collective oscillations of the electrons). For nanoparticules, the confinement results in the creation of surface plasmons (oscillating electrical charges on their surface). The characteristics of these surface plasmons depend on the dielectric constant of the matrix and the metal and on the shape of the nanoclusters. It leads to absorption bands in the visible range and in infrared. Reducing the size increases drastically the absorption.
The physical properties of nanoclusters: summary

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Structure, Phase changes
Large nanoclusters have the same structure as the bulk with somewhat different lattice parameters (in general clusters are slightly contracted). Smaller clusters might have structures that differ from the bulk materials. Structural magic numbers occur when an exact amount of atoms is needed for a specific structure, to minimize the energy (jellium model). The general tendency is to form structures where the total surface energy (and internal energy) is minimized.
Another effect caused by a high surface to volume ratio in clusters is a substantially lower melting temperature as compared to bulk materials.

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Electronic, optical, magnetic properties, reactivity

The electronic structure of a cluster varies from both that of a single atom and that of bulk material. As particles shrink in size, the continuous density of states in bulk is replaced with a set of discrete energy levels.
Nanomaterials For Environmental Applications Roberto Comparelli, Thesis 2004 Universita di Bari

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Electronic, optical, magnetic properties, reactivity

This leads to interesting optical properties. properties In semiconductors the band gap will be increased as cluster size is decreased a blue shift in the absorption spectrum of the semiconductor (good for tayloring lasers).
Photoluminescence color of colloidal solutions of CdSe nanocrystals passivated with a ZnS shell. The smallest (~1.7 nm) CdSe particles emit blue, the largest (~5 nm) emit red.
Nanomaterial For Environmental Applications Roberto Comparelli, Thesis 2004, Univerista di Bari
Interesting magnetic properties are also observed in small clusters, the magnetic moment of each atom interacting with the moments of the other atoms. It can force all the moments to align in one direction with respect to some symmetry axis of the cluster and the cluster have a net magnetic moment and is magnetized. As cluster size decreases it therefore becomes easier for them to exhibit ferromagnetic behaviour. Reactivity: Reactivity since the electronic structure of nanoclusters depends on their size, their ability to react with other species should also depend on size. This has important applications for the design of catalytic agents.
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What is at nanoscale in nanomaterials? Classification of nanomaterials The physical properties of nanoclusters The mechanical properties of nanomaterials

Elasticity, plasticity, dislocations, hardening, twinning, toughness, The role of grain boundaries Hardness, Ductility , Toughness of nanomaterials

Modeling: the backbone of nanotechnology research Elaboration of nanomaterials Methods of investigation of nanomaterials Study of the nanocomposite TiN-Ni

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Unique mechanical properties

By
reducing the grain size, lighter materials with enhanced mechanical properties can be produced. Nanograins are more resistant since they have no defects inside, contrary to micrograins (nanocrystalline copper is three times more resistant than usual copper). They are also more ductile since nanograin-nanograin glide is much easier. following mechanical properties will be presented.

The
Elastic properties Plasticity Hardness Ductility Toughness
Understanding of these unique properties requires to remind:

Elements
of elasticity Elements of crystallography Dislocations Hardening
The mechanical properties of nanomaterials: Elasticity

Elasticity theory deals with the small, continue and reversible deformations of isotropic elastic materials.
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An elastic material has the three following properties:

It deforms under stress and returns to its original shape when the stress disappears. It is homogenous and uniformly distributed in its occupied volume. It is isotropic.
Elasticity of polycrystals
Materials are commonly not isotropic as they are polycrystalline, with grains having different shapes and orientations. However, as the dimensions of the materials are very large compare to the mean grain, homogeneity and isotropy
hypothesis are sometimes more or less fulfilled. Thus, elasticity theory is also used for polycrystals.
Stress
and strain: Hooke law.
When a material is submitted to an elongation force, its deformation
=l/l is proportional to the applied stress =F/S for low

deformation (elastic domain).
The coefficient of proportionality between the stress
is the Young modulus E such that =E .
and the strain
If the solid is considered isotropic, elongation is accompanied by a
lateral contraction such that r/r= r/r=- l/l where is the Poissons ratio. When the elastic response is no longer sufficient to accommodate the stress, the material plastically deforms. It is called work hardening. The yield stress is the maximum stress for elastic deformation (conventionally, the stress leaving 0.2% remanent strain).
C. Tromas et al, chapter 8, Les Nanosciences 2, Ed. Belin 2006
The mechanical properties of nanomaterials: Plasticity

Plasticity: a non-reversible deformation in response to an applied stress.
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Stress-strain curve of a single crystal

The stress-strain curve exhibits stages. This results from the microscopic nature of plasticity, which is a
consequence of dislocations in the stressed material when stress is larger than the yield stress.
Plastic deformation of a single crystal

When a material plastically deforms, its surface exhibits slip bands. These slip bands are the emergence on the surface of dislocations. The orientations of these bands depends on the crystallographic
In Mtallurgie, du minerai aux matriaux, J. Philibert et al, Masson Paris 1998.
structure of the material. A part of the material is translated compare to the other part.
is the tangential component of the applied stress (shear stress).

It is equal to F/S0 multiplied by the Schmid factor.
Slip bands in an Al single crystal in La matire ltat solide, Guisnier et al, Hachette Paris 1987
The mechanical properties of nanomaterials: Dislocations

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Plane-to-plane sliding?
Using elasticity, it is possible to calculate the maximum value of
the shear stress necessary to move all atoms of a plane. For Cu, it gives 8000 MPa (about G/6, G is the shear modulus) The experimental value is ~0.5 GPa. It means that plasticity occurs through dislocations nucleation and glide.
Dislocations
Crystalline defects (edge and screw dislocations). It costs less energy to move a dislocation. The slip bands are the emergence on the surface of dislocations.
Edge dislocation Dislocation glide caterpillar glide
The mechanical properties of nanomaterials: Crystalline materials

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Crystalline materials: Some solids are crystalline, their atoms being periodically located in three dimensions on a lattice. Crystalline structure: the real space and the real lattice
The
Bravais lattice is a lattice in the real space, it is defined by three primitive vectors. (n1, n2 and n3 are integers). R = n1 a1 + n2 a2 + n3 a3
2D Bravais lattice Fcc Wigner Seitz cell
unit cell (Wigner Seitz cell) is obtained from the Bravais lattice. v = a1.(a2 a3 ) 14 Bravais lattices, 32 crystal classes, 230 space groups.
The
A crystalline structure is a Bravais lattice associated with a base (a set of atoms attached to each node of the lattice). The atomic planes (reticular planes) are characterized by their Millers indexes. (h, k, l are integers). The (hkl) plane cut the directions a1, a2 and a3 on a1/h, a2/k and a3/l.
A (111) plane in a fcc lattice
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Source and multiplication of dislocations

Dislocations
can be generated inside the material (homogenous nucleation) or at surfaces and interfaces (grain boundaries, precipitates).
The best-known mechanism of dislocation generation is the FrankRead source: a dislocation segment pinned at both ends and bowing out under an applied resolved shear stress.
Slip planes
Dislocation
climb occurs in slip planes in the direction of the Burgers vector. Usually, but not always, the slide planes are the denser planes since it corresponds to the planes with the lower friction.

FCC crystals: the glide directions are the <110> directions in the {111} planes CC crystals: the glide directions are the <111> directions in the {110}, {112} and {123} planes.
From single to polycrystal

Single
crystal: During work hardening of single crystals, depending on the initial orientation of the sample, different glide systems can successively operate, corresponding to different stages. Polycrystal: If the grain size is large enough (microscopic range), every grain is more or less homogenously deformed, proportionally to the macroscopic strain. It means that each grain simultaneously activates various glide systems.
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Twinning: another mode of plastic deformation

The two parts of a twin exhibit a mirror symmetry. Only a slight misorientation exists between them, which results from a shear displacement parallel to the twinning plane. It requires from 5 to 35 GPa to nucleate twins in Zn.
Physical Metallurgy Principles R.E. Reed-Hill, PWS-Kent, Boston
Twin scheme and twins in brass In Les matriaux , JP Bailon, Montral, 2000
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Twinning: another mode of plastic deformation

Twins
form primarily in metals that have suffered previous deformation by slip and nucleation centers are positions of highly localized strain in the lattice. Generally speaking, it means that twinning also involves slip. twins effectively reduce the grain size and raise the work hardening rate above what it would be if deformation were to occur by slip alone.
The
Twin in brass In Les matriaux , JP Bailon, Montral, 2000
Twins in a ferritic steel J. Bosansky et al, Materials Science and Engineering A323 (2002) 198205
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Hardening

Hardening of a material occurs when the motion of dislocations becomes difficult, even impossible, in this materials Plastic deformation starts when dislocation climb becomes active under the applied stress. Grain boundaries, precipitates, impurities or other dislocations are common obstacles for easy dislocation glide. Over passing these obstacles requires higher stress and dislocations are sometimes trapped and their motion is stopped.
Hardening processes

Work-hardening: New dislocations are produced which interacts. Tensile strenght is increased. Solid solution: Atoms in solid solution creates elastic distortions and stress field around them. The interactions between dislocations and these stress fields lead to a higher hardness. Thermal treatment: Adjusting the conditions of cooling or annealing, one can get non-equilibrium phases with precipitates that interacts with the dislocations. Grain refinement: Grain boundaries are major obstacles for the dislocations. They pile-up at these grain boundaries and it needs a larger stress to cross it and propagate in an other grain. The smaller the grain size, the larger the surface per unit volume. This effect is described by the Hall-Petch relation: 1 where is the conventional tensile strength, 0 is a constant, k is the Hall-Petch coefficient which 2 depends on the materials and d is the mean grain size. 0
= + kd
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Toughness

The ability of material to absorb energy during deformation up to fracture. A material is generally considered tough if it withstands high levels of loading (tensile, compressive, shear, etc.) and can dissipate strain energy without brittle fracture
Ductile fracture

Extensive plastic deformation takes place before fracture. It is related with the area under the stress-strain curve in tensile test.
Brittle failure
It may occur before any detectable macroscopic plastic deformation for relatively high strength or hard materials at applied stress well below the yield strength. Brittle fracture is the result of rapid crack growth. KIC (MPa.m) is the fracture toughness. For bulk materials, KIC is determined from the load that causes crack propagation in pre-cracked sample under tensile opening loading mode.

The mechanical properties of nanomaterials: Grain boundaries
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What is at nanoscale in nanomaterials? The physical properties of nanoclusters Classification of the nanomaterials The mechanical properties of nanomaterials

Elasticity, plasticity, dislocations, hardening, twinning, toughness,

The role of grain boundaries
Hardness, Ductility , Toughness of nanomaterials

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The properties of nanocrystalline (nc) materials are controlled not only by their small grain size but also by their interfaces, i.e. the grain boundaries. Structure of grain boundaries in nanomaterials
Two points of view:

Amorphous like layer at G.B.: Less ordered material, atomic arrangements with lower density and possibility of void formation. Ordinary G.B. structure: crystalline right up to the G.B.
Experimentally:

Crystallinity is maintained right up to the boundary. Majority of research shows that there isnt significant difference in grain boundaries The early reports on an amorphous layer in some samples were related to incomplete densification.
Modeling
Molecular dynamic simulations demonstrated that in pure metallic samples, in terms of the degree of disorder, the nature of the nanocrystalline grain boundary network is not fundamentally different from that of the coarse-grained counterparts.
HRTEM nc-Ni
HRTEM nc-Cu

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Nanocrystalline materials are polycrystalline solids with an average crystallite size typically in the range 1 to 100 nm. Small grain sizes correspond to extremely numerous grain boundaries. Using a boundary thickness of 1 nm or 0.5 nm and assuming spherical/cubic grains, the volume fraction of atoms in grain boundaries can be as large as 30-50% for 5 nm, 15-30% for 10 nm and about a few % for 100 nm grain sizes.
In the nanometer range, it is generally accepted that grain boundaries act as both sources and sinks for dislocations. Thus, the intrinsic plastic deformation behavior arises from the interplay between dislocations and grain boundaries.
Pile-up of dislocations in a grain (model) J. Schitz, Scripta Materialia 51 (2004) 837
The mechanical properties of nanomaterials: Mechanisms in nanomaterials
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Size effect?
Many observations & MD simulations
Mechanisms?

Many proposed. A few observed. A little established.
Quantitative predictions?
Some propositions, some verifications but not exactly established
The mechanical properties of nanomaterials: Hardness
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The role of grain boundaries Hardness, Ductility , Toughness of nanomaterials

The mechanical properties of nanomaterials: Hardness

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In analogy with yield strength, Hardness can be related to the grain size by a relation deduced from the well-known empirical Hall-Petch equation: H = H0 + kHP d- where H0 and kHP are constants. In conventional coarse grain materials, plastic deformation takes place mainly by dislocation activity, i.e. dislocation glide and dislocation generation by Frank-Read sources. There are several models for H-P effect. At least four different models have been put forward which explain the d-1/2 behavior of the yield stress and give expressions for kHP.
Dislocation pile up based explanation Dislocation density based explanations Slipped plane - shear crack modeling Statistical modeling
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Dislocation pile up based explanation of H = H0 + kHP d-

The original H-P analysis is based on the concept of dislocation pile-ups at grain boundaries, which generates the stress concentration and is responsible for nucleating slip in the neighboring grain. Eshelby et al. (1951) Number of dislocations in a pile up

n number of dislocation in pile constant s average resolved shear stress in the slip plane d grain size G shear modulus b burgers vector
s d n= Gb
Stress acting on the lead dislocation

=/M is the applied shear stress where M is the Taylor factor, which represents the average of the inverse of the Schmid factors for the various grains. In a non textured specimen, M~3. 0 intrinsic lattice resistance to dislocation motion. c the resolved shear stress required to propagate slip across the grain boundary.
2 s d c = ns = Gb
where
s = 0

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Dislocation pile up based explanation of H = H0 + kHP d-

( 0 ) 2 d c = Gb
= 0 + kd 1 2
Thus K H P
Gb c = kM = M
1/ 2
Taking KHP to represent the activation of slip in the neighboring grain, Armstrong and Smith have proposed the following expression where M* = 2.2 is the Sachs orientation factor and is the Poissons ratio.
K HP
M *Gb(2 ) c = M 4(1 )
1/ 2
R.W. Armstrong, in: T.N. Baker (Ed.), Yield, Flow and Fracture of Polycrystals, Applied Science Publishers, UK, 1983, pp. 131. R.W. Armstrong, T.W. Smith, in: C. Suryanarayana, J. Singh, F. Fracs (Eds.), Processing and Properties of Nanocrystalline Materials, TMS, Warrendale, PA, 1996, pp. 345354.

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Dislocation density based explanations of H = H0 + kHP d-

Assumptions:

Grain boundaries act as dislocation sources. Dislocation density is inversely proportional to the grain size.
The basis of the dislocation density model for the effect of d on is the well-known relation between and the dislocation density .
= 0 + Gb

12
y = 0 + MGb1 2
0 is due to all defects other than dislocations M Taylor factor. constant (1/2 for screw and 1/(2 (1-)) edge dislocations respectively), G shear modulus b Burgers vector.
The dislocation density generally increases:

with shear strain =M, where is the uniaxial strain, as d decreases.

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Dislocation density based explanations of H = H0 + kHP d-

Three mechanisms for the increase in as d decreases

grain boundary ledges provide a source for dislocations,

m is the ledge density (typically m = 0.02 0.2).
8m 1 L = d
grain boundaries reduce the average free slip distance s=sd (with s 1).
S =
is the tensile strain.
M 1 Sb d
so-called geometric dislocations are needed to prevent voids and overlaps from occurring at the grain boundary due to the inhomogeneous deformation.
g =
1 4b d
The three dislocation mechanisms may act either independently or concurrently, and either sequentially or simultaneously.

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Dislocation density based explanations of H = H0 + kHP d- . The Hansen analysis.

The stress is divided into two parts.
1 / 2 ( ) = 0 ( ) + k ( ) D B
0() is independent of the grain size. size It is the stress flow of the grain interior, related to the density of dislocations accumulated in dislocation boundaries. k() DB1/2 is grain-size dependent. dependent (DB is the average distance between grain boundaries). It is the strength contribution due the additional resistance to dislocation motion caused by the presence of grain boundaries. The stress 0() and k() are constants at a given strain.
The mechanical properties of nanomaterials: Hall Petch explanations Slip plane - shear crack based explanations of H = H0 + kHP d-

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It treats a slip plane within a grain as a shear crack. It gives:
K HP = M c rc
where c is the critical stress required to operate a dislocation source at a distance rc ahead of the crack and M is the Taylor factor.
The mechanical properties of nanomaterials: Hall Petch explanations Statistical modeling of H = H0 + kHP d-
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It gives:
K HP =
MKGb
Where:
KHP depends on obstacle strength,
l is the mean spacing between obstacles
Both of these constants are difficult to determine independently. Furthermore, if the obstacles are dislocations, as would often be the case, then this model requires the dislocation density to be independent of the grain size, in direct conflict with the previous explanations.

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H = H0 + kHP d-
The presented models are capable of explaining the form of the HallPetch equation, but the meaning of the slope KHP remains the object of some debate. The Hall-Petch formulae gives unrealistic strength at nano size region/
Example of a steel having a strength = 600 MPa at d=10 m and 0 =400 Mpa.
18000 Strength (Mpa)
12000
6000
0 1
10
100 1000 10000 100000 Grain Size (nm)
The mechanical properties of nanomaterials: Hardness experimental results
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Experimental results
y = 0 + kd
1 2
H = H 0 + k HP d 1 2

0 is the stress in the absence of grain boundaries, k is a constant.
d is the grain size.
H0 is the hardness in the absence of grain boundaries, kHP is the Hall-Petch constant.
d is the grain size.
Yield strength in Cu nanograins Hardness of Ni and Ni(W) nanograins GJ Fan et al, Materials Science and Engineering A 409 (2005) 243248
There is a material softening (inverse Hall-Petch) with grain size for d< 20 nm
The mechanical properties of nanomaterials: Hardness experimental results
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Experimental results
Nanostructured coatings
1-2 nm 5-10 nm TiN VN
N4 Si 3
Nanomultilayers Superlattices (1D)
Nanocomposite coatings (3D)
TiN/VN Substrate
nc-TiN/a-Si3N4 Substrate
TiN
65
10 nm
60
TiN/VN
Hardness (GPa)
45 35 25 15 5 0 5 10 15 20 25 30
Hardness (GPa)
55
TiN/NbN
50 40 30 20 10 0
Vepek et al. (PA-CVD) Vaz et al. (Rf-RMS)
inverse HallPetch effect
Multilayer period (nm)
5 10 15 20 Si content (at. %)
25
/20
The mechanical properties of nanomaterials: Inverse Hall-Petch Effect
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Inverse Hall Petch Effect

Strengthening with grain refinement, rationalized by H-P mechanism, holds up for ultra fine crystalline (ufc) regime. By decreasing grain size into the nanometer regime (<100 nm), this process invariably breaks down and hardness versus grain size relationship departs markedly from the H-P relation. A softening for the very small grain size (i.e. less than 10-20 nm).
Nanomaterials
Strength/Hardness
Hall-Petch
Mterial Behavior H-P relation
Strength/Hardness
100
101
Grain Size (nm)
102
103
104
105
UFC materials Conventional grain size materials
10
100
1000
10000 100000
Grain Size (nm)
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Inverse Hall Petch Effect

A number of investigators have suggested that the inverse HallPetch relation can be attributed to the increased grain boundary activity due to:

grain-boundary sliding and/or the diffusional mass transfer via grain-boundary diffusion.
Conventional mechanisms for the grain boundary diffusion are described using: The Nabarro-Herring creep, based on the vacancy flow through the crystal lattice. lattice It predicts a steady-creep rate:
&=
14D1 2 d k BT
where D1 is the lattice diffusivity and is the atomic volume.
The Coble creep is based on the vacancy flow along the grain boundaries. It predicts a steady-creep rate:
&=
148D b e 3 d k BT
where e is the thickness of the grain boundary and D2 is the diffusivity along the grain boundary.
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Inverse Hall Petch Effect: numerous models

Most of the models proposed to explain the IHPE behavior fall into at least one of four categories:
Dislocation-based models: Dislocation motion is the primary agent for plastic flow in nanocrystalline and very small crystallite sizes affect the behavior of dislocations. Diffusion-based models: Various diffusion processes such as the Coble creep. Grain-boundary-shearing models: observed in various molecular dynamics simulations. Two-phase-based models: A nanocrystalline material is a composite material with at least two phases, namely a grain-boundary phase and a grain-interior phase.
In the context of this lively and continuing discussion, a new model was recently suggested based on the nature of dislocation absorption by grain boundaries.
Pdis is the probability of a dislocation being absorbed by a grain boundary.
= 0 + k (1 Pdis ) d 1 / 2
The mechanical properties of nanomaterials: Hardness: summary
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Hardness of nanocrystalline materials

Conventional grain size: Dislocation mediated plasticity
Nanocrystalline material (d<20nm): Grain boundary mediated plasticity
Dislocation Glide Source: Franck-Read Dislocation Glide Source: G. B. Partial dis. Glide Source: G. B. G. Boundary sliding
1
10
100
10 10
104
2 10 10 103 Grain Size (nm) Size (nm) Grain

5
104
105
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The role of grain boundaries Hardness, Elasticity, Ductility, Toughness of nanomaterials

The mechanical properties of nanomaterials: Elastic properties

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Intrinsic elastic moduli of porosity-free nanostructured materials are essentially the same as those of conventional grain size materials until the grain size becomes very small, e.g. <5 nm. Below this grain size, as the number of atoms associated with the grain boundaries and triple junctions becomes very large, elastic modulus decreases. Such decrease in elastic modulus is linked to the increase of the Poissons ratio. Modeling of nanocrystalline Cu.

At 0K, ~100 GPa in nc-Cu compare to ~150 GPa. At 300K, ~80 GPa compare to the experimental value of 124 GPa for macroscopic Cu.
J. Schiotz et al, PHYSICAL REVIEW B VOLUME 60, NUMBER 17, 1999
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mechanical instability or fracture. In the micrometric range, metals are more ductile if their mean grain size is low (enhanced grain boundary diffusivity). However, if the grain size is lower than ~100 nm, metals become more fragile. It could be the result of the difficulty for dislocations to nucleate and to glide in such small grains. Nanocrystalline materials exhibit no real improvement of the ductility, ductility compare to micromaterials. In metals, the increase in ductility provided by diffusional mechanisms is apparently insignificant compared to the loss of dislocation-controlled ductility. Typical ductility of less than 2 % was obtained for nc-metals with grain
size less than 25 nm while the same metals, in conventional grain size regime, exhibit 40-60% tensile elongation (ductility)
X. Zhang et al, App. Phys. Lett. 81, 5 2002
Ductility is defined as the percentage of elongation or uniform plastic flow prior to
Zn
However, nanocomposite materials, i.e. polyphase materials, may exhibit a good ductility. The ductility and therefore the toughness will be enhanced provided the particle size d becomes of the same size as the width of the shear localization s (sd).
Sam Zhanget al, Surface & Coatings Technology 200 (2005) 1530 1534
For Al, Cu, Ni, Pd
H. S. KIMA et al, App. Phys. Lett. 79, 25, 2001

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Toughness
As the failure mechanism of high strength materials like nanomaterials is governed by brittle fracture, toughness is a key mechanical property used in material designing (design criteria), instead of strength or hardness alone.
Toughening mechanisms

crack deflection, crack tip shielding (by dislocations, microcracks, phase transformation and ductile phase), crack-wake bridging (by grains, continuous-fibers, short whiskers, second ductile phase), Multilayering.
In nanomaterials
Indeed, the original design concept of superhard coatings aimed at obtaining superhardness by preventing all possible plastic deformation mechanisms. The zero plastic deformation means clearly zero ductility and reduced toughness and fracture toughness.

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Toughness in nanomaterials
One way to improve nanomaterials toughness is to combine a hard nanocrystalline phase with a soft metal matrix (nanocomposites). The concept of hard nanocrystalline carbide and amorphous diamond-like carbon (DLC) phases.
To maintain grain size at ~10 nm to restrict initial crack size and create a large volume of grain boundaries; To separate the nanograins within an amorphous matrix thickness above 2 nm to prevent interaction of atomic planes in the adjusted nanocrystalline grains and facilitate grain boundary sliding, but less than 10 nm to restrict path of a straight crack; To produce nanocrystalline grains with random orientation (high angle grain boundaries) to minimize grain incoherence strain and facilitate grain boundary sliding.
Toughening can be done using multilayer design.

The number and thickness of layers are combined to govern the resulted toughness.
S. Zhang et al. / Surface & Coatings Technology 198 (2005) 28
Scratch testing: WC/DLC A.A. Voevodin, J.S. Zabinski / Thin Solid Films 370 (2000) 223231
Modeling: the backbone of nanotechnology research
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What is at nanoscale in nanomaterials? The physical properties of nanomaterials The mechanical properties of nanomaterials Modeling: the backbone of nanotechnology research

Introduction
Ab-initio methods Molecular dynamics Classical and kinetic Monte-Carlo

Elaboration of nanomaterials Classification of the nanomaterials Methods of investigation of nanomaterials Study of the nanocomposite TiN-Ni
Modeling: Introduction
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The backbone of nanotechnology research

The need to be able to predict

the size and shape of the materials, what characteristics a particular experiment might exhibit. Numerical experiments allow to study and predict chemical, physical, mechanical properties of materials when real experiments reach their limit: very low size, very fast processes, very high pressure and temperature
Since the nanoworld sometimes drastically differs from microworlds, our perception of this world, often based on our experience of the bulk properties, could be unreliable. Comparison with numerical experiments allows the scientists to work and practice in confidence. It requires to work with a large number of atoms and to simultaneously use concepts from classical and quantum mechanics.
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The backbone of nanotechnology research

Understanding the behavior of nanomaterials is important both from basic science point of view and for future applications.
Appropriate modeling tools are needed to treat several characteristic time and length scales. For example, chemical reactions occur rather fast since they involve electron dynamics, while growth and mechanical properties involve atomic motions and thus are characterized by different time scales.
Numerical experiments will not always provide answers. They are done within the frame of one theory which is built from or validated by established experimental results. Therefore, numerical results are only valid within this frame. Calculations should never be considered as a proof and always be compared to experiments. The computational physicist has to know the liability range of the model he is using, and whether computed results could be safely trusted or not.
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Various models suitable at different length and time scales

Atomistic methods

Ab initio methods Molecular dynamics Quantum Monte-Carlo
Mesoscopic methods

Classical Monte-Carlo Kinetic Monte-Carlo
Modeling: Ab-initio
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Introduction

Ab-initio methods
Molecular dynamics Classical and kinetic Monte-Carlo

Modeling: Ab-initio
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The principles of the Ab-initio methods

Materials' properties result from quantum mechanical interactions described by solutions of a Schrodinger equation.
Interactions between the various particles (electrons, nucleus) are described using potentials. The determination of the potential is made without any assumptions coming from the properties of the investigated material Ab-initio (from the beginning).
It starts from the Schrdinger equation H=E.

Zi Z j e 2 1 p i2 p2 Zi e 2 1 e2 n + + + Where H = 2 M 2 m 2 2 r r i, j R i R j n ,n ' n i , n R i rn i i n' i

i, j denotes for the nucleus, n, n denotes for the electrons R, P are the position and momentum of nucleus, R, p are the position and momentum of electrons, M, m are the mass of nucleus and electrons. Z is the atomic number.

Modeling: Ab-initio
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Solving the Schrdinger equation requires some assumptions. The Born-Oppenheimer approximation: electrons are lighter than nucleus and move fastly. The wave function can be written as a product of a wave function N(Ri) for the nucleus and a wave function for the electrons E(Ri, rn): N(Ri ,rn)= N(Ri) E(Ri, rn).
The electrons part
p2 Zi e 2 1 e2 n H el = + 2 n ,n ' rn rn ' i,n R i rn i 2m H el E (R i , rn ) = V E (R i , rn )
The nucleus part
H nucl
Zi Z j e 2 Pi2 1 = + +V 2 M 2 i i, j R i R j i
H nucl N ( R i ) = E N (R i )
Modeling: Ab-initio
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Solving the Schrdinger equation gives either the wave function or the electronic density.
The Density Functional Theory (DFT) is currently used since it allows an easier treatment of the electronic interactions, which leads to lower computer time. Using DFT, the potential V is a function of both the position of the nucleus and the electronic density. And this potential should be minimised. Development of efficient algorithms have made DFT the primary method for calculating properties such as:

band structures, cohesive energies, chemisorption energies, activation barriers.
DFT is inefficient if the atoms are allowed to move as, for example, during the geometrical optimization of a molecule. Car and Parrinello introduced a DFT based method which gives the possibility of ab initio quantum molecular dynamics simulations through a fictive dynamic motion of the electronic density.
R. Car, M. Parrinello, Phys. Rev. Lett. 55 (1985) 2471.
Modeling: Ab-initio
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Examples of the Ab-initio calculations
Ab initio study of nanostructures of Ultra thin ZnS films B.K. Agrawal et al, Progress in Crystal Growth and Characterization of Materials 52 (2006)
Optimized structures of SiC, SiC2, Si2C, Si2C2 and SiC3 microclusters. B.K. Agrawal et al, Progress in Crystal Growth and Characterization of Materials, 52 (2006)
Modeling: Ab-initio
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Introduction Ab-initio methods

Molecular dynamics
Classical and kinetic Monte-Carlo

Modeling: Molecular dynamics

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The principles of Molecular Dynamics

The total energy of the system is calculated as a function of the nuclear positions. Atoms are treated as classical particles and the quantum mechanical motion governed by the Schrodinger equation is replaced by Newton's equation of classical mechanics.
Fi = m i a i Fi = U i
Solving the equations requires: Boundary conditions Appropriate potential.
Basic limitation appears when the processes (such as atomic diffusion) are time multiscale phenomena. The time step must be small enough (~1015 s) for the dynamics of the vibration modes (~10-13 s). However, residence times between hops are ~s and the interactions responsible for aggregation occur within milliseconds to minutes.

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Principles of Molecular Dynamics: the boundary conditions

If the objective is to simulate nanoclusters, then surfaces are free. If the objective is to study the volumic properties of materials, it should require to use a huge number of particles in order to neglect the effect of surface. But it is time consuming. It is more efficient to use periodic boundary conditions.

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Principles of Molecular Dynamics: the potentials

The potential is an explicit expression of the nucleus-nucleus interactions and contains implicit contributions of the ion-electron or electron-electron interactions. The expression of the potential is not formally known and is only an approximate function of the positions of the nucleus. It is not possible to have a universal potential and several expressions have been derived for each class of materials (insulator, metals, crystals, amorphous matter).
The potential is therefore a mathematical expression U=F(R1, R2,,RN) which includes calculated or fitted parameters, according to experimental observations. It can be written in the form:
U = f1 (R i ) + f 2 (R i , R j ) +
i i, j

i , j, k
f 3 (R i , R j , R k ) + ...
The first term is usually set to zero in the absence of an external field. The second term is known as the pair-energies term and is generally the most important. In practice, the fifth term is never used.
L. Pizzagali, Mat. Sciences (Medziagotyra) 10, 2, 2004

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Principles of Molecular Dynamics: examples of potentials

The pair potentials: when dominant interactions are of the Van der Waals type.

Hard-sphere potential: Soft-sphere potential: Square well potential: Morse potential:
F(r)= if rr0 and F(r)=0 if r>r0. F(r)=(/r)n. F(r)= if rr0, F(r)=- if r0 rar0 and F(r)=0 if r>ar0. F(r)=D [exp(-2(r-r0)-2exp(-(r-r0)]
Lennard-Jones potential: F(r)= [ (/R)12- (/R)6]
Potentials derived from the Embedded Atom Model (EAM) are suitable for metals.
U = Fi (i ) +
i
1 ij (R ij ) 2 i j
Fi is the energy required to embed the atom i in the background electron density i. ij is the electrostatic repulsion pair.
i = a j ( R ij )
i j
Covalent bonds in semiconductors have a complicated dependence on coordination and bond angles. Suitable potentials have been developed for this class of materials. The potential proposed by Stillinger-Weber is the sum of a pair potential plus a three-body contribution.

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Principles of Molecular Dynamics: examples

AFM deformation of a nanotube by a Li-needle A. Maiti, Microelectronics Journal, 2007
Modeling of the mechanical properties of nanotubes by the molecular structural mechanics approach C. Li, T-W Chou, Composites Science and Technology 66 (2006) 24092414
Modeling: Monte-Carlo
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Introduction Ab-initio methods Molecular dynamics
Classical and kinetic Monte-Carlo

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Principles of Monte-Carlo modeling

The deterministic equations of MD are replaced by stochastic transitions. Stochastic algorithms to explore the system phase space and to make averaging according to statistical physics. It starts from an initial state of a system of N particles. Then, the positions of one or more particles are stochastically changed. The change in potential energy Ep is calculated and the acceptation of this new state depends on the previous state. It leads to a set of states known as the Markov chain, representative of all possible states of the system. The acceptation of a new state with a higher energy avoids to stay in a local minimum of energy. The acceptation criterion depends on the statistical nature of the system (microcanonical, canonical or grand canonical ensembles). The Monte Carlo methods are nondeterministic.

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Principles of Monte-Carlo modeling, the Metropolis algorithm

The studied variable is A, which gets the values Ai for the state i of the system. The probability pi to get a given state i with an energy Ei is p i = e The average value of the variable A is < A >=
E i
with =kBT.
Ai
i
pi
pi
i
The probability for the system to go from a state to another one is such that:
W ( j i) p j ( E j E i ) = =e W (i j) p i
For the Metropolis algorithm, the probability to go from a state i to a state j is:

W(ij)=1 if Ej<Ei. W(ij)=exp[-(Ej-Ei)] if EjEi.
A new random number between 0 and 1 is selected. The new state is accepted is r < exp[-(Ej-Ei)].
Modeling: Kinetic Monte-Carlo

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Principles of Kinetic Monte-Carlo

A time scale is associated to the change from a state i to a state j. The probability to get a system in state i at time t is p(i, t), the rate of transition from the state i to the state j is W(ij). Thus the evolution of p(i,t) is governed by the master equation:
p p(i, t + dt ) p(i, t ) = = [W ( j i) p( j, t ) W (i j) p(i, t )] t dt j

( E j E i )
The transition rate for a event i has a rate i e

Where i is a frequency prefactor typically of the order of 10-13 s and Ei is the free energy barrier for the process. The prefactor i represents the timescale of the fastest process.
Kinetic Monte Carlo allows to model huge system (a few 106 atoms) at large time scales (up to hours).
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Methods of investigation of nanomaterials Study of the nanocomposite TiN-Ni
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Bottom-up approach

an atom by atom construction process One or two steps Physical and chemical processing
Top-down approach

decomposition of bulk material One or two steps Mainly physical processing
Elaboration of nanomaterials: the bottom-up-approach
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Classification of nanomaterials Methods of investigation of nanomaterials Study of the nanocomposite TiN-Ni

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An atom by atom construction

It starts with atoms, ions, or molecules, to form nanostructured building blocks, e.g. crystallites, or nanoscale clusters, which are then assembled into final bulk materials. One step processes

Electrodeposition: from chemical compounds in vapor liquid phase Chemical vapor deposition (CVD): chemical compounds are used either in vapor or liquid phase. Physical vapor deposition (PVD): when it is from the vapor phase, material is extracted from a source either by heating or ion bombardment. Sol-Gel processes: from colloidal solutions. It allows preparing free-standing nanoparticles or nanocrystals directly in solution.
Two step processes

Nanoparticles production by CVD, PVD and chemical routes + compaction

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Electrodeposition
The electrodeposition consists of different steps

stabilization of the particles in the bath transport of the particles from the solution toward the electrode adhesion of the particles to the substrate.
Surfactants are added to industrial plating bath to prevent particle aggregation. The efficiency (rate) of the electrodeposition is determined by the flow intensity, electrode polarization and ionic strength of the solution. Electrophoresis is the movement of an electrically charged substance under the influence of an electric field. This movement is due to the Lorentz force,
Fe: Lorentz or electrophoretic force Fb: buoyancy or Archimedes force Fh:hydrodynamic force Fg: gravitation force
C. Filitre et al, Colloids and Surfaces A: Physicochem. Eng. Aspects 222 (2003) 55 /63

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CVD
Volatile precursors react and/or decompose on the substrate surface to produce the desired deposit. A variety of CVD processes which differ by which chemical reactions are initiated and conditions of processing. Examples:

LPCVD performed at low pressure, which improves deposit uniformity and composition. PECVD Plasma-Enhanced which boost the chemical reaction rates of the precursors. HWCVD hot filament (Hot Wire) is used to chemically decompose the source gases.
PECVD HWCVD
SEM of a 40-nm-thick PTFE HWCVD coating on a carbon nanotube.
Kenneth K.S. Lau et al, Thin Solid Films 501 (2006) 211 215
Masaaki Nagatsu et al, Carbon 44 (2006) 33363341

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PVD
Material to be deposited is placed in an energetic environment (like submitted to ion or electron beam) and particles of material escape its surface and travel to the cooled substrate surface to form a solid layer. Processing is done under vacuum to allow a sufficient mean free path of the particles. Examples of PVD:

Thermal evaporation: using an electrical wire to melt the material. Molecular beam epitaxy is a particular sophisticated form of thermal evaporation. Electron beam evaporation: melting is done by the electron beam. Sputtering by an ion beam: Rare gas Ions sputter the material target. Deposition can be assisted using another reactive beam. Pulsed laser deposition: it is an ablation process by pulses of focused laser which vaporizes the material.

Tse et al, Surface and Coatings Technology 180 181 (2004) 470477
TiN/Ag multilayers prepared by RDIBS
Reactive Dual Ion Beam Sputtering (RDIBS)

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Sol-Gel

A transition from a liquid phase (colloidal solution sol") into a solid phase ( "gel") phase. Organometallic precursors (TMOS, TEOS, Zr(IV)-Propoxide, Ti(IV)-Butoxide... ) submitted to hydrolysis and condensation reactions:

M-O-R + H2O M-OH + R-OH (hydrolysis) M-OH + HO-M M-O-M + H2O (water condensation) M-O-R + HO-M M-O-M + R-OH (alcohol condensation)
Tadao Sugimoto, Journal of Colloid and Interface Science 309 (2007) 106118
C. J. Brinker and G. W. Scherer, Sol-Gel Science - The Physics and Chemistry of Sol-Gel Processing, New York, Academic Press, 1990.
AgCl aggregates

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Reverse micelles as nanoreactors

Reverse micelles are formed from surfactants in a mixture of water and oil (like isooctane). Surfactants are molecules with a polar hydrophilic head (attracted by water) and a hydrophobic hydrocarbon chain (attracted by oil). The surfactant most used is sodium di(2-ethylhexyl)sulfosuccinate usually called Na(AOT). The ratio w = [H2O]/[Na(AOT)] determines the reverse micelle size (the nanoreactor) and affects the size of the nanocluster nucleating and growing in it.
I. Isabelle Lisieckia, Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 499507

Co nanoclusters
R = [NaBH4]/[Co(AOT)2], where the sodium borohydride (NaBH4) is a reducing agent.
Elaboration of nanomaterials: the top-down approach
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Classification of nanomaterials Methods of investigation of nanomaterials Study of the nanocomposite TiN-Ni

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Decomposition of a bulk material

Introduction of a high density of crystal defects (dislocations, grain boundaries) into a former course grain polycrystalline or single crystal by heavy plastic deformation (extrusion, shear, wear ) These methods do not always enable the dimensional and structural characteristics to be adequately monitored. one step process

Implantation, ion bombarding Severe plastic deformation Ball milling or mechanical alloying + compaction
two step process


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Growth of nanocrystals during ion bombardment

Ion bombardment is a way to introduce additional elements in a matrix, together with a high density of defect. Example of Si nanocrystals formed in silica by ion-implantation and thermal annealing.
Silicon nanocrystal memories have attracted much attention in recent years. To fully exploit their potential advantages over conventional floating gate memory, it is essential to control as accurately as possible Si nanocrystal size and depth distribution. Si nanocrystals are produced by implantation of a few keV Si+ ions (~1 1016 cm2) into ~100 nm thick silicon dioxide films. Such implantations lead to a Gaussian depth distribution of silicon in the SiO2 matrix and produce a peak excess Si concentration. After annealing (~1000C) production of spherical nanocrystals with diameters ~ a few nm.
Sharma et al, University of Cambridge, Department of Materials Science and Metallurgy

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Mechanical alloying
The main characteristic is the production of crystalline solid solutions far from equilibrium.
Conditions:
Balls are made of WC or hard steel, with diameter in the mm range. The initial material is a powder with average grain size a few m. The ratio of mass powder/balls is low, usually 1/10. Milling duration: a few hours. The temperature rise is usually lower than 200C. To prevent contamination, milling can be performed under inert atmosphere and the metallic powders are very pure to enhance their ductility so that a protective coating forms around the balls.
The decrease in size occurs through fracture and welding

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Mechanical alloying
The nanometric range is obtained after a few hours.
G. Gonzales et al, Journal of Alloys and Compounds 434435 (2007) 437441
The solid solutions start by first mixing together lumps of the components, each of which might contain many millions of identical atoms. It evolves into an intimate mixture of different kinds of atoms without the participation of diffusion or of melting. It is done through solid state reactions assisted by severe plastic deformation that occurs during ball milling of the elemental powders.
M. Krasnowski, T. Kulik, J. Alloys Compd. (2007)
Nanocomposites obtained by mechanical alloying in FeAlTiC system.

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Mechanical alloying, consolidation

Consolidation of milled powders into bulk, full-density compacts preserving nanometric grain size, which is crucial for possible application of nanophase materials, is not easy to achieve.
Extensive grain growth typically occurs during conventional elevated temperature consolidation. The high temperature is required for good consolidation of powder to bulk materials, that is to remove all porosity and to obtain good interparticle bonding. bonding One of the consolidation methods which, by careful control of the temperature, pressure and processing time, allows to retain nanocrystalline structure is high pressure hot-pressing.
Sintering of nanocrystalline FeAl intermetallic

To build a bridge between the particles and to reduce porosity. Atomic diffusion: heating below the melting point of the material to favor the adhesion until its particles adhere to each other.
Sintering of nanocrystalline FeAl intermetallic

pressure of 7.7 GPa temperature of 1000 C t=180 s.

M. Krasnowski, Intermetallics 15 (2007)
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What is at nanoscale in nanomaterials? The physical properties of nanomaterials The mechanical properties of nanomaterials Modeling: the backbone of nanotechnology research Elaboration of nanomaterials Classification of nanomaterials

Transmission Electron Microscopy X Ray Diffraction Atomic Force Microscopy Nanohardness
Methods of investigation of nanomaterials: Interaction material-radiation
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Interaction between material and radiation

Electron beam and X-ray can be both considered as radiations

Electron is characterized by its momentum or its wavelenght 0 through the de Broglie equation which relates both parameters, where h is Planck's constant, me is the electron mass and U is the acceleration voltage. For a 200kV voltage, the wavelength is 0.0025 nm. X-ray is an electromagnetic wave with wavelength smaller than ~100 nm. The related particle is the photon. The wavelength of a monochromatic beam produced by a copper cathode is 0.154 nm.
0 =
h h = me v 2m e eU
0 =
h h = me v 2m e eU
Two types of interactions

1. Absorption An electron losses its energy through inelastic interactions and elastic interactions. The penetration depth is given by
0.1 U1.5 ( keV ) x (m) = (g.cm 3 )
The absorption of X photons in solids depends on the number of electrons that can accept a transfer of energy from the photon (Z atomic number). Depending on the angle of incidence, the penetration depth ranges from ~10 nm up to several 100 nm.
I = I 0 e x
where is the linear attenuation coefficient.

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Two types of interactions

2. diffraction
Although the intensity of the electron or X Ray beam is affected by the volume and the density of the investigated material, crystalline material mostly interacts by diffraction. diffraction The characteristics of the diffracted beam is obtained from the theory of diffraction using a Fourier analysis.
Diffraction by crystalline material

Diffraction grating

N diffracting line separated by p and with width a. The diffracted intensity is given by this well-known formulae. The width of the diffraction peak is inversely proportional to the size of the diffracting volume (Np).
sin a sin Np I0 = I0 a Np
2

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Diffraction by crystalline material: the reciprocal space and the reciprocal lattice
The reciprocal space: If r = r1 a1 + r2 a2 + r3 a3 is a vector of the real space, the
vector s = s1 b1 + s2 b2 + s3 b3 with the unit vectors of the reciprocal such that ai.bi=2ij.
The reciprocal lattice

A vector of the reciprocal lattice can be written G = h b1 + k b2 + l b3. (h, k, l are integers). A vector R = n1 a1 + n2 a2 + n3 a3 of the real lattice and a vector G obey exp(iG.R)=1
2D Bravais lattice
2D reciprocal lattice
A vector R = n1 a1 + n2 a2 + n3 a3 of the real lattice and a vector G obey exp(iG.R)=1.

The distance dhkl between two adjacent (hkl) planes is equal to 2/|G|. The wave vector k (2/) is a vector of the reciprocal space.

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Diffraction results from the interaction between the beam (electrons or X photons) and the electrons of the atoms regularly spaced in the real lattice. The theory of diffraction (elastic diffusion, energy does not change) gives that the difference between the wave vector k of the incident beam and the wave vector k of the diffracted beam differs by k = G.

It means that the intensity of the diffracted beam differs from zero only when the angle between the incident beam and the diffracted beam obeys the previous relation.
Since the diffusion is elastic (k=k= 2/) and dhkl= 2/|G|, it gives the well-known Braggs relation: =2 dhkl sin.

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The intensity of the diffracted beam in a direction (h, k, l) is given by:

I hkl = Vdiff Fhkl
Vdiff is the diffracting volume

Fhkl = i fi exp (2i ( hxi + kyi + lzi ) is the structure factor. Fi is the atomic diffusion and xi, yi, zi denote for the position of the i atom in the unit cell. For the fcc structure and identical atoms, the structure factor differs from zero if the Miler indices have the same parity. For the cc structure, the sum of the Miller indices have to be par.

Two lattices are associated to a crystalline structure: the real lattice and the reciprocal lattice. A diffraction pattern (TEM or XRay) is a map of the reciprocal lattice of the crystal. An image (TEM) is a map of the real lattice. lattice
Methods of investigation of nanomaterials: TEM
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Methods of investigation of nanomaterials: Conventional TEM

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Conventional Transmission Electron Microscopy

The condenser lens illuminates a part of the sample in either parallel of focused mode The objective lens gives the diffraction diagram close to its focal plane (f = 1 to 3 mm). It governs the resolution (typically 0.1 nm). The thickness of samples is a few 100 nm for the 300 keV TEM and up to 1 m for the GeV TEM. The diffraction diagram or the intermediate image can be observed on the screen using the projective lens. Using the bright field contrast (transmitted beam), it is possible to image dislocations, precipitates, stacking faults, grain boundaries, interfaces The dark field contrast (diffracted beam) allow characterizing the crystalline imperfections in the sample. Phase contrast mixed the transmitted and the diffracted beam. The obtained interferences evidence rows of atoms.
Stress induced by 10 nm de Ga0.8In0.2>As on GaAs(001): the extinction lines are used to calculate the radius of curvature and the stress field.
Methods of investigation of nanomaterials: TEM- CBED

Convergent
The
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Beam Electron Diffraction
electron beam is focused on the sample (diameter ~1 nm). Due to the large angle of aperture, the diffraction spots are transformed to disks with a fine structure inside (HOLZ lines: High Order Laue Zones) CBED allows to study:

the thickness of the sample, the interaction potential, the local variations of the inter-reticular distances, the symmetry group of the crystallites inside the sample
http://www.emal.engin.umich.edu/ courses/Bilello460/sld037.htm
GaNi on sapphire A. calculated, b. experimental
CBED diffraction of NiAl film on Si
http://www.crhea.cnrs.fr/CRHEA/gal-met.htm
Methods of investigation of nanomaterials: TEM: HRTEM

High-resolution
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transmission electron microscopy
Phase-contrast imaging: imaging the image is obtained, not from the amplitude, but from the interferences of the waves associated with the electrons after interactions with the atomic potentials in the material. The contrast of this image depends on the transfer function of the microscope, it is not a direct image of the sample. Thus, the interpretation is not straightforward and depends on the focus and settings of the microscope. It requires to perform image processing and simulations using Fourier analysis.
Cu cuboctahedron in the [110] orientation Top row: computer simulation, bottom row: experimental image.
J, Urban et al, Cryst. Res. Technol. 35 2000 67 731743
Methods of investigation of nanomaterials: TEM, analysis

Micro-analysis

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Analysis on thin samples allows analyzing a small volume of material. This volume is about 10-3 m3. Energy-dispersive X-ray spectroscopy (EDX) and Electron energy loss spectroscopy (EELS) are the two principal and complementary techniques.
Energy-dispersive
X-ray spectroscopy
Due to the interactions with the electrons, excited inner electrons going to their initial states emit X-Rays characteristic of the species present in the material.
Electron
energy loss spectroscopy
When an incident electron ionizes an atom, its kinetic energy decrease is equal to the sum of the ionization energy and kinetic energy transferred to the excited electron.
EELS spectrum of two elements A and B: two energy losses EA et EB. SA et SB correspond to the area under the peaks after subtracting the background. (Encyclopedia universalis 2007)
Methods of investigation of nanomaterials: X Ray Diffraction
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Methods of investigation of nanomaterials: X Ray Diffraction

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X-Ray diffraction
configurations are routinely used to study the nanomaterials
the conventional -2 configuration, the fixed low angle conditions or Grazing Incidence X-Ray Diffraction.
Two

Various

characteristics of the nanomaterials can be deduced from X-Ray diffraction analysis:
Inter-reticular distances dhkl, Texture: preferential orientation of the grains, Grain size, Residual stress.
X-ray
microdiffraction
X-rays focused to a spot size of one micron or less. X-ray microdiffraction can measure local variations in stress, orientation, and plastic deformation between grains and within individual grains..
X-ray microdiffraction facility at the Advanced Light Source (ALS), Lawrence Berkeley National Laboratory (LBNL)
Methods of investigation of nanomaterials: XRD - -2

The

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Bragg-Brentano configuration
It is the conventional -2 configuration. While the sample turns by , the detector turns by 2. Only the planes parallels to the surface are on Braggs position and participate to the diffraction.
Bragg-Brentano spectra of TiO2 nanorods R. Comparelli, thesis 2004, UNIVERSITA DEGLI STUDI DI BARI
Methods of investigation of nanomaterials: XRD - GIXRD

The

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fixed angle configuration
The angle between the surface and the incident beam is fixed. Diffracted intensity is obtained for the planes which obey the Braggs relation. These planes make an angle (-) with the surface. For thin deposited layers or thin modified surfaces, the angle is very low (~1) and it is called the Grazing Incidence X-Ray Diffraction (GIXRD). When the angle is smaller than the critical angle (~0.1), an evanescent wave propagates parallel to the surface and gives information on the lateral order on this surface.

GIXRD
-2
GIXRD of TiN nanograins A.R. Akbari, Thesis, Poitiers, 2007
The differences are due to the texturing of the material.
Methods of investigation of nanomaterials: XRD - Texture

The
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texture measurement
Deposited materials are often textured. This arises to minimize the total energy of the material. The degree of preferred orientation of coatings can be quantitatively described using the texture coefficient Tc. where I(hkl) is the intensity of the reflection from the (hkl) plane, I0(hkl) is the intensity from the same plane in a standard reference sample, and n is the number of reflections considered. In perfect randomly oriented crystals, Tc=1 for all {hkl} planes.
Tc =
I ( hkl ) I 0 ( hkl ) 1 n (I (hkl ) I 0(hkl ) ) n 1
Since texture deals with the planes parallel to the surface, it needs to use the -2 configuration.
Texturing of TiN deposited films as a function of the bias voltage and the thickness G. Abadias et al, JOURNAL OF APPLIED PHYSICS 99, 113519, 2006
For low thickness, TiN films shows a 002 preferred orientation.
Methods of investigation of nanomaterials: XRD - Grain size

XRD
It
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diffraction peak width
is affected by the small domain sizes in nanocrystalline solids.
The
broadening or full-width of the diffraction line is measured at half maximum intensity (FWHM). alternative measurement is the integral breadth: the area under the peak divide by the peak height.
An
The experimental obtained broadening is a convolution of :

the size effect G, the microstrain broadening MS (strain which varies from grain to grain or within a grain due to the local environment (vacancies, dislocations, stacking faults) while the macrostrain (uniform strain) is due to an external load). Grain Macrostrain produces peak shifts and microstrain produces peak broadening. the instrumental broadening I, due to non-monochromatic radiation, slit sizes and an imperfect focus.
wilkinson class notes, web.chemistry.gatech.edu

XRD
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diffraction peak broadening
A simplified method for deconvolution of is based on the assumptions that the instrumental and the intrinsic profiles can be approximated by a Cauchy or Lorentzian (C) or Gaussian (G) function.
CC (Cauchy approach, Lorentzian) GG (Gaussian approach) CG (Cauchy-Gauss approach)
t = Instrument al + Grain + Microstrai n

2 2 2 2 t = Instrument al + Grain + Microstrai n
2
Instrumental Grain + Microstrain =1 t t

0,35
-5 2
y=0.20891-0.00229x+3.50529*10 x -2.77367*10 x +1,2481*10 x 2 R =0,99201
-7 3
-9 4
Integral Peak Width ()
Correction
from the instrumental broadening
0,30 0,25 0,20 0,15 0,10
Experimental Best fit
Made using a calibration sample under identical conditions for the X-ray apparatus. A powder of LaB6 is currently used, as its XRD spectrum exhibits numerous peaks.
20
40
60
80
100 120 140
2 ()

Grain
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size estimation
Conventional
Williamson-Hall analysis
K
the size broadening varies as G = where L is the grain size, the XL cos ray wavelength, the diffraction angle and K~ 0.9. the microstrain is expressed as MS = 4 tan where is the microstrain.
It gives the sample broadening (CC approach) :
Sample =Grain + MStrain = total - Instrumental.

Sample cos = K + 4 sin L

Grain
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size estimation
Williamson-Hall analysis Sample cos =
Conventional
K + 4 sin L
Neglecting the microstrain leads to the well-known Scherrers equation:
Grain =
A linear plot against sin for the available allows to extract:

K L cos
The grain size. The microstrain.
cos /
sin / cos / versus sin / for various SnO2 polycrystals C. O. Paiva-Santos et al, Materials Structure, vol. 6, number 2, (1999)
Grain size of TiN nanocrystals A.R. Akbari, Thesis, Poitiers, 2007
Methods of investigation of nanomaterials: XRD - Residual stress

Residual
A It
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stress measurement
usual method in measuring residual stresses with XRD is the so called Sin2 method.
consists in measuring the variations of inter-reticular distance of {hkl} planes at diffraction peak position (2hkl) as a function of the two Euler angles and . strain measured in a direction e is given by = ln(d /d0) = ln(sin0/ sin) where
d (d0) is the (unstrained) inter-reticular distance,

The
(0) is the angular position of the diffraction peaks.
Using linear theory of elasticity, it gives the general sin2 equation:

= S2 ( sin2 + sin2) + S1 (11 + 22)

= 11 cos2 + 22 sin2 + 12 sin2 is the main
stress in the direction.

= 13 cos + 23 sin is the shear stress in the

direction. S1 and S2 are radiocrystallographic elastic constant which can be expressed as a function of the Young modulus E and the Poisson ratio . S2=(1-)/E and S1=-/E

Residual
When
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stress measurement
shear stresses are negligible
The biaxal shear stress = O.

and consequently ln(1/ sin) depend linearly upon sin2. ln(1/ sin) = S2 ( sin2) + S1 (11 + 22) ln (sin0)
When
the in-plane stresses are isotropic
= 11 = 22 = 12 = .
ln(1/ sin) = S2 ( sin2) + 2S1 ln (sin0)
The
sin2 plot
Plotting ln(1/ sin) versus sin2 gives a straight line. Its slope is proportional to . The intercepts permits to determine the stress-free lattice parameter a0.
Sin2 plot for a 150 nm platinum film Badawi et al, J. Appl. Cryst. (2003). 36, 869879


Residual
The

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stress measurement for textured materials
classical Sin2 method cannot be used for textured coatings.

absence of some reflections and thus limited range of angles, nonlinear behavior.
Typical sin2 curve for a textured sample showing the non-linear behaviour
The
crystallite group method (CGM)

A method developed for stress evaluation in textured materials and coatings. In CGM, also known as the ideal direction method, all crystallites with the same orientation are treated as being one crystal. After determining the strains for a selected group, the stress state can be evaluated using single crystal elastic data and respective formulas developed for a given lattice and crystallographic planes.

Residual
The
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stress measurement for textured materials
crystallite group method (CGM) applied to a fcc structure

For FCC crystalline structure with [111] and [200] preferred orientation, the CGM method gives the following equations for biaxial stress:
2 S ln d = 2S12 + J + 44 sin 2 + ln d 0 2 3
[111] [200]
4.32 4.3 Lattice parameter 4.28 4.26 4.24 4.22 4.2 4.18 0 0.2
ln d = 2S12 + (S11 S12 ) sin 2 + ln d 0
J = S11 S12 S44 / 2
TiN- 5 at. % Ni RT
TiN (111) TiN (200)
0.4
0.6
0.8
CGM method applied to a TiN-Ni nanocomposite textured materials A.R. Akbari, Thesis, Poitiers
sin2
Methods of investigation of nanomaterials: Atomic Force Microscopy
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High Resolution Transmission Electron Microscopy X Ray Diffraction Atomic Force Microscopy Nanohardness
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From the lecture of C. TROMAS, Universit Universit de Poitiers
Historical

17e Century: First optical microscope. 1923: De Broglie associates wave and particle. 1927: The tunneling effect. 1931: Development of a transmission electron microscope (Ruska and Knoll). 1938: Scanning electron microscope (Von Ardenne). 1981: Gerd Binnig et Heinrich Rohrer built the Scanning Tunneling Microscope (STM).
Gerd Binnig
Heinrich Rohrer

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General scheme
a cantilever with a sharp tip, fine scanning and motion using piezos, Feedback loops.
Some types of scanning probe microscope

STM: STM Scanning Tunneling Microscope (Tunnel effect) AFM: AFM Atomic Force Microscope (Van der Waals
forces, capillary forces, chemical bonding, electrostatic forces)
20 m
MFM: MFM Magnetic Force Microscope (Magnetic force prvails)
X, Y Z
Cantilever Interaction
Piezo scan
Computer
Detector Sample

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Interaction between two atoms or molecules

It is given by the Lennard-Jones potential.
U (r ) =
r12 r 6
F(r ) =
U ' ' = 13 + 7 r r r
Potentiel de Lennard Jones U(r)
U (r ) =
r12 r 6
Distance r
The first term corresponds to short range repulsive force (Coulomb force between electrons when the orbitals starts to overlap. The second term represents a long range attractive force between the dipolar moments of the atoms or molecules. It is the Van der Waals force:

Keesom interaction: between two permanent dipoles. Debye interaction: between a permanent and an induced dipoles. London interaction: between two induced dipoles.

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Interaction between the tip and the surface

It requires to sum interactions between all atoms from the tip and the sample. The integral potential for the the two types of forces are:

Van der Waals force W=-AR/6D where R is the tip radius, D the distance between the tip and the surface and A the Hammeker constant. Coulomb force W=-C/D7 where C is a constant.
C AR W (D) = 7 6D D
R
short range interactions
The capillary force should be also taken into account.

long range interactions

Scheme
The
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and modes of an AFM

It uses the repulsive part of the interaction force. The feedback loop is used to keep a constant force between the tip and the surface during scanning. It means the cantilever has a constant deflection.
primary modes of operation are the static mode and dynamic modes.
Static mode
Dynamic mode
The cantilever is forced to oscillate at its resonance frequency. The force between the tip and the surface change the amplitude, the phase and the frequency of the oscillations. These changes are used to produce an electronic image. In tapping mode, the cantilever motion is such that it comes in contact with the sample at the end of each period. No friction force and the capillarity force can be ignored (10 min to register an image). For MFM, the tip is magnetic. It first scans the surface in tapping mode (close to the surface) so that the main part of the force is non-magnetic. Thus, the second scan is made at a constant but larger distance from the surface so that the main part of the force is magnetic.
Piezoelectric ceramic
Photodiode
Laser Cantilever oscillations Tip Exciting Piezo
Tip
Sample
Scanning piezo

Example
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of a phase contrast
sin ( ) = 0 A ( 0 ) A ( ) + kA 0 A ( ) QE ps
Topographic image
Phase image
200 nm
Lignin on cellulose J. Tamayo, R. Garca, Instituto de Microelectrnica de Madrid, CSIC

Nano
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engineering
AFM or STM can be used to individually move atoms and to produce nanostructures.
The tip can be transformed to become functional. Nanolithography and measurement of forces between individual molecules.
Quantum corral: 48 Fe atoms moved by STM at low temperature. The radius is 0.713 nm M.F. Crommie, C.P. Lutz, D.M. Eigler. Science 262, 218-220 (1993).

Nano
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engineering: Nanolithography on silicon (AFM)

A
250 nm
C 1 m
R. Garca, M. Calleja, H. Rohrer, J. Appl. Phys. 86, 1898, (1999)
1 nm
20 nm
Period of the array: 40 nm
Methods of investigation of nanomaterials: Nanohardness
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High Resolution Transmission Electron Microscopy X Ray Diffraction Atomic Force Microscopy Nanohardness

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The nanoindentation technique routinely gives two mechanical properties:

the hardness the Young's modulus
As the indenter penetrates into the sample, both elastic and plastic deformation occurs. The material surface profile changes which results in the formation of a hardness impression conforming to the indenter shape. During indenter withdrawal, only the elastic portion of the deformation is recovered and the plastic indent remains.
Then, the hardness and Young's modulus can be determined by solving the elastic contact problem. The unloading data are treated assuming that the displacement recovered is largely elastic. The contact area and the mechanical properties are determined from the data of one complete cycle of loading and unloading. The most frequently used model is the Oliver-Pharr method.

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The nanoindentation cycle
hc=h- hs is the contact depth and defined as the depth of the indenter in contact with the sample under load. h is the total indentation depth, hs is the specimen surface displacement, hf is the final displacement after complete unloading, hmax represents the displacement at the peak load Pmax. S is the initial unloading contact stiffness obtained from upper portion of the unloading curve: S=dP/dh.


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Hardness and Stiffness
Nanoindentation hardness H is defined as the indentation load divided by the projected contact area, A, of the indentation.
H=
Pmax A
S= 2
The contact stiffness is
Er A
where is a constant that depends on indenter geometry, =1.034 for a Berkovich indenter tip, Er is the reduced elastic modulus, which includes the effects of non-rigid indenters on 2 the load-displacement behaviour, via the equation: 1 (1 2 ) (1 i )
Er
Ei
where E and are respectively the Young's modulus and Poisson's ratio of the specimen and Ei and i the corresponding quantities of the indenter. For a diamond indenter, Ei=1141 GPa and i = 0.07.

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Stiffness
Oliver and Pharr showed that unloading curve is usually not linear but is better described by a power law: m
P = B(h h f )
where B and m are empirically determined fitting parameters.
dP = Bm(h max h f ) m 1 Unloading (contact) stiffness S is therefore S = dh h = h max
Contact depth hc = hmax

Pmax S
where is a constant that depends on the indenter geometry, =0.75 for the Berkovich indenter tip.
Since the load frame deforms together with the sample and the indenter, the compliance of both the load frame and the specimen has to be considered. Deconvolution required a calibration procedure.

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Stiffness
Compared to hardness measurements, the elastic modulus obtained from nanoindentation of thin films is more strongly affected by the substrate. This is because the elastic field under the indenter is not confined to the film itself; it extends into the substrate to a quite long range, especially when the film thickness t is small.

As a result, the substrate stiffness is observed to influence the measured contact stiffness at small indentation depths relative to the film thickness, i.e. at h/t<0.1. In such cases, the modified Kings analysis can be used to estimate the film modulus.
( t h ) 2 ( t h ) ( 1 1 (1 i2 ) (1 2 ) s) 1 e a + e a = + Er Ei E Es
The effective film thickness is equal to t-h where h is the total indenter displacement.
Study of the nanocomposite TiN-Ni: Objective
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What is at nanoscale in nanomaterials? The physical properties of nanomaterials The mechanical properties of nanomaterials Modeling: the backbone of nanotechnology research Elaboration of nanomaterials Classification of nanomaterials The mechanical properties of nanomaterials


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What is the important property for wear resistant coatings? Hardness or Toughness?
Superhard
100
Hard and tough
Toughness (MPam1/2)
80 60 40 20 0 0 500 1000 1500 2000 2500 3000
pe rf or m
an
High performance: High hardness Improved toughness Question: How to improve materials strength/hardness and in the same time their toughness?
ig h
Strength (MPa)
ce
222/252
Titanium Nitride (TiN) Coatings
CVD : 1970 High Td (Ceramic substrates) PVD : 1985 Td 550C (Metallic substrates)
Microelectronic
Applications
Properties High hardness: 20-23 GPa Tribology & wear: High wear resistance Cutting tools: Chemical inertness Life increase up to 4-20 times Stability & Corrosion resistance Forming tools: Extrusion dies, Plastic molding Thermal conductivity Optical Tissue compatibility Medical & functional Golden color Diffusion barrier in integrated circuits TOxid 600C Decorative
Decorative
Plastic molding
Punching tools
Cutting tools
223/252
Recent design concepts

Nanostructured coatings Higher hardness
5-10 nm
Substrate
Substrate
TiN
65 55
TiN/VN
60 Hardness (GPa)
TiN/NbN
Hardness (GPa)
50 40 30 20 10
HTiN
Vepek et al. (PA-CVD) Vaz et al. (Rf-RMS)
45 35 25 15 5 0 5 10 15 20 25 30
HTiN
Multilayer period (nm)

U. Helmersson et al., JAP, 62 (1987) 481. M. Shinn et al., J. Mater. Res. 7 (1992) 901.
5 10 15 20 Si content (at. %)
25
S. Vepek et al., Thin Solid Films, 268 (1995) 64. F. Vaz et al., Surf. Coat. Technol. 133-4 (2000) 307.
10 nm
TiN VN
TiN/AlN
nc-TiN/a-Si3N4
Si3N4
1-2 nm
Nanomultilayers Superlattices (1D)
Nanocomposite coatings (3D)
224/252
Problems
Nanocrystalline materials have extremely limited ductility and toughness. Blocking grain boundaries decreases even more material ductility.
Eloangation to failure (%) Elongation to failure (%)
Strength/Hardness
70 60 50 40 30 20 10 0
10
100
1000
10000 100000
Elongation Failure, %
Conventional grain Nanomaterials UFC materials size materials
80
Cu Ag Al
Grain Size (nm)
Grain Size, nm
Koch C.C. MRS Bulletin 24(2), (1999) 5454-58.
A possible solution
Deposition TiN-Ni nanocomposite: embedding TiN in ductile Ni. Controlling hardness and toughness by adjusting the soft metallic Ni phase thickness, Ni having no chemical affinity with N.
TiN Ni
Study of the nanocomposite TiN-Ni: Elaboration
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226/252
Reactive Dual Ion Beam Sputtering (RDIBS)

A primary ion beam to sputter the composite target (TiN + Ni), A secondary reactive ion beam (Ar + N2) to assist the deposit. Operating pressure: 3.3 10-2 Pa. Rotative substrate holder.
Primary gun Target
General conditions
Ar Beam: 1.2 keV, 80 mA RT, 200, 300 and 400 Assistance : Ar/N2: 50 eV, 40 mA 54 2.7 0.5
Sputtering Substrate temperature, Ts (C) Assistance or Bias Mean free path (cm) Deposition rate (nm/min) Thickness (m)
Assistance gun
Sample holder
227/252
Substrates
304L SS or Ti6Al4V (technological applications) which have low wear resistance. Duplex treatment: Plasma nitrided 304L SS & Ti6Al4V, M2 High speed steel. Si (001) for easier structural characterizations
Characterization Properties
Chemical composition (TiN stoichiometry, Ni content) Chemical state (detecting Ni bonds) Phase composition Grain size Texture Residual stress Hardness and Elastic modulus Toughness Adhesion Wear resistance
Techniques
RBS XPS XRD, SAD XRD, HRTEM XRD CGM (Sin2 ) Nanoindentation High load indentation, Scratch test Scratch test Pin on disc, 3D profilometry
Mechanical
Structural
Study of the nanocomposite TiN-Ni: Structure

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229/252
Chemical composition by RBS

Main elements: Ti + N + Ni > 97 at.% Ar: ~2 at.%, Mo: 0.8 at.% ,Ta: 0.02 at.% O: trace level

1.2
RDIBS
1.0
N/Ti
0.8 0.6 0.4 0.2 0.0 0

Ts=RT Ts=200C Ts=300C Ts=400C
+
Ni (at. %)
10
15
20
25
0.67<x<~0.75 -Ti2N + -TiN0.75
~0.75<x<~1.2 Single phase -TiNx
Chemical composition by RBS

N/Ti ~ constant and independent of Ni content TiN is understoichiometric: N/Ti~0.85

230/252
Phase composition by XRD

TiN is the only crystalline phase (NaCl type structure) No peak from Ni or Ni compounds.
e=0.5 m
Effects of Ni addition
Changes in peak intensity: Texture evolution to (200). Peak broadening: TiN grain size reduction Peak shifting: Coatings contain residual stresses
231/252
Phase composition by TEM

The only crystalline phase: TiN
Cross sectional sample TiN-11 at.% Ni, Ts=300C
Plan view TiN-35 at.% Ni, Ts=RT

232/252
Grain size by XRD

Grain size by TEM

Integral breadth : TiN (200) XRD reflection Correction for instrumental peak broadening
For TiN-11 at.% Ni deposited at Ts=300C.
using C-G method grain size (Cauchy) & microstrain (Gaussian part)
Deconvolution of microstrain and size

HRTEM : 5-8 nm while for XRD: ~6 nm The interplanar distance corresponds to TiN.
The size reduces with the addition of Ni

(quite independent of temperature).
14 RDIBS 12 10 8 6 4 2
A
Moirs fringes
TiN (200)
Grain Size (nm)
TiN (200)
d(200)=0.21 nm
10
15
20
25
5 nm
Ni (at .%)
Grain A
233/252
Composition by Electron Energy Loss Spectroscopy (EELS)

Ti
elemental map with L3 and L2 edges
Ni
elemental map with M2,3 edge
Ni segregates during
film growth
vacuu m vacuum
Growth interruption
TiN-Ni
Renucleation of TiN
TiN grain size
TiN TiN-Ni
reduction
234/252
Ni coverage and nanostructure

14 RDIBS 12
2.0 1.8 RDIBS 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0
0 5 10 15 20 25
Grain Size (nm)
10 8 6 4 2
Ni Coverage (ML)
Ts=RT Ts=200C Ts=300C Ts=400C 0 5 10 15 20 25
Ni (at .%)
Ni (at. %)
The nanocomposite structure of nc-TiN/a-Ni is attained. TiN Grain size: dTiN= f(C) 12 to 4 nm : decreases with Ni Ni coverage: tNi = f(CNi) 0 to 2 ML : increases with Ni
15
20
Ni
Study of the nanocomposite TiN-Ni: Mechanical properties

235/252

Study of the nanocomposite TiN-Ni: Mechanical properties: STRESS

236/252
Residual stress using the Crystallite Group Method (CGM)

Measurements: SIEFERT 4 circle XRD equipments CGM is adapted to textured materials a selected grain population with the same texture considered as a single crystal.
(111) Oriented grain population
2 S ln a , = 2 S12 + J + 44 sin 2 + ln a0 3 2
J = S11 S12 S44 / 2

Lna, ()
1.460 1.455 1.450 1.445 1.440 1.435
Ts=300C
TiN
(111) (200)
(200) Oriented grain population
ln a , = 2S12 + ( S11 S12 ) sin + ln a0

2
Lnabulk
The elastic constants of TiN were used to deduced the stress.
1.430
0.0
0.2
0.4
sin2
0.6
0.8
1.0
Study of the nanocomposite TiN-Ni: Mechanical properties: STRESS

Compressive Residual Stress (GPa)
237/252
Residual stress as a function of the Ni content

Origin of residual stress: crystal defects (compressive) + grain/phase boundary (tensile). The stress reduction corresponds to the development of the TiN/Ni interface. interface
9 Intrinsic Stresses 8 7 6 5 4 3 Substrate: Si 0 5 10 15 20 25

measured Polynomial Fit
Ts=300C

4.29 4.28 4.27 4.26 4.25 22.5
Ni (at. %)
4.30 4.28 4.26
(200)p (311)
RDIBS
Ts=300C (200)p (311) abulk (220) (111)
ahkl ()
Ni (at.%)
4.24 4.22 4.20 4.18 4.16 0 5
Stress Free
(220) (111) (200)n (220)n
ahkl ()
4.24 4.23 4.22 4.21 4.20 4.19 4.18 4 5 6
Compressive Stress (GPa)
10
Experimental evolution of the lattice parameter with the stress, as Ni is added
(220)n (200)n
Theoretical evolution of the lattice parameter with the stress.
Compressive Residual stress (GPa)

238/252
The mechanical properties depend on the structural parameters

Ni
TiN grain
Nanocomposite nc-TiN/a-Ni
nanocrystalline TiN0.85 with grain size dNi in the range 4-12 nm parameter dNi surrounded by amorphous like Ni with a thickness TNi about 1-2 monolayers.
The mechanical properties

Hardness, Toughness, Wear resistance. They depends on the two parameters dNi and TNi that characterize the microstructure of the nanocomposite
Study of the nanocomposite TiN-Ni: Mechanical properties: Hardness

239/252
Hardness of the nanocomposite ncTiN-aNi

Measurement using a CSEM nanoindentation tester. Indentation depth < 1/10 of the film thickness. 60 Indentation load: 1.5 mN.
55 50 45 40 35 30 25 20 15 0 5 10 15
RDIBS
Hardness (GPa)
T s =RT T s =200C T s =300C T s =400C
Ni (at.%)
20
25

A maximum of Hardness Hmax ~45 GPa at 6-7 at.% Ni. An enhancement of 30-40 % compare to TiN, depending on the deposition temperature. Hardness always larger than ~ 20 GPa, up to 20 at.% Ni.

240/252
Effects of TiN grain size and Ni coverage on hardness

55
Hmax at TiN crystallite size 7-9 nm

RDIBS Ts=RT Ts=300C Ts=400C Ts=200C
Hmax at roughly Ni coverage of 1 ML

55 50 RDIBS Ts=RT Ts=200C Ts=300C Ts=400C
Hardness (GPa)
Hardness (GPa)
50 45 40 35 30 25 20 15 3 4 5 6 7 8
45 40 35 30 25 20
9 10 11 12 13 14 15
15
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
TiN Grain Size (nm)

Ni coverage (ML)
Hardness enhancement is:

due to the blocking of TiN grain boundaries by Ni. similar as nc-TiN/a-ceramic coatings.
S. Vepek et al., Thin Solid Films, 268 (1995) 64, F. Vaz et al., Surf. Coat. Technol. 133-4 (2000) 307.

241/252
Is the hardness enhancement due to the residual stress?

Comparison of the stress and the Hardness evolutions: The hardness starts to
increase while the stress always decreases.
50
Hardness (GPa)
45 40 35
8 7 6
30 25 20 15
0 5 4 3 25
Ni (at. %)
10
15
20
Hardness enhancement is due to the development of the nanocomposite structure. not due to the residual stress or ion bombardment effects.
Compressive Residual Stress (GPa)
Study of the nanocomposite TiN-Ni: Mechanical properties: Toughness

242/252
Toughness
Using High load indentation Microindentation with a Vickers indenter. Scratch test CESM Revetest Rockwell C indenter r=0.2 mm (from LSGS Nancy)
TiN
TiN-15 at.%
TiN-22.5 at.% Ni

Decreased crack density Circular cracking
Increased toughness

243/252
Toughness, Scratch test

Cracking Film toughness Spalling and buckling Film/substrate adhesion 0N 40 N
RDIBS TiN on M2 HSS
RDIBS TiN-22.5 at.% Ni on M2 HSS
Multipass scratch tracks after 20 passes under 7N load for TiN and TiN-Ni coatings deposited at 300C on M2 HSS.

244/252
Toughness, Scratch test: Critical loads : RDIBS coatings on M2 HSS

Ni at.%
0 5.5 11 18.4 22.5
LC1: First cracking

12.8 20 26 32 Toughness increase 8.3
LC2:Coating spallation LC3: Transverse spallation LC4: Exposed surface

37 30 35 35 Adhesion increase 20 23 Not observed Not observed Not observed Not observed 27 Not observed Not observed Not observed Not observed
K IC P a
Load Crack length
Toughness enhancement: at least 4 times

First cracking
The enhanced film toughness is the result of the coverage by the Ni amorphous layers.
0 LC1 LC2
(N) LC3
40
Study of the nanocomposite TiN-Ni: Mechanical properties: Wear resistance

245/252
Wear resistance

SEM: Image of wear track, wear and cracking details f/N curves: wear life (the number of revolutions before collapse) 3D profilometry: wear track depths and removed material volume
Net removed material volume NRV=Vr-Vp=(Sr-Sp)L
1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0
Friction Coefficient
RDIBS TiN TiN 15 at.% Ni
Ts=400C
Coating Life (Breakthrough)
200
400
600
800 1000 1200 1400
Number Loading of cycles

246/252
Wear tracks: RDIBS coatings on 304SS at 300C

Wear resistance starts to decrease as the coating becomes harder. As the thickness of Ni around the grains increases, the wear resistance is improved.
2N- 1500 loading cycles

Hardness (GPa)
50 45 40 35 30 25 20 15 0 5 10 15 20 25
2N- 5000 loading cycles 2 1 3 4
Ni (at. %)

247/252
Wear life: RDIBS coatings on 304SS and M2SS at 300C

T s=300C 304L SS 1N 2N 4N
Ts=300C M2 HSS
2N
4N
5000 4500 4000 3500 3000 2500 2000 1500 1000 500 0 0 4 10 11 Ni (at.%) 15 21.5
5000 4500 4000 3500 3000 2500 2000 1500 1000 500 0
(NLC) f
(NLC)f
5.5
13 Ni (at.%)
18.4
22.5
Wear life evolution with Ni content

2N and 4N: a first decreases for 4 at.% Ni and then an increase. 4N: TiN-21.5 at.% Ni exhibit > 7 times wear life enhancement than TiN

The highest wear life for coatings corresponds to higher toughness. High wear resistance is not related to high hardness.

248/252
Wear resistance: The net removed volume (coatings on 304SS at 300C)

50
Ni 22.5
Net Removed Volume (NRV) (1000 m3)
40 30 20 10 0
M2 Substrate
Load=2N 5000 Rev.
18.4
13
0 5 10
Ni (at. %)
15
20
25
5.5
Wear track analysis:

For CNi > 18 at.% : NRV 20 times < for TiN NRV at Hmax > than for TiN.

249/252
Wear and toughness enhancements mechanisms (coatings on 304SS at 300C)

4 1500 loading cycles 11 4N 4N 21.5 Ductile cracks Ni
1N
Brittle cracks
Straight edge cracks

Crack deflection
How Ni coverage in nanocomposite structure lead to higher toughness? Increase in cracking threshold load (more than 4 times) Decrease in density of large brittle cracks Replacement of brittle cracks with ductile cracks Macroscopic crack deflections Enhanced wear with Ni is due to the increase in film toughness

250/252
Wear resistance and the role of a duplex treatment

Duplex treatment is performed by nitriding, which enhanced the hardness of the substrate. 304L SS Nitrided 304L SS
4N - 1500 loading cycles
Nitriding
Du ple x
TiN-21.5 at.% Ni Continuous material removal
TiN-21.5 at.% Ni
Cracking
Coating
20kV
x200
100 m
12 35 BES
Reduced substrate plastic deformation

Decreased of pile up formation Decreased or no cracking Increased wear resistance

251/252
ncTiN-aNi
A nanocomposite

TiN Grain size ~ a few nm. Ni amorphous layer ~1-2 monolayers

Hardness (GPa)
60 55 50 45 40 35 30 25 20 15 0 5
RDIBS
With ~ the hardness of nc-TiN

H > 20 GPa. TiN
Ni (at.%)
10
15
20
25
And an improved toughness and wear resistance

~5 times enhanced
TiN
TiN-Ni
Conclusion
252/252
Nanomaterials
In 1959
Feynman (Caltech physics professor and Nobel Laureate (1965)), gave a lecture on the possibility of science research from the bottom up: There is plenty of room at the bottom.
The principles of physics, as far as I can see, do not speak against the possibility of maneuvering things atom by atom.
Nowadays: the science of small will have a HUGE impact in society

Nanotechnology, from a business perspective, will create better and entirely new materials, devices, and systems. It means new jobs due to new markets. It is projected that by the year 2010, the demand for nanotechnology products and services in the U.S. alone will hit the $1 trillion dollar amount. Nanotechnology applications can be summarized into several basic areas: Smart Materials, Sensors, Nanoscale Biostructures, Energy Capture and Storage, Magnets, Fabrication, Electronics.
Atom in japonese IBM

Nano Materials

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Nanomaterials

What is at nanoscale in nanomaterials?

Definitions Nanostructures Nanostructurized materials Nanocomposites

The physical properties of nanoclusters and nanomaterials

The mechanical properties of nanomaterials

Modeling: the backbone of nanotechnology research

Introduction Ab-initio methods Molecular dynamics Classical and kinetic Monte-Carlo

The bottom-up approach The top-down approach

Methods of investigation of nanomaterials

Study of the nanocomposite TiN-Ni

Objective Elaboration Structure Mechanical properties

What is at nanoscale in nanomaterials?: The nanoworld

What is at nanoscale in nanomaterials?

What is at nanoscale in nanomaterials?: The nanoworld

Material: Transformed matter to allow this matter to ensure a given

What is at nanoscale in nanomaterials?: The nanoworld

What is at nanoscale in nanomaterials ?

What is at nanoscale in nanomaterials?: Nanoclusters and nanograins

What is at nanoscale in nanomaterials?

What is at nanoscale in nanomaterials?: Nanoclusters and nanograins

Material: Material is functional matter.

Grains in bulk gold

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Self organization Specific properties

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Array of 25 Fe atoms dots

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Silver dendrite grown at 130 K on a platinum (111) surface

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From nanoclusters to nanomaterials

1D: nanotubes 2D: multilayers 3D: embedded clusters

SEM pictures of carbon nanotubes

diameters in the range 1-10 nm

Multilayers of Fe-Pt-C on Si with a period of a few nm.

HRTEM of embedded silver clusters in (a) C and (b) BN.

D. Babonneau, LMP, Poitiers

What is at nanoscale in nanomaterials?: Nanoclusters and nanograins

From nanoclusters to nanomaterials

3D: nanograins in thin films

10nm FePt thin film

Nanomaterials: at least one dimension at the nanometric range

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NEMS based devices

Faster switches and ultra sensitive sensors

Current applications of nanotechnology and time line for anticipated advances.

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Nanotube field-effect transistor

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Nanotubes for neural networks

B. Increased magnification of one nanotube pad

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The ruby color is probably due to embedded gold nanoparticles.

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Crystal structure and dense planes

A (788) vicinal surface, close to the (111) plane.

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