Mechanics of Nanomaterials (Ae 244)

Instructors: Chiara Daraio & Julia Greer

California Institute of Technology

Chiara’s contact: daraio@caltech.edu

Julia’s contact: jrgreer@caltech.edu

Office hours: by appointment

Class meets: Tuesday and Thursday in 308 Firestone From 2-3.30pm

Class webpage: http://www.its.caltech.edu/~msjang/

TA: Jang, MinSeok, msjang@caltech.edu

 Ae 244. Course Description

This course will cover the basics of the mechanics of both nano-
structures and nano-structured materials.
• Synthesis and processing methods,
• analytical characterization techniques,
• resulting material properties and applications will be covered.

The emphasis will be on relation between microstructural and mechanical

properties.
Specifically, the course will give an overview of properties of
nanostructured metals/ceramics/composites, nanowires, nanotubes,
quantum dots, and nano-particles with their applications in electronics,
sensors, and bio-medicine.

Innovative experimental methods and microstructural characterization

techniques developed for studying nanoscale phenomena will be
described.
Recent advances in the application of nanomaterials in engineering
systems and IP-related aspects of nano-materials will also be covered.
 Master Schedule and Outline (Ae 244)

Week/Date Section Topic Instructor

Week 1/Oct. 2 Intro Why is nano-scale special? Chiara
How are nano-materials different?
Week 1/Oct. 4 Julia
Definition of nanostructures, nanostructured
materials, nanoscale precipitates
Week 2/Oct. 9 Synthesis Bottom Up Chiara
Top Down
Week 2/Oct. 11 Julia
Week 3/Oct. 16 Applications Micro-fluidics, fuel cells, biomedical, bio- Julia
mimicking
Week 3/Oct. 18 Julia
flexible electronics, solar cells, PVs
Week 4/Oct. 23 Characterization 1) Electron scattering overview Chiara
2) E-scattering based techniques overview: SEM
Week 4/Oct. 25 Chiara
(BS, SE, EBSD), EDS (FIB)
Week5/Oct. 30 Characterization FIB Julia
Week5/Nov. 1 Force-based techniques: AFM, Nanoindentation, Julia
SPM

…
 Master Schedule and Outline (Ae 244)

Week 6/Nov. 6 Properties Mechanical properties 1 – Buckling, Julia

Dislocation, plasticity in nanostructures
Week 6/Nov. 8 Mechanical properties – Special on Chiara
Nanotubes: defects, deformations, dynamics
Week 7/Nov. 13 Properties Quantum Effect, transport, Field emission, Julia
thermal, magnetic, chemical, Optical
Week 7/Nov. 15 Proposal/Patent writing Chiara

Week8/Nov. 20 Guest Lecture on Atomistic Simulations for Nanomaterials WAG III

Week 8/Nov. 22 THANKSGIVING
Week 9/Nov. 27 Properties Nanostructured: Hall Petch, nanograins Chiara
Week 9/Nov. 29 Field trip to labs Field trip to labs TA/Chiara
Week 10/Dec. 4 Experimental methods: New methods for nanomechanics Chiara
Week 10/Dec. 6 Students final presentations Chiara
 Class Requirements and grading scheme

GRADING %

• 1 midterm (take-home exam), 30 %

• 1 patent application, 20 %

• 1 final project (mini-proposal) 20 %

• HWs: ~4 expected, one on each major topic (intro/synthesis, 30 %

characterization, properties, applications)
100 %
• 1 field trip to visit all the labs
 CLASS POLICIES

• Zero tolerance on late homework assignments (no credit given for late HWs)

• 4 homework assignments (due every other Friday starting Oct. 12th)

• Collaborative HWs solutions are NOT an option, though students are welcome and

encouraged to discuss among themselves.

• Midterm is a take-home, open books and notes.

• Provisional patent application exercise to be completed individually.

• Final project (Mini Proposal) to be prepared in small groups (2-3 students max).
 COURSE OBJECTIVES

• Understanding nanomaterials: synthesis, properties and applications in multiple

engineering fields.
• Study how the structure of materials can be controlled down to the nanometer scale
through various processing methods.
• Study structure-property relationships at the nanoscale.
• Study applications involving nanostructured materials, patenting issues and grant writing.
• Develop effective interdisciplinary communication skills.
• Critically evaluate topics in the emerging field of nanomaterials (i.e., distinguish progress
from hype, stimulate creative thinking).
 SUGGESTED READING MATERIAL

Reference Books
*Nanomaterials: Synthesis, Properties and Applications, ed. A. S. Edelstein and R. C.
Cammarata, IoP (UK), 1996
*Handbook of Nanoscience, Engineering and Technology, ed. W.A.Goddard III, D.W.
Brenner, S. E. Lyshevski, G.J. Iafrate, CRC Press, 2007
Fundamentals of Microfabrication, M. J. Madou, Second Edition, CRC Press, 2002.
Silicon VLSI Technology: Fundamentals, Practice, and Modeling by James D. Plummer,
Michael D. Deal, and Peter B. Griffin (Hardcover - Jul 14, 2000)
Nano/Microscale heat transfer by Z.M. Zhang, McGraw-Hill, 2007

* Books on Reserve in the SFL library

Articles
M.A. Meyers, A. Mishra, D.J. Benson, Mechanical properties of nanocrystalline
materials, Progress in Materials Science 51 (2006) 427–556

Additional readings will be assigned with the lectures and uploaded on the class
webpage.
INTRODUCTION
 INTRODUCTION: Where did it all start?

“There is Plenty of Room at the Bottom”

Richard Feynman, December 29th 1959, APS Meeting
http://www.zyvex.com/nanotech/feynman.html

“What I want to talk about is the problem of manipulating and

controlling things on a small scale.
As soon as I mention this, people tell me about miniaturization,
and how far it has progressed today. They tell me about electric
motors that are the size of the nail on your small finger. And there
is a device on the market, they tell me, by which you can write the
Lord's Prayer on the head of a pin. But that's nothing; that's the
most primitive, halting step in the direction I intend to discuss. It is
a staggeringly small world that is below. In the year 2000, when
they look back at this age, they will wonder why it was not until
the year 1960 that anybody began seriously to move in this
direction.
Why cannot we write the entire 24 volumes of the Encyclopedia
Brittanica on the head of a pin?”
 INTRODUCTION: Where did it all start?

M.C. Hersam, 2005

Caltech, BS (1932)

The three scientists received the Nobel Prize in 1956

 INTRODUCTION: Where did it all start?

The first planar

integrated circuit, 1960.
Designed and built by
Lionel Kattner and Isy
Haas under the direction
of Jay Last at Fairchild
Semiconductor

Founder and co-founder and Chairman Emeritus of Intel Corporation,

Caltech, PhD (1954)
INTRODUCTION: Where did it all start?

M.C. Hersam, 2005

INTRODUCTION: Where did it all start?

M.C. Hersam, 2005

 INTRODUCTION: Where did it all start?

Nanostructures in nature

• Magnetotactic bacteria
• Ferritin (protein complex for intracellular
iron storage)
• Molluscal teeth, Gecko feet…
(H. A. Lowenstam, Science 27 July 1962: Vol. 137. no.
3526, pp. 279 – 280)

Afarensis, FCD

http://www.metridium.com SCHRODL, MICHAEL y GRAU, JOSÉ H.

Rev. chil. hist. nat., 2006, 79,1,3-12.
 INTRODUCTION: Where did it all start?

Nanostructures in history

Late Roman, 4th century AD

This extraordinary cup is the only complete example of a very special type of glass, known as dichroic, which changes
colour when held up to the light. The opaque green cup turns to a glowing translucent red when light is shone through it.
The glass contains tiny amounts of colloidal gold and silver, which give it these unusual optical properties.
The British Museum
INTRODUCTION: Definitions
 INTRODUCTION: Definitions

Nanotechnology
NanoDevices

NanoStructureS
NanoTools • Electronic
NanoStructureD
• MEMS/NEMS
• Fullerenes • Biodevices/
• Nanotubes Lab-on-a-chip
• Nanoscaled • Fabrication
• Nanowires • Biosensors
microstructures
• Nanofibers Techniques • Drug delivery/
in bulk or thin films • Analysis and
• Nanoparticles Therapeutics
• Nanograins
• Quantum Dots Metrology • Data Storage
• Nanocrystalline • Software for • Catalysis
materials Nanotech • Nanoscaled
• Nanocomposites
machines

NanoSystems
Something about NanostructureS
INTRODUCTION: Panoramic view of NanostructureS

CARBON BASED
NANOSTRUCTURES:

-Fullerenes
- Carbon Nanotubes
- Graphene

Wikimedia Commons
 INTRODUCTION: Panoramic view of NanostructureS: Carbon 1/3

1) BUCKYBALLS (Fullerene)

C60 Molecule (1985):

by R.E. Smalley, R.F. Curl and H.W. Kroto
– Nobel Prize 1996.

Graduate Students:
James Heath and Sean O’Brien

RELEVANCE:
It was a new form of Carbon, besides
graphite, diamond and amorphous
www.nanotech-now.com
 INTRODUCTION: Panoramic view of NanostructureS: Carbon 2/3

2) Carbon Nanotubes

Single sheet of graphite rolled up

by Sumio Iijima of NEC in 1991
(though origin of discovery is debated)

RELEVANCE:
Another new form of Carbon, has
excellent mechanical, thermal and
chemical properties.
Wikimedia Commons
 INTRODUCTION: Panoramic view of NanostructureS: Carbon 3/3

is a single planar sheet of sp²-bonded

3) Graphene
carbon atoms. Graphenes are the 2-D
counterparts of 3-D graphite

A new rising star, The NYT titles:

“Thin Carbon Is In: Graphene Steals
Nanotubes’ Allure” April 10th, 2007

RELEVANCE:
Electrons behave as if they had no mass
(2D electron gasses)
Room T quantum Hall effect

NYT
 INTRODUCTION: Panoramic view of NanostructureS: Nanoparticles 1/3

NANOPARTICLES
Particles with size <100nm
They are a a bridge between bulk materials
and atomic or molecular structures.
The properties of materials change as their
size approaches the nanoscale and as the
percentage of atoms at the surface of a
material becomes significant
RELEVANCE:
variety of potential applications in
biomedical, optical, and electronic fields.
Quantum confinement in semiconductor
particles, surface plasmon resonance in
some metal particles and
superparamagnetism in magnetic
materials.

In the figure: “polymeric micro- and

nanoparticles in a wide variety of different
shapes and sizes using commonly-available lab
chemicals and equipment. (Credit: Image
courtesy of University of California - Santa
Barbara).”
From ScienceDaily.com
 INTRODUCTION: Panoramic view of NanostructureS: Nanoparticles 3/3

QUANTUM DOTS
is a semiconductor nanostructure that confines the
motion of conduction band electrons, valence band
holes, or excitons (bound pairs of conduction band
electrons and valence band holes) in all three spatial
directions.

Image of fluorescence in various sized CdSe Q.D.s

Dr. D. Talapin, University of Hamburg

2 nm 6 nm

RELEVANCE:
Have superior transport and
optical properties.

Used in diode lasers, labeling

and optical sensors.
Y. Galperin, 2007
 INTRODUCTION: Panoramic view of NanostructureS: Nanowires
NANOWIRES
structures that have a lateral size
constrained to tens of nanometers or less
and an unconstrained longitudinal size. At
these scales, quantum mechanical
effects are important — hence such wires
are also known as "quantum wires".
GaN NIST nanowires that emit ultraviolet light
TYPES:
• metallic (e.g., Ni, Pt, Au),
• semiconducting (e.g., Si, InP, GaN. ..),
• insulating (e.g., SiO2,TiO2),
• molecular nanowires are composed of
repeating molecular units either organic
(e.g. DNA) or inorganic.
RELEVANCE:
Have “new” electrical properties.
Proposed for computing, solar
cells and metamaterials
 INTRODUCTION: Panoramic view of NanostructureS: Nanofibers

NANOFIBERS

Nanofibers are defined as fibers with

diameters less than 100 nanometers.
They can be produced by interfacial
polymerization and electrospinning.

Nordson.com

RELEVANCE:
Low density, large surface area to
mass, high pore volume, and tight
pore size make the nanofiber
nonwoven appropriate for a wide
range of applications from medical to
to high-tech and aerospace,
capacitors, transistors, drug delivery
systems, battery separators, energy
storage, fuel cells, and information
technology
INTRODUCTION: Why is nanoscale special?

M.C. Hersam, 2005

M.J. Biggs
INTRODUCTION: Why is nanoscale special? - INTERFACES

M.J. Biggs
INTRODUCTION: Why is nanoscale special? – QUANTUM EFFECTS

“The Heisenberg uncertainty principle gives a

lower bound on the product of the standard
deviations of position and momentum for a
system, implying that it is impossible to have a
particle that has an arbitrarily well-defined
position and momentum simultaneously.”

M.J. Biggs
 INTRODUCTION: Why is nanoscale special? - THERMAL

Thermal fluctuations can be commensurate with

the size of nano-systems, making their design
and use very difficult (they influence, for
example, the rates of chemical reactions and
error rates in nanomechanical systems).

One example:
“For very small ferromagnetic (FM) particles the magnetic
anisotropy energy (responsible for keeping the magnetization
oriented in certain directions) is comparable to the thermal
energy (kT). When this happens, the particles become
superparamagnetic; as thermal fluctuations randomly flip the
magnetization direction between parallel and antiparallel
orientations. b, When the ferromagnetic nanoparticle is placed
close to an antiferromagnetic (Anti-FM) surface the exchange
bias interaction at the FM/Anti-FM interface provides additional
anisotropy energy, which stabilizes the magnetization in one
direction and prevents superparamagnetism.”

J. Eisenmenger and I.K. Schuller, Magnetic

nanostructures: Overcoming thermal fluctuations,
Nature Materials 2, 437 - 438 (2003)
INTRODUCTION: Why is nanoscale special? - THERMAL

M.C. Hersam, 2005

INTRODUCTION: Why is nanoscale special? - DISCRETENESS

M.J. Biggs
…On to NanostructureD
 INTRODUCTION: Panoramic view of NanostructureD Materials

2) Nanoscaled microstructures in bulk or thin films they are single or multi-

phase polycrystals with nanoscale (1x10-9–250x10-9 m) grain size.

Uniform
ultrafine
grain
structure

2-Phase
ultrafine
grain
structure
Dispersion of nanoscaled
precipitates
Nanocrystalline NiTi, TEM bright field image.
Progress in Materials Science 51 (2006) 427-556
Europhys. Lett., 71 (1), p. 98 (2005)
 INTRODUCTION: Why is nanoscale special?

Properties of Nanostructured Materials:

• Mechanics:
- Elasticity changes (E, G ↓ as grain size ↓ )
- Mechanical Strength ( ↑ as grain size ↓ ) [Hall-Petch or Inverse Hall Petch?]
−1
σ y = σ 0 + kyd 2

σ0=lattice friction, ky = HP slope, d=grain size

- Ductility:
in metals ↑ as grain size ↓
in ceramics ↑ fracture toughness
Ductile Brittle Transition
• Diffusion
• Magnetic
Progress in Materials Science 51 (2006) 427-556
• Thermal and Electrical conductivity
 INTRODUCTION: NANOTOOLS

New Physics in the Numerical, Theoretical and Experimental techniques

to Process and Study nanomaterials

• Synthesis techniques for nanostructures and nanostructured materials:

- TOP DOWN
- BOTTOM UP

• New and old experimental methods devised for their testing and characterization
- Electron Scattering techniques Light Source
a b
- Force based techniques
Resist
- MEMS and in-situ testing SiO2 Mask
Si
Negative Resist Positive Resist

• Numerical methods and multiscale modeling c

Etching Etching
d
 INTRODUCTION: NANODEVICES

New Physics in the Numerical, Theoretical and Experimental techniques

to Process and Study nanomaterials

• Electronic
• MEMS/NEMS
• Biodevices/
• Lab-on-a-chip
• Biosensors Reed/Yale

• Drug delivery/
• Therapeutics
• Data Storage
• Catalysis
www.mse.umd.edu
• Nanoscaled machines
©Copyright 1999 David Morgan-Mar
 INTRODUCTION: NNI

The National Nanotechnology Initiative (NNI) [http://www.nano.gov/]

Reed/Yale
 INTRODUCTION: NNI

The National Nanotechnology

Initiative (NNI)
[http://www.nano.gov/]