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HRTEM
ANANDH SUBRAMANIAM
Department of Applied Mechanics
INDIAN INSTITUTE OF TECHNOLOGY DELHI
New Delhi- 110016
Ph: (+91) (11) 2659 1340, Fax: (+91) (11) 2658 1119
anandh333@rediffmail.com, anandh@am.iitd.ernet.in
http://web.iitd.ac.in/~anandh
March 2007
REFERENCES
Transmission Electron Microscopy
David B. Williams and C. Barry Carter
Plenum Press, New York, 1996.
Monographs in Practical Electron Microscopy in Materials Science
J.W. Edington
Philips, Eindhoven, 1974.
High-Resolution Electron Microscopy for Materials Science
Daisuke Shindo and Kenji. Hiraga
Springer-Verlag, Tokyo, 1998.
Experimental High-Resolution Electron Microscopy
John C.H. Spence
Oxford University Press, 1988.
High-Resolution Electron Microscopy
John C.H. Spence
Oxford University Press, 2003.
OUTLINE
When do we see anything ? Contrast
How do we see fine detail ? Resolution
How can we see better ? The TEM
What is meant by High-Resolution?
What things are there to be seen ? Imaging (as we go along)
HRTEM
Nanostructures by HRTEM: Image Gallery
HRTEM = High-Resolution Transmission Electron Microscopy
TEM of Nanomaterials
How can we define nanostructures in a general way ?
What do we want to see in nanostructured materials ?
Why do we want to see these details ?
0.66 nm
Grain-1
1.4 nm
IGF
Grain-2
[0001]
(b)
N. Shibata, S.J. Pennycook, T.R. Gosnell, G.S. Painter, W.A. Shelton, P.F. Becher
Observation of rare-earth segregation in silicon nitride ceramics at subnanometre dimensions
Nature 428 (2004) 730-33.
HAADF-STEM images of the interface between the IGF and the prismatic surface of an Si3N4 grain. The -Si3N4 lattice structure is superimposed on
the images. a) La atoms are observed as the bright spots (denoted by red arrows) at the
edge of the IGF. The positions of La atoms are shifted from that of Si atoms based on the
extension of the -Si3N4 lattice structure; these expected positions are shown by open
green circles. b) reconstructed image of a, showing the La segregation sites more clearly.
The predicted La segregation sites obtained by the first-principles calculations are shown by
the open white circles.
N. Shibata, S.J. Pennycook, T.R. Gosnell, G.S. Painter, W.A. Shelton, P.F. Becher
Observation of rare-earth segregation in silicon nitride ceramics at subnanometre dimensions
Nature 428 (2004) 730-33.
40 nm
16 nm
22 nm
aFWHM ~ 3.2 nm
I I
I
C
I I
1
Contrast
(difference in intensity between
two adjacent areas)
Amplitude contrast
Phase contrast ~ Fringes
* But not bright or dark contrast (these terms refer to intensity and not to contrast)
Absorption contrast
Amplitude Contrast
Contrast
Mass-thickness contrast
small effect in a thin specimen
Diffraction contrast
Thickness Fringes
Bend Contours
Fresnel Fringes
Moir Patterns
Lattice Fringes
In most of the situations both type of contrasts contribute to an image- although one
will tend to dominate
Optical Microscope
0.61
sin
Green light
= 550 nm
~ 300 nm
1000 atomic diameters
TEM
1.22
~ 1/ 2
E
2x
30x
10x
Rayleigh criterion
Not a fundamental rule but a practical definition.
Figure of merit in terms of the eyes ability to distinguish separate
images of two self-luminous incoherent point sources.
A single point source will not be imaged as a point even if aberrations
are absent.
Any physical limit in the path of the rays (outer boundary of the lens /
aperture) will lead to diffraction effects.
Diffraction point is imaged as a disc (Airy disc).
Fully resolved
P1
P2
P1 P2
P1 P2
High-resolution
but not a lattice fringe image
(b)
(a)
1.2 nm
22 nm
nm
Lens
f
v
BACK
FOCAL PLANE
Diffraction
Pattern
IMAGE PLANE
(Gaussian Image Plane)
Backscattered
Electrons (BSE)
Incident
High-kV Beam
Characteristic
X-rays
Auger Electrons
Absorbed Electrons
Secondary
Electrons (SE)
Visible Light
SPECIMEN
Electron-Hole Pairs
Bremsstrahlung
X- rays
Elastically
Scattered Electrons
Inelastically
Scattered Electrons
Direct
Beam
Incident electron
beam With
Uniform intensity
Thin specimen
Scattered electrons with
varying intensity
Image
Incident electron
beam direction
Thin specimen
Diffraction
pattern
Forward scattered
beam directions
le
c
i
t
r
Pa
Scattering
Wa
ve
t
p
e
c
con
con
cep
t
Elastic
~ (1-10)0 Forward
Z has important effect
Inelastic
~ < 10 Forward
Coherent
Incoherent
Coherent
incident beam
Incoherent elastic
backscattered electrons
Secondary electrons
from with in the specimen
Thin specimen
Incoherent elastic
forward scattered electrons
Coherent elastic
scattered electrons
Incoherent inelastic
Direct beam scattered electrons
Coherent
incident beam
Incoherent elastic
backscattered electrons
Incoherent elastic
backscattered electrons
Secondary electrons
from with in the specimen
Bulk
specimen
elastic
Ze
r elastic V
N 0 T t
probability of scattering by the specimen P QT t
A
Transition metals 100 keV electrons
(Mean free path ( MFP ))
MFP
A
N 0 T
elastic 10 22 m 2
Mass-thickness
contrast
inelastic 10 22 10 26 m 2
M FP 10 s of nm
Elastic Scattering
A
Electron
Cloud
Nucleus
Forward scattered
Z contrast imaging atomic resolution microanalysis
Back scattered
I nc
re a
sin
g
f()
()
Au
Al
0.2
Cu
0.4
(Sin)/ (1)
0.6
-22
Au
24
Log10 ( )
Cu
(m2 )
C
-26
60
120
180
Bremsstrahlung
X-ray
Characteristic x-rays
Inelastic
Scattering
(Energy Loss)
Secondary electrons
Collective interactions / Oscillations
Electron-hole pairs and cathodoluminescence
Radiation damage
Characteristic x-rays
Vacuum
Conduction Band
Incoming electrons
(~100 keV)
Valence Band
Energy
E
levels L
L3
E L2
L2
E L1
L1
EK
Nucleus
Characteristic x-rays
(1016s later)
Secondary electrons
Topography in SEM
(resolution using FEG ~ 1nm at 30 keV)
+
STEM ( high-resolution)
Slow SE
~ 50 eV
100s ev
For surface chemistry
-few keV
Auger
electrons
Fast SE
( 50 -200 keV)
Inner shells
Up to 50%
Energy loss
Conduction band
Semiconductors
Band gap
hole
Valence band
H cathodoluminescence (CL)
spectroscopy
Bias
OR
Plasmons
10-22
Elastic scatter
10-23
(m2 )
Ionization
10-24
K
FSE
Secondary Electrons
10-25
10-26
SE
Aluminium
100
200
300
400
Imaging System
Nonrelativistic
wavelength (nm)
Relativistic
wavelength (nm)
Mass
(x mo)
Velocity
(x 108 m/s)
100
0.00386
0.00370
1.196
1.644
120
0.00352
0.00335
1.235
1.759
200
0.00273
0.00251
1.391
2.086
300
0.00223
0.00197
1.587
2.330
400
0.00193
0.00164
1.783
2.484
1000
0.00122
0.00087
2.957
2.823
Fully resolved
Unresolved
P1
th
P2
0.61
P1 P2
P1 P2
voltage
Cant increase as lens aberrations with
Can be increased by a larger lens aperture but electron lenses
are not good
Resolution
Electron Source
Imaging System
Lenses
Spherical Aberration
Chromatic Aberration
Astigmatism
Apertures Control
Lenses aberrations
Spherical Aberration
rsph = Cs 3
Cs ~ Focal lengh
~ (1-3 mm)
Chromatic Aberration
E
rchr = Cc
Current high tension supplies are stable to 1 in 106 (100 keV beam 0.1 eV)
For electrons passed through a sample (50-100 nm thick) E = (15-25) eV
Astigmatism
rast = f
Lens
CS = 0
CS 0
dmin
Spherical aberration
Astigmatism is corrected
Assume
Specimen is thin low chromatic aberration
rsph limits the resolution
Further resolution f(Rayleigh criterion, aberration error)
min
opt
c s c s
3
0.91
1
4
0.77
cs cs
1
4
1
4
1
4
0.0037nm
3mm
opt
r 0.3nm
15mrad
opt
HREM
min
r 0.15nm
min
Useful magnification
Take resolution on specimen ~ 2 Magnify the resolution of eye 0.2 mm
0.2 103
6
10
M useful 0.2 109
Phonon excitation
(~ 0.2 eV, 5-15 mrad)
EELS
Plasmon excitation
(~5-25 eV, < 0.1 mrad)
p ~ 100nm
Surface plasmon
Bulk plasmon
Transverse waves
Half the energy of
bulk plasmons
Longitudinal waves
COLLECTIVE OSCILLATIONS
PLASMONS
Collective oscillations of free electrons
Most common inelastic interaction
Damped out in < 1015 s
Localized to < 10 nm
Predominant in metals
(high free electron density)
PHONONS
Collective oscillations of atoms
Can be generated by other inelastic
processes. (Auger / X-ray energy)
Will heat up the specimen
Small energy loss < 0.1 eV
Phonon scattered electrons
to large angle (5 15 mrads)
Diffuse background
Plasmon excitation
Longitudinal wave like oscillations of weakly bound electrons
Rapidly damped (lifetime ~10-15 sec, localized to < 10 nm)
Dominate in materials with free electrons (n) (Li, Na, Mg, Al )
But occur in all materials
EP = f(n) microanalytical information
Carry contrast formation, limit image resolution through chromatic aberration
Can be removed by energy filtering
Ionization Edge
Io
Bonding effects
ELNES
EXELFS
Plasmon peak
40
80
300
250
Energy-loss (eV)
350
400
450
Energy Resolution
Using FEG DSTEM Krivanek et al. [Microsc. Microanal. Microst. 2, 257 (1991).] detected single atom of Th on C film
EELS
2.761
19000
No visible
Grain
Boundary
18000
17000
counts
16000
Si peak at
1839 eV
Sr L2,3 peaks
15000
14000
13000
Grain Boundary
12000
11000
10000
20000
1850
1900
1950
2000
2050
eV
2100
2150
2200
2250
19000
18000
counts
17000
Dislocation
structures at
the Grain
boundary
16000
15000
14000
Grain
13000
12000
11000
1850
1900
1900
1950
2000
2000
2050
eV
2100
2100
2150
eV
GB2
3x4
MX2
3x4
Dist 5 nm
VG microscope
2200
2200
2250
EELS microanalysis
[1]
EELS microanalysis
detection of a single atom of Th
on C film
ELNES
[1]
[1]
L3
Graphite
L2
CuO
Diamond
Cu
v
v
280
290
300
310
320
Energy-loss (eV)
920
940
960
980
Energy-loss (eV)
Change in Cu L edge as Cu metal
is oxidized
[1] Chapter 40 in Transmission Electron Microscopy by David B. Williams and C. Barry Carter, Plenum Press, New York, 1996.
Seeing is believing ? ! ?
2D image of 3D specimen
Diffraction contrast
Contrast depends on lenses + apparatus
Absorption contrast is usually small
Phase contrast related to specimen and not to topography (or depth)
Real space
h(r )
Point spread function
Specimen
Diffraction pattern
Reciprocal space
f ( x, y ) f ( r )
F (u )
H (u )
Contrast transfer function
Image
G(u )
g ( x, y ) g (r )
Fourier transform
g ( r ) f ( r ) h( r )
G(u ) H (u ) F (u )
H (u ) A(u ) E (u ) B(u )
Contrast transfer
function
Aberration function
Envelope function Property of lens
Aperture function
B(u ) exp[i (u )]
3 4
u
2
s
(u ) ( f u )
2
(u ) f (f , , u, Cs )
High resolution implies ability to see two closely spaced features in the
sample (real r space) as distinct
This corresponds to high spatial frequencies large distances from the
optic axis in the diffraction pattern (reciprocal (u) space)
Rays which pass through the lens at such large distances are bent
through a larger angle by the objective lens
Due to an imperfect lens (spherical aberration) these rays are not focused
at the same point by the lens
Point in the sample disc in the image (spreading of a point in the
image)
Objective lens magnifies the image but confuses the detail (hence the
resolution is limited)
Each point in the final image has contributions from many points in the
specimen (no linear relation between the specimen and the image)
Is a linear relationship possible?
f ( x, y ) A( x, y ) e i x , y
V(x,y,z)
f ( x , y ) e i x , y
Phase change = f(Vt)
f ( x, y ) e i Vt x , y
Weak Phase Object approx.
f ( x, y ) 1 Vt ( x, y )
Including
absorption
f ( x, y ) e[ i Vt x , y ( x , y )]
Vt ( x, y ) V ( x, y, z )dz
d
Vt ( x, y ) Vt ( x, y )
E
WPOA For a very thin specimen the amplitude of the transmitted wave function will be linearly
related to the projected potential
In vacuum
h
2meE
Phase change
h
2me( E V ( x, y, z )
2
2
V ( x, y, z ) dz d V ( x, y, z ) dz
d ' dz
dz d
E
Vt ( x, y ) Vt ( x, y )
E
Vt ( x, y ) V ( x, y, z )dz
x x 2 x3 x 4
1
1! 2! 3! 4!
g ( r ) f ( r ) h( r )
WPOA
( x, y ) [1 Vt ( x, y )] h( x, y )
( x, y ) [1 Vt ( x, y )] [Cos ( x, y ) i Sin( x, y )]
I = *
Neglecting 2
I [1 2 Vt ( x, y )] Sin( x, y )
B(u ) exp[i (u )]
B(u ) 2Sin[ (u )]
T (u ) A(u ) E (u ) 2Sin[ (u )]
Approximately
T (u ) 2 A(u ) Sin[ (u )]
Or
T (u ) 2 A(u ) Sin[ (u )]
T(u) = 2 Sin()
+2
2.5
2
u (nm1)
Teffective(u)
T(u) = 2 Sin()
f Scherzer Cs
3
1
4
s
T (u ) 2 A(u ) Sin[ (u )]
uScherzer =1.51 C
1
4
s
u (nm1)
rScherzer = 0.66 C
1
2
3
4
3
4
Instrumental resolution
limit can use nearly
intuitive arguments to
Damping envelope interpret the contrast
Information limit
IMAGE SIMULATION
(a)
(b)
Thickness dependency of lattice images of a Si crystal (200 kV, f = 65 nm). Thickness changes from 1nm
(a) to 86 nm (r) in steps of 5 nm.
High-Resolution Electron Microscopy for Materials Science by Daisuke Shindo and Kenji Hiraga, Springer-Verlag, Tokyo, 1998.
ADVANCES
Spherical aberration correctors for illumination as well as imaging lens systems,
Electron beam monochromators reducing the energy spread of the electron beam
to < 0.1 eV
High-energy resolution spectrometers (Sub-eV mandoline filter for EELS)
Imaging energy filters
Advanced specimen holders for in-situ experiments
High-sensitivity and high-dynamic-range detectors for images, diffraction patterns,
electron energy loss spectra (EELS) and energy dispersive X-ray spectra (EDXS)
Advanced methods
It is possible to record phase contrast images with point resolutions of well below
0.1 nm, or alternatively, scan electron probes of size < 0.1 nm across the
specimen, recording high-angle scattering or high-energy resolution spectra from
areas as small as a single atomic column.
ELECTRON HOLOGRAPHY
(a)
(b)
High-resolution (a) amplitude and (b) phase images of the aberration-corrected object wave
reconstructed from an electron hologram of [110] Si, obtained at 300 kV on a CM 30 FEG
TEM. The characteristic Si dumbbell structure is visible only after aberration correction.
A. Orchowski et al., Phys. Rev. Lett. 74, 399, 1995.
FRESNEL RECONSTRUCTION
RT
HT
Cooled
to RT
RT
2.3 nm
A
HTnm
20
20
nm
B
2.5 nm
B
Cooled to RT
20 nm
20
nm
3.2 nm
-40
C
20 nm
20
nm
-20
20
0
Distance ()
40
NANOSTRUCTURES
IMAGE GALLERY
NANOTUBES
HRTEM image of a BN multi-walled
nanotube (inner shell distance of ~ 0.33 nm).
D. Golberg et al., J. of Appl. Phys. 86, 2364, 1999.
(a)
(b)
(c)
NANOLAYERS
(a)
(b)
NANOPARTICLES
[110]
[001]
(a)
(b)
(c)
[110]Al
NANOTWINS
Twin Plane
[011]
NANO(poly)CRYSTALLINE MATERIAL
MOIR FRINGES
2 >10-50 mrad
3 < 10 mrad
Specimen
1
2
HAADF
detector
3
BF detector
ADF detector
HAADF-STEM images of the interface between the IGF and the prismatic surface
of an -Si3N4 grain.
N. Shibata, S.J. Pennycook, T.R. Gosnell, G.S. Painter, W.A. Shelton, P.F. Becher
Observation of rare-earth segregation in silicon nitride ceramics at subnanometre dimensions, Nature 428 (2004) 730-33.