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AP 5301/8301

Instrumental Methods of Analysis
and Laboratory
Zhengkui XU
Office: G6760
Tel: 34429143
Email:apzkx@cityu.edu.hk

Course Objectives
• Basic understanding of materials
characterization techniques
Physical basis – basic components and their functions
Common modes of analysis
Range of information provided by the techniques
Recent development of the techniques
• Emphasis on applications
Typical examples and case studies
How to use different techniques to solve
different problems in manufacturing and
research


Microscopy and Related Techniques

• Light (optical) microscopy (LM) or (OM)
• Scanning electron microscopy (SEM)
Energy dispersive X-ray spectroscopy (EDS)
& Wavelength dispersive X-ray spectroscopy
(WDS)
• X-ray diffraction (XRD)/X-ray fluorescence
(XRF)
• Transmission electron microscopy (TEM)

Surface Characterization Techniques
• Scanning probe microscopy (AFM & STM)
• Secondary ion mass spectroscopy (SIMS)
• Auger electron spectroscopy (AES)
• X-ray photoelectron spectroscopy (XPS)
Non-Destructive Analysis
Processing-structure-property
Chemical
composition
Microstructure
Processing·structure·property
Properties
Intrinsic
Materials
Selection
Materials
Processing
Extrinsic
(Characterization)
(Characterization)
Crystal
Structure
( )
Microstructure
50 µm
Grain
boundary
Grain
Grain
Boundary
phase
Pore within grain
Grain
boundary
pore
impurity
Secondary (amorphous) phase
Nature, quantity and distribution of phases in the ceramics,
e.g., crystals, glass, porosity, grain boundary and impurity
(secondary) phase.
Phase - A homogeneous portion of a system that has uniform physical
and chemical characteristics.

http://en.wikipedia.org/wiki/Phase_(matter)
Scale and Characterization Techniques
XRD,TEM,STM SEM OM
Grain I
Grain II

atomic
Valve
Turbo
charge
1
SiC turbine blades
TEM image
Grain 1
Grain 2
2nm
Intergranular
amorphous phase
crack
Effect of Microstructure on
Mechanical Property
o
f
· d
-1/2
d-grain size
50µm 10µm
a b
Mechanical test: o
fa
> o
fb
Mechanical property

Microscopic analysis: d
a
< d
b
Microstructure


OM images of two polycrystalline samples.
Identification of Fracture Mode
4µm
Intergranular fracture
20µm
Intragranular fracture
Cracks
Cracks
Pores
Grain
boundary
OM and SEM
50µm
5µm
Growth
step
OM - 2D
SEM – 3D
BaTiO
3
High Resolution Z-contrast Imaging
Atomic Ordering in Ba(Mg
1/3
Nb
2/3
)O
3



(STEM)
[110]
o I Z
2
First Place Winner (TEM category) in the 1998 Ceramographic
Contest at 100
th
Annual Meeting of Am. Ceram. Soc. Z. Xu et al.
http://www.youtube.com/watch?v=egPQZw0QkVw
100%
Simulation
0 20 40 60 80 100
Occupancy (%)
Sr Ti O
100%
Profile
60%
SrTiO
3
C.L. Jia, M. Lentzen & K. Urban, Science 299, 870 (2003)
Aberration-corrected high-resolution
transmission electron microscopy
STM - Seeing Atoms
STM image showing single-atom
defect in iodine adsorbate lattice
on platinum. 2.5nm scan
Iron on copper (111)
Optical Microscopy
• Introduction
• Lens formula, Image formation and
Magnification
• Resolution and lens defects
• Basic components and their functions
• Common modes of analysis
• Specialized Microscopy Techniques
• Typical examples of applications
http://micro.magnet.fsu.edu/primer
http://www.doitpoms.ac.uk/tlplib/optical-microscopy/index.php
Physics of
http://www.doitpoms.ac.uk/vidlib/browse.php
http://micro.magnet.fsu.edu/primer
How Fine can You See?
• Can you see a sugar cube? The
thickness of a sewing needle? The
thickness of a piece of paper? …
• The resolution of human eyes is of the
order of 0.1 mm.
• However, something vital to human
beings are of sizes smaller than 0.1mm,
e.g. our cells, bacteria, microstructural
details of materials, etc.
Microstructural Features
which Concern Us
• Grain size: from <µm to the cm regime
• Grain shapes
• Precipitate size: mostly in the µm
regime
• Volume fractions and distributions of
various phases
• Defects such as cracks and voids: <µm
to the cm regime
• … …
What is a Microscope?
A microscope is an instrument designed to make
fine details visible. The microscope must accomplish
three tasks:

1. To produce a magnified image of the specimen
(magnification).

2. To separate the details in the image (resolution).

3. To render the details visible to the eye, camera,
or other imaging device (contrast).
Introduction- Optical Microscopy
• Use visible light as illumination source
• Has a resolution of ~o.2µm
• Range of samples characterized - almost
unlimited for solids and liquid crystals
• Usually nondestructive; sample preparation
may involve material removal
•Main use – direct visual observation;
preliminary observation for final charac-
terization with applications in geology, medicine,
materials research and engineering, industries,
and etc.
• Cost - $15,000-$390,000 or more


http://www.youtube.com/watch?v=bGBgABLEV4g&feature=endscreen&NR=1
Old and Modern
Light Microscopes
http://www.youtube.com/watch?annotation_id=annotation_100990&f
eature=iv&src_vid=L6d3zD2LtSI&v=ntPjuUMdXbg
http://www.youtube.com/watch?v=X-w98KA8UqU&feature=related
http://www.youtube.com/watch?v=sCYX_XQgnSA&feature=related <2min
Simple Microscope

Low-power magnifying glasses
and hand lenses
2x 4x 10x
A microscope is an instrument used to see objects that are
too small for the naked eye. The science of investigating small
objects using such an instrument is called microscopy.
Refraction of Light
Incident angle u
1

Refracted angle u
2
Normal

N - Refractive index of material
- Speed of light in vacuum
- Velocity of light
in material
Materials N
Air 1.0003
Water 1.33
Lucite 1.47
Immersion oil 1.515
Glass 1.52
Zircon 1.92
Diamond 2.42


Sinu
1
V
1
N
2
= =
Sinu
2
V
2
N
1
Snell’s Law
N > 1
Light path bends at interface between two transparent
media of different indices of refraction (densities)
air
http://micro.magnet.fsu.edu/primer/java/refraction/refractionangles/index.html
Focusing Property of A Curved Surface
In entering an optically more dense medium (N
2
>N
1
), rays
are bent toward the normal to the interface at the point of
incidence.
normal
Curved (converging) glass surface
F
f
N
2
N
1
F - focal point f – focal length
Focal plane
Air
Curvature of Lens and Focal Length
N
2
N
1
Normal
N
1
N
2
F
F
f
1

u
1
u
2
u
1
> u
2
Centerline of the lens
Optical axis
Bi-Convex Lens
The larger curvature angle u
The shorter focal length f
f
2

f
1
< f
2
Converging (Convex) Lens
f
The simplest magnifying lens

f · curvature angle and lens materials (N)
the larger N, the shorter f
lucite glass diamond
N: 1.47 1.51 2.42
Focal plane
F
f
http://www.youtube.com/watch?v=hDRb9HAK5s4
http://www.youtube.com/watch?v=K5LeAV0Ztkg
Image Formation by a Converging Lens
Two fundamental properties of lenses:
1. Deviating a light beam parallel to its own axis, then making
it to pass through the focus;
2. Leaving unaltered the path of the rays which pass through
the lens center.
The A ray (principal ray) passes through the lens center and is not
deflected.
The B ray comes to the lens moving parallel to the axis and passes
through F1.
The C ray which in a similar way passes through F2 and leaves the
lens parallel to the optical axis.
Any two of these three characteristic rays can be utilized to
determine the size and placement of the image formed by the
lens.



http://www.youtube.com/watch?v=-k1NNIOzjFo&feature=related
Magnifier – A Converging Lens
nearest distance of distinct vision (NDDV)
retina
I’
I’

If o’-o’ is ~0.07mm, u
o
=0.016
o
Ray diagram to show the principle of a single lens
NDDV-ability to distin-
guish as separate
points which are
~0.07mm apart.

u
o
- visual angle
subtended at the eye
by two points o’-o’ at
NDDV.
Magnification
m= =
I-I o”-o”
I’-I’ o’-o’
m = u/u
o
o”
o”
u
o u
o
25cm
h
o-object distance
Virtual
image
Real
inverted
image
A
B
f
-i
cornea
http://www.youtube.com/watch?v=_5dEO-LRV-g
http://www.youtube.com/watch?v=lBKGP6Fh9vs
1 1 1

_
=
_
+
_
f O i

Lens Formula
f-focal length (distance)
O-distance of object from
lens
i-distance of image from
lens
I
1
O
i

i
O
= = m
o
Magnification
by objective
Lens formula and magnification
Objective lens
-Inverted
image
f f
h
o
h
i
h
i
h
o
http://micro.magnet.fsu.edu/primer/java/lenses/converginglenses/index.html
Maximum Magnification of a Lens
• Angular magnification is maximum when
virtual image is at “near point” of the eye,
i.e. 25 cm (i = -25 cm)
• Using the lens formula, o = 25f/(25+f )
• u
0
~ h/25 and u ~ h/o
f f
f
o h
o h
m
25
1
25 25
25
0
+ =
+
= = = =
u
u
1/f = 1/O + 1/i
f in cm
Magnification when the Eyes
are Relaxed
• The eyes can focus at points from infinity to
the “near point” but is most relaxed while
focus at infinity.
• When o = f, i = ·
• For this case, u
0
~ h/25 and u ~ h/f
f
m
25
0
= =
u
u
1/f = 1/O + 1/i
Limitations of a Single Lens
• From the formula, larger magnification
requires smaller focal length
• The focal length of a lens with
magnification 10× is approximately
2.5cm while that of a 100× lens is
2.5mm.
• Lens with such a short focal length
(~2.5mm) is very difficult to make
• Must combine lenses to achieve high
magnifications
Image Formation in Compound Microscope
• Object (O) placed just outside focal point of objective lens
• A real inverted (intermediate) image (I
1
) forms at or close to
focal point of eyepiece.
• The eyepiece produces a further magnified virtual inverted
image (I
2
).
• L – Optical tube length
25cm
Compound microscope consists of two converging lenses,
the objective and the eyepiece (ocular).
http://www.youtube.com/watch?v=RKA8_mif6-E
Magnification of Compound
Microscope
• Magnification by the objective m
0
= s’
1
/s
1

• Since s’
1
~ L and s
1
~ f
0
, therefore
magnification of objective m
o
~ L/f
o

• Magnification of eyepiece m
e
= 25/f
e

(assuming the final image forms at ·)
• Overall magnification M = m
o
m
e


|
|
.
|

\
|
|
|
.
|

\
|
÷ =
e o
f f
L
M
25
=
How Fine can You See with an
Optical Microscope?
 Magnification M = 25L/f
o
f
e

If we can make lenses with extremely
short focal length, can we design an
optical microscope for seeing atoms?
 Can you tell the difference between
magnification and resolution?
 Imagine printing a JPEG file of
resolution 320×240 to a A4 size print!!
Empty Magnification
Higher resolution Lower resolution
Diffraction of Light
Sinu=ì/d
film
1
st
2
nd
3
rd

Light waves interfere constructively
and destructively.
Distribution
http://micro.magnet.fsu.edu/primer/java/diffraction/basicdiffraction/index.html
http://www.youtube.com/watch?v=-mNQW5OShMA
Resolution of an Optical Microscope –
Physical Limit
 Owing to diffraction, the
image of a point is no
longer a point but an
airy disc after passing
through a lens with
finite aperture!
 The disc images
(diffraction patterns) of
two adjacent points may
overlap if the two points
are close together.
 The two points can no
longer be distinguished
if the discs overlap too
much
Resolution of Microscope –
Rayleigh Criteria
Rayleigh Criteria: Angular separation
¢ of the two points is such that the
central maximum of one image falls
on the first diffraction minimum of
the other
¢ =u
m
~ 1.22ì/d
Resolution of Microscope –
Rayleigh Criteria
Image 1
Image 2
http://micro.magnet.fsu.edu/primer/java/imageformation/rayleighdisks/index.html
Resolution of Microscope – in
terms of Linear separation
 To express the resolution in
terms of a linear separation r,
have to consider the Abbe’s
theory
 Path difference between the
two beams passing the two
slits is
 Assuming that the two beams
are just collected by the
objective, then i = o and
d
min
= ì/2sino
ì o = + sin sin d i d
I II
I II
Resolution of Microscope –
Numerical Aperture
 If the space between the specimen and the
objective is filled with a medium of refractive index
n, then wavelength in medium ì
n
= ì/n
 The d
min
= ì/2n sino = ì/2(N.A.)
 For circular aperture
d
min
= 1.22ì/2(N.A.)=0.61ì/(N.A.)
where N.A. = n sino is called numerical aperture
Immersion oil n=1.515
http://micro.magnet.fsu.edu/primer/java/imageformation/rayleighdisks/index.html
NA of an objective is a measure of its ability to
gather light and resolve fine specimen detail at
a fixed object distance.
NA = n(sin o)
n: refractive index of the imaging medium between
the front lens of objective and specimen cover glass
Numerical Aperture (NA)
o
Angular aperture
One half of A-A
NA=1 - theoretical
maximum numerical
aperture of a lens
operating with air as
the imaging medium
(s72 degrees)
http://micro.magnet.fsu.edu/primer/java/microscopy/immersion/index.html
Factors Affecting Resolution
 Resolution = d
min
= 0.61ì/(N.A.)
 Resolution improves (smaller d
min
) if ì+ or n| or o|
 Assuming that sino = 0.95 (o = 71.8°)








 (The eye is more sensitive to blue than violet)
Wavelength
Red
Yellow
Green
Blue
Violet
Air (n= 1) Oil (n = 1.515)
0.42 m µ
0.39 m µ
0.35 m µ
0.31 m µ
0.27 m µ
0.28 m µ
0.17 m µ
0.20 m µ
0.23 m µ
0.25 m µ
650 nm
600 nm
550 nm
475 nm
400 nm
The smallest distance between two specimen points
that can still be distinguished as two separate entities

d
min
= 0.61ì/NA NA=nsin(o)
ì – illumination wavelength (light)
NA – numerical aperture
o-one half of the objective angular aperture
n-imaging medium refractive index
d
min
~ 0.3µm for a midspectrum ì of 0.55µm
Resolution of a Microscope (lateral)
Optical Aberrations

• Spherical (geometrical) aberration – related to the
spherical nature of the lens
• Chromatic aberration – arise from variations in the
refractive indices of the wide range of frequencies in
visible light

Two primary causes of non-ideal lens action:
Astigmatism, field curvature and comatic aberrations
are easily corrected with proper lens fabrication.
Reduce the resolution of microscope
Aberration in optical systems (lenses intended to produce a
sharp image) generally leads to blurring of the image. It
occurs when light from one point of an object after transmission
through the system does not converge into a single point.
http://www.youtube.com/watch?v=XGjg64rayfM Aberration of microscope
Defects in Lens
 Spherical Aberration –
Peripheral rays and axial
rays have different focal
points (caused by spherical
shape of the lens surfaces).
 causes the image to appear
hazy or blurred and slightly
out of focus.
 very important in terms of
the resolution of the lens
because it affects the
coincident imaging of points
along the optical axis and
degrade the performance of
the lens.
http://micro.magnet.fsu.edu/primer/java/aberrations/spherical/index.html
 Chromatic Aberration
 Axial - Blue light is refracted to
the greatest extent followed by
green and red light, a
phenomenon commonly referred
to as dispersion
 Lateral - chromatic difference of
magnification: the blue image of a
detail was slightly larger than the
green image or the red image in
white light, thus causing color
ringing of specimen details at the
outer regions of the field of view
Defects in Lens
A converging lens can be combined
with a weaker diverging lens, so that
the chromatic aberrations cancel for
certain wavelengths:
The combination – achromatic doublet
weaker diverging lens
http://micro.magnet.fsu.edu/primer/java/aberrations/chromatic/index.html
 Astigmatism - The
off-axis image of a
specimen point
appears as a disc or
blurred lines instead
of a point.
 Depending on the
angle of the off-axis
rays entering the
lens, the line image
may be oriented
either tangentially
or radially
Defects in Lens
o
A
http://micro.magnet.fsu.edu/primer/java/aberrations/astigmatism/index.html
http://www.youtube.com/watch?NR=1&v=6YxffFmi4Eo&feature=endscreen
 Curvature of Field
- When visible light
is focused through a
curved lens, the
image plane
produced by the lens
will be curved
 The image appears
sharp and crisp
either in the center
or on the edges of
the viewfield but not
both
Defects in Lens
http://micro.magnet.fsu.edu/primer/java/aberrations/curvatureoffield/index.html
 Coma - Comatic
aberrations are
similar to spherical
aberrations, but they
are mainly
encountered with off-
axis objects and are
most severe when the
microscope is out of
alignment.
Defects in Lens
Coma causes the image of a non-axial point to be reproduced
as an elongated comet shape, lying in a direction
perpendicular to the optical axis.
http://micro.magnet.fsu.edu/primer/java/aberrations/coma/index.html
Depth of focus (f mm)
The distance above and below
geometric image plane within
which the image is in focus
The axial range through which
an object can be focused without
any appreciable change in image
sharpness
(F µm)
M NA f F
M NA f F
Axial resolution – Depth of Field
Depth of Field Ranges (F µm)
F is determined by NA.
NA f F
0.1 0.13 15.5
0.4 3.8 5.8
.95 80.0 0.19
http://micro.magnet.fsu.edu/primer/anatomy/objectives.html
Optical Microscopy
 Introduction
 Lens formula, Image formation and
Magnification
 Resolution and lens defects
 Basic components and their
functions
 Common modes of analysis
 Specialized Microscopy Techniques
 Typical examples of applications
Scanning Electron Microscopy
Do review problems (1-9) on OM
Read “dispersion and refraction of
light and lens”
http://www.doitpoms.ac.uk/tlplib/optical-microscopy/questions.php