CHAPTER 2

CLASSIFICATION OF NANOMATERIALS
CLASSES OF MATERIALS
• In this book, we distinguish seven classes:
• Metallic
• Ceramic
• Polymeric
• Composite
• Electronic
• Biomaterials
• Nanomaterials
Metallic Materials

• Metallic materials consist principally of one or more metallic elements.

• Examples of metallic elements: copper, nickel, and aluminum,
• Examples of nonmetallic elements: carbon, silicon, and nitrogen.
• When a particular metallic element dissolves well in one or more
additional elements, the mixture is called a metallic alloy.
• The best example of a metallic alloy is steel
• composed of iron and carbon
• Metallic materials exhibit metallic-type bonds and thus are
• good thermal and electrical conductors
• ductile
at room temperature.
Ceramic Materials

• Ceramic materials are composed of at least two different elements.

• Among the ceramic materials, there are predominantly:
• ionic in nature - consist of a mixture of metallic elements and
nonmetallic elements
• covalent in nature - consist mainly of a mixture of nonmetallic elements
• Examples of ceramic materials are glasses, bricks, stones, and
porcelain.
• Because of their ionic and covalent types of bonds, ceramic materials
are hard, brittle, and good insulators.
• Very good corrosion resistance properties.
Polymeric Materials

• Polymeric materials consist of long molecules composed of many

organic molecule units, called mer (therefore the term polymer).
• Polymers are typically divided into:
i. natural polymers such as wood, rubber, and wool;
ii. biopolymers such as proteins, enzymes, and cellulose;
iii. synthetic polymers such as Teflon and Kevlar.
• Among the synthetic polymers there are:
• elastomers, which exhibit large elongations and low strength
• plastics, which exhibit large variations in properties.
• Polymeric materials are in general good insulators and have good
corrosion resistance.
Composite Materials

• Composite materials are formed of two or more materials with very

distinctive properties, which act synergistically to create properties
that cannot be achieved by each single material alone.
• Typically, one of the materials of the composite acts as a matrix,
whereas the other materials act as reinforcing phases.
• Composite materials can be classified as metal-matrix, ceramic-
matrix, or polymer-matrix.
• For each of these composite materials, the reinforcing phases can be a
metal, a ceramic, or a polymer, depending on the targeted
applications.
Electronic Materials

• The electronic class of materials is a bit broader than the previous

classes because electronic materials can encompass metals,
ceramics, and polymers, such as:
• the metal copper that is used as interconnects in most electronic chips
• the ceramic silica that is used as optical fibers
• polymer polyamides - used as a dielectric.
• The term electronic materials used to describe materials that exhibit
semiconductor properties.
• The most important of these materials is silicon - used in practically
all electronic components.
• Other materials such as germanium and gallium arsenide are also
part of this class.
Biomaterials

• The biomaterials class is related to any material, natural or

synthetic, that is designed to mimic, augment, or replace a biological
function.
• Biomaterials should be compatible with the human body and not
induce rejection.
• This class of materials is rather broad and can comprise metals,
ceramics, polymers, and composites.
• Typically these materials are used in prostheses, implants, and surgical
instruments.
• Biomaterials should not be confused with bio-based materials, which
are the material parts of our body, such as bone.
Nanomaterials

• The nanomaterial class of materials is extremely broad because it

can include all the previous classes of materials,
• composed of a structural component at the nanoscale
• exhibit one of the dimensions at the nanoscale.
• The prefix nano represents a billionth of a unit, so the nanoscale is
normally considered to span from 1 to 100 nanometers.
• Nanomaterials are typically categorized as
• 0-D (nanoparticles)
• 1-D (nanowires, nanotubes, and nanorods)
• 2-D (nanofilms and nanocoatings)
• 3-D (bulk)
which represent the number of dimensions that are NOT at the nanoscale
Classification of nanomaterials
• Nanomaterials can be classified as
• zero-dimensional (0-D),
• one-dimensional (1-D),
• two-dimensional (2-D),
• three-dimensional (3-D).
• This classification is based on the number of dimensions,
which are NOT CONFINED to the nanoscale range (<100 nm).
0D nanomaterials
• Beginning with the most clearly defined category, zero-dimensional
• Nanomaterials are materials wherein all the dimensions are measured
within the nanoscale (no dimensions, or 0-D, are larger than 100 nm).
• The most common representation of zero-dimensional nanomaterials
are nanoparticles.
• These nanoparticles can:
■ Be amorphous or crystalline
■ Be single crystalline or polycrystalline
■ Be composed of single or multichemical elements
■ Exhibit various shapes and forms
■ Exist individually or incorporated in a matrix
■ Be metallic, ceramic, or polymeric
1D nanomaterials
• On the other hand, 1-D nanomaterials differ from 0-D
nanomaterials in that the former have one dimension
that is outside the nanoscale.
• This difference in material dimensions leads to
needlelike-shaped nanomaterials.
• One-dimensional nanomaterials include nanotubes,
nanorods, and nanowires.
• Yet, as was the case with 0-D nanomaterials, these 1-
D nanomaterials can be:
• Amorphous or crystalline
■ Single crystalline or polycrystalline
■ Chemically pure or impure
■ Stand alone materials or embedded in within
another medium
■ Metallic, ceramic, or polymeric
2D nanomaterials
• 2-D nanomaterials are materials in which two of the
dimensions are not confined to the nanoscale.
• As a result, 2-D nanomaterials exhibit platelike
shapes.
• Two-dimensional nanomaterials include nanofilms,
nanolayers, and nanocoatings.
• These nanomaterials can be:
■ Amorphous or crystalline
■ Made up of various chemical compositions
■ Used as a single layer or as multilayer
structures
■ Deposited on a substrate
■ Integrated in a surrounding matrix material
■ Metallic, ceramic, or polymeric
3D nanomaterials
• Three-dimensional nanomaterials, also known as
bulk nanomaterials, are relatively diffi cult to
classify.
• However, in keeping with the dimensional
parameters we’ve established so far, it is true to
say that bulk nanomaterials are materials that are
not confined to the nanoscale in any dimension.
• These materials are thus characterized by having
three arbitrarily dimensions above 100 nm.
• The reason for the continued classification of these materials as
nanomaterials is:
1. Despite their nanoscale dimensions, these materials possess a
nanocrystalline structure or involve the presence of features at the
nanoscale.
2. In terms of nanocrystalline structure, bulk nanomaterials can be
composed of a multiple arrangement of nanosize crystals, most
typically in different orientations.
• With respect to the presence of features at the nanoscale, 3-D
nanomaterials can contain dispersions of nanoparticles, bundles of
nanowires, and nanotubes as well as multinanolayers.
• Three-dimensional nanomaterials can be:
■ Amorphous or crystalline
■ Chemically pure or impure
■ Composite materials
■ Composed of multinanolayers
■ Metallic, ceramic, or polymeric
• The distances x, y, and z represent dimensions below 100 nm.
• As we look in more detail at the aforementioned categories, the
straightforward nature of 0-D and 1-D nanomaterials speak for
themselves.
• 2-D and 3-D nanomaterials have detailed explanation.
Single layer 2D nanomaterial
• 2-D nanomaterial is a single-layer material, with a thickness below 100
nm and length and width that exceed nanometer dimensions.
• a material may be categorized as a nanomaterial simply on the basis of
its internal structural dimensions, regardless of its exterior material
dimensions.
• a 2-D nanomaterial is shown with a particular internal structure,
composed of crystals (or grains) with nanoscale dimension.
• The 2-D nanomaterial may be called a nanocrystalline film because of
two features:
(1) the material exhibits an overall exterior thickness with nanoscale
dimensions,
(2) its internal structure is also at the nanoscale.
• However, if the exterior thickness remains at the nanoscale, it is
possible for the same film to have a larger (above 100 nm) internal
grain structure.
• Its still qualify the entire material as a nanoscale material.
• The internal structural dimensions and external surface dimensions
are independent variables for the categorization of 2-D
nanomaterials
Multilayer 2-D nanomaterial
• Generally, 2-D nanomaterials are deposited on a substrate or support
with typical dimensions above the nanoscale.
• In these cases, the overall sample thickness dimensions become a
summation of the film’s and substrate’s thickness.
• When this occurs, the 2-D nanomaterial can be considered as a
nanocoating.
• Yet at times when the substrate thickness does have nanoscale
dimensions or when multiple layers with thicknesses at the
nanoscale are deposited sequentially, the 2-D nanomaterial can be
classified as a multilayer 2-D nanomaterial.
• Within each layer, the internal structure can be at the nanoscale
or above it.
• Many applications, especially in nanoelectronics, require the use of
various kinds of physical features, such as channels, grooves, and raised
lines, that are at the nanoscale.
• Nanofilms, nanocoatings, and multilayer 2-D nanomaterials can be
patterned with various features at various scales.
• In the case of multilayered nanomaterials, the patterns can be made on
any layer.
• These patterns can have different geometries and dimensions at the
nanoscale or at larger scales.
• Most electronic
materials fall into the
category of patterned
2-D nanomaterials
3D nanocomposites
• Bulk nanomaterials are materials that do not have any dimension at
the nanoscale.
• However, bulk nanomaterials still exhibit features at the nanoscale.

• These materials are then called nanocrystalline materials.

• Another group of 3-D nanomaterials are the so-called
nanocomposites.
• These materials are formed of two or more materials with
very distinctive properties that act synergistically to
create properties that cannot be achieved by each single
material alone.
• The matrix of the nanocomposite, which can be polymeric,
metallic, or ceramic, has dimensions larger than the nanoscale,
whereas the reinforcing phase is commonly at the nanoscale.
• Distinctions are based on the types of reinforcing
nanomaterials added, such as nanoparticles, nanowires,
nanotubes, or nanolayers.
• Examples of the type of 3-D nanomaterial.
• Within the nanocomposite classification, we should also
consider materials with multinanolayers composed of various
materials or sandwiches of nanolayers bonded to a matrix
core.
Basic types of large-scale nanomaterials bulk forms. The filler materials,
whether 0-D, 1-D, or 2-D nanomaterials are used to make film and bulk
nanocomposites
General characteristics of nanomaterial classes
and their dimensionality.
SIZE EFFECTS: SURFACE-TO-VOLUME RATIO
• The larger surface area of nanomaterials (compared to their
volume) plays a larger role in dictating these materials’
important properties.
• a nanomaterial’s shape is of great interest because various
shapes will produce
• distinct surface-to-volume ratios and therefore different
properties.
• The expressions that can be used to calculate the surface-to-
volume ratios in nanomaterials with different shapes are as
follows:
• We start with a sphere of radius r.
• This is typically the shape of nanoparticles used in many applications.
• In this case, the surface area is given by

• whereas the volume of a sphere is given b

• Thus, the surface-to-volume ratio of a sphere is given by

• Next, consider a cylinder of radius r and height H—for
example, a nanowire.
• In this case, the volume V = πr²H, whereas the surface area A
=2πrH.
• Thus, the surface-to-volume ratio is given by
• Let’s now turn to a cube of side L.
• In this case, the volume and surface area of the cube are given
by V =L³ and A =6L² , respectively.
• Therefore the surface-to volume ratio of a cube is given by

• With the help of a few simple calculations, we can determine

how much of an increase in surface area will result.
Example
• Calculate the number of spherical nanosized particles generated by the 10 micron
particle. Assume that the volume remains constant.
• Calculate the number of nanosized particles generated by the 10 micron particle.
We get ; V (10 µm) =.
• Then calculate the volume of a sphere with 10 nm.
We get V (10 nm) =
• Because the mass of the 10 micron particle is converted to a group of nanosized
particles, the total volume remains the same.
• Therefore, to calculate the number of nanosized particles generated by the 10
micron particle, we simply need to divide V (10 µm) by V (10 nm)in the form:

• so far we can conclude that one single particle with 10 microns can generate 1
billion nanosized particles with a diameter of 10 nm, whereas the total volume
remains the same.
SIZE EFFECTS: QUANTUM EFFECTS
• In bulk crystalline materials, the atomic energy levels spread out into
energy bands.
• The valence band, which is filled with electrons, might or might
not be separated from an empty conduction band by an energy
gap.
• A band gap is an energy range in a solid where no electron states can
exist due to the quantization of energy in quantum mechanics.
• For conductor materials such as metals, there is typically no band gap.
• Therefore, very little energy is required to bring electrons from the
valence band to the conduction band, where electrons are free to
flow.
• For insulator materials such as ceramics, the energy band gap is quite
significant and thus transferring electrons from the valence band to the
conduction band is diffi cult.
• In the case of semiconductor materials such as silicon, the band
gap is not as wide, and thus it is possible to excite the electrons from
the valence band to the conduction band with some amount of energy.
• This overall behavior of bulk crystalline materials changes when the
dimensions are reduced to the nanoscale.
• For 0-D nanomaterials, where all the dimensions are at the nanoscale,
an electron is confined in 3-D space.
• Therefore, no electron delocalization (freedom to move) occurs.
• For 1-D nanomaterials, electron confinement occurs in 2-D, whereas
delocalization takes place along the long axis of the
nanowire/rod/tube.
• In the case of 2-D nanomaterials, the conduction electrons will be
confined across the thickness but delocalized in the plane of the sheet.
• Therefore, for 0-D nanomaterials the electrons are fully confined.
• On the other hand, for 3-D nanomaterials the electrons are fully
delocalized.
• In 1-D and 2-D nanomaterials, electron confinement and delocalization
coexist.
• Under these conditions of confinement, the conduction band
suffers profound alterations.
• The effect of confinement on the resulting energy states can be
calculated by quantum mechanics, as the “particle in the box”
problem. (infinite potential well or the infinite square well) –
• particle free to move in a small space surrounded by impenetrable barriers.
• In this treatment, an electron is considered to exist inside of an
infinitely deep potential well (region of negative energies), from
which it cannot escape and is confined by the dimensions of the
nanostructure.
• In 0-D, 1-D, and 2-D, the effects of confinement on the energy state
can be written respectively as
• Where;
• ħ≡h/2π, h is Planck’s constant,
• m =mass of the electron,
• L =width (confinement) of the infinitely deep potential well,
• nx, ny, and nz are the principal quantum numbers in the three
dimensions x, y, and z.

• the smaller the dimensions of the nanostructure (smaller L), the wider
is the separation between the energy levels, leading to a spectrum of
discreet energies.
• In this fashion, the band gap of a material can be shifted toward higher
energies by spatially confining the electronic carriers.
• Another important feature of an energy state E n is the
number of conduction electrons, N (E n), that exist in a
particular state.
• As En is dependent on the dimensionality of the system, so
is the number of conduction electrons, N (En),.
• This also means that the number of electrons dN within a
narrow energy range dE, which represent the density of
states D(E), i.e., D(E) =dN/dE, is also strongly dependent on
the dimensionality of the structure.
• Therefore the density of states as a
function of the energy E for
conduction electrons will be very
different for a
• quantum dot (confinement in three
dimensions),
• quantum wire (confinement in two
dimensions and delocalization in one
dimension),
• quantum well (confinement in one
dimension and delocalization in two
dimensions),
• bulk material (delocalization in threed
imensions)
• Because the density of states determines various properties,
the use of nanostructures provides the possibility for
tuning these properties.
• For example, photoemission spectroscopy, specific heat,
the thermopower effect, excitons in semiconductors, and the
superconducting energy gap are all influenced by the density
of states.
• Overall, the ability to control the density of states is
crucial for applications such as infrared detectors, lasers,
superconductors, single-photon sources, biological tagging,
optical memories, and photonic structures.
FINISH!