Analytical

Transmissions Electron Microscopy (TEM)

Part I:
The microscope
Sample preparation
Imaging
Part II:
Diffraction
Defects
Part III

Spectroscopy

MENA 3100: Diff

Repetision:
Electron Diffraction: Powder X-ray diffraction:

Small wave length Larger wave length

Large Ewald sphere Small Ewald sphere
-- Perfect crystals plane Ring pattern
Very sensitive to changes in the crystal Larger driffrationangle
Lower intensity
structure Easier to interpret
Small diffraction
Strong intensity – short exposure time
Directly observed on the viewing
screen
Obtained from very small crystals 
 Electron matter interactions
Coherent incident
high-kV beam

Second electrons
sample Incoherent elastic From within the specimen (SEM)
backscattered electrons (SEM)
Characteristic
X-rays (EDS)
Auger electrons (XPS)
Visible light
Sample
Incoherent inelastic
Bremsstrahlung scattered electrons
X-rays (EDS) (EELS)
Direct beam
Incoherent elastic
(imaging, diffraction,
Coherent elastic forward scattered
EELS)
scattered electrons (STEM, Electrons (STEM,
Diffraction, EELS) diffraction,EELS)
 The characteristic energy transitions
Observable with EELS and EDS

MENA 3100: Spectroscopy

 Empty states

Valence electrons

M shell
L shell
K shell

MENA 3100: Spectroscopy

 Empty states

3d
M shell 3p
3s Lα1
L2,3
2p
L shell
2s L1 EELS

Kα1 Kβ1 K
K shell 1s
EDS

MENA 3100: Spectroscopy

 Energy dispersive X-ray spectroscopy

M
L
Lα
kα
K
kβ

hν

MENA 3100: Spectroscopy

 EELS Eo Eo
K-edge (Si) – 1s orbital

L-edge (Si) M L K
– 2s and 2p orbital

Filled bands

Conduction band

Eb(L)=Eo-Eb(cond.band-L) Eb(K)=Eo-E(cond.band-K)
Energy Dispersive X-ray Spectroscopy
(EDS)

MENA 3100: Spectroscopy

 EDS spectrum

MENA 3100: Spectroscopy

 X-ray Spectroscopy
EDS: Energy Dispersive Spectroscopy
EDXS: Energy Dispersive X-ray Spectroscopy
X-EDS: X-ray Energy Dispersive Spectroscopy
EDX: Energy Dispersive X-ray analysis

MENA 3100: Spectroscopy

 Quantification
Peak intensities are proportional to concentration and specimen thickness.

They removed the effects of variable specimen thickness by taking ratios of intensities
for elemental peaks and introduced a “k-factor” to relate the intensity ratio to
concentration ratio:

𝐶𝐴
  𝐼𝐴
=𝐾 𝐴𝐵
𝐶𝐵 𝐼𝐵

Each pair of elements requires a different k-factor, which depends on detector efficiency,
ionization cross-section and fluorescence yield of the two elements concerned.

MENA 3100: Spectroscopy

 The Detector

MENA 3100: Spectroscopy

 Detection Mechanism

MENA 3100: Spectroscopy

 Oxford

MENA 3100: Spectroscopy

 EDS
SEM TEM

MENA 3100: Spectroscopy

 EDS mapping

MENA 3100: Spectroscopy

 Recent advances

MENA 3100: Spectroscopy

 Comparison Low Z element

MENA 3100: Spectroscopy

 Comparison on resolution

MENA 3100: Spectroscopy

 Artefacts in EDS
1. Si escape peak:
A small fraction of the energy is lost and not transformed into
electronhole pairs

2. Sum peak:
Two photons will enter the detector at exactly the same time. The analyzer then
registers an energy corresponding to the sum of the two photons.

Likely to occur if:

- The input count rate is high.
- The dead times are > 60%.
- There are major characteristic peaks in the spectrum.

MENA 3100: Spectroscopy

3. Fluorescence:
This is a characteristic peak from the Si (or Ge) in the detector dead layer.

4. Sample preparation artefacts (ion milling , grids, reaction to solvent)

- Cu/Ni slot
- Thickness variations due to milling
- Contaminants and reaction products

MENA 3100: Spectroscopy

 Electron Energy Loss Spectroscopy
(EELS)

MENA 3100: Spectroscopy

 Omega filter

MENA 3100: Spectroscopy

 Gatan Imaging Filter (GIF)
Post column energy filter

MENA 3100: Spectroscopy

Microscope outline
Electron gun

Condenser aperture

Sample holder Objective aperture

Intermediate aperture Objective lens
Diffraction lens
Projector lenses Intermediate lens

Fluorescent screen

Gatan Imaging Filter

For EELS
MENA 3100: Spectroscopy
 Projector crossover

Viewing screen

Slit 90o magnetic

Detector prism

Multipole lenses Beam trap aperture

 Energy Losses

• Zero Loss (includes quasi-elastic scattering)

• Intra-/Inter-band transitions (band gap)

• Cherenkov losses

• Bremsstrahlung

• Plasmon losses

• Core losses

MENA 3100: Spectroscopy

 EEL Spectral background

MENA 3100: Spectroscopy

Low-Loss EELS Core-Loss EELS
Low-Loss EELS
 Single electron outer shell
excitation
Zero Loss Peak

Elastic scattering: Inelastic scattering:

Coulomb attraction by nucleus Coulomb repulsion (outer shell electrons)
 The Zero Loss Peak (ZLP)

MENA 3100: Spectroscopy

 Low-Loss EELS: Bulk plasmons
Outer-shell inelastic scattering involving many atoms of the
solid.
Collective effect is known as a plasma resonance

An oscillation of the valence electron density

50xalh2_l ow.dat

h: Planck constant
Plasmon peak
N: n/V : Valence electron density

e: Elementary charge

me: Electron mass

50 40 30 20 10 0 -10
Binding Energy (eV) εO: Permittivity of free space
 Low-Loss EELS: Surface plasmons

Surface plasmon (Es):

  𝐸𝑝
Vacuum/metal interface: 𝐸𝑠 =
√2
ZLP
  𝐸𝑝
Dielectric/metal boundary: 𝐸𝑠 =
√1 − ε 2100

2000

1900

1800

1700
Slice1

1600

1500

1400

1300

  2 2
1200

𝐸 +𝐸 Counts
1100

√
1000

900

800

𝑎 𝑏
700

Interface between two metals: 𝐸 𝑠 =

600

500

400

300

2
200

100

0
-5 0 5 10 15 20 25 30 35 40 45 50 55
Energy -Loss (eV)

A. Thøgersen,et al.  Journal of Applied Physics 109, 084329 (2011). 

 Low-Loss EELS: Energy filtering

Kundmann M., Introduction to EELS in TEM, EELS course 2005 San Francisco
 Low-Loss EELS: Energy filtering

Kundmann M., Introduction to EELS in TEM, EELS course 2005 San Francisco
 Low-Loss EELS: Energy filtering

EFTEM imaging of Si/aSi/ITO (Indium Tin Oxide)

stack sample for REC

Si

ITO

TEM image
 Low-Loss EELS: Energy filtering

EFTEM imaging of Si/aSi/ITO (Indium Tin Oxide)

stack sample for REC

TEM image EFTEM (16 eV) EFTEM (23 eV)

 Low-Loss EELS: Thickness

 
𝐼𝑝 t = thickness
𝑡=λ 𝑝 λp = plasmon mean free path

𝐼𝑜 Ip = Intensity of the plasmon peak

Io = Intensity of the zero loss peak
Core-Loss EELS (Energy-Loss Near-Edge Structure)
 Eo Eo
K-edge (Si) – 1s orbital

L-edge (Si) M L K
– 2s and 2p orbital

Filled bands

Conduction band

Eb(L)=Eo-Eb(cond.band-L) Eb(K)=Eo-E(cond.band-K)
 Core-Loss EELS: Peak shape

Shape of the edge is a signature of the

transition:

• K-edges: 1s states -- typical sawtooth

profile

• L2,3-edges -- have a delayed

maximum but can contain intense
narrow peaks at the onset, known as
“white lines”, corresponding to
transitions to narrow d bands.
MENA 3100: Spectroscopy
 Microanalysis

MENA 3100: Spectroscopy

EFTEM:

MENA 3100: Spectroscopy

MENA 3100: Spectroscopy
 Spectral Imaging (SI)

STEM-SI EFTEM-SI

B.Chaffer et al. Analytical and Bioanalytical Chemistry

(2008) 390, Issue 6, pp 1439-1445

MENA 3100: Spectroscopy

 Spectral Imaging (SI)

STEM-SI EFTEM-SI

MENA 3100: Spectroscopy

MENA 3100: Spectroscopy
MENA 3100: Spectroscopy
 EDS vs. EELS

MENA 3100: Spectroscopy

 Applications

MENA 3100: Spectroscopy