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Literature

General

• D. B. Williams und C. B. Carter: Transmission Electron Microscopy, New

York: Plenum Press (1996).

• L. Reimer: Transmission Electron Microscopy, Band 36, 4. Aufl. (Springer

Series in Optical Sciences , Berlin: Springer (1997).

Analytical TEM

• D. B. Williams: Practical analytical electron microscopy in materials sci-

ence, Weinheim: Verlag Chemie (1984).

• D. C. Joy, J. A. D. Romig und J. I. Goldstein (Hrsg.): Principles of Analyti-

cal Electron Microscopy, New York: Plenum Press (1986).

• Egerton: Electron Energy-Loss Spectroscopy in the Electron Microscope,

2. Aufl., New York: Plenum Press (1996).

• L. Reimer: Energy-Filtering Transmission Electron Microscopy (Springer

Series in Optical Sciences 71), Berlin: Springer (1995).

• J. C. H. Spence und J. M. Zuo: Electron microdiffraction, Oxford: Claren-

don Press (1992).

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High-Resolution TEM

• P. Buseck, J. Cowley und L. Eyring (Hrsg.): High-Resolution Transmission

Electron Microscopy, New York: Oxford University Press (1988).

• J. C. H. Spence: Experimental High-Resolution Electron Microscopy, 2.

Aufl., New York: Oxford University Press (1988).

• J. M. Cowley: Diffraction Physics, 2. Aufl., Amsterdam: North Holland

(1981).

• S. Horiuchi: Fundamentals of High-Resolution Transmission Electron

Microscopy, Amsterdam: North-Holland (1994).

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Significance of TEM

• materials science:

macroscopic properties of materials

´
microscopic structure and composition

• transmission electron microscopy (TEM):

– imaging at high spatial resolution (down to atomic scale)

– complimentary information from diffraction patterns

– complimentary information from microanalysis

· composition
· bonding
· electronic structure

• imaging of the interior of materials

– compare scanning electron microscopy: high spatial resolution and

chemical analysis, however only at the surface

– compare scanning probe microscopy (scanning tunneling micros-

copy, atomic force microscopy):
atomic resolution, however only at the surface

• local information

– compare X-ray diffraction: averaging, “statistical” information

• TEM delivers images

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– often “intuitively” interpretable

– however: complications, particularly in HRTEM

• “direct” imaging of atom arrangements (in projection)

– crystals (and quasi crystals)

– in particular: defects in crystals

· interfaces (grain boundaries, phase boundaries)
· stacking faults, antiphase boundaries, inversion domain bounda-
ries, …

– however: projection of three-dimensional object to two-dimensional

image
· cannot image single point defects
· crystal defects need to be oriented parallel to the projection di-
rection

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Part 1

Analytical

Transmission

Electron Microscopy

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Principle

• interaction between electron beam and specimen:

primary beam
back-scattered secondary
electrons electrons

characteristic
Auger X-rays
electrons
light

“absorbed” electron-hole
specimen
electrons pairs

Bremsstrahlung

elastically in -elastically
scattered scattered
electrons undiffracted electrons
beam

• conventional TEM (CTEM), including electron diffraction (ED), and

high resolution transmission electron microscopy (HRTEM):

elastically scattered electrons

• analytical (transmission) electron microscopy (ATEM):

inelastically scattered electrons

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• important methods of ATEM:

1. energy-dispersive X-ray spectrometry: XEDS

(energy-dispersive X-ray spectroscopy)
Æ analyze X-rays emitted by the specimen
Æ element-characteristic information

2. electron energy-loss spectrometry: EELS

(electron energy-loss spectroscopy)
Æ analyze transmitted electrons
Æ element-characteristic energy losses,
local information on electron states

Æ microscopic distribution of atomic species (elements)

Æ chemical bonds (oxidation state), local variation of the atomic coor-

dination, local information on the electron band structure (band
gap)

• advantages compared to other experimental methods:

– lateral resolution less than 1"nm (10-9 "m)

· compare, for example, X-ray fluorescence: averaging over mac-
roscopic regions of the object, “statistical” information

– analysis of materials interior

– compare, for example, scanning tunneling spectroscopy:

atomic resolution, however only probes the surface

– particular advantage of ATEM:

combination of analytical information with high spatial resolution
imaging (down to atomistic structure!)

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• instrumentation

– XEDS detector, EELS spectrometer

– special transmission electron microscopes

– example: “dedicated” scanning transmission electron microscope

STEM

PEELS
E magnetic prism
detector
E + ∆E
BF detector
ADF detector

HAADF detector

Grigson coils

specimen
objective lens/aperture

XEDS detector

scanning coils

condensor lenses

cold field-emission gun

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Inelastic Electron Scattering

• basis of analytical TEM: inelastic electron scattering

• interaction of primary electrons with valence electrons of the specimen,

inner shell electrons, nuclei of the atoms

• the closer a primary electron approaches the nucleus of an atom, the

larger can be the energy loss during inelastic scattering

• but: no unique correlation between energy loss and scattering angle

• cross-section for inelastic scattering decreases with increasing energy

(accelerating voltage) of the primary electrons

• example: aluminum

P: plasmons; K, L: inner-shell ionization; FSE, SE: fast and slow secondary electrons.

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• subdivision of inelastic scattering processes:

– processes that generate X-rays

– processes that “generate” secondary electrons

– processes that lead to collective excitations of atoms

(phonons, for example)

Generation of X-rays

• distinguish:

– characteristic X-rays

– Bremsstrahlung

• characteristic X-rays

– ionization Æ atom looses inner electron

– outer electron drops into the vacant state

vacuum
primary electron
LB
VB

E EL3
EL2
EL1
characteristic
EK X-rays

nucleus scattered electron

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fi emission of
· characteristic X-rays
(hn"= energy difference between two electron states)
· Auger electrons

• ratio between X-ray emission and emission of Auger electrons:

fluorescence yield w

– approximately:
Z4
w=
a+ Z 4
Z: atomic number; a: constant, a"≈ 106 for K shell.

w 1

10-1
10-2
10-3
10-4
10 20 30 40 50
Z

fi light elements have poor fluorescence yield

fi XEDS is not particularly suited to detect light elements

Æ EELS

• emission of X-rays always requires:

energy loss of the primary electron > hn

– reason: emission of X-rays or Auger electrons does not immediately

transfer the atom to its ground state

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– instead: cascade of transitions

– example of a transition cascade in Cu

1. ionization of a K-shell electron: Ec"="8,98"keV
2. emission Cu Ka: 8,048"keV
3. emission Cu La: 0,930"keV
4. photon or phonon by re-occupation of the M state with an elec-
tron from the conduction band: 2"eV

• nomenclature of electronic energy levels

nucleus

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Bremsstrahlung

• primary electron penetrating the electron cloud of an atom:

– elastic interaction with the nucleus

Æ deceleration

fi emission of Bremsstrahlung

• yield of Bremsstrahlung:

– Kramers relation for cross-section:

KZ (E 0 - E )
N [E] =
E
N[E]: number of Bremsstrahlung photons with energy E;
E0 : energy of the primary electron;
K: Kramers constant;
Z: atomic number.

– conclusion:
· small energy loss of primary electron is particularly probable
· large energy loss is rather unlikely

– example (schematic):

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Plasmons and Phonons

• collective excitation of atoms by primary electron

• plasmon: excitation of the (quasi-) free electrons (valence electrons)

• phonon: excitation of collective vibrations of the atomic nuclei

1. Plasmons

– vibration of an electron gas

– corresponding quasi particles: plasmons

atoms primary electron

plasmon
electron gas

electron after energy loss

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– plasmons exist in any material with quasi free or loosely bound elec-
trons

Æ metals

– example: Aluminum
(large density of states at the Fermi edge)

– typical average free path length: 100"nm

– scattering in forward direction

– plasmon scattering provides information on density of states at the

Fermi edge

Æ application: measure changes in composition via observing changes

in the plasmon energy

2. phonons
primary electron
atoms

coupling

electron after energy loss

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– primary electron generates collective vibrations of atoms

– corresponding quasi particles fi phonons

– excitation of phonons also by other processes:

· emission of photons (X-rays)
· emission of Auger electrons

– phonons ¤ specimen heating Æ irradiation damage

– typical energy loss of the primary electron: only ≈"0.1"eV

– but: large scattering angles (large momentum transfer)

fi diffuse background in diffraction patterns

fi phonon scattering:
· no useful imaging contrast
· no useful information on local composition of the specimen

– ... so far!

– next generation instruments with improved energy resolution may

be able to perform phonon spectrometry

– potential new applications:

· mechanical properties of interatomic bonds
· in combination with microscopes that can form an electron probe
of atomic dimensions:
probe mechanical properties of individual interatomic bonds
· thermal properties of materials

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XEDS: X-ray Energy-Dispersive

Spectrometry

Principle

• inelastic scattering of primary electrons in the specimen

fi ionization of atoms, deceleration of primary electrons

fi Bremsstrahlung

fi later: re-occupation of vacant electron states

fi emission of element-characteristic X-rays, spectrum reveals peaks with

the shape of a normal distribution

• example: XEDS spectrum of Cu

N
Cu-K a

Cu-L
Cu-K b

0
0 2 4 6 8 10
energy[keV]

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XEDS Instrumentation

• Principle of an XEDS spectrometer:

– charge pulse proportional to energy hn of the X-ray photon

– charge pulse Æ voltage pulse

– amplification by field-effect transistor

– evaluation by electronic system

– store in corresponding channel of a multi-channel analyzer (MCA)

• spectrometer as add-on attachment to a conventional microscope

• detector (in the microscope column)

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X-rays
-500V

to FET
p (dead layer)
gold contact layer ≈ 100µm

i (Li-drifted)

electrons gold contact layer

holes

• function:

– standard: Si solid state detector

Æ p-i-n diode, operated in reverse direction

– i-region: Li-drifted Æ Si(Li) detector (“silly”)

– X-ray photons fi generation of electron-hole pairs

– average energy required (≠ band gap): 3,8"eV at T"="77"K

– typical X-ray photons, in contrast, have energies > 1"keV

fi one X-ray photon typically generates thousands of electron-hole pairs

(however: detector efficiency < 100"%)

– number of electron-hole pairs is proportional to energy of the X-ray

photon

– internal electric field p-i-n diode fi separation of electron-hole pairs

– extended i-region required (3"mm), in order to obtain sufficient ab-

sorption of the X-rays

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– charge pulse, however very small: ≈"10-16"C

Æ separate and collect charges by high dc voltage (500"V)

– contacts: gold layers

– electron pulse serves as input signal for field-effect transistor (n-

channel FET); hole pulse is not used

– finally: amplification and storage

• dead layer:

– layer on front side of detector: Li-concentration not perfectly event,

fi recombination of charge carriers

– obstructs detection of “soft” X-rays (light elements)

• liquid N2 -cooling of the detector useful to avoid:

– thermal excitation of electrons into the conduction band; a process

that generates noise in the spectrum

– thermally activated diffusion of Li; substantial diffusion would de-

stroy the active layer (i-layer)

– noise in the field-effect transistor; this kind of noise would obscure

the signal of soft X-rays

• problems introduced by liquid N2 cooling:

– must avoid condensation of carbohydrates from the microscope

“vacuum” onto the cold detector (corresponds to cooling trap)

– a “window” must separate the detector from microscope vacuum

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Detector Windows

• Beryllium

– Be foil, thickness ≈"10"µm

– withstands atmospheric pressure

– however: expensive

– transparent for the largest part of the relevant spectrum of X-rays

– however: strong absorption at energies below ≈"1"keV

fi Ka radiation of elements lighter than Na (Z"="11) cannot be de-
tected
fi particularly not: B, C, N, O – important in ceramic materials

• ultra-thin windows (UTW)

– thickness"<"100"µm

– material: formerly polymers, now Al-polymer, BN, diamond

– withstands atmospheric pressure

– yet transparent down to Ka radiation of boron (192"eV)

• windowless XEDS detectors

– alternative of window: requires to keep microscope vacuum free of

carbohydrates and water vapor

– example: partial pressure of water"<"10-8 "Pa

– enables detection of Be-Ka irradiation (110"eV)

· 1 electron-hole pair requires 3,8"eV
fi 110"eV corresponds to only 29 electron-hole pairs!

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• comparison of efficiencies between Si(Li) detectors with different win-

dows for soft X-rays:
efficiency
1,0

0,8

0,6

window-less
0,4
polymer UTW
atmosph. UTW
0,2 Be

0,0
0,0 1,0 2,0 3,0 4,0
E [keV]

Germanium Detectors

• draw-backs of Si detectors:

– efficiency drops above ≈"20"keV

– reason: Si becomes “transparent” for X-rays

– consequence: cannot take advantage of “medium voltage” transmis-

sion electron microscopes

• advantage of “medium voltage” transmission electron microscopes (ac-

celerating voltage 300 - 400"kV):

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– generate Ka radiation from many elements

– Ka radiation particularly suitable for quantitative evaluation

– but: Ka radiation highly energetic fi Si detectors can only deal with

Ka up to Z"= 47 (Ag)

– solution: Ge detectors

• advantages of Ge detector material

– can be fabricated with higher purity (intrinsic)

fi no Li

fi no problems with interdiffusion on warming up or irradiation

(problem for accelerating voltages of 300 - 400"kV)

– all kinds of windows possible, as for Si detectors

– Ge requires only 2,9"eV to generate one electron-hole pair

fi better signal-to-noise ratio

– with ultra-thin window:

detection of all elements – from boron up to uranium(!)

• disadvantages of Ge as detector material

– for heavy elements only small yield of Ka irradiation

fi only small intensity

– higher leakage currents than Si detectors

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Pulse Processing and Dead-Time Ratio

• ideally: high counting rate, without shifting or distorting the spectrum

fi requires high signal-to-noise ratio of all components

• typical range of energies

– Si detector
· 20"keV
· MCA with 2048 channels"fi 10"eV per channel

– Ge detector
· 40"keV
· MCA with 2048 channels"fi 20"eV per channel

• adjustable parameters:

– time constant t

– dead-time ratio

• time constant

– time available for the pulse processor in order to process the last
pulse

– typically 10 - 50"µs

– larger time constant ¤ better accuracy, but smaller counting rate

– usually one optimizes the counting rate, not the accuracy

• dead-time ratio

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– percentage of time the detector needs to switch off to allow the pulse
processor to evaluate the signal

– closely related to t

– the more X-ray photons arrive at the detector per second, the larger
the dead-time ratio

– the dead-time ratio can be expressed as

Ri - Re
Ri

Ri : input pulse rate; Re: output pulse rate (rate of counts).

– a dead-time ratio larger than 50"% means:

· the detector receives too many pulses per second
· the detection of X-ray photons tends to be inefficient
fi reduce the beam current!

Energy Resolution of the Detector

• definition of the energy resolution, R:

R := + P 2 + I 2 + X 2

R: energy resolution; P: parameter characterizing the quality of he associated elec-

tronics; X: effect of leakage current and incomplete charge collection; I: intrinsic line
width of the detector.

• intrinsic line width of the detector:

I = 2, 35 FeE
F: Fano factor (Poisson statistics); e: energy to create an electron hole pair in the de-
tector; E: energy of the X-ray photons.

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fi energy resolution can only be specified for specific analysis conditions

• standard (Institute of Electrical & Electronics Engineers, IEEE):

Mn-Ka line, generated by a well-defined source (Fe55 with 103 "cps and
8"µs pulse processor time constant)

• typical energy resolution

– Si detectors: ≈"140"eV at Mn-Ka

– Ge detectors: ≈ 114"eV (record)

Artifacts in XEDS Spectra

• “Escape-Peaks”

– phantom peaks, caused by fluorescence

– generated in the following way:

– a small fraction of the X-ray photons absorbed by the detector is not

converted to electron-hole pairs

– these photons cause the detector material to fluorescence (absorb the

photon and emit photons that are characteristic of the detector mate-
rial)

– case of Si detectors:
· Si-Ka photon escapes from the detector
· energy of Si-Ka photons: 1,74"eV
· fidetector does not register energy E, but E"-"1,74"keV
· fiadditional peak (“escape” peak), 1,74"keV below the actual
peak at E

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· example of Si escape peaks:

• additional peaks caused by “inner” fluorescence

– incident X-ray photons cause fluorescence of the material in the ac-

tive layer of the detector

fi spectrum exhibits characteristic peaks of detector material (Si, Ge)

– typical magnitude of these peaks: corresponding to a Si or Ge con-

tent of 0,1 to 1"%

– peaks of the Au contact layers rarely show up in the spectrum

• sum peaks

– phenomenon:
instead of evaluating a single X-ray photon, the detector simultane-
ously evaluates two photons

– reason for this problem:

electronics cannot switch-off the detector fast enough

fi strong peaks may be accompanied by a phantom peak at twice the

energy

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– sum peaks predominantly occur if

· the X-ray intensity is too high
· the dead-time ratio is too large (>"60"%)
· the main peak is very strong

– example: Mg

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The XEDS-TEM Interface

• problem:

– specimen is not the only source of X-rays

– Bremsstrahlung also originates from other parts of the microscope

fi XEDS detector needs a collimator

Collimator

• realization:
primary electron beam

pole piece
window Si or Ge

desired
d (solid anglelW)
detector
S
a specimen

collimator
electrons pole piece
undesired!

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• definition of the acceptance angle W:

A Cos[d ]
W=
S2
A: active detector surface (≈"30"mm2 ); S: distance specimen region - detector; d:"angle
between line normal to the detector and line from the detector to the specimen.

• detector efficiency:

– maximize acceptance angle W

(problem with TEM as compared to SEM: small count rate)

fi position detector close to the specimen (as close as possible)

– typical distance: S!≈!1 to 3"cm, fi W "≈ 0,3 to 0,03"sr

– limitation: upper pole piece of the objective lens

– one cannot substantially increase the pole-piece gap, since this

would increase the aberrations of the lens (spherical aberration,
chromatic aberration)

Acceptance Angle

• acceptance angle a: angle between plane of the specimen (untilted) and

line to the center of the detector

• minimize absorption of X-rays in the specimen

fi maximize acceptance angle a

• problem: increasing a requires to decrease W

– ideal acceptance angle of a "="90° implies to position the detector

above upper pole piece

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fi W becomes small, because the detector needs to “view” the specimen

through the hole of the pole piece

– if detector resides below the upper pole piece, a is limited to a small

value (typically a"="20°)

• for ideally thin TEM specimens absorption does not cause problems

• thicker specimens:

– increase acceptance angle by tilting the specimen towards the detec-

tor (side-entry stage: rotate specimen holder around its axis)

– disadvantage: tilting may reduce signal-to-background ratio

Optimum Position for XEDS Analysis

• reduce absorption:

Æ use adequately thin specimens

Æ appropriately position the specimen with respect to the detector

– region of interest should not be on the same side of the specimen

hole as the detector, but on the opposite side

– rotation holders facilitate this setup

– when using standard specimen holders, load specimen with the re-
gion of interest rotated to the appropriate position

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• optimum geometry for XEDS measurement of concentration profiles

across interfaces:

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System and Spurious X-rays

• overview:
primary electron beam
electrons
pole piece desired X-rays
spurious X-rays

anti-contaminator
back-scattered electrons

specimen

XEDS specimen-
generated
continuum
fluorescence
scattered
electrons
backscattered
electrons anti-contaminator

pole piece

transmitted electrons

• Bremsstrahlung from the illumination system

– electron hit the condensor aperture

– spurious X-rays cannot be distinguished from corresponding radia-

tion from the specimen

– test: “hole count”"–"record XEDS spectrum with the electron beam

focused on the specimen hole

– solution: massive condensor apertures

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• Bremsstrahlung from the objective lens aperture

– disturbes XEDS spectrum

– can damage the detector

* before introducing the XEDS detector, take out the objective lens ap-
erture!

– strong Bremsstrahlung may also originate from massive parts of the

specimen

* after introducing the XEDS detector, do not switch to “Low Mag”!

• Bremsstrahlung from the specimen

– generates fluorescence from other components of microscope

– especially from the specimen holder fi beryllium!

fi it is difficult to trace small amounts of an element in the specimen if

this particular element is present in large quantities in the specimen
holder or other components of the microscope

• Bremstrahlung from the specimen holder, pole pieces, and collimator

fi mainly Cu and Fe

• back-scattered electrons

– from the above-mentioned regions

– reach the XEDS detector

– can produce electron-hole pairs, too

fi uncontrolled disturbance

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Qualitative XEDS

• “qualitative” evaluation of XEDS spectra: essential to prepare quantita-

tive evaluation

• qualitative XEDS includes to:

– optimize the conditions for recording spectra

– identify all element-characteristic peaks

– identify artifacts

– identify all relevant elements in the specimen

Optimizing the Conditions for Recording Spectra

• goals:

– high count rate

– fast recording of spectra (drift…)

– identification of relevant elements and optimization of sensitivity

– identify and exclude artifacts

• parameters:

– accelerating voltage (!)

– beam current

– condensor aperture

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– spot size

– local foil thickness (?)

– …

• which microscope?

– increasing the accelerating voltage

· reduces the cross-section for inelastic scattering (ionization)
· improves the brightness of the electron source
· improves the signal-to-background ratio

– improvement in brightness roughly balances decreasing cross-

section for inelastic scattering

fi in total, higher accelerating voltage is an advantage for XEDS

• practice:

– observe large energy interval (0 - 40"keV)

– large number of counts

· high beam current
· large spot size (if possible)–"sacrifice high spatial resolution

– keep time constant t small

· improves rate of pulse processing
· improves statistics
· reduces recording time
· disadvantage: reduced energy resolution –"not important for
qualitative evaluation

– dead-time ratio"< 60"%

· sufficiently thin region of the specimen

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· adjust beam current

• peak identification

– computer can do that, but

· requires sufficient energy calibration
· peak overlap may introduce errors

– manual peak identification

· idea: identify families of peaks –"consistent?
· for a Ka line there should be a corresponding Kb line…
· for a Ka and a Kb line at E">"8"keV there should be a corrspond-
ing La line…
· etc.

• examples of XEDS spectra

– light elements

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– elements of medium atomic number:

– heavy elements:

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• example of overlapping maxima:

Æ requires de-convolution (option of the software package)

• significance of peaks in XEDS spectra

b
– intensity I A of the peak above the background I A

– integrate signal and background over the same interval of N chan-

nels

– the peak is “significant” at the 99"% level of confidence if

n=N n= N
 I A [n] > 3  I Ab [ n]
n =1 n =1

– if necessary, improve sensitivity

· not by inadequate increase of the intensity (beam current, speci-
men thickness –"this reduces the energy resolution and favors the
formation of sum peaks)

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· instead: extend recording time!

• example for the effect of extending the recording time:

N

Fe-Ka

200
600s

100
60s
10s

0
5,0 6,0 7,0 8,0
E [keV]

• extending the recording time, however, may introduce further prob-

lems:

– contamination
· solution: scan the beam

– specimen drift
· solution: interrupt XEDS and readjust specimen position

– additional artifacts in the spectrum,

for example:
· Si or Ge peaks from the detector material
· peaks from other microscope components (often Cu or Fe)

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Quantitative XEDS

• XEDS with bulk specimens (SEM, electron micro probe):

requires “ZAF” correction

– Z: atomic number

– A: absorption

– F: fluorescence

• advantage TEM:

– thin specimen, foil!

fi weak absorption

fi weak fluorescence

fi better spatial resolution!

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Cliff-Lorimer Ratio Technique

• quantitative analysis of an alloy AB:

what are the relative parts of A and B?

• distinguish:

– mole fractions nA [x], nB[x]:

dimension-less

– mass fractions XA [x], XB[x]:

in wt"% (“weight” percent; should be mass percent!)

– concentrations CA [x], CB[x]:

in m-3 (atoms per unit volume)

Æ determine intensities IA and I B of the corresponding peaks, above the

background of the spectrum

• assumption: absorption and fluorescence may be neglected

• Ansatz:

XA I
= k AB A
XB IB

IA, IB: “intensity” of the peaks"–"corresponds NA, NB in the limiting case of very long
measurement under “ideal” conditions.

• “k factor” kAB

– conversion from relative peak intensities to relative amounts of ele-

ments A and B at x

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– convention: kAB refers to the mass fractions XA [x], XB[x] of A and B

at x"– not their mole fractions, and
X A + XB = 1

– kAB is denoted as “k factor” or “Cliff-Lorimer factor”

– kAB is not constant, see below

• simplest case: quantitative evaluation of Ka peaks

(and include Kb if required)

• evaluation of L and M peaks is usually more elaborate, owing to peak

overlap

• quantitative evaluation requires two steps:

1. subtract background

2. integrate intensity over the region of relevant peaks (A-Ka B-Ka)

• pre-requisite:
record XEDS spectrum under adequate experimental conditions

– sufficient number of counts

– make sure that spurious radiation is negligible (specimen tilt?)

– thin part of the specimen was facing the detector

(to minimize absorption)

– suppress dynamical electron diffraction (strong Bragg reflections) as

much as possible

Æ if necessary, slightly tilt the specimen

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Background Subtraction

• background originates from Bremsstrahlung

• at small energies:
only weak background because Bremsstrahlung is absorbed by

– detector

– specimen

Æ typical experimental observation:

N

8000 theoretical

6000

4000

2000
experimental

0
0 5 10 15 20
E [keV]

fi different strategies for background subtraction"–"depending on whether

– relevant peaks are at low or high energies

– peaks overlap or not

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Window Methods

• simplest case:

– two well-separated peaks

– background varies only slowly below these peaks

• strategy A:

– choose energy interval (“window”) around the peak

– approximate background by straight line

– background intensity U: area below the line

– signal S: area below the peak and above the line

– example:

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• strategy B:

– two windows of equal width, one before and one after the peak(s)

– window width should roughly correspond to peak width (FWHM)

– integrate counts over both windows N

fi average the results to obtain an estimate for the background below

the peak(s)

Æ this method works well only for slowly varying background

• problems of both strategies:

– cannot deal with overlapping peaks

– not suited for peaks at low energies, where the Bremsstrahlung

background varies rapidly (see above)

– solution for these cases: calculate the background

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Calculation of the Bremsstrahlung Background

• Kramers-relation for scattering cross-section (see above):

KZ (E 0 - E )
N [E] =
E
N[E]: number of Bremsstrahlung photons with energy E; E0 : energy of the primary
electron; K: Kramers constant; Z: atomic number.

• constant K includes

– detector efficiency and efficiency of pulse processing

– absorption in the specimen

• originally developed for bulk specimen, Kramers-relation seems to work

for TEM, too

• example of calculated background:

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– three overlapping peaks at low energy

Æ widow methods fail…

Digital Filtering

• works without knowing the “physics” of Bremsstrahlung

• make use of rapid variation of the signal near peaks versus slow varia-
tion of the signal in the Bremsstrahlung background

• difference persists even in low-energy region, where background varies

more rapidly owing to absorption
.

• digital filtering: convolute spectrum with “top hat” function

top-hat funcion
+2
K [x]
0
-1
N [x]

spectrum

linear
filtered
spectrum (K * N )[ x]

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– example

– after filtering:

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fi filtering yields second derivative of spectrum with respect to en-

ergy: d2 N/dE 2

fi removes slowly varying, linear increasing background

Peak Integration

• depending on method for background subtraction:

– window method:
· integrate counts above the background line

– Kramers calculation:
· after background subtraction, fit a Gauß function to the peak
· integrate
· problems: peak shape may vary with counting rate, performance
limits of the detector may introduce a “tail”, …

– digital filtering:
· fit peaks to reference peaks
(minimizing square deviation)
· computer system should have a library of reference peaks
· disadvantage: laborious, and library must refer to similar ex-
perimental conditions

• each one of these methods can work sufficiently well

• apply consistently to standard and specimen

• if the net intensities I A , IB of the peaks above background have been de-
termined:

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Æ insert in Cliff-Lorimer equation

• only remaining unknown: k factor

Determination of k Factors

• if “standard” specimen with known concentrations XA , XB of elements A

and B available:

– record XEDS-spectrum

– subtract background, integrate over peaks

Æ IA , IB

fi determine kAB:
XA IB
k AB = ⋅
XB I A

• fabrication of good standard specimens can turn out to be difficult …

• k factors are not constants, but “sensitivity parameters”, which depend

on

– material

– detector

– accelerating voltage

– method of evaluating the spectrum (!)

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• alternative strategy: calculate k factors from quantitative theory, taking

into account

– atomic number

– transition probabilities between different electron states

– accelerating voltage

– detector efficiency

• advantages:

– fast

– automatic

– integrated in the XEDS computer system

• disadvantages:

– less accurate than working with standards (typical error: 20%)

– different software packages use different parameters and produce

different results

Error Limits of XEDS

• pulse counting is statistical process

• goal: determine intensity I A of a characteristic peak

IA : mean of the statistical ensemble

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• IA corresponds to experimental value for the ideal case of very long (in-
finite) counting time

• practical strategy: estimate I A from NA , the counts obtained near the

exact position of the peak after counting for a finite amount of time

• experimental experience: counts NA of a characteristic peak follow a

normal-distribution (Gauß distribution) centered on the ideal energy of
the corresponding electron transition

• detection of X-ray photons is a “rare” event Æ Poisson-statistics

fi standard deviation of the Poisson distribution (special case of the

binomial/normal-distribution):

s IA = I A ª NA

– NA deviates from the mean I A of the (infinite) statistical ensemble

· by less than N A with a probability of 68,3%
· by less than 2 N A with a probability of 95,5%
· by less than 3 N A with a probability of 99,7%

• how does the error propagate to the concentration ratio XA /XB one ob-
tains with the Cliff-Lorimer method?

• error sAB in the concentration ratio X":="XA /XB:

– errors skAB , sI A , sI B in kAB, IA , and IB all increase the error in X

– the above errors are statistically independent

fi calculate resulting error by the Gauß law of error propagation:

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2 2 2
Ê ∂X ˆ 2 Ê ∂X ˆ 2 Ê ∂X ˆ 2
sAB ª Á ˜ s kAB + Á ˜ s +Á ˜ s
Ë ∂k AB ¯ Ë ∂I A ¯ IA Ë ∂I B ¯ I B

∂/∂… : partial derivation, taken at the mean values of the independent vari-
ables"–"thus with the values kAB, NA , NB.

– inserting the Cliff-Lorimer relation one obtains

2 2 2
Ê NA ˆ 2 Ê k AB ˆ 2 Ê k AB N A ˆ 2
sAB ª Á ˜ s +Á ˜ s +Á- ˜ s ,
Ë N B ¯ kAB Ë N B ¯ IA Ë N B2 ¯ IB

and for the relative error:

2 2
s AB k AB k AB
ª s k + 2 s I + 2 s I2
2 2
N A / NB AB NA A NB B

• example: 3% relative error can be achieved when counting ≈"104 pho-

tons above the background for every peak to be evaluated

• smallest errors reported (with experimentally determined k factors):

≈"1"% at the 95"% level of confidence

• main source of error in XEDS: poor counting “statistics” (NA too small),
because:

– thin foil (poor yield), but thick foil reduces spatial resolution

– XEDS detector only “views” small solid angle – most X-ray photons
are lost!

– electron source not bright enough (but: $$$)

Æ counting time too small, but long counting times increase problems
with drift and contamination

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