What is Nanotechnology

A basic definition:
Nanotechnology is the engineering of functional systems at the molecular scale. This covers both current work and concepts that are more advanced. In its original sense, 'nanotechnology' refers to the projected ability to construct items from the bottom up, using techniques and tools being developed today to make complete, high performance products.

Isotopes
isotopes = same number of protons, different number of neutrons Similar chemical properties, quite different nuclear properties!

Energy and Bond Formation

Comparison of Bonding

Covalent Bond
Shared electrons One electron from an orbital in atom A One electron from an orbital in atom B They become spin paired

Metallic Bonding

Arises from a sea of donated valence electrons (1, 2, or 3 from each atom).

Adapted from Fig. 2.11, Callister 6e.

Primary bond for metals and their alloys high electrical conductivity. Why?

 Bonds between atoms without electron transfer or sharing Low bonding energies Hydrogen Bonds
Water molecules are polar

Secondary Bonds

Van der Waals Bonds

Attraction of opposite charges
Electron density fluctuates around an atom Instantaneous dipole-induced dipole interaction

Hydrogen Bonds in H2O -

O H + H+

Hydrogen Bonds in H2O -

O
-

H +
H+

H+

O H +

Graphite Van der Waals Bonds

Graphite

Graphite

Graphite
Soft and slippery Many strong covalent bonds holding the structure together but only in 2 dimensions. The layers are free to slide easily over one another. Graphite powder is used as a lubricant.

Brittle

All of the bonds are directional within a layer and stress across a layer will tend to break them. Graphite rods used for electrolysis easily break when dropped. Only three of the valence (outer shell) electrons are used in sigma bonding. The other electron is in a 'p' orbital which can overlap laterally with neighbouring 'p' orbitals making giant molecular pi orbitals that extend over the whole of each layer. Electrons are free to move within these delocalised pi orbitals.

Electrical conductor

Insoluble in water.

There are only very weak Van der Waal's attractions between the carbon atoms and the water molecules whereas the carbon atoms are bonded very tightly to one another. Many strong covalent bonds holding the layers together - it requires massive amounts of energy to pull it apart

Very high melting point

Diamond

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Diamond
Hard Many strong covalent bonds holding the structure together.

Brittle

Insulator

All of the bonds are directional and stress will tend to break the structure (In a malleable substance, such as for example a metal, the bonding is non-directional and can still act if the particles are displaced with respect to one another). All of the valence (outer shell) electrons are used in bonding. The bonds are sigma and the electrons are located between the two carbon nuclei being bonded together. None of the electrons are free to move There are only very weak Van der Waal's attractions between the carbon atoms and the water molecules whereas the carbon atoms are bodned very tightly to one another. Many strong covalent bonds holding the structure together - it requires massive amounts of energy to pull it apart

Insoluble in water.

Very high melting point

Diamond

Nanocarbon
Properties & Applications
Electrical Mechanical Thermal Storage

Fullerenes

Discovered in 1985
Nobel prize Chemistry 1996 Curl, Kroto, and Smalley

Fullerenes

Epcot center, Paris

Architect: R. Buckminster Fuller

Nanoclusters and Nanostructured Materials

Nanoclusters and Nanostructured Materials

Nanoclusters constitute an intermediate state of matter between molecules and solids Nanocluster sizes range from sub-nanometer to about 10 nanometres in diameter and are of technological interest in numerous areas of applied science (e.g. materials science, catalysis, (opto)electronics). The difference between: (i) Nanoclusters consisting of up to a couple of hundred atoms, and (ii) larger aggregates containing 103 or more atoms which are more often called nanoparticles.

 Nanoclusters, have properties and structures which are very sensitive to their composition and size (i.e. every atom counts) which can lead to new and interesting properties not realised in the corresponding bulk material. Nanostructures and materials formed by their assembly through use of a variety of theoretical approaches (e.g. Global optimisation, Molecular dynamics) using both classical and electronic structure methods.

Van der Waals Nano-clusters

These are having binding energy / strength less than 0.3 ev / atom. They possess following properties 1. Balance between induced dipole force & quantum closed shell interaction. 2. Long range attraction results in to induced dipole force. 3. Short range repulsion results into quantum closed shell electronic interactions.

Ionic Nano-cluster
Ionic nano-clusters passes bond energy per strength varying from 2.2 to 4.3ev/atom. They are formed by electrostatic force.

Metalic Nano-cluster
Metalic nano-clusters have completed bonding that varies from metal to metal. Due to this variation , the bond energy/strength varies from 0.7 ev to 3.3 ev per atom.

Carbon Nanotubes

Introduction Applications Growth Techniques Growth Mechanism

 A Carbon Nanotube is a tube-shaped material, made of carbon, having a diameter measuring on the nanometer scale. A nanometer is one-billionth of a meter, or about one ten-thousandth of the thickness of a human hair. Carbon Nanotubes have many structures, differing in length, thickness, and in the type of helicity and number of layers. Although they are formed from essentially the same graphite sheet, their electrical characteristics differ depending on these variations, acting either as metals or as semiconductors. As a group, Carbon Nanotubes typically have diameters ranging from <1 nm up to 50 nm. Their lengths are typically several microns, but recent advancements have made the nanotubes much longer, and measured in centimeters.

 Carbon Nanotubes can be categorized by their structures: Single-wall Nanotubes (SWNT) Multi-wall Nanotubes (MWNT) Double-wall Nanotubes (DWNT)

What is a Carbon Nanotube?

CNT is a tubular form of carbon with diameter as small as 1nm. Length: few nm to microns.

CNT is configurationally equivalent to a two dimensional graphene sheet rolled into a tube.
A CNT is characterized by its Chiral Vector: Ch = n 1 + m 2, Chiral Angle with respect to the zigzag axis.

Armchair (n,m) = (5,5) = 30

Zig Zag (n,m) = (9,0) = 0

Chiral (n,m) = (10,5) 0 < < 30

Why do Carbon Nanotubes form?

Carbon Graphite (Ambient conditions) sp2 hybridization: planar Diamond (High temperature and pressure) sp3 hybridization: cubic Nanotube/Fullerene (certain growth conditions) sp2 + sp3 character: cylindrical Finite size of graphene layer has dangling bonds. These dangling bonds correspond to high energy states. Eliminates dangling bonds Nanotube formation + Total Energy Increases Strain Energy decreases

CNT Properties

CNT Properties (cont.)

CNT: Implications for electronics

Carrier transport is 1-D. All chemical bonds are satisfied CNT Electronics not bound to use SiO2 as an insulator. High mechanical and thermal stability and resistance to electromigration Current densities upto 109 A/cm2 can be sustained. Diameter controlled by chemistry, not fabrication. Both active devices and interconnects can be made from semiconducting and metallic nanotubes.

MWNT: The possibilities

MWNT: Lip-Lip Interaction Model

High Coordinated C atoms

Low Coordinated C atoms

H-atoms

SWNT Growth Mechanism

Is uncatalyzed growth possible?
Simulations & Observations No! Spontaneous closure at experimental temperatures of 2000K to 3000K. Closure reduces reactivity.

Catalytic SWNT Growth Mechanism

Transition metal surface decorated fullerene nucleates SWNT growth around periphery.

Catalyst atom chemisorbed onto the open edge. Catalyst keeps the tube open by scooting around the open edge, ensuring and pentagons and heptagons do not form.

Applications
Electrical
1. 2. 3. 1. 2. 1. 2. 3. Field emission in vacuum electronics Building block for next generation of VLSI Nano lithography Lithium batteries Hydrogen storage Bio-sensors Functional AFM tips DNA sequencing

Energy storage Biological

Biological applications: Bio-sensing

Many spherical nano-particles have been fabricated for biological applications. Nanotubes offer some advantages relative to nanoparticles by the following aspects:
1. 2. 3. Larger inner volumes can be filled with chemical or biological species. Open mouths of nanotubes make the inner surface accessible. Distinct inner and outer surface can be modified separately.

Biological applications: AFM tips

Carbon nanotubes as AFM probe tips:
1. 2. 3. Small diameter maximum resolution Excellent chemical and mechanical robustness High aspect ratio

Resolution of ~ 12nm is achieved

Biological applications: Functional AFM tips

Molecular-recognition AFM probe tips:
Certain bimolecular is attached to the CNT tip This tip is used to study the chemical forces between molecules Chemical force microscopy

Biological applications: DNA sequencing

Nanotube fits into the major grove of the DNA strand Apply bias voltage across CNT, different DNA base-pairs give rise to different current signals With multiple CNT, it is possible to do parallel fast DNA sequencing

Top view and side view of the assembled CNT-DNA system

Challenges and future

Future applications:
1. 2. 3. Already in product: CNT tipped AFM Big hit: CNT field effect transistors based nano electronics. Futuristic: CNT based OLED, artificial muscles

Challenges
1. 2. 3. Manufacture: Important parameters are hard to control. Large quantity fabrication process still missing. Manipulation of nanotubes.

Conclusion
Their phenomenal mechanical properties, and unique electronic properties make them both interesting as well as potentially useful in future technologies. Significant improvement over current state of electronics can be achieved if controllable growth is achieved. Growth conditions play a significant role in deciding the electronic and mechanical properties of CNTs.