• Not its own industrial sector• Enabling • Convergent • Disruptive

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Vertical industrial sectors

Nanotechnology

Societal implications

Industrial sectors depend on materials and devices made of atoms and molecules, so all can be improved by NS and NT

Time scales

• Protein unfolding:• CPU clock speed:

• Surfactant dynamics:• Molecular collisions:

• Atomic vibrations:

Smaller size faster response

50-100s

10-9 s

10-10 s

10-12 s

10-14 s

Historical Perspectives of the Atom

• Concept of atom 2600 years old. Hindu philosopher: atoms are infinitesimal, indivisible parts of matter

• Estimation of atom size 2200 years ago: 10-10 (0.1 nm)

• Leucippus and Democritus (4th and 5th century): concept of atomism: matter is comprised of “imperceptible, individual particles that differ only in shape and position”

• Modern concept of atom (1660’s): Boyle’s study of gases – matter is “composed of discrete particles, separated by a void”

• Dalton (1805): elements are made of atoms, which can not be divided into smaller particles or destroyed in chemical reactions

– 1 Da: one atomic mass unitDemocritus

Pre-18th Century – Colored Glass

• Roman period (30 BC - 640 AD)– Lycurgus Cup (4th century AD) – gold and silver

nanoparticles responsible for change in color

• Medieval period (500 – 1450 AD)– Stained glass – gold and silver nanoparticles trapped in

glass matrix

• Renaissance Period (1450 – 1600 AD)– Deruta Deramicists – Au, Ag, Cu nanoparticles to produced

colored metallic glazes on pottery

19th Century - Photography

• Humphry Davy (ca. 1800): used light sensitive

compound AgCl for stenciling letters – AgCl

decomposed into Ag NPs when exposed to

light

• Joseph Niepce (1827): first successful

photograph

• Loius Daguerre (1839): first commercially

viable print, daguerreotype

• Tabot (1840): Developed method for coating

paper with AgCl to create first negative

photographic image

• Michael Faraday (1857): First preparation of

gold colloids. He determined that colorful

appearance of colloidal solution due to “gold

reduced to exceedingly fine particles…”

http://www.forensicgenealogy.info/History_of_Photography.html

An early Daguerreotype print

Catalysis

• Early catalysis (ca. 3000 B.C.): Soap as the product of a catalytic process

• Kirschof (late 17th century): first demonstration of controlled catalytic process –acid hydrolysis of starch to produce glucose

• Davy (ca. 1800 ): first demonstration of heterogeneous catalytic reaction – heating of Pt wire in air to produce water

• Sabatier (ca. 1900): discovered process of catalytic hydrogenation – catalysts are composed of “finely divided particles”

Zeolite catalysts (1960): Plank and Rosinski use zeolite to convert petroleum to gasoline more efficiently

http://www.physorg.com

SEM image of molybdenum disulfide produced by ultrasonic spray pyrolysis

20th Century – pre-1950

• Mie Theory (1908): Theory of light scattering that related optical properties of particles to their size.

• Electron microscope (1931): Knott and Ruska - enabled visual observation of objects smaller than wavelength of visible light

• Transistor (1947): Bardeen, Shockley and Brattain – beginning of microelectronics

The transistor developed at Bell Labs in 1947

ww

w.porticus.org

20th Century – 1950’s

• Erwin Mueller (1951) improves electron microscope and becomes the first man to “see” an atom.

• Discovery of DNA (1953): Watson, Crick, Wilkins, and Franklin

• Tunneling Phenomena (1958): Leo Esaki discovered that electrons could “tunnel” through a potential barrier

• “There’s Plenty of Room at the Bottom” (1959): Feynman lecture that posed the problem of manipulating and controlling things on a small scale

http://abyss.uoregon.edu

20th Century – 1960’s

• Ferrofluids (1960): NASA researchers discover nanosized magnetic iron particles in solution could be controlled with magnet

– Hard drives– Sensors– Drug delivery– Hazardous waste clean up

ww

w.cm

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Illustration of Moore’s Law

Nanoscale ferromagnetic particles in synthetic oil controlled by magnetic field

http://www.slipperybrick.com

• Moore’s Law (1965): Gordon Moore noted that number of transistors per IC had doubled every two years

20th Century – 1970’s

• John People’s Gaussian software (1970): Pioneered the use of computers to predict behavior of atoms and molecules

• First use of term “Nanotechnology” (1974): Norio Taniguchi in reference to “production of technology to get extra high accuracy and ultra fine dimensions . . . on the order of 1 nanometer.”

• Surface Enhanced Raman Spectroscopy (1977):Light scattering technique used for nanoscale study of chemical reactions of molecules in electrochemistry, catalysis, materials synthesis, and biochemistry

http://www.eiclabs.com

SERS: To enhance emitted light from a molecule it can be attached to a metallic surface.

20th Century – 1980’s

• Self-assembled monolayers (SAMS)

– Jacob Sagiv (1980) – octadecyltrichlorosilane assembly on glass

– David Allara (1983) – monolayer assembly of thiol groups on gold

• Scanning tunneling microscope (1981): Binning and Rohrer – allowed observation and control of nanoscale particles, atoms, and molecules

http://ww

w.ifm

.liu.se/

Monolayer assembly on gold surface in thiol solution

STM image of Si(111) surface

http://www.omicron.de

20th Century – 1980’s

• The “Buckyball” (1985): Smalley, Curl,

and Heath – Discovered C60

nanoparticle

• Atomic Force Microscope (1986):

Binning and Gerber – 3-D images of

surface topography at high

magnification

http://www.udel.edu

C-60 molecule

AFM image of biopolymer surface

20th Century – 1980’s

• Single-electron tunneling transistor (1987):

Fulton and Dolan build first nanodevice to

demonstrate controlled movement of individual

electrons

• Quantum Dots (1988): Brus et. al., nano-sized

crystal semiconductor materials that

demonstrate quantum confinement effect

CdSe nanocrystals by Rosenthal group

http://www.ptb.de

A SET by PTB group in Germany

20th Century – 1990’s

• Manipulation of atoms (1990): Eigler and Schweizer used STM to arrange individual Xe atoms on surface

• Discovery of carbon nanotubes (1991): Sumio Iilima at NEC discovered multiwalled CNTs. Two years later signle-wall CNTs were fabricated at IBM

Standing-wave patterns in the local density of states of Fe adatoms on Cu(111) surface.

http://www.almaden.ibm.com/vis/stm/stm.html

http://www.almaden.ibm.com/st/past_projects/nanotubes/

SWCNT

20th Century – 1990’s

• Inorganic materials assembled from DNA and gold colloids (1996): Mirkin and Letsinger - Bio-inorganic architecture at the nanoscale

• Development of Dip-Pen Nanolithography (1999): Mirkin uses AFM tip to write with chemicals at the nanoscale

www.llnl.gov

Dip-Pen Lithography patterns