Analytical

Transmissions Electron Microscopy

(TEM)

TEM is based on three

possible set of techniqes
Diffraction

From regions down to a few

nm (CBED).

Imaging

Spectroscopy

With spatial resolution

down to the atomic level
(HREM and STEM)

Chemistry and elecronic

states (EDS and EELS).
Spatial and energy
resolution down to the
atomic level and ~0.1 eV.

200 nm

Introduction
EM and materials
The interesting objects for TEM is not the average structure
or homogenous materials but
local structure and inhomogeneities

Defects

Interfaces

Precipitates

Basic TEM
Electron source (HV= 200kV)
Apertures

Magnetic lenses
Sample holder

Vacuum in the column

better than 10-6 Pa

Fluorescence screen
Recording media
(Film/CCD/ TV)

Pedals for tilting the sample

Instrumentation
Filament

Similar components as a transmission light microscope

Anode

The diffraction limit on resolution

is given by the Raleigh criterion:
1. and 2. condenser lenses

d=0.61/sin, =1, sin~

Sample

Objective lens

Compared to the lenses in an

optical microscope they are very
poor!

Intermediate lenses

The point resolution in a TEM is

limited by the aberrations of the
lenses.
Projector lens

-Spherical
- Chromatic
-Astigmatism

Resolution limit
Year
1940s
1950s
1960s
1970s
1980s
1990s
2000s

Resolution
~10nm
~0.5-2nm
0.3nm (transmission)
~15-20nm (scanning)
0.2nm (transmission)
7nm (standard scanning)
0.15nm (transmission)
5nm (scanning at 1kV)
0.1nm (transmission)
3nm (scanning at 1kV)
<0.1 nm (Cs correctors)

http://www.sfc.fr/Material/hrst.mit.edu/hrs/materials/public/ElecMicr.htm

The electron source

Two types of emission guns:
Thermionic emission
W or LaB6
Field emission
W Cold FEG

ZrO/W Schottky FEG

Electron interaction with the specimen

e-

Backscattered electrons
Auger electrons
Cathodoluminescence

Secondary electrons
X-rays

Absorbed electrons
EBIC

Specimen

Elastically scattered
electrons

Inelastically scattered
electrons

Transmitted electrons

Gas
Heating
Cooling

TEM specimens
TEM grids

The interesting objects for EM

is not the average structure
or homogenous materials but
local structure and inhomogeneities

Cooling
Standard
Heating

3 mm

Operating modes
Convergent beam

Parallel beam

Can be scanned
(STEM mode)

Specimen
Spectroscopy and mapping
(EDS and EELS)

Imaging mode
or

Diffraction mode
A.E. Gunns

MENA3100 V13

Simplified ray diagram

b
a

Parallel incoming electron beam

3,8

Si

Sample

1,1 nm
PowderCell 2.0

Objective lense

Diffraction plane
(back focal plane)

Image plane

A.E. Gunns

MENA3100 V13

Image or diffraction mode

Filament

Anode

1. and 2. condenser
lenses
Spesimen

Objective lens

Bi-prism

Objective aperture
Selected area aperture

Diffraction plane
Image plane

Intermediate lenses

Projector lens
Viewing screen

A.E. Gunns

STEM detectors (BF and HAADF)

Image or diffraction pattern

MENA3100 V13

Simplified ray diagram

b
a

Parallel incoming electron beam

3,8

Si

Sample

1,1 nm
PowderCell 2.0

Objective lense

Diffraction plane
(back focal plane)

Image plane

Electron diffraction
Elastic scattered electrons

Inelastic scattered electrons

Only the direction of v is changing.

(Bragg scattering)

Direction and magnitude of v change.

Elastic scattering is due to Coulomb interaction

between the incident electrons and the electric
charge of the electron clouds and the nucleus.
(Rutherford scattering).
The elastic scattering is due to the average
position of the atoms in the lattice.

Energy is transferred to electrons and atoms

in the sample.
-It is due to the movements of the atoms
around their average position in the lattice.
- It give rise to a diffuse background in the
diffraction patterns.

Reflections satisfying Braggs law:

2dsin=n
Electrons interacts 100-1000 times stronger with matter than X-rays
-more absorption (need thin samples)
-can detect weak reflections not observed with x-rays

Selected area diffraction

Parallel incoming electron beam

Specimen with two

crystals (red and blue)

Objective lense

Diffraction pattern

Selected area
aperture

Image plane

Pattern on the screen

Diffraction with large SAD aperture,

ring and spot patterns
Poly crystalline sample

Four epitaxial phases

Similar to XRD from polycrystalline samples.

The orientation relationship between the

phases can be determined with ED.

Why do we observe many reflections

in one diffraction pattern?

A.E. Gunns

MENA3100 V13

Example: Study of unknown phase in a BiFeO3 thin film

Metal organic compound on Pt

BiFeO3

Heat treatment at 350oC (10 min) to remove

organic parts.

Pt
TiO2

Lim

Process repeated three times before final heat

treatment at 500-700 oC (20 min) .
(intermetallic phase grown)

SiO2
Bi

Bi
O
O

Si

Bi

Bi
Fe
O

Bi
Fe

Fe
O

O
O
O

200 nm

Fe

Bi

Fe

Fe

Bi

Bi

O
O
O

Bi

Bi
Bi

Fe

Goal:

Fe

Fe

O
O

BiFeO3 with space grupe: R3C

and celle dimentions:
a= 5.588 c=13.867
c

O
Fe

Bi

Fe
Bi

Bi

O Fe

Bi
Bi
Po wd erCell 2 .0

Determination of the Bravais-lattice of an unknown crystalline

phase
Tilting series around common axis
27o

15o

50 nm

10o

0o

Chemical analysis by use of EDS and EELS

Ukjent fase
BiFe2O5

BiFeO3

x 1000
counts
CCD
x 1000
counts
CCD

1_1evprc.PICT
Nr_2_1evprc.PICT
40
14
35
12

O-K
Fe - L2,3

30
10
25
8
20
6

BiFeO3
Ukjent fase

4
15
2
10
-0
5

500
1400
eV pr. kanal
-0 eV forskyvning,
200
600
-0

200

Energy
(eV)
400 Loss 600
Energy Loss (eV)

800
800

1000
1000

Other analysis Techniques

One of the main strengths of TEM is the ability to obtain diffraction (structural information) and images from the same
area at the same time from the same sample from a small volume.
There are, however many more analysis techniques available:-

Energy Dispersive Spectroscopy (EDS) for compositional analysis.

Electron Diffraction for crystallographic analysis.
Dark Field imaging enhanced contrast using crystallography.
High Resolution TEM (HRTEM) with resolution to atomic scale.
Scanning TEM (STEM) for increased resolution\contrast.
Electron Energy Loss Spectroscopy (EELS) to examine local electronic environment allowing mapping of elemental
distribution to atomic level.
Tomography to produce 3 dimensional models of samples.
Low dose and Cryo TEM to allow analysis of beam sensitive materials e.g. polymers and biological samples.

Energy Dispersive Spectroscopy (EDS)

EDS analysis in the TEM can be performed on very small areas due to very small interaction volume.
In SEM the interaction volume is ~ 1m3 from a 0.1m probe size.
In TEM the interaction volume is of the order of nm (~10-8 m3 for a FEG TEM) due to very thin samples and very
small probe sizes.

Comparison of interaction volumes in an SEM, Thermionic TEM and FEG TEM showing much smaller interaction
volume for TEM.

Electron Diffraction
Diffraction patterns give crystallographic information about a material from site specific small volumes, unlike XRD
which is a bulk analysis technique.
Can determine if a material is amorphous, crystalline or poly crystalline quickly and effectively.

a)

b)

c)

a)Amorphous material, b) Crystalline material and c) polycrystalline material

Lattice parameter information, unit cell details and any periodicity present in the sample arising from structural
transformations or ordering processes can be seen.

Superlattice structure gives information about the long range make up of a material.

SuperLattice Reflections
Patterns a) to c) are electron diffraction patterns taken from CaTiO3 super lattice reflections are seen showing the
presence of Cation Shifts (cs), In-phase tilting (it) and antiphase tilting(at).
a)

000

001

b)

010

c)

0-11

at

001

1-10

000

cs

000

at

-110
It(ii)
It(i)

cs

001

e)

d)

f)

010
cs

10-1

1-10

o2 000

000

it

0-11

001 patterns from Sr(Zn )Nb )O the same osuperlattice

1
Patterns d) to f) are electron diffraction
reflections are seen as in
1/3
2/3
3
cs

CaTiO3, but with additional ordering reflections

Both CT and SZN have the same tilt system

a
(o1 and
t

(a-a-c+)

o1

o2).

o1

000

at
o2

so are related, but SZN

has
-110

10-1

o1
it
long range

CT space group is Pnma (orthorhombic), SZN is P21/c (Monoclinic - = 125.501).

it

ordering as well.

SuperLattice in XRD and ED

In XRD traces the appearance of superlattice reflections is influenced by the
size difference of the cations.

Ordering Peak
Intensity

Intensity
2Theta

SMN ordering
peak in XRD

The ordering peak (~20 2 Theta) in SMN is much larger (Approx. 12X) than
the same peak in SZN.
Consequently, the ordering peak in SZN is easy to overlook. This is not a

2Theta

SZN ordering
peak in XRD

problem in Electron Diffraction.

Major perovskite
reflection
Major perovskite
reflection
(hk0)In phase
tilting reflection
<111> electron diffraction
pattern of CT

(hkl)anti phase
tilting reflection
1/3

<110> electron diffraction

pattern of SMN

(hkl)ordering
reflection

Superlattice reflections are clearly visible in electron diffraction patterns.

Electron diffraction therefore provides a powerful tool for the investigation of superlattice reflections in materials
(e.g. Tilting, ordering and layered structures).

Symmetry Analysis
Convergent Beam Electron Diffraction (CBED) is a powerful tool for analysing and identifying symmetry in
materials.
a)

b)

a)Convergent Beam Electron Diffraction (CBED) pattern showing Six fold rotational symmetry and b)Selected
area Diffraction Pattern (SADP) of same area.
Unknown materials can be analysed and their space groups be found to aid identification\characterisation.

Symmetry Analysis 2
Overlaying of CBED patterns gives a map of the crystal which you can navigate around to find the region\ zone axis
(direction) of interest.

<111>

Overlayed CBED patterns for a FCC system.

<110>

<100>

Dark Field Imaging

Dark Field images are formed from specific diffracted beams, giving orientation contrast.
Bright Field images are formed using spot A.
A typical Dark Field images would be formed using spot B.
Bright field images contain information from all electrons that have passed through the sample therefore subtle
features are hidden.
With Dark Field images, a specific plane can be viewed in order to see specific crystallographic features such as
dislocations, regions of ordering or strain fields etc.

Dark field images typically have considerably higher contrast than bright field images although the intensity is
greatly reduced.

Dark Field Image formation

Can select the spot by moving the aperture or tilting the beam to bring the selected spot to the optical axis of the
microscope.

Image formation for a Bright Field, Displaced Aperture Dark Field (DADF) and Centred Aperture Dark Field
(CADF) image.

Dark Field Imaging Example

c)

a)

b)

001
at

000

110

d)

010
000
1.0 m

10-1

cs

Image a) illuminated with Cation Shift (cs) spot in c).

Image b) illuminated with Antiphase tilt (at) spot in d).
c) and d) both <110> zone axis diffraction patterns (ZADP).
Clear crystallographic difference between the two area is seen visually.

1.0 m

Dark Field Imaging Example 2

b)
a)

300nm

Image a) Dark Field image of unshadowed and unstained DNA, Image b) illuminated with ordering superlattice
reflection regions of ordering clearly visible.