Nanotechnology
Lecture 2 Fullerene
Definition
1nm=10-9m
Human Red Blood Cells=8000nm
There is Plenty of Room at the Bottom
（1918~ 1988）
R.P.Feynman
The Origin and Development of
Nanotechnology
• Feynman——《There is Plenty of Room at
the Bottom 》
• The Invention of the Scanning Tunneling
Microscope(STM)
• The Nanotechnology Developed Rapidly
in1990s, and the New Words Came Fast
• One of the 9 Major Key Technologies in the
Future Global Technology Development
Why?--a materials perspective
“quantum size effect”： dominant when the
nanometer size range is reached. a number of
physical (mechanical, electrical, optical, etc.)
properties change when compared to
macroscopic systems.
For example:
opaque
substances
become
transparent
(copper); stable materials turn combustible
(aluminum); insoluble materials become soluble
(gold). A material such as gold, which is
chemically inert at normal scales, can serve as a
potent chemical catalyst at nanoscales.
Image of reconstruction on a clean
Gold(100) surface, as visualized using
scanning tunneling microscopy. The
positions of the individual atoms
composing the surface are visible
Why?--Simple to complex: a
molecular perspective
•Molecular
self-assembly:
automatically
arrange
themselves into some useful
conformation.
• through a bottom-up approach
to prepare small molecules to
almost any structure
The DNA structure at left (schematic shown) will
self-assemble into the structure visualized by atomic
force microscopy at right. Image from Strong
How?--Tools and techniques
•Tools: The atomic force microscope (AFM) and
the Scanning Tunneling Microscope (STM) are
two early versions of scanning probes that
launched nanotechnology
•They can be used to look at surfaces
and to move atoms around. By
designing different tips for these
microscopes, they can be used for
carving out structures on surfaces and
to help guide self-assembling
structures.
Typical AFM setup. A microfabricated cantilever with a sharp tip is deflected by
features on a sample surface, much like in a phonograph but on a much smaller
scale. A laser beam reflects off the backside of the cantilever into a set of
photodetectors, allowing the deflection to be measured and assembled into an
image of the surface
Bottom-up approaches
•These seek to arrange smaller components
into more complex assemblies
•Molecular self-assembly seeks to use
concepts of supremolecular chemistry, and
molecular recognition in particular, to cause
single-molecule components to automatically
arrange themselves into some useful
conformation.
Sarfus image of a DNA biochip
elaborated by bottom-up
approach.
Top-down approaches
•These seek to create smaller devices by
using larger ones to direct their assembly.
•Solid-state silicon methods for fabricating
microprocessors
•Solid-state techniques can be used to create
devices known as nanoelectromechanical
systems or NEMS, which are related to
microelectromechanical systems or MEMS.
This device transfers energy
from nano-thin layers of
quantum wells to nanocrystals
above them, causing the
nanocrystals to emit visible
light.[11]
The Self-Cleanliness on the Surface of
Lotus Flower
Gooses and Ducks Keep Dryness
under the Water
No Washing Nano Suit
Fullerene
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Introduction of Fullerene family (what is?)
Fullerene (discovery, naming)
Types of Fullerene and related structures
Properties
Synthesis (to fabricate)
Potential and current applications
What is Fullerene?
A Fullerene is any molecule composed entirely of
carbon, in the form of a hollow sphere, ellipsoid,
or
tube.
Spherical
fullerenes
are
also
called buckyballs, and cylindrical ones are
called carbon nanotubes or buckytubes.
C60 in solution
Buckminster fullerene C60 (left) and carbon
nanotubes (right) are two examples of structures
in the fullerene family.
Allotropes of carbon
Allotropes :
different structural modifications of an
element; the atoms of the element are
bonded together in a different manner.
Allotropes of carbon:
•Diamond (hardest natural mineral)
•Graphite(dry lubricant, graphene)
•Amorphous carbon (coal and soot)
•Fullerene family (C60, carbon nanotubes
etc)
Diamond and graphite are
two allotropes of carbon:
pure forms of the same
element that differ in
structure.
Fullerene-History
•The existence of C60 was predicted by Eiji Osawa of Toyohashi University of
Technology in a Japanese magazine in 1970
•With mass spectrometry, discrete peaks were observed corresponding to
molecules with the exact mass of sixty or seventy or more carbon atoms. In
1985, Harold Kroto etc ， discovered C60, and shortly thereafter came to
discover the fullerenes. Kroto, Curl, and Smalley were awarded the 1996
Nobel Prize in Chemistry for their roles in the discovery of this class of
compounds.
•Minute quantities of the fullerenes, in the form of C60, C70, C76, and C84
molecules, are produced in nature, hidden in soot and formed by lightning
discharges in the atmosphere.
Buckminsterfullerene C60
The Icosahedral Fullerene C540
Discovery of Carbon C60
• 1985, Robert F. Curl, … discovered a new
form of carbon，that 60 or 70 carbon
atoms could cluster together to form a
cage-like molecule.
• The molecular structure resembled the
pattern of a soccer ball or the geodesic
designs of Buckminster Fullerenes. Thus
the name buckyballs or fullerenes.
• Since then the discovery has led to new
research in polymers, semiconductors,
and other various areas.
• Nobel Prize to their finders in 1996
Existence in the nature
•In 1992, fullerenes were found in a family of
minerals known as Shungites in Karelia, Russia.
•In 2010, fullerenes (C60) have been discovered
in a cloud of cosmic dust surrounding a distant
star 6500 light years away. Using NASA's
Spitzer infrared telescope the scientists spotted
the molecules' unmistakable infrared signature.
Sir Harry Kroto, who shared the 1996 Nobel
Prize in Chemistry for the discovery of
buckyballs commented: "This most exciting
breakthrough provides convincing evidence that
the buckyball has, as I long suspected, existed
since time immemorial in the dark recesses of our
galaxy”
Naming--Fullerene
• The substance of the Fullerene was named after
the American inventor, architects and
philosophers Richard Buckminster Fuller (1895
till 1983). As an architect, R.B.Fuller designed
the constructions which exist of 5-corners and 6corners, for example, the American pavilion to
the Expo in '67 in Montréal(geodesic dome).
• Fullerenes are similar in structure to graphite,
which is composed of stacked graphene sheets of
linked hexagonal rings; but they may also contain
pentagonal (or sometimes heptagonal) rings.
Buckminster Fuller
Buckminster Fuller
Richard Buckminster Fuller, c. 1917.
Born
July 12, 1895
Milton, Massachusetts, United States
Died
July 1, 1983 (aged 87)
Los Angeles, United States
Occupation
Visionary, designer,architect,
author, inventor
Spouse
Anne Fuller
Children
2: Allegra Fuller Snyder and Alexandra
who died in childhood
Richard Buckminster Fuller, c. 1917
The Montreal Biosphère by Buckminster Fuller, 1967
After the IUPAC nomenclature the C60 has the
following name:
[29.29.0.0.2,14.03,12. 04,59.05,10.06,58.
07,55.08,53.09,21. 011,20.013,18.015,30.
016,28.017,25.019,24. 022,52. 023.50.026,49.027,47.
029,45.032,44.033,60. 034,57.035,43.036,56.
037,41.038,54.039,51. 040,48.042,46]hexaconta1,3,5(10),6,8,11,13(18),
14,16,19,21,23,25,27,29(45),30,32(44),33,35(43),
36,38(54),39(51),40(48),41,46,49,52,55,57,59-triacont
IUPAC--International Union of Pure and Applied Chemistry
FULLERENE MOLECULAR MODELS C56-C76
C56
(Td)
Model
C58 (C3v)
C56 (Td)
Rotating Animation
C60(C2v)
C76 (D2)
C60(C2v)
C72 (D6d)
Different structure buckyballs
C20
C26
C60
C70
Another fairly common fullerene is C70, but fullerenes with 72, 76,
84 and even up to 100 carbon atoms are commonly obtained. In
mathematical terms, the structure of a fullerene is a trivalent
convex polyhedron with pentagonal and hexagonal faces. In graph
theory, the term fullerene refers to any 3-regular, planar graph
with all faces of size 5 or 6 (including the external face). It follows
from Euler's polyhedron formula, V − E + F = 2, (where V, E, F are
the numbers of vertices, edges, and faces), that there are exactly
12 pentagons in a fullerene and V/2 − 10 hexagons.
Fullerene Family
Fig. 3.1: A schematic representation of the structures of graphite,
diamond and fullerenes. While the two-dimensional sheets formed by
hexagons are packed one over another in graphite, the diamond
structure is three-dimensional. Only two fullerenes are shown. The
smaller one is buckminsterfullerene, C60. structure. The double bonds
are localized exocyclic to the pentagons giving [5] radialene character
to the pentagons and cyclohexa-1,3,5-triene character to the
hexagons.
Synthesis(discover) of C60
Fig. 3.2:
The experimental set-up used to discover C60. The
graphite disk is evaporated with a Nd:YAG laser and the
evaporated carbon plasma is cooled by a stream of helium coming
from a pulsed valve. The clusters of carbon are produced in the
integration cup and are expanded into vacuum. The ions are
detected by time of flight mass spectrometry
synthesis and purification of fullerenes
Fig. 3.4:
Schematic illustration of the processed involved in the
synthesis and purification of fullerenes. Graphite rods are evaporated
in an arc, under He atmosphere. The soot collected is extracted with
toluene and subjected to chromatography.
Properties & Applications
•In April 2003, fullerenes were under study for
potential medicinal use: binding specific
antibiotics to the structure to target resistant
bacteria and even target certain cancer cells
•use of fullerenes as light-activated antimicrobial
agents
C60 in solution
Fullerenes are stable, but not totally unreactive.
Solubility
Fullerenes are sparingly soluble in many solvents
Solutions of pure buckminsterfullerene have a deep purple color.
Solutions of C70 are a reddish brown. The higher fullerenes C76 to C84
have a variety of colors
Properties & Applications
Fig. 3.6:
(Bottom) Mass spectrum of a laser evaporated C60 film showing
coalescence of fullerenes. Mass peaks are seen at (C60)n (Ref.64). (Top) Collision of
high energy ions on C60 results in the addition of C2s to C60. The mass spectrum here
shows the addition of a number of such species (Ref.65). Combined figure originally
published in, T. Pradeep, Current Science, 72 (1997) 124.
Properties & Applications
Hydrated Fullerene
Hydrated fullerene C60HyFn is a stable, highly
hydrophilic,
supra-molecular
complex
consisting of С60 fullerene molecule enclosed
into the first hydrated shell that contains 24
water molecules: C60@(H2O)24.
C60HyFn water solution with a
C60 concentration of 0.22 mg/mL
Superconductivity
that intercalation of alkali-metal atoms in solid C60 leads to metallic
behavior. In 1991, it was revealed that potassium-doped C60 becomes
superconducting at 18 K. This was the highest transition temperature for a
molecular superconductor. Since then, superconductivity has been
reported in fullerene doped with various other alkali metals
Properties & Applications
Fig. 3.8: Normalized DC electrical resistivity ρ（T）of a K3 C60 single
crystal. The Tc observed is 19.8K. ρ0 is the resistivity at T=280K.
Reprinted with permission from Xiang, et al. (Ref.95). Copyright (1992)
AAAS.
Summary and Reference
1 a interesting video: http://v.youku.com/v_show/id_XMjM4NDcwMzcy.html
2 Our course website:
http://cc.usst.edu.cn/Able.Acc2.Web/Template/View.aspx?courseType=0&co
urseId=458&topMenuId=49182&menuType=4&action=view&type=&name=
3 Quite useful website:( wikipedia website)
http://en.wikipedia.org/wiki/Fullerene
4 Reference books:
T.PRADEEP NANO –The essentials, understanding nanoscience and
nanotechnology.
Springer handbook of nanotechnology (Bhushan Editor)
NanoArt Gallary
“Ancient of Days” from classical art to quantum art
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