Microstructure Characterization

1. Introduction
Lecturer : Nack J. Kim
POSTECH

njkim@postech.ac.kr
Course description
• Objective
– Diffraction analysis and crystal structure
– Microscopy
– Micro / surface analysis

• Preliminary
– Basic understanding of micro / crystal structure



Overview
• Introduction and concept of microstructure
• X-ray diffraction
• Optical microscopy
• Scanning electron microscopy
• X-ray microanalysis
• X-ray photoelectron spectroscopy / Auger electron spectroscopy
• Secondary ion mass spectroscopy / Atom probe tomography
• Transmission electron microscopy
Others
• Evaluation
– attendance 20%, presentation 30%, examination 50%
• References
- Y. Leng, “Materials Characterization: Introduction to Microscopic and Spectroscopic
Methods”, Wiley (2008).
- D. Brandon & W. D. Kaplan, “Microstructural Characterization of Materials”, 2
nd

edition, Wiley (2008).


2. Concept of microstructural characterization
Why we need characterization ?
process
structure
property
performance
cause-and-effect target-and-means
Modern high performance steels
Performance Property Structure Process
austempering
Intercritical
annealing
Si or Al addition
Characterization in MSE
• What are the Items to be characterized?
– A material may have
• DIFFERENT PROPERTIES depending on THE STATE.
– The items should represent
• no other but THE STATE of the material.
– These items are what should be characterized.
• The items which describe THE STATE are;
– Composition
– Structure
– Morphology
• Composition
– Elemental: Major, Minor, Trace (Impurity),
– Elemental Distribution

• Structure
– Microstructure
• Grain shape and size, distribution,
– Crystal Structure
• Space group, Lattice parameter
• Texture, Clustering, Ordering
– Electronic Structure

• Defects and their concentration
– Point, Line, Planar
What to be characterized
What to be characterized
• Surface
– Morphology
• Porosity (size and concentration), Surface area
– Composition
– Structure
• Defects

• Volume, Thermal Stability, etc.
– Internal stress, Nature of stress and distribution
– Phase Stability
General procedure
Probe source
Input to specimen
Signal-matter interaction
Data collection and
processing
Interpretation
• Matter Wave
– Acoustic, Ultra-sonic
• Electromagnetic (EM) Wave
– RF, IR, Visible, UV, X-ray, gamma-
ray
• Elastic scattering
– XRD spectra, TEM contrast image
• Inelastic scattering
– SE image in SEM, EELS
• 2D / 3D Image
– Microscopy
• Microanalysis
– Spectrum
• Diffraction
– Spectrum or pattern
Consideration in characterization
• Select only the items necessary
– Fit to the purpose of the research
– Not the every item and not the every detail should be characterized
– What characterization techniques to use? The items and the detection
limit (resolution, accuracy, etc.)
• Precision
– Standard deviation of measured value
– An instrumental and human error
• Accuracy
– Deviation from the true value
– Mostly human error
• Mostly we are NOT short of number and distribution of instruments, BUT of
personal earnestness to use it.
• Mostly we are just throwing our problem to instruments, the “black box”,
without understanding the principle/theory, and thinking/planning the
experiment.
• Dangerous is just looking at an convenient and expensive instrument.
Science is NOT a routine job, BUT is an ADVENTURE to find/develop new
technique/knowledge
• A big and sophisticate instrument is a money sink with loss of versatility. The
order of detection limit and precision goes with the order of price, time, and
human salary.

*Rustum Roy, 1982
Consideration in characterization
Nomenclature of Techniques
Ion Electron Visible ray X-ray
Ion SIMS
Electron
TEM, SEM,
AES
EDS
WDS
Visible
ray
OM
X-ray XPS XRF, XRD
• Typically follows (but it is not a definite practice)
– {(Input signal), (underlying physical phenomenon)} + (Analysis)
• Examples:
– Transmission electron microscopy (TEM)
– X-ray Photoelectron Spectroscopy (XPS)
– Secondary Ion Mass Spectroscopy (SIMS)
Input
signal
Microstructural scale
Limitation – human eye
 Limited to “VISIBLE” light : wave length of 0.4 ~ 0.7 µm
 Limited detection time : integration time ~ 0.1 s
 Limited resolution
Sensitivity of human eye is
comparable to the military
night vision camera, which
has longer integration time
Resolution – general concept
각막
망막
수정체
홍채
동공
시신경
유리체
Abbe’s criterion:
For the eye:
α µ
λ
sin
61 . 0
2
= =
d
R
mm R 2 . 0 ≈
13 %
Raleigh criterion
d
Resolution – microscopy
eye
eye
eye
R MR
R MR
R MR

>
<
: eye cannot resolve all the features in magnified image
: magnified image appears blurred in eye
: eye can resolve all the features in magnified image
• Maximum value of R in light microscopy ~ 0.2 µm
• Therefore, effective magnification will be 10
3
• Use electron as probe source
• λ ~ 0.037V
-1/2
nm (V in kilovolt)
• R ~ 0.61λ / α (because α is very small in electron microscopy)
• Sub-nano scale resolution can be obtained
0.2 mm
0.2 mm
0.2 mm

3. Basic crystallography
Lattice and crystal structure
• Lattice point : a point in crystal which has an identical environment
• Lattice : set of lattice points
• Unit cell : a space-filling parallelepiped with origin at a lattice point
(constructed by lattice vectors)
Wallpaper
14 Bravais lattice
P : primitive, I : body-centered, F : face-centered, C : base-centered
Why not tetragonal-C ?
Crystal structure
• Lattice point : imaginary point in space
• Real crystal structure : atomic arrangement

• Crystal structure = lattice point + motif




• Cubic F + Cu at each lattice point = crystal of Cu
• Cubic F + C at 0,0,0 and ¼, ¼, ¼ = crystal of diamond
single or group of atoms
assigned to lattice point
lattice points Motif (Cu at 0,0,0 and Zn at ½, ½, ½)
• Cubic P + Cu at 0,0,0 and Zn at ½, ½, ½ = crystal of brass
Space group
• Combination of atomic arrangement around lattice points in 14
Bravais lattices  230 space group
• It provides criteria for filling the Bravais lattice point with groups
of atom
Crystallographic direction and plane
<u v w> : set of directions having equivalent properties
• Do not take reciprocal
• Always start from the origin
• Put direction in [ ] or in < >
for family of direction
{h k l} : set of planes having equivalent properties
Crystallographic direction and plane
Miller indices are written as [hkil] or (hkil) where, in all cases, the index i
is derived from h and k according to i = -(h+k) . Since the third index i
is not independent of the h and k, it is sometimes even omitted, and the
indices appear as [hk•l].
a1
a2
a3
a1
a2
a3
P
0,0,0
Miller-Bravais
Unit Cell
Miller Unit Cell
Miller:
[110] equals
Miller-Bravais
[1120]
Crystallographic direction and plane
Pyramidal plane (1
st
)
Prism plane (1
st
)
Basal plane
Prism plane (2
nd
)
Crystallographic direction and plane
Stereographic projections
• 2 dimensional presentation of crystallographic plane and direction
* The shortest distance between two points
on a sphere is along the great circle passing
through those points
Wulff net
• Angle between two arbitrary poles can be measured by rotating
the Wulff net until they lie on a great circle
Stereographic projections
• Stereographic projection in cubic system, where plane normal and
crystallographic direction with the same indices coincide

4. Diffraction analysis of crystal structure
Part 1
- Scattering and diffraction
- Conditions to observe diffraction in crystalline materials
(diffraction angle and intensity)
- Representation of diffraction in reciprocal lattice
Scattering of incident radiation
• Incident beam (X-ray, electron, neutron) interacts with matter
(electron or nuclei) to make scattered radiation
Scattering and diffraction
• Scattering implies interacting of incident beam with atom (radiating to all direction)
• When matter has a periodic array of atom, the arranged atom scattered the incident beam
in a specific direction, as we observe the intensity of scattered radiation as a function of
scattered angle (that is why we can use diffraction analysis to examine crystal structure)
Incident beam for diffraction
• The wave length of incident beam should be less than interatomic
spacing of lattice
• Possible candidates for incident beam : X-ray, electron, neutron
• Neutron
- Interaction with nuclei  improved efficiency for light atoms
- Usually penetrating sample
• X-ray
- Interaction with electron  good results for atoms with higher Z
- Diffraction occurs in sub-millimeter surface
• Electron
- Diffraction data is limited to submicron
Diffraction angle from crystal
• Scattered radiation from successive layer of
specific crystallographic plane (hkl) should
be in-phase
• If not, the scattered radiation will cancel out
to each other
Diffraction angle from crystal
θ1 θ1 θ1
x
1 2 1’ 2’
0 cos cos
1 1
= − θ θ x x
Bragg’s law
θ λ sin 2d n =
For cubic crystal:
2 2 2
l k h
a
d
hkl
+ +
=
( )
2 2 2
2
2
2
4
sin l k h
a
+ + =
λ
θ
• Bragg’s law is the minimum condition for diffraction
• This equation predicts, for a particular incident λ and a particular cubic crystal of
unit cell size a, all the possible Bragg angles at which diffraction can occur from
the plane (hkl).
• Diffraction directions are determined solely by the shape and size of the unit cell.
• All we can possibly determine about an unknown crystal by measurement of the
directions of diffracted beams are the shape and size of its unit cell.
• The intensities of diffracted beams are determined by the positions of the atoms
within the unit cell.
Intensity of diffraction
Bragg’s law condition
Structure factor Atomic scattering factor
Diffraction intensity from specific crystallographic plane
• We cannot observe the diffraction peak at all possible angle given by
Bragg’s law
• Atomic scattering factor results from the position of electron in an atom
• Structure factor is led by specific position of atom in the lattice structure
• And others...
Etc…
Atomic scattering factor
• Will the scattering intensity from an atom be the sum of scattering
intensity from all electron belonging to it ?
• Scattered radiation in wave front XX’ will be in phase, however, it is
out of phase at wave front YY’
 interference will decrease the intensity along this direction
Structure factor
• When atoms locate in corner of unit cell (ex. simple cubic structure), Bragg’s law
successfully predicts the angles where the diffraction occurs
• However, extra atoms exist (ex. body-centered position, face-centered position in
cubic lattice), it will affect the intensity of diffracted beam
• Out of phase when n=1 due to the scattering from body-centered
atom: (100) in BCC does not appear
• In phase when n=1 even with the scattering from body-centered
atom: (200) in BCC will appear
(n=1)
Structure factor
• FCC structure
- Extra atoms on plane parallel to (100), (110), (210), (211), …
• BCC structure
- Extra atoms on plane parallel to (100), (111), (210), …
Possible Forbidden
Simple cubic All None
Based centered h and k unmixed h and k mixed
Body centered (h+k+l) even (h+k+l) odd
Face centered h, k, l unmixed h, k, l mixed
Structure factor
• Plane with mixed ion : (200), (220) …  in phase interference
• Alternating plane with different ion : (111) …  in phase for even order diffraction
 out of phase for odd order diffraction
• Increasing or decreasing of diffraction intensity occurs
Structure factor
(100)
(110)
(200) reflection : 2
nd
order (100) reflection, usually not reflection from (200) plane
primitive BCC FCC
Reciprocal space and diffraction
• Reciprocal lattice : imaginary lattice where the direction of vector from origin to
(hkl) lattice point represent the plane normal of (hkl) plane in real lattice and the
magnitude is a reciprocal of plane spacing, 1/d
hkl
• From Bragg’s law, (1/d
hkl
) falls in the range of 0 ~ (2/λ), which constructs a limiting
sphere
• When we overlap this with reciprocal lattice, the reciprocal lattice points in the limiting
sphere have a potential to diffract the incident beam with wavelength λ

• Actually, when we construct another sphere called reflecting sphere with radius (1/ λ)
touching limiting sphere and origin, the reciprocal lattice points on the reflecting
sphere satisfy following vector relationship which is equivalent to Bragg’s law
Reciprocal space and diffraction
k g k = +
0
Reciprocal space and diffraction
• Wavelength of incident beam
- Deceasing wavelength  increasing diameter of sphere
 allowing diffraction with longer reciprocal lattice vector
 diffraction from higher indexed plane
• Angle of incident beam with respect to the crystal
- Rotation of incident beam or crystal rotation about its center allows all the lattice
point lying within limiting sphere to diffract
Reciprocal space and diffraction
• Effective size of reciprocal lattice point
- The size of lattice point is determined by size and imperfection of the crystal
- As crystal size decreases and imperfection increases, the size of lattice point
increase  diffraction occurs finite interval of angle rather than specific points
∆2θ
Reciprocal space and diffraction
• Variation of wavelength of
incident beam
• Inadequate collimation of beam
Both effect introduce errors in XRD analysis
Part 2
- Basic character of X-ray
- X-ray diffraction method
- Details on the intensity of diffracted beam
Generation of X-ray
• Heated filament (cathode) emits electrons by thermionic emission
• Electrons (1mA - 1A) are accelerated by a high voltage (30-150 kV)
• X-rays are produced when high speed electrons hit the metal target (anode)
• “Brehmsstrahlung (continuous)” and characteristic x-rays
Continuous X-ray
• Brehmsstrahlung
- “Braking radiation”, continuous, white radiation
- Decelerated electrons emit radiation (EM)
- Short wave length limit (for e
-
stopped in one impact)

V
eV
hc
v
c
hv eV
SWL
SWL
3
max
min
max
10 4 . 12 ×
=
= = =
=
λ
λ λ
Decelerated
[Å]
Characteristic X-ray
- Excitation energy required to
eject an electron from an inner
shell increases with Z
- Sharp intensity maxima at certain λs.
- Transition between the lower energy levels
Absorption of X-ray
• Mass absorption coefficient, μ/ρ:
a constant of material and independent of
its physical state (solid, liquid, or gas)
x
• For a mixture, a solution, a chemical
compound,…: the weighted average of the
mass absorption coefficients of its
constituents elements
( ) ( ) ( ) ( )
1 2
1 2
/ ... /
i
mixture i
i
w w w µ ρ µ ρ µ ρ µ ρ = + + =

w
i
: the weight fraction of element i
• When X-ray encounter any form of matter,
they are partly transmitted and partly
absorbed.
μ: Linear absorption coefficient
(dependent on the material, density, λ of x-rays)
| |
0
exp
x
I I x µ = −
( )
0
exp
x
I I x µ ρ ρ ( = −
¸ ¸
μ/ρ : Mass absorption coefficient
I
dx
dI
µ − =
Absorption of X-ray
• Discontinuous step called absorption edge
• It corresponds to the wavelength at which the incident X-ray has sufficient energy to
eject inner shell electron  generation of characteristic X-ray (X-ray fluorescence)
• Absorption of X-ray give a clue which target material is better for analysis on specimen
( Which one will be better for diffraction measurement of steel (E
FeK
=7.109 keV,
λ=0.174 nm) ?
Cu Kα radiation with wavelength 0.154 nm, Co Kα radiation with wavelength 0.179 nm)
Generation of monochromatic X-ray
• Filter out the continuous and other
characteristic X-ray (e.g. K
β
).
• A filter made of a material whose
absorption edge lies between the K
α

and K
β
of the target material.
• Such a materials will have an atomic
number one less than that of the target metal
• Example: Ni (Z=28) filter for Cu (Z=29)
radiation.
• The thickness of filter needs to be
compromised between reasonable
suppression of the K
β
component and the
inevitable weakening of the K
α
component.
(Ni)
K
K
hc
W
λ
=
( ) Cu
K L
K
hc
W W
α
λ
= −
Filter
Target
Kα Doublet
• The three strongest characteristic X-rays
λ
Kα1
= 1.540562 Å
λ
Kα2
= 1.544390 Å
λ

= 1.392218 Å
• K
β
can be filtered out easily.
• The λ difference between K
α1
and K
α2
are so small that they are not always
resolved as separate radiation → “K
α
doublet”.
• The intensity ratio of Cu-K
α1
and Cu-K
α2
lines is 2:1.
• The weighted average λ

is calculated as:
1.54184
3
2
2 1
=
+
=
α α
α
λ λ
λ
K K
K
X-ray diffractometer
θ-2θ Coupled Bragg-Brentano Geometry
Powder diffraction - 2θ scan
• General term describing diffraction spectrum formed and the subsequent analysis used
to interpret diffraction results obtained from polycrystalline materials
• Characteristic X-ray
• If the specimen rotating axis is perpendicular to incident beam and diffracted beam,
the crystallographic plane contributing the spectrum will be parallel (when we use
flat specimen, the crystallographic plane parallel to specimen surface will make
diffraction)
Single crystal Laue diffraction
• Determination of orientation of single crystal with respect to the incident beam
• Continuous (white) X-ray
Diffraction intensity
• Factors considering diffraction intensity from crystals
- Scattering from electron : polarization factor
- Scattering from atom : form factor
- Scattering from lattice : structure factor
- Lorentz factor
- Multiplicity factor
- Absorption factor
- Temperature factor
2
2
2
2
1 cos 2
sin cos
M
I F p e
θ
θ θ

| |
+
=
|

\ .
• Overall relative intensity in diffractometer
Diffraction intensity
2
2
2
2
1 cos 2
sin cos
M
I F p e
θ
θ θ

| |
+
=
|

\ .
• Multiplicity factor: The number of different planes in a form having the same
spacing (p = 8 for {111}, p=6 for {100} in cubic)
Combination of atomic
scattering factor and structure factor
Combination of polarization factor
and Lorentz factor (purely geometric)
2M
e

• Temperature factor:
Temperature factor of Fe at 20
o
C
• One of geometric effects
Atomic scattering factor
• Scattering from a single atom – form factor
• Scattered radiation in wave front XX’ will be in phase, however, it is
out of phase at wave front YY’
 interference will decrease the intensity along this direction
• The atomic scattering factor f(θ), or form factor, is defined as the amplitude scattered
by a single atom divided by that scattered by an electron



• In the direction of the incident beam, all the electrons in the atom will scatter in phase:
f(0) = Z. For θ > 0, f(θ) < Z, since at larger scattering angles the electrons around an
atom will scatter increasingly out of phase
• At a fixed value of θ, f will be smaller the shorter wave, since the path differences will
be larger relative to the λ, leading to greater interference between the scattered
beam


( )
electron single a by scattered Amplitude
atom one by scattered Amplitude
= θ f
Atomic scattering factor
• Scattering from a lattice – structure factor
- Diffraction occurs at (h00) plane satisfying
Bragg’s law
- If there is additional atom at position B,
h
a
d d
h h
= = =
00 00 ' 2 ' 1
, sin 2 λ θ δ
λ δ
|
.
|

\
|
=
h a
x
/
' 3 ' 1
- Relationship between path difference (δ)
and phase difference (φ)
a
hx π
π
λ
δ
φ
2
) 2 (
' 3 ' 1
' 3 ' 1
= =
λ
δ
π
φ
=
2
- If position of atom at additional is u=x/a,
hu π φ 2
' 3 ' 1
=
- Expanded into 3-dimensional
) ( 2 lw kv hu + + = π φ
Phase difference between scattering from B
atom at position of [u v w] and scattering from
atom at origin for (h k l) diffraction
Structure factor
• To consider the scattering from every atom in the lattice,
we have to superimpose the individual scattering wave
• Expression of scattering wave in complex plane makes it easy
| | ) ( 2 exp ) exp( sin cos lw kv hu i f i A iA A + + = = + π φ φ φ
| |

+ + =
N
n n n n hkl
lw kv hu i f F
1
) ( 2 exp π : Structure factor of (hkl) diffraction
Intensity of diffraction = | F
hkl
|
2

Structure factor
Calculation of structure factor
FCC structure (Cu) NaCl structure
(0 0 0), (½ ½ 0), (½ 0 ½), (0 ½ ½)
Na (0 0 0), (½ ½ 0), (½ 0 ½), (0 ½ ½)
Cl (½ ½ ½), (0 0 ½), (0 ½ 0), (½ 0 0)
n i n
e ) 1 (− =
π
Diffraction intensity
• Calculation of diffraction intensity of ZnS
Distortion in diffraction intensity
• Preferred orientation

- Standard spectrum has been collected from standard sample with fine powder
- Peak location and relative peak intensity from randomly oriented powder

- However, some manufacturing process generates quite aligned crystallographic
orientation which is called as texture or preferred orientation

- Development of preferred orientation can change the relative peak intensity or even
make certain peak invisible
Random orientation
Strong texture
Distortion in diffraction intensity
• Residual stress
- Residual stress can affect the peak position and
relative intensity

- Macrostrress
: large number of neighboring crystals of the same
phase experience similar stress level
: displacement of the diffraction maxima from the
original position

- Microstress
: the stresses in the individual grains is widely
different and of opposite sign, while the average
stress sums to zero
: peak broadening

- Peak shift or broadening can be used to determine
the residual stress level in the sample
However, the measurement is confined to surface
layer
Distortion in diffraction intensity
• Crystalline size
- Smaller the crystalline size makes the diffraction
peak to be widened

- It comes from incomplete destructive interference
of diffracted beam

- The incident X-ray beam is not perfectly parallel and
it includes a range of incident angle from θ
1
~ θ
2

- The diffracted beam at off-Bragg angle will be
canceled out by destructive interference with
diffracted beam having phase difference of a half
wavelength
Part 3
- Determination of crystal structure and lattice parameter
- Quantifying phase fraction
- Measurement of pole figure
JCPDS cards
• Note that standard X-ray data are obtained from powder sample of perfectly random
orientation
• Relative intensities among diffraction peaks of a non-powder samples can be different from
the standard because perfect randomness of grain orientation in solid samples is rare
• Diffraction data by ICDD (International Center for Diffraction Data)
Crystal structure and lattice parameter
( )
2 2 2
2
2
2
4
sin l k h
a
+ + =
λ
θ
( )
( )
1
2
2
1
2 2
2 2
1
2
1
2
1
2
1
2 2 2
sin
sin
sin
sin
θ
θ
θ κ
θ κ
i i i i i i
l k h
l k h
= =
+ +
+ +
1. X-ray spectrum from an unknown metallic specimen 2. Normalize all the equations relative to
the equation for the first reflection:
3. Confirm that the material has a
BCC structure.
4. Calculate a lattice constant from each peak and report the average value:
(for λ = 0.154056 nm) a = 0.2867 nm ⇒ BCC α-Fe a = 0.2864 nm
Quantifying lattice parameter
( )
R h
θ
θ
θ 2 180 sin
sin /
2 sin −
=

R
h θ
θ
cos 2
2 ≅ ∆
a
a
k
R
h
d
d ∆
= = ⋅ =

=

θ
θ θ
θ
θ
θ
θ
sin
cos cos 2
sin
cos
tan
2
2
• Major error in determination of lattice parameter is placing specimen either above or
below the focal point on the goniometer axis
• Errors in lattice parameter measurements can be reduced by extrapolating the values
calculated from each peak to a (hypothetical) value for θ = 90°
• Plot the lattice parameters as a function of cos
2
θ /sin θ and extrapolate to 0
Quantifying phase fraction
• The apparent lattice parameter for Ni, determined from the individual reflections and
using the known relationship between hkl and the lattice parameter for a cubic
structure, has been plotted as a function of cos2θ/sinθ
• The systematic errors are quite small, and the best value for the measured intensity
parameter is obtained by extrapolating to θ=π/2: a = 0.3522(6)nm
• This is close to the value listed both by the JCPDS (a = 0.35238nm) and in Pearson’s
Handbook of Intermetallic Phases (a = 0.35232nm)
Quantifying phase fraction
• Integrated intensity measured from diffractometer
|
|
.
|

\
|
(
¸
(

¸

|
|
.
|

\
| +
|
.
|

\
|
(
(
¸
(

¸

|
.
|

\
|
|
|
.
|

\
|
=

µ θ θ
θ
π
µ
π
λ
2 cos sin
2 cos 1 1
4 32
2
2
2
2
2 2
4
2
0
3
0
M
e
p F
v m
e
r
A I
I
α
α
µ
1
K
I
P
= For pure material α,
For α in the mixture,
α α
µ
C
K
I
m
1
= (C
α
is volume fraction, µ
m
is absorption coefficient of mixture)
• The linear absorption coefficient depends on the amount of each phase present in the
mixture:
|
|
.
|

\
|
+
|
|
.
|

\
|
=
β
β
β
α
α
α
ρ
µ
ω
ρ
µ
ω
ρ
µ
m
m
ω: the weight fraction of the phase,
ρ: the density of phase
• Rearranging the two equations:
( )
β β α α
α
α
µ µ µ + −
=
C
C K
I
1
β β α α
α α
α
ρ ρ ρ ω
ρ ω
/ 1 ) / 1 / 1 (
/
+ −
= C
Quantifying phase fraction
• Combining with :
| |
β β β β α α α α
α
α
ρ µ ρ µ ρ µ ω ρ
ω
/ ) / / (
1
+ −
=
K
I
• Comparing intensity with pure material:
β
β
β
β
α
α
α
α
α
α
α
α
ρ
µ
ρ
µ
ρ
µ
ω
ρ
µ
ω
+
|
|
.
|

\
|

|
|
.
|

\
|
=
p
I
I
,
Quantifying phase fraction
• If standard sample is not available
(quantification of austenite fraction in quenched steel or TRIP steel)
|
|
.
|

\
|
(
¸
(

¸

|
|
.
|

\
| +
|
.
|

\
|
(
(
¸
(

¸

|
.
|

\
|
|
|
.
|

\
|
=

µ θ θ
θ
π
µ
π
λ
2 cos sin
2 cos 1 1
4 32
2
2
2
2
2 2
4
2
0
3
0
M
e
p F
v m
e
r
A I
I
M
e p F
v
R
m
e
r
A I
K
2
2
2
2
2
2
4
2
0
3
0
2
cos sin
2 cos 1 1
4 32

(
¸
(

¸

|
|
.
|

\
| +
|
.
|

\
|
=
(
(
¸
(

¸

|
.
|

\
|
|
|
.
|

\
|
=
θ θ
θ
π
µ
π
λ
: independent of materials chemistry and quantity
: dependent on θ, (h k l), crystal structure, lattice parameter
µ 2
2
R K
I =
Quantifying phase fraction
• Two phases of austenite and martensite coexist in material with volume fraction of
Cα and Cγ, respectively
α α
γ γ
α
γ
α
α
α
γ
γ
γ
µ
µ
C R
C R
I
I
C
R K
I
C
R K
I
m
m
=
=
=
2
2
2
2
• Combining with
we can evaluate volume fraction
of austenite in steel
1 = +
γ α
C C
Preferred orientation
Anisotropy in wood is well appreciated
Why is this anisotropy happened?
Just orientation of the texture is different
E(111) = 276 GPa
E(100) = 129 GPa
E(average)=209 GPa
Pole figure
The Pole Figure plots the orientation of a given plane normal (pole)
with respect to the sample reference frame. The example below is
a (001) pole figure. Note the three points shown in the pole figure a
re for three symmetrically equivalent planes in the crystal.
It is a kind of stereographic projection of specific pole with respect to the specimen orientation
Pole figure and powder diffraction
Bragg equation: 2d sinθ= λ
- XRD powder diffraction pattern: λ=constant,
measuring I(θ)
Powder
, determining d
hkl

- XRD pole figure measurement: λ, θ
hkl
=constant,
measuring P
hkl
(α,β)=I(θ
hkl
)
sample
/ I(θ
hkl
)
Powder
,
determining texture components
RD
P
111
(α,β) ?
α
β
(001) pole figure showing random orientation
and preferred orientation
TD
RD
Pole figure construction
• Select specific pole of interest (h k l)
which determine diffraction angle, θ
• Starting from φ=0, ϕ=0 (origin),
measure the intensity as increasing
the angle and plot in RD/TD stereogram
TD
Interpretation of pole figure
{100}<011>
{100}<001>
Pole figures of Cu

5. Issues in optical microscopy
- General aspects of optical microscope
- Sample preparation
- Confocal laser microscope
Structure
Resolution
• Abbe image of point source
- Intensity of primary and secondary peak
is 9 : 1
- Width of primary peak is
α µ
λ
δ
sin
2 . 1 =
• Raleigh’s definition of optical resolution
- Separation of two sources of equal
intensity ensures that the maximum of the
primary image peak from one source
should fall on the first minimum of the
image of second source
• µsinα = NA (numerical aperture) ~ 1 for air
~ 1.5 for oil
• Resolution of optical microscope ~ 0.2 µm
α µ
λ
sin
61 . 0 = R
Depth of field
α α µ
λ
α α tan sin
22 . 1
tan
2
tan
= = =
R d
D
f
• Typical value of D
f
in optical microscope ~ 0.5 µm
• This is why very flat surface without any slope is required for specimen preparation
Sample preparation
• Cutting  Mounting  Grinding  Polishing  Etching
Hot mounting Cold mounting Grinding and polishing
Etching
• Generating desired contrast
• Etchant selectively dissolve areas of the specimen
because of the differences in the electrochemical
potential
• Macroetching
- observation of macrostructure
- solidification pattern / chemical uniformity
- strain pattern
• Microetching
- observation of microstructure
- grain size and shape
- revealing constituent phases and carbides
Etching
• Selection of proper etchant is most important
• “Metallographic Etching” by Günter Petzow
• Some etchant is very toxic - safety
3% Nital
- revealing the grain structure
- ferritic / bainitic / martensitic phase
Sodium metabisulfite
- revealing retained austenite
Confocal laser microscope
The reflection beam out of focus are eliminated
from the image by using confocal pinhole
Confocal laser scanning microscope
Confocal laser microscope
• Resolution comparable to conventional optical microscope
• High temperature observation

6. Scanning Electron Microscopy
Part 1
- Structure of SEM
- Electron beam-specimen interaction
- Image contrast (Elements map, BSE, SE)
Structure
Principle
Scanning technology
Construction
• Electron column : electron gun, electromagnetic lens, aperture
• Specimen stage : x, y-translation, z-control, tilt-control
• Detector : SE detector, BSE detector, EDS
• Control console : electron gun / lens control, detector control, magnification control,
viewing and photography controls
Magnification
Pixel by pixel image
Area scanned on screen
Comparison with light microscope
Electron Microscope Light microscope
Source Electron beam Visual light
Wavelength
0.086 Å (20kV) –
0.025 Å(200kV)
7,500Å – 2,000 Å
Medium Vacuum Air
Lens Electromagnetic Glass
Resolution ~ 6 - 60 Å ~ 2,000 Å
Magnification 100 – 450,000 X 10 – 1,000 X
Depth of field Large Small
Contrast Scattering / Diffraction Reflection / Absorption
Depth of field
M
size pixel R d
D
f

≈ = =
α α α
) ( 2
tan
2
tan
Depth of field
Atomic number
& topological info
Topological info
Compositional info
(through thickness)
Compositional info
(surface sensitive)
Electron beam – Specimen interaction
+
≤ 10
o
- -
-
- -
-
+
- -
-
- -
-
-
-
-
-
wide angles small angles
Inelastically scattered primary electrons:
interaction with conduction electron
Elastically scattered primary electrons:
interaction with nuclei
Primary backscattered
electrons
Secondary
electrons
Direction changes, but
electron energy does not
The electron energy changes, but
the direction does not change
much (~0.1
o
)
Characteristic X-ray
~0.1
o
Elastic and inelastic scattering
Interaction volume
E = kT
• Interaction volume : How far can a incident electron travel in the specimen before
being absorbed ?
• Diffusion depth : Depth beyond which the electrons can be assumed to be randomly
scattered. Limiting depth where BSE electron can come out.
• Penetration depth : Depth at which the electron energy is reduced to the thermal energy, kT.
Limiting depth where characteristic X-ray originates.
Beam energy and interaction volume
Iron sample
Generation of secondary electrons
SE coefficient:
• One primary electron can create several secondary electrons
1 > = =
B
SE
B
SE
i
i
n
n
δ
• Inelastic interaction between the incident beam
with electrons in the sample.
• Inelastic interaction between backscattered
electrons and electrons in the sample.
δ
Total
= δ
incident
+ η δ
BSE


δ
BSE
: secondary yield from BSE
η : backscattered yield
Generation of secondary electrons
Electron energy
Electron Energy
E
l
e
c
t
r
o
n

E
m
i
s
s
i
o
n

(
c
u
r
r
e
n
t
)


a
t

a

S
p
e
c
i
f
i
c

E
n
e
r
g
y

10 eV 50 eV
5 eV
Energy of incident electron
Resolution of signals
• Resolution in an SEM is
ultimately determined by
the size of the region from
which signal is produced.
Thus, for the same region
of excitation the resolution
from the three signals
differs and decreases from
secondary to backscatter
to X-rays.
• Factors affecting size of the interaction region:
- Diameter of the primary beam
- Energy of the primary beam
- Atomic weight of the specimen
- Coating of specimen
Resolution of signals
BSE
SE
Image contrast from BSE
light element heavy element
• No significant difference in secondary
electron coefficient depending on Z

• Back-scattered electron coefficient
increases with increasing Z
• Fraction of back-scattered electron
as a function of the average atomic
number
• BSE image of polished surface
Nb-rich intermetallic
compound (heavy)
Alumina matrix
(light)
• Crystallographic (or channeling) contrast of BSE
- The plane orientation affects the penetration of the electron beam into the
crystal because the atomic packing density varies with crystallographic plane.
- The BSE coefficient (η) is dependent on the orientation of crystallographic
planes with respect to the direction of the electron beam (For higher penetration,
the η is lower).
Electron channeling contrast
BSE detector in SEM
Image contrast from SE
• Contrast effects in S.E. image are due to surface topography, or more precisely,
to the local curvature of the surface.
• Changes in local curvature change the probability that a S.E. generated near the
surface can escape. Edges look bright, flat surfaces look dull.
Fracture surface of polycrystalline alumina
r : distance needed to escape from sample
L
s
: mean free path of secondary electron
Image contrast from SE
• Location of ET detector leads to shadowing
• Increasing the detector bias will wash out the shadows.
• Previous image turned upside down.
• We need to know where the detector
is to tell bumps from pits!
Positive voltage
Trajectory effect
S.E. B.S.E.
Resolution nm’s ~10
2
nm
Energy eV’s (<50 eV) ~E
0
(0.8E
0
)

R (interaction volume) ~nm μm’s (R = f(E
o
))
Contrast Topography Z
Yield 100% + < 50%
Summary of SE and BSE
Part 2
- Image quality in SEM
- Focused ion beam microscopy
Operation of SEM
Factors affecting image quality
kV
Probe
current
Aperture
size
Working
distance
Operator
• Acceleration voltage (kV)
⇒ Control of probe diameter
• Current of condenser lens
⇒ Control of probe diameter
⇒ Control of probe current
α
p
: Probe convergence angle
i
p
: Probe current
d
p
: Probe diameter
• Size of objective lens aperture
⇒ Control of probe convergence angle
⇒ Control of probe current
• Z-control of sample stage
⇒ Control of working distance
⇒ Control of probe convergence angle
Acceleration
Voltage
HIGH
LOW
• High resolution
• Unclear surface structure
• More edge effect
• More charge-up
• More damage
• Clear surface structure
• Less edge effect
• Less charge-up
• Less damage
• Low resolution
4
1
4
3
S p
C d λ ∝
Effect of acceleration voltage
probe diameter
α
λ 22 . 1
= d
Effect of acceleration voltage
- resolution and surface structure

- Low voltage (1 kV)
- High voltage (20 kV)
5 kV
20 kV
Effect of acceleration voltage
- edge effect

Effect of acceleration voltage
- specimen charge-up

Generally, specimen
charge-up is reduced by,

• Reducing beam current
• Lowering acc. voltage
• Tilting the specimen
Effect of probe current
Probe Current
HIGH
LOW
• Smooth image • Deteriorated resolution
• More damage
• High resolution obtainable
• Less damage
• Grainy image
2
1
2
2
4
|
|
.
|

\
|

f
p
p
i
d
α βπ
probe diameter
Smooth
Grainy
1 nA
0.1 nA
10 pA
Effect of probe current
Aperture Size
LARGE
SMALL
• Large current
(X-ray analysis)
• Higher resolution
(less diffraction aberration)
• Lower resolution
(larger spherical aberration)
• Smaller depth of field
• Lower resolution
(larger diffraction aberration)
• Higher resolution
(less spherical aberration)
• Greater depth of field
3
2 α
s sph
C d =
α
λ 22 . 1
= d
Effect of aperture size
α α
R R
D
f
2
tan
2
≈ =
Working
Distance
LONG
SHORT
• Greater depth of field • Low resolution
• High resolution
• Smaller depth of field
Effect of working distance
AP
f
r
WD R R R
D
) ( 2 2
tan
2
≈ ≈ =
α α
(tanα ≈ α for small α)
Large OL A.P.
Small WD
Small OL A.P.
Large WD
Effect of aperture size and WD
Conduction coating
• Conduction coating is usual practice in observing non-conducting
material to avoid electrostatic charge-up which deteriorates image
quality.

• However, metallic coating interfere with the chemical microanalysis.
In that case, carbon coating will be another option.

• Or reducing acceleration voltage will effectively avoid charge-up in
specimen.
Focused ion beam microscopy
Filament
Ceramic Base
Filament Support Pins
Why Ga as liquid metal ion source ?

• A liquid metal for room temperature operation (melting point of 29
o
C)
• Long life (up to 1500 hrs)
• Heavy ion sputtering (atomic number 31)
FIB column
• Source
: LMIS (liquid metal ion source) at tip
• Focusing
: electrostatic lens
• Deflection assembly for scanning
• Beam blanking
: need to prevent milling on sample
• Limiting aperture
: control beam current incident on
sample
Ion – matter interaction
• Sputtering
: Neutral atoms / secondary ions
• Backscattered ions
• Lattice defects
: vacancies, interstitials, dislocations
• Secondary electrons
• X-ray
Image contrast
• Secondary electron mode
- Detector biased positive
- Image generated by SE-
- Emitted from to 5 – 10 nm
- Grounded metals very bright,
oxide dark
• Secondary ion mode
- Detector biased negative
- Image generated by SI+
- Emitted from to 0.5 – 1 nm
(very surface sensitive)
- Oxide brighter
- Lower yield, so images noisier
- Ion channeling contrast
SI Detector
SE Detector
Image contrast
SE image SI image
Ion channeling
• Similar to electron channeling, there is strong influence of ion range
due to crystallographic packing of target atoms – ion channeling

• Channeled ions travel deeper into the target material
: reducing sputter yield and number of SI

• Non-channeled ions stop closer to the surface
: increasing both sputter yield and number of SI (increasing contrast)

• Ion channeling contrast on polished surface led by orientation difference
Milling and deposition
• Micro-milling
: ion beam is used to remove appreciable
quantities of sample

• Gas-assisted etching
: reactive gases are delivered to the sample
surface by needle
: interaction of ion beam with the gas causes
formation of evaporable volatile species
which are pumped away by vacuum system

• Gas deposition
: metallorganic gases are delivered to the
sample surface by needle
: dissociation of gas molecules on the exposure
to the ion beam
: deposition of the metallic atom and removal of
organic ligands

Milling and deposition
Sample : Al 6061 T651
• Dual Beam = SEM + FIB
• FIB = Focused Ion Beam
• SE image in SEM - nm resolution
Beams
Coincidence
Point
Fabrication
Characterization
Single Beam
Cut
Tilt
Adjust
Imaging
Cut
Adjust
Re-tilt
Cu
t
Image
Cu
t
Dual Beam
 HR SEM Image Resolution & Damage Reduction
Dual beam FIB system
Single Beam Dual Beam
TEM specimen preparation
Lift-out method
TEM specimen preparation
3D imaging
3D morphology of dendrite
Ion irradiation damage
• Ion implantation – Ga atoms remain in the target material and may reach
critical composition for second phase formation

• Amorphization of surface – loss of crytallinity

• Lattice defects
: Vacancy – displaced or missing atoms from their equilibrium lattice positions
: Interstitials – atoms which are positioned between equilibrium lattice positions
: Dislocations – a missing half-plane of atoms

• Local heating – large displacement of atoms that may occur within the collision
cascade (~10’s of nanometers from surface)
Part 3
- Principles and application of EBSD
EBSD and OIM
In
2
O
3
film grown on MgO substrate
Formation of Kikuchi Pattern in TEM
Bright and dark parallel lines pair
⇒ Sensitive to crystal orientation
Incident Beam
Specimen
nλ=2d sinθ (Bragg’s Law)
Specimen
Ewald
Sphere
Photo from
CAM Michigan
State University
Formation of EBSD Pattern in SEM
• Atoms in the material inelastically scatter
some of the electrons with a small loss
of energy
• Some of these electrons are incident on
atomic planes at angles which satisfy
the Bragg condition
• Diffraction Pattern
: Bright Bands corresponding
to (hkl) plane
EBSD system in SEM
Incident beam size : Increase
⇒ Bad resolution
: Optimum = 70
o
Increase
Orientation determination
- Relationship between sample and crystal coordinate
Rotation matrix with reference coordinate – K
A
& K
P
, K
B
& K
P
⇒ Rotation matrix between K
A
& K
B
: Orientation
Comparison of X-ray and EBSD
X-ray EBSD
Spatial Resolution mm scale 10-50nm
Sample preparation Very Easy Slightly difficult
Data Acquisition Indirect Direct
Site of Orientation Average Unique point
Texture Analysis Macrotexture Microtexture
Analysis of
crystal structure
Possible
Practically not
recommended
Representation of orientation
• Same shape, Different color?
: To present specific orientation, at least two pictures
are required.
ND RD
Misorientation
(
(
(
¸
(

¸

=
33 32 31
23 22 21
13 12 11
21
a a a
a a a
a a a
M
2
) 1 a a a (
cos
33 22 11
− + +
= θ
21 12 13 31 32 23
a a : a a : a a W : V : U − − − =
1
2 1 21
2 21 1
g g M
g M g

⋅ =
⋅ =
g
1
: orientation matrix of lattice1
g
2
: orientation matrix of lattice2





M
21
: Misorientation matrix between
two lattices
Misorientation
• Equivalent misorientation
: In low symmetry materials,
same misorientation can be
presented in several rotation
matrix.
(Cubic :24, Hexagonal : 12)


• Among the equivalent rotation
relationship, the misorientation
shows minimum rotation angle
⇒ Real misorientation
(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

(
(
(
¸
(

¸

0 1 0
1 0 0
0 0 1
1 0 0
0 0 1
0 1 0
0 0 1
0 1 0
1 0 0
0 1 0
1 0 0
0 0 1
1 0 0
0 0 1
0 1 0
0 0 1
1 0 0
0 1 0
0 1 0
0 0 1
1 0 0
0 1 0
0 0 1
1 0 0
0 0 1
1 0 0
0 1 0
0 0 1
1 0 0
0 1 0
0 1 0
0 0 1
1 0 0
0 0 1
1 0 0
0 1 0
0 1 0
0 0 1
1 0 0
1 0 0
0 0 1
0 1 0
1 0 0
0 1 0
0 0 1
1 0 0
0 0 1
0 1 0
0 1 0
1 0 0
0 0 1
1 0 0
0 1 0
0 0 1
0 1 0
1 0 0
0 0 1
0 0 1
0 1 0
1 0 0
1 0 0
0 1 0
0 0 1
0 0 1
0 1 0
1 0 0
0 0 1
0 1 0
1 0 0
1 0 0
0 1 0
0 0 1
Matrices representing the 24
symmetry operations for the
cubic system
Strongly textured Material
PQ map
5 Degree
grain ID
θ θ ≤
gb
15 Degree
grain ID
Identification of grain
Boundary Grain for tion Misorienta Critical
Pixels Adjacent between tion Misorienta
=
=
gb
θ
θ
Identification of grain
a) SE Image c) RD b) ND
d) 3degree grain ID e) Misorientation map f) Misorientation Histogram
Phase identification
10µm
Matrix: Austenite
Oxides
EDS assisted phase identification
Surface may contain residual strain
or damage after etching
Residual strain by mechanical polishing
• Removal of damaged layer
: Electro or chemical polishing, ion milling
: Sample preparation is the key technique to obtain good EBSD results
SE image Phase map
Importance of surface condition
RD map


7. Energy dispersive spectroscopy
Wavelength dispersive spectroscopy
- Principles and application of X-ray spectroscopy
Characteristic and continuous X-ray
Level to level transition Deceleration of the electrons
in Coulombic field
X-ray spectroscopy
• Determination of presence and quantities of chemical elements
by detecting characteristic X-ray that are emitted from atoms
irradiated by a high-energy beam.

• Chemical elements can be identified either from the X-ray
wavelength or energy.

• X-ray florescence spectroscopy and microanalyzer in electron
microscopy.

• XRF uses X-ray radiation to excite the emission of characteristic
X-ray from sample.

• Microanalyzer in electron microscopy uses primary electron beam
to excite the emission of characteristic X-ray from sample.

Selection rule in transition
n : principal quantum number defining shell
l : angular quantum number
m : magnetic quantum number defining the number of energy state in subshell
s : spin quantum number defining two spin moments
J : total momentum (l+s)
• Change in n must be at least 1 (∆n ≥ 1)
• Change in l must be 1 (∆l = ± 1)
• Change in J must be either 0 or 1 (∆J = ± 1 or 0)
Transition from L1 to K is forbidden
Features in characteristic X-ray
Fluorescent yield
• Atom’s ability to generate characteristics X-ray varies.
• Emission competition between X-ray photon and Auger electron.
• Competition among generations of K, L and M series of the X-ray.
• Fluorescence yield – relative effectiveness of X-ray generation.
~ 4
X-ray spectroscopy is intrinsically disadvantageous for detection of light elements
X-ray fluorescence spectroscopy
Wavelength dispersive spectroscopy
• Consisting of X-ray tube, collimator, analyzer crystal and photon counter.
• WDS provides better resolution than EDS although its instrument is rather complicated.
• Resolution in wavelength is 0.002 – 0.02 (∆λ/λ) which corresponds to energy resolution ~10 eV.
(one order magnitude better than EDS)
• Modern WDS system can detect elements from upward of C (Z=6).
Analyzing crystal
• In WDS system, analyzing crystal determines
the range of detectable atomic number.

• Wavelength detected by crystal,

• Maximum achievable angle ~ 73
o
.

• Maximum wavelength of characteristic X-ray
being diffracted is about 1.9d

• Longer wavelength (lighter element) requires
analyzing crystal with larger plane spacing
n
d θ
λ
sin 2
=
WDS spectrum
• Ni-base super alloy (a) LiF crystal and (b) TAP crystal
• Combinatory use of analyzing crystal is required to scan wide range of wavelength.
• Although an analyzing crystal with small d-spacing limits the range of detectable atomic
numbers, the small d-spacing can increase angular dispersion which provides higher
resolution.
θ λ
θ
cos 2d
n
d
d
=
Energy dispersive spectroscopy
• Detector collects the signals of characteristic X-ray energies from a whole range of
elements in a specimen at the same time.
• EDS system does not have moving part such as rotating detector, so it is structurally
simple.
• Typical resolution of EDS is ~140 eV that is worse than WDS ( ~10 eV)
• Lightest element that can be detected is O (Z=8), not C (Z=6)
• Low cost and fast analysis
Detector in EDS system
• Si detector is commonly used.
• The average energy of photon needed to
generate an electron-hole pair is ~3.8 eV
in Si diode
• The higher photon energy comes, the more
pairs are generated.
• The characteristic X-ray photon is separated
by their energy levels according to the number
of electron-hole pairs they generate.
2 2
)] ( 35 . 2 [ FE e R
i noise
+ = σ
- Electronic noise which is strongly
dependent on temperature.
- Detector usually operates at the
temperature of liquid nitrogen.
EDS spectrum
• EDS is a standard part of modern SEM and TEM.
• The reason to use EDS rather then WDS is compactness.
• EDS in electron microscopy uses high energy electron beam as a source to excite
characteristic X-ray.
• EDS in electron microscopy is useful for analyzing the chemical elements in microscopic
volume because the electron beam can be focused on a very small area (microanalysis).
Emission volume
3 gram/cm
3
10 gram/cm
3
• The characteristic X-ray are excited from a volume under the surface of the specimen,
not from an area on the surface.

• In particular, EDS analysis using SEM, the EDS signal are emitted from a lateral area
that is much larger than the probe diameter.

• To obtain a better spatial resolution, we should choose an accelerating voltage that is not
much higher than that necessary to excite the required characteristic X-ray.
X-ray production regions with different mass
densities.
Emission volume
• For thin specimen as used in TEM, the spatial resolution is of less concern.

• The lateral size of the emission volume is not significantly larger than the probe size
because the thinness of specimen limits the spread of the emission volume.
Analysis mode - point analysis
STEM BF image of Ti-Mo-Nb
steel aging at 650
o
C for 24 hrs
1
2
1
2
Analysis mode - line scan
30nm
~7nm ~4nm
Ti-Mo-Nb steel aging at 650
o
C for 24 hrs
Center
Edge
Matrix
Ti-Mo steel aging at 700
o
C for 120 hrs
Ti
Nb
Mo
Analysis mode - elements mapping

8. X-ray photoelectron spectroscopy
Auger electron spectroscopy
- Principles and application of surface sensitive spectroscopies
Surface analysis
Why do we need to know the chemistry of surfaces?
• Reactions at surfaces
• Substrates for deposition
• Oxidation processes
• Corrosion
We need to measure the surface and near-surface chemistry!
IF steel
AHSS (Si, Mn)
Vacuum
• The SI unit of pressure is the Pascal (1 Pa = 1 N m
-2
)
• Normal atmospheric pressure (1 atm)
1 atm = 101325 Pa or 1013 mbar (1 bar = 10
5
Pa)
• 1 Torr = 1 mmHg, 1 atm = 760 Torr (i.e. 1 Torr = 133.3 Pa)
Rough vacuum 1 - 10
-3
Torr Rotary vane pump
Medium vacuum 10
-3
- 10
-5
Torr Booster pump
High vacuum 10
-6
- 10
-8
Torr
Diffusion pump
Turbo molecular pump
Ultra-high vacuum < 10
-9
Torr
Titanuim Sorption pump
Sputter ion pump
Surface analysis in vacuum
- Reduce the change of low-energy electrons being scattered by
gas molecules on their way to reach the detector
Mean free path (λ):
Average distance between collisions with gas molecule
P N
RT
P N d
RT
A
A
σ
π
λ
44 . 1
2
2
= =
Where,
d: Diameter of molecule
σ: Collision cross section (= πd
2
)
N
A
: Avogadro’s number (= 6.022 x 10
23
molecules/mole)
R: Gas constant (= 8.3144 J/K mole)
P: Pressure

Surface analysis in vacuum










Degree of
Vacuum

Pressure
(Torr)

Gas Density
(molecules m
-3
)

Mean Free
Path (m)

Time /
monolayer (s)

Atmospheric

760

2 x 10
25


7 x 10
-8


10
-9


Low

1

3 x 10
22


5 x 10
-5


10
-6


Medium

10
-3


3 x 10
19


5 x 10
-2


10
-3


High

10
-6


3 x 10
16


50 1

UltraHigh

10
-10


3 x 10
12


5 x 10
5
10
4

Collision Free Conditions  P < 10
-4
Torr

UHV reduces the chance of low energy electrons being
scattered by gas molecules on their way to the detector.
Maintenance of a clean surface  P < 10
-9
Torr
Reduce the contamination of specimen surface during experiment
Principles of XPS and AES
Φ + + =
B K
E E hν
3 , 2 3 , 2 1 1
) (
BL L KL BL BK
E E E E + ≈ −
Φ − − =
B K
E h E ν
K
E
3 , 2 1
L KL
E
3 , 2 1 3 , 2 1
) (
BL BL BK L KL
E E E E − − ≈
Surface sensitivity
Escape depth ≈ Inelastic mean free path (λ)
 the distance that (photo-)electrons of can travel
without losing energy
E
c
= hν - (E
B
+ φ)

δE = Electron energy loss
(contribute to a background)
• We are measuring Secondary Electrons emitted
from the surface in XPS.
• The secondary electrons which are emitted are
only from the near surface region of the
specimen, due to the limited mean free path of
the secondary electrons.
• For most materials the XPS measurement is
limited to 2-5 atomic layers at the surface.
Equipment
XPS
AES
X-ray sources for XPS
• Mg Kα and Al Kα exhibit line widths less than 1.0 eV and also have sufficient energy (>1000 eV)
for photoelectron emission
XPS spectrums
1. Photoemission from core electron levels
2. Auger emission excited by X-rays
3. Photoemission from valence levels
4. A step-like background (increasing with binding energy)
E
K
= hν – (E
B
+ φ)
Background:
Photoelectrons with
energy loss, δE
Peak:
Photoelectrons without
energy loss
E
K
shift by 233 eV when we change the radiation from Al Kα to Mg Kα
XPS peak identification
E
B
= hν – (E
K
+ φ)
Chemical shift in XPS
Chemical shift: Change in binding energy of a core electron of an element
due to a change in the chemical bonding of that element.
Withdrawal of valence electron charge increase in binding energy
(oxidation)
Addition of valence electron charge decrease in binding energy
Qualitative view:
Core binding energies are determined by:
Electrostatic interaction between it and the
nucleus, and reduced by:
• Electrostatic shielding of the nuclear charge
from all other electrons in the atom (including
valence electrons)
• Removal or addition of electronic charge as a
result of changes in bonding will alter the
shielding
Chemical shift in XPS
Binding energy of 1s electron in carbon increases
with being bonded to more electronegative atom
• XPS peaks give additional information on the chemical bonding state of material.
For example, oxidation states of metals
AES spectrums
• Differential mode is more widely used because
the Auger peaks are more obvious than direct mode
• Principal Auger KLL peaks of light elements.
• The Auger signal is sensitive to changes in
chemical bonds, which result in shifts of the
main peak, and a change in shape of minor
peaks.
• Chemical shift in AES is significantly larger than
the shift in XPS but more difficult to interpret.
AES peak identification
AES element imaging
Auger electrons are a type of secondary electrons, so like XPS, this is
a near surface technique.
Spatial Resolution:
Defined by the beam size and the
backscattered electron volume
• Diameter of electron beam can be as small as
about 10 nm when a FE-gun is used.
• Focusing of X-ray beam is difficult because it is
electrically neutral and can not be focused with
electromagnetic field.
Depth profiling
Calibration of depth scale:
• Sputtering rate determined from the time required to sputter through a
layer of the same material of known thickness.
• After the sputtering analysis, the crater depth is measured using depth
profilometer. A constant sputtering rate is assumed.
Depth profiling of oxidation layer
Steel substrate
Al oxides line
MnO layer
Dew point -10℃
Al oxide layer
Dew point -30℃

9. Secondary ion mass spectroscopy
3-Dimensional atom probe tomography
- Principles and application of SIMS and 3DAP
Surface analysis by SIMS
We have used sputtering to obtain a depth-profile in XPS and Auger. Why not measure the
ions we remove during sputtering, rather than a photon or electron?
Ar
+
, Ga
+
, Cs
+
,
O
2
+
, Xe
+
(E = 1 - 20 keV)
Neutrals
Secondary Ions
SE’s
• The majority of the secondary particles
are neutral, only ~1% of total secondary
particles are ionized.
• Secondary ions go into an analyzer
where we measure the mass-to-
charge ratio, which is used to identify
the type of ion.
• More than one-to-one knock-out of a
surface ion but a series of collisions
(collision cascade)
Interaction with ion beam
a) Direct collision of sputtering is extremely
fast, occurs in the range of 10
-15
-10
-14
s after
the primary ion strikes the surface.
b) Indirect collision (Collision cascade):
The primary ions induce a series of collision.
Atoms in the solid transfer impact energy to
surface atoms after a series of collisions
(10
-14
-10
-12
s)
c) Thermal collision (transient vaporization)
occurs when the density of ions is high.
(10
-13
-10
-10
s)
Advantage of SIMS
Advantages of SIMS over electron spectroscopy:
• Detection of all chemical elements (H-U) in the periodic table, including hydrogen
which cannot be detected by the AES and XPS (because of poor core level definition)
;
• Detection of elements in concentration as low as 10
-9
(ppb detection limit), while AES
and XPS detection limits are concentration levels of 0.1 atom%;
• Limitation of the detection to the top one or two atomic layers of a solid surface (<
1 nm); and
• Distinguish between different isotopes of elements.
• Large dynamic range
Disadvantages:
• Destructive
• Complexity of ion yield(difficulties in quantitative analysis)
Signal intensity of secondary ion
η θ α
m m p m
Y I I
+
=
I
p
: Primary ion flux
Y
m
: Sputtering yield
α
+
: Probability for positive ions
θ
m
: Fractional concentration of
species m in the surface layer
η: Transmission of detector system
(ion detected / ion emitted = 0 ~ 1)
• A sputtered particle faces competition between ionization and neutralization processes
when it escapes a sample surface.
• Ionization probability represents the chance of a sputtered particle being an ion.
Positive ion yield under bombardment of 13.5 keV O
-1
Signal intensity of secondary ion
• Ionization probability is strongly affected by the electronic properties of the sample matrix.
• I
m
<< I
oxide
• Significant variation in secondary ion yield with chemical elements and chemical states of
the surface, which makes quantitative analysis difficult.
In most cases the yield of singly ionized atom
s predominates.
Static and dynamic SIMS
• Sputtering is, fundamentally, a process damaging a surface
• Therefore, the chemical structure of the surface may be destroyed during SIMS
measurement

• Dynamic SIMS – high flux of primary ion bombardment enabling depth profiling
• Static SIMS – low flux of primary ion to avoid the possibility that any surface area is
bombarded by ions twice
Lifetime of surface (time scale in which whole surface is affected by primary ion beam)
I
p
= 1 µA /cm
2
(1 µA = 6.2 × 10
12
ion/sec)
σ ~ 10 nm
2
/ion = 10
-13
cm
2
/ion


- Life time of surface is less than 2 sec.
- It is too short to SIMS measurement
without surface damage

- I
p
should be reduced to 2.7 nA /cm
2
to secure 10 min of lifetime of surface in static SIMS
Instrumentation
Sample
Primary ion
source
Mass spectrum (I
SI
vs m/z)
Surface imaging
Depth profiling
UHV environment
(10
-9
-10
-10
Torr)
Focused energetic
(1-30 keV) ion beam
(Ar
+
, Ga
+
, Cs
+
, O
2
+
, Xe
+
)

Sputtering of surface
atoms by momentum
transfer

Static SIMS
• Ion dosage <10
13
/cm
2
• Non-destructive
• Surface composition: ~ 5nm
Dynamic SIMS
• Ion dosage >10
13
/cm
2
• High sputter rate
LMI source
Time-of-flight mass analyzer
2 / 1
2 / 1
) 2 (
|
.
|

\
|
=

z
m
V L t
• The m/z (mass to charge) of ions is analyzed by measuring their flight time in the analyzer.
• Heavier ions will have longer flight times in the tube.
• To measure the time of flight, precisely pulsed primary ions should be used (pulse period ~
10 ns).
• The ions are reflected by a mirror.
• The mirror is composed of a series of precisely spaced rings to which a gradually increasing
electric field is applied.
• Ions with higher kinetic energy will penetrate further into the mirror before being reflected.


Peak identification
Negative ToF SIMS spectrum of Sodium Nitrate (NaNO
3
)
• SIMS spectra express the intensity
of secondary ion versus m/z
• Spectra can be either that of positive
ion or negative ion
• We can identify individual ions, ion
cluster and molecular fragments
according to their m/z which requires
experience and knowledge of materials
SIMS image
10 μm
O
2
-
source
BO
2
-
micrograph
Boron imaging in low carbon steel
• SIMS can be operated in scanning mode because it is equipped with X-Y deflector on the
primary ion beam.

• Secondary ions emitted in each pixel generate 2D image

• Each pixel comprise signal from a single selected mass to charge ratio

• Common diameter of ion beam for scanning image is 200 nm to 1 µm
Na contamination in Al pattern
SIMS image
Calcium phosphate coated Ti
• Proper ion for element image should be selected
• Check artifact from topographic effects
10
-1
10
0
10
1
10
2
10
3
SIMS AES, XPS
• Elemental detection limit (Z)
H

He

Li

Be

B

SIMS AES, XPS
• Depth resolution (Å)
10
-1
10
0
10
1
10
2
10
3
SIMS, AES, XPS
• Beam diameter (μm)
10
-1
10
0
10
1
10
2
10
3
AES
SIMS XPS
• Impurity detection limit (ppm)
3D atom probe
K. Hono, National Institute for Materials Science, Japan
• Field ion microscope
• Sharp metal tip is produced and placed on UHV chamber which
is backfilled with an imaging gas such as He or Ne.
• At 20 – 100 K, application of positive voltage to tip ionizes the
adsorbed gas and emitted the ionized gas atom from the tip.
• Ions are emitted in a direction roughly perpendicular to the surface
which gives natural magnification in image (M ~ r
screen
/ r
tip
) .
3D atom probe
V
dc
V
p
m/n=2eV
e
(t/l)
2
• Field evaporation of surface atom by high electric field.
• Lateral position of atom is measured by position sensitive detector.
• Mass to charge of atom is evaluated by ToF.
• 3 dimensional atomic position image can be constructed.
• Combined with FIB sampling, an atomic resolution at desired place can be obtained.
Electrical conductive
No ceramics analysis
Narrow analysis area 10×10× 200 nm
3

Not usable for microanalysis
High field stress on tip apex: s=F
2
/4p > s
y
Frequent specimen rupture
Laser assisted field evaporation
Needle like specimen (tip)
Difficult to analysis grain boundary,
interfaces, powder, surfaces
Site specific specimen preparation by FIB
3D atom probe
Boron in medium carbon steel
C.G. Park et al. 2010, Ultramicroscopy

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