Module 1

Quantum size effect/ Quantum confinement effect

The electron energy levels are quantized in nanomaterials. It no longer follows the
classical physical laws but quantum mechanical ones. These properties have no equivalent
with microscopic systems. The quantum confinement effect observed with the particles of
diameter in the same order of magnitude as the wavelength of the wave function of electrons.
In this case, the energy spectrum changes from continuous to discrete. As a simple
explanation the electron in a nanoparticle can be imagined as an electron in a box. Here the
energy levels are considered as the solutions of the schrodinger wave equation for a box of
give size and geometry.










Properties of nanomaterials and size effect
In microscopic view of an atomic level, a solid surface is in an unsaturated state that
the continuity of bonds is broken up. Atoms, ions and molecules at the surface and interface
has high energy and enhanced reactivity. The surface energy is a an additive quantity which
increases with total surface area. Atoms, ions or molecules constructing a solid surface
cannot diffuse, even if potential energy differs between adjacent ones, because the activation
energy required for surface diffusion is in general quite high, and hence homogenization of
the surface cannot be achieved as taking place on liquid surface. Due to these two features,
the solid surface shows unique characteristics that cannot be expected from bulk structure of
the solid. Especially for nanomaterials, the number of atoms, ions or molecules making up
the particle becomes larger on the surface rather than within the particle. The surface energies
of nanomaterials are higher than bulk surfaces. For this reason, a number of unique
characteristics specific to nanomaterials appear. These characteristics give strong effects not
only to quantum size effect specific to nanomaterials but also to phenomena relating to
powder handling such as adhesion and coagulation. Therefore, to understand and control the
characteristics of the particle surface are often key technology for success in researches and
developments with regard to nanomaterials.








With the decreasing particle size, the solid particles generally tend to show different
properties from the bulk material and even the physical properties like melting point and
dielectric constant themselves which have been considered as specific properties may change,
when the particles become in several nanometer size. These changes in the fundamental
properties with the particle size is called size effect in a narrower sense. On the contrary, in
a broader sense, it could also include the change in the various characteristics and behaviors
of particles and powders with the particle size. The nanomaterials have various unique
features in the morphological/structural properties, thermal properties, electromagnetic
properties, optical properties, mechanical properties, electrical properties.

Increase of surface area
On the other hand, as the micronization of solid particles, the specific surface area
increases generally in reversal proportion to the particle size. When the particle of 1cm is
micronized to 1_m and 10nm, the specific surface area becomes ten thousand times and

million times, respectively. As the increase in the specific surface area directly influences
such properties like the solution and reaction rates of the particles, it is one of major reasons
for the unique properties of the nanoparticles different from the bulk material together with
the change in the surface properties of the particles itself.

Thermal properties melting point
As the atoms and molecules located at the particle surface become influential in the
nanometer order, the melting point of the material decreases from that of the bulk material
because they tend to be able to move easier at the lower temperature. For example, the
melting point of gold is 1336 K as a bulk but starts to decrease remarkably below the particle
size of about 20 nm and drastically below 10 nm and then becomes more than 500 degrees
lower
A proportion of number of surface atoms to that of bulk atoms increases with decrease
in particle size. Accordingly, the melting point of nanomaterials falls as much as
corresponding surface energy. Many researchers have reported melting points of
nanoparticles and some examples are shown in Figs. Below and
A melting point of Au declines suddenly when a particle size is less than 15 nm and a
decrease of almost 200 K can be observed at about 6 nm. As shown in Fig. 1.5.2, it has been
reported that there is a linear relationship between a ratio of a melting point of nanoparticle
(Tm) to that of bulk material (To) and a reciprocal number of a particle diameter.







Melting point of Au nanoparticles
Optical properties
Optical property of nanomaterial is greatly different according to whether the nanomaterial is
insulator, semiconductor or metal. Below figures shows typical band structure model. In the
insulator or the semiconductor, the valence band is completely occupied with the electron and
the conduction band is emptied









Surface Plasmon Resonance (SPR) in metal nanoparticles
The conduction bands of a conductor (metal) are partially filled with electrons; no gap
exists in electronic excitation. Conducted electrons in metal form a kind of plasma state, and
the intraband transition of conduction electrons is described as the collective motion of free
electrons. The oscillation of electrons by this collective motion, in other words, the repetitive
oscillations of electrons to shield polarization caused by external fields such as light and
electron rays, is referred to as plasma oscillation. This oscillatory wave is expressed as a
particle and referred to as a plasmon.
The contribution of a conduction electron is interpreted using the classical Drude
model, which regards electrons as traveling within a stationary field with an ionic core
resembling that of a gas, but it assumes their interaction with other electrons and ions as a
mere damping term. An electric field, generated when an electronic gas deviates from a
stationary ionic field as a whole, acts as the restoring force. This is the principle by which
plasma oscillations occur. Interband transition also has a certain contribution in real particles.
Therefore, optical response is described as their mixed state. It is not often the case that real
metal nanoparticles are completely isolated one by one in a vacuum: they are surrounded by a
medium with different dielectric constants as a practically important morphology. Light
incidence onto transparent insulators such as metal nanoparticle-dispersed glass brings about
a mode of vibration called a surface plasmon that is localized on the metal nanoparticle
surface. A dielectric function varies at the interface of different substances to try to be
continuous. Consequently, a mode of vibration with its resonance frequency that is deviated
from the ordinary plasma frequency occurs, which creates a surface plasmon. Beautiful colors
appear when incident light and surface plasmons resonate. This phenomenon has been known
and used commonly for many years, as in optical glasses such as stained glass in European
cathedrals since the Middle Ages. The effect of surface plasmons is manifested brilliantly in
ultrafine particles with a large surface fraction. Recently, metal nanoparticle systems have
been attracting attention [3, 4] because of their enhanced nonlinear optics (NLO) properties
by single electronic electrical conduction phenomenon because of Coulomb blockade and
surface Plasmon.
Optical spectra of Ag nanoparticles with different size
As the size of particles becomes in the several nanometers range, they absorb the light
with a specific wavelength as the plasmon absorption caused by the plasma oscillation of the
electrons and the transmitted light with different color depending upon the kind of metal and
particle size is obtained. Also the shape of particles can shift the Plasmon resonance






Above figure shows the plasmon absorption of silver nanoparticles (left), where the
spectral absorption intensity differs depending upon the particle size which is determined by
the concentration of the surfactant used for their preparation. In right figure the Plasmon
absorption changes with change in shape of the gold nanomaterials. In case of gold
nanoparticles, it is reported that the maximum light absorption wavelength is 525 nm for the
particles of 15nm but it is enlarged by about 50 nm for 45 nm particles. In this way, these
gold and silver nanoparticles show the color phenomena with splendid tinting strength, color
saturation and transparency compared with the conventional pigments for the paint in the
submicron size and the tinting strength per unit volume of silver nanoparticles becomes about
100 times higher than that of organic pigments. Furthermore, since the nanoparticles are
smaller than the wavelength of visible light and the light scattering by the particles becomes
negligible, higher transparency can be obtained with the nanoparticles than the conventional
pigment. On the other hand, concerning the light emitting performance, the indirect transition
type substances like silicon and germanium, which do not emit the light as bulk material, give
high light emitting efficiency as the direct transition type substances as a result of quantum
effect, when the particle

Optical properties of semiconductor nanomaterials

The electronic density of states is discretized in nanostructured semiconductor particles
because of the spatial confinement. In that case, the condition of an exciton ( electron-hole
pair) is determined by the competition of the spatial confinement and the Coulomb
interaction. Since the semiconductor becomes increasingly smaller, the magnitude of the
Coulomb interaction extends over a bulk crystal, but the increase of the confinement energy
prevails. Accordingly, the smaller it gets, the less the relative contribution of the Coulomb
interaction becomes and the spatial confinement becomes dominant. In a region with a high
obstacle potential and strong confinement, electrons and holes are no longer freely mobile.






















These semiconducting quantum dots are considered to be alternative to dyes and light
emitting sources



Electrical properties
In general, it is recognized that the electrical properties of the large particles are same
as that of the bulk materials, as well as the crystal symmetry. Namely, the electrical
properties such as dielectric and ferroelectric properties are the intrinsic independent of the
shape and size. The Quantum confinement causes the increase in bandgap of the
naomaterials. At very small size the energy levels are quantized and the overlapping of bands
metal starts disappearing.







In semiconductor nanostructures, analogous to the particle-in-a-box model from
introductory physical chemistry, exciton( electron hole pair) quantum confinement results
in discrete energy levels rather than the continuous bands of a bulk semiconductor crystal.
Since the gap between adjacent energy levels is infinitesimally small for a bulk
semiconductor, the bandgap is considered as a fixed value. In contrast, since the dimensions
of a quantum dot are extremely small, the addition/subtraction of a single atom will
significantly change the nanocrystal dimensions and bandgap and electrical conductivity.
It is also very difficult to estimate the electrical properties of the nanosystems.
Deposition of the electrodes on the nanoparticles seems to be very difficult. However, the
dielectric constant is affected by the void, the grain boundary and so on. Therefore, the
intrinsic dielectric constant of the nanoparticles cannot be determined by this method.
Namely, it is concluded that the result was affected not only by the size effect but also by the
other extrinsic effect such as the low dielectric phase of pores.
The one dimensional nanowires, nanorods and nanotubes shows a significant
difference in the conductivity along the direction. This is very useful in certain
nanodevices.The bandgap of the CNT can be tuned by their structure. Depending on the
chirality of the carbon the conductivity varies. The size also affect the conductivity. CNT is
dispersed in polymers and ceramics to obtain conducting composites. The band gap of
semiconducting metaloxides can be modified by varying the size.












Magnetic properties
The spin state of electrons in an atom determine the magnetic property of the atom.
Depending on this spin state of the electrons, the atoms may be classified into mainly:
Diamagnetic and Paramagnetic.
(a) Diamagnetic atoms (or ions) are those in which there are no uncoupled or
uncompensated electron spins.
(b) Paramagnetic atoms (or ions) are those with uncoupled or unpaired electron spins in the
orbital giving rise a net magnetic (spin) moment.
The magnetic moment of an uncoupled electron is given as Bohr magneton, B. One Bohr
magneton represents the magnetic moment of one uncoupled electron. Therefore, for
example, the net magnetic moment for the Fe3+ atom is 5B, since it has 5 uncoupled
electrons.

Magnetic characteristics of nanosized materials
Nanoparticles have small volume in the similar range to molecule one. Magnetism of
not only nanoparticles but also magnetic molecules appears by interactive effect between
magnetic moments. Electron motion on the atomic nucleus orbit is regulated by energy,
angular momentum and spin (atomic magnetic moment). Energy is described by orbit radius
around the nucleus. If it has larger energy, the orbit radius becomes larger. Angular
momentum is a counterpart of integrated intensity. Spin corresponds to electron rotation.
Magnetism of molecule depends on both orbital motion (energy and angular momentum) and
spin. The characteristics of nanosized magnetic substance are deviated from the bulk ones.
Specific surface area becomes larger with decreasing particle size, and then the influence of
surface property becomes serious not to be neglected.
Nanostructuring help in design of soft or hard magnets. Also due to quantum
confinement effects the new properties arise like Gaint Magneto Resistance(GMR), which is
useful in storage devices. Also ferro to superparamagnetic transition is possible with nanosize
materials.
Generally ferromagnetic substance would be metals or unstable oxides. Magnetic
characteristics such as saturation magnetization decrease proportionally with size reduction of
magnetic substance. The relationship between particle size of spherical magnetite (Fe3O4)
and saturation magnetization is described in Fig. below.








The abscissa shows particle diameter (nm), and ordinate shows the saturation
magnetization (Am2/kg) of spherical magnetite. It became clear that saturation magnetization
suddenly decreased in proportion to particle size in the nanoregion. The decrease in saturation
magnetization is not preferable, and the higher characteristics should be maintained in spite
of nano-sizing. A lot of studies have been conducted by the modification of composition or
the surface coating onto magnetic particles in order to find out excellent magnetic substance
which maintains higher magnetic properties. For example, the oxidation resistance of iron
oxide for magnetic recording media could be improved by the introduction of surface coating.
Iron-based magnetic metal particles have been studied to achieve higher performance of
magnetic recording. Reducing the size of iron-based metal particles is much required to
obtain high signal and low noise of media such as magnetic tapes. The particle size of latest
metal particles is about several decades nanometer, and the size reduction of metal particles
would be further continued. Iron-based acicular metal particles have high magnetic
performance such as saturation magnetization and coercive force. However, it was a problem
that they were chemically unstable and consequently the magnetic properties might be
deteriorated by surface oxidation for instance. The surface coating with carbon was
investigated in order to improve the chemical stability such as oxidation resistance. The
magnetization of the uncoated metal particles reduced remarkably with time progress.
However, reduction in the magnetization of the carbon-coated metal particles was very small.
And then it became clear that carbon coated metal particles were chemically stable enough
compared to the uncoated metal particles. Serious problems caused by reducing the size of
metal particles would be chemical and thermal stabilities. They will be cleared by both
modification of composition and introduction of surface coatings such as carbon coating to
commercialize nanosized magnetic substances.

The above materials were taken from the following references. Absolutely the Full
credit goes to the authors of those materials. I t shall used only for academic purpose by
students. Other malpractices will be subjected to copy right violation.

References
1. Nanomaterials, in Materials chemistry by Fahlman B.D, Springer publ.
2. Small dimensions and material properties, in Miniaturization and material
properties by G. Schmid, M.Decker, H.Ernst, by H.Fuchs, W.Grunwald, A.
Gruwald, H. Hofmann, M.Mayor, W. Rathgeber, U.Simon, D.Wyrwa,
Europaeische Akademie publ.
3. Physical properties of nanomaterials, J uh Tzeng Lue,, Encyclopedia of
nanoscience and nanotechnology.
4. Nanoparticle Technology- Handbook by Masuo Hosokawa, Kiyoshi Nogi,
Makio Naito, Toyokazu Yokoyama