Mechanics of Nanomaterials (Ae 244)

Instructors: Chiara Daraio & Julia Greer

California Institute of Technology
Chiaras contact: daraio@caltech.edu
Julias 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 nanostructures 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?

How are nano-materials different?
Definition of nanostructures, nanostructured
materials, nanoscale precipitates

Chiara

Bottom Up
Top Down

Chiara

Micro-fluidics, fuel cells, biomedical, biomimicking

flexible electronics, solar cells, PVs

Julia

1) Electron scattering overview

2) E-scattering based techniques overview: SEM
(BS, SE, EBSD), EDS (FIB)

Chiara

FIB

Julia

Force-based techniques: AFM, Nanoindentation,

SPM

Julia

Week 1/Oct. 4

Week 2/Oct. 9

Synthesis

Week 2/Oct. 11
Week 3/Oct. 16

Applications

Week 3/Oct. 18
Week 4/Oct. 23

Characterization

Week 4/Oct. 25
Week5/Oct. 30
Week5/Nov. 1

Characterization

Julia

Julia

Julia

Chiara

Master Schedule and Outline (Ae 244)

Week 6/Nov. 6

Properties

Week 6/Nov. 8

Mechanical properties 1 Buckling,

Dislocation, plasticity in nanostructures

Julia

Mechanical properties Special on

Nanotubes: defects, deformations, dynamics

Chiara

Quantum Effect, transport, Field emission,

thermal, magnetic, chemical, Optical

Julia

Week 7/Nov. 13

Properties

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) 427556

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, JOS 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
NanoStructureD
Fullerenes
Nanotubes
Nanowires
Nanofibers
Nanoparticles
Quantum Dots

Nanoscaled
microstructures
in bulk or thin films
Nanograins
Nanocrystalline
materials
Nanocomposites

Fabrication
Techniques
Analysis and
Metrology
Software for
Nanotech

NanoSystems

Electronic
MEMS/NEMS
Biodevices/
Lab-on-a-chip
Biosensors
Drug delivery/
Therapeutics
Data Storage
Catalysis
Nanoscaled
machines

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 OBrien

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

3) Graphene

is a single planar sheet of sp-bonded

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.

Y. Galperin, 2007

Used in diode lasers, labeling

and optical sensors.

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".

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

GaN NIST nanowires that emit ultraviolet light

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 multiphase polycrystals with nanoscale (1x10-9250x10-9 m) grain size.

Uniform
ultrafine
grain
structure

2-Phase
ultrafine
grain
structure
Nanocrystalline NiTi, TEM bright field image.
Europhys. Lett., 71 (1), p. 98 (2005)

Dispersion of nanoscaled
precipitates
Progress in Materials Science 51 (2006) 427-556

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?]

y = 0 + kyd

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

- Ductility:
in metals as grain size
in ceramics fracture toughness
Ductile Brittle Transition
Diffusion
Magnetic
Thermal and Electrical conductivity

Progress in Materials Science 51 (2006) 427-556

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
- Force based techniques
- MEMS and in-situ testing

Light Source

a
Resist

Mask

SiO2
Si

Numerical methods and multiscale modeling

Negative Resist

Positive Resist

Etching

Etching

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
Nanoscaled machines

www.mse.umd.edu

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/]