Unit 5- Nanomaterials

Dr. Shikha Kumari

IILM University, Greater Noida
Books
• Introduction to nanotechnology by CP Poole Jr. and F.J. Owens, Wiley and Sons

• Nano-structured materials and nanotechnology by Hari Singh Nalwa, Academic press

• Engineering Physics by H.K. Mallik and A. K. Singh, Mc Graw Hill

• Introduction to Nanoscience and Nanotechnology, KK Chattopadhyay, A N Banerjee, Phi

Learning Pvt Ltd., New Delhi, 2012, ISBN-978-81-203-3608-7

• Nanotechnology Science Innovation & Opportunity, Lynn E Foster, Pearson publication, 2008,
ISBN-9788131711187.
Richard Feynman concept about nanotechnology
• First ever concept was presented by Dr. Richard Feynman in 1959.

• Richard Feynman’s famous presentation “ There is plenty room at the bottom”.

• It was presented in 1959 at American Physical Society.

• Major Questions in the presentation were.

• Why Can’t we manipulate materials atom by atom?

• Why can’t we control the synthesis of individual molecules?

• Why can’t we write all the human knowledge on the head of the pin?

• Why can’t we build machines to can accomplish these things?

History
• Feynman solicit the Physicists in 1959 “ to make the electron microscope 100 times better”

• This was achieved 22 years later.

• Not only seeing the atoms but also their manipulation became a reality in 1981 when Gerd
Binnig and Heinrich Rohrer of IBM, Zurich research lab invented the Scanning Tunneling
Microscope for which they were awarded Nobel Prize in 1986.

• The term Nanotechnology was coined by Norio Taniguchi in 1974.

INTRODUCTION
• Nano-science: It deals with the study of phenomena at a very small scale ( ~ 1- 100 nm)
where properties of matter differ significantly from those at larger scales.

• Nanotechnology: The design, characterisation, production of objects at nanoscale ( ~ 1- 100

nm) is called nanotechnology.

• Nanomaterials are one of the main products of nanotechnology.

• Nanotechnology has been involved in almost all fields, including electronics, magnetics, optics,
optoelectronics, information technology, therapeutic and biomedicine.

• Nanoscale is so special because, at nanoscale the surface to volume ratio increases and
quantum effects (quantum confinement) become prominent. So the behaviour of such
materials is different from the bulk.
What are Nanomaterials
.
What are nano-materials
• Nanomaterials are defined as particles in the form of crystals, rods or spheres having size
between 1nm - 100nm at least in one dimension. The word nano is a unit prefix that originated
from the Greek word that means dwarf.

• Nano materials are the materials that are formed by the assembly or repetition of nanometer-
sized building blocks. The building blocks may be zero-dimensional or one-dimensional or two-
dimensional which are separated by different types of boundaries.

• Nanomaterials are made up of carbon, ceramics, chemical precursors, ferrites, metals,

minerals, polymers, semiconductors, silica.

• At nanoscale the physical, chemical and biological properties of material differ in fundamental
and valuable ways from the properties of individual atoms and molecules or bulk matter.

• Nanomaterials show unique properties like increased strength, toughness, hardness, ductility,
melting point, efficient electrical properties, magnetic properties, catalytic properties, optical
properties, and so on as compared to bulky materials.
Classification of Nanomaterials
• On the basis of reduction in size of material in different dimensions, Nanomaterials are
classified into three groups.

• 3D - all dimensions are at macro scale, no dimension at nanoscale

• 2D - two dimension at macro scale and one dimension at nanoscale. Examples: Nanofilms,
nanosheets, nano-coatings, and so on.

• 1D - one dimension at macro scale and two dimension at nanoscale. Nanowires, nanotubes,
etc. are some examples of one-dimensional nanomaterials.

• 0D - all dimension at nanoscale, no dimension at macro scale. Such materials have all three
length scales L (length along X-axis, Y-axis, and Z-axis) in the nanoscopic range. Examples:
x

Quantum dots, metallic nanoclusters, nanosphere, etc.

Classification of Nanomaterials
Density of States
Density of state is the total number of energy states available
Properties of Nanomaterials
SURFACE PROPERTIES:

• When a bulk material is subdivided into materials on the nano scale, the total volume remains
the same but the collective surface area is increased. This results in increase of surface to
volume ratio at nanoscale as compared to bulk materials.

• There are more number of atoms or molecules on the surface as compared to its number
inside the volume in a nanomaterial.

• The molecules or atoms at the surface of a nanomaterial possess high surface energy and
have high reactivity and have greater tendency to agglomerate. Thus, as the nanomaterials
have significant proportion of atoms existing at the surface, this has profound effect on
reactions that occur at the surface such as catalysis reactions and detection reactions.

• The melting point of nano materials are reduced as compared to bulk counterpart due to larger
surface atoms present
Properties of Nanomaterials
ELECTRICAL PROPERTIES:

• In bulk metals, the valence and conduction bands overlap, electrons can move freely in all
directions ie. electron delocalisation takes place.

• When the scale is reduced, electron confinement occurs. For example in 1D nanomaterial, one
dimension is in macro scale and two dimensions are in nanoscale so electron delocalisation
takes place along the axis on the nanotube or nanowire.

• Due to electron confinement , the energy bands are replaced by discrete energy states which
make the conducting material to behave like either semiconductor or insulator.

• For example, carbon nanotubes can be either conductors or semiconductors depending on

their nano structure. Another example is super capacitors which has effectively no resistance
which disobey ohm’s law.
Properties of Nanomaterials
OPTICAL PROPERTIES:

• In nanosized semiconductors there exists discrete energy states. Thus bands split and become
discrete. Light of only certain wavelengths of certain dimensions are absorbed. This leads to
emission of certain monochromatic wavelengths.

• Due to quantum confinement, energy gap increases. Thus more energy is required for
absorption. Higher energy means shorter wavelength of light is emitted resulting in blue Shift.

• Tuning the nanosize of a semiconductor means tuning of bandgap leading to light of certain
wavelength being emitted. Thus the same material emits different colours depending on its size.

• Scattering of light depends on the size of a particle. By using nanomaterials in sunscreens, the
wavelength of scattered light shifts towards shorter wavelengths and appear transparent instead
of white.
Properties of Nanomaterials
MAGNETIC PROPERTIES:

• The magnetic properties of a magnet are described by its magnetisation curve (called hysteresis curve
which is the variation of intensity of magnetisation with applied magnetic field).

• These curves show the property like whether a magnet can be used as permanent magnet or a
electromagnet etc.

• The size of the material can change the property of a magnet by changing the magnetisation curves.
Thus nano-structuring of bulk magnetic materials leads to changes in the curves which can produce soft
or hard magnets with improved properties
Properties of Nanomaterials
MECHANICAL PROPERTIES:

• Mechanical properties of nanomaterials may reach the theoretical strength, which are one or
two orders of magnitude higher than that of single crystals in the bulk form.

• The enhancement in mechanical strength is simply due to the reduced probability of defects.

• Carbon nanotubes are 100 times stronger than steel but six times lighter.
Applications of Nanomaterials
Automobile industry: Lightweight construction, coatings if window screens and car bodies, Tires,
sensors, painting

Chemical industry: Fillers for paint systems, switchable adhesives, magnetic fluids

Engineering: wear protection for tools and machines, lubricant free bearings

Electronic industry: data memory, displays, conductive and antistatic coating

Construction: construction materials, thermal insulation, flame retardants

Medicine: drug delivery system, agents in cancer therapy, medical rapid tests, prosthesis and implants

Energy: fuel cells, solar cells, capacitors, batteries

Cosmetics: sunscreen, cosmetics, skin creams, toothpaste

Food and drinks: package materials, additives, storage life sensors, clarification of fruit juices.
Quantum well
• It is 2-D nanocrystal. It is also called nano layers.

• In this electrons are confined to move in two dimensions by forcing them to occupy a planar
region

• It is a kind of structure in which one thin well layer is sandwiched by two barrier layers.

• Quantum well can be used to create compact and fast computer chips, highly efficient
microscopic lasers and optoelectronic devices. They form the basis of laser in CD players and
microwave receivers. Blue light semiconductor laser uses quantum well.
 Quantum wires
• It is a 1-D nanocrystal with two confined and one unconfined direction.
.
• It is a cable or wire similar in function to copper wire but made with nanotube usually made of
carbon.

• A quantum wire is an electrically conducting wire in which quantum effects influence the
transport properties.

• Quantum wires are usually conductors but may also be made as insulators or semiconductors.
 Quantum Dots
• It is a 0-D nanocrystal made from semiconductor material.
.
• It is man-made crystal that exhibit unique optical and electronic properties, including the ability
to transport electrons and emit light of various colours when exposed to UV light.

• The electrons inside the dots are trapped and can only occupy defined energy levels.

• It has wide range applications in solar cells, displays, lighting and medical imaging.

• Few examples of semiconductor Quantum Dots: CdSe, ZnSe, ZnS, ZnO

 Graphene
.
• It is an atom-thick planar sheet of sp2 bonded carbon atoms densely packed in a honeycomb
lattice.

• Graphene is the basic structural element of some carbon allotropes including graphite, carbon
nanotubes and fullerenes.

• Properties: (i) It is transparent, light weight and flexible

(ii) It is 200 times stronger than steel by weight due to its tightly packed carbon atoms.
(iii) It has ability to conduct heat and electricity with great efficiency
(iv) It is biocompatible and non toxic for cells.

• It is used in computer displays and flat panel TVs, ATM touch screens, solar cells,
semiconductors, batteries, composite industries, and many more.
 Graphene
.

•
 Carbon Nano-Tubes (CNT)
. • Carbon nanotubes are sheets of graphite rolled up to make a tube i.e. carbon macromolecules
in cylindrical form.

• Carbon Nanotubes have many structures, differing in length, thickness, and in the type of
helicity and number of layers.

• CNTs typically have diameters ranging from <1 nm up to 50 nm.

• There are two types of carbon nanotubes: (i) single wall carbon nanotubes and (ii) multi wall
carbon nanotubes.

• Depending on how the graphite sheet is rolled, CNT’s can be divided into three categories:
(i) Zig-zag (ii) Armchair (iii) Chiral
 Single-wall Carbon Nano-Tubes (CNT)
. • Single-wall nanotubes (SWNT) are tubes of graphite that are normally capped at the ends. They
have a single cylindrical wall.

• The structure of a SWNT can be visualized as a layer of graphite, a single atom thick, called
graphene, which is rolled into a seamless cylinder.

• Most SWNT typically have a diameter of close to 1 nm.

 Multi-wall Carbon Nano-Tubes (CNT)
• There are two structural models of multi wall nanotubes.
. • In the Russian Doll model, a carbon nanotube contains another nanotube inside it (the inner
nanotube has a smaller diameter than the outer nanotube).
• In the Parchment model, a single graphene sheet is rolled around itself multiple times, resembling a
rolled up scroll of paper.
• Multi wall carbon nanotubes have similar properties to single wall nanotubes, yet the outer walls on
multi wall nanotubes can protect the inner carbon nanotubes from chemical interactions with outside
materials. Multi wall nanotubes also have a higher tensile strength than single wall nanotubes.
 Ways to roll a graphite sheet
.

•
 Properties of CNT
.
• CNT’s are very light and flexible, thermally stable and durable and possess extraordinary
tensile strength.

• Depending on the way the graphite structure spirals around the tube, CNT’s can be insulating,
semiconducting or conducting.

• CNT’s are hydrophobic and can easily bind to proteins. Thus serve as chemical and biological
sensors.
 Applications of CNT
.
• Carbon nanotubes are utilised in energy storage, device modelling, automotive parts, boat
hulls, sporting goods, water filters, thin-film electronics, coatings, actuators, and
electromagnetic shields.

• CNT are used windmill blades because they light weight. This can increase efficiency and
produce electricity at faster rate.

• It is used in filtration process to separate particles of size greater than nanotube diameter.

• It is used in spacecraft and aeroplanes to reduce weight and stress on various components
 Scanning Electron Microscopy (SEM)
• SEM involves scanning and producing materials surface images from a convergent beam of
. electrons which interact with the sample material’s atoms.

• The interaction generates various signals, such as secondary electrons, backscattered electrons,
and X-rays. These signals are then detected to create an image of the sample's surface.
 Application of SEM
• It is used in a variety of fields including Industrial uses, nanoscience studies, Biomedical studies,
. Microbiology.

• Used for spot chemical analysis in energy-Dispersive X-ray Spectroscopy.

• Used in the analysis of cosmetic components which are very tiny in size.

• Used to study the filament structures of microorganisms.

• Used to study the topography of elements used in industries.

 Transmission Electron Microscopy (TEM)
• TEM is a technique that transmits a beam of electrons through a thin sample and produces his
. resolution images of its internal structure.

• The electrons pass through and interact with the atoms of the sample. The electrons that pass
through the sample are then detected and used to create an image of the sample's internal
structure.
 Application of TEM
TEM is used in a wide variety of fields From Biology, Microbiology, Nanotechnology, forensic
. studies, etc. Some of these applications include:

• To visualise and study cell structures of bacteria, viruses, and fungi

• To view bacteria flagella and plasmids

• To view the shapes and sizes of microbial cell organelles

• To study and differentiate between plant and animal cells.

• Its also used in nanotechnology to study nanoparticles such as ZnO nanoparticles

• It is used to detect and identify fractures, damaged microparticles which further enable repair
mechanisms of the particles.