5.

Transmission Electron Microscopy

Dr Acha Hessler-Wyser
Bat. MXC 134, Station 12, EPFL+41.21.693.48.30.

Centre Interdisciplinaire de Microscopie Electronique CIME

Intensive SEM/TEM training: TEM

Acha Hessler-Wyser

Outline
a. b. c. d. e. TEM principle A little about diffraction TEM contrasts Examples Structure analysis

Intensive SEM/TEM training: TEM

Acha Hessler-Wyser

EPFL: Philips CM300 300000V

Intensive SEM/TEM training: TEM

Acha Hessler-Wyser

Canon

EPFL: Philips CM300 300000V

Illumination Echantillon Projection

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a. TEM principle

Intensive SEM/TEM training: TEM

Acha Hessler-Wyser

a. TEM principle
Lenses, general principle of optical geometry
First approximation: thin lens
plan focal image plan focal objet

Fi Fi fi

F
o

Fo

fo

In particular, an image of the source placed at the object focal point F0 of the condensor 2 will give a parallel illumination onto the sample

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a. TEM principle
Parallel or converging illumination

A third lens is needed to make sure to have a parallel illumination

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b. a little about diffraction

Interaction of electrons with the sample
Incident beam
Backscattered electrons BSE secondary electrons SE Characteristic X-rays visible light

Auger electrons

1-100 nm

absorbed electrons

Specimen

electron-hole pairs

direct beam

elastically scattered electrons

Bremsstrahlung X-rays inelastically scattered electrons

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b. a little about diffraction

Auger electrons

1-100 nm

How about diffraction ???

Incident beam
Backscattered electrons BSE absorbed electrons Specimen electron-hole pairs direct beam

secondary electrons SE Characteristic X-rays visible light

elastically scattered electrons

Bremsstrahlung X-rays inelastically scattered electrons

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b. a little about diffraction

Mean free path
It is the distance an electron travels between interactions with 1 A atoms:

Scatter from isolated atoms

"=

QT

N 0# T $

The interaction cross section represents the chance of a particular electron to have any kind of interaction with an atom. ! The total scattering cross section is the sum of all elastic and inelastic scattering cross sections:

" T = " l + " inl

If a specimen contains N atoms/vol, it has then a thickness t, the probability of scattering from the specimen is given by QTt:
N" # QT = N" T = 0 T A

QT t =

N 0" T ( #t) A

with QT the total cross section for scattering from the specimen in units of cm-1, N0 the Avogadro's number (atoms/mole), A the atomic weight (g/mole) and ! the atomic density ! !
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Acha Hessler-Wyser

b. a little about diffraction

The atomic scattering factor
An incident electron plane wave is given by: When it is scattered by a scattering centre, a spherical scattered wave is created, which has amplitude "sc but the same ! ! phase: ! e 2 $ik % r " sc ( r ) = " 0 f (# ) ! r where f(#) is the atomic scattering factor, k the wave vectors of the ! incident or scattered wave, and r the distance that the wave has propagated.
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! ! ! " ( r ) = " 0 e 2 #ik $ r

b. a little about diffraction

The atomic scattering factor
The incident electrons wave has a uniform intensity. Scattering within the specimen changes both the spatial and angular distribution of the emerging electrons. The spatial distribution (A) is indicated by the wavy line. The change in angular distribution (B) is shown by an incident beam of electrons being transformed into several forward-scattered beams.

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b. a little about diffraction

The atomic scattering factor
The atomic scattering factor is related to the differential elastic scattering cross section by d# 2
f (" ) = d$

f(#) is a measure of the amplitude of an electron wave scattered from an isolated atom. ! $f(#)$2 is proportional to the scattered intensity. f(#) can be calculated from Schrdinger's equations, and we obtain the following description:
! E $ #1+ 0 2 & ! " m0 c % # ! f (! ) = # 8! 2 a0 # sin " " 2 $ & & ( Z ' fX ) & %
2

f(#) depends on %, # and Z

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b. a little about diffraction

The atomic scattering factor
fn = 10+14 m f 10+14 m fX 10+14 m

(sin#)/%& 0.1
1H 63Cu

0.5 -0.378 0.67 0.466

0.1 4'530 51'100

0.5 890 14'700

0.1 0.23 7.65 19.4

0.5 0.02 3.85 12

-0.378 0.67 0.466

118'000 29'900

Atomic scattering factors for neutrons (independent of #!), electrons and X rays, are a function of scattering angle and wave length % [].

fn : f fX = 1 : 104 : 10 Tir de L.H. Schwartz and J.B. Cohen, Diffraction from Materials
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b. a little about diffraction

The structure factor
The amplitude (intensity) of a diffracted beam depends on the lattice structure and its atom positions:

Amaille = 1 / r exp[2#ir]
with ri th position of an atom i: and K = g: K = h a* + k b* + l c*

i = atomes maille

! f ($ ) exp[2#iK " r ]
i i

ri = xi a + yi b + zi c

The structure factor is given by the sum of all scattering centres (the atoms) of the crystal that can scatter the incident wave:

Fhkl =

i = atomes maille

! f exp[2"i(hx + ky + lz )]
i i i i

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b. a little about diffraction

Interaction: diffusion and diffraction
rtr o diffu s

Each point of the object re-emits a spherical wavelet. When all combined together, they are doing the resulting wave (transmitted, scattered or backscattered) If wavelets are coherent (phase relation well defined), resulting wave is the sum of the wavelets (interference) and the observed intensity Ic is the squared resulting wave modulus (usually called "diffraction").

objet

$ e2 !ik"r +ai Ic (r ) = && * = ' + A i' (r ) ' i r )

%$ e#2 !ik"r +ai ' (' + A i (r ) (' i r *)

% ( ( *

If wavelet phases are not correlated (uncoherent), they cannot interfere and the observed intensity Iinc is the sum of the intensity of each wavelet (usually called "diffusion").

$ ' e2 !ik"r +ai ' e#2 !ik"r +ai Iinc (r ) = + &i&i * = + ' A i (r ) A i (r ) ' r r i i )
16

% 2 ( = + Ii (r ) ( i *

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transmis

s diffu

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b. a little about diffraction

Diffraction: Coherent elastic scattering plane wave
el

sample: random atoms? lattice? spherical wavelets

n Fres

me<<matom<<msample

ity intens f only i !!! n!

!The energy transfer (loss) from the electron to the sample is usually negligible. !If electrons go through a thick sample: "Multiple interaction occur: dynamical effects "Diffraction patterns complex to interpret
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b. a little about diffraction Diffraction and Fresnel fringes

Fresnel fringes can also be used to correct the astigmatism in the objective lens.
b) Irregular fringes, astigmatism. c) Underfocussed, uniform fringes d) Focussed, min of contrast, no fringes e) Overfocussed, uniform fringes

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b. a little about diffraction

Fraunhofer diffraction
Parallel illumination
Electrons arriving all parallel onto the objective lens are focussed in a single point: a transmitted spot or a diffracted spot
a radiation a sample (crystal?)

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b. a little about diffraction

The Bragg's law
Considering an electron wave incident onto a crystal, Bragg's low shos that waves reflected off adjacent scattering centres must have a path difference equal to an integral number of wavelengths if they have to remain in phase (constructive interference) In a TEM, the to total path difference is 2dsin# if the reflecting hkl planes are spaced a distance d apart and the wave is incident and reflected at an angle #B. n%=2dsin#'
Faisceau incident "# "# "# A B C "# d Faisceau diffract

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b. a little about diffraction

The Bragg's law
2 sin" dhkl = n !# dhkl = n !/2 sin"#
diffrence de " chemin parcouru

"

!
distance

entre plan atomiques

Elastic diffraction
|k| = |k|
k k g = k-k

Periodic arrangement of atoms in the real space: g : vector in the reciprocal space

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c. TEM contrasts
Imaging mode

Echantillon

Lentille objectif

Plan focal

Plan image

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c. TEM contrasts
Diffraction mode

Echantillon

Lentille objectif

Plan focal

Plan image

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c. TEM contrasts
Diffraction mode
Direct correlation between the back focal plane (first diffraction pattern formed in the microscope) of the objective lens and the screen

Imaging mode
Direct correlation between the image plane (first image formed in the microscope) of the objective lens and the screen

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c. TEM contrasts
Diffraction: Zone axis
Several (hi ki li) planes intersect with a common direction [u v w] (zone axis) of the crystal. If electron beam is along [u v w ] direction, they all will be in Bragg condition. They satisfy the zone equation: hu+kv+lw=0 Each family of crystalline plane generates diffract in a single direction. This corresponds to a single spot the the focal plane.

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Acha Hessler-Wyser

c. TEM contrasts
Diffraction patterns for fcc

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Acha Hessler-Wyser

picture from Morniroli

c. TEM contrasts
Different type of contrasts
Thickness contrast Z contrast HAADF (D)STEM
Obj. ap.! SA ap.!

Diffraction contrast => BF and DF Phase contrast The objective aperture allows to select a transmitted spot to increase the contrast in image mode The selected area aperture allows to select a region from which the diffraction pattern is considered
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c. TEM contrasts
Bright field (BF), dark field (DF)
Bright fied (BF) : the image is formed with the transmitted beam only (0! Dark field (DF): the image is formed with one selected diffracted beam (hkl It gives information on regions from the sample that diffract in that particular direction. Note the particular case ot the DF mode: the incident beam is tilted.
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c. TEM contrasts
Bright field (BF), dark field (DF)
100 nm

Bright field

Dark field

P.-A. Buffat!
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Acha Hessler-Wyser

c. TEM contrasts
Bright field (BF), dark field (DF)

Nickel based superalloys Contrast $/$!

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Acha Hessler-Wyser

c. TEM contrasts
Bright field (BF), dark field (DF)
Segregation of chemical species in OMCVD AlGaAs structures on patterned substrates
1.1 A B

1
III

c(Ga)normalized

0.9

Can vertical quantum wells emit light?

We need local

0.8

0.7

0.6
I/1

II/1

II/2

0.5 0

I/2

concentrations to model the electronic properties

350

50

100

150

200

250

300

distance/nm

Because of the Z dependence of the structure factor, we can observe a chemical contrast in dark field mode!
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c. TEM contrasts
Thickness fringes
If we admit at this stage that a transmitted beam and a diffracted beam can interact in the material, we can calculate the intensity of each one. It varies periodically with the thickness t, resulting in equal thickness fringes.

Champ clair
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Champ sombre
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c. TEM contrasts
Exctinction distance
This intensity depends on the extinction distance: #Ve cos$ B
"g = %Fg
)g [nm]
(111) (200) (220) Al 72 87 143 Ag 29 33 46 Au 23 25 35

and thus on the crystal orientation and the atomic number of the sample atoms. !

We usually admit that kinematic (400) 237 75 55 theory is valid as long as the diffracted beam intensity/incident beam intensity is lower than 10%. Thus, the thickness limit is )g calculated for $g $g
t < t max " #

"

10
33

metals at 300 kV
Acha Hessler-Wyser

Intensive SEM/TEM training: TEM

c. TEM contrasts
Thickness fringes and chemical contrast

TEM dark eld image g=(200)dyn!

HRTEM zone axis [001]!

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HRTEM zone axis [001]!

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Acha Hessler-Wyser

Fast assessment of thicknesses of complex multilayer structures by TEM, in collaboration with Dr. E. Gini, IQE-ETHZ, Prof. K.Melchior

TEM: contrastes
Thickness fringes and chemical contrast

Quanum wires InP/GaInAs. Cleaved wedge method The bending of the fringes indicates clearly the presence of a chemical concentration gradient close to the interfaces.

P.-A. Buffat
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TEM: contrastes
Bended samples
When a sample is deformed, the diffraction conditions are not the same in two different regions. In bright field, the diffracting area appears in dark. It is then possible to observe lines with a different contrast: they are called bend contour.

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Acha Hessler-Wyser

TEM: contrastes
Bended samples
When a sample is deformed, the diffraction conditions are not the same in two different regions. In bright field, the diffracting area appear in dark. It is then possible to observe lines with a different contrast: they are called bend contour. Each line can be associated with a family of diffracting planes.

(tir de J.V. Edington, Practical Electron Microscopy in Materials science)

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Acha Hessler-Wyser

Intensive SEM/TEM training: TEM

d. Structure analysis
Zone axis
Each diffraction spot corresponds to a well defined familly of atomic planes. On a diffraction pattern, the distances between the diffracted spots depend on the lattice parameter, but their ratio is constant for each Bravais lattice. Quick structure identification, manual or computer assisted.

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d. Structure analysis
Diffraction pattern indexing
Simulation: Software JEMS (P. Stadelmann) If we propose possible crystal, it calulates its electron diffraction for all orientations and compares with experimental diffraction pattern.

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d. Structure analysis
Camera length
Diffraction spots are supposed to converge at infinity. The projective lenses allow us to get this focal plane into our microscope: The magnification of the diffraction pattern is represented by the camera length CL.

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d. Structure analysis
Camera length
Diffraction spots are supposed to converge at infinity. The projective lenses allow us to get this focal plane into our microscope: The magnification of the diffraction pattern is represented by the camera length CL. tg(2#hkl) = R/CL For small angles, # ! sin# ! tg# and with the Bragg's law 2dhklsin#hkl=n% we have: dhklR= %CL (=cte)
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dhkl

2#hkl CL

d. Structure analysis
Phase identification
The detailed analysis of the diffrated spots gives us the crystalline structure of the sample. If the microscope is perfectly calibrated, it is then possible to get the crystal interplanar distance, and thus its lattice parameter. However, usually, we have possible strucures and diffraction allows us to choose between the candidates.

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d. Structure analysis
Phase identification
0-13 1-2-2

[831]

Hexagonal %-(AlFeSi)

40-3

0-20

FIB lamella of ! 50 nm thickness, GJS600 treated Bright Field micrograph, 2750x (Philips CM20) Simulated diffraction on JEMS software
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[304]

Monoclinic Al3Fe
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d. Structure analysis
Powder diagram
Polycrystaline TiCl All reflexions (i.e. all atomic planes with structure facteur) are present They are also called "ring pattern" Angular relations between the atomic planes are lost.
222 311 220 200 111

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c. TEM contrasts
High resolution contrast (HRTEM)

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c. TEM contrasts
Scanning transmission (STEM)
High angle thermal diffuse scattering ~z2 = z-contrast incoherent imaging: no interference effects dedicated STEM: beam size ~0.1-0.2nm Limitation: beam formation by magnetic lens: Cs !!!

High Angle Annular Dark Field =HAADF

Analytical EM: probe-size ~1nm for EDX and EELS analysis

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HRTEM

Acha Hessler-Wyser

HAADF-STEM

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Acha Hessler-Wyser