History of Nanomaterials

Ref. Review on Natural, Incidental, Bioinspired, and Engineered Nanomaterials:

History, Definitions, Classifications, Synthesis, Properties, Market, Toxicities, Risks,
and Regulations; Nanomaterials 12, 177 (2022) 1
 Some Examples of Ancient Objects That Incorporated
Nanomaterials
• Nanomaterials and nanotechnology are not new AFM
ideas.
• Nanostructured materials were unknowingly used by
the ancient people in various applications and
structures for the last thousands of years.
• Evidences were found only after the inventions of
advanced techniques like TEM, SEM, STM, AFM,
Nanoindentation, etc.

SEM
TEM

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The famous 4th century Roman 'Lycurgus Cup' is known to contain
nanoparticles of gold, copper and silver. As a result, the cup shows
interesting optical property with two distinct colours visible
depending on the direction of light illumination.

Ref. The History of Nanoscience and Nanotechnology: From Chemical–Physical

Applications to Nanomedicine; Molecules 25, 112 (2020) 3
Hair sample from ancient Egyptian burial sites showed
the presence of PbS2 nanoparticles of few nanometer size.
It was required for efficient hair dying. Romans too.
~ 2600 BC

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Ancient Chinese luncheon porcelain plate 'Famille
Rose' is found to contain gold nanoparticles of
different size that provide the plate a decorative
glaze.
~ 800 AC

Stained ceramics with Au or Ag

nanoparticles

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The ruby-red glass windows used in
medieval time (5th - 15th centuries)
is found to contain gold nanoparticles

Stained glass with Au or Ag

nanoparticles

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(C) Nanoparticles in medieval church windows.
(D) Transmission electron microscopy (TEM) images of the Au
and Ag NPs used in coloured window glasses in medieval
churches.

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A special steel 'Wootz' (Seric steel) that is
believed to be made in India and used to make
very strong and sharp swords is found to contain
carbon nanotubes.

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Ancient warrior with a sword: The
swords may contain various forms of
nanomaterials

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 Egyptians used ink containing
nanoparticles of black pigment.
~ 2600 BC

Ancient Paintings in Chauvet-Pont-

d’Arc and Lascaux caves containing
nanostructures (~40000 BC)

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Nanomaterials in Nature
Insects and lizards are able to stick to walls
because of the nanostructures on their feet.

Spiders' webs are made of superstrong

nanofibres.

Butterflies' wings contain shiny reflective

nanocrystals.

Chloroplasts in plant cells are nanofactories

that harness the Sun's energy to make glucose.

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Animals and insects with widely varying body weight, such as flies,
spiders, and geckos, can adhere to and move along vertical walls
and even ceilings. Terminal elements (circles) in animals with hairy
attachment pads. Note that adhesion structures are finer in animals
with heavier body mass.

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Schematic description of softwood structure from the cellular to the nano scale.
Secondary cell walls (S1, S2, and S3) are nanofiber-reinforced composites of
cellulose fibrils embedded in an organized matrix of amorphous cellulose,
hemicelluloses, and lignin. Cellulose is organized in highly ordered elementary fibrils
(~3 nm in diameter) that are grouped into bundles to form microfibrils with amorphous
polysaccharides 13
Images at different magnifications of lotus leaves (Nelumbo nucifera) with
self-cleaning properties 14
15
• Examples of colourful feathers in birds.
• (a) Female silver-breasted broadbill (Serilophus lunatus,
Eurylaimidae).
• (b) Male eastern bluebird (S. sialis, Turdidae).
• (c) Male plum-throated cotinga (Cotinga maynana, Cotingidae).
• (d) Scanning electron microscopy photograph of the basic
nanostructure with a thin (≤1 μm) disordered layer of spongy β-
keratin bars, at the periphery of medullary barb cells from the
pale blue-grey primary covert feathers of S. lunatus,
• (e) Transmission electron microscopy photograph of the channel-
type nanostructure made of β-keratin and air in the barb cells
from the royal blue contour feathers of S. sialis.
• (f) Transmission electron microscopy photograph of the sphere-
type nanostructure made of β-keratin and air in barb cells of the
dark turquoise blue contour feathers of C. maynana.
• Scale bars: (d) 250 nm; (e,f) 500 nm.
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Insects and electron microscopy images (TEM and SEM) of their wings with their
respective water contact angle of water droplets on the wing surface. (A) Isoptera
schedorhinotermes sp.; (B) Hymenoptera vespa sp.; (C) Hemiptera
meimuna microdon; (D) Orthoptera Acrida cinerea; (E) Odonata hemicordulia tau,
and (F) Lepidoptera Papilio Xuthus 17
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• Bioinspired nanomaterials that respond to
stimuli
• (a) A chameleon in the relaxed (green colour, left) and
excited (yellow colour, right) state. The transmission
electron microscope images on the right of each panel
show the periodic changes in regular arrays of
guanine nanocrystals.
• (b) The colour change of an artificial film upon
stretching and compression

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 The idea of Nanotechnology

American theoretical Physicist (1918 – 1988)

Nobel Prize in Physics in 1965

29th December, Caltech

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$1000 Challenges
• In December 1959, Feynman
offered two challenges relating to
nanotechnology at the annual
meeting of the American Physical
Society, held that year at Caltech,
offering a $1000 prize to the first
person to solve each of them.

• The first one required someone to build a working electric motor that
would fit inside a cube 1/64 inches (0.40 mm, much smaller than a pin
head) on each side.
• William Howard McLellan (American electrical engineer), at that time
living in California, achieved this feat by November 1960 and won the
prize. His 250-microgram 2000-rpm motor consisted of 13 separate
parts.
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 The Second of $1000 Challenges
• The second challenge was for anyone who could find a way to
inscribe a book page on a surface area 25,000 times smaller than its
standard print.
• The prize for the second challenge was claimed only much later, by
Tom Newman in 1985.
• Tom Newman was a graduate student at Stanford University in
1985.
• Newman claimed the prize when he wrote the first page of Charles
Dickens' A Tale of Two Cities, at the required scale, on the head of a
pin with a beam of electrons.
• The main problem he had before he could claim the prize was
finding the text after he had written it; the head of the pin was a
huge empty space compared with the text inscribed on it.
• Scientists have since made structures smaller and smaller.
• This type of work is now called Nanotechnology, a term first used in
1974 by Norio Taniguchi, a materials scientist in Japan. 23
 Scanning Tunneling Microscopy (STM): Invention

• Scanning Tunneling Microscope (STM) is the first in the probe microscopes

family:
• Invented in 1981 by the Swiss scientists
(IBM Zurich) Gerber Binnig (right) and
Heinrich Rohrer (left)
• Awarded Nobel Prize in physics in 1986
• Resolution < 0.1 Å, Magnification > 100,000,000x
• Applicable to conducting and semiconducting samples

2.69 nm

Atomic resolution of Si surface (1981)

At present clarity of Si(111) 7x7

reconstructed surface
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Inventions:
TEM 1931 STM 1981 STM 1981

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 STM allowed scientists to see the nanoworld
• As scientists have steadily made things smaller, they have new
pieces of equipment to help them.
• Using an STM, it is possible to see individual atoms and even
move them around.
• In 1989, an STM was used to move 35 Xenon atoms onto a tiny
piece of nickel. The spelled the name of the company that the
scientists worked for.

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Evolution Timeline of Nanoscience and Nanotechnology (p.1)
Year Event
4th
Lycurgus Cup (Colored glass).
Century
500–1450 Cathedrals (Stained glasses windows).
1450–1600 Deruta Pottery (Iridescent/metallic clusters).
1857 Michael Faraday (Synthesis of colloidal ruby gold nanoparticles).
1908 Gustav Mie (Light scattering nanoparticles).
1928 Edward Synge (Near-field optical microscope).
1931 Max Knoll and Ernst Ruska (invention of transmission electron microscope (TEM)).
1936 Erwin Müller (Invention of field electron microscope).
William Shockley, Walter Brattain and John Bardeen (Discovery of the semiconductor
1947
transistor).
1951 Erwin Müller (Invention of field-ion microscope, first to see atoms on the surface).
1953 James Watson and Francis Crick (Discovery of DNA).
1956 Arthur Von Hippel (Molecular Engineering).
1958 Leo Esaki (Electron tunneling).
1959 Richard Feynman (There’s Plenty of Room at the Bottom).
1960 Charles Plank and Edward Rosinski (Zeolites and catalysis).
1963 Stephen Papell (Invention of Ferrofluids). 27
Evolution Timeline of Nanoscience and Nanotechnology (p.2)
1965 Gordon E. Moore (Moore’s Law).
1970 Eiji Osawa (Predicted the existence of C60 in the form of icosahedron).
1974 Norio Taniguchi (First use of the term “Nanotechnology”).
1974 Mark A. Ratner and Arieh Aviram (Molecular electronics).
1977 Richard P. Van Duyne (Discovery of Surface Enhanced Raman Spectroscopy (SERS)).
1980 Jacop Sagiv (Discovery of Self-Assembly Monolayers (SAMs)).
1981 Gerd Binnig and Heinrich Rohrer (Invention of Scanning Tunneling Microscope (STM)).
1981 Alexey Ekimov (Discovery of nanocrystalline Quantum Dots in a glass matrix).
1981 Eric Drexler (Molecular Engineering).
1982 Nadrian Seeman (Development of the concept of DNA Nanotechnology).
1983 Louis Brus (Discovery of colloidal Quantum Dots).
1985 Richard Smalley, Robert Curl and Harold Kroto (Discovery of Buckminsterfullerenes C60).
Gerd Binnig, Christoph Gerber and Calvin F. Quate (Invention of Atomic Force Microscope
1986
(AFM).
1987 Dimitri Averin and Konstantin Likharev (Single-Electron Tunneling (SET) transistor).
Donald Eigler and Erhard Schweizer (Arranged of individual Xenon atoms to form the
1990
letters IBM).
1991 Sumio Iijima (Discovery of Multi-wall Carbon nanotubes).
1992 Charles T. Kresge (Discovery of mesoporous silica MCM-41).
1993 Sumio Iijima and Donald Bethune (Discovery of Single-wall Carbon nanotubes).
1996 Chad Mirkin and Robert Letsinger (SAM of DNA+gold colloids). 28
Evolution Timeline of Nanoscience and Nanotechnology (p.3)

1997 Zyvex (First nanotechnology company founded).

1998 Cees Dekker (Creation of a Transistor using carbon nanotubes).
1999 Chad Mirkin (Development of Dip-pen Nanolithography (DPN)).
2000 Mark Hersam and Joseph Lyding (Feedback-Controlled Lithography (FCL).
2000 President Bill Clinton announces US National Nanotechnology Initiative (NNI).

Carlo Montemagno (Molecular nanomachines: molecular motor (rotor) with nanoscale

2001
silicon devices).

2002 Cees Dekker (Carbon nanotubes functionalized with DNA).

President George W. Bush signed into law the 21st Century Nanotechnology Research
2003
and Development Act.

2003 Naomi Halas (Development of gold nanoshells).

2004 Andre Geim and Konstantin Novoselov (Discovery of graphene).
2004 Xu et al. (Discovery of Fluorescent Carbon dots).
2005 James Tour (Nanocar with turning buckyball wheels).
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Evolution Timeline of Nanoscience and Nanotechnology (p.4)
2006 Paul Rothemund (DNA origami).
2007 J. Fraser Stoddart (artificial molecular machines: pH-triggered muscle-like).

Osamu Shimomura, Martin Chalfie and Roger Y. Tsien (Nobel Prize in Chemistry
2008
for the discovery and development of the green fluorescent protein, GFP).

2009 Nadrian Seeman (DNA structures fold into 3D rhombohedral crystals).

IBM (Development of an ultra-fast lithography to create 3D nanoscale textured
2010
surface).
Leonhard Grill (scanning tunneling microscope (STM) describes the electronic
2011
and mechanical properties of individual molecules and the polymer chains).

Jean-Pierre Sauvage, Sir J. Fraser Stoddart and Bernard L. Feringa (Nobel Prize
2016
in Chemistry for the design and synthesis of molecular machines).

2017 Nobel Prize in Physics 2017: Gravitational waves.

2018 World’s smallest tic-tac-toe game board made with DNA.
2018 Shrinking objects to the nanoscale. 30