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Nanotechnology,
Nanostructures and
Nanostructured materials

C.S. Casari - Introduction to Nanoscience 2017-18

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What is Nanoscience?
Nanoscience involves the study of materials, objects,
systems and phenomena at a very small scale, i.e.
about 1-100 nanometers

3.5 gold atoms

1 nm

C.S. Casari - Introduction to Nanoscience 2017-18

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What is nanotechnology?

Nanotechnology:

• Strict definition:
a technology able to manipulate atoms and
molecules and to exploit quantum confinement
effects

• Ethimolgical definition:
a technology working at a scale L < 1 m

Nanotechnology deals with materials for which:

• At least one size is at the nm scale (<100 nm)
• At least one size is small enough to show up quantum effects (typically <10 nm)

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Some nanotechnology milestones

1959 R.P. Feynman gives the talk “There’s plenty of room at the bottom”
1974 Norio Taniguchi introduces the term “nanotecnology”
1981 Invention of STM (Nobel prize in 1986)
1986 Invention of AFM
1986 Fullerene discovery by Smalley e Kroto (Nobel prize in 1996)
1989 D.M. Eigler at IBM manipulates 35 atoms to form the IBM logo
1990 First Journal on Nanotechnology
1991 Observation of carbon nanotubes by S. Iijima
1993 First nanotechnology laboratory at Rice University (USA)
2004 Groundbreaking studies of graphene (Nobel prize in 2010)
2013 Atomic movie by IBM
2016 Nobel Prize in Chemistry "for the design and synthesis of molecular machines"

C.S. Casari - Introduction to Nanoscience 2017-18

Low dimensional systems 5

2D 1D 0D

Quantum well Quantum wire Quantum dot

Quantum Quantum Quantum

Well Wire Dot
Confined 1 2 3
dimensions Nc
Nc+Nf = 3
Degrees of 2 1 0
freedom Nf

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Dimensionality

Quantum well Quantum wire Quantum dot

5 nm

Graphene Nanotubes Fullerenes

C.S. Casari - Introduction to Nanoscience 2017-18

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From single systems to assembled
materials

Single atoms

50 nm

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Nanostructured materials

Nanostructured Materials

Film
Nanoparticles, nanotubes

Dispersed Assembled
Multilayer

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Fabrication strategies

Top-down Bottom-up

1-100 nm

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Lithography
Shadow photolithography

• Deposition of a Resist
• Application of a mask
• Exposure to light
• Resist development
• Removal of resist


2b

s
d

To increase resolution  must be reduced:

• Deep UV <300 nm
• Extreme UV 10 nm
C.S. Casari - Introduction to Nanoscience 2017-18
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Lithography

Particella Ec Velocità 
To increase again we can change km/s
from photons to other particles. elettroni 1 eV 600 1.2 nm
We use de Broglie relationship:
10 eV 1800 0.4 nm

1 keV 18000 40 pm

Protoni H+ 1 eV 14 28 pm
h h
  10 eV 44 9 pm

p mv 1 keV 440 0.9 pm

1 MeV 14000 28 fm

Ioni Ar+ 1 eV 2 5 fm

1 keV 30 0.16 fm
2E
v 1 MeV 2000 0.005 fm
m
• Electron beam
• Focused ion beam FIB

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Soft Lithography
Replica molding

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Bottom-up approaches
Liquid phase processes:
• Sol-gel
• Electrodeposition
• Colloidal synthesis

Vapor phase processes:

• PVD (physical vapor deposition)
• CVD (chemical vapor deposition)

Other bottom-up techniques:

• Self-assembling
• Atomic Manipulation
• Cluster beans
• Dip pen nanolithography

C.S. Casari - Introduction to Nanoscience 2017-18

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2-D systems Electronic properties
z

y Lx, Ly >> d
d
Ly x
Lx

2
 ( z)  sin( d nz z ) Confined direction
d

 ( x)  Ae ik x x

Unconfined direction
 ( y )  Ae
ik y y

 ( x, y, z )   ( x) ( y) ( z )

C.S. Casari - Introduction to Nanoscience 2017-18

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2-D systems Electronic properties

 2 2 2
En z  n
2 z
2ma
 2 k x2
Ek x 
2m
 2 k y2
Ek y 
2m

C.S. Casari - Introduction to Nanoscience 2017-18

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2-D systems: examples

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2-D systems: realization of a
quantum well
A B

Ec

Ec

Ef Ef

Ev

Ev

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2-D systems: realization of a
quantum well

GaN
InGaN

InGaN

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1-D Systems Electronic properties
z
2
 ( x)  sin( d nx x)
y d Confined
direction
2
x
 ( z)  sin( d nz z )
L>>d d
d
 ( y )  Ae
ik y y
Unconfined direction
d

  2 2 2 2 
E  E ( k y )  En x  En z 
 2 k y2

2m  2md 2
nx  nz   
 E

E12 =E21
E11

ky

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Sistemi monodimensionali, mascroscopici lungo una direzione (z) e

confinati lungo 2 dimensioni (x,y): Nanotubo di carbonio
• Nanowire WOx

• Nanorod
• Nanotube

Pt su Ge(001)

Z >>100nm Z >>100nm Z >>100nm

X,Y= 1-10nm X,Y=10-100nm R=1-100nm

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1-D Systems: examples

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1-D Systems: carbon nanotubes

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0-D Systems Electronic properties

2
 ( x)  sin( d nx x)
d
2
 ( y)  sin( d n y y ) Confined direction
d
d 2
 ( z)  sin( d nz z )
d
E  ( x, y, z )   ( x) ( y ) ( z )
E222

 2 2 2
E221 =E122 = E212
E  En x  En y  En z 
2md 2
n x n 2
y  n 2
z 
E211 =E121 = E112

E111

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Size dependent electronic
properties

Au cluster

Au55

Ag clusters

F. Baletto Rev. Mod. Phys. (2005)

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0-D systems: examples

STM image of a dot of 27 atoms TEM image of a colloidal PbSe nanocrystal

of Pd on MoS2

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Technology:
more computing capabilities
Moore’s law:
‘The number of devices in a CPU
doubles every two years’

22 nm

?
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Technology:
store more and more data
Current CD and DVD media have storage scale in
micrometers

New nanomedia (made when gold self-assembles

into strips on silicon) has a storage scale in the
nanometer scale

That is 1,000 times more

storage along each dimension
(length, width)… or 1,000,000
times greater storage density
in total!

C.S. Casari - Introduction to Nanoscience 2017-18

Optical properties 28

C.S. Casari - Introduction to Nanoscience 2017-18

Optical properties 29

Ag evaporated n glass
0.5

0.4 6 nm

Absorbance
0.3
4 nm
0.2

0.1
2 nm
0.0
400 500 600 700 800
wavelength (nm)

1 nm Ag 2 nm Ag 3 nm Ag 4 nm Ag 6 nm Ag 8 nm Ag

C.S. Casari - Introduction to Nanoscience 2017-18