Transmission electron microscopy in

materials science

A. Mogilatenko, H. Kirmse
Humboldt-Universität zu Berlin,
Institut für Physik, AG Kristallographie
Newtonstrasse 15, D-12489 Berlin

Telefon 030 2093 7868, Fax 030 20937760

E-mail: anmog@physik.hu-berlin.de
holm.kirmse@physik.hu-berlin.de
Web: http://crysta.physik.hu-berlin.de/ag_tem/
Raum 2‘403
pdf-Dateien der Vorlesungen unter:
http://crysta.physik.hu-
berlin.de/~kirmse/
Teaching
„Inorganic Materials"
Vorlesungen zur
Elektronenmikroskopie:
Teil 1, Teil 2
Introduction and short history
 First transmission electron microscope
First TEM built in 1931 by
Max Knoll and Ernst Ruska
in Berlin

1931: magnification 17
resolution > light microscope
1933: magnification 12.000
Nobel Prize in Physics 1986 resolution < light microscope
 Ray diagram in light microscopy and
TEM
lamp illumination electrons

electromagnetic
glass lens condensor lens
lens
specimen
electromagnetic
glass lens objective lens
lens
first image

projective lens electromagnetic

glass lens
lens
final image
eye
ocular
fluorescent
eye screen
Theory of image formation and resolution
limit
1866 - starts working with Carl Zeiss
1873 - theoretical description of
resolution limit

d
2n sin
: wavelength
Ernst Abbe: n: refractive index of medium
1840-1905 between object and objective
: opening angle of rays originating
from object and collected by objective
„… it is poor comfort to hope that human ingenuity will find ways and
means of overcoming this limit.“
 Resolution: Light Microscopy
no lens imperfections =>
resolution is limited by diffraction at edges of lens system

d
2n sin ! To get a better resolution –
decrease the wave length!

Light optics:
: wavelength 400 .. 800 nm
n: refractive index of medium 1 .. 1.5 (air .. immersion system)
between object and objective
: opening angle of rays originating from object 70°
and collected by objective
=> d ~ 250 nm
Monument in Jena (Germany)
 Wave-Particle Duality
Louis de Broglie, 1924
h h h
p 2m0eV
2m0eV 1
eV
2m0c 2 !
with 100 keV electrons travell
at about 1/2c!
V: acceleration voltage, m0: electron mass
e: electron charge, c: velocity of light
 Wave-Particle Duality

wave  particle
coherent ↔ incoherent elastic ↔ inelastic

imaging, spectrometry
high resolution imaging,
diffraction
 Electron wavelength
/ pm

V / kV
V = 300kV => = 1.97 pm => resolution only ~ 0.1 nm ?
„magnetic lenses of TEMs have similar quality as
bottom of bottle of champagne would have for light microscope“
TEM – multi lens system
 How can I focus electron beam?
electric field E
electron charge e => force F E
F = -e*E
force in opposite direction of electric field
magnetic induction B
electron velocity v => Lorentz force
F = -e(v x B)
force perpendicular to magnetic field and electron
velocity direction

B
 Magnetic electron round lens

~ 1 - 2 Tesla

Williams & Carter

 Magnetic electron round lens

Wine glass
with water =
optical lens with
huge aberrations

Electron lenses are

bad lenses too!!!

“if the lens in your own eyes would be as bad as

electromagnetic lenses, then you would be legally blind“
Williams & Carter
 Ray diagram
(Strahlengang)

lens

object

optic
axis
 Ray diagram

back focal image

lens plane plane
Brennebene Bildebene
object

optic
axis
optische
Achse

d1
d2
 Ray diagram

back focal image

lens plane plane
Brennebene Bildebene
object

optic
axis

d1
d2
 back focal image
lens plane plane

object

optic
axis

diffraction
pattern
 Perfect imaging by a round lens
the same focus for all rays

Object
marginal ray

paraxial ray

Objective lens Image plane

Spherical aberration (Öffnungsfehler) - off-axis rays
are focused stronger!
disk of least
confusion
marginal ray

paraxial ray

marginal focus
paraxial focus
Objective lens
Image plane
A point object is imaged as a disk of finite size –
limits the resolution!
Improvement in resolution

sub-Å
resolution

H. Rose, Journal of Electron Microscopy: 1-9 (2009)

 Problems / disadvantages in TEM

• time consuming specimen preparation is required

• only small sample regions can be investigated
(~ 1 nm…some µm)
• electron beam damage

damage dose:
living objects: 10-4 – 1 e/nm²
bio molecules: 103 – 105 e/nm²
anorganic substances: 106 – 1011 e/nm²
Rose equation: links resolution d and contrast c
c * d > 5/n0.5
n: number of electrons per unit area
example: c = 5 %; d = 0.3 nm => n > 105 e/nm²
 Electron beam induced segregation effects

Electron beam damage in InGaN QWs - In-clustering

Smeeton et al., Appl. Phys. Lett. 83 (2003) 5419

Interaction of electrons and matter
 primary electrons Energy-Dispersive
100…400 keV X-ray
backscattered Spectrometer
electrons
X-rays
secondary
electrons

10…200 nm thin crystalline

specimen

diffracted Electron Diffraction,

beam Conventional imaging,
High resolution imaging

direct
beam High-Angle
Annular Dark-Field
Detector
elastically and inelastically
scattered electrons
Electron Energy Loss
Spectrometer
 Electron forward scattering from thin specimen
coherent
• single scattering
incident beam
• plural scattering (>1)
• multiple scattering (>20)

thin specimen

incoherent
elastic
coherent scattered
elastic scattered incoherent electrons
electrons inelastic scattered (> ~10°)
(1…10°) electrons
(< 1°)
direct beam
 Scattering of electrons

Bulk material TEM specimen

50 nm

1 nm

50 µm 200 nm

Monte-Carlo Simulation of the paths

of electrons (acceleration voltage: 100 kV) Full width at
trough Silicon of different thicknesses half maximum

12 nm
 TEM/STEM

IMAGING DIFFRACTION SPECTROSCOPY

Phase
Amplitude Selected Energy Electron
contrast
contrast (high- area dispersive energy loss
(diffraction resolution diffraction X-ray spectroscopy
contrast) imaging) spectroscopy

Electron Z-contrast Convergent Micro-/ X-ray Energy-filtered

holography imaging beam nano- mapping TEM (EFTEM)
diffraction diffraction

Lorenz
microscopy Tomography
TEM specimen preparation
Why sample preparation for Transmission Electron
Microscopy

• Electrons with properties of particles and waves

• Strong interaction between electrons of the

beam and atoms of the samples scattering

• Sufficient intensity/number of transmitted

electrons only for small thickness (about 100 nm)

• Essential thickness depends on, e.g.,

materials properties, acceleration voltage, and
requirements of individual investigation method
 Demands on sample preparation

• No change of materials properties including:

– Structure (amorphous, polycrystalline,
crystalline)
– Chemistry (composition of the bulk material,
of surfaces, and of interfaces)
• But:
Artifacts inherent in every preparation
method!
• Criterion of appropriate preparation technique:
Influence on structural and chemical
properties as small as possible!
Shape of the sample

• TEM sample holders

• Limits of sample size:

– Diameter: 3 mm
due to the furnace
of the TEM sample
holder
– Maximum
thickness of
sample edge: ca.
100 µm
 Aim of investigation Type of sample

• Structural properties • Particles

– size distribution of • Bulk material
entities • Epitaxial structures
– area density
Materials properties
– structural defects
• Hardness
• Chemical properties
• Sensitivity for
– composition chemical solutions
– modification
– interface sharpness
• Electronic properties
• Magnetic properties Preparation strategy
 TEM preparation of small particles

• Dispersion in a non
dissolving liquid (e.g.:
methanol, water, etc.) in an
ultrasonic bath
• Transfer to a carbon film
supported by a copper grid

Evaporation of a droplet Dipping

 TEM grids

and many
more

holey carbon film lacey carbon film

 CaF2 with Pd particles (after reaction)
transmission electron microscopy bright-field image
Pd-CaF_HF25_slotB2; hrtem01_particel01_ovw_3kx

Humboldt-Universität zu Berlin,
Institut für Physik (AG Kristallographie), Institut für Chemie (AG Festkörperchemie)
 0.16 nm

0.16 nm

Lattice plane distances d (nm)

CaF2 Pd PdF2 PdO
0.24 nm
0.31541 0.22458 0.30756 0.30431
0.27315 0.19451 0.26868 0.26680
0.19314 0.13754 0.23832 0.26430 0.27 nm
0.16472 0.11730 0.21748 0.21521 0.27 nm
0.15770 0.11230 0.18834 0.20060
0.13657 0.09725 0.17757 0.16751
0.12533 0.08925 0.16061 0.15358
0.12216 0.08699 0.15378 0.15215

Matrix (after reaction)

high-resolution transmission electron microscopy imaging
Pd-CaF_HF25_slotB2; hrtem01_particle03_25kx

Humboldt-Universität zu Berlin,
Institut für Physik (AG Kristallographie), Institut für Chemie (AG Festkörperchemie)
TEM preparation of epitaxial structures
 Plan-view and cross-sectional TEM
preparation
Plan view (PVTEM) Cross section (XTEM)
Initial sample Formatting Gluing in a cylinder
and sawing

Thinning of substrate face-to-face gluing

Mechanical thinning

Cutting of a disc Gluing of dummies

Dimpling
Dimpling
Ultrasonic disc cutting
Ion-beam milling
Ion-beam milling
 Mechanical thinning damage

Beilby layer: change of

Region 1 chemical composition,
strong deformation, amorphisation

macro-deformed layer:
Region 2 tilt of grains,
increased dislocation density

micro-deformed layer:
Region 3 weak tilt of grains,
dislocation density as grown

~ 100 nm Situation after sawing

Next preparation step has to remove the damage!
 Dimple grinding

Detail of a dimple grinder

Principles of dimpling technique

sample
thickness in the
Dimpler grinder of Gatan center ~ 20 µm
 Ion-beam milling

sample

Layout of a vacuum
Ion gun arrangement for milling of chamber with two ion guns
both sides of the sample;
possible ions: Ar+, Xe+, I+, ...
acceleration voltage: 1...5 kV
usual angle : < 10°
 GaAs
Ga(Sb,As)

(In,Ga)As
GaAs

GaAs

TEM Philips CM200 FEG cS, GaAs spacer thickness: 4.5 nm

HRTEM of Ga(Sb,As) QD on (In,Ga)As seed QD

TU#5294cs/2, links: qdot4_012c.jpg, rechts: qdot5_012c.jpg

Humboldt-Universität zu Berlin, Institut für Physik, AG Kristallographie

Forschungszentrum Jülich GmbH, Institut für Festkörperforschung
 Contrast in TEM

most
most most important in
important important HRTEM
for for
amorphous crystalline
samples samples
Amplitude contrast: mass-thickness contrast
total cross section Qtot for scattering from sample (thickness t):
Avogadro number density
N0 tot
t)
Q tot t atomic weight of atoms
total scattering cross section A
of an isolated atom ! product t is called „mass thickness“

Thicker and /or higher mass (Z) areas

will scatter more electrons and appear
darker in the image
 Amplitude contrast: diffraction contrast

primary beam Bragg’s law:

n·λ = 2·d·sinθ
sample

objective lens

objective aperture

intermediate lenses
Two beam conditions:
projective lenses Tilting the specimen unitl direct
beam and one diffracted beam are
strong!
imaging plane
 Phase contrast: high resolution TEM
2-beam
primary beam
condition
sample

objective lens

objective aperture

multiple-beam
condition
intermediate lenses
projective lenses

imaging plane
 Phase shift due to the inner potential of
specimen
Electron beam Path through the vacuum:


2 m e E  – Plancks constant
m – electron mass
e – electron charge
E – electron energy

Path through the specimen:


'
2me E V x, y, z
d
V x, y , z – inner potential
energy
Phase shift due to the inner potential of
specimen
Plane wave
local charge energy

0 r, t

V x, y , z

mean inner potential

x
atomic nucleus
object exit wave
t

Object r,t projected potential: Vt x, y V x, y, z dz
(thin sample) 0
 Phase shift due to the inner potential of
specimen
Electron beam Phase shift:
dz dz
d 2 2 V x, y , z
'
with (interaction constant)
E
Total phase shift:
z
d V x, y, z dz Vt x, y

d ! phase change depends on potential V

which electrons see, as they pass
through sample
HRTEM – Imaging Process
y

Object
x
Diffraction pattern

gy

gx

Image

x
 Role of optical system
transfer of each point in specimen into region in final image
f(x,y): specimen (transmission) function describes specimen
g(x,y): extended region of point x,y in image
h(r-r`): weighting term: point spread function

gr f r' h r r' dr' f r t r r'

point f(x,y) 2 points

optical system

disc each point in final image has contributions

image g(x,y)=g(r) from many points in specimen
 HRTEM: contrast transfer function
T(u) ! opposite sign of T(u) -
information
oposite contribution to
point limit
contrast
resolution
u < point resolution:
u, [nm ] images are directly
-1

interpretable
u > point resolution: no
direct interpretation is
possible
E u sin χ(u)
Eu
No simple correspondence between the image
intensity and the atom column positions!
Additional calculations are necessary!
f - defocus
2 1 3
u f u Cs u4 - wave length
Cs - spherical aberration
2 u - spatial frequency
 1
Contrast transfer sin u sin f u 2
Cs 3
u4
2

Optimum for f : Scherzer Minimization of Cs

 Example: HRTEM simulation for GaAs

projected
potential

same thickness,
only defocus
change

by courtesy of Prof. Kerstin Volz

HRTEM of an isolated ZnTe nanowire

- visualization of crystal structure

- analysis of defects
HRTEM of an isolated ZnTe nanowire

{211}

{111} {110}
HRTEM of an isolated ZnTe nanowire

{211}

{111} {110}

Twin formation