NE226 Characterization of Materials

Instructor:

Guoxing Miao

Semester:

May 5 (Tue.) July 28 (Tue.)

Classroom:

QNC 1502

Normal lectures:

Tue. /Wed./Thur. 9:30 am 10:20 am;

No lectures:

July 1 (Wed. Canada Day); week of June 15 (midterm);

3 makeup lectures: May 6, May 20, June 3 (Wed.) 11:30 am -12:20 pm;
No tutorials:

1st week; midterm week; week of July 27 (last week of semester)

3 additional lectures
Week #:

Homework 1

7M

10

11

12

13

14/15F

Homework 2

(a reminder about additional classes will be posted on your LEARN calendar)

1

+
+

Midterm

Additional lecture

Homework assignment

 Course website:
Log onto your Waterloo Learn account
(https://learn.uwaterloo.ca/)
All lecture notes are posted onto LEARN before the
lectures
Office hours: Monday in non-exam weeks, 1:303:00 pm, EIT 4009
or email: guo-xing.miao@uwaterloo.ca
My office on a regular day: RAC2-1120
15 min walking/5 min biking from QNC
or
IQC shuttle:
White van with IQC logo printed on it, stops in front
of DC and NH, runs every 25 minutes except breaks at
9:20 am, 11:55 am, and 3:30 pm.
Your TAs:
Grigory Chugunov grigc01@yahoo.com
Jianjin Dong
jianjin.dong89@gmail.com
3

RAC2

Shuttle start (RAC1)

You are here

Shuttle stop 1
(DC)

x
shuttle stop 2
(NH)
4

Tutorials:

Fri. QNC 1507: 4:30-5:20 (101), 1:30-2:20 (102), 2:303:20 (103)

2 assignments:

Week of May 18 (3rd week) and week of July 6 (10th

week), due in the following week -- Turn in the
completed assignments either at one of the lectures or
to my office by the end of Friday (EIT 4009, slide under
the door in case I am not in there). Late homework not
accepted. Marked assignments can be picked up in any
of the office hours.

Midterm exam:

Week of June 15 (tba)

Final exam:

Aug. 3 Aug. 14 (tba)

 Grading scheme: assignments 2x10%, midterm 30%, final exam

60%
All the collected assignments / exams will be scanned and saved
digitally for future references
You will find some of the exam questions quite similar, but not
identical, to the assignments and the tutorial questions
Do your homework and attend the tutorials
Closed-book exams, only simple calculators allowed

NE226

Course outline (36 lectures)

1. Introduction (3)
Solids (2)
UHV techniques (1)
2. Microscopy (12)
Optical microscopy (3)
SEM (4)
TEM (2)
STM (2)
AFM (1)
3. Structural analysis (9)
XRD (5)
Midterm >==========<
LEED (2)
RHEED (1)
Ion scattering (1)

4. Spectroscopy (11)
XPS (1)
UPS (1)
AES (1)
XAS (1)
XRF (1)
EELS (1)
FTIR (1)
Raman (2)
Ellipsometry (1)
SIMS (1)
5. Summary (1)

>==========< Final
(Lectures not in sync with labs)

Textbooks

Required textbook, reserved in the library -> Materials Characterization: Introduction to

Microscopic and Spectroscopic Methods, by Yang Leng
Required textbook, available for free through UW library as ebook -> Encyclopedia of
Materials Characterization, by CR Brundle, CA Evans, S Wilson
Optional reading, reserved in the library -> Materials Characterization Techniques, by S
Zhang, L Li, A Kumar
7

Your background knowledge

NE 121
Chemical Principles
NE 125
Introduction to Inorganic Chemistry, Materials
Science & Engineering
NE 225
Structure of Matter: From Nanoscale to Bulk
NE 232
Quantum Mechanics (ongoing)
8

A. Introduction to atoms
Protons
+
Neutrons

Nuclei
+
Electrons

Atoms
+
Atoms

Molecules
+
Molecules

Size of an electron:
~ point

Solids

H
H

Size of an atom:
~ 10-10 m

Size of a nucleus:
~ 10-15 m

C
H

Molecule
10-10 ~ 10-8 m

Solid
~1m

Discrete electron levels within an atom

Copper atom as an example

N
M

Valence electrons located in the outer

most shell, reactive
Deep core electrons can only be reached
with very high energies, but can be used
to separate elements that are chemically
and physically close to each other

K
What are isotopes?
Why energy quantized? Why only
two levels shown for 2p?

10

s, p, d?

orbital angular momentum quantum number

Isotropic
(no angular node)

l=0

l=1

Two pockets
(one angular node)

l=2

x2-y2

px

pz

xz

Note, px+ipy and px-ipy

are the actual ml=+/-1
wave functions, pz
corresponds to ml=0;

py

z2

yz

xy

Four pockets
(two angular node)
11

Crystal field 101:

Useful to remember the electron cloud shapes, as they sometimes determine
the fine energy levels in a material (e.g crystal fields);
y

x
Two x2-y2 orbits along x,
significant e-e overlap and
higher energy

Two xy orbits along x, less

e-e overlap and lower
energy

In a cubic crystal for example, the 3d orbitals tend to split into T2g and Eg levels,
with the former containing xy, yz, xz states (up to 6 electrons) and the latter x2y2, z2 states (up to 4 electrons). T2g is usually lower in energy as described
above (in tetrahedral or octahedral crystal fields).
Instead of a lone atoms, all degenerate, d-levels, the 5 orbitals become
crystal-field split levels (max 10 electrons):

Eg
T2g

12

5d orbital:

n = 5;
l = 2;
total nodes n-1 = 4;
angular nodes l = 2;
radial nodes n-1-l = 2;
x

(Phases?)
Quantum mechanically, a wave package not
only has magnitudes (probability) as you see in
the picture, it also has phases (red/blue colors
illustrating opposite phases across a node, i.e.
zero points)

5dxy
13

Summary on atom electronic structure

n: Principle quantum number (electron shell number),
K, L , M, N, n = 1, 2, 3, 4,
l: angular momentum quantum number,
s, p, d, f, l = 0, 1, 2, 3,
s: spin angular momentum quantum number,
for electrons
Number of orbitals: 2l+1 defined by quantum mechanics.
(for example, p state can hold 21+1=3 orbitals, i.e. m=-1,0,+1; and each orbital
can hold 2 electrons with different spins => max 6 electrons on p orbitals)
J: total angular momentum quantum number (combining orbital and spin
angular momentum, i.e. l and s, quantum mechanically),
l+s or l-s
(for example, p orbitals will split into J=3/2 and J=1/2 levels; they can hold 4 and 2
electrons, respectively. Note, spin component already considered here so no need
to multiply by 2 any more.)
Further reading on electronic orbitals such as f-orbitals:
http://chemwiki.ucdavis.edu/Physical_Chemistry/Quantum_Mechanics/Atomic_Th
eory/Electrons_in_Atoms/Electronic_Orbitals
14

B. Forming Crystals
Building blocks

The glue

Atoms (molecules)

Covalent bonding
Polar bonding
Ionic bonding
Metallic bonding
Intermolecular bonding
Hydrogen bonding

The structures

Graphene

Diamond

Graphite

15
http://www.smallscalechemistry.colostate.edu/PowerfulPictures/ChemicalBonding.pdf

Covalent Bonding
A little bit quantum mechanism:
Electrons have particle-wave duality, they each have a wave function of
Electrons are Fermions, which means their total wave function is anti-symmetric
(Pauli exclusion principle: no two electrons occupy same state)

2
(1+2)

spatial

(1-2 )

spin

(| > | >)
| >

(| > +| >)
| >

16

Covalent Bonding - continue

Anti-bonding

H-H spacing
bonding

Symmetric, bonding configuration is much more stable -> H2

Saturated, a third H atom is not possible because it is guaranteed to be

anti-bonding with one of the existing H atoms -> no H3
Strong, roughly increases with bond numbers, and decreases with larger
atoms
1eV ~ 12,000 K, does the energy scale make sense? (Free energy G=E-TS)
17

Ionic Bonding

NaCl crystal (rock salt structure)

Charge transfer increases system energy, but
bringing the ions close to each other lowers
Coulomb energy
Strong bonding , weaker for larger atoms
strongest between column II and VI (Alkaline
earth / Chalcogen)
(not I-VII, not III-V, why?)
Boiling points: NaCl 1413C, MgO 3597C

18

Polar Bonding

Electronegativity tells how easy for an atom to catch an extra electron

19

Polar Bonding

ionic

polar

covalent

20

Metallic Bonding

Randomly placed, freely roaming electrons -> metallic

Sort of like covalent bond, but with more vacant bonds than the electrons
can fill. Electrons are more like a gas, no fixed bonds forming
Weak in Alkali, strong in the middle of transition metals

(boiling points: Cu 2562C, Na 883C, W 5660C)

21

Boiling points (1000K):

Diamond
NaCl
MgO
Na
Cu
W

4.8
1.7
3.9
1.2
2.8
5.9

Refractory metals
(high melting point, hardness, density)

22

Intermolecular Bond
(Dipole bonding)

Permanent dipoles - polar molecules:

E~

-2

(attraction or repulsion?)

Instantaneous dipoles nonpolar molecules (Van de Waals force):

(Phenomenological)

~ ~

~ ~

(Weak bonding; solids tend to be soft with low melting point; responsible
for many surfaces forces such as surface tension, friction, etc.)

23

Hydrogen Bonding
Water molecule bond angle:
104.5; Diamond: 109.5

Water molecules

Ice crystal

Snow flakes

Attraction between Hs partial positive charge and another electronegative atom

(H bond donors, often N, O, F)
Having features of covalent and dipolar bonding
Unique to H atom because of their small size
Responsible for increased melting point, solubility, surface tension, and viscosity
in many compounds

24

C. Crystal structures
z

O
x

Basis vectors: , ,

O
x

Basis vectors: , ,
or , + + ,

Definition of basis vectors is not unique, and the axis may not be perpendicular to each other

25

7 Basic Crystal structures

26

7 Basic Crystal structures

27

7 Basic Crystal structures

Parallelogram
faces

Rhombus
faces

a=b=c
= = 90
28

7 Basic Crystal structures

a
b

29

Crystal structures
7 crystal systems

4 lattice type
=
14 Bravais lattices

30

D. Miller indices
Natural facets
Cleave planes

Common Notions:
Round bracket (hkl): a certain crystal
plane
{}: a group of planes
Square bracket [hkl]: a crystal
direction in real space
<>: a group of vectors
Negative signs are placed on top, such
as (11 0)

y
x

31

Illustration of Miller Indices

2D cubic:

a2

a1

(010)
(Passing [010] and parallel to [100])

(110)
(Passing [100] and [010])

(120)
(Passing [100] and [0 0])

32

Miller indices
Plane of (h k l) passes through the [1/h 0 0], [0 1/k 0], [0 0 1/l] lattice
points in the real space
Mathematical definition of reciprocal lattice vectors:
1 =

2 =

2 3
1 (2 3 )

3 1
1 (2 3 )

1 2
3 =
1 (2 3 )
1

In cubic, they become , , ; reciprocal lattice of cubic is still cubic

(unit of reciprocal lattice: 1/length)

33

a
a

(120) Planes
Real space spacing = a/ 5
Reciprocal vector length = 5/a

34

2D orthorhombic

b
a

(120) Planes
Spacing = / 42 + 2

Reciprocal vector length =

1
2

4
2

42 +2

35

Real space lattice

2D monoclinic
dashed lines -> (120) planes
red vector -> [120] vector

a2

a1

(120) planes
Spacing = 1 2 / (21 2 )2 +22 2
Reciprocal vector length = inverse of above

36

Real space lattice

Reciprocal space lattice

90

a2
a3

b2

a1

b1

(120) planes
Spacing = 1 2 / (21 2 )2 +22 2
Reciprocal vector length = inverse of above

(2D reciprocal lattice is a 90 rotation of its real space lattice)

1 =

2 =

2 3
1
~
1 (2 3 ) 1

3 1
1
~
1 (2 3 ) 2

1 2
1
3 =
~
1 (2 3 ) 3

37

To help understanding the reciprocal vectors and Miller indices:

Vector [hkl] is in real space, you can count h, k , l units on the 3 axis in real
space to get this vector;
Vector (hkl) is in the reciprocal space (though the corresponding planes are in
the real space), you can count h, k, l units in the reciprocal space to find this
vector;
To get atomic planes (hkl) in real space (these indices are inverse of the real
space dimensions, hence reciprocal), you can count 1/h, 1/k, 1/l units on the
three axis and connect them to find the corresponding planes;
The vectors defined by Miller indices are like wave vectors, it is best viewed
as a frequency, a frequency with respect to length instead of time
-> Think about a plane wave in electromagnetics
cos(t+ )

frequency
wave vector
in time
or frequency in space
Why vector then? Unlike time, our space is 3D,
thus has 3 corresponding components as well

-> large wave vector means faster oscillations in space

The larger the Miller indices, the smaller the plane spacing

38

Miller indices in hexagonal lattices

2)
Plane (11

120

4 indices (h k i l)
redundant
-(h+k)
39

Quasicrystals
Dan Shechtman, Nobel Chemistry 2011

Ordered, but no translational symmetry. Have rotational

symmetry, such as the pentagons seen above

40

E. Examples of Miller indices in real crystals

Single crystal silicon:
The diamond structure
(two interpenetrating FCC lattices)

5.43

(001) surface

Square

(011) surface

Rectangular

3.84
x

(111) surface

hexagonal
41

Silicon wafers

Prime flat always set along [011]

Silicon natural cleave surface -> (111)

z
y

(the flats are cut by the Si wafer venders by

default to label the crystal orientations)

Looking downward from (100), four equivalent

cleave surfaces; downward from (111), three.
(100) wafer cleave into 90 angles; (111) wafer
into 60.

(100)
(111)
More than one way to form the cleave surfaces.
42

(100) wafer

x
z
y

Cleaving in the (111) plane would

1]
look like a line along [0
directions, ie., perpendicular to
the flat.
Cleaved surface is cos-1(1/ )=
54.7 with respect to the wafer
surface.

(111)

Prime flat
[011]

) leads to cleaving
Cleaving in (
1] too, but its
planes along [0
angle is now -54.7 with the wafer
surface.
1
) plane leads to
Cleaving in (
cleave lines parallel to the flat,
can also form two equivalent
cleave planes
43

(100) wafer

x
z
y

Cleaving in the (111) plane would

1]
look like a line along [0
directions, ie., perpendicular to
the flat.

)
(1
Prime flat
[011]

Cleaved surface is cos-1(1/ )=

54.7 with respect to the wafer
surface.

) leads to cleaving
Cleaving in (
1] too, but its
planes along [0
angle is now -54.7 with the wafer
surface.
O
1
) plane leads to
Cleaving in (
cleave lines parallel to the flat,
can also form two equivalent
cleave planes
44

(100) wafer

z
y

Cleaving in the (111) plane would

1]
look like a line along [0
directions, ie., perpendicular to
the flat.

1
)
(

Prime flat
[011]

Cleaved surface is cos-1(1/ )=

54.7 with respect to the wafer
surface.

1)
(

) leads to cleaving
Cleaving in (
1] too, but its
planes along [0
angle is now -54.7 with the wafer
surface.
1
) plane leads to
Cleaving in (
cleave lines parallel to the flat,
can also form two equivalent
cleave planes
45

What you will see in reality

(100) Si wafer

Rectangles
(easy to cleave)

46

(111) wafer

x
z
y

(111)
Wafer surface

1) plane would
Cleaving in the (1
]
look like a line along [10
directions, ie., -30 with respect to
the prime flat projection.
Cleaved surface is cos-1(1/3)=
70.5 with respect to the wafer
surface.

-30

1)
(1

Prime flat
[011]

) plane
Cleaving in the (11
appears +30 with respect to the
prime flat projection.

) plane would
Cleaving in the (1
]
look like a line along [01
directions, ie., perpendicular to
the prime flat projection.
47

(111) wafer

x
z
y

(111)
Wafer surface

)
(11
O

Prime flat
[011]

1) plane would
Cleaving in the (1
]
look like a line along [10
directions, ie., -30 with respect to
the prime flat projection.
Cleaved surface is cos-1(1/3)=
70.5 with respect to the wafer
surface.

+30

) plane
Cleaving in the (11
appears +30 with respect to the
prime flat projection.

) plane would
Cleaving in the (1
]
look like a line along [01
directions, ie., perpendicular to
the prime flat projection.
48

(111) wafer

x
z
y

(111)
Wafer surface

)
(
Prime flat
[011]

1) plane would
Cleaving in the (1
]
look like a line along [10
directions, ie., -30 with respect to
the prime flat projection.
Cleaved surface is cos-1(1/3)=
70.5 with respect to the wafer
surface.
) plane
Cleaving in the (11
appears +30 with respect to the
prime flat projection.

) plane would
Cleaving in the (1
]
look like a line along [01
directions, ie., perpendicular to
the prime flat projection.
49

What you will see in reality

(100) Si wafer

(111) Si wafer

Rectangles
(easy to cleave)

Triangles, parallelograms
(hard to control)

50

F. Materials deposition techniques

- classifications of multi-crystal systems

Single crystal
(Long range ordering)

Poly-crystal
(short range ordering)
51

Textured
(highly ordered in one direction)

Epitaxial
(Long range ordering)
52

Common Materials Deposition Methods

Electroplating
Cations are driven towards the
cathode, and pick up electrons
there and deposit as neutral
metals
The anode metal keeps losing
electrons and then dissolve in
the solution as positive ions

53

Chemical vapor deposition (CVD)

CVD
Mix gas-phase precursors in
the chamber for reactions
High temperature typically
required
Plasma enhancement

54

Thermal evaporation
Evaporate, or sublime, solid
materials
Substrate is held at relatively
lower temperatures for the
material to condensate
High-energy electron beam for
e-beam evaporation

Sources heated up to 3000+C

55

(Magnetron) Sputtering
High electric field ionizes the
process gas molecules
-> gas ions accelerated towards the
target and bombard the surface
-> momentum transfer sputter out
target materials
-> deposit onto the substrates
facing the target
(Magnetic field traps the plasma,
enhancing the ionization efficiency)
Commonly
used
for
mass
production of polycrystalline metal
films
Blue - oxygen
Violet - argon

Colors related to atomic energy levels

56

Molecular beam epitaxy (MBE)

(Million Buck Evaporator)
Multi-cell thermal evaporation
Ideal for epitaxial growth of multi-element
compounds, such as metal superlattices,
semiconductors, oxides, etc.
UHV (ultra-high-vacuum) environment
required, often with many in-situ
characterization tools
Crucible
Knudsen cell (K-cell):
Source is equilibrium vapor
Well thermal shielded
External water cooling

Water cooled enclosure

Radiation shields
Heater filament

57

The need for vacuum?

Atmosphere pressure = 760 mm Hg = 760 torr = 1 bar = 105 Pa
High vacuum 10-5 10-8 torr; ultra-high vacuum (UHV) 10-9 10-12 torr
To put things into perspective,
Pressure on the moon ~ 10-11 torr ~ 4105 molecules/cc
Molecule mean free path,
~ 100 m under 10-6 torr vacuum
Impingement rate of gas molecules,
~ 1 monolayer of molecules / second under 10-6 torr vacuum
Typical thin film growth rate ~ monolayer / second
(if 10-10 torr instead, 1 monolayer per 3 hours, contamination level << 0.01%)
58

Summary of the common thin film deposition methods

Chemical route
Liquid phase deposition

Electroplating

Chemical vapor deposition (CVD)

Physical route (PVD)

Thermal evaporation

Sputtering

Molecular beam epitaxy

59