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Advanced nanomaterials
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“Introduction to Nanomaterial”
H.Hofmann
Powder Technology Laboratory
IMX
EPFL
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Contents
1 INTRODUCTION 6
3.1 INTRODUCTION 19
3.2 INORGANIC NANOTUBES 20
3.2.1 INTRODUCTION 20
3.2.2 GENERAL SYNTHETIC STRATEGIES 26
3.3 FUNCTIONAL MATERIALS BASED ON SELF-ASSEMBLY OF POLYMERIC SUPRAMOLECULES 28
3.4 MOLECULAR BIOMIMETICS: NANOTECHNOLOGY THROUGH BIOLOGY 32
3.4.1 SELECTION OF INORGANIC-BINDING PROTEINS THROUGH DISPLAY TECHNOLOGIES 34
3.4.2 CHEMICAL SPECIFICITY OF INORGANIC-BINDING POLYPEPTIDES 36
3.4.3 PHYSICAL SPECIFICITY OF PEPTIDE BINDING 37
3.4.4 PEPTIDE-MEDIATED NANOPARTICLE ASSEMBLY 38
3.5 REFERENCES 40
4 MECHANICAL PROPERTIES 41
4.1 INTRODUCTION 41
4.2 METALS 41
4.2.1 GRAIN SIZE EFFECTS IN PLASTICITY AND CREEP 42
4.2.2 METAL PLASTIC DEFORMATION: A COMPARISON BETWEEN CU AND NI NANOPHASE SAMPLES
49
4.2.3 HARDNESS 53
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6 THERMODYNAMIC 89
6.1 NANOTHERMODYNAMICS 89
6.1.1 HILL’S THEORY 90
6.1.2 TSALLIS’ GENERALIZATION OF ORDINARY BOLTZMANN-GIBBS THERMOSTATICS 96
6.1.3 THERMODYNAMICS OF METASTABLE PHASE NUCLEATION ON NANOSCALE 100
6.1.4 NANOTHERMODYNAMIC ANALYSES OF CVD DIAMOND NUCLEATION 112
6.2 THERMODYNAMICS OF MELTING AND FREEZING IN SMALL PARTICLES 117
6.2.1 THEORY – VANFLEET AND AL. MODEL 117
6.3 PHASE DIAGRAMS 128
6.3.1 GOVERNING EQUATIONS 128
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8 MAGNETISM 219
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9 APPLICATIONS 267
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1 INTRODUCTION
Nanomaterials are materials which are characterised by an ultra fine grain size
(< 50 nm) or by a dimensionality limited to 50 nm. Nanomaterials can be created with
various modulation dimensionalities as defined by Richard W. Siegel: zero (atomic
clusters, filaments and cluster assemblies), one (multilayers), two (ultrafine-grained
overlayers or buried layers), and three (nanophase materials consisting of equiaxed
nanometer sized grains) as shown in the above Figure 1-1.
i
Figure 1-1 : Definition of nanomaterials following Siegel
2. Multilayers (MD=1)
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Figure 1-2 : Classification schema for nanomaterials according to their chemical composition and the
dimensionality (shape)of the crystallites (structural elements) forming the nanomaterial. The boundary
regions of the first and second family of nanomaterials are indicated in black to emphasize the
different atomic arrangements in the crystallites and in the boundaries. The chemical composition of
the (black) boundary regions and the crystallites is identical in the first family. In the second family, the
(black) boundaries are the regions where two crystals of different chemical composition are joined
together causing a steep concentration gradient.
The latter three categories can be further grouped into four families as shown in
Figure 1-2.
• In the most simple case (first family in the Figure 1-2), all grains and interfacial
regions have the same chemical composition. Eg. Semicrystalline polymers
(consisting of stacked lamellae separated by non-crystalline region),
multilayers of thin film crystallites separated by an amorphous layer (a-
Si:N:H/nc-Si)iietc.
• In the third family includes all materials that have a different chemical
composition of its forming matter (including different interfaces) eg. Ceramic of
alumina with Ga in its interface.iii
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• The fourth family includes all nanomaterials formed by nanometer sized grains
(layers, rods or equiaxed crystallites) dispersed in a matrix of different
chemical composition. Precipitation hardened alloys typically belong to this
family. Eg. Nanometer sized Ni3Al precipitates dispersed in a nickel matrix-
generated by annealing a supersaturated Ni-Al solid solution- are an example
of such alloys. Most high-temperature materials used in modern jet engines
are based on precipitation-hardened Ni3Al/Ni alloys.
These materials have created a high interest in recent years by virtue of their
unusual mechanical, electrical, optical and magnetic properties. Some examples
are given below:
• Nanophase ceramics are of particular interest because they are more ductile
at elevated temperatures as compared to the coarse-grained ceramics.
• Nanosized metallic powders have been used for the production of gas tight
materials, dense parts and porous coatings. Cold welding properties combined
with the ductility make them suitable for metal-metal bonding especially in the
electronic industry.
• Single nanosized magnetic particles are mono-domains and one expects that
also in magnetic nanophase materials the grains correspond with domains,
while boundaries on the contrary to disordered walls. Very small particles have
special atomic structures with discrete electronic states, which give rise to
special properties in addition to the super-paramagnetism behaviour. Magnetic
nano-composites have been used for mechanical force transfer (ferrofluids),
for high density information storage and magnetic refrigeration.
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• Nanostructured metal-oxide thin films are receiving a growing attention for the
realisation of gas sensors (NOx, CO, CO2, CH4 and aromatic hydrocarbons)
with enhanced sensitivity and selectivity. Nanostructured metal-oxide (MnO2)
find application for rechargeable batteries for cars or consumer goods. Nano-
crystalline silicon films for highly transparent contacts in thin film solar cell and
nano-structured titanium oxide porous films for its high transmission and
significant surface area enhancement leading to strong absorption in dye
sensitized solar cells.
• Polymer based composites with a high content of inorganic particles leading to
a high dielectric constant are interesting materials for photonic band gap
structure produced by the LIGA.
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• First the size effect, in particular the quantum size effects where the normal
bulk electronic structure is replaced by a series of discrete electronic levels,
• and second the surface or interface induced effect, which is important because
of the enormously increased specific surface in particle systems.
While the size effect is mainly considered to describe physical properties, the
surface or interface induced effect, plays an eminent role for chemical processing, in
particular in connection with heterogeneous catalysis. Experimental evidence of the
quantum size effect in small particles has been provided by different methods, while
the surface induced effect could be evidenced by measurement of thermodynamic
properties like vapour pressure, specific heat, thermal conductivity and melting point
of small metallic particles. Both types of size effects have also been clearly separated
in the optical properties of metal cluster composites. Very small semiconductor (<10
nm), or metal particles in glass composites, and semiconductor/polymer composites
show interesting quantum effects and non-linear electrical and optical properties.
The numerous examples, which are not complete, by far, indicate that these
materials will most probably gain rapidly increasing importance in the near future. In
general, properties, production and characterisation methods and their inter-relations
are however not yet satisfactorily understood. Hence, efforts need to be made to
enable the directed tailoring of nanophase, nanoscopic and nanocomposite materials
needed for future technical and industrial applications.
Table 1-1 : Some typical properties of nano-structured materials and possibilities of future applications
Property Application
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Bulk
Single magnetic domain Magnetic recording
Small mean free path of electrons in a solid Special conductors
Size smaller than wavelength Light or heat absorption, Scattering
High & selective optical absorption of metal particles Colours, filters, solar absorbers,
photovoltaics, photographic
material, phototropic material
Grain size too small for stable dislocation High strength and hardness of
metallic materials
Surface/ Interface
Large specific surface area Catalysis, sensors
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Table 1-2 : Some examples of present and potential applications with significant technological
vi
impact:
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More specifically the following issues have to be considered for the future
development of nanomaterials:
In the following chapters we will review the various developments that have been
revolutionising the application of nanomaterials. We will attempt to correlate the
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improvements in the material properties that are achieved due to the fine
microstructures arising from the size of the grains and/or dimensionality.
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?
? ? ?
? ?
? ?
? ? ?
?
At the beginning of last century, increasing attention was focused on the physical
chemistry of colloidal suspensions. By referring to them as "the world of neglected
dimensions", Oswald was the first to realize that nanoscale particles should display
novel and interesting properties largely dependant on their size and shape. vii
However, it is only in the last two decades that significant interest has been devoted
to inorganic particles consisting of a few hundred or a few dozen atoms, called
clusters. This interest has been extended to a large variety of metals and
semiconductors and is due to the special properties exhibited by these nanometer-
sized particles, which differ greatly from those of the corresponding macrocrystalline
material.
Matter that is constituted of atoms and molecules as such, has been widely classified
and satisfactorily explained. However, an ensemble of atoms, or molecules forming
the so-called ‘Clusters’ are far from being properly understood. Elemental clusters
are held together by various forces depending on the nature of the constituting
atoms:
Inert gas clusters are weakly held together by van-der-waals interactions, eg. (He)n
Semiconductor clusters are held with strong directional covalent bonds, eg. (Si)n
Metallic clusters are fairly strongly held together by delocalised non-directional
bonding, eg. (Na)n
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No. Of Shells 1 2 3 4 5
No. of atoms M13 M55 M147 M309 M561
Percentage of 92% 76% 63% 52% 45%
atoms
viii
Figure 2-2 : Idealized representation of hexagonal close packed full-shell ‘magic number’ clusters.
Note that as the number of atoms increases, the percentage of surface atoms decreases.
100000 120
100
Surface atoms (%)
10000
Total no. of atoms
80
1000
60
100
40
10 20
1 0
0 10 20 30 0 5 10 15 20 25
Cluster size (nm) Size of cluster (nm)
(1) (2)
Figure 2-3 : (1) Total Number of atoms with size of the cluster. (2) Number of surface atoms for a
-3 -26
hypothetical model sphere of diameter 0.5 nm and density 1000 Kgm with a mass of 6.5 10 Kg
-29 3 -19 2
occupying a volume of about 6.5 x 10 m with a geometrical cross-section of 2 x 10 m (in terms of
-27
atomic mass the sphere is considered to have a mass of 40 amu, where 1 amu = 1.67 x 10 Kg).
ix
Calculated by (a) considering dense structures (Square), and (b) method suggested by Preining (dark
x
circle).
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increasing size of the cluster as shown in fig: . When an ensemble of atoms add up to
form a few nanometer sized clusters, they form what we call ‘nanoparticles’, since
only a few atoms forming clusters are called ‘molecular clusters’. Agglomeration of a
few atoms have been studied in great details by physicists working with molecular
beams. Today, the mystery related to larger ensemble of atoms (in other words
‘nanomaterial’) are getting clearer due to active research being carried over across
the world over the last decade or two.
Table 2-1 : Idealized representation of the variation of cross section, total mass, number of molecules
ix
and the effective surface atoms in clusters. Note (a) considering dense structures (Square), and (b)
x
method suggested by Preining (dark circle).
In the table, we see that the smaller particles contain only a few atoms, practically all
at the surface. As the particle size increases from 1-10 nm, cross-section increases
by a factor of 100 and the mass number of molecules by a factor of 1000. Meanwhile,
the proportion of molecules at the surface falls from 100% to just 25%. For particles
of 20nm size, a little more than 10% of the atoms are on the surface.
Of course this is an idealized hypothetical case. If particles are formed by macro
molecules (that are larger than the present example), number of molecules per
particle will decrease and their surface fraction increase. The electronic properties of
these ensemble of atoms or molecules will be the result of their mutual interactions
so that the overall chemical behaviour of the particles will be entirely different from
the individual atoms or molecules that they are constituted of. They will also be
different from their macroscopic bulk state of the substance in question under the
same conditions of temperature and pressure.
xi
Table 2-2 : Particle size, surface area and surface energy of CaCo3. (the surface energy of bulk
-2
CacO3 (calcite) is 0.23 Jm .)
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The idea of tailoring properly designed atoms into agglomerates has brought in new
fundamental work in the search for novel materials with uncharacteristic properties.
Among various types of nanomaterials, cluster assembled materials represent an
original class of nanostructured solids with specific structures and properties. In
terms of structure they could be classified in between amorphous and crystalline
materials. In fact, in such materials the short-range order is controlled by the grain
size and no long-range order exists due to the random stacking of nanograins
characteristic of cluster assembled materials. In terms of properties, they are
generally controlled by the intrinsic properties of the nanograins themselves and by
the interactions between adjacent grains. Cluster assembled films are formed by the
deposition of these clusters onto a solid substrate and are generally highly porous
with densities as low as about one half of the corresponding bulk materials densities
and both the characteristic nanostructured morphology and a possible memory effect
of the original free cluster structures are at the origin of their specific properties.xii
From recent developments in the cluster source technologies (thermal, laser
vaporisation and sputtering),xiii,xiv it is now possible to produce intense cluster beams
of any materials, even the most refractory or complex systems (bimetallic,xv oxides
and so on), for a wide range of size from a few atoms to a few thousands of atoms.
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3.1 Introduction
A major goal of material science is to produce hierarchical materials that are
ordered on all length scales, from the molecular (1–100 Å) via the nano (10–100 nm)
to the meso (1–100 mm) scale. In these materials, the larger-scale properties can be
controlled by choosing the appropriate molecular characteristics.
“Nanocomposites” are a special class of materials originating from suitable
combinations of two or more such nanoparticles or nanosized objects in some
suitable technique, resulting in materials having unique physical properties and wide
application potential in diverse areas that can be formed into a useful object which
can be subsequently used. Novel properties of nanocomposites can be derived from
the successful combination of the individual characteristics of parent constituents into
a single material. To exploit the full potential of the technological applications of the
nanomaterials, it is thus extremely important to endow them with good processability.
Nanocomposites are either prepared in a host matrix of inorganic materials (glass,
porous ceramics etc) or by using conventional polymers as one component of the
nanocomposites. The second type of nanocomposites which are a special class of
hybrid materials are termed “polymeric nanocomposites”. These materials are
intimate combinations (up to almost the molecular level) of one or more inorganic
materials (nanoparticles , eg.) with a polymer so that unique properties of the former
can be mixed with the existing qualities of the polymer to result in a totally new
material suitable for novel applications. In most of the cases such combinations
require blending or mixing of the components, taking the polymer in solution or in
melt form. xvi Resulting nanocomposites have found successful applications in
versatile fields viz. battery cathodes, xvii microelectronics, xviii nonlinear optics, xix
sensors,xx etc.
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3.2.1 Introduction
In 1991, Iijima observed some unusual structures of carbon under the transmission
electron microscope wherein the graphene sheets had rolled and folded onto
themselves to form hollow structures. Iijima called them nanotubes of carbon which
consisted of several concentric cylinders of grapheme sheets. Graphene sheets are
hexagonal networks of carbon and these layers get stacked one above the other in
the c-direction to form bulk graphite. Following the initial discovery, intense research
has been carried out on carbon nanotubes (CNTs). The nanotubes can be open-
ended or closed by caps containing five-membered rings. They can be multi-
(MWNTs) or singlewalled (SWNTs). We show a typical high-resolution electron
microscope (HREM) image of a multi-walled nanotube in Figure 3-1.
Figure 3-1 : A typical TEM image of a closed, multi-walled carbon nanotube. The separation
between the graphite layers is 0.34 nm. [C.N.R. Rao, M. Nath, Inorganic nanotubes, Dalton Trans.,
2003, p.p. 1-24]
Depending on the way the graphene sheets fold, nanotubes are classified as
armchair, zigzag or chiral as shown in Figure 3-2. The electrical conductivity of the
nanotubes depends on the nature of folding.
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Figure 3-2 : Schematic representation of the folding of a graphene sheet into (a) zigzag, (b)
armchair and (c) chiral nanotubes. [C.N.R. Rao, M. Nath, Inorganic nanotubes, Dalton Trans., 2003,
p.p. 1-24]
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Figure 3-3 : Comparison of the structures of (a) graphite and inorganic layered compounds such as
(b) NbS2/TaS2; (c) MoS2; (d) BN. In the layered dichalcogenides, the metal is in trigonal prismatic
(TaS2) or octahedral coordination (MoS2). [C.N.R. Rao, M. Nath, Inorganic nanotubes, Dalton Trans.,
2003, p.p. 1-24]
When viewed parallel to the c-axis, the layers show the presence of dangling bonds
due to the absence of an X or M atom at the edges. Such unsaturated bonds at the
edges of the layers also occur in graphite. The dichalcogenide layers are unstable
towards bending and have a high propensity to roll into curved structures. Folding in
the layered transition metal chalcogenides (LTMCs) was recognized as early as
1979, well before the discovery of the carbon nanotubes. Rag-like and tubular
structures of MoS2 were reported by Chianelli who studied their usefulness in
catalysis.
The folded sheets appear as crystalline needles in low magnification transmission
electron microscope (TEM) images, and were described as layers that fold onto
themselves (Figure 3-4).
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Figure 3-4 : Low-magnification TEM images of (a) highly folded MoS2 needles and (b) a rolled sheet
of MoS2 folded back on itself. [C.N.R. Rao, M. Nath, Inorganic nanotubes, Dalton Trans., 2003, p.p. 1-
24]
xxii
These structures indeed represent those of nanotubes. Tenne et al first
demonstrated that Mo and W dichalcogenides are capable of forming nanotubes
(Figure 3-5 a).
Figure 3-5 : TEM images of (a) a multi-walled nanotube of WS2 and (b) hollow particles (inorganic
fullerenes) of WS2. [C.N.R. Rao, M. Nath, Inorganic nanotubes, Dalton Trans., 2003, p.p. 1-24]
Closed fullerene-type structures (inorganic fullerenes) also formed along with the
nanotubes (Figure 3-5 b). The dichalcogenide structures contain concentrically
nested fullerene cylinders, with a less regular structure than in the carbon nanotubes.
Accordingly, MX2 nanotubes have varying wall thickness and contain some
amorphous material on the exterior of the tubes. Nearly defect-free MX2 nanotubes
are rigid as a consequence of their structure and do not permit plastic deformation.
The folding of a MS2 layer in the process of forming a nanotube is shown in the
schematic in Figure 3-6.
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Figure 3-6 : Schematic illustration of the bending of a MoS2 layer. [C.N.R. Rao, M. Nath, Inorganic
nanotubes, Dalton Trans., 2003, p.p. 1-24]
Considerable progress has been made in the synthesis of the nanotubes of Mo and
W dichalcogenides in the last few years (Table 3-1 and Table 3-2).
Table 3-1 : Synthetic strategies for various chalcogenide nanotubes [C.N.R. Rao, M. Nath,
Inorganic nanotubes, Dalton Trans., 2003, p.p. 1-24]
Table 3-2 : Synthetic strategies for various chalcogenide nanotubes [C.N.R. Rao, M. Nath,
Inorganic nanotubes, Dalton Trans., 2003, p.p. 1-24]
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There has been some speculation on the cause of folding and curvature in the
LTMCs. Stoichiometric LTMC chains and layers such as those of TiS2 possess an
inherent ability to bend and fold, as observed in intercalation reactions.
The existence of alternate coordination and therefore of stoichiometry in the LTMCs
may also cause folding. Lastly, a change in the stoichiometry within the material
would give rise to closed rings.
Transition metal chalcogenides possess a wide range of interesting physical
properties. They are widely used in catalysis and as lubricants. They have both
semiconducting and superconducting properties (see paragraph 7). With the
synthesis and characterization of the fullerenes and nanotubes of MoS2 and WS2, a
wide field of research has opened up enabling the successful synthesis of nanotubes
of other metal chalcogenides. It may be recalled that the dichalcogenides of many of
the Group 4 and 5 metals have layered structures suitable for forming nanotubes.
Curved structures are not only limited to carbon and the dichalcogenides of Mo and
W. Perhaps the most well-known example of a tube-like structure with diameters in
the nm range is formed by the asbestos mineral (chrysotil) whose fibrous
characteristics are determined by the tubular structure of the fused tetrahedral and
octahedral layers. The synthesis of mesoporous silica with well-defined pores in the
2–20 nm range was reported by Beck and Kresgexxiii. The synthetic strategy involved
the self-assembly of liquid crystalline templates. The pore size in zeolitic and other
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Several strategies have been employed for the synthesis of carbon nanotubes. They
are generally made by the arc evaporation of graphite or by the pyrolysis of
hydrocarbons such as acetylene or benzene over metal nanoparticles in a reducing
atmosphere. Pyrolysis of organometallic precursors provides a one-step synthetic
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Surfactant-assisted synthesis of CdSe and CdS nanotubes has been reported. Here
the metal oxide reacts with the sulfidizing/selenidizing agent in the presence of a
surfactant such as TritonX.
Sol–gel chemistry is widely used in the synthesis of metal oxide nanotubes, a good
example being that of silica and TiO2. Oxide gels in the presence of surfactants or
suitable templates form nanotubes. For example, by coating carbon nanotubes
(CNTs) with oxide gels and then burning off the carbon, one obtains nanotubes and
nanowires of a variety of metal oxides including ZrO2, SiO2 and MoO3. Sol–gel
synthesis of oxide nanotubes is also possible in the pores of alumina membranes. It
should be noted that MoS2 nanotubes are also prepared by the decomposition of a
precursor in the pores of an alumina membrane.
Boron nitride nanotubes have been obtained by striking an electric arc between HfB2
electrodes in a N2 atmosphere. BCN and BC nanotubes are obtained by arcing
between B/C electrodes in an appropriate atmosphere. A greater effort has gone into
the synthesis of BN nanotubes starting with different precursor molecules containing
B and N. Decomposition of borazine in the presence of transition metal nanoparticles
and the decomposition of the 1 : 2 melamine–boric acid addition compound yield BN
nanotubes. Reaction of boric acid or B2O3 with N2 or NH3 at high temperature in the
presence of activated carbon, carbon nanotubes or catalytic metal particles has been
employed to synthesize BN nanotubes.
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Figure 3-7 : Comb-shaped supramolecules and their hierarchical self-organization, showing primary
and secondary structures. Similar schemes can, in principle, be used both for flexible and rodlike
polymers. In the first case, simple hydrogen bonds can be sufficient, but in the latter case a synergistic
combination of bondings (recognition) is generally required to oppose macrophase separation
tendency. In (A through C), the self-organized structures allow enhanced processibility due to
plastization, and solid films can be obtained after the side chains are cleaved (D). Self-organization of
supramolecules obtained by connecting amphiphiles to one of the blocks of a diblock copolymer (E)
results in hierarchically structured materials. Functionalizable nanoporous materials (G) are obtained
by cleaving the side chains from a lamellae-within-cylinders structure (F). Disk-like objects (H) may be
prepared from the same structure by crosslinking slices within the cylinders, whereas nano rods (I)
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result from cleaving the side chains from a cylinder-within-lamellae structure. Without loss of
generality, (A) is shown as a flexible polymer, whereas (B) and (C) are shown as rodlike chains. [O.
Ikkala, G.T. Brinke, Functional Materials Based on Self-assembly of polymeric supramolecules,
Science, New Series, Vol. 295, No. 5564 (Mar. 29, 2002), pp. 2407-2409]
The simplest case is a flexible polymer having bonding sites along its backbone
(Figure 3-7 A). Therefore, the backbone is typically polar, and repulsive nonpolar side
groups can be connected by complementary bonds, leading to comb-shaped
supramolecules, which in turn self-organize. We have extensively used hydrogen
bonding or coordination to bond side chains to the polymer backbone. Antonietti et
al. xxv have used ionic interactions in polyelectrolyte-surfactant complexes to form
comb-shaped polyelectrolyte surfactant complexes. The resulting self-organized
multidomain structures may be aligned, using, for example, flow, in order to approach
monodomains. One can also tune the properties by tailoring the nature of the side
chains. For example, if the side chains are partly fluorinated, low surface energy
results, which allows for applications that lead to reduced friction. In another case,
the backbone consists of the double helix of DNA, and self-organization is achieved
by ionically bonding cationic liposomes or cationic surfactants to the anionic
phosphate sites. This allows for materials design beyond the traditional scope of
biochemical applications. For example, dyes can be intercalated into the helices,
suppressing their aggregation tendency and leading to promising properties as
templates for photonic applications. In such a structure, the polymer backbone may
contain two or even more kinds of binding sites where different additives can be
bonded (Figure 3-7 B). Side chains can also have two separate functions. For
example, in addition to providing a repulsive side chain required for self-organization,
the side chains may contain an acidic group that acts as a dopant for a conjugated
polymer such as polyaniline, which leads to electronic conductivity. To introduce
further degrees of freedom in tailoring the self-organized phases and their
processing, polyaniline may first be doped by a substance such as camphor
sulphonic acid and subsequently connected to hexyl resorcinol molecules using their
two hydrogen bonds (Figure 3-7 C). The alkyl chains of the hydrogen-bonded hexyl
resorcinol molecules act as plasticizers, leading to thermoplastic processibility of the
otherwise infusible polymer. They enforce self-organization where camphor sulfonic
acid-doped polyaniline chains are confined in nanoscale conducting cylinders,
leading to increased conductivity. The concept can be applied even to rodlike
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Figure 3-8 : In molecular biomimetics, inorganic-binding proteins could potentially be used as (i)
linkers for nanoparticle immobilization; (ii) functional molecules assembled on specific substrates; and
(iii) heterobifunctional linkers involving two (or more) binding proteins linking several nanoinorganic
units. (I1: inorganic-1,I2: Inorganic-2, P1 and P2: inorganic specific proteins, LP:linker protein, FP:
fusion protein). [Sarikaya, C. Tamerler, A.K.Y. Jen, K. Schulten F. Baneyx, Molecular biomimetics:
nanotechnology through biology, Nature Materials, vol 2, 2003, p.p. 577-585]
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There are several possible ways of obtaining polypeptide sequences with specific
affinity to inorganics. A number of proteins may fortuitously bind to inorganics,
although they are rarely tested for this purpose. Inorganic-binding peptides may be
designed using a theoretical molecular approach similar to that used for
pharmaceutical drugs. This is currently impractical because it is time consuming and
expensive. Another possibility would be to extract biomineralizing proteins from hard
tissues followed by their isolation, purification and cloning. Several such proteins
have been used as nucleators, growth modifiers, or enzymes in the synthesis of
certain inorganics. One of the major limitations of this approach is that a given hard
tissue usually contains many proteins, not just one, all differently active in
biomineralization and each distributed spatially and temporally in complex ways.
Furthermore, tissue-extracted proteins may only be used for the regeneration of the
inorganics that they are originally associated with, and would be of limited practical
use. The preferred route, therefore, is to use combinatorial biology techniques. Here,
a large random library of peptides with the same number of amino acids, but of
different sequences, is used to mine specific sequences that strongly bind to a
chosen inorganic surface.
Since their inception, well-established in vivo combinatorial biology protocols (for
example, phage display (PD) and cell-surface display (CSD)) have been used to
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identify biological ligands and to map the epitope (molecular recognition site) of
antibodies. Libraries have also been screened for various biological activities, such
as catalytic properties or altered affinity and specificity to target molecules in many
applications including the design of new drugs, enzymes, antibodies, DNA-binding
proteins and diagnostic agents. The power of display technologies relies on the fact
that an a priori knowledge of the desired amino acid sequence is not necessary, as it
can simply be selected and enriched if a large enough population of random
sequences is available. In vitro methods, such as ribosomal and messenger RNA
display technologies, have been developed for increased library size (1015) compared
to those of in vivo systems (107–10).
Combinatorial biology protocols can be followed in molecular biomimetics to select
polypeptide sequences that preferentially bind to the surfaces of inorganic
compounds chosen for their unique physical properties in nano- and biotechnology.
Libraries are generated by inserting randomized oligonucleotides within certain
genes encoded on phage genomes or on bacterial plasmids (step 1 in Figure 3-9).
Figure 3-9 : Phage display and cell-surface display. Principles of the protocols used for selecting
polypeptide sequences that have binding affinity to given inorganic substrates. [Sarikaya, C. Tamerler,
A.K.Y. Jen, K. Schulten F. Baneyx, Molecular biomimetics: nanotechnology through biology, Nature
Materials, vol 2, 2003, p.p. 577-585]
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Table 3-3 : Examples of polypeptide sequences exhibiting affinity for various inorganics.
[Sarikaya, C. Tamerler, A.K.Y. Jen, K. Schulten F. Baneyx, Molecular biomimetics: nanotechnology
through biology, Nature Materials, vol 2, 2003, p.p. 577-585]
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surfaces with various morphological features. On the other hand, because powders
are non-descriptive, the selected polypeptides may exhibit little or no homology and
‘solve’ the binding problem through different strategies. Binders selected for a given
size, morphology, crystallography or stereochemistry may share a higher degree of
homology. For example, a GEPI binding to a material of a certain size may also bind
to a smaller particle of the same material, but less strongly. Similarly, a GEPI binding
strongly to a specific crystallographic surface may bind with an altered affinity to
another surface of the same material. Finally, a GEPI strongly binding to a material of
composition A may bind less strongly to a material B with a different composition but
having similar structure (for example, perovskites). Therefore, if one seeks highly
specific binders, the physical and chemical characteristics of the material must be
known. An alternative approach is that, once a relatively large number of binders
have been identified by panning on powders, a subset specific for morphology, size
or surface could be identified on well-defined materials.
a) b) c)
f)
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d) e)
Figure 3-10 : Effect of GEPI on nanocrystal morphology. a–c, One of the two mutants (RP1) from a
library of goldbinding GEPIs were tested in the formation of flat gold particles, shown in a, similar to
those formed under acidic (b) or boiling (c) conditions. Particles formed in the presence of vector-
encoded alkaline phosphatase and neutral conditions do not result in morphological change of gold
particles (not shown). d-e, The atomic force microscope images show quantum (GaInAs) dots
assembled on GaAs substrate; d, through high-vacuum (molecular beam epitaxy) strain-induced self-
assembly, and e, through 7-repeat GBP1. f, Schematic illustration of e. PS: polystyrene substrate, GA:
glutaraldehyde, GBP: 7- repeat GBP1, and gold: 12-nm-diameter colloidal gold particles. [Sarikaya, C.
Tamerler, A.K.Y. Jen, K. Schulten F. Baneyx, Molecular biomimetics: nanotechnology through biology,
Nature Materials, vol 2, 2003, p.p. 577-585]
For example, quantum dots can be produced using vacuum techniques, such as
molecular beam epitaxy, shown in Figure 3-10 d for the GaInAs/GaAs system.
However, this can only be accomplished under stringent conditions of high
temperature, very low pressures and a toxic environment. A desirable alternative
would be not only to synthesize inorganic nanodots under mild conditions, but also to
immobilize/self-assemble them. Inorganic particles have been functionalized with
synthetic molecules, including thiols and citrates, and with biological molecules, such
as lipids, amino acids, polypeptides and ligand-functionalized DNA. Using the
recognition properties of the coupling agents, novel materials have been generated
and controlled growth has been achieved. These molecules, however, do not exhibit
specificity for a given material. For example, thiols couple gold as well as silver
nanoparticles in similar ways. Likewise, citrate ions cap noble metals indiscriminately.
A desirable next step would be to use GEPIs that specifically recognize inorganics for
nanoparticle assembly. An advantage of this approach is that GEPI can be
genetically or synthetically fused to other functional biomolecular units or ligands to
produce heterobifunctional (or multifunctional) molecular entities. Figure 3-10 e and f
shows the assembly of nanogold particles on GBP1-coated flat polystyrene surfaces,
which resembles the distribution of quantum dots obtained by high-vacuum
deposition techniques (Figure 3-10 d). The homogenous decoration of the surface
with nanogold suggests that proteins may be useful in the production of tailored
nanostructures under ambient conditions and aqueous solutions. Furthermore, the
recognition activity of the protein could provide an ability to control the particle
distribution, and particle preparation conditions could allow size control. This
approach makes it possible to pattern inorganic-binding polypeptides into desirable
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arrays to produce inorganic particles through templating using, for example, dip-pen
lithography.
3.5 References
Sarikaya, C. Tamerler, A.K.Y. Jen, K. Schulten F. Baneyx, Molecular biomimetics:
nanotechnology through biology, Nature Materials, vol 2, 2003, p.p. 577-585
O. Ikkala, G.T. Brinke, Functional Materials Based on Self-assembly of polymeric
supramolecules, Science, New Series, Vol. 295, No. 5564 (Mar. 29, 2002), pp. 2407-
2409
C.N.R. Rao, M. Nath, Inorganic nanotubes, Dalton Trans., 2003, p.p. 1-24
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4 MECHANICAL PROPERTIES
4.1 Introduction
One of the very basic results of the physics and chemistry of solids is the insight that
most properties of solids depend on the microstructure, i.e. the chemical composition,
the arrangement of the atoms (the atomic structure) and the size of a solid in one,
two or three dimensions. In other words, if one changes one or several of these
parameters, the properties of a solid vary. The most well-known example of the
correlation between the atomic structure and the properties of a bulk material is
probably the spectacular variation in the hardness of carbon when it transforms from
diamond to graphite. The important aspects related to structure are:
• atomic defects, dislocations and strains
• grain boundaries and interfaces
• porosity
• connectivity and percolation
• short range order
4.2 Metals
The microstructure of a material is controlled by the processing steps chosen for its
fabrication. Such microstructural design affects the nature of the phases present,
their topology (i.e. geometrical distribution and interconnection) and their dispersion
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k HP
τ= (4. 1)
D
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Figure 4-1 : Compilation of yield stress data for several metallic systems. [R.A. Masumura, P.M.
Hazzledine, C.S. Pande, Yield stress of fine grained materials, 1998, Acta-Materialia]
It is seen that the yield stress-grain size exponent for relatively large grains
appears to be very close to -0.5 and generally this trend continues until the very fine
grain regime (~100 nm) is reached. The reported data show three different regions:
1. A region from single crystal to a grain size of about 1 mm where the classical
Hall-Petch description can be used.
2. A region for grain sizes ranging from about 1 mm to about 30 nm where the
Hall-Petch relation roughly holds, but deviates from the classical -0.5
exponent to a value near zero (to ascertain such behaviour, a wide range of
grain sizes extending into the ultra-fine grain size regime is required).
3. A region beyond a very small critical grain size where the Hall-Petch slope is
essentially zero, with no increase in strength on decreasing grain size or
where the strength actually decreases with decreasing grain size.
There is universal agreement regarding the first region, i.e. relatively large grain
sizes. Early hardness measurements had already established a distinct increase in
hardness as grain sizes decrease as compared to their annealed coarse grained
counterparts, and this increase follows the Hall-Petch relationship reasonably well.
The trend is less well established for finer grains (Region 2). Some of the deviation
from Hall-Petch strengthening could simply be due to pores in the material (as
evidenced by lower densities) leading also to a lower shear stress for the
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deformation mode and lower shear modulus. Indeed, the lower modulus has been
ascribed to a decrease in bulk density. Additional complications arise due to
impurities at the grain boundaries such as oxides and impurities inside the grain
such as trapped or diffused gas. In spite of the above difficulties, once the totality of
the data is taken into consideration, it is fairly safe to conclude that the increase in
strength on grain refinement in the middle region is somewhat less than predicted by
the Hall-Petch relation.
The third region is much more controversial and is going to be discussed later.
Figure 4-2 : Grain size strengthening, as explained by pile-ups of dislocation loops against grain
boundaries (a). this mechanism must break down when the diameter d of the smallest loop no longer
fits into a grain of size D (b). [E. Arzt, Size effects in materials due to microstuctural and dimensional
constraints: A comparative review, 1998, Acta Meteriala]
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2Td Gb
The characteristic length, i.e. the loop diameter ( d (τ ) = = ), must now be
bτ τ
compared with the grain size D as the relevant size parameter
d (τ ) = D (4. 2)
2Td Gb
τ= = (4. 3)
bD D
Figure 4-3 : The limiting condition is shown as the heavy line where the shear strength τ is plotted
schemetically as a function of grain size D. Hall-Petch behavior can only be found to the right of this
line; abnormal or inverse behavior may result otherwise. The dotted line reflects schematically the
Gb D
τ≈ ln
equation D r0 (4. 6). [E. Arzt, Size effects in materials due to microstuctural and
dimensional constraints: A comparative review, 1998, Acta Meteriala]
For Cu, as an example, the critical grain size estimated in this way is about
50nm; this value is in reasonable agreement with experimental results, as shown in
Figure 4-4.
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Figure 4-4 : Inverse Hall-Petch behaviour in nanocrystalline Cu (H-H0 denotes the hardness increment,
D the grain size): the classical behaviour breaks down at a grain size of about 50 nm, in agreement with
2Td Gb
τ= =
an estimate based on the loop diameter [equations
d (τ ) = D (4. 2) bD D (4. 3)].
xxviii
Replotted after Chokshi et al. [E. Arzt, Size effects in materials due to microstuctural and
dimensional constraints: A comparative review, 1998, Acta Meteriala]
The plastic behaviour of nanocrystalline materials with grain sizes below the
critical value is not fully clear. It has been argued that because of the viscous
behaviour of amorphous materials (which can be considered the limiting case for grain
refinement) the grain size strengthening effect will have to be reversed once the grain
size D starts to approach the grain-boundary thickness δb. One possible explanation
for such a softening effect comes from a re-consideration of the line tension Td in
2Td Gb
equation τ = = (4. 3). The more refined expression
bD D
Gb² r1
Td = ln (4. 4)
4π r2
contains a lower (r0) and an upper (r1) cut-off distance for the stress field of the
dislocation. In conventional materials r1 generally lies in the micrometer range and
therefore significantly exceeds r0 (for which values between 2 and 10b are commonly
assumed); this justifies replacing the logarithmic term by a constant. However, in
nanocrystalline materials it is reasonable to equate r1 to the grain size, which now
gives r1 ≈ r0 and makes T sensitive to the value of the grain size D. Therefore, we now
have a case in which the characteristic length (d) is a function of the size parameter
(D). The resulting strength increment is given by
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Gb D
τ= n (4. 5)
2πD r0
This expression vanishes rapidly as the grain size D approaches the lower cut-
off distance r0. An even more refined expression has been obtained by Scattergood
and Kochxxix.
The dislocation density ρ scales inversely with grain size D, the obstacle
spacing is L~1/√p~√D, which yields
Gb D
τ≈ ln (4. 6)
D r0
Figure 4-5 : Diffusional creep is driven by gradients in normal tractions on grain boundaries (a). Fine
arrows delineate the paths for transport of matter. This mechanism ceases to operate (b) once a grain
boundary dislocation loop no longer fits into a grain facet (d > D’). Note the analogy with Figure 4-2 for
lattice dislocations [E. Arzt, Size effects in materials due to microstuctural and dimensional constraints:
A comparative review, 1998, Acta Meteriala]
•
For maintaining a constant strain rate ε by diffusion of atoms from grain boundaries
under compression to those under tension, the following shear stress τ is required
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•
ε kTD 2
τ= (4. 7)
C1 Dv Ω
In addition to this, the triple lines in nanocrystalline materials can also act as fast
• •
ε kTD 2 ε kTD 3
diffusion paths. Equations τ = (4. 7) and τ = (4. 8) reflect grain
C1 Dv Ω C 2δ b Db Ω
size effects which are opposite in direction and far stronger than those of dislocation
plasticity (Hall-Petch effect). They are due to the increase, with finer grain size, in the
volume fraction of ‘disordered' material which can act as short-circuit diffusion path,
and to the higher density of sinks and sources for matter.
It is still a matter of debate whether grain-boundary softening, which has occasionally
been reported for nanocrystalline materials, can be attributed to these effects at room
temperature.
One can note that in very small grains the rate of creep may no longer be controlled
•
ε kTD 2
by the diffusion step [as is tacitly assumed in equations τ = (4. 7)
C1 Dv Ω
•
ε kTD 3
and τ = (4. 8)], but by the deposition and removal of atoms at the grain
C 2δ b Db Ω
boundaries. Ashbyxxx have shown that for such ‘interface-controlled’ diffusional creep
the grain size dependence is much weaker
1
• 2
ε kTGbb 1 / 2
τ = D (4. 9)
C 4 Deff Ω
This result was obtained by modeling the interface reaction as the climb motion of an
array of grain-boundary dislocations. Here Deff is an effective diffusivity, bb the Burgers
vector of a boundary dislocation and C4 another numerical constant. The
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Gbb
τ= (4. 10)
D'
The value of bb corresponds to the difference in Burgers vector between two lattice
dislocations and is therefore only a fraction of b. Hence, a stress window will exist in
which plasticity due to lattice dislocations is suppressed or slowed down [at stresses
2Td Gb
below that given by equation τ = = (4. 3)], but diffusion creep operates
bD D
because grain-boundary dislocations are still present and mobile.
In the previous paragraph we have studied the relation between yield stress and
grain size. Now two questions are still not answered:
1. Whether the grain boundaries in nanocrystalline materials are unusual or
whether they have the short main structure of most grain boundaries found in
conventional polycrystalline materials
2. What is the influence of the grain size on the plastic deformation mechanism
In this paragraph, we will focus on the question of dislocation activity in two different
materials Cu and Ni. Swygenhoven and al. xxxi xxxii worked on molecular dynamics
simulations on nanocrystalline Ni and Cu samples in the grain size range 5-12nm.
They studied the interfaces responsible for the plastic deformation, aiming at
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Figure 4-6 : Strain rate as a function of mean grain size for Cu and Ni. [H. Van Swygenhoven, A.
Caro, D. Farkas, A molecular dynamics study of polycrystalline fcc metals at the nanoscale Grain
boundary structure and its influence on plastic deformation, 2001, Materials Science and Engineering
A.]
Figure 4-6 shows the strain rate versus the inverse of the grain size for the Ni and
Cu samples. The strain rates under these conditions are high compared with actual
experimental values, but for these small sample sizes (10–25 nm) any relative
velocity is still four orders of magnitude smaller than the velocity of sound.
At the smallest grain sizes explored the strain rate for a given applied stress
increases with decreasing grain sizes. This behaviour indicates that the Hall–Petch
slope is negative at these very fine grain sizes. An energy balance indicates that at
these sizes the total amount of grain boundary remains constant during deformation.
These observations suggest an important characteristic of plasticity in nanophase
metals under the present conditions: there is no damage accumulation during
deformation, similar to the case of superplasticity. Careful examination of the
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samples confirms the absence of intra-grain defects. Swygenhoven and al. [4]
discussed the deformation mechanism in terms of a model based on Grain Boundary
viscosity controlled by a self-diffusion mechanism at the disordered interface,
activated by thermal energy and stress.
When similar load is applied on samples with larger average grain sizes, the
deformation rate is much smaller. These observations indicate a transition to another
deformation mechanism. They analyzed the atomic structure of Ni and Cu samples
with larger grain sizes, deformed at those stress levels that give approximately the
same strain rate as in the sample with the very small grain sizes, and compare the
structures at similar values of plastic deformation. In this way they take into account
the different elastic contribution in very fine-grained samples due to the reduction of
the Young’s modulus.
Figure 4-7 : Slice of the 12 Ni sample, deformed until a plastic deformation level of 1.4%. Open gray
symbols are perfect f.c.c., full gray are good f.c.c., red are h.c.p., green and blue are other 12- and
non-12-coordinated atoms, respectively. [H. Van Swygenhoven, M. Spaczer, A. Caro, Microscopic
description of plasticity in computer generated metallic nanophase samples: A comparison between
Cu and Ni, 1999, Acta Materialia.]
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Figure 4-8 : Shockley partial dislocation traveling through a grain in the 12 nm Ni sample. Black atoms
are the hcp atoms forming the intrinsic stacking fault in a (1, 1, −1) plane. [H. Van Swygenhoven, A.
Caro, D. Farkas, A molecular dynamics study of polycrystalline fcc metals at the nanoscale Grain
boundary structure and its influence on plastic deformation, 2001, Materials Science and Engineering
A.]
Its glide plane is (1, 1, −1); the dislocation line at this time is mainly composed of two
segments, aligned approximately along 1,−1,0 and 011 directions. The Burgers
vector being a/6 − 1,2,1 ; two possible additional partials could give perfect a/2 011
or a/2 1,−1,0 dislocations. Both segments in the figure are of mixed character. The
and 1,−1,0 have both a Schmid factor of 0.37, which is the largest possible value in
this grain.
Evidences of stacking faults inside the grains in Ni are observed at a slightly higher
grain size (11 nm) compared to Cu (8 nm), probably due to the higher stacking fault
energy. In Cu, Swygenhoven and al. have observed partial dislocations which glide
on slip systems that are not necessarily those favoured by the Schmid factor.
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4.2.3 Hardness
Normally, one would expect that the introduction of a very high fraction of boundaries,
which is the case of nanostructured polycrystals, will result in a further increase in
hardness since the boundaries are thought to play the role of barriers to dislocation
motion, thus hindering deformation. The aforementioned experimental findings
prompted various researchers to propose models in terms of viscous flow or grain
boundary sliding, different dislocation mechanism taking place for small grain sizes,
or by rule-of-mixtures approaches.
In this following section, we are going to study a model xxxiii that obtains the total
hardness involving the grain size, the grain boundary width, the hardness
characteristics of coarse grain counterparts and an extra parameter describing the
arrangement of triple junctions.
In the present formulation the grain boundary phase is considered as having similar
mechanical behaviour to the grain interior phase, rather than being amorphous.
Moreover, the effect of triple grain boundary junctions and the associated
disclinations is considered. Such considerations amount, in effect, into assuming that
the strength of the nanostructured polycrystal does not depend only on their volume
fraction but also scales with the grain dimension in a way similar to the grain interior,
with an enhanced fraction of triple junctions providing a different scenario for the
available acting deformation mechanisms.
The total hardness may be assumed to obey a rule of mixtures relation of the form
Where H, HG and HGB are the total, grain interior and grain boundary hardness
respectively, while f denotes the volume fraction of the grain boundaries region.
By assuming a tetrakaidecahedra grain configuration, H=HG(1-f) + HGBf (4. 11) can
be rewritten in the form
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(d − δ ) 3 d 3 − (d − δ ) 3
H= H G + H GB (4. 12)
d3 d3
Where the coefficients have their usual meaning though now assigned to each region
separately. For the dependence of hardness on the grain size d, a power of -1/2 is
used. It may be noted that HG is the hardness contribution of the bulk due to the
existence of the grain boundaries necessary to form dislocation pile-ups, while HGB is
an analogous contribution of the boundaries due to the existence of triple junctions
which act as sources and sinks of dislocations and may be thought to possess the
properties of disclination dipoles.
To find kGB the Hall-Petch approach (see paragraph 4.2.1.2) is used and we can find
r1
ln
= kG
r0
k GB (4. 14)
r1c
ln
r0
Where r1c is the critical transition grain size. For grain sizes D<Dc the movement of
the glide dislocation is no longer prohibited by the dislocation line, a situation known
as “Orowan bypassing”.
Thus, the relation predicting the total hardness of the nanocrystalline materials, when
taking into account the special contribution of the boundaries, is written in its final
form as
r1
ln
(d − δ ) d − (d − δ ) r0
3 3 3
H = H OG + kG + d −1 / 2 (4. 15)
d3 d3 r1c
ln
r0
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r1
ln
(d − δ ) d − (d − δ ) r0
3 3 3
It is worth noting that equation H = H OG + kG + d −1 / 2
d3 d3 r1c
ln
r0
(4. 15) bears some resemblance with a similar expression obtain for the yield
stress by using interphase disclination arguments.
Gω lθ
σ≈ log (4. 16)
2π (1 − υ ) α H
Where G is the shear modulus, υ the Poisson’s ratio, ω the disclination power, α H
the boundary length and θ a numerical factor estimated close to 0.1.
The hardness dependence on grain size for metals are given in Figure 4-9 a) and b)
and for intermetallics in Figure 4-9 c) and d).
Figure 4-9 : Hardness of coarse grained and nanocrystalline metals [(a),(b)] and intermetallics
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[(c),(d)]. [D.A. Konstantinidis, E.C. Aifantis, On the ‘anomalous’ hardness of nanocrystalline materials,
1998, Nanostructured Materials]
4.3.1 Density
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1000
800
Strength (MPa)
600
400
5
Toughness (MPax m 1/2 )
0 10 20 30
SiC c ontent (vol %)
Figure 4-11 shows strength and fracture toughness for various Si3N4/SiC
nanocomposites as a function of SiC volume fraction. All data were obtained from
different publications of Niihara and his co-workers. Nanocomposites derived from
the classical powder route are represented by solid symbols and nanocomposites
fabricated from an amorphous Si-C-N powder by open symbols. With few exceptions,
all data point follows a defined trend. The toughness increased from approximately
5MPa√m for mopnolithic Si3N4 to 6 MPa√m for manocomposites with ≥ 10 vol% SiC.
This increase is accompanied by a modest increase in strength from 900 MPa to
1100 MPa.
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Figure 4-11 : Strength and fracture toughness for various Si3N4/SiC nanocomposites as a
function of SiC volume fraction
4.3.3.1 Critical flaw size reduction (c-mechanism): Zener grain size boundary
pinning
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3 r
R≅ (4. 17)
4 Vf
Where R is the average matrix grain boundary radius of curvature, depending on the
3 r
radius (r) and the volume fraction (Vf) of spherical inclusions. Equation R≅
4 Vf
(4. 17) is
often given in the form
3 r
In Figure 4-12 the Zener model (equation R≅ (4. 17)) is compared with
4 Vf
experimental data where R is plotted as a function of 1/Vf. the radius of SiC
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nanoparticles used in the calculation was taken to be 150 nm, which is typical for the
materials studied. The model agrees well with the experimental data but large SiC
volume fractions. However, one has to consider that SiC particles are not completely
inert during sintering.
It has been found that α-SiC particles change their morphology form as received
irregular fragments to spherical after sintering. Furthermore, for high SiC volume
fractions SiC particles can form agglomerations or sinter together forming large
particles. This has to be taken in account if better agreement is to be obtained
between the model and experimental results at high SiC volume fraction because
3 r
equation R≅ (4. 17) predicts larger matrix grains for larger SiC particle
4 Vf
sizes.
However, the reduction of the matrix grain size is obvious when taken into
account that monolithic alumina sintered under the same conditions possess a much
larger grain size of about 20 µm.
Zhao et al.xxxiv 55
suggest that SiC particles only indirectly influence the strength by
enabling the compressive stress induced by the grinding process to be retained in the
surface region of the test specimens. Another theory is that cracks in nanocomposites
can heal during annealing. Alumina and Al2O3/SiC nanocomposites are indented with
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ο
a Vicker’s piramid to generate radial cracks. After annealing at 1300 C in Ar for 2 h
the material behave completely differently. xlvii 110
Whereas cracks in alumina grow,
cracks in nanocomposites close, thus explaining the strength increase of annealing
nanocomposites.
Possible reasons for the crack healing have not yet found and more systematic work
is needed. However, by taking into account internal stresses, one has to distinguish
between the stresses introduced by the Vicker’s indentation (comparable to
machining-introduced stresses), stresses introduced by the thermal expansion
mismatch of Al2O3 and SiC and, finally, stresses due to the thermal anisotropy of
alumina grains. Fang et al.xlvii 110
observed that residual stresses introduced by
Vicker’s indentation fully relax in alumina after an annealing procedure whereas
compressive stresses are still present in nanocomposites.
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interfacial fracture energy between SiC and alumina is twice that of the alumina grain
boundary fracture energy.
α* = ∫ T
T plastic
0
(α particle − α matrix ) dT (4. 19)
The thermal expansion misfit stress, σT, inside a single spherical inclusion in infinite
matrix can be described by the following expression after Selsing:liii 118
α*
σT =
1 + vm 1 − 2v p (4. 20)
+
2 Em Ep
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E and υ are Young’s modulus and Poisson’s ratio of the matrix (m) and the particles
(p). The tangential, σT, and the radial, σT, stress distributions in the matrix around the
particle are given by:
σT r
3 3
r
σT = − σ Tr = σT
2 x
(4. 21)
x
Where r denotes the radius of the inclusion and x is the radial distance from the
inclusion surface. Assuming Tplastic as 1500oC and the room temperature
α*
σT =
1 + vm 1 − 2v p
+
2 Em Ep
thermoelastic data given in Table 4-1, equation ( (4. 20) leads
to a compressive hydrostatic stress inside the SiC particle of 2.0 GPa for the
Al2O3/SiC and 4.3 GPa for the MgO/SiC system. Tensile hydrostatic stresses of
500MPa and 600MPa can be calculated for the Si3N4/SiC and the Al2O3/TiN systems,
respectively. Evidently, a change in fracture mode occurs only in systems with high
compressive stresses within the nano-particles such as Al2O3/SiC and MgO/SiC.
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σp −2(1 − V f ) β α *
=
Em (1 − V f )( β + 2)(1 + vm ) + 3βV f (1 − vm )
(4. 22)
σm 2V f β α *
=
Em (1 − V f )( β + 2)(1 + vm ) + 3βV f (1 − vm )
1 + vm E p
where β= .
1 − 2v p Em
In the case of αm>αp, the average thermal stresses are compressive inside the
particles and tensile in the matrix. For Vf=0, equation
σp −2(1 − V f ) β α *
=
Em (1 − V f )( β + 2)(1 + vm ) + 3βV f (1 − vm )
( (4. 22) provides the same value for the
σm 2V f β α *
=
Em (1 − V f )( β + 2)(1 + vm ) + 3βV f (1 − vm )
stresses inside the particles as the Selsing model.liii 118
Another boundary condition is
given by mechanical equilibrium with 〈σm〉(1−Vf)+〈σp〉Vf=0.
Figure 4-14 shows experimental results together with a prediction using equation
below. A stress-free temperature of 1500oC, below which plastic deformation is
insignificant, is assumed. (By considering that internal stresses at the surface of a
nanocomposite are not relieved after annealing at 1300oC, as observed by Fang et
al.,xlvii 110
the stress-free temperature must be somewhere between 1300 and 1550oC
which is the minimum hot-pressing temperature to get fully dense nanocomposites).
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Figure 4-14. Average residual microstresses in the matrix 〈σm〉 and nano inclusions 〈σp〉 for Al2P3/SiC
nanocomposites. ( , ) adapted from Todd et. al; ( , ) Ref. 120)
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For discussion of the grain boundary strengthening effect due to internal stresses it is
helpful to review the stress fields around the SiC particles. For the model presented in
this review, a superposition of stresses in an arrangement of several boundaries
including a grain boundary is assumed. Figure 4-15 shows the configuration assuming
nine particles in a cubic-body-centred arrangement with an average nearest particle
spacing equivalent to a SiC volume fraction of 2.5%. One particle is located in the
plane. The remaining particles are the same distance from that plane. Each particles
causes a stress field which can be calculated using the Selsing equation. The total
stress at each point in the x-y-plane highlighted in Figure 4-15 can easily be calculated
assuming a simple superposition. Obviously, the particle at the grain boundary
generates high tensile stresses immediately around it and the other eight particles
nearby to the plane generate compressive stresses up to 120 MPa. SiC particles
within the Al2O3 grain boundaries strengthen the grain boundaries due to radial
compressive stresses. The influence of SiC particles within grain boundaries is still
unclear, but could be expected to generate countervailing tensions across the
boundary.
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but also their morphology changes completely. Furthermore, the matrix grain size is
reduced with a narrow size distribution due to the grain boundary pinning by inert SiC
particles. Dislocation network plays only a minor role.
A clear identifications of the toughening mechanism in nanocomposites remains
difficult because, first, the toughness increase is small or even absent and, second,
there is no single persuasive mechanism (Table 4-2). A balance exists between
mechanisms decreasing toughness, i.e. crack deflection or grain boundary
strengthening. All these mechanisms depend highly on specific processing and
microstructural details. However, it appears that grain boundary strengthening due to
local radial compressive stress components around SiC particles or due to a riveting
effect is the most likely nanocomposite effect. The mechanism explains the transition
in fracture mode as well as the improved resistance to wear and machining damage.
Mechanism Comment
Zener grain boundary Matrix grain sizes are drastically reduced
pinning mechanism (c- (typical for nanocomposites)
mechanism)
Reduction in processing Strength increase can be fully explained
flaw size (c-mechanism) by observed change in processing flaw
type (careful processing is very important)
R-curve effects (K- Steep rising R-curve behaviour is
mechanism) proposed (no experimental evidence)
Crack Deflection (K- Cracks seem to be reflected at SiC
mechanism) particles (importance for toughening is
unclear)
Thermal expansion Fracture mode is changed to
mismatch (grain transcrystalline if α particle < α matrix (eg. For
boundary strengthening) Al2O3/SiC)
Average internal stresses Average tensile stresses in matrix if
(grain boundary α particle < α matrix (toughness is reduced)
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strengthening)
Local stress distribution Local compressive stresses in matrix
(grain boundary grain boundaries if α particle < α matrix (can
strengthening) explain change in fracture mode)
4.5 References
R.A. Masumura, P.M. Hazzledine, C.S. Pande, Yield stress of fine grained materials,
1998, Acta Materialia
E. Arzt, Size effects in materials due to microstuctural and dimensional constraints: A
comparative review, 1998, Acta Meteriala
Chokshi, A. H., Rosen, A., Karch, J. and Gleiter, H., Scripta metall., 1989, 23, 1679
H. Van Swygenhoven, A. Caro, D. Farkas, A molecular dynamics study of
polycrystalline fcc metals at the nanoscale Grain boundary structure and its influence
on plastic deformation, 2001, Materials Science and Engineering A.
H. Van Swygenhoven, M. Spaczer, A. Caro, Microscopic description of plasticity in
computer generated metallic nanophase samples: A comparison between Cu and Ni,
1999, Acta Materialia.
D.A. Konstantinidis, E.C. Aifantis, On the ‘anomalous’ hardness of nanocrystalline
materials, 1998, Nanostructured Materials
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MATERIAL
The theory of heat conduction by lattice waves in solids can be used to understand
how the conductivity is influenced by lattice defects, grain boundaries and extended
imperfections. At high temperatures one must also consider conduction by
electromagnetic radiation within the solid, which is governed by analogous
considerations. The thermal conductivity by mobile carriers, whether waves or
particles, can be expressed in general in the form
1
κ = Cvl (5. 23)
3
where C is their specific heat per unit volume, v their speed and l their mean free
path. If the carriers are waves (lattice waves or electromagnetic waves) ranging over
a spectrum of frequencies f, this must be generalized to
C ( f )vl ( f )df
1
κ=
3∫
(5. 24)
where C( f )df is the contribution to the specific heat per unit volume from waves in
the frequency interval df, v is the group velocity of the waves and l(f) their
attenuation length, usually a function of frequency. Also, fm denotes an effective
upper limit to the spectrum because either v or l become very small for f\ fm. In the
present discussion fm is the upper frequency limit of the acoustic branch, as
discussed in the next section. The energy content of waves consist of quanta,
phonons or photons respectively, and these quanta can also be considered as
particles which carry heat. The present treatment emphasizes the wave nature of the
carriers of heat.
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Lattice waves are just elastic or ultrasonic waves, but their spectrum extends to very
high frequencies, where their wavelength λ is of atomic dimensions, and where the
relation between f and the wavelength λ is modified. At low frequencies λ=v/f, but at
high frequencies, due to the discrete atomic structure of the lattice, this relation holds
no longer. The displacement field of the wave has the form of a progressive wave, so
that the displacement u(r,t) varies with position r and time t as
where the wave-vector q has magnitude 2π/λ and points in the propagation direction,
and ω is the angular frequency ω = 2π f. At high frequencies ω is then no longer
proportional to q. The relation between frequency and wave-vector for a discrete
lattice is shown schematically in Figure 5-1.
Figure 5-1 : Dependence of frequency ω on the wave-vector q for a discrete lattice in the principal
direction. Curve A is the acoustic branch, the only type in simple lattices. Curve O is an optical branch,
present in complex crystals and describing vibration of atoms within molecular units. [P.G. Klemens,
M. Gell, Thermal conductivity of thermal barrier coatings, Materials Science and Engineering A245
(1998), p.p. 143-149]
The slope of the curve defines the group velocity v=dω/dq, that is the speed by
which a wave transports energy.
The Debye theory of lattice vibrations makes the simplification that v is constant, but
that the lattice wave spectrum is terminated at the Debye frequency fD chosen so that
the number of normal modes agrees with the number of atoms. However, when the
basic structural unit contains N atoms of varying mass, the spectrum divides into
acoustic modes, of the progressive wave form, (curve A in Figure 5-1), and into
optical modes (curve O) vibrations of the N atoms in each structural unit relative to
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each other. Only the former, with upper frequency fm = fD / N⅓, have appreciable
group velocity and transport heat. This approximation is used here. In the limit
T > hfm/k, which is the case of interest here, each wave or normal mode has, in
thermal equilibrium, energy kT, and C(T) ∝ f². Here k and h are the Boltzmann and
Planck constants, respectively.
The difference between acoustic and optic vibrations is shown schematically in
Figure 5-2.
Figure 5-2 : In crystals composed of molecular units, such as ceramic oxides, the lattice waves are of
two types: acoustic and optical. [P.G. Klemens, M. Gell, Thermal conductivity of thermal barrier
coatings, Materials Science and Engineering A245 (1998), p.p. 143-149]
The optic vibrations are vibrations of the atoms in the lattice; the term ‘optic’ refers to
their strong interaction with infrared electromagnetic waves in the case of ionic solids.
In an ideal solid, one that is perfectly harmonic (obeying linear elasticity), structurally
perfect and without external boundaries the lattice waves would be normal modes.
This means that the energy content of each wave would remain constant. Thermal
equilibrium between the waves could not be established. Real solids depart from this
ideal behavior. The lattice forces have anharmonic components, so that there are
departures from linear elasticity, or terms in the strain energy which are cubic in
strain. Also there are always lattice defects and, of course, boundaries. All these
cause some exchange of energy between the waves, which are no longer true
normal modes. The large number of normal modes results in sufficient randomness
in these interactions, so to establish thermal equilibrium. To treat thermal equilibrium
properties it suffices to know that these interactions exist. To study transport
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properties and estimate the attenuation lengths one must consider these interactions
in detail.
The thermal conductivity is limited by various interaction processes, which transfer
energy between the waves and establish thermal equilibrium. These are
schematically shown in Figure 5-3 and correspond to the different types of departures
from ideal behavior.
Figure 5-3 : Interaction processes between lattice waves (a) due to anharmonic interactions, (b)
scattering of waves by lattice defects, and (c) reflection of waves by boundaries and interfaces. [P.G.
Klemens, M. Gell, Thermal conductivity of thermal barrier coatings, Materials Science and Engineering
A245 (1998), p.p. 143-149]
where B ∝ µa 3 vf m , µ being the shear modulus and a3 the volume per atom. It is thus
inversely proportional to the mean square thermal strain kT/µa3. The intrinsic
conductivity becomes then
µv / ( f D T )
3 −2 / 3 2
κi = N (5. 27)
4
and this describes, reasonably well, the thermal conductivity of structurally perfect
dielectric crystals near and above their Debye temperature hfD/k. Weak binding,
large atomic masses and structural complexity (large N) all tend to reduce the
intrinsic conductivity. Note that if one writes κ = ∫ k ( f )df , then in the intrinsic case
make equal contributions to the intrinsic conductivity. This contrasts to the specific
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heat, which for acoustic modes is mainly due to their highest frequencies, since for
f<fm, C ( f ) ∝ f 2 .This is shown schematically in Figure 5-4.
Figure 5-4 : Spectral contributions from lattice waves as function of frequency to the vibrational
specific heat (a), and to the intrinsic thermal conductivity (b). [P.G. Klemens, M. Gell, Thermal
conductivity of thermal barrier coatings, Materials Science and Engineering A245 (1998), p.p. 143-149]
Figure 5-5 : Reduction in the thermal conductivity, which is the area under the curve, at high
frequencies due to point defects (δkp), and at low frequencies due to grain boundaries and other
extended imperfections (δkB). [P.G. Klemens, M. Gell, Thermal conductivity of thermal barrier
coatings, Materials Science and Engineering A245 (1998), p.p. 143-149]
And expessed by
κ = κ i − δκ B − δκ P Eq 5.1
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Where δκB and δκP are the reductions due to boundaries and point defects. Point
defects are small regions of volume a3 in which the value of the wave velocity v is
locally changed by δv.
Since the intrinsic attenuation length li (f, T) has a different dependence on wave
frequency f than that due to point defects, it is convenient to define a frequency f0 at
which the two attenuation lengths are equal, i.e li (f0, T) = lp (f0) Similarly one can
define a frequency fB such that li (fB, T) = L, where L is the grain diameter.
Then
fB f
δκ B = κ i arctan m
fm fB
Eq 5.2
f f
δκ P = κ i 1 − 0 arctan m
fm f 0
Note that the equation for δκP also holds if f0> fm.
For a substitutional atom of mass ∆M+M instead of M the change in velocity is
1 ∆M
δv = . Thus one finds
2v M
∆M
2
l
4π a v f
3 3 −4
= c 4
Eq 5.3
lP ( f ) M
where c is the defect concentration per atom. Effective values of ∆M/M can be
obtained for other defects, including vacancies. If κi is known, one can deduce li (f, T)
and thus obtain δκP; this has been done for many systems, e.g. for cubic zirconia.
Cubic zirconia presents a further difficulty: it only exists if it contains stabilizing
solutes together with the accompanying vacancies needed for charge neutrality. Thus
the intrinsic thermal conductivity and li must first be estimated in terms of its elastic
and anharmonic parameters. The resulting uncertainty of perhaps 30% in κi
translates into a 15% uncertainty in κ. There is rough agreement for various solutes
and concentrations at room temperatures. At high temperatures the theoretical
values are always less than the data. This was shown for several different solutes
and concentrations. This suggests the presence of a radiative component. Values of
δκB can be calculated for various grain diameters, and the resulting lattice thermal
conductivities are shown for zirconia containing 7wt% yttria in Figure 5-6.
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Figure 5-6 : Theoretical reductions in the thermal conductivity of ZrO2 containing 7 wt% Y2O3 due to
point defects and grain boundary scattering for various grain sizes. [P.G. Klemens, M. Gell, Thermal
conductivity of thermal barrier coatings, Materials Science and Engineering A245 (1998), p.p. 143-149]
5.2.1 Theory
The two mechanisms important for the heat transport in nonmetallic solids at high (of
the order of Debye or higher) temperatures are:
1. the phonon relates to the movement of atoms in the crystalline lattice
2. radiative mechanisms is due to the electron transitions between the energy
levels in these atoms
If we neglect the relation between the energy levels and spacing between the atoms,
then both mechanisms can be considered independently. This assumption seems to
be reasonable, if the amplitude of the atomic oscillation is considerably lower than the
lattice constant. We can then write
κ = κ ph + κ r Eq 5.4
where κ is the thermal conductivity, κph and κr are its phonon and radiative
components, and consider each of them separately.
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k B2TZt SΦ (σ ) 1 / θ
κ ph =
3πℏa 2 d ∫0
B ( x)dx Eq 5.5
where
2
9 x 4e x 1 T
B( x) θ 4 x x − ,θ = Eq 5.6
2 (e − 1) 2 θ TD
T is the temperature, TD is the Debye temperature, ћ and kB are the Planck and
Boltzmann constants, a is the lattice constant, d is the grain size, S is the main area
of the intergrain boundary (the “neck” size), and Z is the coordination number.
Deviation of this parameters from its mean value is determined with the parameter of
disorder Φ. It has been estimated as
−1
2σ 2
Φ = 1 + Eq 5.7
Z
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k B2TZt SΦ (σ ) 1 / θ
σ is the mean relative deviation of S . κ ph
3πℏa 2 d ∫0
= B ( x)dx Eq 5.5 results in
yields
k B2TD Zt SΦ(σ )
κ ph = Eq 5.8
20πℏa 2 d
k B2TZt SΦ (σ ) 1 / θ
The main difference between κ ph =
3πℏa 2 d ∫0
B ( x)dx Eq 5.5 from the one
derived in Ref. lviii arises from the factor Z/3π. Indeed, in the absence of porosity the
value of Z S is the total surface area of the grain and therefore it is a constant. In
these experiments, however, it is not so because of complexity of the grain shape
and porosity. The factor Z/3π is valid if Z>>1. In particular, for Z~12.
To consider the phonon-phonon scattering we suppose that some additional resistors
(the value of which is ri = κi d, where κi is the bulk part of TC) are series connected to
the boundary ones (Rij). This leads to the following expression for TC:
1/ θ κ i B( x) Zt SΦ
κ ph = k B T ∫ dx Eq 5.9
0
3πℏk κ i a 2 d + k B TD B( x) Zt SΦ
−1
B
experimentally. The t value describes interface transparency for the phonon hopping.
To estimate it, the equations of movement for each atom at the interface have to be
solved. We will not carry out this procedure, but we will consider the t value as an
adjustable parameter. It depends only on the interface structure and is independent
of the grain size and porosity. So, it should be similar for nanostructures prepared
using the same technology. This fact will be tested experimentally in this paper.
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∫ C (ω )l (ω )dω
c
κr = Eq 5.10
3 ε
V
0
where c, ω, and l(ω) are the photon speed, frequency, and mean free path, ε is the
dielectric permittivity,
ℏ ∂ ω3
CV (ω )dω =
dω Eq 5.11
π c ∂T e
2 3 ℏω / k BT
− 1
l (ω ) =
c c
~ Eq 5.12
2πωσ 2πN e e 2 / m *
effective mass of the electron, τ is the electron relaxation time; at high temperatures it
can be estimated as τ = ћ/(kBT), so that
N ee2ℏ
σ= Eq 5.13
m * k BT
− Eg
3/ 2
2πm * k B T
N e = 2 exp Eq 5.14
( 2πℏ ) 2
2 k
B T
where for the band gap and effective mass values we have E g ≈ 8.7 eV, m* ≈ 0.35me
(e and me are the charge and mass of the free electron). Then
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k B4T 3 ∞ x 4 dx
κr = ∫ Eq 5.15
3π 2 cℏ 3 2πN e e 2 / m * 0
x (e x − 1) 2
N ee2ℏ k B4T 3 ∞ x 4 dx
Using σ = Eq 5.13 and κ r = ∫ Eq 5.15 for
m * k BT 3π 2 cℏ 3 2πN e e 2 / m * 0
x (e x − 1) 2
T=2000 K yields κ r ≈ 11W /(mK ) , and l ≈ 14cm . This means that a perfect Al2O3
crystal shows no resistance to the photon transport. The resistance could arise from
the impurities or intrinsic defects (the energy level of the defect closest to the top of
the valence band is Ei=0.3 eV). The latter can be responsible for heat resistance if
their density is rather large, so that l becomes smaller than thickness of the specimen
k B4T 3 ∞ x 4 dx
L. The effect can be estimated by κ r = ∫ Eq 5.15,
3π 2 cℏ 3 2πN e e 2 / m * 0
x (e x − 1) 2
where Ne~Ni exp(−Ei/kBT) and m* is effective mass of the hole, Ni is the defect
density. However, this yields κr that is usually small, if l<<L.
It is easy to understand the reason. The electron density is low at low temperature.
N ee2ℏ
This means long mean free paths both of electrons and photons [ σ = Eq
m * k BT
5.13]. Increase of the temperature leads to increase of the photon part of the heat
capacity (which is proportional to T3), but also to rapid decrease of the photon mean
free path (which exponentially depends on temperature).
Appreciable contribution to the radiative component could originate from the electron
levels localized less than 0.1 eV from a band edge. They can be the electrons from
impurity or surface levels segregated from the conductive or valence bands
(electrons from dangling bonds). In the latter case, the density of the levels can be
24 p
roughly estimated as N i ≤ , where D is the pore size. Such levels become
πa 2 D
ionized at T≥1000 °K. Then N e→Ni becomes independent of temperature, so that κr
increases as T3.
Crystal disorder decreases the phonon mean free path and so decreases the
radiative component. To estimate this effect we take into account that wavelength of
the heat photons at T=1000 K is of about 5000 nm, so that it significantly exceeds the
grain size. This allows us to use a continuum approximation: We consider the
electromagnetic wave propagation in the media with the position dependant dielectric
permittivity. In the first approximation (with respect to ratio of the grain size to the
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photon wavelength) this effectively change the permittivity, however, in the second
approximation this leads to decay of the electromagnetic waves due to the structural
disorder. The decay length considerably exceeds not only the grain size, but also the
wavelength.
To consider the propagation of electromagnetic waves in a granular material we find
the solution of the Maxwell equations in the media with the dielectric
permittivity ε (r ) = ε + ξ (r ) , where ε is the average permittivity, which is independent of
r, and the random function ξ(r) is its deviation. This allows us to express the electric
and magnetic fields of the waves via the correlation function W (r − r ' ) = ξ (r ' )ξ (r ) ,
square deviation of the permittivity and ℜ ≈ d is the correlation length. Unlike the
commonly used Gauss correlation function, this one is more appropriate for the
steplike random values (ε(r) = ε1 = ε in the grains or ε(r) = ε2 = 1 in the pores).
We found that disorder leads to the effective correction to the permittivity
ε~ = ε − ϑ 2 / 3ε and attenuation of the electromagnetic waves γ ∝ ω 4 ℜ 3 . The effective
mean free path is
−4
1 1 1 ω
= + = 3ϑ − 2 ℜ −3 where l SC (ω ) = γ −1 Eq 5.16
l eff l (ω ) l SC (ω ) c
∫ C (ω )l (ω )dω
c
The effective mean free path l eff (ω ) substitutes l (ω ) in κ r = Eq
3 ε
V
0
1
−
5.10. It is apparent this is approximately the smallest value between l (ω ) ∝ ω 2
and
k BT
l SC (ω ) = ω −4 . In the perfect crystal l (ω ) << l SC (ω ) , and the value of ω = is
ℏ
∞
∫ C (ω )l (ω )dω
c
effectively the upper limit for the integral κ r = Eq 5.10. In the
3 ε
V
0
k BT
smaller than . In the first case the disorder has no appreciable influence on κr, in
ℏ
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k BT
the second one the value of ω 0 < becomes the effective upper limit of
ℏ
∞
∫ C (ω )l (ω )dω
c
κr = Eq 5.10; this decreases the radiative component κr.
3 ε
V
0
5.2.2 Experiment
Table 5-1 : Experimental data used in calculation. [L. Braginsky, V. Shklover, H. Hofmann, P.
Bowen, High-temperature thermal conductivity of porous Al2O3 nanostructures, Physical review B 70,
134201 (2004)]
The porosity, grain size as well as the contact area between the grains were
determined using image analysis methods applied to SEM pictures of polished and
thermally etched samples. Additionally TEM studies of the samples FD1/1, FD1/2,
and FD1/3 sintered at different conditions (Figure 5-7) were performed with TEM
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Philips CM300, operating at 300 kV. The samples were coated with carbon layer to
avoid charging.
Figure 5-7 : TEM images. (a) Smaller grain size, lower density sample FD1/2, scale bar 200 nm. (b)
Larger grain size, higher density sample FD1/3, scale bar 200 nm. (c) Two sintered grains in powder
FD1/2. The interface (indicated with an arrow) has a thickness, 1 nm. Both grains are crystalline, but
oriented differently and the crystalline fringes can be easily seen only on one of them. Scale bar 2 nm.
[L. Braginsky, V. Shklover, H. Hofmann, P. Bowen, High-temperature thermal conductivity of porous
Al2O3 nanostructures, Physical review B 70, 134201 (2004)]
The laser flash method was used for measurements of heat diffusivity in a “TC-
3000H/L SINKU-RIKO” device as described in Refslix,lx.
The results of the TEM study of our samples are presented in Figure 5-7, where the
structure of the interfaces between the α−Al2O3 grains is shown. This is important,
because it influences the phonon propagation in nanopowder. The TEM study shows,
that
1. The interfaces between the a−Al2O3 grains are very thin (~1 nm, Figure 5-7)
2. No epitaxial relation between the neighboring crystalline α−Al2O3 grains was
observed.
Table 5-1 presents results of the structure measurements of our specimens together
with the values of the parameter t for each of them. These values of t ensure the best
1/ θ κ i B( x) Zt SΦ
fit of κ ph = k B T ∫ dx Eq 5.9 with measured
0
3πℏk B−1κ i a 2 d + k B TD B( x) Zt SΦ
temperature dependence of TC (Figure 5-9). The value of t does not vary significantly
for the specimens of each set, but change approximately two times for the specimens
of different sets. This means that the parameter t depends on the intergrain interface
structure, but it is independent of the grain size and porosity.
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To understand this, we recall that ~0.5 wt % of MgO was added during the
preparation of FD2/1–FD2/3. This amount is much larger than solubility of MgO in
alumina, therefore most of the added MgO should be located at the grain boundaries
affecting the t value.
Figure 5-8 : (Color online) Temperature dependence of TC of the sample FD1/2: measured (dots) and
calculated (solid line). Different types of the dots label the different series of the measurements.
Dashed line indicates TC of the bulk Al2O3 single crystal. [L. Braginsky, V. Shklover, H. Hofmann, P.
Bowen, High-temperature thermal conductivity of porous Al2O3 nanostructures, Physical review B 70,
134201 (2004)]
Figure 5-8 presents results of our TC measurements for the FD1/2 specimen along
with temperature dependence of Al2O3 thermal conductivity in the bulk that was
measured in Reflxi. It is apparent that our experimental dots do not show significant
temperature dependence. In addition, TC of our structures is much less than that of
the bulk single crystal; this confirms the approximations of our model. Indeed, as a
result of nanostructuring the mean free path of phonons is determined by the grain
boundaries, and it is independent of the phonon frequency and the temperature. This
is the main reason why the short wavelength phonons, which prevail at high
temperatures, are mostly responsible for the heat transport. In the single crystals, on
the contrary, the phonon mean free path, which is determined by the phonon-phonon
interaction, decreases with the frequency as l ∝ ω −2 , so that the phonons of any
frequency are of equal importance for TC. This enables one to estimate roughly the t
k B2TD Zt SΦ (σ )
value from κ ph = Eq 5.8. The results are close to that of Table 5-1.
20πℏa 2 d
Measured values of thermal conductivity as a function of temperature are presented
in Figure 5-9.
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Figure 5-9 : (Color online) Temperature dependence of TC of the smaples: measured (dots) and
calculated (solid line). Different types of the dots indicate the different series of the measurements. [L.
Braginsky, V. Shklover, H. Hofmann, P. Bowen, High-temperature thermal conductivity of porous
Al2O3 nanostructures, Physical review B 70, 134201 (2004)]
We see that theoretical curves as a rule demonstrate more rapid decrease with
temperature than observed. This means that the expression
1/ θ κ i B( x) Zt SΦ
κ ph = k B T ∫ dx Eq 5.9 overestimates the influence of
0
3πℏk κ i a 2 d + k B TD B( x) Zt SΦ
−1
B
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that affect the phonon hopping from one grain into another. Since the in-grain
phonon-phonon scattering affects only the density of the phonon states inside the
grain, but it does not change the thermal conductivity.
The radiative component alone causes an increase of TC at high temperatures. This
k B4T 3 ∞ x 4 dx
follows from κ r = ∫ Eq 5.15, if Ne is independent of
3π 2 cℏ 3 2πN e e 2 / m * 0
x (e x − 1) 2
specimen FD1/3; however, its value is comparable with the experimental errors. The
grain size dependence of TC following from
1/ θ κ i B( x) Zt SΦ
κ ph = k B T ∫ dx Eq 5.9 is close to that estimated with
0
3πℏk κ i a 2 d + k B TD B( x) Zt SΦ
−1
B
κi
κ ph = Eq 5.17
κi
1+
Gk d
κi
Where Gk is the Kapitza conductance. Indeed, κ ph = Eq 5.17 results
κi
1+
Gk d
1/ θ κ i B( x) Zt SΦ
from κ ph = k B T ∫ dx Eq 5.9, if we substitute x by its
0
3πℏk κ i a 2 d + k B TD B( x) Zt SΦ
−1
B
k B2TD Zt SΦ (σ )B ( x )
Gk = Eq 5.18
3πℏa 2 d 2
In particular, at low temperatures when κi>>κph this expression accepts the form
k B2TD Zt SΦ (σ ) 1 / θ
3πℏa 2 d 2 ∫0
Gk = B ( x)dx Eq 5.19
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the influence of the small size pores. Indeed, this value should be equal to d 2 in the
absence of pores. If we assume a cubic shape of grains and suppose the pores lie
along the cube edges then for the porosity we obtain
3π d − x 4 d − x
2
p= 1 − 9 d Eq 5.20
4 d
Where x is the “neck” size ( S = x 2 ). For the model of spherical grains such an
estimation has been carried outlxii. The main deviation of both estimations is due to
the large size pores, i.e., the pores of about or greater than the grain size. To
estimate their influence, we have to remove some resistors from our net, so that their
resistivity becomes equal to infinity; this means the absence of the neighbours for
some grains due to the large scale porosity. This factor can be related to the
cohesion C of each sample, which can be measured experimentally. Cohesion is an
average ratio of the number of boundaries grain/pore to the number boundaries
grain/grain along some straight line in the TEM pattern. Assuming a homogeneous
distribution of the pores, we can estimate the density of the nonremoved resistors in
the net as
C
η= Eq 5.21
2−C
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5.3 References
P.G. Klemens, M. Gell, Thermal conductivity of thermal barrier coatings, Materials
Science and Engineering A245 (1998), p.p. 143-149
L. Braginsky, V. Shklover, H. Hofmann, P. Bowen, High-temperature thermal
conductivity of porous Al2O3 nanostructures, Physical review B 70, 134201 (2004)
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6 THERMODYNAMIC
6.1 Nanothermodynamics
With the advancement of techniques of creating and characterizing materials, a huge
of ‘‘small’’ sizes grains (micrometers), nanosystems, molecular magnets, and atomic
clusters, has been formed and displays a variety of interesting physical and chemical
properties. It is important and timely to develop the new theoretical tools to address
experimental findings. On the other hand, the rapid progress in the synthesis and
processing of materials with the structures at the nanometer size has created a
demand for greater scientific understanding of the thermodynamics on nanoscale.
The issue of application of the thermodynamics on nanoscale has been continuously
attracted, since the nucleation reaction was discovered in the early 1930s. For
instance, a good example is the renowned publication of two books with the title
‘‘Thermodynamics of Small Systems’’ by Hill in early 1960s, and recently, the
thermodynamics of small systems is renamed ‘‘nanothermodynamics’’.
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decreases, one has to consider the fluctuations. Based on the nucleation reactions,
the first considerations are on the temperature fluctuations. The quantitative
measurements of temperature fluctuations were realized by superconducting
magnetometers. Interestingly, it is well explained in the following statement by the US
National Initiative on Nanotechnology that the fluctuations play an important role:
‘‘There are also many different types of time scales, ranging from 10-15 s to several
seconds, so consideration must be given to the fact that the particles are actually
undergoing fluctuations in time and to the fact that there are uneven size
distributions. To provide reliable results, researchers must also consider the relative
accuracy appropriate for the space and time scales that are required; however, the
cost of accuracy can be high. The temporal scale goes linearly in the number of
particles N, the spatial scale goes as O(N log N), yet the accuracy scale can go as
high as N7 to N! with a significant prefactor.’’ Therefore, these valuable hints motivate
researchers to pursue the thermodynamic description at the nanometer size for the
nucleation of the metastable phase. Up to date, there are two kinds of fundamental
approaches to open out the thermodynamics on nanoscale based on the microscopic
and macroscopic viewpoints, respectively. One would go back to the fundamental
theorem of the macroscopic thermodynamics and establish the new formalism of the
nanothermodynamics by introducing the new function(s) presenting the fluctuations
or the surface effect of nanosystems. Another one could directly modify the equations
of the macroscopic thermodynamics and establish the new model of the
thermodynamics on nanoscale by incorporating the Laplace–Young or Gibbs–
Thomson relation presenting the density fluctuation of nanosystems in the
corresponding thermodynamic expressions. The fundamental outlines of these
approaches will be given in the following section.
In the early 1960s, Hill addressed the subject of the thermodynamics of small
systems due to his interest in thermodynamics of polymers and macromolecules. In
order to clarify the relationship between the macroscopic thermodynamics and the
nanothermodynamics of Hill, first of all, go back to the fundamental theorem and
recapitulate the foundations of the thermodynamics of macroscopic systems.
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Where S is the entropy (an extensive state function), and it is a function of the
extensive variables (U, V, N) in one-component system, T the absolute temperature,
P the pressure, V the volume, µ the chemical potential, and N is the number of
particles. The differential form of Eq. U(S, V, N) = TS - PV + µN (6. 28) may be
represented as
∂U
µ = (6. 30)
∂N S ,V
∂U
T = 6. 31)
∂S N ,V
∂U
P = − (6. 32)
∂V S , N
Eq. dU = SdT + TdS – VdP – PdV + Ndµ + µdN (6. 29) will change into the
∂U
following form by employing one of the above three equations µ = (6.
∂N S ,V
∂U
30)- P = − (6. 32).
∂V S , N
This is the celebrated Gibbs–Duhem relation, and implies that the changes in the
intensive quantities (µ, T, P) are not independent. However, the usual choice (T, P) is
made in the literature, defining an equation of the state for the system. In particular,
the Gibbs–Duhem relation implies that
∂µ V
= (6. 34)
∂P T N
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and
∂µ S
=− (6. 35)
∂T P N
It is well known that three other functions, besides the internal energy, U, are very
useful in applications to the specific physical situations.
The enthalpy is
∂T ∂P
= − (6. 40)
∂V S ∂S V
∂T ∂V
= (6. 41)
∂P S ∂S P
∂S ∂P
= (6. 42)
∂V T ∂T V
and
∂S ∂V
= − (6. 43)
∂P T ∂T P
If one combines eq. dU = SdT + TdS – VdP – PdV + Ndµ + µdN (6. 29) with SdT –
VdP + Ndµ = 0 (6. 33) we have the following Gibbs generalized relation
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For example, if the system is a small one-component spherical aggregate that has a
nonnegligible surface free energy term proportional to N2/3, equation
dU = TdS − PdV + ∑ µ i dN i (6. 44) is no longer applicable. This equation can be
i
generalized further to include small systems, by adding another term. But this
addition must be made at the ensemble level rather than at the single-system level.
The reason for this is that an ensemble of B equivalent and noninteracting small
systems is itself a macroscopic system, and hence we can use equation
dU = TdS − PdV + ∑ µ i dN i (6. 44), rewritten for an ensemble, as a reliable
i
starting point:
dU t = TdS t − PdVt + ∑ µ i dN it
i
Ut ≡ BU
St ≡ BS
Vt ≡ BU
Where E ≡ (∂ Ut/ ∂ B)St,Vt,Nit. The motivation is that, for a small system, Ut will also be
a function of B. E is a kind of system (rather than molecule) chemical potential, called
the “sub-division potential.” If the systems of the ensemble are macroscopic and are
subdivided in order to increase B in eq dU t = TdS t − PdVt + ∑ µ i dN it + EdB (6.
i
46) (e.g., in an extreme case, each system is cut in half to double B ), this will not
have a noticeable effect on Ut, St, Vt, Nit are all held constant as in E ≡ (∂ Ut/ ∂ B).
That is, surface effects, edge effects, system rotation and translation, etc., are all
negligible for macroscopic systems, and hence E is essentially zero: the term E d B
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to the equation. But the effects just mentioned are not negligible if an ensemble of
small systems is subdivided to increase B in eq dU t = TdS t − PdVt + ∑ µ i dN it + EdB
i
Here, new equivalent small systems are added to create the ensemble (subdivision is
not used). Division by B then yields, for a single small system,
U = TS − PV + ∑ µ i N it + E (6. 48)
i
BdU + UdB , and similarly for dSt, dVt, dNit the terms in dB drop out in view of eq
U = TS − PV + ∑ µ i N it + E (6. 48). The remaining equation is (for a single small
i
system)
small system has the same energy-heat-work relation as in a macrosystem (with the
Ni constant) and also the same chemical potential terms. However, eq
dU = TdS − PdV + ∑ µ i dN i (6. 49) cannot be integrated to give eq
i
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The left-hand side is zero in macroscopic thermodynamics. Note that T, P, and the µi
are all independent in eq dE = − SdT + VdP − ∑ dµ i N i (6. 50). A macrosystem has one
i
∂E
−S =
∂T p ,µi
∂E
V = (6. 51)
∂P T , µi
∂E
N i =
∂µ i T , p , µi
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associated with translation, rotation, and the vibrational motion of and within the
molecules of the chain. Now suppose, in contrast, that the bath includes the
individual molecules at chemical potential µ and that these molecules can go on and
off the two ends of the aggregate. At equilibrium, there will be a mean number N of
molecules in the aggregate. The environmental variables here are µ and T. If µ is
chosen so that N in the µ, T case is the same as N in the N, T case above, the
entropy S will be larger in the µ, T case because of fluctuations in N that are not
present in the N, T case. However, this extra entropy becomes negligible as the
aggregate approaches macroscopic size (by adjusting µ).
To study such effects using theoretical models, the applicable set or sets of
environmental variables must play a primary role. For given environmental variables,
the particular statistical mechanical partition function appropriate for these variables
must be chosen in order to deduce the thermodynamic properties associated with
these environmental variables. This is in contrast with the treatment of macroscopic
systems: the partition function used is optional and can be selected merely for
convenience.
It is interesting that the basic equations of nanothermodynamics are the same for all
sets of environmental variables but the thermodynamic properties are often not the
same.
It is worth noting that Chamberlin et al. have extended Hill’s idea by considering the
independent thermal fluctuations inside bulk materials. In detail, they adapt Hill’s
theory to obtain a mean-field model for the energies and size distribution of clusters
in condensed matter. Importantly, the model provides a common physical basis for
many empirical properties, including non-Debye relaxation, non-Arrhenius activation,
and non-classical critical scaling
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from Hill’s approach by considering that each of the nanosystems fluctuates around
the temperature of the reservoir, while nanosystems are coupled to the reservoir.
This means that the Boltzmann–Gibbs distribution has to be averaged over the
temperature fluctuations induced by the reservoir.
The formalism of nonextensive statistical mechanics has been developed over the
past 13 years as a powerful and beautiful generalization of ordinary statistical
mechanics. It is based on the extremization of the Tsallis entropies:
1
Sq = 1 − ∑ p iq (6. 52)
q −1 i
subject to suitable constraints. Here the pi are the probabilities of the physical
microstates, and q is the entropic index. The Tsallis entropies reduce to the
Boltzmann Gibbs (or Shannon) entropy S1 = −∑ p i log p i for q → 1, hence ordinary
i
Hence there is additivity for q = 1 only. This property has occasionally lead to
unjustified prejudices, using arguments of the type “entropy must be extensive”. In
the following, however, we will see that the nonadditivity property is not at all a “bad”
property, but rather a natural and physically consistent property for those types of
systems where nonextensive statistical mechanics is expected to work.
Broadly speaking, the formalism with q ≠ 1 has so far been observed to be relevant
for two different classes of systems. One class are systems with long-range
interactions, the other one are systems with fluctuations of temperature or of energy
dissipation. For the first class of systems, the concept of independent subsystems
does not make any sense, since all subsystems are interacting. Hence there is no
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where
1
β
1
1 1 q −1 q −1−1
f (β ) = β exp −
(q − 1)β 0
(6. 55)
1 (q − 1)β 0
Γ
q −1
is the probability density of the χ2 distribution. The above formula is valid for arbitrary
Hamiltonians H and thus of great significance. The left-hand side of eq.
∞
(1 + (q − 1)β 0 H )
1
−
q −1 = ∫ e − βH f ( β )dβ (6. 54) is just the generalized Boltzmann
0
q < 1. However, in that case the distribution function f(β) is more complicated and
1
β
1
1 1 q −1 q −1−1
different from the simple form f ( β ) = β exp −
1 (q − 1)β 0 (q − 1)β 0
Γ
q −1
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(6. 55). In particular, for q < 1 one has f(β) = f(β,H), i.e. the probability density
of the fluctuating temperature also depends on the Hamiltonian H. This is physically
less plausible, because usually one assumes that the heat bath is independent of the
Hamiltonian. Hence in the following we will restrict ourselves to the physically more
interesting case q > 1.
For q > 1, the χ2 distribution obtained in eq.
1
β
1
1 1 q −1 q −1−1
f (β ) = β exp − (6. 55) is a universal distribution
1 (q − 1)β 0 (q − 1)β 0
Γ
q −1
that occurs in many very common circumstances. For example, it arises if β is the
sum of squares of n Gaussian random variables, with n = 2/(q−1). Hence one
expects Tsallis statistics with q > 1 to be relevant in many applications. For fully
developed turbulent hydrodynamic flows, where Tsallis statistics has been observed
to work very well, β−1 is not the physical temperature of the flow but a formal
temperature related to the fluctuating energy dissipation rate times a time scale of the
order of the Kolmogorov time. In the application to scattering processes in collider
experiments, β−1 is a fluctuating inverse temperature near the Hagedorn phase
transition.
1
β
1
1 1 q −1 q −1−1
The constant β0 in eq. f ( β ) = β exp − (6.
1 (q − 1)β 0 (q − 1)β 0
Γ
q −1
55) is the average of the fluctuating β,
∞
E ( β ) = ∫ βf ( β )dβ = β 0 (6. 56)
0
(E denotes the expectation with respect to f(β)). The deviation of q from 1 can be
related to the relative variance of β. One has
E(β 2 ) − E(β ) 2
q −1 = (6. 57)
E (β ) 2
We can now give physical meaning to eq. S qΙ +ΙΙ = S qΙ + S qΙΙ − (q − 1) S qΙ S qΙΙ (6. 53) for q
> 1. Consider two independent subsystems Ι and ΙΙ that are composed into one
system Ι + ΙΙ . In system Ι (as well as ΙΙ ) the fluctuations of temperature T are
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S qΙ +ΙΙ = S qΙ + S qΙΙ − (q − 1) S qΙ S qΙΙ (6. 53) . It is physically plausible that this correction
term is proportional
• to the relative strength of temperature fluctuations as given by q − 1 and
• to the entropies in the single S qΙ and S qΙΙ systems. Hence we end up with eq.
For most physical applications the fluctuations of β (or the relevant value of q) are
observed to be dependent on the spatial scale r. For example, in the turbulence
application detailed measurements of q(r) have been presented in []. q turns out to
be a strictly monotonously decreasing function of the distance r on which the velocity
differences are measured. Similarly, for the application to e+e− annihilation, q(r) turns
out to be again a strictly monotonously decreasing function of the scale r, which in
this case is given by r ∼ ћ/Ecm, where Ecm is the center-of-mass energy of the beam.
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spontaneous formation of the critical nucleation of the new phase. For this reason, W
is the energy barrier (critical energy of cluster formation, ∆G*) of the nucleation.
Therefore, the nucleation work plays an important role in the formation of a new
phase. However, it is well known that the initially homogeneous system is also
heterogeneous in characterized by the non-uniform density and pressure. Therefore,
the determination of ∆G* is a hard problem. Namely, the case above makes it
impossible to derive the nucleation work only from the method of the thermodynamics
of uniformly dense phases. In CNT (Classical Nucleation Theory), the critical nucleus
is regarded as a liquid drop with a sharp interface (a dividing surface) that separates
the new and parent bulk phases. Matter within the dividing surface is treated as a
part of a bulk phase whose chemical potential is the same as that of the parent
phase. In the absence of knowledge of the properties of the microscopic clusters
including the surface tension, the bulk thermodynamic properties with several
approximations are used to evaluate the nucleation work in the discussions below.
In 1878, Gibbs published his monumental work with the title ‘‘On the Equilibrium of
Heterogeneous Substances,’’ and his other publications have a special place in
thermodynamics of the phase’s mixture and equilibrium. Concretely, Gibbs extended
the science of thermodynamics in a general form to heterogeneous systems with and
without chemical reactions. Especially, he introduced the method of the dividing
surface (DS) and used it to derive an exact formula for ∆G* in the nucleation of a new
phase in the bulk parent phase. In detail, with the aid of an arbitrarily chosen
spherical DS, he divided the heterogeneous system consisting of the density
fluctuation and the parent phase into two homogeneous subsystems, which are
corresponding to the microscopical and macroscopical subsystems, respectively. The
macroscopically large subsystem equals the parent phase with the uniform density
and pressure before the fluctuation formed. The microscopically small subsystem is
an imaginary particle (nucleus) replaced a reference new phase with the uniform
density and pressure, and surrounded by the large subsystem. The imaginary particle
substitutes for the real nucleus of the new phase, which is created by the density
fluctuation. As Gibbs described the difference between the imaginary particle (globule
by Gibbs definition) and the density fluctuation by the following statement: ‘‘For
example, in applying our formulas to a microscopic globule of water in steam, by the
density or pressure of the interior mass we should understand not the actual density
or pressure at the centre of the globule, but the density of liquid water (in large
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quantities) which has the temperature and potential of the steam.’’ Furthermore, very
recently, Kashchiev detailedly expatiated the difference between the imaginary
particle and the real density fluctuation by the following statement:
I. ‘‘the nucleus size depends on the choice of the DS and may therefore be very
different from the characteristic size of the density fluctuation;
II. the surface layer of the nucleus is represented by the mathematical DS and is
thus with zero thickness, whereas that of the density fluctuation is diffuse and
can extend over scores of molecular diameters;
III. the pressure and molecular density of the nucleus are uniform, and those of
the fluctuation are not and might even be hard to define when ‘at its centre the
matter cannot be regarded as having any phase of matter in mass;
IV. the uniform pressure and density of the nucleus are equal to those of a
reference bulk new phase rather than to those at the center of the fluctuation.’’
Therefore, based on these approaches above, Gibbs showed that the reversible work
W (free energy of nucleation), required to form the critical nucleus of a new phase, is
Where A and V are the area and volume of the specific surface energy of a specially
chosen DS, Pl the pressure of the new bulk reference phase at the same chemical
potential as the parent phase, and Pv is the pressure of the parent phase far from the
nucleus. γT is the ‘‘surface of tension,’’ called by Gibbs, of the specific surface energy
of a specially chosen DS, and it is called as the surface tension at the present day.
In the Gibbs’ analysis, he found out that the classical Laplace–Young equation is
valid in his DS, and governs the pressure of droplets across a curved interface. For a
spherical droplet with the critical nucleus radius r*, the Laplace–Young equation
reads
2γ T
Pl − Pv = (6. 59)
r*
2γ T
Further, for the spherical critical nucleus, Gibbs showed that with eq. Pl − Pv =
r*
(6. 59), eq. ∆G* = Aγ T − V ( Pl − PV ) (6. 58) becomes
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16π γ T3
∆ G* = (6. 60)
3 ( Pl − Pv ) 2
16π γ3
∆G* = (6. 61)
3 ( Pl − Pv ) 2
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µ l ( Pl ) − µ l ( Pv ) = ∫ Vm dP (6. 62)
Pv
Where Vm is the molar volume of a new phase and µl ( Pl ) and µl ( Pv ) are the chemical
potential of matter in the new phase at the pressures Pl and Pv. When the critical
droplet and the metastable vapour locate the condition of the unstable equilibrium,
one can obtain
µ v ( Pv ) = µ l ( Pl ) (6. 63)
µ v ( Pv ) − µ l ( Pl ) ∆µ
Pl − Pv = = (6. 64)
Vm Vm
µ v ( Pv ) − µ l ( Pl ) ∆µ 16π γ3
Eq. Pl − Pv = = (6. 64) turns into Eq. ∆G* =
Vm Vm 3 ( Pl − Pv ) 2
(6. 61), one can obtain the second form of the nucleation work
16π γ 3Vm2
∆ G* = (6. 65)
3 ( ∆µ ) 2
As Obeidat et al. stated [], the form of the nucleation work is most useful if the
chemical potential difference between a new phase and its parent phase can be
obtained. However, the actual performance is quite complicated due to the lack of the
accurate potentials for most substances. In order to obtain the ∆µ, we have to adopt
some necessary approximations. Generally, if we assume the supersaturated and
saturated vapors are the ideal gases and the droplet is an incompressible liquid, the
difference of the chemical potential ∆µ is more commonly derived from the
approximate system. In detail, under the above assumptions, we have
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Where Pev is the equilibrium-vapor pressure. With eq. Pl = Pev (6. 66),
Pl
When the new bulk phase and the parent phase are in the state of thermodynamic
equilibrium, one can obtain
With eqs. µ l ( Pv ) = µ v ( Pev ) + Vm ( Pv − Pev ) (6. 67) and µ l ( Pev ) = µ v ( Pev ) (6. 68), eq.
µ v ( Pv ) − µ l ( Pl ) ∆µ
Pl − Pv = = (6. 64) becomes
Vm Vm
Pv
µ v ( Pv ) − µ v ( Pev ) = kT ln (6. 70)
Pev
Where k is the Boltzmann constant, T the absolute temperature, and Pv is the actual
P
pressure. With Eq. µ v ( Pv ) − µ v ( Pev ) = kT ln v (6. 70),
Pev
Eq. ∆µ = µ v ( Pv ) − µ v ( Pev ) − Vm ( Pv − Pev ) (6. 69) becomes
P
∆µ = kT ln v − Vm ( Pv − Pev ) (6. 71)
Pev
P
In Eq. ∆µ = kT ln v − Vm ( Pv − Pev ) (6. 71), compared with the first term on the
Pev
right, the second term on the right is almost extremely small, and it is customary to
16π γ 3Vm2
neglect it. Therefore, Eq. ∆G* = (6. 65) will become the third form of
3 ( ∆µ ) 2
the nucleation work
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16π γ 3Vm2
∆G* = (6. 72)
3 P
kT ln v
Pev
Applying the first two forms of the nucleation work requires the knowledge of the
droplet reference pressure or chemical potential. Usually, this information is
unavailable, and the experimental results are, instead, compared with the rates
predicted using the third form, because the supersaturation ratio is readily
determined from the experimental data. Naturally, the size of the critical nucleation,
the critical energy, the phase transition probability, and the nucleation rate would be
obtained by the determined nucleation work.
In summary, from the point of CNT above, one can see that there is an important
approximation, i.e., assuring γT = γ0 = γ. Namely, the surface tension (γT) of a
specially chosen DS, the real interface energy (γ0) between the bulk parent and new
phases at the phase equilibrium, and the experimental interface energy of a flat
interface (γ) are approximated to equal. Furthermore, CNT indicates that the
Laplace–Young equation seems to be capable of predicting well the size of nuclei
built up of less than a few tens of molecules. However, on the other hand, it is well
known that the CNT describes that a stable new phase forms from a metastable
parent phase.
MPNUR, such as CVD (Chemical Vapor Deposition) diamond, CVD c-BN, HSRC
(Hydrothermal Synthesis and the Reduction of Carbide) diamond, and c-BN (cubic
boron nitride) nucleation, seems to be impossible from the standpoint of
thermodynamics, because the nucleation happens in the strongly unstable region of
the metastable structural state in terms of the thermodynamic equilibrium phase
diagram, and violates the second law of thermodynamics. For this issue, as Hwang
and Yoon stated regarding CVD diamond [], ‘‘Something must be wrong either in
interpreting the experimental observation or in applying thermodynamics.’’ In fact, in
the early 1965s, Garvie pointed out that MPNUR likely arises out of the capillary
pressure built up in the nuclei. Namely, the nanosize-induced additional pressure
could be so large that the high-pressure metastable phase tends to become more
stable than the low-pressure stable phase, as shown in Figure 6-1.
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Figure 6-1 : A sketch map of MPNUR mechanism. A region is the metastable structural state of M
phase, and B region is the new stable state of M phase by the nanosize-induced additional pressure
driving. The inset shown in the sketch map displays the spherical nuclei nucleated on the hetero-
substrate. [C.X. Wang, G.W. Yang, Thermodynamics of metastable phase nucleation, Materials
Science and Engineering, 2005, p.p. 157-202]
VS
∆G (r , P, T ) = × ∆g + ( Ane γ ne + Asn γ sn − Ase γ se ) (6. 73)
Vm
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Where Vs and Vm are the volume of the spherical clusters with the metastable
structural phase and its molar volume, ∆g the Gibbs free energy of molar volume
depending on the pressure P and temperature T in the phase transition, Ane and γne
the interface area and the energy between the spherical clusters of the metastable
structural phase and the environment gas phase, Asn and γsn the interface area and
the energy between the spherical clusters of the metastable phase and the hetero-
substrate, and Ase and γse are the interface area and the energy between the hetero-
substrate and the environment gas phase. The formation of the spherical clusters
with the metastable structural phase produces two interfaces, i.e., the interface Ane
between the spherical clusters and the environment gas phase and the interface Asn
between the spherical clusters and the hetero-substrate, and makes the original
interface Ase (be equal to Asn) between the hetero-substrate and the environment
gas phase vanish. According to the geometry, the volume Vs of the spherical clusters
of the metastable structural state, the interface area Ane between the spherical
clusters of the metastable state and the environment gas phase, and the interface
area Asn between the spherical clusters and the hetero-substrate are expressed as
πr 3 (2 + m )(1 − m )2
Vs = (6. 74)
3
γ se − γ sn
m = cos θ = (6. 77)
γ ne
Where θ is the contact angle between the spherical clusters of the metastable
structural state and the hetero-substrate, as shown in the inset of Figure 6-1. Here,
γne is assumed to be approximately equal to the surface tension value of the
metastable structural phase (γ), γse for the interface energy between the hetero-
substrate and the environment gas phase is taken to be equal to the surface tension
value of the hetero-substrate, and the interface between the spherical clusters and
the hetero-substrate is assumed to be incoherent interface; therefore
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γ ne + γ se
γ sn = (6. 78)
γ ne
4 ∆g (2 + m )(1 − m )2
∆G (r , T , P, T ) = πr 3 × + 4πr 2γ (6. 79)
3 Vm 4
f (θ ) =
(2 + m)(1 − m )2 (6. 80)
4
is called as the heterogeneous factor, and its value is in the range of 0–1. Especially,
when the clusters nucleated on the homo-substrate, its value is 1.
According to thermodynamics, we have
∂∆g (T , P )
= ∆V (6. 81)
∂P T
Then the difference of the Gibbs free energy per mole can be defined by
∆g (T , P ) − ∆g (T , P0 ) = ∫ 0 ∆VdP ≈ ∆V ( P − P O ) = ∆V × ∆P
P
(6. 82)
P
Where ∆V is the mole volume difference between the metastable and the stable
phase. When the conditions are near the equilibrium line, one can approximately
∆g (T , P ) = ∆V × ∆P (6. 83)
On the other hand, due to the nanosize-induced additional pressure ∆Pn, the clusters
enduring pressure will increase by the same amount. Under the assumptions of
spherical and isotropic clusters, the nanosize-induced additional pressure is denoted
by the Laplace–Young equation, i.e.
2γ
∆P n = (6. 84)
r
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obtain the size-dependent equilibrium phase boundary line between the metastable
and the stable phases, and it can be approximately defined as
2γ
P = Pb − (6. 85)
r
Where Pb is the equilibrium phase boundary equation between the metastable and
the stable phases. From Figure 6-1, one can see that the equilibrium phase boundary
between the metastable and the stable phases can be expressed by
P b = k 0T + b0 (6. 86)
Where k0 and b0 are the slope and intercept in the P coordinate axis of the
equilibrium phase boundary line between the metastable and the stable phases. With
2γ
Eq. P b = k 0T + b0 (6. 86), Eq. P = P b − (6. 85) can be defined as
r
2γ
P = k 0T + b0 − (6. 87)
r
2γ
∆P = P − k 0T − b0 + (6. 88)
r
2γ
With Eq. ∆P = P − k 0T − b0 + (6. 88), Eq. ∆g (T , P ) = ∆V × ∆P (6. 83) can be
r
denoted by
2γ
∆g (T , P ) = ∆V × P − k 0T − b0 + (6. 89)
r
2γ
With Eq. ∆P = P − k 0T − b0 + (6. 88), Eq.
r
4 ∆g (2 + m )(1 − m )2
∆G (r , T , P, T ) = πr 3 × + 4πr 2γ (6. 79) can be expressed as
3 Vm 4
2γ
∆V × P − k 0T − b0 +
∆G (r , P, T ) = πr ×
4 3 r 2
+ 4πr γ f (θ ) (6. 90)
3 Vm
∂∆G (r )
When = 0 , the critical size of the high-pressure phase is obtained as
∂r
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2 V
2γ + m
3 ∆V
r* = (6. 91)
k 0T + b0 − P
2 V
2γ + m
3 ∆V
Substituing Eq. r * = (6. 91) into
k 0T + b0 − P
2γ
∆V × P − k 0T − b0 +
Eq. ∆G (r , P, T ) = πr ×
4 3 r 2
+ 4πr γ f (θ ) (6. 90), the critical
3 Vm
energy of the high-pressure phase nuclei is given by
2 V
3
2 Vm
2
2γ + m
2γ +
4 3 ∆V ∆V + − ∆
( )
∆G r , P, T = π
*
×
k
P − k T −b + 0 T
2 ∆V
b0 P + 4π
3 V
k T + b0 − P
f (θ )
3 k 0T + b0 − P Vm
0 0
+ 0
3 Vm
6. 92)
On the other hand, it is well known that the phase transition is determined by the
probability. We have studied the nanosize effect on the probability of the phase
transformation based on the thermodynamic equilibrium phase diagram. The
probability of the phase transformation from the metastable phase to the stable
phase is related not only to the Gibbs free energy difference ∆g(T, P), but also to an
activation energy (Ea - ∆g(T, P)), which is necessary for the phase transition, as
shown in Figure 6-2.
Figure 6-2 : The schematic diagram of Gibbs free energy vs. coordinate. [C.X. Wang, G.W. Yang,
Thermodynamics of metastable phase nucleation, Materials Science and Engineering, 2005, p.p. 157-
202]
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E − ∆g (T , P) E
f = exp − a − exp − a (6. 93)
RT RT
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Figure 6-3 : Carbon thermodynamic equilibrium phase diagram. The G region means a
metastable phase region of the diamond nucleation upon CVD; the D region means a new stable
phase region of the CVD diamond nucleation with respect to the effect of the nanosize-induced
additional pressure. The inset shows the relationship between the nanosize-induced additional
pressure and the nuclei size. [C.X. Wang, G.W. Yang, Thermodynamics of metastable phase
nucleation, Materials Science and Engineering, 2005, p.p. 157-202]
It is well known that the graphite nucleation would be prior to diamond nucleation in
the G region from the point of view of thermodynamics. Therefore, the diamond
nucleation would not happen unless the graphite nucleation is restrained or stopped.
For the issue, the most popular explanation is that the atomic hydrogen plays an
important role. Atomic hydrogen is an essential factor in CVD diamonds due to its
higher etching rate for the graphite phase and less etching rate for the diamond
phase. Unfortunately, some researchers have reported that diamond films are grown
upon CVD with a hydrogen-free environment. Further, Gruen [] concluded that CVD
diamonds do not require the reactant gas mixtures consisting primarily of hydrogen,
and the microstructure of diamond films can change continuously from micro- to
nanocrystalline when hydrogen is successively replaced by a noble gas such as
argon. Moreover, they pointed out that a chief function of the atomic hydrogen is to
reduce the secondary nucleation rates. Therefore, these experiments clearly indicate
that, besides enhancing the growth of the diamond nuclei, the atomic hydrogen may
have little function for the diamond primary nucleation. Our question is: would the
diamond nucleation be really in the strongly unstable region of the diamond structural
phase upon CVD?
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The nucleation of CVD diamonds should happen in the D region of Figure 6-3 on the
basis of the nanosize-induced additional pressure. When we assume the surface
tension of diamond is 3.7 J/m2, the dependence relationships of the nanosize-
induced additional pressure based on the Laplace–Young equation and the size of
diamond clusters can be obtained, as shown in the inset of Figure 6-3. From the
inset, one can see that the additional pressure increases with the crystal particle’s
size decreasing. Notably, when the radius is less than 4 nm, the additional pressure
goes up to above 2.0 GPa, which is above the phase equilibrium line shown as the D
region, i.e., the diamond stable region, in Figure 6-3. In other words, the nanosize-
induced additional pressure could drive the metastable region (G region) of the
diamond nucleation into the new stable region (D region) in the thermodynamic
equilibrium phase diagram of carbon. These deductions are supported by the
experimental cases from the CVD diamonds on non-diamond substrates. For
instance, Lee et al. reported that the size of the nuclei of CVD diamonds on Si
substrates is in the range of 2–6 nm []. Consequently, the nanosize-induced
additional pressure of 1–3 nm radius of the diamond nuclei would be enough to drive
the G region into the D region. Therefore, the nucleation of CVD diamonds should
happen in the D region based on our nanothermodynamic approach.
2γ
∆V × P − k 0T − b0 +
According to Eq. ∆G (r , P, T ) = πr ×
4 3 r 2
+ 4πr γ f (θ ) (6.
3 Vm
90), γ = 3.7 J/m2, Vm = 3.417x10-6 m3 mol-1, ∆V = 1.77x10-6 m3 mol-1, k0 = 2.01x106,
and b0 = 2.02x109 Pa, one can obtain the relationship curves between the size of the
diamond critical nuclei and the pressure at the temperature of 1300 K upon the CVD
diamond case, and it is displayed in Figure 6-4, in which the inset shows the
dependent relations of the pressure and the critical radius at the given various
temperatures.
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Figure 6-4 : The relationship curves between the radii of the critical nuclei and the pressure at the
temperature of 1300 K upon CVD systems. The inset shows the dependence relation of the pressure
and the critical radii at given various temperatures. One can see that, in faith, the radii of the critical
nuclei of diamond upon CVD for a broad range of pressures and temperatures are less than 5 nm.
Namely, the nucleation of CVD diamond could occur in the stable phase region of diamond. [C.X.
Wang, G.W. Yang, Thermodynamics of metastable phase nucleation, Materials Science and
Engineering, 2005, p.p. 157-202]
Clearly, we can see that the radii of the critical nuclei are less than 5 nm in a broad
range of the pressure and temperature. The diamond nucleation upon CVD seems to
be in the stable phase region of diamond due to the driving of the nanosize-induced
additional pressure of the diamond nuclei. In addition, from this figure, one also can
see the very weak dependence of the pressure on the critical radius. In other words,
at the given temperatures, the critical radii are hardly changed with the external
pressure change, because the external pressure is quite small compared with the
nanosize-induced additional pressure.
2 V
2γ + m
3 ∆V
Based on Eq. r * = (6. 91), the value of the surface tension of silicon
k 0T + b0 − P
(1.24 J/m2), and the given parameters above, we display the relationship curves
between the pressure and the critical energy of CVD diamonds at the temperature of
1200 K, as shown in Figure 6-5, in which the inset displays the dependent relations
of the pressure on the critical energy at the given various temperature.
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Figure 6-5 : The relationship curves between the pressure and the critical energy of the nucleation
upon CVD diamond at the temperature of 1200 K, and the inset showing the curves at various given
temperatures. [C.X. Wang, G.W. Yang, Thermodynamics of metastable phase nucleation, Materials
Science and Engineering, 2005, p.p. 157-202]
Obviously, one can see in Figure 6-5 that the critical energy of the diamond nuclei
slowly increases with the pressure increasing at a given temperature, and
approximately remains as unchanged. The case results from the too little external
pressure compared with the nanosize-induced additional pressure. These results
indicate that the critical energy of the diamond nucleation upon CVD is quite low
(10-16 J), suggesting that the heterogeneous nucleation of CVD diamonds does not
require high forming energy.
Apparently, the low forming energy of the heterogeneous nucleation of CVD
diamonds implies that it is not difficult to nucleate diamond, and the diamond
nucleation could happen in the diamond stable region (G region) as shown in Figure
6-3. Based on the analyses above, the diamond nucleation upon CVD would happen
in the diamond stable region in the carbon phase diagram from the point of view of
thermodynamics. In fact, when the size of the crystalline particles is in the nanometer
scale, the additional pressure induced by the curvature of the nanometer-sized
particles is so high as to exceed the equilibrium pressure between diamond and
graphite, i.e., going up to break through the phase equilibrium boundary line, which
means that the additional pressure could drive the thermodynamic phase region of
the diamond nucleation from the metastable to the stable as shown in Figure 6-3.
Therefore, the diamond nucleation upon CVD is not actually the ‘‘thermodynamic
paradox,’’ and ‘‘violating the second law of thermodynamics.’’ These results indicate
that the presence of the atomic hydrogen is not a vital factor to grow diamonds upon
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CVD from the viewpoint of the nanothermodynamics above. However, why did most
experimental studies all show that the atomic hydrogen plays a very important role in
CVD diamonds? In fact, it is recognized experimental evidence that the atomic
hydrogen etching the graphite phase (more etching rate to the graphite phase and
less etching rate to the diamond phase) and helping the sp3 hybridization of carbon
atoms. Naturally, the diamond nucleation could be enhanced in the low-pressure gas,
only when the graphite phase forming is restrained or stopped by the atomic
hydrogen or other factors. Thus, the presence of the atomic hydrogen could increase
the rates of the diamond growth. Accordingly, the effect of the atomic hydrogen on
the diamond growth is much larger than that on the diamond nucleation upon CVD.
In other words, the influence of the atomic hydrogen on the diamond nucleation
would be small from the point of view of the experimental investigations involved in
how to enhance the diamond nucleation upon CVD.
In conclusion, aiming at a clear insight into the nucleation of CVD diamonds, we
studied the diamond nucleation from the point of the view of a nanoscaled
thermodynamics. Notably, these theoretical results show that the diamond nucleation
would happen in the stable phase region of diamond in the thermodynamic
equilibrium phase diagram of carbon, due to the nanosized effect induced by the
curvature–surface tension of the diamond nuclei. In other words, at the nanometer
size, the diamond nucleation is prior to the graphite nucleation in competing growth
of diamond and graphite upon CVD.
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about its effect on the particle). The particle’s temperature will be held constant, and
we will explore the Helmholtz free energy difference between the particle when it has
a liquid layer with a solid core and when it is fully solid. We assume that both the
solid and liquid phases are incompressible. Our interest is the shift of the melting and
freezing points due to finite size effects, so we must include both the surface energy
(γ) and the surface stress (σ). We will assume that both of these surface quantities
are isotropic and independent of particle size and temperature. We will also assume
that the only effect of the matrix will be to vary the surface energies and surface
stresses of the particle. There can be confusion on the use of the terms surface
energy and surface stress. γ is the surface energy and has units of energy per area.
γ times the area is the energy attributed to the surface; it is the energy required to
make new surface. It can also be thought of as the energy of the unsatisfied bonds
on the surface, but as we will see later, it also includes the surface-induced order or
disorder in the bulk of the material. σ is the surface stress and also has units of
energy per area. This is the energy required to alter a given surface by elastically
deforming that surface, including the energy of the stretched or compressed bonds
within the surface. These two surface quantities are related. σ, the surface stress, is
the change in the total energy of the surface with a small change in its area.
d (γA) ∂γ
σ= =γ + A (6. 94)
dA ∂A
For the surface of a liquid the molecules are free to move and therefore cannot
d (γA) ∂γ
sustain a bond stress. Thus, the second term in Eq. σ = =γ + A (6. 94) is
dA ∂A
zero and the surface stress is equal to the surface energy. The final surface will be
just like the original yet there will be more or less of it. Solids can sustain stresses.
d (γA) ∂γ
Thus, the second term in Eq. σ = =γ + A (6. 94) can be significant and is
dA ∂A
of the same order of magnitude as the surface energy. It may be either positive or
negative. The choice of which surface quantity to use depends upon whether new
surface is being created (γ) or an existing surface is being modified (σ).
The free energy of the fully solid particle is
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γ is used because the solid matrix surface must be created, and µ (T, P), a function
of the local temperature and pressure, is the chemical potential per particle. With a
spherical geometry assumed, the surface area (As) and the volume (Vs) are just
functions of the number of atoms in the particle (Ns).
Here, and for the rest of the paragraph, a single subscript will refer to the volume
specified by the subscript, and a double subscript will refer to the surface specified by
the two subscripts. For example, in the above equation, the number of atoms in the
solid volume is Ns the surface area of the solid volume is As and the solid-matrix
surface energy is γsm
The local pressure (P) is the externally applied pressure (P0) plus the increase in
pressure due to the surface. The external pressure (P0) is all pressures except those
that arise from the particle itself. The increase in pressure, using the Laplace-Young
equation for a solid or liquid sphere of radius r, is
σ
P − P0 = 2 (6. 96)
r
The surface stress (σ) is used because the surface is attempting to compress the
particle and change its area. The chemical potential is analyzed about the bulk
melting point (T0) and the externally applied pressure (P0). We will assume that the
externally applied pressure is small enough that there is no shift in the bulk melting
point from standard values. At this reference point, the chemical potential per particle
is the same for the solid and liquid phases. Only first-order terms are kept, to give
∂µ ∂µ
µ (T , P ) = µ (T0 , P0 ) + (T − T0 ) + ( P − P0 ) (6. 97)
∂T ∂P
That is
Where s is the entropy per particle and υ is the volume per particle. The pressure
due to the surface can be significant, but because of the assumed incompressibility
and small linear expansion coefficient, we can neglect second-order terms in
pressure. The second-order term in temperature is at most a few percent of the first-
order terms and will also be neglected. The final free energy of a crystalline particle is
2σ 2σ
Fsolid = µ (T0 , P0 )N s + s s (T − T0 ) N s + υ s sm N s − sm + P0 Vs + γ sm As (6. 99)
rs rs
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2σ 2σ
Fliquid = µ (T0 , P0 )N l + s l (T − T0 ) N l + υ l lm N l − lm + P0 Vl + γ lm Al (6. 101)
rl rl
2σ 2σ sl 2σ 2σ
Fcore = µ (T0 , P0 )N c + s s (T − T0 ) N c + υ s lm + N c − lm + sl + P0 Vc + γ sl Ac
rl rc rl rc
(6. 102)
The volumes ( υ ) and entropies (s) are labeled for the phase (solid or liquid) to which
they apply. Again, surface stress terms cancel. This cancellation of the surface stress
is a result of the assumed incompressibility of the phases. An incompressible
material can have no net work done by changes in the pressure. Therefore, the
change in the chemical potential is countered by another term to leave no net change
in the free energy due to pressure.
The free energy difference between these two situations is now
The total number of atoms is conserved (Nl + NC - Ns) = 0. Entropy terms can be
written as the difference between the liquid and solid entropy per particle and the
number of liquid particles.
− (s l N l + s c N c − s s N s )(T − T0 ) = T0 (s l − s s )N l 1 −
T
(6. 105)
T0
N l − P0 (Vl + Vc − Vs ) + γ lm Al + γ sl Ac − γ sm As
T
∆F = l 0 1 − (6. 106)
T0
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There is a bulk term due to the temperature difference from the bulk value, a volume
change term, and surface terms that are proportional to the surface areas. From
geometrical considerations given below, the PV terms can be rewritten as a function
of Nl.
1 1
− P0 (Vl + Vc − Vs ) = − P0 − N l (6. 107)
ρl ρs
Where ρ is the density (atoms per volume) of the labeled phase. This term is small
compared to the latent heat term and will be neglected. For example, at atmospheric
pressure this is about 10-4 times the latent heat term, unless the temperature is very
near the bulk melting point.
We would like to take into account the ordering or disordering induced by the surface.
Vanfleet and al. took their cue from Van Der Veen and they derived a correction to
the surface energies, due to surface-induced ordering or disordering. A surface will
attempt to propagate its order into the volume of which it forms the surface. The order
will be related to a correction to the energy for each unit of volume. This effect will be
screened by intervening material and is analogous to a screened potential. Using the
screened potential decay of the interaction we will write that the energy, due to the
surface, at a distance r from an area dA will be
−r
exp
ξ
dE ∝ dA (6. 108)
r
Where ξ is the scale length for the screening. The total contribution, at a point, due to
the surface would then be the integral over the surface of the above. For a flat
surface this integration gives C exp (-t / ξ), where C is the constant of proportionality
(units of energy per unit volume) and t is the perpendicular distance from the surface.
Therefore, for a flat surface, the total contribution to the energy due to the surface is
the integral over the volume of C exp (-t / ξ), plus a surface term.
−z −z
E surface = Aγ * + ∫ C1 exp 1 dV + ∫ C 2 exp 2 dV (6. 109)
1 ξ1 2 ξ2
The 1’s and 2’s designate which side of the surface is the volume to be integrated. If
we limit our interest to a thickness t on each side of the surface and integrate we
have
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− t −t
E surface = Aγ * + C1ξ1 1 − exp 1 + C 2ξ 2 1 − exp 2
(6. 110)
ξ1 ξ2
For t’s much larger than the scale lengths, the energy per unit area due to the
surface is γ = γ * + C1ξ1 + C 2ξ 2 . This is the observed surface energy that we find in the
literature. The limit of t going to 0 gives γ*, which we will call the skin energy. If the
presence of the surface increases the order for a short distance into the bulk, the
energy will be lowered, and C will be negative. Increasing the disorder of the material
will raise the energy and C will be positive. If we now ask what is the energy per area
due to the surfaces, for non-interacting solid-liquid liquid-matrix surfaces a distance t
apart, where the solid and matrix are considered infinite, we have
E − t − t
= γ lm + γ sl + C lmξ l 1 − exp + C ml ξ m + C ls ξ l 1 − exp + C sl ξ s
* *
(6. 111)
A ξl ξl
Van Der Veen stated that there must be no difference between the energy of a solid
surface, and a solid surface with a liquid layer, if the liquid layer has zero thickness.
We will make that assumption but will see shortly that this imposes some conditions
under which this model can be applied. Requiring that the above equation give γsm in
the limit of t = 0 results in γ sm = γ lm
*
+ γ sl* + C ml ξ m + C sl ξ s . Letting t now be large
compared to the scale length, the mismatch between the observed values of the
surface energies is
∆γ = γ sm − γ sl − γ lm = γ sm − γ lm
*
+ γ sl* − C lmξ l − C ml ξ m − C ls ξ l − C sl ξ s = −(C lm + C ls )ξ l (6. 112)
Because the presence of the surface will impose ordering on the liquid, both Clm and
Cls will be negative and therefore ∆γ is positive. We know that there are materials
where this is not the case. When ∆γ < 0 we cannot impose the constraint that
E − t − t
= γ lm + γ sl + C lmξ l 1 − exp + C ml ξ m + C ls ξ l 1 − exp + C sl ξ s
* *
Eq. (6. 111)
A ξl ξl
give γsm, when t = 0. ∆γ < 0 is also the non-wetting condition, therefore, a flat liquid
layer would be unstable in that situation. Thus, for the moment, we will confine our
interest to ∆γ > 0 and assume that Eq.
∆γ = γ sm − γ sl − γ lm = γ sm − γ lm
*
+ γ sl* − C lmξ l − C ml ξ m − C ls ξ l − C sl ξ s = −(C lm + C ls )ξ l (6.
112) holds. The energy of these two surfaces separated by a thickness t can now be
written as
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− t
E = Aγ sm + (− γ sm + γ sl + γ lm )1 − exp
ξ l
(6. 113)
−t − t
E = Aγ lm + (γ sm − γ lm ) ξl + γ sl 1 − exp
exp
ξ l
This last version is exactly the correction given by Van Der Veen.
To simplify the implementation with spherical geometry, we will make the
approximation that the corrections due to order or disorder propagating into the solid
or matrix are small compared to the contributions due to the order in the liquid. This
approximation will leave us with surface terms and the bulk liquid terms which will be
written as
C lmξ l = −α∆γ
(6. 114)
C ls ξ l = −(1 − α )∆γ
α will be between 0 and 1 and will be approximated for the experiment in question. α
divides ∆γ between the order imposed on the liquid due to the surface with the matrix
and that due to the surface with the solid. If the solid and matrix were very similar, we
would expect α to be near one half. The other extreme would be a very dissimilar
matrix or vapor, in which case α would be small but non zero.
Even if the matrix has no order to impose on the liquid, the surface itself will impose
some order. Therefore, α will never be zero.
Going back to integrating over the surface, but changing to a spherical geometry we
get
R R−r (R + r )
E (r ) ∝ exp − − exp − (6. 115)
r ξ
ξ
R is the radius of the surface and r is the radius of the point in question. The total
energy due to the surface will again be found by integrating the above equation over
the volume. Using the approximation made above, we will limit our interest to
corrections to the bulk surface energies that involve ∆γ. Using the geometry of a
liquid sphere with a solid core, the energy of the solid-liquid and liquid-matrix
surfaces is
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This is more complicated than the simple form given by Van Der Veen, but it takes
into account the disappearance of the solid-liquid surface’s correction when the solid
core disappears.
Using the new correction to the solid-liquid liquid- matrix surface energies results in
the following free energy difference.
T
∆F = l 0 1 − N l + γ lm Al + γ sl Ac − γ sm As + Glm + G sl (6. 119)
T0
This can be written as a function of the number of atoms in the liquid layer by using
the total number of atoms, the solid and liquid densities, and the known geometry to
get
1
3 Ns 3
rs = (6. 120)
4π ρ s
1
3 Ns − Nl 3
rc = (6. 121)
4π ρs
1
3 Ns − Nl Nl 3
rl = +
(6. 122)
4π ρ s ρ l
The thickness of the liquid layer, the volumes, and the areas of each surface follows
normally from these radii.
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Figure 6-6 : Free energy difference from crystalline state as function of fraction of particles in melted
layer. Data are for a lead particle r = 5.0 nm at three different temperatures. (A) T=480 K,
(B) T=502 K and (C)T=540 K. [R.R. Vanfleet, J.M. Mochel, Thermodynamics of melting and freezing in
small particles, Surface Science, 1995, p.p. 40-50]
Figure 6-6 shows the free energy difference versus the fraction of the atoms in the
liquid layer for three different temperatures. The data are for an r = 5 nm lead particle
and the temperatures are as follows: (A) is T=480 K, (B) is 502 K, and (C) is 540 K.
For (A) and (B), there is a minimum in the energy for a liquid layer of finite thickness.
(B) corresponds to the layer being one monolayer in thickness. This minimum arises
from the propagation of the surface order into the liquid, and corresponds to surface
melting as predicted by Van Der Veen et al. []. (A) and (B) also show another local
minimum with all atoms melted, at the extreme right. This second minima is
separated from the surface melted state by an energy barrier. For (C), all atoms in
the liquid state is the minimum of energy. For a given material, both the presence or
the absence of these minima and the height of the barrier are functions of the size of
the particle, the temperature, the surface energies, the scale length, and the dividing
parameter α.
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Figure 6-7 : Melting point (M), freezing point (F), and temperature at which there is a monolayer of
surface melt (S) for lead, as a function of radius of the particle. G is the region below which a cluster
once disordered will remain disordered. Arrows indicate direction of temperature change when
transition occurs. [R.R. Vanfleet, J.M. Mochel, Thermodynamics of melting and freezing in small
particles, Surface Science, 1995, p.p. 40-50]
We have used bulk parameters in Figure 6-7 to calculate melting point, freezing
point, and temperature where the surface melting is equal to one monolayer in
thickness, as functions of particle radius for lead. Figure 6-7 also shows the region
where a disordered particle, once created, would remain disordered. This is the
“frozen in” region. The arrows indicate the direction of the temperature change for
which the transition would be expected to occur. The curves were calculated with a
simple approach of choosing a particle size and then adjusting the temperature until
the melting point, freezing point, surface melt and “frozen in” temperatures were
found. All these points were then strung together to form the curves in Figure 6-7 and
Figure 6-8.
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Figure 6-8 : Melting point (M), freezing point (F), and temperature at which there is a monolayer of
surface melt (S) for platinum, as a function of radius of the particle. G is the region below which a
cluster once disordered will remain disordered. Arrows indicate direction of temperature change when
transition occurs. [R.R. Vanfleet, J.M. Mochel, Thermodynamics of melting and freezing in small
particles, Surface Science, 1995, p.p. 40-50]
For a given size and temperature, the free energy as a function of the number of
atoms in the liquid layer is calculated. The position and depth of the surface melt
minimum is found and the position is compared to the number of atoms in a single
monolayer. Based on this comparison, the temperature is either raised or lowered
and the calculation is repeated. This process is continued until the surface melting
temperature is found to within a step size. The melting point is based upon the
difference between the surface melt minimum and the maximum free energy.
The main features of Figure 6-7 are a difference between the melting and freezing
points, and the disappearance of this difference for small enough particles. In the
region of differing melting and freezing points, the dominant factor in determining
these critical temperatures is the height of the energy barrier. A lower temperature is
required for the liquid-to-solid transition to occur than for the solid-to-liquid transition.
The difference between melting and freezing disappears when the barrier becomes
so small that it can be easily overcome in either direction. At this point the absolute
stability becomes the important factor leading to identical melting and freezing points.
Another feature of Figure 6-7, is the lack of surface melting for the smallest particles.
This is where the melting barrier is surmountable before a surface melt layer will
form. The line labeled “G” in Figure 6-7, indicates the temperature below which a
particle once disordered would stay disordered due to a high free energy barrier.
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Figure 6-9 : Schematic drawing of isolated particle before melting (complete solid) and after melting
(liquid sheath exhibiting zero contact angle with the solid). [W.A. Jesser, G.J. Shiflet, G.L. Allen, J.L.
Crawford, Equilibrium phase diagrams of isolated nano-phases, Mat. Res. Innovat, 1999, p.p. 211-
216]
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the Helmholtz potential is minimized at equilibrium in this case too, provided the
reservoir pressure is zero. Accordingly, thermodynamic equations for the Helmholtz
potential will be applied to the model of a sphere of solid isothermally melting to form
a spherical shell of liquid surrounding a solid core.
The approach is to express in analytical form the difference ∆F in Helmholtz energy
between the final state, a liquid sheath of thickness t surrounding a solid core of
radius Rs, and the initial state, a solid sphere of radius R0. The initial and final states
can be written in terms of the chemical potential µ at the actual pressure P,
temperature T, and composition Xi in the small particle of volume V and area A and
the number of atoms in the spherical particle Ni, where the subscript i refers to a
particular component, and the surface energies of the solid, liquid, and solid-liquid
interface are γs, γl, γsl respectively.
The Helmholtz energy F0 of the initial state can be written
Where the subscript 0 refers to the initial state of a solid sphere and the superscripts
s or l refer to the solid, or liquid phases. The Helmholtz energy for the final state of a
liquid sheath of thickness t surrounding a solid core of radius Rs can be written as
F f = ∑ µ il N il − P lV l + γ l A l + ∑ µ is N is − P sV s + γ s A s (6. 124)
i i
The Helmholtz energy difference between the final and initial states, ∆F is plotted
against the composition and fraction of liquid for constant materials parameters in
order to determine whether and where any minima exist on the energy surface. It will
be assumed that a regular solution model is adequate to represent the bulk chemical
potentials and that a linear relationship exists between the surface and interfacial
energies and composition.
Using a regular solution approach one can incorporate interaction parameters ωl for
the liquid and ωs for the solid. These parameters are taken as temperature, pressure
and composition independent. The final and simplified expression for the Helmholtz
free-energy difference ∆F can be written as
( ) (
∆F = N l kT X Al ln C A + X Bl ln C B + X Al ln X Al + X Bl ln X Bl + N s kT X As ln X As + X Bs ln X Bs )
( ) (
− N 0 A kT ln X 0 A − N 0 B kT ln X 0 B + ω l X Al X Bl N l + ω s X As X Bs N s − X 0 A X 0 B N 0 ) (6. 125)
[(
+ A γ −γ
l s
)+ A γ ]
s sl
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Where
With
and
(
For convenience C A, B ... Γ s X s / Γ l X l )bulk represents the bulk compositions and activity
coefficients for components A and B respectively for the case of the bulk phase
diagram.
The relationship between interaction parameter ω and activity coefficient Γ is
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Table 6-1 : Values of parameters employed for the Bi-Sn binary phase diagram. [W.A. Jesser,
G.J. Shiflet, G.L. Allen, J.L. Crawford, Equilibrium phase diagrams of isolated nano-phases, Mat. Res.
Innovat, 1999, p.p. 211-216]
while for the Bi-rich side of the phase diagram the equation of the solidus is taken as
The values of the parameters used in equation 2 may be found in Table 6-1.
When the above parameters are substituted into equation
( ) (
∆F = N l kT X Al ln C A + X Bl ln C B + X Al ln X Al + X Bl ln X Bl + N s kT X As ln X As + X Bs ln X Bs )
( A B ) s
(
− N 0 A kT ln X 0 A − N 0 B kT ln X 0 B + ω X X N + ω X X N − X 0 A X 0 B N 0
l l l l s
A
s
B
s
) (6.
[(
+ A γ −γ
l s
)+ A γ ]
s sl
125), a ∆F surface versus composition and fraction liquid may be plotted and
analyzed for the presence of local minima. As an illustrative example of a typical ∆F
surface Figure 6-10 is presented for a binary bismuth alloy with lead for two
temperatures.
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Figure 6-10 : Helmholtz free energy surface plotted for the case of a binary bismuth alloy as a function
of composition and fractional amount of liquid for two temperatures. a) intermediate temperature
corresponding to a metastable solid-liquid equilibrium, b) elevated temperature showing a stable
equilibrium corresponding to complete liquid. [W.A. Jesser, G.J. Shiflet, G.L. Allen, J.L. Crawford,
Equilibrium phase diagrams of isolated nano-phases, Mat. Res. Innovat, 1999, p.p. 211-216]
Here one finds a relative minimum whose location is indicated by the broad dot and
an absolute minimum located at the point where only liquid exists. These two minima
are separated by a saddle-point maximum that prevents the system from jumping this
energy barrier. Accordingly, the temperature of this plot corresponds to a metastable
solid-liquid equilibrium. At significantly lower temperatures no local minimum exists
and complete solid is the stable state. At significantly higher temperatures, again no
local minimum exists and the saddle-point maximum disappears so that the free
energy surface is one that continuously decreases as one moves toward the point of
minimum free energy which corresponds to complete liquid. Figure 6-10 b)
represents this latter condition in which the minimum is indicated by the broad dot.
There is no progression of the local minimum continuously to the condition of
complete liquid. Rather there is a discontinuous, abrupt shift of the minimum from a
location away from the point of complete liquid to the point of complete liquid once
the saddle-point maximum disappears. Physically this corresponds to heating the
two-phase particle to a temperature at which a discontinuous transition occurs from
the state of a liquid sheath surrounding a solid core to the state of complete liquid.
Such an abrupt transition is experimentally observed for this binary alloy as well as
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for the solid elements tin and bismuth both of which exhibit no stable solid-liquid
equilibrium.
Figure 6-11 : Phase diagram for the binary alloy Sn-Bi. The bulk phase diagram is shown
superimposed on the phase diagram for isolated spheres of alloy 40 nm in diameter. The nano-particle
phase diagram is the shaded region as given by the thermodynamic calculations and the data points
for each of eight compositions as determined from in-situ TEM measurements. [W.A. Jesser, G.J.
Shiflet, G.L. Allen, J.L. Crawford, Equilibrium phase diagrams of isolated nano-phases, Mat. Res.
Innovat, 1999, p.p. 211-216]
This Figure also includes the phase diagram for bulk Sn-Bi alloys and the
experimentally measured liquidus and solidus lines for the isolated spherical
particles. The experimental data reported here were measured inside a transmission
electron microscope modified for ultra high vacuum so that in-situ deposition of the
isolated nanospheres could be performed. These new data show that for the Sn-rich
side of the phase diagram, the liquid-solid two-phase field pinches off to a line
thereby indicating no stable equilibrium between the liquid and solid phases in this
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region. There was no detectable pinching off observed on the Bi-rich side of the
diagram.
In addition to the pinching off of the two-phase field near the composition of pure tin,
there are two other noteworthy features in the phase diagram. First, one notices that
there is a substantial increase in solubility for the nano-particles as compared to that
in the bulk alloy. The solubility limit of tin in bismuth increased from 1.5% (bulk) to
about 43% in particles of radius 20 nm. A strong increase also occurred in the tin-rich
phase.
Second, because the initial melting event is observed to be discontinuous (the liquid
sheath forms with a minimum finite thickness of about 2 nm) and the final melting
event is also a discontinuous event with the isothermal jump from a thick liquid
sheath surrounding a solid core to a completely liquid sphere, the location on the
phase diagram of the locus of the temperatures at which these discontinuous
transitions occur do not represent liquidus and solidus lines that can be used to
construct the tie lines. The conventional tie lines that describe mass conservation and
are useful for lever-rule calculations extend isothermally beyond the two phase
regions. If a tie line is constructed between the liquidus and solidus lines shown on
the phase diagram, its ends do not correspond to either the solid composition or the
liquid sheath composition. In order to account for these compositions a longer tie line
is required. As the temperature is increased, the tie line changes its length. The two
ends of the tie line demark the compositions of the liquid and solid phases and
sweep out two areas on the phase diagram both of which are detached from the
drawn liquidus and solidus lines that demark the extent of the two phase field. This
feature is shown in Figure 6-12.
Figure 6-12 : Sn-rich segment of a Sn-Bi phase diagram for an isolated sphere of radius 20 nm
showing that the areas swept out by the ends of the tie lines are detached from the two-phase region.
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Note that the two-phase regions and the ends of the tie lines pinch off at about 5% Bi. [W.A. Jesser,
G.J. Shiflet, G.L. Allen, J.L. Crawford, Equilibrium phase diagrams of isolated nano-phases, Mat. Res.
Innovat, 1999, p.p. 211-216]
One can incorporate the size-dependence of the phase diagram by making a three-
dimensional plot of liquidus and solidus temperatures as a function of both
composition and size. One can incorporate a size variable in the phase diagram by
recognizing that the Helmholtz free energy depends upon pressure which exhibits a
discontinuity ∆P across a curved surface of
Accordingly the equilibrium lines shift approximately linearly with reciprocal radius.
The axes of the three-dimensional phase diagram then become temperature,
reciprocal radius, and composition. Figure 6-13 shows a 3-D phase diagram for the
Sn-Bi alloy system.
Figure 6-13 : 3-D phase diagram for an isolated tin-bismuth alloy sphere showing the size
dependence of the liquidus and solidus lines as well as the eutectic isotherm over the range of
–1 –1
reciprocal radius 0 nm to 0.05 nm . Over this size range the eutectic temperature changes from 412
to 320 K and the solubility of Sn in Bi increased from 1.5% to 43%. The dashed lines on the left margin
are reference lines parallel to the 1/R axis. The solid lines on the left margin are projections of the
melting and eutectic temperatures. The solid lines on the bottom margin are projections of the
solubility limits and the eutectic composition. [W.A. Jesser, G.J. Shiflet, G.L. Allen, J.L. Crawford,
Equilibrium phase diagrams of isolated nano-phases, Mat. Res. Innovat, 1999, p.p. 211-216]
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and massive bodies in lattice parameters and the types of atomic structures are
plausible. These difference manifest themselves in normal and tangential
relaxations of nanoparticles.(54) An atom on the surface has fewer neighbours
than one in the volume, all the neighbours of the former being located on one
side only. This breaks the equilibrium of the interatomic forces and gives rise to
both the change of interatomic spacing (normal relaxation) and tensile
deformations which ‘smooth’ verticles and edges (tangential relaxation).
A rough estimate of the average distortion of the interatomic distances a
in nanoparticles caused by surface tension is shown below: (55)
∆a γ
= θ 2κ (6. 135)
a r'
where θ2 is the numerical coefficient of the order of 1 (in the case of isotropic
spherical particles it may be estimated as 2/3), κ is the volume compressibility
coefficient. According to the estimate, the lattice construction is about several
tenths of a percent at typical values of parameters κ ~ 10-11 m3/J, γ ∼ 1 J/m2 for
nanoparticles with radius r ~ 10 nm.
Here it should be mentioned that parameters entering this formula are, in
turn, size-dependent. The surface energy of nanoparticles, for example,
depends on r as follows: (56)*
a a
2
γ ' = γ 1 − θ 3 + θ 4 + ... (6. 136)
r r
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experimental artifacts and difficulties, while others are associated with the
complicated spatial distribution of lattice parameter distortions. In the absence of
oxide layers,(60) absorbed impurities, etc., there is an average overall contraction
in the lattice parameter of a nanoparticle. However, interatomic spacing in the
outer part of nanoparticles may be expanded despite the contracted interior.(61)
Moreover, the degree of distortion varies with crystallographic as a result of the
anisotropy of the volume compressibility coefficient.(62,63) In summary, the
experimental and theoretical results show that the average contraction of the
lattice parameter in the nanoparticles is inversely proportional to nanoparticles
radius r.
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δ 2 a 3 (G − G ')
1/ 3
∆s
c = cb + θ 8 (c s − cb ) (6. 139)
r
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when all the atoms belong to the surface, the surface composition in an
ensemble of nanoparticles would be identical to the average composition in the
(69)
massive alloy. Such a decrease of the surface segregation has been
(70)
observed experimentally. In the opposite of very large particles they will
behave like semi-infinite crystals, and the surface composition would be similar
to that obtained in microscopic samples. In the intermediate range of sizes,
where the number of surface sites is not a negligibly small fraction of the total
number of sites available in the particle volume, there exists a regime where
segregation to the surface tends to decrease the bulk concentration of the
segregant.
The depletion of the segregated atoms, which would follow from
elementary mass-balance considerations, may be impossible if the physical
and/or chemical properties are size-dependent. For instance, the change in the
a a
2
surface energy (see eq. γ ' = γ 1 − θ 3 + θ 4 + ... (6. 136)) may modify the
r r
∆a γ
segregation effect. The lattice contraction (eq. = θ 2κ (6. 135)) and the
a r'
external pressure also affect segregation phenomena.
In their effects on segregation, applying external pressure and
contracting the crystal lattice of nano-objects are to a certain degree equivalent
(71)
to the difference in the atomic radii of the segregant and matrix atoms, which
is described by the relative size mismatch δs. In fact, external pressure P is
connected with the change in the relative size mismatch δs by the simple
∆a γ
relationship (cf. eq. = θ 2κ (6. 135)):
a r'
∆δ s =
P
(κ 1 − κ 2 ) (6. 140)
3
where κ1 and κ2 are the volume compressibility of the segregant and the
solvent, respectively. The hydrostatic stress include by surface tension,
approximated as 2γ / l, may, thus, change the relative size mismatch by ∆δs.
According to the well-known Hume-Rothery rule (if the relative size mismatch
(72)
exceeds the 15% limit, solid solubility will be restricted ) a critical size l*sol
should exist, above which the solid solubility remains qualitatively the same:
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γ (κ 1 − κ 2 )
∆∗sol = θ 2 (6. 141)
0.15 − δ s
6.6 References
C.X. Wang, G.W. Yang, Thermodynamics of metastable phase nucleation, Materials
Science and Engineering, 2005, p.p. 157-202
T. L. Hill, A Different Approach to Nanothermodynamics, Nano letters, 2001 Vol.1,
N°5, p.p. 273-275
C. Beck, Non-additivity of Tsallis entropies and fluctuations of temperature,
Europhysics Letters, 2002, p.p. 329-333
R.R. Vanfleet, J.M. Mochel, Thermodynamics of melting and freezing in small
particles, Surface Science, 1995, p.p. 40-50
W.A. Jesser, G.J. Shiflet, G.L. Allen, J.L. Crawford, Equilibrium phase diagrams of
isolated nano-phases, Mat. Res. Innovat, 1999, p.p. 211-216
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7.1 Introduction
LUMO
Forbidden bandgap
HOMO
Energy
Atom
Molecule
Cluster
Nanoparticle
Semiconductor Metal
Crystalline
Figure 7-1: Size quantization effect. Electronic state transition from bulk metal/semiconductor to small
cluster.
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ligated. lxiii This leads to different mechanical and electronic transport properties,
which account for the catalytic properties of the nanocrystalline particles.lxiv
Certain particle sizes, determined by the so-called magic numbers, are more
frequently observed than others. This is not only due to the thermodynamic stability
of certain structures but is also related to the kinetics of particle growth. In
semiconductor nanoparticles such as CdS, the growth of the initially formed smallest
particles with an agglomeration number k occurs by combination of the particles.
Thus, particles so formed would have the agglomeration number of 2k, 3k and so
on. lxx Metals have a cubic or hexagonal close-packed structure consisting of one
central atom, which is surrounded in the first shell by 12 atoms, in the second shell by
42 atoms, or in principle by 10n2+2 atoms in the nth shell.lxxi For example, one of the
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most famous ligand stabilized metal clusters is a gold particle with 55 atoms (Au55)
first reported by G. Schmid in 1981.lxxii
7.2 Metals
7.2.1 Introduction
ρ S e 2τ
σ= (7. 142)
m*
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w
G =σ (7. 143)
l
For a 3D conductor, this relationship is valid provided that w is replaced by the cross
sectional area A orthogonal to the current flow direction. Similar expressions are also
valid for the thermal transport of energy. The thermal conductance related to the
energy (or heat) current Jx through a sample between two reservoirs is given by
Kx = Jx ∆T , where ∆T is the temperature difference. Depending on whether the
energy is carried by electrons (x = e) or by phonons (x = p) the thermal conductance
is identified as electronic Ke or phononic Kp. Here our focus is on quantum transport
through materials of very small dimensions.
N ∼ 2w/λF, increases with the width of the constriction. Since all these modes can
contribute to the conductance, one still expects the conductance to increase linearly
with w even in the nanodomain. This is almost the case, except with one important
distinction. The width w can change continuously, at least in principle. But the
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number of modes, being an integer, can only vary in discrete steps. The concept
EF
becomes physically more transparent if we rewrite N ~ n . The highest occupied
∈n
єn = EF gives N from a simple counting of the number of discrete eigenvalues. Since
it is a rare coincidence for an eigenvalue to exactly align with the Fermi energy, N is
taken to be the integer which corresponds to the highest occupied level just below
EF. Thus the effect of quantum mechanics due to the reduced dimension w is to
cause the conductance to change in discrete steps in a staircase fashion. We have
yet to find the step height. This simple view is necessarily modified when other
factors explained later start to play a crucial role. Obviously, one then requires a
more detailed analysis.
The characteristic length that comes into play is λF, since only those electrons having
energy close to the Fermi energy carry current at low temperatures. If w >> λF, the
number of conducting modes is very large and so is the conductance. This is typical
in metals where λF ∼ 0.2 nanometres is very small and consequently the observation
Ι
G= (7. 144)
∆V
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e
Ι= (7. 145)
∆t
Ι e
Combining equation G = (7. 144) and equation Ι = (7. 145), and
∆V ∆t
using the fact that the potential difference, ∆V, is equal to electrochemical potential
difference ∆E divided by the electronic charge e, one gets
e²
G= (7. 146)
∆E∆t
Metallic carbon nanotubes providing two conductance channels at the Fermi level are
considered almost perfect one-dimensional (1D) conductors. These tubes, which can
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transport is the consequence of the incident current flux. On the basis of the self-
consistency arguments for reflections and transmissions, he derived his famous
formula for a one-dimensional conductor yielding the conductance
T ∼ 1, the conductance is still finite and equal to 2e2/h. The corresponding resistance
R = G−1 = h/2e2 is attributed to the resistance arising from the reflections at the
contacts where the finite-length conductor is connected to the reservoirs. This leaves
unanswered the question of how the contact resistance can be independent of the
type of contact. Also the infinite conductance within the conductor at perfect
transmission requires an in-depth discussion. Whether the finite conductance of an
ideal channel, 2e2/h, is due to the contact or due to the capacity of the current-
transporting state seems to be a matter of interpretation.
Büttiker developed the multi-probe generalization of the theory. During the last
decade, important progress has been made in mesoscopic physics; the quantum
transport of electrons through constrictions has been a subject of many in-depth
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studies. In particular, the variation of the current through a point contact created by
an STM tip and the measurements of the conductance G through a narrow
constriction between two reservoirs of 2D electron gas in a high-mobility GaAs–
GaAlAs heterostructure showing step behaviour with a step height of 2e2/h have led
to basic confirmation of Landauer’s fundamental ideas.
The step behaviour of G has been treated in several studies. Here we provide a
simple and formal explanation by using a 1D idealized uniform constriction having a
width w. The electrons are confined in the transverse direction and have states with
quantized energy єi . They propagate freely along the length of the constriction. The
propagation constant for an electron with єi < EF is
1/ 2
2m *
γi = (E F − ∈i ) (7. 149)
ℏ²
Whenever the width of the constriction increases by λF /2, a new subband with
energy єi + ћ²γ²i/2m dips below the Fermi level and contributes to the current under
the small bias voltage ∆V. The current is
j
Ι = ∑ 2ni eϑγ i [Di (E F + e∆V ) − Di (E F )] (7. 150)
i =1
Here j is the index of the highest subband that lies below the Fermi level, i.e.
єi ≤ EF + e∆V and єj+1 > EF + e∆V, and ni is the degeneracy of the state i. By
assuming perfect transmission in the absence of any contact resistance and barrier
inside the constriction, i.e. T = 1, and by expressing the group velocity ϑγ i and the
density of states Di (є) in terms of the subband energy є = єi + ћ²γ²i/2m* and dividing
I by ∆V we obtain
j
2e²
G=∑ ni (7. 151)
i =1 h
For a uniform, infinite wall constriction, the states are non-degenerate, i.e. ni = 1, and
hence the increase of w by λF /2 causes G to jump by 2e²/h. As a result, the G(w)
curve exhibits a staircase structure. Since the level spacing in the transverse
quantization is rather small for the low electron density in the 2D electron gas system,
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may deviate from the perfect quantized values. As a result, the effects, such as the
contact and potential barrier, surface roughness, impurity scattering, cause the sharp
step structure of G(w) to smear out. The local widening of the constriction or impurity
potential can give rise to quasi-bound (0D) states in the constriction and to resonant
tunnelling effects.
The length of the constriction, l, is another important parameter. In order to get sharp
step structure, l has to be greater than λF , but smaller than the electron mean free
path le; G(w) is smoothed out in a short constriction (l < λF ). Therefore, G(w) exhibits
sharp step structure if the constriction is uniform, and w ∼λF and λF << l < le. On the
other hand, the theoretical studies predict that the resonance structures occur on the
flat plateaus due to the interference of waves reflected from the abrupt connections
to the reservoirs. The stepwise variation of G with w or EF has been identified as the
quantization of conductance. This is, in fact, the reflection of the quantized
constriction states in the electrical conductance.
We now extend the above discussion to analyse the ballistic electron conductance
through a point contact or a nanowire, in which the electronic motion is confined in
two dimensions, but freely propagates in the third dimension. The point contact (or
quantum contact) created by the indentation of the STM, a nanowire (or a connective
neck) that is produced by retracting the tip from an indentation and also a metallic
SWNT are typical systems of interest. Nanowires created by STM are expected to be
round (though not perfectly cylindrical) and have radius R ∼λF at the neck. The neck
is connected to the electrodes by horn-like ends, and hence the radius increases as
one goes away from the neck. An extreme case for l → 0 is Sharvin’s conductance,
GS = (2e²/h)(πR/ λF )², with contact radius R, where the step structure is almost
smeared out and plateaus disappear. In the quantum regime, where the cross
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section A ∼λF², GS should vanish when A is smaller than a critical cross section set
2e ²
G= Tr (t + t ) (7. 153)
h
Where the elements of the transmission matrix t, tij, are the amplitudes of
transmission from the incoming channels to the outgoing ones. In actual electron
transport through a contact or wire, the electrons of the electrodes with proper
representation (say in Bloch form) enter in the constriction, and pass to the other
electrode after multiply scattering from the walls or from other scattering centres in
the constriction. In the steady state the potential of the wire can be different from that
in the case of a self-consistently calculated potential under zero-current conditions.
Therefore, full calculation of the conductance based on the density functional theory
has to start with the actual states of the electrodes and evaluate the t-matrix for the
self-consistent potential under the steady-state current flow. Various methods at
different levels of sophistication have been applied to calculate the conductance.
The simplest model for representing a nanowire or point contact is a cylindrical or
circular hard-wall potential with varying radius, R(z). The axis of the constriction is
along the z direction; the x- and y-axes are in the transverse plane. An approach
alternative to the circular cross section is the rectangular cross section with sides
Lx(z) and Ly(z), both varying smoothly with z. Many studies employed these models
to show the step behaviour of the conductance. The potential of the constriction
corresponding to a given atomic structure which was omitted in these model studies
has been taken into account first by performing SCF electronic structure calculations,
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or by obtaining the potential from the linear combination of atomic potentials. Then,
the calculated potential is approximated by a potential having cylindrical symmetry:
Vl ( ρ , z ) = φl ( z ) + α l ( z ) ρ ² (7. 154)
[ ]
Ψki ( ρ , z ) = ∑ Anki ( z )e iγ n ( z ) z + Bnki ( z )( z )e −iγ n ( z ) z Φ n ( ρ , z ) (7. 155)
n
Where the transverse state Φ n ( ρ , z ) is the 2D harmonic oscillator solution for a given
constant is given by
γ n ( z) =
2m
[E − Φ l ( z)− ∈n,l ( z )] (7. 156)
ℏ²
The conductance of the wire is calculated by using the transfer-matrix method, where
Vl (ρ, z) is divided into discrete segments of equal widths, and in each segment
zj < z < zj+1, the average values are used. The coefficients Anki and Bnki are
determined from the multiple boundary matching conditions. The total conductance is
calculated by integrating the expectation value of the current operator over the Fermi
surface.
A constriction having more general geometry and potential can be treated by
expressing the current-transporting state in the Laue expansion
zj < z < zj+1, and converted to a matrix equation. The details of the calculations can
be found elsewhere.
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The Green’s function method has been used extensively to study the electrical
conduction through nanowires and also SWNTs. In the self-consistent calculation,
where the wave functions of the bare electrodes, Ψ 0 , are evaluated from a realistic
Hamiltonian, the wave functions of the complete system including the constriction,
Ψ C , are put into the Lippmann–Schwinger form:
Ψ C (r ) = Ψ 0 (r ) + ∫ dr ' dr ' ' G 0 (r , r ' )δV (r ' , r ' ' )Ψ C (r ) (7. 158)
Where δV is the potential difference between the complete and bare systems, and G0
is the Green’s function obtained for the bare system. In the work by Lang the
electrodes are treated in the jellium approximation, and the potentials at the
constriction due to metal atoms are expressed by the pseudopotentials. Once Ψ 0
and Ψ C are expressed in the plane-wave representation, the currents between the
electrodes in the presence and in the absence of the constriction are obtained from
the expectation value of the current operator by summing over all the states of the
jellium electrodes under the bias e δV. The calculations using the Laue-type
expansion have indicated that the division of the current-transporting state in the
electrode by jellium and in the wire by pseudopotential, which essentially neglects the
binding structure at the entrance to the reservoirs, may not fully describe the real
physical system.
In the Green’s function method within the tight-binding representation using empirical
energy parameters, a conducting nanowire or a nanotube is divided into three parts.
These are the left (L), right (R) and central (C) regions; the left and right regions
are coupled to two semi-infinite leads. The central region is the computationally
important part which may include tube junctions, defects or vacancies. Partitioning
the Green’s function into submatrices due to the left, right and central regions, one
can obtain the Green’s function for the central region as
ς Cr = (∈ − H C − Σ L − Σ R ) −1 (7. 159)
The self-energy terms, Σ L and Σ R , describe the effect of semi-infinite leads on the
central region. The functions for the coupling can be obtained as
ΓL , R = i[Σ rL , R − Σ aL , R ] in terms of the retarded (r) and advanced (a) self-energies. An
important part of the problem is calculating the self-energy terms. The surface
Green’s function matching method or computational algorithms are used to calculate
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the Green’s functions of semi-infinite leads and the self-energy terms. These terms
can be obtained by using wave functions of ideal leads also. The transmission
function T, that represents the probability of transmitting an electron from one end of
the conductor to the other end, can be calculated using Green’s functions of the
central region and couplings to the leads:
Here ς Cr , a are the retarded and advanced Green’s functions of the centre, and ΓL, R are
functions for couplings to the leads. This approach is used efficiently to treat
nanotube junctions and nanodevices. Note that the success of the approach depends
on the transferability of the empirical energy parameters.
An atomic size contact and connective neck first created by Gimzewski andMöller by
using a STM tip exhibited abrupt changes in the variation of the conductance with the
displacement of the tip. Initially, the observed behaviour of the conductance was
attributed to the quantization of conductance. At that time, from calculating the
quantized conductance of a perfect but short connective neck, Ciraci and Tekman
concluded that the observed abrupt changes of the conductance can be related to
the discontinuous variation of the contact area. Later, Todorov and Sutton performed
an atomic scale simulation of indentation based on the classical molecular dynamics
(MD) method and calculated the conductance for the resulting atomic structure using
the s-orbital tight-binding Green’s function method. They showed that sudden
changes of conductance during indentation or stretching are related to the
discontinuous variation of the contact area. Recently, nanowires of better quality
have been produced using STM and also by using the mechanical break junction.
The two-terminal electrical conductance of these wires showed abrupt changes with
the stretching.
The radius of the narrowest cross section of the wire prior to the break is only a few
ångströms; it has the length scale of λF , where the discontinuous (discrete) nature of
the metal dominates over its continuum description. Since the level spacing ∆є is in
the region of ∼1 eV at this length scale, the peaks of the density of states D(є) of the
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connective neck become well separated and hence the transverse quantization of
states becomes easily resolved even at room temperature. Furthermore, any change
in the atomic structure or the radius induces significant changes in the level spacing
and in the occupancy of states. This, in turn, leads to detectable changes in the
related properties. Therefore, the ballistic electron transport through a nanowire
should be closely related to its atomic structure and radius at its narrowest part. On
the other hand, irregularities of the atomic structure and electronic potential enhance
scattering that destroys the regular staircase structure. In the following section, we
summarize results that emerged from recent experimental and theoretical studies on
stretched nanowires.
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interlayer spacing at the end of the quasi-elastic stage, the structure becomes
disordered.
But after further stretching, it recovers with the formation of a new layer. In the
yielding stage, |Fz| decreases abruptly; the cross section of the layer formed at the
end of the yielding stage is abruptly reduced by a few atoms. As a typical example,
the force variation and atomic structure calculated by the MD method are illustrated
in Figure 7-2.
Figure 7-2: The variation of the tensile force Fz (in nanonewtons) with the strain or elongation s along
the z-axis of the nanowire having Cu(001) structure. The stretch s is realized in m discrete steps. The
snapshots show the atomic positions at relevant stretch steps m. The MD simulations are performed
at T = 300 [K. S. Ciraci, A. Buldum, I.P. Batra, Quantum effects in electrical and thermal transport
through nanowires, 2001, Journal of Physics Condensed Matter]
When the neck becomes very narrow (having 3–4 atoms), the yielding is realized,
however, by a single atom jumping from one of the adjacent layers to the interlayer
region.
Under certain circumstances, atoms at the neck form a pentagon that becomes
staggered in different layers. The interlayer atoms make a chain passing through the
centre of the pentagon rings. In this new phase, the elastic and yielding stages are
intermixed and elongation, which is by more than one interlayer distance, can be
accommodated. As the cross section of the wire is further decreased the pentagons
are transformed to a triangle. In the initial stage of pulling off, the single-atom
process, in which individual atoms also migrate from central layers towards the end
layers, can give rise to a small and less discontinuous change in the cross section.
The tendency to minimize the surface area, and hence to reduce the strain energy of
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the system, is the main driving force for this type of neck formation. While quasi-
elastic and yielding stages are distinguishable initially, the force variation becomes
more complex and more dependent on the migration of atoms for atomic necks.
Atomic migrations have important implications such as dips in the variation of
conductance with stretch. The simulation studies on metal wires with diameters ∼λF
at the neck, but increasing gradually as one goes away from the neck region, have
shown structural instabilities. Such wires displayed spontaneous thinning of the
necks even in the absence of any tensile strain.
Under prolonged stretching, shortly before the break, the cross section of the neck is
reduced to include only 2–3 atoms. In this case, the hollow-site registry may change
to the top-site registry. This leads to the formation of a bundle of atomic chains
(rope) or of a single atomic chain (see Figure 7-3). We consider this a dramatic
change in the atomic structure of the wire that has important implications. For
example, first-principles calculations indicated that a chain of single Al atoms has an
effective Young modulus stronger than that of the bulk.
Figure 7-3: The top view of three layers at the neck showing atomic positions and their relative
registry at different levels of stretch. m = 15 occurs before the first yielding stage. The atomic positions
in the layers 2, 3 and 4 are indicated by +, • and ◊, respectively. m = 38 and m = 41 occur after the
second yielding stage. m = 46, 47 and m = 49 show the formation of bundle structure (or strands). In
the panels for m = 38–49 the positions of atoms in the third, fourth and fifth (central) layers are
indicated by +, • and ◊, respectively. Atomic chains in a bundle are highlighted by square boxes. [K. S.
Ciraci, A. Buldum, I.P. Batra, Quantum effects in electrical and thermal transport through nanowires,
2001, Journal of Physics Condensed Matter]
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Recent computer simulations have suggested that ultrathin lead wires should develop
exotic, non-crystalline stable atomic structures once their diameter decreases below
a critical size of the order of a few atomic spacings. The new structures, whose
details depend upon the material and the wire thickness, may be dominated by
icosahedral packings. Helical, spiral-structured wires with multi-atom pitches are also
predicted. Recently, helical multishell gold nanowires were observed by high-
resolution electron microscopy. The phenomenon, analogous to the appearance of
icosahedral and other noncrystalline shapes in small clusters, can be rationalized in
terms of surface energy anisotropy and optimal packing. Moreover, the electronic
structure of the wire might carry a measurable imprint of its exotic shape.
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The overall features of electrical conductance have been obtained from a statistical
analysis of the results of many consecutive measurements to deduce how frequently
a measured conductance value occurs. Many distribution curves exhibited a peak
near G0 = 2e²/h for metal nanowires, and a relatively broad peak near 3G0, and
almost no significant structure for larger values of conductance. It appears that the
cross section of a connective neck can be reduced down to a single atom just before
the wire breaks. In certain situations, the connective neck can be a monatomic chain
comprising of a few atoms arranged in a row. In this case, a transverse state
quantized in the neck at the Fermi level is coupled to the states of the electrodes and
forms a conducting channel yielding a plateau in the G(s) curve, and hence a peak in
the statistical distribution curve. The step structure for large necks comprising of a
few atoms cannot occur at integer multiples of G0 due to the scattering from
irregularities, and hence due to the channel mixing.
It should be noted that in the course of stretching, elastic and yielding stages repeat;
the surface of the nanowire roughens and deviates strongly from circular symmetry.
The length of the narrowest part of the neck is usually only one or two interlayer
separations, and is connected to the horn-like ends. Under these circumstances, the
quantization is not complete and the contribution of the tunnelling is not negligible.
Results of atomic simulations point to the fact that neither adiabatic evolution of
discrete electronic states, nor perfect circular symmetry can occur in the neck.
Consequently the expected quantized sharp structure shall be smeared out by
channel mixing and tunnelling.
Contradicting these arguments, the changes in the conductance are, however,
abrupt. This controversial situation has been explained by the combined
measurements of the conductance and force variation with the stretch. The abrupt
changes of conductance in the course of stretching coincide with the sudden release
(or relief) of the measured tensile force. The tensile stress is released suddenly
following the yielding stage, whereby the cross section of the wire is reduced
discontinuously, and hence the electronic structure and the electronic level spacing
undergo an abrupt change near the neck. The variation of the conductance, i.e. G(s),
calculated for stretching the nanowire is presented as an example in Figure 7-4.
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Figure 7-4: Variation of the conductance calculated for the stretching nanowire described in
Figure 7-2. [K. S. Ciraci, A. Buldum, I.P. Batra, Quantum effects in electrical and thermal transport
through nanowires, 2001, Journal of Physics Condensed Matter]
Gmax/Gmin ∼ 10–15, is rather surprising, and perhaps is due to the artifact of applying
It has peaks at the quantized energies of transversely confined states, i.e. when
є = єi. The occupancy of these states becomes strongly dependent on the size and
the geometry of the wire. Sudden reduction in the ballistic conductance will occur
whenever a channel is closed (i.e. a current-transporting state moves above the
Fermi energy, EF). Also, whenever the tensile force along the axis of the wire |Fz|
shows a sudden fall, it is possible that the actual R (or the narrowest cross section,
A) experiences a change only at certain positions of єi relative to EF. Such a
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possibility was pointed out on the basis of earlier works indicating quantum size
effects. In fact, it is known that the surface energy, work function etc for a 2D electron
system show discrete changes as the relevant size (or thickness) changes. This is
explained by noting that the increase occurs when an empty band gets occupied as a
result of size change (explain later). Similar effects have been reported for clusters
treated in the jellium approximation. Stafford et al [] showed that in fact abrupt
changes in conductance and diameter of a uniform wire are correlated, so certain
values of R or A are energetically favourable as if the size is ‘quantized’.
The conductance through a single atom, a nanowire with the ultimate small cross
section, has provided fundamental understanding. On the basis of ab initio
calculations it has been shown that the conductance depends on the valence states
as well as the site where the single atom is bound to the electrode. The coupling to
electrodes and hence the transmission coefficients are expected to depend on the
binding structure. There is a direct link between valence orbitals and the number of
conduction channels in the conductance through a single atom. Lang [] calculated the
conductance through a single Na atom, as well as a monatomic chain comprising
two, three and four Na atoms between two jellium electrodes by using the Green’s
function formalism. He found an anomalous dependence of the conductance on the
‘length’ of the wire. The conductance through a single atom was low (∼G0/3), but
increased by a factor of two in going from a single atom to the two-atom wire. This
behaviour was explained as the incomplete valence resonance of a single Na atom
interacting with the continuum of states of the jellium electrodes. Each additional Na
atom modifies the electronic structure and shifts the energy levels. The closer a state
is to the Fermi level, the higher is its contribution to the electrical conductance.
According to the Kalmeyer–Laughlin theory [], a resonance with the maximum DOS
at the Fermi level makes the highest contribution to the transmission; the
conductance decreases as the maximum shifts away from the Fermi level.
This explanation is valid for a single atom between two macroscopic electrodes
forming a neck with length l < λF. The situation is, however, different for long
monatomic chains. Since the electronic energy structure of a short monatomic chain
varies with the number of atoms, the results are expected to change if one goes
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beyond the jellium approximation and considers the details of the coupling of chain
atoms to the electrode atoms. It is also expected that the conductance will depend on
where the monatomic chain (represented by the pseudopotentials) ends and where
the jellium edge begins.
Gold colloidal nanoparticles are responsible for the brilliant reds seen in stained glass
windows. Silver particles are typically yellow. These properties have been of interest
for centuries, and scientific research on metal nanoparticles dates at least to Michael
Faraday. It was therefore one of the great triumphs of classical physics when in 1908,
Mie presented a solution to Maxwell’s equations that describes the extinction spectra
(extinction = scattering + absorption) of spherical particles of arbitrary size. Mie’s
solution remains of great interest to this day, but the modern generation of metal
nanoparticle science, including applications to medical diagnostics and nanooptics,
has provided new challenges for theory.
The free electrons in the metal (d electrons in silver and gold) are free to travel
through the material. The mean free path in gold and silver is ~50 nm, therefore in
particles smaller than this, no scattering is expected from the bulk. Thus, all
interactions are expected to be with the surface. When the wavelength of light is
much larger than the nanoparticle size it can set up standing resonance conditions as
represented in Figure 7-5.
Figure 7-5: Schematic of plasmon oscillation for a sphere, showing the displacement of the
conduction electron charge cloud relative to the nuclei. [K. Lance Kelly, E. Coronado, L.L. Zhao, G.C.
Schatz, The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric
Environment, 2003, Journal of Physical Chemistry]
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Light in resonance with the surface plasmon oscillation causes the free-electrons in
the metal to oscillate. As the wave front of the light passes, the electron density in the
particle is polarized to one surface and oscillates in resonance with the light’s
frequency causing a standing oscillation. The resonance condition is determined from
absorption and scattering spectroscopy and is found to depend on the shape, size,
and dielectric constants of both the metal and the surrounding material. This is
referred to as the surface plasmon resonance, since it is located at the surface. As
the shape or size of the nanoparticle changes, the surface geometry changes
causing a shift in the electric field density on the surface. This causes a change in the
oscillation frequency of the electrons, generating different cross-sections for the
optical properties including absorption and scattering.
Changing the dielectric constant of the surrounding material will have an effect on the
oscillation frequency due to the varying ability of the surface to accommodate
electron charge density from the nanoparticles. Changing the solvent will change the
dielectric constant, but the capping material is most important in determining the shift
of the plasmon resonance due to the local nature of its effect on the surface of the
nanoparticle. Chemically bonded molecules can be detected by the observed change
they induce in the electron density on the surface, which results in a shift in the
surface plasmon absorption maximum. This is the basis for the use of noble metal
nanoparticles as sensitive sensors. Mie originally calculated the surface plasmon
resonance by solving Maxwell’s equations for small spheres interacting with an
electromagnetic field. Gan was able to extend this theory to apply to ellipsoidal
geometries. Modern methods using the discrete dipole approximation (DDA) allow
one to calculate the surface plasmon resonance absorption for arbitrary geometries.
Calculation of the longitudinal plasmon resonance for gold nanorods generates an
increase in the intensity and wavelength maximum as the aspect ratio (length divided
by width) increases. Thus, the plasmon resonance can be tuned across the visible
region by changing the aspect ratio. The increase in the intensity of the surface
plasmon resonance absorption leads to an enhancement of the electric field, as
exploited in many applications.
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When the electron cloud is displaced relative to the nuclei, a restoring force arises
from Coulomb attraction between electrons and nuclei that results in oscillation of the
electron cloud relative to the nuclear framework. The oscillation frequency is
determined by four factors: the density of electrons, the effective electron mass, and
the shape and size of the charge distribution. The collective oscillation of the
electrons is called the dipole plasmon resonance of the particle (sometimes denoted
“dipole particle plasmon resonance” to distinguish from plasmon excitation that can
occur in bulk metal or metal surfaces). Higher modes of plasmon excitation can
occur, such as the quadrupole mode where half of the electron cloud moves parallel
to the applied field and half moves antiparallel. For a metal like silver, the plasmon
frequency is also influenced by other electrons such as those in d-orbitals, and this
prevents the plasmon frequency from being easily calculated using electronic
structure calculations. However, it is not hard to relate the plasmon frequency to the
metal dielectric constant, which is a property that can be measured as a function of
wavelength for bulk metal.
To relate the dipole plasmon frequency of a metal nanoparticle to the dielectric
constant, we consider the interaction of light with a spherical particle that is much
smaller than the wavelength of light. Under these circumstances, the electric field of
the light can be taken to be constant, and the interaction is governed by electrostatics
rather than electrodynamics. This is often called the quasistatic approximation, as we
use the wavelength-dependent dielectric constant of the metal particle, єi, and of the
surrounding medium, є0, in what is otherwise an electrostatic theory.
Let’s denote the electric field of the incident electromagnetic wave by the vector Eo.
⌢ ⌢
We take this constant vector to be in the x direction so that Eo = Eo x , where x is a
unit vector. To determine the electromagnetic field surrounding the particle, we solve
LaPlace’s equation (the fundamental equation of electrostatics), ∇ 2ϕ = 0, where φ is
the electric potential and the field E is related to φ by E = - ∇ φ. In developing this
solution, we apply two boundary conditions: (i) that φ is continuous at the sphere
surface and (ii) that the normal component of the electric displacement D is also
continuous, where D = є E.
It is not difficult to show that the general solution to the LaPlace equation has angular
solutions which are just the spherical harmonics. In addition, the radial solutions are
of the form rl and r-(l +1), where l is the familiar angular momentum label (l = 0, 1, 2,...)
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of atomic orbitals. If we restrict our considerations for now to just the l = 1 solution
and if Eo is in the x direction, the potential is simply φ = A r sinθ cosΦ inside the
sphere (r < a) and φ = (-Eor + B/r²) sinθ cosΦ outside the sphere (r > a), where A
and B are constants to be determined. If these solutions are inserted into the
boundary conditions and the resulting φ is used to determine the field outside the
sphere, Eout, we get
⌢
⌢ x 3x ⌢ ⌢ ⌢
E out = E o x − αE o 3 − 5 ( xx + yy + zz ) (7. 162)
r r
⌢ ⌢ ⌢
Where R is the sphere polarizability and x , y , and z are the usual unit vectors. We
⌢
⌢ x 3x ⌢ ⌢ ⌢
note that the first term in eq E out = E o x − αE o 3 − 5 ( xx + yy + zz ) (7. 162) is
r r
the applied field and the second is the induced dipole field (induced dipole moment =
αEo) that results from polarization of the conduction electron density.
For a sphere with the dielectric constants indicated above, the LaPlace equation
solution shows that the polarizability is
α = gd a3 (7. 163)
with
∈i − ∈0
gd = (7. 164)
∈i +2 ∈0
⌢
⌢ x 3x ⌢ ⌢ ⌢
Although the dipole field in eq E out = E o x − αE o 3 − 5 ( xx + yy + zz ) (7. 162) is
r r
that for a static dipole, the more complete Maxwell equation solution shows that this
is actually a radiating dipole, and thus, it contributes to extinction and Rayleigh
scattering by the sphere. This leads to extinction and scattering efficiencies given by
8 4
Qsca =
2
x gd (7. 166)
3
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164) plays the key role in determining the wavelength dependence of these cross-
sections, as the metal dielectric constant єi is strongly dependent on wavelength.
For larger particles, higher multipoles, especially the quadrupole term (l=2) become
important to the extinction and scattering spectra. Using the same notation as above
and including the l=2 term in the LaPlace equation solution, the resulting field outside
the sphere, Eout, now can be expressed as
⌢ ⌢ ⌢
x 3x ⌢ xx + zz 5 z ⌢
= E o x + ikE o ( xx + zz ) − αE o 3 − 5 ( xx + yy + zz ) − β Eo − 7 ( x ² x + y ² y + xzz )
⌢ ⌢ ⌢ ⌢ ⌢ ⌢ ⌢
E out 5
r r r r
(7. 167)
α = gd a5 (7. 168)
∈i − ∈0
gd = (7. 169)
∈i +3 / 2 ∈0
∈i − ∈0
Note that the denominator of eq g d = (7. 169) contains the factor 3/2
∈i +3 / 2 ∈0
∈i − ∈0
while in eq g d = (7. 164) the corresponding number is 2. These factors
∈i +2 ∈0
arise from the exponents in the radial solutions to LaPlace’s equation, e.g., the
factors rl and r -(l +1)
that were discussed above. For dipole excitation, we have l=1,
and the magnitude of the ratio of the exponents is (l + 1)/l = 2, while for quadrupole
excitation (l + 1)/l = 3/2. Higher partial waves work analogously.
Following the same derivation, we get the following quasistatic (dipole + quadrupole)
expressions for the extinction and Rayleigh scattering efficiencies:
Qext = 4 x Im g d + g q + (∈i −1)
x² x²
(7. 170)
12 30
8 x4 2 x4 2
= x4 gd + gq + ∈i −1
2
Qext (7. 171)
3 240 900
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We now evaluate the extinction cross-section using the quasistatic expressions, eqs
4, 5 and 9,10 as well as the exact (Mie) theory. We take dielectric constants for silver
that are plotted in Figure 7-6 a and the external dielectric constant is assumed to be 1
(i.e., a particle in a vacuum). The resulting efficiencies for 30 and 60 nm spheres are
plotted in Figure 7-6 b,c, respectively.
Figure 7-6: (a) Real and imaginary part of silver dielectric constants as function of wavelength. (b)
Extinction efficiency, i.e., the ratio of the extinction cross-section to the area of the sphere, as obtained
from quasistatic theory for a silver sphere whose radius is 30 nm. (c) The corresponding efficiency for
a 60 nm particle, including for quadrupole effects, and correcting for finite wavelength effects. In b and
c, the exact Mie theory result is also plotted. [K. Lance Kelly, E. Coronado, L.L. Zhao, G.C. Schatz,
The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric
Environment, 2003, Journal of Physical Chemistry]
The cross-section in Figure 7-6 b shows a sharp peak at 367nm, with a good match
between quasistatic and Mie theory. This peak is the dipole surface plasmon
∈i − ∈0
resonance, and it occurs when the real part of the denominator in eq g d =
∈i +2 ∈0
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(7. 164) vanishes, corresponding to a metal dielectric constant whose real part
is -2. For particles that are not in a vacuum, the plasmon resonance condition
becomes
Re єi/є0= -2, and because the real part of the silver dielectric constant decreases with
increasing wavelength (Figure 7-6 a), the plasmon resonance wavelength for є0 > 1 is
longer than in a vacuum. The plasmon resonance wavelength also gets longer if the
particle size is increased above 30 nm. This is due to additional electromagnetic
effects that will be discussed later.
Figure 7-6 c presents the l = 2 quasistatic (dipole + quadrupole) cross-section as well
as the full Mie theory result for a radius 60 nm sphere. The quasistatic result also
includes a finite wavelength correction. We see that the dipole plasmon wavelength
has shifted to the red, and there is now a distinct quadrupole resonance peak at 357
nm. This quadrupole peak occurs when the real part of the denominator in eq 8
vanishes, corresponding to a metal dielectric constant whose real part is -3/2. For a
sphere of this size, there are clear differences between the quasistatic and the Mie
theory results; however, the important features are retained. Although Mie theory is
not a very expensive calculation, the quasistatic expressions are convenient to use
when only qualitative information is needed.
the Stokes-shifted frequency and the brackets are used to denote an average over
the particle surface. The HRS intensity is similarly (but approximately) determined by
E (ω ) E (2ω )
4 2
. Also, when one makes an aggregate or array of metal
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⌢ ⌢ ⌢
x 3x ⌢ xx + zz 5 z ⌢
E out = E o x + ikE o ( xx + zz ) − αE o 3 − 5 ( xx + yy + zz ) − β Eo − 7 ( x ² x + y ² y + xzz )
⌢ ⌢ ⌢ ⌢ ⌢ ⌢ ⌢
5
r r r r
(7. 167). These expressions determine the near-fields at the particle surfaces quite
accurately for small enough particles; however, the field beyond 100 nm from the
center of the particle exhibits radiative contributions that are not contained in these
equations. To describe these, we need to replace the dipole or quadrupole field by its
radiative counterpart. In the case of the dipole field, this is given by
r × (r × p ) ikr r ² P − 3r (r • P )
E dipole = k ² e ikr 3
+ e (1 − ikr ) (7. 172)
r r5
where P is the dipole moment. Note that this reduces to the static field in eq
⌢
⌢ x 3x ⌢ ⌢ ⌢
E out = E o x − αE o 3 − 5 ( xx + yy + zz ) (7. 162) in the limit k→0 where only the term
r r
in square brackets remains. However, at long range, the first term becomes dominant
as it falls off more slowly with r than the second.
Figure 7-7: E-field contours for radius 30 and 60 nm Ag spheres in a vacuum. Two cross-sections are
depicted for each sphere. (a, b) The plane containing the propagation and polarization axes and (c, d)
the plane perpendicular to the propagation axis. The 30 nm sphere refers to 369 nm light, the main
extinction peak for this size, whereas the larger sphere is for 358 nm light, the quadrupole peak for this
size. Labeled points 1 and 2 illustrate locations for Figure 7-8. [K. Lance Kelly, E. Coronado, L.L.
Zhao, G.C. Schatz, The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and
Dielectric Environment, 2003, Journal of Physical Chemistry]
Figure 7-7 presents contours of the electric field enhancement |E|² around 30 and 60
nm radius silver spheres, based on a Mie theory calculation in which all multipoles
are included. Two planes are chosen for these plots, the xz plane that is formed by
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the polarization and k vectors and the yz plane that is perpendicular to the
polarization vector. The wavelength chosen for the 30 nm particle is the dipole
plasmon peak, so since the dipole field dominates, we see the characteristic p-orbital
shape around the sphere in Figure 7-7 a,c. Note that a small quadupole component
to the field makes the p-orbital lobes slightly asymmetrical. At long range, the
r × (r × p ) ikr r ² P − 3r (r • P )
radiative terms in eq E dipole = k ² e ikr 3
+ e (1 − ikr ) (7. 172)
r r5
become more important, and then, the field has a characteristic spherical wave
appearance.
The wavelength for the 60 nm particle has been chosen to be that for the peak in the
quadrupole resonance, and as a result, the field contours close to the particle in
Figure 7-7 b look like a dxz-orbital (slightly distorted by a small dipole component that
is also present). In addition, Figure 7-7 d, which is a nodal plane for the dxz-orbital,
only shows the weak dipolar component. Note that the peak magnitude of the field for
the 30 nm particle occurs at the particle surface, along the polarization direction. This
peak is over 50 times the size of the applied field, while that for the 60 nm particle is
over 25 times larger. This is responsible for the electromagnetic enhancements that
are seen in SERS, and they also lead to greatly enhanced HRS.
Figure 7-8: Comparison of extinction efficiency, surface-averaged E-field enhancement, and E-field
enhancement for specific points for radius 30 nm (top) and 60 nm (bottom) Ag spheres in a vacuum.
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The two points chosen are point 1, along the polarization direction, and point 2, at a 45° angle relat ive
to the polarization direction and in the xz plane. [K. Lance Kelly, E. Coronado, L.L. Zhao, G.C. Schatz,
The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric
Environment, 2003, Journal of Physical Chemistry]
Figure 7-8 plots the surface-averaged E-field enhancement for the 30 and 60 nm
spheres as a function of wavelength, along with the extinction efficiency. In addition,
the figure includes the E-field enhancement associated with two points on the
sphere: (a) along the polarization direction (point 1) and (b) rotated 45 degrees away
from the polarization direction (point 2). The E-field enhancement associated with
specific points on the surface would be appropriate for understanding a single
molecule SERS experiment, should this be possible for a spherical particle. For both
sphere sizes, the field enhancement due to the dipole resonance peaks to the red of
the extinction. Quasistatic theory predicts that both peaks should occur at the same
wavelength; however, the finite wavelength corrections to the quasistatic result lead
to depolarization of the plasmon excitation on the blue side of the extinction peak,
resulting in a smaller average field and a red-shifted peak.
For the smaller sphere (top panel of Figure 7-8), the E-field enhancement associated
with point 1 is about three times larger than the surface-averaged value, and the
lineshapes are the same. Point 2 shows a smaller enhancement, and it peaks toward
the blue, indicating the influence of a weak quadrupole resonance. For the larger
sphere (bottom), the maximum for point 1 is about 3.5 times greater than the surface
average for the dipole peak. For point 2, we see a maximum at the quadrupole
resonance wavelength, and the enhancement is about three times greater than for
the quadrupole peak in the surface-averaged result. Thus, for the larger sphere, it is
possible for the largest SERS enhancement to be at a location on the surface that is
not along the polarization direction.
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Figure 7-9: (a) A single-wall nanotube is graphene wrapped on a cylinder surface. (b) Nanotubes are
described by a set of two integers (n, m) which indicate the graphite lattice vector components. A
chiral vector can be defined as C = na1 + ma2. Tubes are called ‘zigzag’ if either one of the integers is
zero (n, 0) or called ‘armchair’ if both integers are equal (n, n). [K. S. Ciraci, A. Buldum, I.P. Batra,
Quantum effects in electrical and thermal transport through nanowires, 2001, Journal of Physics
Condensed Matter]
In this way the 2D hexagonal lattice of grapheme is mapped onto a cylinder of radius
R. The mapping can be realized with different helicities resulting in different
nanotubes. Each nanotube is characterized by a set of two integers (n, m) indicating
the components of the chiral vector C = na1 + ma2 in terms of the 2D hexagonal
Bravais lattice vectors of graphene, a1 and a2, as illustrated in Figure 7-9(b). The
chiral vector is a circumferential vector and the tube is obtained by folding the
graphene such that the two ends of C are coincident. The radius of the tube is given
in terms of (n, m) through the relation R = a 0 n² + m² + nm / 2π , where |a1| = |a2| = a0.
When C involves only a1 (corresponding to (n, 0)) the tube is called ‘zigzag’, and if C
involves both a1 and a2 with n = m (corresponding to (n, n)) the tube is called
‘armchair’. The chiral (n, n) vector is rotated by 30◦ relative to that of the zigzag (n, 0)
tube. SWNTs are found in the form of nanoropes, each rope consisting of up to a few
hundred nanotubes arranged in a hexagonal lattice structure.
analogous to the electronic structure of a graphene. Graphene has the lowest π∗∗-
conduction band and the highest π-valence band, which are separated by a gap in
the entire hexagonal Brillouin zone (BZ) except at its K corners where they cross. In
this respect, graphene lies between a semiconductor and a metal with Fermi points at
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the corners of the BZ. You can imagine an unrolled, open form of nanotube, which is
graphene subject to periodic boundary conditions on the chiral vector. This in turn
imposes quantization on the wave vector. This is known as zone folding, whereby the
BZ is sliced with parallel lines of wave vectors, leading to subband structure. A
nanotube’s electronic structure can thus be viewed as a zone-folded version of the
electronic band structure of the graphene. When these parallel lines of nanotube
wave vectors pass through the corners, the nanotube is metallic. Otherwise, the
nanotube is a semiconductor with a gap of about 1 eV, which is reduced as the
diameter of the tube increases. Within this simple approach, (n, m) nanotubes are
metallic if n − m = 3× integer. Consequently, all armchair tubes are metallic. The
conclusion that you draw from the above paragraph is that the electronic structures of
nanotubes are determined by their chirality and diameter, i.e. simply by their chiral
vectors C.
The first theoretical calculations were performed and the above simple understanding
was provided much earlier than the first conclusive experiments were carried out . In
these early calculations, a simple one-band π-orbital tight-binding model was used.
However, different calculations have been at variance on the values of the band gap.
For example, while the σ∗–π∗ hybridization due to the curvature can be treated well
Figure 7-10: (a) The band structure, (b) density of states and (c) conductance of a (10, 10) nanotube.
The tight-binding model is used to derive the electronic structure. The conductance is calculated using
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the Green’s function approach with the Landauer formalism. [K. S. Ciraci, A. Buldum, I.P. Batra,
Quantum effects in electrical and thermal transport through nanowires, 2001, Journal of Physics
Condensed Matter]
In Figure 7-10(a) and (b) the band structure and density of states (DOS) of a (10, 10)
tube are given, based on a tight-binding calculation. Samples prepared by laser
vaporization consist predominantly of (10, 10) metallic armchair SWNTs. As can be
seen in Figure 7-10 (a), band crossing is allowed, and the bonding π- and
In Figure 7-10 (b) the density of states is plotted for the (10, 10) tube. The E−1/2-
singularities which are typical for 1D energy bands appear at the band edges. STM
spectra of nanotubes show densities of states with similar singularities to those
obtained by band calculations. One-dimensional metallic wires are generally unstable
and have Peierls distortion.
The energy gain after Peierls distortion is found to be very small for nanotubes and
the Peierls energy gap can be neglected. The curvature of nanotubes introduces
hybridization also between sp2 and sp3 orbitals, but these effects are small when the
radius of a SWNT is large. However, the π∗- and σ∗-state mixing was enhanced for
small-radius zigzag SWNTs. Recently, it has been shown that the electronic
properties of a SWNT can undergo dramatic changes owing to the elastic
deformations. For example, the band gap of a semiconducting SWNT can be
reduced or even closed by the elastic radial deformation. The gap modification and
the eventual strain-induced metallization seem to offer new alternatives for reversible
and tunable quantum structures and nanodevices.
A nanotube can be an ideal quantum wire for electronic transport; two subbands
crossing at the Fermi level should nominally give rise to two conducting channels.
Under ideal conditions each channel can carry current with unit quantum
kΩ. The contribution of each subband to the total conductance is clearly seen in
Figure 7-10 (c) illustrating the calculated conductance of the (10, 10) nanotube.
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The first electronic transport measurements of nanotubes were carried out using
MWNTs. These measurements found MWNTs to be highly resistive due to defect
scattering and weak localization. The first electronic transport measurements of
individual SWNTs and nanoropes were performed by Tans et al [] and Bockrath et al
[]. In these measurements nanotubes or nanoropes were placed on an insulating
(oxidized silicon) substrate containing metallic electrodes.
Figure 7-11: a) and b) [K. S. Ciraci, A. Buldum, I.P. Batra, Quantum effects in electrical and thermal
transport through nanowires, 2001, Journal of Physics Condensed Matter]
In Figure 7-11 (a) an AFM image of an individual SWNT on a silicon dioxide substrate
is shown with two Pt electrodes. A gate voltage Vg is applied to the third electrode in
the upper left corner to shift the electrostatic potential of the nanotube. The
measurements were performed at 5 mK and step-like features are observed in
current–voltage curves shown in Figure 7-11 (b). Note that the voltage scale is mV
and these steps are not due to the quantized increase of conductance with subbands
shown in Figure 7-10 (c). These steps are due to resonant tunnelling of electrons to
the states of a finite nanotube. The presence of metallic electrodes introduces
significant contact resistances and changes the bent part of the nanotube into a
quantum-dot-like structure. The same phenomena were seen in individual ropes of
nanotubes with oscillations in the conductance at low temperatures.
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Figure 7-12: Variation of the conductance with the gate voltage at temperatures from 1.5 K to 282 K
for a nanorope with metallic tubes. [K. S. Ciraci, A. Buldum, I.P. Batra, Quantum effects in electrical
and thermal transport through nanowires, 2001, Journal of Physics Condensed Matter]
Figure 7-12 shows conductance versus gate voltage for a nanorope for various
temperatures. The average conductance drops with T. Conductance oscillations at
low temperatures are due to the Coulomb blockade effect. The energy levels of the
rope are quantized and the single molecular level spacing ∆ε exceeds the thermal
energy, kBT. On changing the gate voltage, single electrons tunnel to the quantized
molecular levels. Recently, metallic contacts with low resistances have been
achieved which do not show Coulomb blockade oscillations down to 1.7 K. Another
important behaviour in Figure 7-12 is the monotonic decrease of conductance with
decrease of temperature which is a signature of correlated electron liquids. It is well
known that the electrons in one-dimensional systems may form not Fermi liquids but
the so-called Luttinger liquids with electron correlation effects. An important feature of
Luttinger liquids is the separation of spin and charge by formation of quasi-particles.
and also on temperature (G ∝ Tα), which are typical for Luttinger liquids.
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Figure 7-13: (A) A transmission electron micrograph (TEM) image of the end of a nanotube fibre
which consists of carbon nanotubes and small graphitic particles. (B) A schematic diagram of the
experimental set-up. Nanotubes are lowered under SPM control to a liquid metal surface. (C) Variation
of conductance with nanotube fibre position. Plateaus are observed corresponding to additional
nanotubes coming into contact with the liquid metal. [K. S. Ciraci, A. Buldum, I.P. Batra, Quantum
effects in electrical and thermal transport through nanowires, 2001, Journal of Physics Condensed
Matter]
The nanotubes were straight with lengths of 1 to 10 µm. As the nanotubes were
dipped into the liquid metal one by one, the conductance increased in steps of 2e2/h
as shown in Figure 7-13(c). Each step corresponds to an additional nanotube coming
into contact with liquid metal. The electronic transport is found to be ballistic, since
the step heights do not depend on the different lengths of nanotubes coming into
contact with the metal.
On the theory side, different techniques are used to calculate quantum effects on the
conductance of nanotubes. These techniques are based on linear response theory
and use the Landauer formalism.
1. The tip–nanotube–substrate system in STM.
2. Investigation of the Aharonov–Bohm effect in nanotubes.
3. Study of tunnelling conductance of nanotube junctions which are joined by a
connecting region with a pentagon–heptagon pair.
4. Effective-mass theory with envelope functions for similar junctions…
Among these methods, Green’s function methods are found to be the most effective
and hence are widely used for nanotubes with local basis sets.
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Current trends in microelectronics are to produce smaller and faster devices. Owing
to the novel and unusual mechanical and electronic properties, carbon nanotubes
appear to be potential candidates for meeting the demands of nanotechnologies.
There are already nanodevices which use nanotubes. Single-electron transistors
were produced by using metallic tubes; the devices formed therefrom have operated
at low temperatures. For example, a field-effect transistor that consists of a
semiconductor nanotube and operates at room temperature. The nanotube placed on
two metal electrodes and a Si substrate which is covered with SiO2 is used as a
back-gate. The nanotube is switched from a conducting to an insulating state by
applying a gate voltage.
One approach used in making a nanodevice was based on the fact that the defects in
a nanotube can form an intermolecular junction from an individual tube. It was shown
that topological defects like pentagon–heptagon pair defects can change the helicity
and hence the electronic structure of the nanotube. This raises the possibility of
fabricating metal–metal (M–M), metal–semiconductor (M–S) and semiconductor–
semiconductor (S–S) junctions on a single nanotube.
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a) Atomic structure of a
semiconductor–metal
b) The local density of states (LDOS) at cells 1, 2 and 3. Cell 3 is on
junction ((8, 0)–(7, 1)) with a
the (8, 0) side of the tube and cell 1 is at the interface.
pentagon–hexagon pair
defect. Grey balls denote the
atoms forming the defect.
Figure 7-14: a) and b) [K. S. Ciraci, A. Buldum, I.P. Batra, Quantum effects in electrical and thermal
transport through nanowires, 2001, Journal of Physics Condensed Matter]
Figure 7-14 (a), the atomic structure of a M–S junction is shown. An (8, 0) tube
(semiconductor) is joined to a (7, 1) tube (metal) with a pentagon–hexagon defect
(highlighted in grey). The local density of states (LDOS) based on a π-orbital tight-
binding model is presented in Figure 7-14 (b). The LDOS is distorted close to the
interface, but recovers the DOS of a perfect tube away from the interface on both
sides. There is a conductance gap in M–S and S–S junctions and diode-like
behaviour can be achieved. However, in M–M junctions, the conductance depends
on the arrangement of the defects. The junction is insulating for symmetric
arrangement, but conducting for asymmetric arrangement. Kink structures which
consist of such defects have been observed experimentally. M–S junction behaves
like a rectifying diode with non-linear transport characteristics and the conductance
of the M–M junction was suppressed. Other intermolecular junctions include
nanotube–silicon nanowire junctions and Y-junctions which exhibit rectification.
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Two or more nanotubes can form nanoscale junctions with unique properties. A
simple intermolecular nanotube junction can be formed by bringing two tube ends
together. Figure 7-15 (a) illustrates such a junction with two semi-infinite (10, 10)
tubes in parallel and pointing in opposite directions.
Figure 7-15: (a) An intermolecular nanotube junction formed by bringing two semi-infinite (10, 10)
tubes together. l is the contact length. (b) The conductance, G, of a (10, 10)–(10, 10) junction as a
function of energy, E, for l = 64 Å. Interference of electron waves yields resonances in conductance.
(c) Current–voltage characteristics of a (10, 10)–(10, 10) junction at l = 46 Å. [K. S. Ciraci, A. Buldum,
I.P. Batra, Quantum effects in electrical and thermal transport through nanowires, 2001, Journal of
Physics Condensed Matter]
These junctions have high conductance values and exhibit negative differential
resistance behaviour. Interference of electron waves reflected and transmitted at the
tube ends gives rise to the resonances in conductance shown in Figure 7-15 (b). The
current–voltage characteristics of this junction presented in Figure 7-15 (c) show a
negative differential resistance effect, which may have applications in high-speed
switching, memory and amplification devices.
A four-terminal junction can be constructed by placing one nanotube perpendicular to
another and forming a cross-junction (Figure 7-16 (a)).
Figure 7-16: (a) A four-terminal cross-junction with two nanotubes perpendicular to each other. (b)
The resistance of an (18, 0)–(10, 10) junction as a function of tube rotation. The rotation angle, Θ, and
terminal indices are shown in the inset. The tube which is labelled by 2 and 4 is rotated by Θ. The
contact region structure is commensurate at Θ = 30, 90, 150◦.[K. S. Ciraci, A. Buldum, I.P. Batra,
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Quantum effects in electrical and thermal transport through nanowires, 2001, Journal of Physics
Condensed Matter]
7.4 Semiconductor
7.4.1 Introduction
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nanocrystal. It is in this form that the influence of size alone might be most directly
observed. The ability to prepare clusters in the gas phase by laser vaporization must
be considered one of the great achievements of cluster science and led to an
explosion of work in the field. In the case of semiconductors, early work on bare
clusters in the 3-50 atoms range has shown that remarkable changes occur in the
electronic structure in this regime. As there is no clearly identifiable interior in clusters
of this size, it is not too surprising that unique bonding geometries, distinct from those
of the bulk solid, are assumed. As the size produced and studied in the gas phase
continues to increase into the nanocrystal regime, it remains true that this form of
cluster is one in which much fundamental science remains to be done. The inability to
prepare large quantities of mass selected nanocrystals by laser vaporization and the
difficulties associated with direct measurements of structural properties in the gas
phase have also led cluster scientists to pursue other forms of nanocrystals in
parallel with the gas phase studies.
Despite the seeming perfection of a pure cluster in the gas phase, from the point of
view of semiconductor physics, it is in many ways a highly defective system. At the
surface of a pure semiconductor, substantial reconstructions in the atomic positions
occur, and there invariably lie energy levels within the energetically forbidden gap of
the bulk solid. These surface states act as traps for electrons or holes and degrade
the electrical and optical properties of the material. “Passivation” is the chemical
process by which these surface atoms are bonded to another material of a much
larger band gap, in such a way as to eliminate all the energy levels inside the gap.
The ideal termination naturally removes the structural reconstructions, leaving no
strain, and simply produces an atomically abrupt jump in the chemical potential for
electrons or holes at the interface. The termination of Si with SiO2 and that of
Al1-xGaxAs with GaAs are probably the best known examples of successful
passivation. In the first case the passivation is achieved with a disordered material
that can accommodate its local bonding geometry to that of the underlying
semiconductor; in the second case the crystal structures and bond lengths of the two
materials are matched, so that passivation is achieved epitaxially.
Over decades, the ability to control the surfaces of semiconductors with near atomic
precision has led to a further idealization of semiconductor structures: quantum wells,
wires, and dots. Ignoring for a moment the detailed atomic level structure of the
material, it is possible to imagine simple geometric objects of differing dimensionality
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(2,1, and 0), in each case made out of homogeneous semiconductor material and
with perfect surface termination. Such structures should exhibit the idealized
variations in density of electronic states predicted by simple particle in a box type
models of elementary quantum mechanics, with the continuous levels of the 3D case
evolving into the discrete states of the 0-dimensional case (Figure 7-17).
Figure 7-17: Idealized density of states for one band of a semiconductor structure of 3, 2, 1, and “0”
dimensions. In the 3D case the energy levels are continuous, while in the “0D’” or molecular limit the
levels are discrete. [A.P. Alivisatos, Perspectives on the physical chemistry of semiconductor
nanocrystals, 1996, Journal of Physical Chemistry]
Phenomenal success has been achieved in making quantum well films of nanometer
thick layers of alternating GaAs and Al1-xGaxAs, using the techniques of molecular
beam epitaxy. By manipulating steps or defects on a substrate, these same methods
can be employed to form wires or, even most recently, dots. One of the most
powerful features of these methods is the fact that, at the end, the low-dimensional
semiconductor structure is completely embedded inside another material with larger
gap, providing a high degree of surface passivation.
A chemist immediately recognizes the zero-dimensional quantum dot as a rather
large molecule. Indeed, the third ideal of the nanocrystal derives from a long history
of synthetic inorganic cluster chemistry. Chemists have long prepared ever larger
inorganic cluster compounds: collections of inorganic atoms bound to each other and
surrounded by organic ligands that confer solubility and prevent agglomeration.
These clusters are only considered well characterized when they have been
crystallized and their structures determined by X-ray diffraction. Unlike any other form
of nanocrystal, in this case, the precise atomic composition and the location of each
atom are known. In the past decade, chemists have achieved great success in
increasing the number of atoms in the inorganic cores of these cluster compounds, to
the point where they extend clearly into the nanocrystal regime (Figure 7-18). It is of
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considerable interest to note that this form of cluster will naturally assume high-
symmetry shapes, such as tetrahedral or hexagonal prism.
Figure 7-18: Ball and stick model of a Cd32S55 molecule recently synthesized and structurally
characterized. The organic ligands are omitted for clarity. This molecule is a fragment of the CdS zinc
blende lattice. [A.P. Alivisatos, Perspectives on the physical chemistry of semiconductor nanocrystals,
1996, Journal of Physical Chemistry]
From the perspective of solid state physics and materials science, it is perhaps
surprising that nanocrystals of inorganic solids, coated with organic ligands, may
prove one of the most diverse and powerful ideals of a “quantum dot.” This is so
because, as a molecule, the nanocrystal can now be considered not just a
component embedded in the surface of a solid state device, but rather a chemical
reagent. In this form the nanocrystal may be dissolved in a fluid, spun into a polymer,
attached to an electrical circuit, bound to other nanocrystals as dimers, trimers, etc.
or someday perhaps bound to biological molecules. It is important to realize that, in
the construction of optical and electronic materials using components of nanometer
size, it is not only the physical properties of matter that change but also the chemical
methods by which the materials are constructed.
It is not yet established one way or the other whether organic ligands, which turn
nanocrystals into chemical reagents, also act as good passivating layers. One
difficulty arises in matching the large, bulky ligands required to confer solubility with
the compact packing of atoms on the surfaces of the crystallites. Bulky ligands with
many torsional modes confer solubility entropically by mixing with the solvent.
However, their size ensures that invariably some surface sites are unterminated.
Inorganic passivation of nanocrystals still is possible, however. This is clearly
demonstrated in the case of SiO2-coated Si nanocrystals and in the case of oxidized
InP nanocrystals. It is also seen in nanocrystals that are grown inside glass. Indeed,
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there are even analogs to quantum wells, in which layers of inorganic solids are
grown in successive shells around one another, epitaxially. The best documented
example of this is the CdS/HgS/CdS quantum dot quantum well. In each case, the
final product is still small enough that a final layer of ligands bound to the outer
surface is sufficient to confer solubility and open the use of these solid state materials
to the world of chemical synthesis.
Figure 7-19: Density of states in metal (a) and semiconductor (b) nanocrystals. In each case, the
density of states is discrete at the band edges. [A.P. Alivisatos, Perspectives on the physical chemistry
of semiconductor nanocrystals, 1996, Journal of Physical Chemistry]
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For a free particle or a particle in a periodic potential, the energy and the crystal
momentum ћk may both be precisely defined, while the position is not. As a particle
is localized, the energy may still be well-defined; however, the uncertainty in position
decreases, so that momentum is no longer well-defined. The energy eigenfunctions
of the particle may then be viewed as superpositions of bulk k states. In the extended
case, there is a relationship between energy and momentum, and to a first
approximation, the change in energy as a function of the size can be estimated
simply by realizing that the energy of the confined particle arises by superposition of
bulk k states of differing energy.
For a free particle, the dependence of energy on wavevector is quadratic:
E = ℏk 2 / 2 m (7. 174)
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The single-particle wave functions for electrons and holes in the extended solid can
be viewed as linear combination of unit cell atomic orbitals, multiplied by phase
factors between the unit cells. When all the cells are in phase, the wavevector,
k=(2π/λ), is equal to 0; when adjacent cells are out of phase, k takes on its maximum
value, π/a. In a simple one-dimensional single band tight binding model, the
dependence of E on k is
where α, the energy of the linear combination of atomic orbitals inside the unit cell,
determines the center position of the band in energy. 2β gives the width of the band
and is directly related to the strength of nearest-neighbor coupling and inversely
proportional to the effective mass. An expansion of the cos(ka) term for small k
yields a quadratic term as its first term, so that one can see why the effective mass
approximation only describes the band well near either its minimum or its maximum.
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Considering now a real binary semiconductor, such as CdSe, the single particle
states can be viewed as products of unit cell atomic orbital combinations and phase
factors between unit cells (Figure 7-20 A). For example, the highest occupied
molecular orbital or top of the valence band may be viewed as arising from Se 4p
orbitals, arranged to be in phase between unit cells. This will be the maximum of the
valence band, since adjacent p orbitals in phase are σ antibonding (and π bonding).
Similarly, the lowest unoccupied molecular orbital will be comprised of Cd 5s atomic
orbitals, also in phase between unit cells. This is the minimum of the conduction
band, since s orbitals in phase constructively interfere to yield a bonding level. In this
case, the minimum of the conduction band and the maximum of the valence band
have the same phase factor between unit cells.
How does optical absorption arise in the extended solid? The optical absorption
matrix element is given by
where exp(ikr), the envelope functions, denote the phase factors between unit cells,
and the vibrational overlap between ground and excited vibrational states is
determined by Franck-Condon factors, just as for allowed transitions in molecules.
Note that in this case the electronic transition between the unit cell functions is dipole
allowed. The radiative rate is determined from
2π 2
w=∫ µ δ ( E f − Ei + E photon ) ρ ( E fk , Eik )dE (7. 177)
f ℏ
where ρ denotes the joint density of valence and conduction band electronic states
with the same k. The matrix element is factored so that the dipole operator acts on
the electronic wave function within the unit cell, and the phase factors between unit
cells, exp(ikvr) and exp(ikcr), must overlap for the transition to be allowed (kv = kc).
In this case, the transition is dipole allowed within each unit cell. Further, the
transition dipole moment points in the same direction from unit cell to unit cell.
Thus, the electric field of light, which is very long wavelength compared to the size of
the unit cell, can drive all the transition dipoles in phase, and overall the transition is
allowed. In the language of solid state physics, this is a vertical transition, with ∆k=0,
and hence CdSe is called a direct band gap material. At low temperature, the
electronic transition will be accompanied by vibrational excitation of totally symmetric
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modes, in accordance with the Franck-Condon factors. Past the absorption threshold,
the unit cell matrix element for absorption is largely unchanged, and the absorption
efficiency rises steeply at higher incident photon energies because of the large
increase in the joint density of states for vertical transitions. Numerous experiments
show that quantum confinement dominantly affects the absorption spectrum by
changes in the envelope functions and the density of states as a function of the
energy, with relatively less effect on the intrinsic, unit cell based, matrix element for
absorption.
As the size is reduced, the electronic states may be viewed as superpositions of bulk
states. Hence, there is a shift to higher energy, the development of discrete features
in the spectra, and concentration of the oscillator strength into just a few transitions.
Qualitatively, all of these effects can be readily observed in the spectra of Figure
7-21, which show data for CdSe.
Figure 7-21: Optical absorption vs size for CdSe nanocrystals shows the shift to higher energy in
smaller sizes, as well as the development of discrete structure in the spectra and the concentration of
oscillator strength into just a few transitions. [A.P. Alivisatos, Perspectives on the physical chemistry of
semiconductor nanocrystals, 1996, Journal of Physical Chemistry]
The quantitative analysis of these spectra remains a difficult subject, for several
reasons:
• The foregoing picture is a single-particle one and does not include the
substantial effects of correlation. In molecules this is analogous to trying to use
the highly approximate molecular orbital theory, instead of more advanced
quantum chemistry methods. Regrettably, the nanocrystals are too large to
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describe using even moderately advanced methods that are routinely applied
to small molecules.
• Further, in CdSe at least, the large atomic number of the Se ensures that the
coupling between spin and orbital momenta is very strong in the valence
bands (p bands). This coupling is in the j-j, and not the Russell-Saunders, L-S,
coupling regime. When translational symmetry is removed, the mixing of k
vectors can also result in different bands mixing together.
• The shape of the crystallites, which is regular (tetrahedral, hexagonal prisms),
or spherical, or ellipsoidal, will determine the symmetry of the nanocrystals
and will influence the relative spacing of the levels.
• Finally, surface energy levels are completely excluded from this simple
quantum confinement picture. Yet it seems apparent that surface states near
the gap can mix with interior levels to a substantial degree, and these effects
may also influence the spacing of the energy levels.
Theoretical approaches that directly include the influence of the surface, as well as
electronic correlation, are being developed rapidly.
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+ - + - + - + - + - + - + + + + + +
tunnel junction
+ - + - + - + - + - + - + + + + + +
+ - + - + - + - + - + - + + + + + +
Figure 7-22: The left side shows, that the electron cloud shift against the lattice of atoms is not
quantized. The right side shows an accumulation of electrons at a tunnel junction.
I
conduction current
I
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Figure 7-24: The electron-box can be filled with a precise number of electrons.
The current biased tunnel junction is one very simple circuit, that shows the
controlled transfer of electrons. Another one is the electron-box (see Figure 7-24).
A particle is only on one side connected by a tunnel junction. On this side electrons
can tunnel in and out. Imagine for instance a metal particle embedded in oxide, as
shown in Figure 7-25.
metal
particle
oxide
Figure 7-25: Metal particle embedded in oxide. Tunneling is only possible through the thin top layer
of oxide.
The top oxide layer is thin enough for electrons to tunnel through. To transfer
one electron onto the particle, the Coulomb energy EC = e2/2C, where C is the
particles capacitance, is required. Neglecting thermal and other forms of energy, the
only energy source available is the bias voltage Vb. As long as the bias voltage is
small enough, smaller than a threshold Vth = e/C, no electron can tunnel, because
not enough energy is available to charge the island. This behavior is called the
Coulomb blockade. Raising the bias voltage will populate the particle with one, then
two and so on electrons, leading to a staircase-like characteristic.
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e2
Ec = > k BT (7. 178)
2C
h
RT > = 25813Ω (7. 179)
e2
Therefore, these effects are experimentally verifiable only for very small high-
resistance tunnel junctions, meaning small particles with small capacitances and/or
very low temperatures. Advanced fabrication techniques, such as the production of
granular films with particle sizes down to 1 nm, and deeper physical understanding
allow today the study of many charging effects at room temperature.
Based on the Coulomb blockade many interesting devices are possible, such as
precise current standard,lxxiii very sensitive electrometers,lxxiv logic gateslxxv and
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lxxvi
memories with ultra low power consumption, down-scalability to atomic
dimensions, and high speed of operation. Altogether, single-electronics will bring new
and novel devices and is a very promising candidate to partly replace MOS
technology in the near future.
q2
Ec = (7. 180)
4πε d
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An indirect proportionality to the size of the particle. Figure 7-26 to Figure 7-28
compare this electrostatic energy to the other characteristic energies involved in
charging an island with a small number of electrons.
10 1
Electrostatic charging energy e 2 /2c
Change of EF for 1st additional electron in Si
Change of EF for 2nd additional electron in Si
Change of EF for 3rd additional electron in Si
10 0
Energy [eV]
10 -1
thermal energy at 300 k
10 -2
10 -3
10 -1 10 0 10 1 10 2
Particle diameter [nm]
Figure 7-26: Comparison of the change in Fermi energy for the addition of one, two, and three
electrons in Si to the electrostatic charging energy.
10 1
Electrostatic charging energy e 2 /2c
Change of EF for 1st additional electron in Si
Change of EF for 2nd additional electron in Si
10 0
Energy [eV]
10 -1
10 -2
10 -3
10 -1 10 0 10 1 10 2
Particle diameter [nm]
Figure 7-27: Comparison of the change in Fermi energy for the addition of one electron in Si and Al.
The values below 1 nm particle diameter are questionable (see later)
For the sake of simplicity, the relative permittivity ε was assumed to be 10. A more
accurate model for the capacitance of an island is the capacitance of two or more
spheres in a line. A calculation for characteristic spatial dimensions shows an
increase of about 15% of the total capacitance.
For a system of N conductors the charge on one conductor may be written as
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N
qi = ∑ Cijϕ j (i = 1, 2,3,......) (7. 182)
j =1
Where the Cij denote the elements of the capacitance matrix. The diagonal elements
of the capacitance matrix Cij are the total capacitances of the conductors i and the
off-diagonal elements Cij are the negative capacitances between conductor i and j.
e2
The electrostatic charging energy is in analogy to Ec = > k BT (7. 178)
2C
Ec =
1 N
∑ i i 2 ∑∑
2 i =1
q ϕ =
1 N N
(C −1 )ij qi q j (7. 183)
i =1 j =1
ℏ2
* (
3π 2 n )
23
EF = (7. 184)
2m
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NANOMATERIALS
nnet E − EF ,i
= 2sinh F (7. 185)
ni k BT
Where nnet is the net carrier concentration defined as nnet= n-p. Figure 7-26
compares the change in the Fermi energy for the addition of one, two, and three
electrons in Si to the electrostatic charging energy.
The first electron causes the biggest change in Fermi energy. The second and
third electron contribute a change smaller than the thermal energy for room
temperature. Hence, for single-electron devices one will try to build structures with
few free carriers, to achieve a high change in energy when charging an island.
Figure 7-27 compares Si with Al. It is clearly visible that the change is much
bigger in Si. This is caused by two reasons. First, the difference in free carrier
concentration. In metals much more carriers are available and therefore the addition
of one electron has not such a big impact anymore. Second in metals an additional
electron finds a place slightly above the Fermi level. In semiconductors due to the
energy gap the electron needs to be inserted considerably above the Fermi level.
Quantum Confinement Energies
With decreasing island size the energy level spacing of electron states
increases indirectly proportional to the square of the dot size. Taking an infinite
potential well as a simple model for a quantum dot, one calculates by solving
Schrödinger's equation the energy levels to
1 ℏπ N
2
EN = (7. 186)
2m * d
Because of the lower effective mass in Si compared to Al, the quantum confinement
energy is bigger in Si (see Figure 7-28).
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10 1
Electrostatic energy e2 /2c
Confinement energy for metals
Confinement energy for Si
10 0
10 -1
thermal energy at 300 k
10 -2 thermal energy at 77 k
10 -3
10 -1 10 0 10 1 10 2
Particle diameter [nm]
1 ℏπ N
2
7.4.3.2 Tunneling
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1926 in a definite form which is now known as the Schrödinger wave equation. The
continuous nonzero nature of its solution, the wave function which represents an
electron or particle, implies an ability to penetrate classically forbidden regions and a
probability of tunneling from one classically allowed region to another. Fowler and
Nordheim explained in 1928 the main features of electron emission from cold metals
by high external electric fields on the basis of tunneling through a triangular potential
barrier. Conclusive experimental evidence for tunneling was found by L. Esaki in
1957 and by I. Giaever in 1960. Esaki's tunnel diode had a large impact on the
physics of semiconductors, leading to important developments such as the tunneling
spectroscopy, and to increased understanding of tunneling phenomena in solids. L.
Esaki , I. Giaever and B. Josephson received 1973 the Nobel prize for their work
about tunneling in semiconductors, superconductors and theoretical predictions of
the properties of a supercurrent through a tunnel barrier, respectively. The concept of
resonant tunneling in double barriers was first introduced by R. Davis and H. Hosack.
At about the same time C. Neugebauer and M. Webb and some years later H. Zeller
and I. Giaever and J. Lambe and R. Jaklevic studied granular films. They observed a
current suppression at low bias voltage, which is today known as the Coulomb
blockade. It took almost two decades until in 1985 D. Averin and K. Likharev
formulated the `orthodox' theory of single-electron tunneling or short SET, which
quantitatively describes important charging effects such as Coulomb blockade and
Coulomb oscillations. The orthodox theory makes the following assumptions: It
neglects dimensions and shapes of islands. Thus it is a zero-dimensional model. The
tunnel process is assumed to be instantaneous. Actually the tunnel time, the duration
an electron spends below a barrier, is of the magnitude of 10-14 s. Charge
redistributions after a tunnel event are also assumed to be instantaneous. In addition
energy spectra in leads and islands are taken to be continuous. The main result of
the orthodox theory is that the rate of a tunnel event strongly depends on the change
in free energy the event causes.
The formulation of the Coulomb blockade model is only valid, if electron states are
localized on islands. In a classical picture it is clear, that an electron is either on an
island or not. That is the localization is implicit assumed in a classical treatment.
However a preciser quantum mechanical analyses describes the number of electrons
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Clearly, if the tunnel barriers are not present, or are insufficiently opaque, one can not
speak of charging an island or localizing electrons on a quantum dot, because
nothing will constrain an electron to be confined within a certain volume.
A qualitative argument is to consider the energy uncertainty of an electron
∆t ≅ RT C (7. 189)
The time constant for charging capacitance C through tunnel resistor RT, and the
energy gap associated with a single electron is
e2
∆E = (7. 190)
C
Combining these equations gives the condition for the tunnel resistance
h
RT > = RQ = 25813Ω (7. 191)
e2
2
Another line of thought proceeds as follows. The condition N − N 〈〈1 requires that
the time t which an electron resides on the island be much greater than ∆t , the
quantum uncertainty in this time.
h
t >> ∆t ≥ (7. 192)
∆E
The current I cannot exceed e/t since for moderate bias and temperature at most one
extra electron resides on the island at any time. The energy uncertainty of the
electron ∆ E is no larger than the applied voltage Vb.
Vb h
RT = >> 2 (7. 194)
I e
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In fact, more rigorous theoretical studies of this issue have supported this conclusion.
Experimental tests have also shown this to be a necessary condition for observing
single-electron charging effects.lxxvii
Consider two tunnel junctions in series biased with an ideal voltage source as shown
in Figure 7-29. The charges on junction one, junction two, and on the whole island
can be written as
respectively, with n1 the number of electrons that tunneled through the first junction
entering the island, n2 the number of electrons that tunneled through the second
junction exiting the island, and n=n1-n2 the net number of electrons on the island.
C2Vb + ne − q0 C V − ne + q0
V1 = ,V2 = 1 b
CΣ CΣ (7. 196)
where, CΣ = C1 + C2
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Figure 7-29: Two tunnel junctions in series biased with an ideal voltage source. The background
charge q0 is non-integer, and n1 and n2 denote the number of tunneled electrons through junction one
and junction two, respectively.
C2Vb + ne − q0 C V − ne + q0
V1 = ,V2 = 1 b
With CΣ CΣ (7. 196) the electrostatic energy
where, CΣ = C1 + C2
stored in the double junction is
C1C2Vb2 + ( ne − q0 )
2
q12 q22
EC = + = (7. 197)
2C1 2C2 2C∑
In addition, to get the free energy one must consider, the work done by the
voltage source. If one electron tunnels through the first junction the voltage source
has to replace this electron -e, plus the change in polarization charge caused by the
C2Vb + ne − q0 C V − ne + q0
V1 =,V2 = 1 b
tunneling electron. V1 changes according to CΣ CΣ (7.
where, CΣ = C1 + C2
The charge q1 gets smaller, which means that the voltage source `receives'
polarization charge. The total charge that has to be replaced by the voltage source is
therefore − eC2 C∑ and the work done by the voltage source in case electrons tunnel
n1eVbC2
W1 = −
C∑
and (7. 198)
n2 eVbC1
W2 = −
C∑
F ( n1 , n2 ) = Ec − W =
1 1
C∑ 2
{ }
C1C2Vb2 + ( ne − q0 ) + eVb ( C1n2 + C2n1 )
2
(7. 199)
At zero temperature, the system has to evolve from a state of higher energy to
one of lower energy. At non-zero temperatures transitions to higher energy states are
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possible, but have exponentially reduced probability. The change in free energy for
an electron tunneling through junction one and two is given by
e e
∆F1± = F ( n1 ± 1, n2 ) − F ( n1 , n2 ) = 2 ± (VbC2 + ne − q0 ) (7. 200)
C∑
e e
∆F2± = F ( n1 , n2 ± 1) − F ( n1 , n2 ) = ± (VbC1 − ne + q0 ) (7. 201)
C∑ 2
The probability of a tunnel event will only be high, if the change in free energy is
negative - a transition to a lower energy state. The leading term in equations above
causes ∆F to be positive until the magnitude of the bias voltage Vb exceeds a
threshold which depends on the smaller of the two capacitances. This is the case for
all possible transitions starting from an uncharged island, n=0 and q0=0. For
symmetric junctions (C1 = C2) the condition becomes
This suppression of tunneling for low bias is the Coulomb blockade. The Coulomb
blockade can be visualized with an energy diagram Figure 7-30.
filled energy
states
emptyenergy
states
EF
EF
gap
-eVb
Figure 7-30: Energy diagram of a double tunnel junction without and with applied bias. The Coulomb
blockade causes an energy gap where no electrons can tunnel through either junction. A bias larger
than e/C overcomes the energy gap.
Due to the charging energy of the island, a Coulomb gap has opened, half of which
appears above and half below the original Fermi energy. No electrons can tunnel into
the island from the left or right electrode, or out of the island. Only if the bias voltage is
raised above a threshold can electrons tunnel in and out, and current will flow.
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The same fact, the existence of a Coulomb blockade, is clearly visible in the IV-
characteristic, Figure 7-31.
Figure 7-31: IV-characteristic of a double tunnel junction. The solid line gives the characteristic for
q0=0 and the dashed line for q0=0.5e. The Coulomb blockade is a direct result of the additional
2
Coulomb energy, e /2C, which must be expended by an electron in order to tunnel into or out of the
island.
For low bias no current flows. As soon as Vb exceeds the threshold the junction
behaves like a resistor.
However, the background charge q0 can reduce, or for q0 = ± ( 0.5 + m ) e even
eliminate the Coulomb blockade. This suppression of the Coulomb blockade due to
virtually uncontrollable background charges is one of the major problems of single-
electron devices.
If an electron enters the island via junction one, it is energetically highly favorable for
another electron to tunnel through junction two out of the island. Thus an electron will
almost immediately exit the island after the first electron entered the island. This is a
space-correlated tunneling of electrons (see Figure 7-32). After a varying duration
another electron might first exit the island via junction two and again, immediately a
new electron will tunnel through junction one, entering the island and establishing
charge neutrality on the island. If the transparency of the tunnel junctions is strongly
different, for example RT 1 << RT 2 = RT a staircase like IV-characteristic appears, as
shown in Figure 7-33.
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junction one
I t
junction two
Figure 7-32: Space-correlation of tunneling in a double tunnel junction. A tunnel event in junction one
is immediately followed by an event in junction two and vice versa. The duration between those tunnel
pairs is varying.
I q
4 4
3 3
2 2
3 1
0 0
0 2 4 6 Vb 2 4 6 Vb
-1
-2
-3
-4
Figure 7-33: For strongly differing tunnel junctions a staircase like IV-characteristic appears.
Depending on which tunnel junction is more transparent, and the direction in which the charge carriers
flow, the island will be populated or depleted by an integer number of carriers with increasing bias
voltage. If carriers enter the island through the more transparent junction and leave through the
opaque one the island will be populated with excess carriers. If they have to enter through the opaque
junction and leave through the transparent one, the island is depleted of carriers.
Carriers enter the island through the first tunnel junction and are kept from the high
resistance of the second junction from immediately leaving it. Finally the carrier will,
due to the high bias, tunnel out of the island, which quickly triggers another electron
to enter through junction one. For most of the time the island is charged with one
excess elementary charge. If the bias is increased more electrons will most of the
time populate the island. The charge characteristic is shown on the right side of
Figure 7-33. If the asymmetry is turned around and the second junction is more
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transparent then the first one RT 2 << RT 1 = RT the island will be de-populated and the
charge on the island shows a descending staircase characteristic. Carriers are
sucked away from the island through the transparent junction and can not be
replenished quickly enough through the opaque one. However, the IV-characteristic
does not change.
Adding to the double tunnel junction a gate electrode Vg which is capacitively coupled
to the island, and with which the current flow can be controlled, a so-called SET
transistor is obtained (see Figure 7-34).
The formulas derived in Section 7.4.3.3 for the double junction can be modified to
describe the SET transistor. Substituting
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C2Vb + ne − q0 C V − ne + q0
V1 = ,V2 = 1 b
in CΣ CΣ (7. 196), the new voltages across the
where, CΣ = C1 + C2
junctions are
V1 =
(C 2 + C g )Vb − C gVg + ne − qo
,
C∑
(7. 205)
C1Vb + C gVg − ne + qo
V2 =
C∑
with C∑ = C1 + C2 + C g
The electrostatic energy has to include also the energy stored in the gate capacitor,
and the work done by the gate voltage has to be accounted for in the free energy.
The change in free energy after a tunnel event in junctions one and two becomes
∆F1± =
e
C∑
e
{ }
2 ± ( C2 + Cg )Vb − C gVg + ne − q0
(7. 206)
±
∆F =
1
e
C∑
{VbC1 + VgCg − ne + q0 }
Figure 7-35: Stability plot for the SET transistor. The shaded regions are stable regions.
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stability plot, parallel to the x-axis, the current will oscillate with a period of e/Cg. As
opposed to the Coulomb oscillations in a single junction, which were explained in the
introduction, where the periodicity in time of discrete tunnel events is observed, these
are Coulomb oscillations which have a periodicity in an applied voltage, where
regions of suppressed tunneling and space correlated tunneling alternate. Figure
7-36 shows the qualitative shape of the current oscillations
I
0
-1 0 1 2 Vg
Increasing the bias voltage will increase the line-width of the oscillations,
because the regions where current is allowed to flow grow at the expense of the
remaining Coulomb blockade region. Thermal broadening at higher temperatures or
a discrete energy spectrum change the form of the oscillations considerably.
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Dot
Source Drain
e 2 /C
EF
By using the split-gate techniques, one can form tunnel barriers which isolate
a puddle of electrons, often called a "dot", from the leads. To add one electron to the
dot costs a "charging energy" e2/C. The total capacitance of a sub-micron-sized dot
to the surrounding gates and leads can be very small, less than 1 fF (10-15 F), so this
energy is greater than the thermal energy for temperatures of a few Kelvin or less.
Thus at such temperatures, transport through the dot is determined by Coulomb
charging. Smaller dots can give even higher temperatures of operation.
For an electron to tunnel onto the dot, when the applied bias is small, there
must be no net energy cost of adding an electron. Thus tunneling can only occur
when the size of the dot is such that it would be neutral if it contained an integer N
plus a half electrons. Since it can only contain an integer number, the net charge on
the dot will be ±e/2, depending on whether there are N or N+1 electrons in the dot.
The charging energy is then (±e/2)2/C, which is the same in both cases. Hence
changing the number of electrons in the dot between N and N+1 costs no energy, so
electrons can flow on and off the dot with ease, and a current can flow. If the size of
the dot is changed slightly, the charging energy in the two cases is no longer the
same, and so the current falls to zero, only rising again when the size of the dot has
changed by one electron. This is called the Coulomb Blockade (CB) of tunnelling.
Sweeping a gate (shown shaded in the figure) changes the size of the dot and thus
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the conductance between the leads (source and drain) has periodic peaks rising from
zero to a value which may be as high as 2e2/h.
This effect can be seen in metal and semiconductor dots. In the latter, the quantum-
mechanical energy levels of the electrons are also important, as their wavelength is
comparable to the size of the dot, thus the term "quantum dot" is used. The number
of electrons in a semiconductor dot can also sometimes be reduced all the way to
zero, close to which the spacing of CB peaks becomes less regular as the energy
spacing of the electronic states, and the mutual Coulomb interactions of the electrons
in the dot, cannot be ignored.
Several results have been published on devices which "pump" one electron at
a time through the circuit, giving a current equal to ef, where e is the charge on an
electron and f is the pumping frequency. All of these devices have relied on the same
principle, that of Coulomb Blockade by an isolated region of electrons (known as a
quantum dot). These are generally defined electrostatically using surface gates, with
electrons able to move in and out of the quantum dot across tunnel barriers.
Lowering the entrance barrier allows a single electron to tunnel onto the dot. The
entrance barrier is then raised, and the exit lowered so an electron may move off the
dot on the other side of the device. The reliance on quantum-mechanical tunneling
limits the frequency of operation of these "electron turnstiles" to about 10MHz. This
corresponds to a current of a few picoamps, which is too small to be measured to the
required level of accuracy (parts per billion) at the moment. However researchers
have demonstrated that the devices are stable to this level, and attempts are being
made to improve the accuracy of the measurements.
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Figure 7-38: A schematic of the device structure of the artificial atom consisting of an inverted
heterostructure of a degenerately doped substrate upon which is grown a layer of aluminum gallium
arsenide and a layer of undoped gallium arsenide. (from The Foundations of Next-Generation
Electronics: Condensed-Matter Physics at RLE, RLE Currents Vol. 10, No. 2: Fall 1998; MIT, USA)
Considered one of the simplest types of artificial atoms, the metallic Single-
Electron Transistor (SET) is a nanoscale device that was developed in 1987. A
metallic SET consists of a metal particle isolated from its leads by two tunnel
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junctions (which are similar to diodes) and capacitively coupled to a common gate
electrode. The tunnel junctions create what is known as a Coulomb island, which the
electrons can enter only by tunneling through one of the insulators. Coulomb
repulsion prohibits more than one extra electron at a time on the island (near the
gate). Thus, electronic circuits can be made to pump or count electrons one at a time.
Because an SET’s electrical resistance is highly sensitive to the electrical fields from
nearby charges, it can easily detect not only single electrons, but also charges as
small as 1 percent of an electron’s electrical field. The current as a function of bias
across the tunnel barriers can also be measured in order to observe the so-called
Coulomb staircase, a stepwise increase of current as electrons are added to the
metal particle.
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Today it is really the intrinsic, or single particle, line widths that are a matter of greater
concern.
Ignoring for a moment the effects of the size distribution, it is of great importance to
understand just how much oscillator strength can be compressed into a narrow
region of the spectrum by the method of quantum confinement. In typical
semiconductor nanocrystals, the energy level spacing is on the order of 0.15-0.3 eV.
If the integrated oscillator strength over 0.15 eV of the bulk spectrum could be
compressed into lines with widths on the order of 0.1-0.5 meV, nanocrystals would
fulfill an important and new limit in nonlinear optical materials. Recall that the
polarizability scales with volume, so that the sharp, intense (radiative rates on the
order of picoseconds) transitions of the nanocrystals could be readily manipulated by
off-resonant electric fields. A prototype optical switch with gain, for instance, would be
one in which the transmission of a highpower laser beam near the absorption
threshold of the nanocrystals is modulated by a weaker, off-resonant pulse, via the ac
Stark effect.
Many techniques have been employed to measure the average homogeneous
spectra of nanocrystals, despite the presence of inhomogeneous broadening. These
include transient hole burning, luminescence line narrowing, and photoluminescence
excitation. A direct measure of the average homogeneous line width comes from
three-pulse photon echo experiments. In these experiments, two pulses interfere in
the sample to create a spatial grating. The third pulse scatters off this grating. When
the delay between the first and third pulse is changed, the signal oscillates at the
vibrational period of any vibrations which happen to be strongly coupled to the
electronic excitation. For example, in high-quality CdSe nanocrystals, a single mode
at 210 cm-1 is observed in both the photon echo and resonance Raman experiments.
When the first and second pulse are coincident in time, the maximum amplitude
grating is prepared for the third pulse to scatter from. If the second pulse is delayed
by more than the electronic dephasing time with respect to the first, then the
amplitude of the grating will be greatly diminished. Thus, the intensity of the scattered
light from the third pulse as a function of the delay between the first two pulses
provides a measure of the homogeneous line width. This is shown in Figure 7-39.
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Figure 7-40: Different contributions to the total line width of CdSe nanocrystals, as determined in the
three-pulse photon echo experiments. [A.P. Alivisatos, Perspectives on the physical chemistry of
semiconductor nanocrystals, 1996, Journal of Physical Chemistry]
The homogeneous line widths of nanocrystals remain a major topic of research. Vast
improvements in the structural quality of samples, and in the size distributions, have
resulted in no particular narrowing of the apparent homogeneous spectra.
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Furthermore, there appear to be some intrinsic limits to the narrowness of the lines in
nanocrystals which arise from strong coupling to low-frequency vibrations. Currently,
the spacings between nanocrystal electronic transitions appear to only slightly
exceed the line widths, so that despite the large shifts to higher energy. Further work,
particularly in the area of inorganic passivation, is warranted. Given the multiple
sources of inhomogeneous broadening (size, shape, local fields, defects, etc.), the
advent of single-molecule spectroscopy and near-field scanning probe microscopy
shows great promise as tools to aid in deciphering the nature of the intrinsic
photophysics of nanocrystals.
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emitting state comes from low-temperature studies of the vibronic coupling of the
emission, which show that there is a well-defined localization temperature.
Independent of the exact origin of the luminescence, it does appear to be one
property which can be manipulated in useful ways. For example, two reports of light-
emitting diodes made with polymers and CdSe nanocrystals have appeared within
the past year. In the first instance, nanocrystals were assembled in layers a few
nanocrystals thick on the surface of PPV, an electroluminescent polymer. The PPV
itself was grown on a layer of indium tin oxide, a transparent hole-injecting contact.
Finally, the nanocrystal layer was coated with a film of Mg/Ag, the electron-injecting
contact. This complete assembly electroluminesces when a voltage is applied. The
recombination of electrons and holes may take place either in the polymer layer
(which emits green light) or in the nanocrystal layer. The nanocrystal emission shifts
with size. Thus, these LEDs provide a variety of means for tuning the output color.
This advance is particularly important, since it constitutes the first example of
electrical, rather than purely optical, investigation of semiconductor nanocrystals.
7.5 References
A.P. Alivisatos, Perspectives on the physical chemistry of semiconductor
nanocrystals, 1996, Journal of Physical Chemistry
S. Ciraci, A. Buldum, I.P. Batra, Quantum effects in electrical and thermal transport
through nanowires, 2001, Journal of Physics Condensed Matter
S. Eustis, M. A. El-Sayed, Why gold nanoparticles are more precious than pretty
gold: Noble metal surface plasmon resonance and its enhancement of the radiative
and nonradiative properties of nanocrystals of different shapes, 2005, The royal
Society of Chemistry
K. Lance Kelly, E. Coronado, L.L. Zhao, G.C. Schatz, The Optical Properties of Metal
Nanoparticles: The Influence of Size, Shape, and Dielectric Environment, 2003,
Journal of Physical Chemistry
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8 MAGNETISM
8.1 Introduction
The phenomenon of magnetism, that is, the mutual attraction of two pieces of
iron or iron ore, was surely known to the antique world. The ancient Greeks have
been reported to experiment with this mysterious force. The name magnetism is said
to be derived from a region in Turkey which was known by the name of Magnesia
and which had plenty of iron ore.
Over the past several decades, amorphous and more recently nanocrystalline
materials have been investigated for applications in magnetic devices requiring
magnetically soft materials such as transformers, inductive devices, etc. Most
recently, research interest in nanocrystalline soft magnetic alloys has dramatically
increased. This is due, in part, to the properties common to both amorphous and
crystalline materials and the ability of these alloys to compete with their amorphous
and crystalline counterparts. The benefits found in the nanocrystalline alloys stem
from their chemical and structural variations on a nanoscale which are important for
developing optimal magnetic properties.
In the following sections, we will first revisit the magnetic properties of matter
and then pass on to discuss about the magnetic nanomaterials.
8.1.1 Concept
The magnetic field parameters at a given point in space are defined to be the
magnetic field strength H, the magnetic flux density or magnetic induction B and the
magnetization of the material M. Inside a magnetic material:
B = µ0 (H + M ) (8. 207)
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Finally, we need to define the magnetic moment, µm, through the following equation:
M = µm / V (8. 209)
Table 8-1 : Magnetic units. A is ampere, cm is centimeter, m is meter, emu is electromagnetic unit, B
is magnetic induction, H is magnetic field strength, M is magnetization of a substance per unit volume.
[K. J Klabunde, Nanoscale Materials in Chemistry, Wiley-Interscience, 2001]
8.1.2 Phenomena
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8.2.1 Introduction
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The magnetic moment of transition metals decreases in general with the increase of
number of atoms (size) in the clusters. However, the moment of different transition
metal clusters are found to depend differently on the number of atom per clusters (N).
Fe-clusters
3
Magnetic moment per atom
2.5 Bulk Fe
2
Co-clusters
1.5 Bulk Co
1
Ni-clusters
Bulk Ni
0.5
Rh-clusters
0
0 100 200 300 400 500 600 700 800
Cluster Size (N) [Number of atoms]
Figure 8-1: Magnetic moment per atom in units of Bohr magnetron for iron, cobalt, nickel and rodium
clusters as a function of cluster size (number of atom). The enclosed data points show the sizes of the
respective clusters at which they attain bulk moments. Only the maximum error in the data for each
lxxxii Erreur ! Signet
clusters are shown. Iron, cobalt and nickel data are from W. A. de Heer et al. and Billas.
non défini. Erreur ! Signet non défini.
The rodhium data is from Cox et. al.
Among the ferromagnetic 3d transition metals, Nickel clusters attain the bulk
moment at N=150, whereas Cobalt and Iron clusters reach at the corresponding bulk
limit at N=450 and N=550 respectively (Figure 8-1). In icosahedral configuration these
numbers correspond to 3, 4 and 5 shells respectively. lxxxiii However one needs to
confirm the bulk like behaviour only after measuring the temperature dependence of
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magnetic moment for clusters. The spin imbalance at 3d-orbital has been correlated
to the measured moment as:
2
n ( + ) − n( −) = µ x (N ) (8. 210)
gx
Where gx is the bulk g-factor for the respective metal. The results show that in the
lower size limit the clusters have high spin majority configuration and the behaviour is
more like an atom, but with the increase of size an overlap of the 3d-band with the
Fermi level occurs, which reduces the moment towards that of the bulk with slow
oscillations.Erreur ! Signet non défini. In analogy with the layer-by-layer magnetic moments
in the studies of surface magnetism, the clusters are assumed to be composed of
spherical layers of atoms forming shells and the value of moment of an atom in a
particular shell is considered to be independent of the size of cluster. The magnetic
moment values of the different shells are optimized to fit with the total moment per
atom maintaining the overall trend of observed decrease with size. It is generally
observed that the per atom moment for the surface atoms in the 1st layer are close to
that of an atom and deep layers correspond the bulk. The intermediate layers show
an overall decreasing trend. For both nickel and cobalt, there are oscillations in the
values at least up to the 5th shell. For nickel, the second layer is found to have a
negative coupling with the surface atoms and the 3rd-4th layers in iron are
magnetically dead. The model gives more or less close agreement with the
experimental results for cobalt and nickel. But in a more realistic model one has to
account for both the geometric shell closing as well as the electronic structure.
However this model provides a good first order picture to understand the magnetic
behaviour of 3d transition metal clusters.
Though the 4d transition metals are non-magnetic, the small clusters of
rhodium are found to be magnetic following the calculations. lxxxiv Within the size
range N=10-20, the moment varies between 0.8 to 0.1µB per atom but the clusters
become non-magnetic within N=100. Due to reduced size, the individual moments on
the atoms in clusters are aligned. First principal calculations show that the ground
state of Rh6 is non-ferromagnetic, while Rh9, Rh13 and Rh19 clusters have non-zero
magnetic moments. Rh43 is found to be non-magnetic as the bulk. Ruthenium,
palladium, Chromium, Vanadium and Aluminium clusters are found to be non-
magnetic.Erreur ! Signet non défini.
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The magnetic interaction in rare earth solids are RKKY type which is mediated
by the conduction electrons. Since in clusters, structure and filling up of the
conduction band differs from that in the bulk, rare-earth clusters are expected to
exhibit an altogether different magnetism compared to the bulk. Magnetic properties
of gadolinium, terbium and dysprosium clusters show a very size-specific
behaviour.Erreur ! Signet non défini. Gd22 behaves super-paramagnetically (8.3.4) but Gd23
shows a behaviour like a rigid magnetic rotor as if the moment is locked to the cluster
lattice. Gd17 shows super-paramagnetism near room temperature but at low
temperatures it shows locked-moment behaviour. It indicates that there are at least
two groups of clusters sharing the same number of atoms which might correspond to
two different isomers, either magnetic or structural. But it is not clear whether the two
isomers co-exist in the beam or there occurs a phase transition of any kind. The
behaviour of other clusters from N=11-30, is like Gd22 or Gd23 or Gd17. Similar is the
case for Tb and Dy clusters. Tb17, Tb22, Tb27, Dy22 and Dy27 show super-
paramagnetic behaviour but Tb23 and Tb26 show locked-moment behaviour. In fact
Tb26 is temperature dependent like Gd17. Assuming the clusters to be spherical with a
moment of inertia and a body fixed moment which rotates with the cluster,
calculations show a very complex precession and nutation when the rotational kinetic
energy becomes comparable to the magnetic potential energy. With two parameters
viz. the rotational temperature and the magnetic moment, a fit of the experimental
data for Gd with several initial conditions and a rotational temperature of 5K, shows
an agreement at least for sizes lower than N=30.
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nanoscale diameters, which are denoted by type A. These non interacting systems
derive their unique magnetic properties strictly from the reduced size from the
components, with no contribution from interparticle interactions. At the other extreme
are bulk materials with nanoscale structure denoted by type D, in which a significant
fraction (up to 50%) of the sample volume is composed of grain boundaries and
interfaces. In contrast to type A systems, magnetic properties here are dominated by
interactions. The length of the interactions can span many grains and is critically
dependent on the character of interface. Due to this dominance of interaction and
grain boundaries, the magnetic behaviour of type D nanostructures cannot be
predicted simply by applying theories of polycrystalline materials with reduced length
scale. In type B particles, the presence of a shell can help prevent particle
interactions, but often at the cost of interaction between the core and the shell. In
many cases the shells are formed via oxidation and may themselves be magnetic. In
type C materials, the magnetic interactions are determined by the volume fraction of
the magnetic particles and the character of the matrix they are embedded in.
Figure 8-2 : Schematic representation of the different types of magnetic nanostructures. Type-A
materials include the ideal ultrafine particle system, with interparticle spacing large enough to
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approximate the particles as noninteracting. Ferrofluids, in which magnetic particles are surrounded
by a surfactant preventing interactions, are a subgroup of Type-A materials. Type-B materials are
ultrafine particles with a core-shell morphology. Type-C nanocomposites are composed of small
magnetic particles embedded in a chemically dissimilar matrix. The matrix may or may not be
magnetoactive. Type-D materials consist of small crystallites dispersed in a noncrystalline matrix. The
nanostructure may be two-phase, in which nanocrystallites are distinct phases from the matrix, or the
ideal case in which both the crystallites and the matrix are made of the same material.
8.3.1.1 Ferrofluid
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2R σ ,µ
,µ
The particles are free to move in the carrier fluid under the influence of an applied
magnetic field, but on average the particles maintain a spacing S to nearest
neighbours. In a low density fluid, the spacing S is much larger than the mean
particle radius 2R, and magnetic dipole – dipole interactions are minimal.
Applications for ferrofluids exploit the ability to position and shape the fluid
magnetically. Some applications are:
• rotary shaft seals
• magnetic liquid seals, to form a seal between region of different pressures
• cooling and resonance damping for loudspeaker coils
• printing with magnetic inks
• inertial damping, by adjusting the mixture of the ferrofluid, the fluid viscosity
may be change to critically damp resonances accelerometers,
• level and attribute sensors
• electromagnetically triggered drug delivery
lxxxv
Table 8-2: Material Parameters of a typical ferrofluid:
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8.3.2 Anisotropy
In many situations the susceptibility of a material will depend on the direction in which
it is measured. Such a situation is called magnetic anisotropy. When magnetic
anisotropy exists, the total magnetization of a ferromagnet Ms will prefer to lie along a
special direction called the easy axis. The energy associated with this alignment is
called the anisotropy energy and in its lowest form is given by
Where θ is the angle between Ms and the easy axis. K is the anisotropy constant.
Most materials contain some type of anisotropy affecting the behaviour of the
magnetization. The most common forms of anisotropy are:
• Crystal anisotropy
• Shape anisotropy
• Stress anisotropy
• Externally induced anisotropy
• Exchange anisotropy.
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direction, then less easy for the [110] direction, and most difficult for the [111]
directions. These directions and magnetization curves for iron are given in Figure 8-4.
The [100] direction is called the easy direction, or easy axis, and because the other
two directions have an overall smaller susceptibility, the easy axis is the direction of
spontaneous magnetization when below Tc (Curie Temperature). Both iron and
nickel are cubic and have three different axes, whereas cobalt is hexagonal with a
single easy axis perpendicular to the hexagonal symmetry. Figure 8-4 also gives
magnetization curves for cobalt and nickel.
Figure 8-4 : Magnetization curves for single crystals of iron, cobalt and nickel along different
directions. [K. J Klabunde, Nanoscale Materials in Chemistry, Wiley-Interscience, 2001]
You may now imagine a situation in which the system has spontaneous
magnetization along the easy axis but a field is applied in another direction.
Redirection of the magnetization to be aligned with the applied field requires energy
(through the change in M ⋅ H ), hence the crystal anisotropy must imply a crystal
anisotropy energy given by equation Ea = K sin²θ (8. 211) for a uniaxial material.
This energy is an intrinsic property of the material and is parametrized, to lowest
order, by the anisotropy constant K=K1 which has units of erg per cm3 of material.
Roughly speaking K1 is the energy necessary to redirect the magnetization. For a
uniaxial material with only K1, the field necessary to rotate the magnetization 90°
away from the easy axis is
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KS =
1
(N a − N c )M 2 (8. 213)
2
Stress anisotropy result from internal or external stresses that occur due to
rapid cooling, application of external pressure etc. Anisotropy may also be induced by
annealing in a magnetic field, plastic deformation, or by ion beam irradiation.
Exchange anisotropy occurs when a ferromagnet is in close proximity to an
antiferromagnet or ferromagnet. Magnetic coupling at the interface of the two
materials can create a preferential direction in the ferromagnetic phase, which takes
the form of a unidirectional anisotropy. This type of anisotropy is most commonly
observed in type – B particles, when an antiferromagnetic or ferromagnetic oxide
forms around a ferromagnetic core.
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The most obvious finite-size effect in magnetic fine-particle systems consists in the
fact that each entity (magnetic particle) has a very small volume compared to the
typical sizes of the magnetic domains in the corresponding bulk materials. In a sense,
the volume of a particle is so small (commonly, a few tens or hundreds of nm3) that it
can be considered as a zero-dimension magnetic system, which strongly affects its
magnetic behaviour. In real systems, the size of the particles is usually not uniform
and distributed following a function f(V) which is satisfactorily described by a
logarithmic-linear distribution of the form
1 ln ²(V / V0 )
f (V ) = exp − (8. 214)
2π σV 2σ ²
Where V0 is the most probable particle volume and σ is the standard deviation of
ln(V). The validity of this simple assumption has been experimentally verified in many
systems by transmission electron microscopy (TEM) and other indirect techniques
such as x-ray diffraction and magnetic granulometry.
One fundamental question related to the finite and small volume of the particles is
how such volume determines the internal domain structure. In magnetic bulk
materials, it is well known that there exists a multidomain structure constituted by
regions of uniform magnetization separated by Domain Walls (DWs). The size and
shape of these domains depends on the interplay between the exchange,
magnetostatic and anisotropy energies of the system. As the volume of the magnetic
system decreases, the size of the domains and the width of the walls are reduced,
modifying, at the same time, their inner structure. Below a certain critical volume, the
energy cost to produce a DW is greater than the corresponding reduction in the
magnetostatic energy. Consequently, the system no longer divides in smaller
domains, instead maintaining the magnetic structure of a single domain. This critical
value depends on the saturation magnetization of the particle, anisotropy energy and
exchange interactions between individual spins. For example, for spherical particles
the critical diameter is within 10–800 nm. Typical values for Fe and Co metallic
particles are 15 and 35 nm, respectively, while for SmCo5 it is as large as 750 nm.
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In many fine-particle systems, f(V) is narrowand centred at very small V0 below the
critical value, so that all the particles constituting the system can be considered as a
single domain.
This is the situation that we are going to assume in what follows. In thermal
equilibrium, the resulting magnetization of a particle points in a direction tending to
minimize its total anisotropy energy, which for a single-domain particle can be
considered as proportional to its volume, at least, in first approximation (Figure 8-6).
The total anisotropy of the particle can often be assumed to have uniaxial character,
being determined by a single constant K. Therefore, the anisotropy energy can be
expressed as
where θ is the angle between anisotropy axis and magnetization, and KV is the
anisotropy energy barrier (8.3.2) separating both easy directions for magnetization,
which in zero magnetic field correspond to θ = 0 and θ = π. Taking into account the
spread of volumes f(V) given by equation E(θ) = kV Sin2θ (8. 215) and
1 ln ²(V / V0 )
f (V ) = exp − (8. 214), it is a matter of fact that the magnetization
2π σV 2σ ²
of the particles will behave as if it were driven by an energy barrier distribution
f ( E B0 ) , where E B0 = kV.
Under the application of a magnetic field H forming an angle ψ with the anisotropy
axis, the energy of a particle is modified as
Where Ms is the spontaneous magnetization of the particle, and the axis system is
defined in Figure 8-5.
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Figure 8-5 : Definition of the axis system for a fine particle. The uniaxial-anisotropy axis is along the z-
axis. [X. Batle, A. Labarta, Finite-size effects in fine particles: magnetic and transport properties,
Journal of Physics, 2002, ppR15-R42].
Under zero field, the equilibrium direction for the magnetization vector M coincides
with the anisotropy axis, while when a magnetic field is applied, it rotates away from
the anisotropy axis towards the field direction, forming an angle ψ−θ with H, and the
stability problem can be reduced to a two-dimensional one (ϕ = 0). In this case, and
if H is lower than a certain critical value known as switching field at zero temperature,
0
H SW , E(θ) has two minima at different heights which are separated by an energy
barrier. When the field is applied opposite to the magnetization, the unstable
minimum is separated from the stable one by an energy barrier EB, which can be
approximated by the following expression:
κ
H
E B ( H ) = E 1 − 0
0
B (8. 217)
H SW
the minimum value of the field at zero T, at which EB vanishes, and the magnetization
inverts its orientation. When H is applied along the anisotropy axis and in the
κ
H
opposite direction to magnetization, equation E B ( H ) = E 1 − 0 0
B (8. 217) is
H SW
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κ
H
not a simple analytical expression. However, equation E B ( H ) = E 1 − 0 0
B (8.
H SW
217) works quite well with κ ≈ 1.5, provided that the applied field forms an angle of a
few degrees with the anisotropy axis. On the other hand, Pffeifer gave the following
0
1.14 H SW
κ = 0.86 + (8. 218)
Ha
A method frequently used to characterize the nature and strength of the particle
0
anisotropy consists in the determination of H SW as a function of ψ . The resulting
curve turns to be the so-called Stoner Wohlfarth (SW) astroid. In fact, the SW astroid
represents the set of fields (applied opposite to the particle magnetization) at which
0
irreversible jumps occur. For uniaxial anisotropy, H SW can be evaluated from
equation E (θ ) = − KV sin ²θ + HM S (cos θ cosψ + sin θ sinψ cos ϕ ) (8. 216) with the
θ = d²E/dθ
conditions dE/dθ θ ² = 0, since irreversible jumps occur when the energy
obtained expression is
Ha
0
H SW = (8. 219)
(sin 2/3
ψ + cos 2 / 3 ψ ) 3 / 2
Many groups have attempted to study the reversal process in single particles but the
experimental precision did not yield quantitative information.
Single domain
Multi domain
Hc
Super
Paramagnetic
D
Dc
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Figure 8-6 : Qualitative illustration of the behaviour of the coercivity in ultrafine particle systems are
the particles size changes.
As the particles size continues to decrease (towards some critical particle diameter,
Dc) below the single domain value, the spins get increasing affected by thermal
fluctuations and the system becomes superparamagnetic. Particles with sufficient
shape anisotropy can remain single domain to much larger dimensions than their
spherical counterparts.
In a granular magnetic solid with a low volume fraction, one has a collection of single
domain particles each with a magnetic axis along which all the moments are aligned.
In the absence of a magnetic field, parallel and anti parallel orientations along the
magnetic axis are energetically equivalent but separated by an energy barrier of CV,
where C is the total anisotropy per volume, and V is the particle volume. Since the
size of each single domain remains fixed, under an external field, only the magnetic
axes rotate. Thus the measured magnetization M of a granular magnetic field solid
with a collection of single domain particles is the global magnetization
M .H
M= = M S cos θ (8. 220)
H
Where θ is the angle between the magnetic axis of a particle. M S , is the saturation
magnetization, H is the external field, and the average <cos θ> is taken over many
ferromagnetic particles. The hysterisis loop of a granular solid is thus a signature of
the rotation of the magnetic area of the single-domain particles. This should be
contrasted with the hysterisis loop of a bulk ferromagnet, in which the sizes and the
direction of the domains are altered drastically under an external field.
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M HC
(a) (c)
MS
MR
H
MC
T
TB
(b)
M
(d)
χ
e
MS c
MS/2
f
b
d
a
T T
TB TB
Figure 8-7 : (a) Hysterisis loop at 5K; (b) temperature dependence of saturation magnetization (MS)
and remnant magnetization (MR=MS/2); (c) temperature dependence of field cooled (FC) and zero-field
cooled (ZFC) susceptibility. At the blocking temperature (TB), MR and HC vanish, whereas the ZFC
susceptibility shows a cusp like feature.
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8.3.4 Superparamagnetism
Below the Curie temperature of a ferromagnet or ferrimagnet, all the spins are
coupled together and so cooperate to yield a large moment. This moment is bound
rigidly to the particle by one or more of the variety of anisotropies that we have
discussed (8.3.2). With decreasing particle size, the energy Barrier EB decreases
until the thermal energy kT can disrupt the bonding f the total moment to the particle.
Then this moment is free to move and respond to an applied field independent of the
particle. This moment is the particle moment and is equal to
It can be quite large, thousands of Bohr magnetons. An applied field would tend to
align this giant (super) moment, but kT would fight he alignment just as it does in a
paramagnet. Thus, this phenomenon is called superparamagnetism.
It is good to notice that if the anisotropy is very weak (zero), one would expect that
the total moment µp could point in any direction, hence the Langevin law would apply.
The phenomenon of superparamagnetism is, in fact, timescale-dependent due to the
stochastic nature of the thermal energy. The anisotropy energy EB represents an
energy barrier to the total spin reorientation; hence the probability for jumping this
barrier is given by Arrhenius law:
EB
τ = τ 0 exp (8. 222)
kT
Where τ 0 is the attempt time by supposing that the particle spins are rigidly coupled
E
equation τ = τ 0 exp B (8. 222), together with this assumption, is known as the
kT
Neel–Brown model. If the characteristic time window of an experiment is much
shorter than τ at a fixed temperature, the particle moment remains blocked during
the observation period (blocked regime), while, in the opposite situation, the rapid
fluctuations of the particle moment mimics the atomic paramagnetism (SPM regime).
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In the intermediate regime, the probability that the magnetization has not switched
after an observation time t is given by
−t
P(t ) = exp (8. 223)
τ
A method used to verify the Neel–Brown model in real systems is the scaling of the
switching field distributions measured at different T and rates of field ramping.
Thermal activation leads to a switching field distribution from the SW model, the
mean switching field being given by
k T cT 1 / κ
H SW = H 0
1 − B ln κ −1 (8. 224)
E B υε
SW
Where c = k B H SW
0
/(τ 0αE B ) , ε = (1 − H / H SW
0
) and υ is the field sweeping rate. From
the equation above, it is evident that Hsw measured at different T and υ can be
collapsed in a single master curve when they are plotted as a function of the scaling
variable (T ln(cT / υ εκ−1))1/κ . In fact, the collapse is obtained by choosing the
appropriate values of κ and c (obtaining κ = 1.5, as expected for measurements with
the field slightly deviated from the anisotropy axis, see paragraph 8.3.3.1). This
scaling procedure has been successfully applied to analyse data obtained above
about 0.5K from single-particle experiments carried out with different kind of
nanoparticles.
At very low temperatures, (below about 0.5 K) strong deviations from the Neel–Brown
model have been reported in this kind of scaling when it was applied to single-particle
experiments. The deviations consisted in a saturation of Hsw and σ (width of the
switching field distribution), and a dependence of Hsw on υ faster than the prediction
of the Neel–Brown model. All these anomalies have been attributed to the
prevalence of a nonthermal process by which the particle magnetization escapes
from the metastable state through the energy barrier by macroscopic quantum
tunnelling (MQT). The theoretical models propose that there is a crossover
temperature TB, below which quantum tunnelling dominates the reversal process,
whereas above TB, the escape rate from the metastable state is given by thermal
activation, and the Neel–Brown model is accomplished. Consequently, TB is the
temperature at which the thermal and quantum rates coincide.
The main parameters determining the particular value of TB for a given system are:
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Where f (E)dE is the fraction of particles having energy barriers in between E and E
∞
−t
+ dE, and M0 is the initial magnetization. In equation M (t ) = M 0 ∫ dEf ( E )exp
0 τ (E)
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(8. 225) and for the sake of simplicity, the particle moment has been assumed
to be volume independent, although, in fact, it is proportional to it. This assumption
does not significantly affect the results, providing that for a logarithmic-linear
distribution, f (E) and Ef (E) (which is equivalent to Vf (V)) are similarly shaped
functions. Let us introduce the function p(t, T,E), which is defined by
t − E
p (t , T , E ) = exp − exp (8. 226)
τ 0 kT
Taking into account that p(t, T,E) for a given t varies abruptly from 0 to 1, as the
energy barrier E increases, we can approximate p(t, T,E) by a step function whose
discontinuity Ec(t, T ) moves towards higher energies as time elapses. Consequently,
the integral is cut off at the lower limit by the value of Ec(t, T ) and can be written as
∞
M (t ) ≅ M 0 ∫ dEf ( E ) (8. 227)
Ec
Where Ec(t, T ) = kBT ln(t/ττ0) is the only time-dependent parameter and signals the
position of the inflection point of p(t, T,E). In fact, the narrow energy range spanned
by the step at Ec(t, T ) can be understood as the experimental window of the
measurements. The experimental window can be swept over f (E) by varying the
∞
temperature or the observation time. From equation M (t ) ≅ M 0 ∫ dEf ( E ) (8. 227), it
Ec
can be deduced that M(t) obtained after integration is a function of the parameter
Ec(t, T ), which acts as a scaling variable. The existence of this scaling variable
implies that measuring the magnetization as a function of the temperature at a given
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As an example of this scaling method, Figure 8-8 shows the scaling of the relaxation
curves obtained at different temperatures for a sample consisting on Fe0.78C0.22
particles with a mean diameter of 3.6 nm, dispersed in stable dilution with a
hydrocarbon oil. In this sample, the dipolar interaction among particles was estimated
to be very small. Figure 8-8 shows all the relaxation curves corresponding to
different temperatures collapsed into a single master curve when plotted as a
Figure 8-8 : The resulting scaling for a sample composed of FeC nanoparticles dispersed in a
hydrocarbon oil is shown. Open and full circles correspond alternatively to adjoining temperatures,
which are indicated above the corresponding interval (K units). The solid line is the theoretical curve
∞
calculated by fitting the scaling curve to equation M (t ) ≅ M 0 ∫ dEf ( E ) (8. 227) with a
Ec
logarithmic-linear distribution of energies. The values of the fitted parameters are: σ = 0.44 ± 0.05 and
E0 = 287 ± 50K (position of the maximum of the energy barrier distribution). [X. Batle, A. Labarta,
Finite-size effects in fine particles: magnetic and transport properties, Journal of Physics, 2002,
ppR15-R42].
One of the most interesting aspects of these results is that, in fact, measuring the
relaxation at a given temperature is completely equivalent to measuring it at different
temperature but shifting the observation time window according to the law
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T ln(t/ττ0). In this sense, the method enables us to obtain the relaxation curve at a
dividing the T ln(t/ττ0) axis by this temperature. For instance, in the case shown in
Figure 8-8, we can obtain the relaxation curve at the lowest measured temperature of
1.8K at times as large as 10119 s, which is obviously an experimentally inaccessible
time. The validity of the T ln(t/ττ0) scaling method to analyse the relaxation behaviour
has been proved in many systems of non or slightly interacting fine particles.
Moreover, from the T ln(t/ττ0) scaling of relaxation data, insight can be gained into the
microscopic details of the energy barrier distribution producing the relaxation. If f (E)
is nearly constant in the range of energy barriers which can be overcome during the
∞
observation time, then equation M (t ) ≅ M 0 ∫ dEf ( E ) (8. 227) can be approximated
Ec
by
t
M (t ) ≈ M 0 1 − k B Tf ( EC ) ln
(8. 228)
τ 0
Where Ec is the mean energy barrier within the experimental window. From equation
t
M (t ) ≈ M 0 1 − k B Tf ( EC ) ln (8. 228)) we can define the viscosity parameter as
τ 0
1 ∂M
S =− = f ( EC )k BT (8. 229)
M 0 ∂ (ln(t ))
Therefore, as Ec is varied, the magnetic viscosity maps the energy barrier distribution
at low enough temperatures for which the width of p(t, T,E) (equation
t − E
p (t , T , E ) = exp − exp (8. 226)) function around the inflection point is
τ 0 kT
small compared to the width of the energy distribution and the scaling hypothesis is
fulfilled. As an example of the applicability of the method, in Figure 8-9, we show S/T
derived from the data of Figure 8-8 as a function of T ln(t/ττ0). In Figure 8-9, the
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respect to the temperature is also shown, the agreement between both sets of data
being very good.
Figure 8-9 : Numerical derivative of the data of Figure 8-8 with respect to the scaling variable (open
circles) and the logarithmic-linear distribution (dashed line) obtained by fitting the data of Figure 8-8 to
∞
the equation M (t ) ≅ M 0 ∫ dEf ( E ) (8. 227). The differential of the thermoremanence relative to
Ec
the saturation magnetization versus the temperature is also shown in full circles for comparison. [X.
Batle, A. Labarta, Finite-size effects in fine particles: magnetic and transport properties, Journal of
Physics, 2002, ppR15-R42].
If f (E) is almost constant over a certain range of energies, then S will be linear in T
over the corresponding temperature range; consequently, relaxation as a function of
time will follow a time logarithmic decay at fixed T. This behaviour is only
accomplished in a narrow region around the maximum of a bell-shaped energy
barrier distribution (see for instance, the region around the inflection point of the
master curve shown in Figure 8-8).
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the final equilibrium values is performed. Moreover, for fields smaller than the
switching field corresponding to the smallest barriers, the relaxation curves at
different fields and fixed T can be collapsed into a single curve, in a way similar to T
ln(t/ττ0) scaling for curves at fixed field, but in this case, the additional shifts in the T
ln(t/ττ0) axis necessary to get field scaling give the field dependence of the mean
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the total energy of the assembly being a relevant magnitude. In this limit, relaxation is
governed by the evolution of the system through an energy landscape with a
complex hierarchy of local minima similar to that of spin-glasses. It is worth noticing
that in contrast with the static energy barrier distribution arising only from the
anisotropy contribution, the reversal of one particle moment may change the energy
barriers of the assembly, even in the weak interaction limit. Therefore, the energy
barrier distribution may evolve as the magnetization relaxes.
Three models have been developed to introduce particle interaction:
- Shtrikmann and Wohlfarth
For a weak interaction limit, the relaxation time is
EB
τ = τ 0 exp (8. 230)
k B (TB − T0 )
function of the observation time window of the experiment, τm, at least in a range of
time covering eight decades. The increase of TB with the strength of the dipolar
interactions (e.g. increasing particle concentration or decreasing particle distances)
has been predicted by this model and also experimentally confirmed.
- Morup and Tronc
For the weak interaction limit, the opposite dependence of TB with the strength of the
interactions is predicted. Morup suggested that two magnetic regimes, governed by
opposite dependencies of TB, occur in interacting fine particles. At high temperatures
and/or for weak interactions, TB signals the onset of a blocked state and TB
decreases as the interactions increase. In contrast, at high temperatures and/or for
strong interactions, a transition occurs from an SPM state to a collective state which
shows most of the features of typical glassy behaviour. In this case, TB is associated
with a freezing process and it increases with the interactions.
Non-equilibrium dynamics, showing ageing effects in the relaxation of the residual
magnetization, have been observed in interacting fine-particle assemblies, but some
important differences with spin-glasses have been established. In the last few years,
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several works demonstrated that for concentrated frozen ferrofluids and assemblies
of nanoparticles dispersed in a polymer, the relaxation depends on the waiting time,
tw, spent at constant temperature before the magnetic field is changed (Figure 8-10).
Figure 8-10 : The relaxation rate S versus log10(t) at different wait times for the concentrated sample
(a) and for the most diluted sample (b). The measurements were performed on a ferrofluid consisting
of closely spherical particles of maghemite with a mean diameter of 7 nm. [X. Batle, A. Labarta, Finite-
size effects in fine particles: magnetic and transport properties, Journal of Physics, 2002, ppR15-R42].
This phenomenon is absent in the most diluted samples, confirming that it is due to
dipole–dipole interactions (Figure 8-10). Ageing effects on the magnetic relaxation
are the fingerprint of the existence of many minima in the phase space. However, a
complex hierarchy of energy minima is not an exclusive feature of spin-glasses and
ageing has also been found in other cluster-glass systems not having a true phase
transition. In fact, the non-equilibrium dynamics of interacting fine particles largely
mimics the corresponding of spin-glasses, including ‘memory experiments’ in which
ageing is studied at different heating or cooling rates and/or cycling the temperature.
The main differences between the dynamics of canonical spin-glasses and that of
fine particles are:
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Another feature that differentiates the low-temperature collective state from the spin-
glass one is its extreme sensitivity to the application of an external magnetic field. In
particular, it has been shown that the collective state of strong interacting particles
can be erased by a field-cooling process with an applied magnetic field of moderate
strength which yields an asperomagnetic state. It has also been demonstrated that
the dynamics of these systems are strongly affected by the initial magnetic moment
configuration, in such a way that the collective state determines the dynamic
behaviour only in low-cooling-field experiments, while at high cooling fields the
dynamics are mostly dominated by the intrinsic energy barriers of the individual
particles.
Surface effects result from the lack of translational symmetry at the boundaries of the
particle because of the lower coordination number there and the existence of broken
magnetic exchange bonds which lead to surface spin disorder and frustration.
Surface effects dominates the magnetic properties of the smallest particles since
decreasing the particle size increases the ratio of surface spins to the total number of
spins. For example, for fcc Co with a lattice constant of 0.355 nm, particles having
about 200 atoms will have diameters around 1.6 nm and 60% of the total spins will be
at the surface. This represents more than half of the spins. Consequently, the ideal
model of a superspin formed by all the spins of the particle pointing in the anisotropy
direction and coherently reversing due to thermal activation is no longer valid, since
misalignment of the surface spin yields strong deviations from the bulk behaviour.
This is true, even for particles with strong exchange interactions such as many
ferrimagnetic oxides with magnetically competing sublattices, since broken bonds
destabilize magnetic order giving rise to frustration which is enhanced with the
strength of the interactions. As a consequence of the combination of both finite-size
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and surface effects, the profile of the magnetization is not uniform across the particle
and the magnetization of the surface layer is smaller than that corresponding to the
central spins.
Many experimental results for metallic and oxide particles indicate that the anisotropy
of fine particles increases as the volume is reduced because of the contribution of
what is known as surface anisotropy. For instance, the anisotropy per unit volume
increases by more than one order of magnitude for 1.8 nm fcc Co particles being
3 × 107 erg cm−3 compared with the bulk value of 2.7 × 106 erg cm−3. Even an
anisotropy value one order of magnitude larger than the preceding case has been
reported for Co particles embedded in a Cu matrix. In fact, surface anisotropy has a
crystal-field nature and it comes from the symmetry breaking at the boundaries of the
particle. The structural relaxation yielding the contraction of surface layers and the
existence of some degree of atomic disorder and vacancies induce local crystal fields
with predominant axial character normal to the surface, which may produce easy-axis
or easy-plane anisotropies. This can be justified by noting that the axis of the local
^
crystal field, n , may be evaluated from the dipole moment of the nearest-neighbour
atomic positions with respect to the position of a given surface atom as follows:
^ nn
n i ∝ ∑ ( Pj − Pi ) (8. 231)
j
Where Pi is the position of the ith atom and the sum extends to the nearest
^
neighbours of this atom. Since at the surface some of the neighbours are missing, n i
is non-zero and directed approximately normal to the surface. The effect of these
local fields is obtained by adding a term of the form KS ξ2 , where Sς is the component
of the spin along a vector normal to the surface and, K < 0 corresponds to the easy-
axis case and K > 0 to the easyplane one. When |K| is comparable to the
ferromagnetic exchange energies, spin configurations like those shown in Figure
8-11 are obtained. These result from the competition of surface anisotropy and
ferromagnetic alignment. Another kind of surface anisotropy was suggested that
anisotropy parallel to the surface of the cylinder. In general, the surface anisotropy
makes the surface layer magnetically harder than the core of the particle.
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NANOMATERIALS
Figure 8-11 : Surface spin arrangement of a ferromagnetic particle with a surface anisotropy of the
form KS ξ2 . Both cases corresponding to K <0 (radial) and K >0 (tangential) are displayed. [X. Batle, A.
Labarta, Finite-size effects in fine particles: magnetic and transport properties, Journal of Physics,
2002, ppR15-R42].
6
K eff = K b + KS (8. 232)
d
Where Kb is the bulk anisotropy energy per unit volume, Ks is the surface density of
anisotropy energy and d is the diameter of the particle. It is worth noticing that for a
spherical particle and based on symmetry arguments, surface anisotropy (normal to
the surface) would average to zero. However, this is not true for a nanometric particle
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NANOMATERIALS
6
with a few atomic layers. For instance, applying equation K eff = K b + KS (8.
d
232) for a 2 nm particle of fcc Co with Kb = 2.7×106 erg cm−3 and Ks ≈ 1 erg cm−2,
the surface contribution to the total anisotropy, Keff , is about 3 × 107 erg cm−3, which
is one order of magnitude larger than the bulk contribution, and Keff = 3.3 × 107 erg
cm−3.
This example is representative of the major role of surface contribution to the total
anisotropy in fine-particle systems, for which the anisotropy energy is governed by
surface anisotropy.
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Figure 8-12 : Schematic illustration of electron tunneling in F/I/F tunnel junctions: (a) Parallel and (b)
antiparallel orientation of magnetizations with the corresponding spinresolved density of the d states in
ferromagnetic metals that have exchange spin splitting ∆ex . Arrows in the two ferromagnetic regions
are determined by the majority-spin subband. Dashed lines depict spinconserved tunneling. [I. Zutic, J.
Fabian, S. Das Sarma, Spintronics: Fundamentals and applications, Reviews of modern physics,
volume 76, 2004, pp 323-410]
253
NANOMATERIALS
Where conductance G and resistance R=1/G are labeled by the relative orientations
of the magnetizations in F1 and F2 (it is possible to change the relative orientations,
between ↑↑ and ↑↓, even at small applied magnetic fields ~10 G). TMR is a particular
manifestation of a magnetoresistance that yields a change of electrical resistance in
the presence of an external magnetic field. Due to spin-orbit interaction, electrical
resistivity changes with the relative direction of the charge current (for example,
parallel or perpendicular) with respect to the direction of magnetization. Assuming
constant tunnelling matrix elements and that electrons tunnel without spin flip,
∆R R↑↓ − R↑↑ G↑↑ − G↑↓
equation TMR = = = (8. 233) yields
R↑↑ R↑↑ G↑↓
2 P1 P2
TMR = (8. 234)
1 − P1 P2
The prediction of Jullière’s model illustrates the spinvalve effect: the resistance of a
device can be changed by manipulating the relative orientation of the magnetizations
M1 and M2, in F1 and F2, respectively. Such orientation can be preserved even in the
absence of a power supply, and the spin-valve effect displays the giant
magnetoresistance (GMR) effect can be used for nonvolatile memory applications.
GMR structures are often classified according to whether the current flows parallel
(CIP, current in plane) or perpendicular (CPP, current perpendicular to the plane) to
the interfaces between the different layers, as depicted in Figure 8-13.
Figure 8-13 : Schematic illustration of (a) the current in plane (CIP), (b) the current perpendicular to
the plane (CPP) giant magnetoresistance geometry. [I. Zutic, J. Fabian, S. Das Sarma, Spintronics:
Fundamentals and applications, Reviews of modern physics, volume 76, 2004, pp 323-410]
Most of the GMR applications use the CIP geometry, while the CPP version is easier
to analyze and relates to the physics of the tunneling magnetoresistance effect. The
254
NANOMATERIALS
8.4.1.3 Applications
While many existing spintronic applications are based on the GMR effects, the
discovery of large room-temperature TMR has renewed interest in the study of
magnetic tunnel junctions, which are now the basis for the several magnetic random-
access memory prototypes. Future generations of magnetic read heads are expected
to use MTJ’s instead of CIP giant magnetoresonance. To improve the switching
performance of related devices it is important to reduce the junction resistance, which
determines the RC time constant of the MTJ cell. Consequently, semiconductors,
which would provide a lower tunneling barrier than the usually employed oxides, are
being investigated both as the nonferromagnetic region in MTJ’s and as the basis for
an all-semiconductor junction that would demonstrate large TMR at low
temperatures.
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NANOMATERIALS
Figure 8-14 : Pedagogical illustration of the concept of electrical spin injection from a ferromagnet (F)
into a normal metal (N). Electrons flow from F to N: (a) schematic device geometry; (b) magnetization
M as a function of position—nonequilibrium magnetization δM (spin accumulation) is injected into a
normal metal; (c) contribution of different spin-resolved densities of states to both charge and spin
transport across the F/N interface. Unequal filled levels in the density of states depict spin-resolved
electrochemical potentials different from the equilibrium value µ0. [I. Zutic, J. Fabian, S. Das Sarma,
Spintronics: Fundamentals and applications, Reviews of modern physics, volume 76, 2004, pp 323-
410]
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NANOMATERIALS
When a charge current flowed across the F/N junction (Figure 8-14), spin-polarized
carriers in a ferromagnet would contribute to the net current of magnetization entering
the nonmagnetic region and would lead to nonequilibrium magnetization δM,
depicted in Figure 8-14(b), with the spatial extent given by the spin diffusion length.
Such a δM, which is also equivalent to a nonequilibrium spin accumulation, was first
measured in metals by Johnson and Silsbee (1985, 1988d). In the steady state δM is
realized as the balance between spins added by the magnetization current and spins
removed by spin relaxation.
Spin polarization not only of electrons, but also of holes, nuclei, and excitations can
be defined as
The ratio of the difference Xs = Xλ – X-λ, and the sum Xs = Xλ + X-λ of the spin-
resolved λ components for a particular quantity X. To avoid ambiguity as to what
precisely is meant by spin polarization, both the choice of the spin-resolved
components and the relevant physical quantity X need to be specified.
Conventionally, λ is taken to be ↑ or + (numerical value +1) for spin up, and ↓ or -
(numerical value -1) for spin down, with respect to the chosen axis of quantization. In
ferromagnetic etals it is customary to refer to ↑ (↓) as carriers with magnetic moment
parallel (antiparallel) to the magnetization or, equivalently, as carriers with majority or
minority spin.
The spin polarization of electrical current or carrier density, generated in a
nonmagnetic region, is typically used to describe the efficiency of electrical spin
injection. Silsbee (1980) suggested that the nonequilibrium density polarization in the
N region, or equivalently the nonequilibrium magnetization, acts as the source of spin
electromotive force (emf) and produces a measurable ‘‘spin-coupled’’ voltage
VS ∝ δM . Using this concept, also referred to as spin-charge coupling, Silsbee
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Figure 8-15 : Spin injection, spin accumulation, and spin detection: (a) two idealized completely
polarized ferromagnets F1 and F2 with parallel magnetizations are separated by the nonmagnetic
region N; (b) density-of-states diagrams for spin injection from F1 into N, accompanied by the spin
accumulation-generation of nonequilibrium magnetization δM. At F2 in the limit of low impedance
(Z=0) electrical spin is detected by measuring the spin-polarized current across the N/F2 interface. In
the limit of high impedance (Z=∞) spin is detected by measuring the voltage Vs~δM developed across
the N/F2 interface; (c) spin accumulation in a device in which a superconductor is occupying the
region between F1 and F2. [I. Zutic, J. Fabian, S. Das Sarma, Spintronics: Fundamentals and
applications, Reviews of modern physics, volume 76, 2004, pp 323-410]
F1 serves as the spin injector (spin aligner) and F2 as the spin detector. This could
be called the polarizer-analyzer method, the optical counterpart of the transmission of
light through two optical linear polarizers.
From Figure 8-15 it follows that the reversal of the magnetization direction in one of
the ferromagnets would lead either to Vs→ -Vs , in an open circuit (in the limit of
large impedance Z), or to the reversal of charge current j→ -j, in a short circuit (at
small Z). Spin injection could be detected through the spin accumulation signal as
either a voltage or a resistance change when the magnetizations in F1 and F2 are
changed from parallel to antiparallel alignment.
The generation of nonequilibrium spin polarization has a long tradition in magnetic
resonance methods. However, transport methods to generate carrier spin
polarization are not limited to electrical spin injection. For example, they also include
scattering of unpolarized electrons in the presence of spin-orbit coupling and in
materials that lack inversion symmetry, adiabatic and nonadiabatic quantum spin
pumping, and proximity effects.
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σ = σ1 + σ 2 (8. 236)
Now, each layer in a GMR- structure acts as a spin selective valve. In case of
parallel-alignment-layer the contribution towards conductance due to spin up electron
is highly leading to higher valve of total conductance. However, for antiparallel
alignments the magnetic layers results in appreciable scattering for electrons in both
spin direction and hence a lower total conductance. If the F layers are much thinner
than λ↑ the spin up conductance in the parallel magnetization state is limited by
strong spin-dependent scattering in the buffer layer and in the AF layer. The contrast
with spindown conductance can then be enhanced by increasing the F-layer
thickness. It is to be noted that only a part of F-layer which is of the order of λ↑/2 from
the interface responds to the above situation.
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(a) 293 K
8
sat(%)
6
R/R
4
2
0
12 (b) 5 K
10
sat(%)
8
R/R
6
4
2
0
0 20 40 60
free F-layer thickness (nm)
Figure 8-16 : Dependence of the MR ratio on the free magnetic layer thickness, measured at 293 K
(a) and at 5K (b), for (X/Cu/X/Fe50Mn50) spin valves, grown on 3nm Ta buffer layer on Si(100)
substracts, with X=Co (squares), X=Ni66Fe16Co18 (traingles) and (X= Ni80Fe20) (+), measured at 5K.
Layer thickness: tCu = 3nm (but 2.5 for F=(X= Ni80Fe20); tF(pinned layer)=5nm (but 6nm for F=
lxxxvii
Ni66Fe16Co18) .
260
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∆R(GMR)(1-cosθ )
∆R(H)= +∆R(AMR) sin 2θ (8. 237)
2
π
The AMR-term represents the resistance change due to the change of angle ( −θ )
2
between the magnetization of the free layer and the current direction. The presence
∂R
of AMR effect increases the sensitivity ∂H if an operating point between H=0 to
R
H=+Ha is chosen. Experiment shows that due to AMR effects the sensitivity of the
spin valve is almost 50% higher then expected from GMR effect. It is suggestive for
practical purpose to operate a material around the field H=0, where the element is
magnetically most stable.
All three contributions are influenced by the microstructure of the material and
hence control of the coupling field requires very good control of the deposition
condition. This issue is very relevant for sensor application. Most of the cases the
coupling field is equal or greater than the anisotropy field. Fortunately, in a sensor
element the resulting shift of the switching field is balanced by:
• Application of a bias magnetic field from a current though an integrated bias
conductor.
• The magnetostatic coupling between the pinned and the free layer which
arises as a result of the stray magnetic field origination from the magnetization
of a pinned layer, which is directly along the long axis of the stripe.
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Interlayer coupling influences the switching field interval due to the following
two effects:
• The magnetization of the pinned layer is not quite fixed upon the rotation of
the free layer. This increases the switching field interval. This effect increases
upon an increases of the ratio between the coupling field and the exchange
biasing field.
• Lateral fluctuations in the coupling field increase the switching field interval.
Where θ is the angle between the biasing direction and the magnetization of
the pinned F layer. The exchange biasing field varies inversely with the thickness of
the pinned layer.
To obtain exchange biasing the AF layer thickness should generally exceed
critical valve.
In conclusion, we must say that exchange-biased spin valve layered structures
show a combination of properties that are attractive for the application in low field
sensors, such as read head in hard disk and tape recording. For a yoke-type GMR
head an output gain of a factor 10 has been obtained compared with a barbar-pole
biased AMR head. The following factors contribute to operational gain:
• Larger MR ratio.
• Larger sheet resistance.
• Larger flux efficiency of the head, due to the small thickness of the magnetic
layer.
Future developments are expected to focus on exchange-biased spin valve
materials with a high thermal stability, on the improvement of the effective softness,
of the free magnetic layer while remaining a high GMR ratio, and on relation between
micromagnetic aspects such as domain wall nucleation and propagation and sensor
noise.
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For typical magnetic storage media, the superparmagnetic limit imposes a minimum
particle size of about 10 nm, that is a maximum recording density of several terabits
per square inch. This is almost four order of magnitude higher than the density of 1
Gbit/inch2 found in top-of-the-line disc drives today. While the current particle size is
already close to the superparamagnetic limit the number of particle / bits is still more
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than 103. There are many signal to noise issues on the way towards reducing this
number and reaching the theoretical limit. Inconsistent switching of different particles
and an irregular domain structure require averaging over many particles. Controlling
coercivity, size, orientation and position of magnetic non-particles will be essential for
reducing the number of particles needed to store a bit. For example a large
crystalline anisotropy can produce a higher switching barrier than the shape
anisotropy above. Single domain nanoparticle with high saturation magnetization and
coercivity are being optimized for this purpose. The orientation of segregated grains
can be controlled using multilayered structures where the first layer acts as seed for
small grains and subsequent layers shape the crystalline orientation for the desired
anisotropy. A further improvement would be the more from longitudinal to
perpendicular recording where demagnetizing field does not destabilize the written
domains.
The ultimate goal in magnetic storage in single-particle-per-bit on quantized
recording. It is aimed at producing single domain particles close to the
superparamagnetic limit with uniform switching properties. Lithography is currently
the method of choice for producing regular arrays of uniform magnetic dots. Dot
arrays with a density of 65 – 250 Gbit/inch2 have been produced by electron beam
lithography.
8.6.2 Sensors:
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Present activities with GMR are directed towards, lowering the switching field
while keeping a large magneto-resistance. To obtain the best of both characteristics
one obtains soft permalloy layer for easy switching with a high-spin co-layer that
enhances the magnetoresistance.
Another type of non-volatile magnetic storage device avoid moving parts
altogether at the expense of having to pattern the storage medium. This is a
combination of magnetic memory elements with semi-conductor circuits that sense
and amplify the magnetic state (MRAM).
Further into the future are logic devices based on magnetic nanostructures. A
bipolar spin switch has been demonstrated that acts like a transistor.
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