Introduction to

Nanophysics
Prof. J. Raynien Kwo

Department of Physics
National Tsing Hua University
Feb. 21, 2013
 What is the size for a “nano” ?

One (nm) equals to 1/1000000000 (10-9) meter

10-3 m , Macro
10-6 m , Micro
10-9 m , Meso

1
R. Feymann Already Knew about this !

“ There’s plenty of
room at the bottom ! ”
in 1959.

2
 Physicists noticed the “Nano ”
as early as …..
• 4th Century, Roman glassmaker: the color of glasses can be
changed by mixing in metal particles
• In 1883, Films containing silver halides for photography were
invented by George Eastman, founder of Koda.k
• 1908, Gustay Mie first provided the explanation of the size
dependence of color.
• Vision from Feynman in 1959: “There is plenty room at the
bottom”, and also recognized there are plenty of nature-given
nanostructures in biological systems.
• 1950-1960, small metal particles were investigated by physicists.
• 1957, Ralph Landauer realized the importance of quantum
mechanics plays in devices with small scales.
• Before 1997 => mesoscopic (or low dimensional) physics :
quantum dots, wells, wires…..are known already.
3
Major Topics of Nanoscience and Technology

Nano
Materials

Nano
Science and
Technology

Nanoproducts Nano Processing

(Devices and and
Systems) Characterization

4
 What is the Nano Technology?
 Science and Technology Down scaling to size
under100 nm:

Via the “Top-down” lithographic pattering.

-- Moore’s law !

 Manipulate the atomic and molecular

structures：“Bottom-up” nano materials, growth
and assembly.
Feymann: There’s plenty of room at the bottom
5
 Major Driving Force pushing for Nano
Is due to the bottle neck met in Microelectronics
Moore‘s Law :
A 30% decrease in the size of
printed dimensions every two years.

6
Metal-Oxide-Feld Effect Transistor

1960 Kahng and Atalla, First MOSFET

1970 First IC, 1 kbit, 750 khz microprocessor
8
 Bottom-up Nano systems & Self-Assembly
enabling of designing large molecules and nano materials

11
 The First Lesson :

Bulk-to-nano Transition

12
Ex: size-dependence of melting temperature

Ag

Ph. Buffat and J-P. Borel, Phys. Rev. A13, 2287 (1976)
13
 Ex: size-dependence of color

powered cadmium selenide

larger
smaller

14
Ex: size-dependence of magnetism

A. J. Cox et al. Phys. Rev. B49, 12295 (1994)

15
 The Second Lesson :

• The ability of growing the nano scale

materials and structures

• The ability of detecting and manipulating

on the nano scale.

16
(I) Advance in thin film growth:
Such as Molecular Beam Epitaxy, atomic layer
depostion, laser MBE, etc…
 For Nano electronics in metals, oxides, and
semiconductors

(II) Detection at nano scale : STM, AFM,

MFM, STEM, Cs-TEM
 In 1982, Binning, and Rohrer in IBM invented
scanning tunneling microscope.
 In 1986, Binning, Quate, and Gerber invented the
atomic force microscope AFM. 17
 Integrated MBE Multi-chamber System

Now located in the Nano

Technology Center, ITRI,
Hsin Chu, Taiwan

For Metal, Oxide and

Semiconductor Films
On the Nano scale
18
Scanning Tunneling Microscope (STM)

19
 Quantum Corral
of 7.13 nm radius, 48 Fe atoms

Fe

Crommue, Luts, and Eigler, Science 262, 218-220, 1993 20

 Scanning Transmission Electron Microscope Laboratory

2-Å STEM 1-Å STEM

E~0.2 eV E~0.9 eV

Prof. C. H. Chen and

Electron Dr. M.-W. Chu.

Mono-
chromator

Cs EDX
corrector

EELS
EELS
 Spherical Aberration Corrected (球面相差)
Cs-STEM by C. H. Chen at CCMS, NTU
Cs
lens sample

Cs
corrector

focus confusion!

Cs corrected
lens sample

JEOL 2100;
2009四月底 Cs
裝機完成 corrector
 High-Angle ADF: Si dumbbell, 1.36 Å spacing
15s exposure 60s exposure

(440);
Si [110] 0.96Å
Drift ~1Å /min !!
(004):
1.36Å
 InGaAs/InAlAs superlattices on InP Substrate

InAlAs
InGaAs
InGaAs
InP

• Determining the interface

location and sharpness is easy.
• The In-distribution seems to
be inhomogeneous in the InAlAs
InP-substrate

layer (blue arrows).

• Note that InP substrate is In-

InGaAs
InGaAs

terminated (red arrow).

InAlAs
Atomic Resolution STEM Imaging: Z-contrast

2-Å Electron Probe SrTiO3

Z-contrast

Sr Ti

cubic; a = 3.905 Å
Electronic Exc.: Electron Energy-Loss Spectroscopy (EELS)

Ei,ki Coulomb Interaction

sample e2
v( r )  
j r  rj
Ef,kf
  vq  q eiqr
Ei,ki q
E  Ei  E f
E, q , where q the electron density operator
q  ki  k f

Inelastic Scattering (∆E) Probability

d 2
2

~   f v(q)  i   ( Ei  E f  E )
d d E f
1
~  S ( , q) X-ray
q4
1  1 
~  Im   ( , q)  EELS
q2  
 Spectral Imaging at Ultimate Spatial Resolution

Plasmonic Mapping: Chemical Mapping:

STEM-EELS (2-Å Probe) STEM-EDX (1-Å Probe)

27 nm
8 nm
Au Au
81 nm

Dark Mode 1.82 eV

Bright Mode 2.38 eV

1.47 Å

M.-W. Chu et al., Nano Lett. 9, 399 (2009). M.-W. Chu et al., Phys. Rev. Lett. 104, 196101 (2010).
The Third Lesson:
The importance of
Quantum Physics

28
 The cause for variation of scaling
• Influence of Boundary
--Increase of proportion of boundaries
--Existence of surface / edge modes
--Geometrical reconstruction

• Decrease of the number of particles

decrease of confinement , increase of purturbation

• Different scaling for different physical entity

Quantum Effect:
=> Most likely to have new breakthough !
29
 The connection of materials wave
with mechanics
h = Planck constant
(6.62610-34 joule-sec)

DeBroglie: Einstein:
 = h/p E=h=p2/2m

自由電子: th (300 K )  6.2nm
Wave length Free electrons
(半導體中10nm  
Semiconductors  100nm)
原子: th (300 K )  0.2nm
Atoms
 Bulk Limit Nano Limit

Bulk
materials L
 << L

Nano
~L
31
Major Qauntum Effect
at the nano scale

• Interference
• Quantization
• Tunneling
• Quantum Spin

32
(I) Interference

33
The wonder of electron in waves

Classical mechanics

Electron source ?

34
The wave property of electrons

35
 Double Slit Interference of Electrons

Electron source

36
 L

L
 y  
d d
dsin = m
constructive interference
y
dsin = (m+1/2) d 
L
distructive interference
37
 ~
~

L ~ 1m
L
y  
d
 ~ 700nm d ~ 101 mm  104 m  7mm
 ~ 0.17nm
y  1.7 m

38
(II) Quantization

39
Confinement of the materials wave

Standing Wave

Quantizations

40
 The Qauntization of Energy

n 3 n
L 
2

n2 h nh
p 
 2L
 E  1/ L2
2 2 2
p nh
n 1 En   2
2m 8mL
41
L
 Quantum well: 1D confinement

AlGaAs
MOSFET: 2D electron Gas
GaAs
二維電子氣

EF
e
AlGaAs
GaAs
42
 Quantum wire: 2 D-Confinement

x
z
y

SEM images of MoOx nanowires on graphite surfaces

Science 290, 2120-2123, (2000)
43
Quantum dot: 3 D - Confinement

44
Quantum Dots of various shape

45
Absorption in scattering
From red to yellow  E  hc /   1/ L2
larger 0

powdered Cadmium Selenide

larger

smaller

46
The Advent of Carbon Era ?
Carbon Nanotube

50
 Carbon Nanotube

Carbon Nanotube based Transistors / Electronics

51
 Exfoliated Graphene
Monolayers and Bilayers
Reflecting microscope images.

20 m

Monolayer Bilayer

K. S. Novoselov et al., Science 306, 666 (2004).

Band Structure near K Points

~10 eV

Relativistic Dirac fermion.

General Properties of Graphene

Electrically:
High mobility at room temperature,
Large current carrying capability

Mechanically:
Large Young’s modulus.

Thermally:
High thermal conductance.
Exotic Behaviors
-Quantum Hall effect

-Barry Phase

-Ballistic transport

-Klein’s paradox

-Others
.
.
Quantum Hall Effect

Y. Zhang et al, Nature 438, 201(2005)

Electron scattering from a potential barrier
(1929)

As the potential approaches infinity, the reflection diminishes,

the electron always transmittes
 Another emerging wonder material : Silicene
• Graphene-like two-dimensional silicon
• Could be more compatible with existing silicon-based electronics
• Potential application as a high-performance field effect transistor

Nature, Scientific Reports 2, # 853, 2012

To grow Silicene, Germanine, and Superconductivity in alkaline or

even Tinene on insulating or alkaline earth elements doped
semiconducting substrate. silicene (CaC6 Tc=13K; CaSi6 Tc = ? )
 Combined spectroscopic and microscopic
study underway
Synchrotron radiation core level
Scanning Tunneling Microscopy
photoemission from NSRRC

60s = 1 ML
(III) Tunneling

67
nm

68
 Quantum Tunneling is the major effect
for the failure of Transistor at nano scale

69
 Scanning Tunneling Microscope (STM) –
Physicist used to detect the nano structures

Nature 409, 304(2001)

70
Doping-structure correlation at fullerene/metal interface
(interface engineering)
C60/Cu(111) case:
“optimal” doping (e.g., 3 e- per C60) achieved purely through interface reconstruction.
Combined techniques of STS, STM, PES, LEED I-V, and ab-initio theory are used in this study.
Naïve case! Reality…
thought to be true structure-doping correlation

Implication: electronic property of molecule-electrode contact must consider

structural details at the interface

W. W. Pai et al., Phys. Rev. Lett. 104, 036103 (2010)

(IV) Quantum Spin

72
 Spin and Nano technology
Electron Spin is the smallest unit of magetism,
Came from Quantum Mechanics


N

73
Often being used for
magnetic recording
~30 billion market

Spintronics  Electronics

74
New generation
of computer
Compulttion and storage
in one shot

When turn-on,
it is ready!

75
Quantum behavior of ferromagnets
-Spin as a quantum qubit

 /2 |1 qubit   | 0   |1

Due to superposition
  /2 | 0 More information!

76
Can we take the “charge” out of Spintronics ?
To generate pure spin current !
 Spintronics vs Electronics

 Reducing the heat generated in traditional electronics is

a major driving force for developing spintronics.
 Spin-based transistors do not strictly rely on the raising or
lowering of electrostatic barriers, hence it may overcome
scaling limits in charge-based transistors.
 Spin transport in semiconductors may lead to
dissipationless transfer of information by pure spin currents.
 Allow computer speed and power consumption to move
beyond limitations of current technologies.

78
Reliable generation of pure spin currents !

 Spin Hall effect (2004)

 Spin Pumping (2006)

 Inverse Spin Hall effect (2006)

 Spin Seebeck effect (2008)

 Spin Caloritronics (2010)

79
Major Qauntum Effect
at the nano scale

• Interference
• Quantization
• Tunneling
• Quantum Spin

80
 The Fourth Lesson:

Innovations of
nano structures and
nano materials
for various applications
 Overview of Advanced Materials Laboratory
Pt-Ru NP on CNx NT Ag NP on Si NT
Au NP @ SiOx NW GaN Nanobridge

100 nm

Fuel Cells, SERS:

Color-selective Optical Supercapacitors Molecule/Bio-sensing
Switch, SPR-enhanced High-gain Photo-detector,
Sensor Solar Cells, Bio-sensor
Li-Chyong Chen
Center for Condensed Matter Sciences
National Taiwan University
 The Nano-world at CCMS-AML:
a Fruitful Research Field with Technology Implications
JACS 123, 2791 (2001) APL 83, 1420 (2003)
APL 81, 22 (2002) Nano. Lett. 4, 471 (2004)
JACS 127, 2820 (2005) Chem. Mater. 17, 553 (2005)
APL 88, 241905 (2006) Wire/Rod Adv. Func. Mater. 15, 783 (2005)
APL 90, 213104 (2007) APL 86, 203119 (2005)
Adv. Func. Mater. 18, 938 (2008) US Patent 6,960,528,B2
Small 4, 925 (2008) Nanotip APL 89, 143105 (2006)
Analytical Chem. 81, 36 (2009) Nature Nanotech. 2, 170 (2007)
Nano Lett. 9, 1839 (2009
APL 79, 3179 (2001)
APL 81, 4189 (2002)
Adv. Func. Mater. 12, 687 (2002)
APL 86, 203119 (2005) Tube
Chem. Mater. 17, 3749 (2005)
JACS 128, 8368 (2006)
PRB 75, 195429 (2007) Core-shell APL 81, 1312 (2002)
Nano. Lett. 3, 537 (2003)
JACS 130, 3543 (2008)
Chapter 9, pp. 259-309,
Adv. Func. Mater. 14, 233 (2004)
Nanowires and nanobelts, Z.L.
Wang Ed., Kluwer (2004)
Adv. Func. Mater. 16, 537 (2006)
APL 90, 123109 (2007) Belt Other Thin Films:
Adv. Mater. 19, 4524 (2007) APL 86, 21911 (2005)
APL 86, 83104 (2005)
APL 86, 161901 (2005)
APL 87, 261915 (2005)
Adv. Mater. 14, 1847 (2002)
Nature Mater. 5, 102 (2006) Peapod Brush JVST B 24, 87 (2006)
APL 88, 73515 (2006)
Adv. Mater. 21, 759 (2009)
Si Nanotips-Array and their Hetero-junctions:
On-chip, IC-compatible
* Antireflection:
Broadband (uv-terahertz), Omnidirectional (>70o)
* Electroluminescence in ZnO/SiNTs:
IR emission, x10 higher; turn-on ~3V, x2 lower than film
* Magneto-resistance in LSMO/SiNTs:
p-CMR
Room-temp. MR at lower bias and magnetic field
n-Si

ZnO/SiNT IR-LED

Nature-Nanotechnology Nano Letters Promising high-density memory:

2 (2007) 770 9 (2009) 1839 On-going
 A Man-made Moth Eye
Broadband and Quasi-omni-directional Anti-reflection Properties with
Biomimetic Silicon Nanostructure
Y. F. Huang, et al., Nature Nanotechnology 2, 770-774 (2007) & US Patent 2005
Featured by NPG Asia Materials, March 2008

Wavenumber (cm-1)
UV-VIS-NIR 4000 3000 2000 1000 500
100 100
Si-Wafer-N+
Si substrate
80 ECR 833-SiNTs -N+-R%
Mid - IR Si substrate
SiNTs , L= 1.6 m
Reflectance (%)

ECR 852 SiNTs-N+

80
Reflectance (%)
Reflectance (%)

60 SiNTs , L= 5.5 m
ECR 835-SiNTs-N+ SiNTs , L= 1.6 m
SiNTs , L= 16.0 m SiNTs , L= 5.5 m
40 60 SiNTs , L= 16 m
Y Axis Title

10
40

1 20

0.1 0
0.2 0.5 1.0 1.5 2.0 2.5 2.5 5 10 15 20
Wavelength (μ m)
Wavelength ( m) Wavelength
X Axis Title (μ m)

Many plants and animals have tiny surface structures that absorb certain wavelengths of light.
These naturally formed nanostructures provide the colors in butterfly wings, camouflage for
cicadas and enable moths to capture as much light as possible when flying at night.
Now, we have created nanostructure surfaces which mimic moth eye and surpass its function
in anti-reflection in that they absorb almost all incident light.
 Building a Nano-scale Bridge On-chip
On-chip Fabrication of Well Aligned and Contact Barrier-Free GaN
Nanobridge Devices with Ultrahigh Photocurrent Responsivity
R. S. Chen, et al., Small 4, 925-929 (2008)

GaN nano-bridge
h
wafer process
W
probe

h+e- Ni
GaN NW doped
GaN

c-plane Sapphire 5μm

• Nanowire: Naturally formed core-shell structure, 1D electron gas-like property

• On-chip process for building GaN nanobridge devices, which provide a large
surface area, short transport path, and high responsivity for next-generation
sensors and detectors
 A Color-selective Nanoswitch
Photosensitive Gold Nanoparticle-embedded Dielectric Nanowires
M. S. Hu, et al., Nature Materials 5, 102-106 (2006)
A Fast Breaking Paper
(in each individual field, only 1 was selected bimonthly among the Highly Cited Papers)
(http://esi-topics.com/fbp/2007/august07-Li-ChyongChen.html)

In ancient Arabian story of “Ali Baba and the Forty Thieves”, the treasure is in a
cave, of which the mouth is sealed by magic. It opens on the words "Open
Sesame" and seals itself on the words "Close Sesame".
The nanopeapod (i.e., gold nanoparticle-embedded dielectric nanowire) will open
to green light but shut for lights of other colors.
 Next-generation Energy Solution (I):
Fuel Cell with Low-loading of Precious Metals
Ultrafine Pt Nanoparticles Uniformly Dispersed on Arrayed Carbon Nanotubes
with High Electrochemical Activity at Low Loading of Precious Metal
C. L. Sun, et al., Chemistry of Materials 17, 3749-3753 (2005)
C. H. Wang, et al., J. Power Sources 171, 55-62 (2007)
20 100
0.4 mg/cm2 Pt-Ru/CNT-carbon cloth
15
2 nm 3.0 mg/cm2 60% Pt-Ru/C (ETEK)
Number 4.0 mg/cm2 30% Pt-Ru/C (Home made)
10

5
80 4.0 mg/cm2 20% Pt-Ru/CNT (Home made)

2
P / mW/cm
0
1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4

Diameter(nm)

60

40

20

0
0 100 200 300 400 500 600
2
j / mA/cm
• Direct methanol fuel cell is promising power generator with a wide range of
applications from portable electronic devices to automobiles.
• Nanotubes-Pt/Ru composites are highly efficient in loading precious metals.
Only one tenth of metal loading, in comparison to the conventional, is needed.
 Next-generation Energy Solution (II):
High-performance Supercapacitor
Ultrafast Charging-discharging Capacitive Property of RuO2 Nanoparticles on
Carbon Nanotubes Using Nitrogen Incorporation
W. C. Fang, et al., Electrochemistry Communications 9, 239-244 (2007)
W. C. Fang, et al., J. Electrochemical Society 155, K15-K18 (2008)
70 1.50 2

Potential (V vs. Ag/AgCl)

Scan rate = 600 mV/s
I = 23 mA/cm Nanocomposites

Capacitance (mF/cm )
2
Scan rate = 600 mV/s
RuO2 films

0.75
0

CNx NTs
RuO2 films
CNx NTs-RuO2 0.00
-70
0.0 0.2 0.4 0.6 0.8 1.0 0 5 10 15 20
RuO2on N-doped E (V vs. Ag/AgCl) Time (s)

CNT composites • 4 fold increase in capacitance

(BEI)
• Optimal capacitance of 1380 F/g at 600 mV/s
(theory: 1450 F/g)
(SEI) • Output current as high as 23 mA/cm2
• Stable at high scan rate
• 10 fold increase in charge-discharge rate
The Fifth Lesson:

Nano photonics
and
Bio-applications
 Nano-photonics and Plasmonics
Near-field examination of blue-ray discs
Dr. Juen-Kai Wang, CCMS, NTU

S-SNOM setup

Scattering-type SNOM reveals sub-10 nm optical signature.

The optical contrasts of the dark and the bright regions in near-field image of phase-
change layer correspond to amorphous and polycrystalline AgInSbTe, respectively.
Small bright spots with a size of ~30 nm emerge within the dark region, corresponding to
the nano-sized ordered domains in the TEM image.
s-SNOM provides a direct optical probe in nanometer scale for high density optical
storage media.
J. Y. Chu et al., Appl. Phys. Lett. 95, 103105 (2009).
Creating Monodispersed Ordered Arrays of Surface-Magic-Clusters
and Anodic Alumia Nanochannels by Constrained Self-organization
Dr. Juen-Kai Wang, CCMS, NTU

Prof. Yuh-Lin Wang 王玉麟

IAMS Academia Sinica, Taiwan
A High Sensitivity and High Speed Biomedical Diagnostic
Technology using SERS
Dr. Juen-Kai Wang, CCMS, NTU

Prof. Yuh-Lin Wang 王玉麟 93

IAMS Academia Sinica, Taiwan
 SERS detection of bacterial cell wall
Dr. Juen-Kai Wang, CCMS, NTU

Sensitive and stable SERS profiles based on our substrates readily reflect different
bacterial cell walls found in Gram-positive, Gram-negative, and mycobacteria group.
Characteristic changes in SERS profile are recognized in the drug-sensitive bacteria of
antibiotic exposure, which could be used to differentiate them from the drug-resistant ones.
H.-H. Wang et al., Adv. Mater. 18, 491 (2006); T.-T. Liu et al., PLoS ONE 4, e5470 (2009).
The End