1

Electron Electron Microscopy Microscopy

in Materials Science in Materials Science
Prof. Dr. Ulrich Krupp
lecture+seminar,
www.mb.uni-siegen.de/LMW
Organization Organization of of the the EM EM Course Course
1st day
9.00-10.30 1 Introduction/ 2 SpecimenPreparation
10.45-12.00 3 Main Componentsof a SEM/TEM
12.30-14.00 lunch break
14.00-15.00 4 InteractionsElectron-Matter ElectronContrast SEM
15.00-16.30 Practical CourseSEM 1
2nd day
9.00-12.00 5 ElectronDiffraction ElectronContrast TEM
12.00-13.00 lunch break
13.00-15.00 6 SEM ChannelingContrast and Electron
Diffraction Techniques
15.00-16.00 Practical CourseTEM 1
2
Organization Organization of of the the EM EM Course Course
3rd day
9.00-11.00 7 Analytical ElectronMicroscopy
11.00-12.00 Practical CourseSEM2
12.00-13.00 lunch break
13.00-14.30 Practical Course- Analytical ElectronMicroscopy
14.30-16.00 8 CaseStudies+Discussion
Literature Literature (SEM) (SEM)
P.F. Schmidt (ed):
Praxis der Rasterelektronenmikroskopie und Mikrobereichsanalyse
Expert-Verlag, 1994 (in German)
J .I. Goldstein, P. Etchlin, D.E. Newbury:
Scanning Electron Microscopy and X-ray Microanalysis
Plenum Publishing Corp., New York 1992
L. Reimer:
Scanning Electron Microscopy
Springer-Verlag, Berlin 1985
V. Randle:
Microtexture Determination and its Applications
The Institute of Materials, London 1992 (EBSP)
WWW SEM course(in German)
http://www.reclot.de/kapitel/0kurs.htm
3
Literature Literature (TEM) (TEM)
E. Hornbogen, B. Skrotzki
Werkstoffmikroskopie
Springer-Verlag, 1993 (in German)
M. v. Heimendahl:
Electron Microscopy of Materials
Academic Press, New York 1980 (Engl.) vieweg1970 (Deutsch)
Wiliams, D.B.; Carter, C.B.:
Transmission Electron Microscopy A Textbook for Materials Science
Plenum Press, New York 1996
J . W. Edington:
Practical Electron Microscopy in Materials Science
TechBooks, Herndon1976
1 1 Introduction Introduction
sperms
Light Light Microscopy Microscopy 1674 1674
Robert Hooke
Antony van Leeuwenhoek
The light microscope opened the first door to the microcosm,
the electron microscope opened the second door,
what will we see when we open the third door?
E. Ruska 1985
4
Invention Invention of of Electron Electron Microscopy Microscopy
Ernst Ruska(1906-1988)
TEM 1931, Nobel Price 1986
Manfred von Ardenne (1906-1988)
SEM 1937-39
Resolution SEM/TEM Resolution SEM/TEM
0,5m
Ti-oxideon superalloyCMSX-6 after exposureat 1000C to air
0,2m
SEM TEM
5
High Resolution TEM High Resolution TEM
5 grain
boundary
0.5nm
Depth Depth of Focus OM/SEM of Focus OM/SEM
optical microscopy
(Trochodiscuslongispinus, marineorganism)
scanningelectronmicroscopy
Goldsteinet al.: SEM/X-raymicroanalysis, Plenum, New York 1992
6
Depth Depth of Focus of Focus
Depth Depth of Focus of Focus
2mm
7
Scanning Scanning Electron Electron Microscopes Microscopes 1 1
CamScan Philips XL30 LaB
6
Scanning Scanning Electron Electron Microscopes Microscopes 2 2
Large chamber SEM MIRA
8
Scanning Scanning Electron Electron Microscopes Microscopes 2 2
SEM examinationof an
ancient terracotta
warrior (XiAn, China)
Scanning Scanning Electron Electron Microscopes Microscopes 2 2
microgripper
in a SEM
9
Transmission Transmission
Electron Electron
Microscopy Microscopy
Hitachi H8100 LaB
6
Direct Direct Microscopy Microscopy (LM, TEM) (LM, TEM)
light source
specimen
eye
light source
(transmission)
electronsource
specimen
screen
eye
light microscopy(LM)
TEM
10
Indirect Indirect Microscopy Microscopy (SEM) (SEM)
eye
electronsource
specimen
screen
detector
scanningcoils
electron/specimen
interactions
2 SpecimenPreparation
11
Specimen Specimen Preparation Preparation (SEM) (SEM)
dry/ fat free(cleaningin ethanol, dryingin vacuum)
conductive(non-conductivespecimens: sputtering, C coating)
OIM/channelingcontrast (electropolishing/ finepolishing)
50m
specimenholder
double-facedC adhesives
(conductive)
Ar
+
Au
Specimen Specimen Preparation Preparation (SEM): (SEM): Sputtering Sputtering
glowdischarge
specimen
Ar leakvalve
vacuumapprox. 10-15Pa (rotarypump)
anode
target (Au,Ag..)
high voltage(-1-3kV, 5-15mA)
12
Specimen Specimen Preparation Preparation (TEM) (TEM)
central requirement:
electrontransparency metallic substrates: d=approx. 50...200nm
cutting grindingand polishing
punchingsmall discs(diameter: 3mm)
thinning
cyclindrical specimenholder
Specimen Specimen Preparation Preparation (TEM) (TEM)
central requirement:
electrontransparencybythinning
creatinga hole withelectron-transparent rim
by
electrolythical jet-polishing/thinning
or
ionpolishing
3mm
80-120m
electron-transparent rim
13
Electrolythical Electrolythical Polishing Polishing/ /Thinning Thinning
pump
photo diode
specimen
electrolyte
Ion Ion Polishing Polishing/ /Thinning Thinning
dimplegrinding
specimen
dimple
grinder
ionpolishing Ar
+
Me
vacuumchamber
Ar
+
guns
14
Specimen Specimen Preparation Preparation by by
Focussed Focussed Ion Ion Beam BeamMilling Milling (Ga (Ga
+ +
) )
FEI dual beam(Ga
+
/FE-SEM)
laser-processedLiNbO
3
Specimen Specimen Preparation Preparation by by
Replica Replica Technique Technique
polycrystallineAl
2
O
3
vapor deposition
electrontransmission
intensity
15
Specimen Specimen Preparation Preparation by by
Extraction Extraction Replica Replica Technique Technique
Mo
2
C / M
23
C
6
carbides
in 10 CrMo9 10 steel
1 differential etching
2 film application
3 matrixetching
TEM TEM Specimen Specimen Holder (Double Holder (Double Tilt Tilt) )
retainer / circlip
tweezers
specimensupport
16
4 Main 4 Main Components Components
(TEM/SEM) (TEM/SEM)
TEM HV generation
(up to 1200kV !!)
window
SEM SEM Schematic Schematic Representation Representation
vacuum
chamber
e
-
gun
column
(lenses,apertures)
detector
e
-
beam
(focussed/scanned
on specimen)
17
SEM SEM Schematic Schematic Representation Representation
filament
high voltage
(30kV)
anode
IGP
electron beam
column
(upper part 10 mbar)
-8
Wehnelt cap
apertures
monitor
condenser lenses
objective lens
aperture
specimen
scanning coils
vacuum system
rough pump/ODP BSE detector
SE-detector
vacuum chamber (10 mbar)
-5
stigmator
vacuum system
filament (cathode)
Wehnelt cap
anode
condenser lens
condenser aperture
specimen
objective lens
obejctive aperture
selector aperture
intermediate lens
projective lens
fluorescent phophorous screen
camera
diffracted intensities
200 kV
TEM TEM Schematic Schematic
Representation Representation
18
Rotary ( Rotary (vane vane) pump ) pump - -
Drehschieberpumpe Drehschieberpumpe
specimenchamber
intakefitting
outlet valve
oil
stator
slide(Schieber) withspring
rotor
volume increase
Vacuum VacuumSystem: System:
Oil Diffusion Pump Oil Diffusion Pump - -
ldiffusionspumpe ldiffusionspumpe
chamber
10
-6
mbar
rotary
pump
water
water
evaporatingoil
heater
deflected oil vapor sweeps
gas molecules away
baffle
19
Molecular Molecular Drag Pump Drag Pump- -
Turbomolekularpumpe Turbomolekularpumpe
chamber
(10
-6
mbar)
rotor
magnet bearing
rotarypump
stator
Ion Ion Getter Getter Pump Pump - - Ionengetterpumpe Ionengetterpumpe
Ti atoms
gas atoms
ions
electrons
cathode:
-4 - -6 kV
ionisation
2. adsorption
at getter film
1. collision
ions with cathode
20
LaB LaB
6 6
Filament Filament
heatingcurrent
LaB
6
singlecrystal
graphitering
ceramicbase
heatingrod
FEG FEG Field Field Emission Emission Gun Gun
W singlecrystal sharptip(diameter <100nm)
extraction
voltage
HV
(E>10
7
V/cm)
21
Wehnelt Wehnelt cap cap Wehnelt Wehnelt Zylinder Zylinder
filament tip
Wehnelt cap
height adjustment
Wehnelt Wehnelt cap cap Wehnelt Wehnelt Zylinder Zylinder
22
Working Working Principle Principle: :
Electromagnetic Electromagnetic Lens Lens
electron
Lorentz force
F=-e(v x B)
(electronvelocityx magneticfluxdensity)
Working Working Principle Principle: :
Electromagnetic Electromagnetic Lens Lens
f
1/f=1/q+1/p
B
r
: rotational force on e
-
=>rotation
B
z
: radial force on e
-
=>focussing
23
Condenser Condenser/ /Objective Objective Lens Lens
condenser lens
obejectivelens
d
2
final spot size
f focus
weakexcitation strongexcitation
electronsthat do
not pass through
final lensaperture
max. probe current min. spot size
Influence Influence of of the the Spot Spot Size Size (SEM) (SEM)
spot size:
resolution low high
noise low high
SE signal
low high
SE imaging
BSE imaging
EDS microanalysis
1 2 3 4 5 6
24
Influence Influence of of the the Aperture Aperture Diameter (SEM) Diameter (SEM)
(XL30 (XL30 fixed fixed) )
final aperture
focusdepth
resolution low high
noise
SE imaging
EDS microanalysis
low high
low high
Objective Objective Lens Lens with with Asymmetrical Asymmetrical
Pole Pole Pieces Pieces (SEM) (SEM)
25
Scanning Scanning
(SEM, also (SEM, also
STEM) STEM)
objective lens
aperture
final aperture: D
specimen
scanning coils
(Ablenkspulen)
stigmator
z
x
y (movement by
motor stage)
tilt
electron beam
scanned section/gerasterter Probenausschnitt
Image Generation in Image Generation in the the SEM SEM
interactions
electron beam <=>specimen surface
secondary electrons
back-scattered electrons
X-rays
B x B
1000 lines
depth
of focus T
b x b

26
4 4 Interactions Interactions Electrons Electrons Matter Matter - -
Electron Electron Contrast Contrast SEM SEM
5 5 Electron Diffraction Electron Diffraction - -
Electron Contrast Electron Contrast TEM TEM
6 SEM 6 SEM Channeling Contrast Channeling Contrast and and
Electron Diffraction Techniques Electron Diffraction Techniques
Interactions Interactions Electrons Electrons Matter Matter
K
L
M
electron beam
stroke out
of secondary electron
nucleus
elastically deflected
electron
=> BSE
=> SE
K
L
M
27
Electron Electron Penetration Penetration Depth Depth
ca. 1-10nm
SE1
SE2
BSE
X rays
penetration depth
(dependent on E ) R
0
ca. 0,5R
electron beam
Auger-e
-
specimen current
specimen
AE
SE BSE
N(E)
50 eV
(convention)
E
0
2 keV
E
Electron Electron Penetration Penetration Depth Depth
foil on Cu grid
HV:
1kV 3.5kV 20kV
polymer
copper
diameter of the interaction volume: approx. 2m
polymer
copper
polymer
copper
28
Secondary Secondary Electrons Electrons (SE) (SE) Detector Detector
Secondary Secondary Electrons Electrons (SE) (SE) Detector Detector
Everhart Thornley Detector
specimen
light guide photo multiplier
(successive acceleration
+multiplication at dynodes)
collector
+300V
scintillator photo cathode
behind quartz window
electrical
signal
29
Contrast Contrast Formation: Formation:
Topography Topography & & Edges Edges
primary electron beam (PE)

SE
PE
I
x
Human Human Hair Hair
30
Secondary Secondary Electrons Electrons Gain Gain
: leaving electrons/
incident electrons
: SE gain
: BSE coefficient
negative charging
conductive specimens!
E
0
Back Back- -Scattered Scattered Electrons Electrons (BSE) (BSE) Detector Detector
BSE
SE
electron beam
+
amplifier
Al coating
gold
nsilicon
-
p silicon
+
SE-Detektor
BSE-semiconductor
detector
elastic scattering
inelastic collision BSE at
detector
generation of
electron/hole pairs
p/n transition inhibits
recombination
31
BSE BSE Detector Detector
SE Detector
Material Material Contrast Contrast
light elements (lowZ) dark
heavy elements(high Z) - bright
Al-Si alloy (with Si precipitates)
SE image
BSE image (same position)
32
Contrast Contrast information information: :
Material Material
and and
Topography Topography
BSE detector B A
5 5 Electron Diffraction Electron Diffraction - -
Electron Contrast Electron Contrast TEM TEM
33
Electron Electron Diffraction Diffraction - - Bragg Bragg s s law law
x x
d

primary electron
beam diffracted intensity
lattice planes
2x =2d sin =N
transmitted intensity
E
0
=100kV: =0.0037nm, Cu (111) planes =>=0,5
Debye Debye- -Scherrer Scherrer Diagrams of Diagrams of Polycrystals Polycrystals
500nm
selected area diffraction TEM micrograph (TlCl standard)
electron beam
specimen
diffractionrings
(DS diagrams)
34
Electron Electron Diffraction Diffraction
in in the the TEM TEM
vacuum system
filament (cathode)
Wehnelt cap
anode
condenser lens
condenser aperture
specimen
objective lens
obejctive aperture
selector aperture
intermediate lens
projective lens
fluorescent phophorous screen
camera
diffracted intensities
200 kV
diffraction spots
Bragg diffraction
at lattice planes
2
x
y
z
The The Reciprocal Reciprocal
Lattice Lattice
reciprocal lattice
camera length L
real lattice
2d sin =N (Bragg)
2d N
R

2
2 =tan R/L (geometry)
R/2L
: very small!
beam|| zone axis
d R = L
diffraction constant
R =const./d
g
35
The The Reciprocal Reciprocal Lattice Lattice
R: phosphorous screen
g: reciprocal lattice
000
420
R
2
R
1
Evaluation of Evaluation of Diffraction Diffraction Pattern Pattern
R
2
/R
1
36
Diffraction Diffraction
Pattern Pattern
for for different different
Zone Zone Axis Axis
[101] [111]
[211] [100]
[110] [111]
fcc
bcc
Kinematical Kinematical Theory Theory

x
y
r k
0
k
change of wave direction at the atoms =>amplitude/phase differences
primary beam ()
secondary waves()
( )

=
n
n n
i f A exp
resultant amplitude:
37
The The Ewald Ewald Sphere Sphere
primary beam
lattice planes
s
k
o
>>g
plane of the
diffraction pattern
k
k
0
g
2
The The Ewald Ewald Sphere Sphere
two-beam case
(Bragg case)
symmetrical case
(Laue case)
38
Amplitude Phase Diagrams Amplitude Phase Diagrams
Origin Origin of of Wedge Wedge Fringes Fringes 1 1
diffracted intensity 0 max 0 max .....
transmitted intensity I
0
min I
0
min ......
image bright dark bright dark ......
39
Origin Origin of of Wedge Wedge Fringes Fringes 2 2
diffracted transmitted
edge
boundary
Stacking Stacking Faults Faults
stackingfaultsin Al-20Si
from: Hornbogen/Skrotzki: Werkstoffmikroskopie, Springer 1993
40
Bend Bend Contours Contours
Al +Ge particles
from: Hornbogen/Skrotzki: Werkstoffmikroskopie, Springer 1993
+
-
Dislocations Dislocations
b
g
image
primary beam
Burgers vector
diffracted beam
planar dislocation arrangement
(Ti alloy LCB, /2=600MPa)
500nm
41
Dislocations Dislocations: : Pile Pile- -Up Up at at Grain Grain Boundary Boundary
grain
boundary
Dislocations Dislocations
High High- -Resolution Resolution
TEM TEM
Si single crystal
(image taken at magnific. 30000000)
42
Convergent Convergent
Electron Electron
Diffraction Diffraction
Kikuchi Kikuchi
Pattern Pattern
convergent electron beam
specimen
Kossel cone
bright line (dark line)
Fe alloy
[110]
[111]
[211]
6 6 SEM SEM Channeling Contrast Channeling Contrast and and
Electron Diffraction Techniques Electron Diffraction Techniques
43
Influence Influence of of the the Tilt Tilt Angle on Angle on the the
BSE BSE contrast contrast
Channeling Channeling Contrast Contrast
electron beam electron beam
crystalline lattice
44
Imaging Imaging of of Dislocation Dislocation Structures Structures
PSB in deformed single-crystalline Cu
(R. Richter, TU Dresden)
Electron Electron Channeling Channeling Pattern Pattern
Si single crystal Si single crystal
rocking beam
incident e
-
beam
scanning
latticeplanes
latticeplanes
45
Bragg Bragg s s law law
x x
d

primary electron
beam diffracted intensity
lattice planes
2x =2d sin =N
The The EBSD EBSD Technique Technique
( (electron electron back back- -scattered scattered diffraction diffraction) )
striping (streifender)
incident electron beam
46
Bragg Bragg Diffraction Diffraction of of Electrons Electrons
x x

phosphorous screen:
intersection with cone =>parallel lines
Kossel cones

The The EBSD EBSD Technique Technique

quartz window
phosphorous screen
47
EBSD EBSD Calibration Calibration
Si single crystal
specimen known orientation
[111]
[011]
[001]
Stereographic Stereographic Projection Projection
[001]-
directions
N
S
standard projection of cubic lattice
[001]
[010]
[100]
48
1 SEM image
2 EBSD pattern
EBSD EBSD measurements measurements
3 indexing
4 pole figure
Orientation Orientation Imaging Imaging Microscopy Microscopy
Hough transformation:
49
Orientation Orientation Imaging Imaging Microscopy Microscopy
different colors correspond
to individual orientations
micro texture analysis
grain boundary engineering
phase analysis
...
7 Analytical
Electron Microscopy
50
X X- -Ray Emission Ray Emission
K
L
M
electron beam
nucleus
electron changes
energy level =>
characteristicX-rays
electron deceleration
in the Coulomb field
continuousX-rays
(Bremsstrahlung)
K
L
M
Characteristic Characteristic X X- -Rays Rays
incident electron (PE)
emitted electron
K
L I
L II
L III
1s
2s
2p
1. ionisation
51
Characteristic Characteristic X X- -Rays Rays
2. X-ray emission
K
L I
L II
L III
characteristic X-rays
K
1
1s
2s
2p
X X- -Ray Ray
Characteristic Characteristic
Energies Energies
Z
Fe
M
K
L

52
Intensity
Energy E
L

characteristic
X-rays
Bremsstrahlung
E
0
EDS EDS spectrum spectrum
( (energy energy dispersive dispersive X X- -ray ray spectroscopy spectroscopy) )
I
E
example: brass (Messing)
[keV]
EDS EDS detector detector
Cu-rod in vacuum
N (l)
2
specimen
take-off angle
PE
UTW(ultradnnes Polymerfenster)
Si(Li)
53
EDS EDS detector detector
X-Ray quantum
Au contact
Si(Li) crystal
Al layer
FET-
preamplifier
(field effect trasnitsor)
voltage step: mV/ns
500-700 V
generation of
electron/hole pairs
Si inactive layer
(Totschicht)
LED
main amplifier/ADC
multi chanel analyzer
X-ray energy
t
Pulse Pulse Pile Pile Up Up
X-ray energy
t
peak too high due to
pulse pile up
within DT ->reject
100s =DT (dead time)
54
Pulse Pulse Pile Pile Up Up
input (cps)
output
no signal anymore:
pulse pile up
Sum SumPeaks Peaks
2 Al K X-rays simultaneous
55
Escape Escape Peak Peak
Cu K quantum generates Si K quantum
Regions Regions of of Interest Interest Line Line Scan Scan
energy
example: brass (Messing)
intensity
energy
Background (noise/Bremssstrahlung))
improvement by narrow energy window
intensity
56
Regions Regions of of Interest Interest Line Line Scan Scan
NiCrMo-Schicht
Stahl
NiCrMo scale
steel
Element Element Mapping Mapping
Al Ti
100m
57
Monte Carlo Simulation Monte Carlo Simulation
characteristicTa X-rays
WDS WDS crystal crystal spectrometer spectrometer
( (wavelength wavelength dispersive dispersive X X- -ray ray spectroscopy spectroscopy) )
x x
d

Bragg: 2x =2d sin =N

characteristic X-rays
diffracted X-rays (certain )
proportional counter
(Proportionlazhlrohr)
latticeconstant
of the crystal
(Monochromatorkristall)
58
WDS WDS crystal crystal spectrometer spectrometer
electron
beam (PE)

r
r =2r
Krist.
crystal (J ohannson)
on Rowland circle
proportional counter
Gas Gas Flow FlowProportional Proportional Counter Counter
Ar outlet Ar inlet
high voltage
(+1 to +3kV)
signal
(to pre amplifier)
isolator
FPC window
X-rays are absorbed by Ar atoms =>ejectionof photo electrons
(up to 50000 counts/s amplificationup to 2000)
thin wire (W)
x-ray photon
59
Comparison Comparison EDS/WDS EDS/WDS
EDS
WDS
characteristic X-rays
emission line
natural width
Quantitative X Quantitative X- -Ray Analysis Ray Analysis
=> => background background subtraction subtraction
continuous Bremsstrahlung absorption (<2keV)
background modelingor background filtering
2 4
6
8
energy [keV]
60
Quantitative X Quantitative X- -Ray Analysis Ray Analysis
=> => Geometry Geometry of of the the Detector Detector
working distance W (10mm), intersection distance d (10mm),
elevation angle E (35), azimuth angle A (45), Scale S (50mm)
surface tilt M (0) => TAKE OFF=35
TEM different !!
Quantitative X Quantitative X- -Ray Analysis Ray Analysis
=> ZAF => ZAF Corrections Corrections
atomic number effect (Z)
Fe+Cr
electron beam (PE)
FeCr alloy
Cr
BSE yield
(different to pure
substances)
TEM:
thin foil!!
61
Quantitative X Quantitative X- -Ray Analysis Ray Analysis
=> ZAF => ZAF Corrections Corrections
absorption (A) and fluorescence effects(F)
Fe+Cr
electron beam (PE)
FeCrNi alloy
Cr
Fe
Fe
Fe
absorption
Fluorescence
8 Case Studies & Discussion
62
Biological Biological Specimens Specimens
fly detail of the wing surface - vacuum dried
(alterantive: environmental SEM)
Phase Phase Characterization Characterization
Ti nitride in NiCr alloy (deep etched/EDS)
63
Phase Phase Characterization Characterization
Ti sulfidein CMSX-6 (polishedand Au sputtered)
Phase Phase Characterization Characterization
phase in SRR99 (electropolished - perchloricand aceticacid)
64
Phase Phase Characterization Characterization/Analysis /Analysis
( ( phase phase in in Ni Ni- -base base superalloy superalloy CMSX CMSX- -6) 6)
200nm
EDS 1
EDS 3
EDS 2
Fracture Fracture Surfaces Surfaces
striations
dimples
65
Damage Damage Analysis Analysis
broken implant (=>metal fatigue)
3D Images of 3D Images of Fracture Fracture Surfaces Surfaces
about 5tilt
66
Damage Damage Analysis Analysis
corrosion corrosion EDS EDS analysis analysis