Carbon Nanostructures

Unique nature of carbon bond.

• Diverse nature of bond.
• Eg. Organic molecules of life, carbon nanotubes, etc.

Carbon molecules – Nature of carbon bond:

Electronic structure of carbon atom.
Carbon has 6 electrons: (1s2 2s2 2p2)
When bonded to atoms in molecules: 1s2 2s 2px 2py 2pz .

1s2 electrons do not participate in bonding.

1
2s – spherically symmetric orbital.
px, py, pz – very directed charge distribution oriented
perpendicular to each other.

2
Charge distribution associated with these orbitals mixes
(overlaps) with the charge distribution of each other atom being
bonded to carbon.

3
In carbon, energy separation between 2s and 2p levels is very
small.
This allows admixture of the 2s wavefunction with one or more
2pi wavefunctions.
The unnormalized wavefunction  in a valence state can be
designated by the expression
 = s + p,
where p indicates an admixture of pi orbitals.
With this sp3 hybridization, the directions of the p lobes and
angles between them change.

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Acetylene H – C  C – H Linear compound (180)
Ethylene H2C=CH2 Trigonal planar compound (120)
Methane CH4 Tetrahedral compound (10928)

Three types of hybridization are shown in Table.

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In general, most organic compounds have these bond angles:
• Diamond 10928 .
• Graphite & Benzene 120.
Diamond
• sp3 hybridization.
• Tetrahedrally bonded carbon atoms.
Graphite
• sp2 hybridization.
• Layered structure.
• Each layer is called graphite sheet.
• Hexagons of carbon atoms.
• It is a planar structure.
• Hexagonal sheets are bound by van der Waals forces.

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New carbon structures:
Until 1964, generally believed that bond angles other than 180,
120 and 10928 are not possible in hydrocarbons.
In 1964: Square carbon molecule C8H8 called cubane  90
bond angle.
In 1983: Dodecahedron shaped molecule C20H20 formed by
joining pentagons having C-C bond angles ranging from 108 to
110.

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Carbon clusters:
Small carbon clusters:
Carbon clusters can be made using the same apparatus
described in Fig.4.2.
Typical mass spectrum
obtained. There are
clusters for every N
upto 30.
C60  Explanation
and structure for C60
won Nobel prize.

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Clusters having linear or closed nonplanar monocyclic
geometries:
When N odd  linear structures with sp hybridization.
When N even  closed structures that differ from conventional
hybridization concept.

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Discovery of C60:
Light transmission through interstellar dust.
This dust is the small particles of matter that fill the regions of
outer space between stars and galaxies.
When light from distant star passes through the cosmos and
arrives on the Earth, the intensity is reduced. This is called
optical extinction.
5.6 eV or 220 nm (UV)
Initially, it was believed
that small particles of
graphite scatter the light.
(Absorption)

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Some research groups prepared graphite dust by carbon arc
evaporation in the atmosphere.
Spectroscopic methods such as IR and Raman spectroscopy
that measure vibration frequencies of molecules were used.
4 additional IR absorption bands that did not originate from
graphite were observed.
From theoretical modeling, these IR bands were identified to
come from C60 molecules.

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Structure of C60 :
C60 named after Buckminster Fuller.
Initially called buckminsterfullerene, later fullerene.
Has 12 pentagons, 20 hexagons.
Symmetrically arranged to form a molecular ball.
Soccer ball has the same geometric configuration as fullerene.

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Structure of C60 crystal:
The ball-like molecules bind with each other in solid state to
form a crystal lattice having fcc Fig.5.7.

In the lattice, each C60 molecule is

separated from its nearest
neighbour by 1 nm (the distance
beween their centres is 1 nm).
The molecules have van der Waals
bond.
C60 is soluble in benzene:
Single crystals of it can be grown
by slow evaporation from benzene
solutions.

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Alkali doped C60:
In the fcc fullerene structure, 26% of the volume of the unit cell
is empty.
So, alkali atoms can fit into these empty spaces.
K3C60 : Can be formed when C60 crystals and Potassium metal
are kept in evacuated tubes and heated to 400C.

The potassium atoms

diffuse into the empty
spaces.
Alkali atoms occupy,
two tetrahedral sites
and an octahedral site
per C60 molecule.

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C60 crystal is an insulator.
When doped with an alkali, it becomes electrically conducting.
In K3C60, K+ and C603–.
Since C60 has three extra electrons that are loosely bound, C60
crystal becomes electrically conducting.
Hence, C60 is said to be electron-doped.

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Superconductivity in C60 :
Zero resistivity.
Perfect diamagnetism,  = – 1.
C60 crystals with K doping: Transition temperature Tc = 18 K.

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Cs2RbC60: Tc = 33 K.
Graphite: Intercalated with K atoms.
• Crystalline graphite becomes superconducting at few tenths of
a Kelvin.
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Larger and Smaller Fullerenes:
C70, C76, C80, C84.
C20, C22.

Other Buckyballs:
Cage structures of Si.
• Pure Si cannot form closed structures.
• Si can form caged structure around a Tungsten atom in the
form of a hexagonal cage.
• Potential applications: Components in quantum computers,
chemical catalysts, new superconducting materials.

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N20 cluster should be stable – theoretical prediction.
• Dodecahedral structure.
• It will be a very powerful explosive, about 3 times more
powerful than the presently available most energetic material.

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Carbon nanotubes

Preparation:
Laser evaporation:
 Graphite is kept in a Quartz tube which is inserted in to a
furnace kept at 1200C
 Graphite target contains smalls amounts of Co and Ni that
act as catalytic nucleation sites for the formation of the
nanotubes.
 Pulsed laser beam evaporates carbon from graphite.
 Ar gas sweeps the carbon atoms to cold Cu collector.
 Condensation occurs to form nanotubes.
 Nanotubes: 10-20 nm diameter, 100 m length.

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Carbon arc method:
 Potential of 20-25V applied across carbon electrodes.
 Electrode diameter 5-20 m diameter, separated by 1mm, at
500 Torr pressure in He flow.
 Carbon atoms ejected from +ve electrode. Nanotubes form
on –ve electrode.
 To produce single-walled nanotubes, a small amount of Co,
Ni or Fe is incorporated as a catalyst in the central region of
the +ve electrode.
 This method produces single-walled nanotubes of diameters
1-5 nm with a length of 1 m.
 If no catalysts are used, the tubes are nested or multiwalled
types (MWNT).

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Chemical vapour deposition method

 Decompose a hydrocarbon gas such as methane (CH4) at

1100C.
 Carbon atoms are produced when the gas decomposes.
 The carbon atoms condense on a cooler substrate that may
contain various catalysts such as iron.
 This method produced tubes with open ends, which does not
occur when other methods are used.
 This procedure allows continuous fabrication and may be the
most favorable method for scaleup and production.

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 The mechanism of nanotube growth is not understood. Metal
catalyst such as Co or Ni is necessary for the growth of
SWNTs.
 One proposal referred to as “scooter mechanism” .
 It suggests that atoms of the metal catalyst attaches to the
dangling bonds at the open end of the tubes.
 These atoms scoot around the rim of the tube and attract
carbons atoms as they arrive.
 Generally, when nanotubes are synthesized, the result is a mix
of different kinds, some metallic and some semiconducting.

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A method to separate semiconducting nanotubes from the
metallic nanotubes:
The separation was accomplished by depositing bundles of
nanotubes of which some are metallic and some are
semiconducting, on a Si wafer.
Metal electrodes were then deposited over the bundle.
Using the silicon wafer as an electrode, a small bias voltage
was applied that prevents the semiconducting tubes from
conducting.
A high voltage is then applied across the metal electrodes,
thereby sending a high current through the metallic tubes but
not the nonconducting tubes.
This causes the metallic tubes to vapourize, leaving behind only
the semiconducting tubes.
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Structure of Carbon Nanotubes

 Nanotubes have different structures.

 These various structures have different properties.
 Different structures are explained by considering the way
graphite sheets are rolled into tubes.
 Nanotubes can be formed when a graphite sheet is rolled up
about the axis T.
 Ch vector is called circumferential vector.
 T vector is called translation vector.
 Ch vector is  to T.
 Three examples of nanotube structures constructed by rolling
the graphite sheet about the T vector having different
orientations in the graphite sheet.

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Armchair structure is obtained when T  C-C bonds.
Zigzag structure is formed when T  C-C bonds.
Chiral structure is obtained when T vector has different
orientations.
Looking down the tube of the chiral structure, one would see a
spiraling row of carbon atoms.
Generally nanotubes are closed at both ends.
The tubes are essentially cylinders with each end attached to
half of a large fullerene-like structure.
In SWNTs, metal particles are found at the ends of the tubes,
which is evidence for the catalytic role of the metal particles in
their formation.

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 (n,m)

Ch = na1 + ma2 (n, n)

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n=m 34
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Electrical Properties

 Carbon nanotubes have the most interesting property that they

are metallic or semiconducting, depending on the diameter and
chirality of the tube.
 Chirality refers to how the tubes are rolled w.r.t. the direction of
the T vector in the graphite plane.
 Synthesis generally results in a mixture of tubes two thirds of
which are semiconducting and one third metallic.
 The metallic tubes have the armchair structure.

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 Figure shows the variation of energy gap of semiconducting
chiral carbon nanotubes with the reciprocal of the diameter.

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 STM has been used to investigate the electronic structure of
carbon nanotubes.
 In this measurement, the position of the STM tip is fixed above
the nanotube and the voltage V between the tip and the sample
is swept while the tunneling current I is monitored.
 The measured conductance G = I/V is a direct measure of the
local electronic density of states.
 The DOS is a measure of how close together the energy levels
are to each other.
 The figure gives the STM data plotted as the differential
conductance, which is (dI/dV)/(I/V), versus the applied voltage
between the tip and carbon nanotube.
 The data show clearly the energy gap in materials at voltages
where very little current is observed.
 The voltage width of this region measures the gap, which for
the semiconducting material shown in the figure is 0.7eV.
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 At higher energies sharp peaks are observed in the density of
states, referred to as van Hove singularities. They are
characteristic of low dimensional conducting materials.
 The peaks occur at the bottom and top of a number of
subbands.
 If the electron wavelength is not a multiple of the circumference
of the tube, it will destructively interfere with itself, and therefore
only electron wavelengths that are integer multiples of the
circumference of the tubes are allowed.
 This severely limits the number of energy states available
for conduction around the cylinder.

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 The dominant remaining conduction path is along the axis
of the tubes, making carbon nanotubes function as one
dimensional quantum wires.
 The electronic states of the tubes do not form a single wide
electronic energy band, but instead split into one dimensional
subbands that are evident in the data.
 These states can be modeled by a potential well having a depth
equal to the length of the nanotube.

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 In the metallic state the electrical conductivity of the
nanotubes is very high.
 It is estimated that they can carry a billion amperes per
square cm.
 Cu wire fails at 1 million amperes per square cm because
resistive heating melts the wire.
 One reason for the high conductivity of the carbon tubes is that
they have very few defects to scatter electrons, and thus a
very low resistance.
 High currents do not heat the tubes in the same way that they
heat copper wires.
 Nanotubes also have a very high thermal conductivity,
almost a factor or 2 more than that of diamond. This means
that they are also very good conductors of heat.
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 Magnetoresistance is a phenomenon whereby the resistance
of a material is changed by the application of a dc magnetic
field.
 Carbon nanotubes display magnetoresistive effects at low
temperatures.
 Figure shows a plot of the magnetic field dependence of the
change in resistance R of nanotubes at 2.3 K and 0.35 K
compared to their resistance R in zero magnetic field.
 This is a negative magnetoresistance effect because the
resistance decreases with increasing dc magnetic field.

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When a dc magnetic field is applied to the nanotubes, the
conduction electrons acquire new energy levels associated with
their spiraling motion about the field.
It turns out that for nanotubes these levels, called Landau
levels, lie very close to the topmost filled energy levels (the
Fermi level).
Thus there are more available states for the electrons to
increase their energy and the material is more conducting.

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Vibrational properties

 Atoms in a molecule or nanoparticle continuously vibrate.

 The structure of CO2 is O=C=O.
 Each molecule has normal modes of vibration. These are
determined by the symmetry of the molecule.
 For example, CO2 molecule has 3 normal
modes.
 Symmetric stretch mode consists of an in-
phase elongation of the two C=O bonds.
 Asymmetric stretch consists of stretches of
the C=O bond length, where one bond
length increases while the other
decreases.
 Bending is the third mode.
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Fig. Vibrational modes of CO2.

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 Similarly carbon nanotubes also have normal modes of
vibration.
 Figure illustrates two of the normal modes of nanotubes.
 A1g mode involves an “in and out” oscillation of the diameter of
the tube.
 E2g mode involves squeezing down in one direction and
expanding in the perpendicular direction. That is, essentially
oscillating between a sphere and an ellipse.

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 The frequencies of these two modes are Raman-active and depend on the
radius of the tube.
 Figure is a plot of the frequency of the A1g mode as a function of the radius.
 The dependence of this frequency on the radius is now routinely used to
measure the radius of nanotubes.

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Mechanical properties

 CNTs are very strong.

 If a weight W is attached to the end of a thin wire nailed to the
roof of a room, the wire will stretch.
 Stress S on the wire is defined as the load or the weight per
unit cross sectional area A of the wire
W
S
A

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The strain e is defined as the amount of stretch L of the wire
per unit length L
L
e
L
where L is the length of the wire before the weight is attached.

Hooke's law states that the strain of the material is proportional

to the applied stress, within the elastic limit of that material.

Thus, we have S  Ee

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 LW
 The proportionality constant E 
A L
is Young’s modulus and it is a property of a given materials.
 It characterizes the elastic flexibility of a material.
 The larger the value of Young’s modulus, the less flexible the
material.
 Young’s modulus of steel is about 30,000 times that of rubber.
 CNTs have Young’s modulus ranging from 1.28 to 1.8TPa
(1 TPa  107 atm).
 Young’s modulus of steel is 0.21 TPa, i.e. CNT has 10 times
more.
 Thus, CNTs are very stiff and hard to bend.

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 The deflection D of a cylindrical hollow beam of length L with a
force F on the end and the inner and outer radii of ri and ro, has
been shown to be
FL3
D
3EI
where I is the areal moment of inertia given by  (ro4  ri 4 ) / 4 .

 Since the wall thickness of carbon nanotubes is about 0.34 nm,

4 4
ro  ri is very small, somewhat compensating for the larger
value of E.

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 When carbon nanotubes are bent, they are very resilent.
 They buckle like straws but do not break. Can be straightened
back without any damage.
 Most materials fracture on bending because of the presence of
defects such as dislocations or grain boundaries.
 CNTs have very few defects in their walls. So, they do not
break.
 Another reason why they do not fracture is that as they are bent
severely, the almost hexagonal carbon rings in the walls
change in structure but do not break.
 This a unique result of the fact that the carbon-carbon bonds
are sp2 hybrids and these sp2 bonds can rehybridize as they
are bent.
 The degree of change and the amount of s-p admixture
both depend on the degree of bending of the bonds. 56
 Strength is not the same as stiffness.
 Young’s modulus is a measure of how stiff or flexible a material
is.
 Tensile strength is a measure of the amount of stress needed
to pull a material apart.
 The tensile strength of CNTs is about 45 GPa.
 High strength steel alloys break at about 2 GPa.
 Thus CNTS are about 20 times stronger than steel.
 Nested nanotubes also have improved mechanical properties,
but they are not as good as their single walled counterparts.
 For example, multiwalled nanotubes of 200 nm diameter have a
tensile strength of 7 GPa and modulus of 0.6 TPa.

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