Lesson 1

X-rays & Diffraction

Nicola Döbelin
RMS Foundation, Bettlach, Switzerland

October 16 – 17, 2013, Uppsala, Sweden

Electromagnetic Spectrum

X rays:
Wavelength λ: 0.01 – 10 nm
Energy: 100 eV – 100 keV

Interatomic distances in crystals: Generation of X-radiation:

typically 0.15 – 0.4 nm Shoot electrons on matter

Interference phenomena only

for features ≈ λ

2
 Generation of X-rays

Accelerated electron impinges on matter:

Bremsstrahlung (Deceleration radiation)

Electron is deflected and decelerated by the atomic nucleus.

(Inelastic scattering)

Deflected electron emits electromagnetic radiation.

Wavelength depends on the loss of energy.

3
Bremsstrahlung

Continuous spectrum

40 kV, 20 mA
Intensity

30 kV, 20 mA

20 kV, 20 mA

0.00 0.05 0.10 0.15 0.20 0.25 0.30

Wavelength (nm)

4
Bremsstrahlung

Continuous spectrum

30 kV, 40 mA
Intensity

30 kV, 30 mA

30 kV, 20 mA

0.00 0.05 0.10 0.15 0.20 0.25 0.30

Wavelength (nm)

5
Characteristic Radiation

Cu Eb (eV)
0
M4,5 (3d)
M2,3 (3p) 76
M1 (3s) 122

M L K
L3 (2p3/2) 933
L1 (2p1/2) 952

L1 (2s) 1097

Kα1 Kα2 Kβ

K1 (1s) 8979

Wavelength of Kα1, Kα2, Kβ, Lα... are characteristic for the atomic species.

6
X-rays: Spectrum
Kα1

Kα1

Kα2

Kα2
Intensity

Kβ

Kβ

Mo

Cu

0.00 0.05 0.10 0.15 0.20 0.25 0.30

Wavelength (nm)

7
 X-ray Tube

Target (Cu, Mo, Fe, Co, ...)

Acceleration e‒
Be window
Voltage
Vacuum

Filament

Filament
Current

Generator settings: kV mA

8
 Old X-ray tubes

Lifetime of a few years:

- Vacuum decreases
loss of intensity
- Tungsten from filament deposits
on target
contaminated spectrum (characteristic
W spectrum starts to appear)

- Monitor the intensity

- Replace old tubes

Caution:
Beryllium is toxic & carcinogenic!
- Never touch the windows!
- Use appropriate covers!

9
Focal Point

Typical target size: Take-off angle

Length: 10-12 mm (typically 6°)
Width: 0.4-1.0 mm

Target

Point focus

Line focus

10
 X-rays: Summary

• Generated in an X-ray tube

• Spectrum contains Bremsstrahlung (continuous) and

characteristic radiation (Kα1, Kα2, Kβ) of target material

• Tube is characterized by:

• Target material
• Size and shape of target
• Aceleration voltage and
current

11
Diffraction Basics

Interaction of X-rays with matter:

- Absorption (photoelectric effect, giving rise to fluorescence)

- Elastic scattering (Thomson scattering)
- Inelastic scattering (Compton scattering)

Absorption Photoelectric effect, Fluorescence

CuKα1 Fe atom

FeKα1

1. Absorption and ionization

2. Relaxation and emission of characteristic radiation

12
 Elastic Scattering

Fe atom

CuKα1 λp

λs
CuKα1

Electron oscillates in the electric field, Secondary wave is in phase

emits photons of the same wavelength as (+ 180°) with primary wave.
the incoming radiation (λs = λp).

13
Crystal Lattice

Crystal: Periodic arrangement of atoms/ions/molecules in 3 dimensions.

Electrons of each atom become a source of

scattered radiation (spherical waves)

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 Positive interference (amplification)
Negative interference (extinction)

More sources in ordered arrangement

=
More distinct interference pattern

xx.xx.xxxx 15 Tagung
Image: http://www.forbes.com/
Bragg’s Law

n · λ = 2 · d · sin(θ)

θ d
θ 2θ

Diffracted beam looks like a «reflection», but it is scattered radiation

16
 Bragg’s Law

CuKα1 = 0.154056 nm
a = 0.2 nm
b = 0.5 nm

2θ = 17.72°
θ = 22.65°
d = 0.2 nm
2θ = 45.30° θ = 8.86°

d = 0.5 nm

a
b a
b

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 Lattice Planes and Miller Indices

d(-210) Definition:
A lattice plane is a plane
which intersects atoms of
a unit cell across the whole
3‐dimensional lattice.
d(010)
- Each lattice plane
generates a diffraction
peak.

- The 2θ angle of the

peak depends on the
b plane’s d-spacing.

a - Diffraction peaks can

d(100) d(110) be labelled with the
plane’s Miller index.

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Single Crystal

A single crystal must be rotated

to bring each lattice plane in
diffraction condition.

2θ 2θ
2θ

19
Polycrystals, Powders

In an ideal powder every

possible orientation of
crystals occurs.

In a random powder
no orientation is preferred.

In an ideal powder all possible diffraction peaks

are generated, regardless of sample orientation.

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 Diffraction Cones

Diffraction at an angle 2θ° from

the primary beam

All possible rays form a cone = diffraction cone = Debye cone

21
Diffraction Cones

Powder sample: (120)

(100)

(010)

One Debye Cone for each lattice plane spacing (d value)

22
Debye Ring

Gray Value

2θ Angle

23
Powder Diffractometer

Diffraction Cones
«Secondary Beams»

X-ray tube
Primary Beam X-ray Detector
scanning X-ray intensity
vs. 2θ angle
Powder
Sample

24
Powder Diffraction Pattern

Lesson 2: All about powder diffractometers

2000

1500
Intensity (cts)

1000

500

0
10 20 30 40 50 60
Diffraction Angle (°2θ)

25
Monochromatic X-radiation

Diffraction angle θ depends on wavelength λ:

n · λ = 2 · d · sin(θ)

Polychromatic X-ray Beam

We need monochromatic X-radiation!

http://fineartamerica.com

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 Monochromatic X-radiation

Kα1

Kα2
Kα1
Intensity

Kβ

Cu

Kα2
0.00 0.05 0.10 0.15 0.20 0.25 0.30
Wavelength (nm)
Kβ

Bremsstrahlung

X-ray Beam from Tube

Monochromator: Remove every wavelength but Kα1

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 Monochromator

X-radiation is absorbed by solid matter.

Absorption coefficient depends on wavelength.
There are steps (absorption edges) in the spectrum.

Ni
Absorption Coefficient

«K» edge Ni
K: 0.14879 nm
L-I: 1.22988 nm

0.00 0.05 0.10 0.15 0.20 0.25 0.30

Wavelength (nm)

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Ni-Filter
Kα1

Ni

Kα2

Intensity
Kβ

Cu

0.00 0.05 0.10 0.15 0.20 0.25 0.30

Wavelength (nm)

Cu Radiation

Ni filter

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Ni-Filter
Kα1

Ni

Kα2

Intensity
Kβ

0.00 0.05 0.10 0.15 0.20 0.25 0.30

Wavelength (nm)

Cu Radiation Ni-filtered Cu Radiation

Ni filter
Kβ and Bremsstrahlung attenuated
No elimination of Kα2

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Ni-filtered Diffraction Pattern

500000 CuKα1

400000

300000
Intensity

CuKα2

200000

100000

0
27 28 29 30 31 32
Diffraction Angle (°2θ)

31
Ni-filtered Diffraction Pattern

CuKα1 & CuKα2 duplet

20000

18000

16000

14000

12000
CuKα Satellites
Intensity

10000 (= CuKα3)

8000
Absorption Edge
CuKβ
6000

4000

2000 Impurity Remaining Bremsstrahlung

0
27 28 29 30 31 32
Diffraction Angle (°2θ)

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Ni Filter: Primary or Secondary Beam

Kα1
Primary beam filter
Kα2
Cu Radiation Ni-filtered primary beam

Kα1
Ni filter

Kα2
Secondary beam filter
Kβ
Bremsstrahlung
Ni filter
Cu Radiation

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Kβ Filter

Target Kα1 (nm) Kα2 (nm) Kβ (nm) Kβ Filter Absorption

Element Edge λK (nm)
Cr 0.228975 0.229365 0.20849 V 0.2269
Fe 0.193631 0.194002 0.17567 Mn 0.1896
Co 0.178900 0.179289 0.16208 Fe 0.1744
Ni 0.165794 0.166178 0.15002 Co 0.1608
Cu 0.154059 0.154441 0.139225 Ni 0.1488
Mo 0.709317 0.713607 0.63230 Zr 0.6889
Ag 0.559422 0.563813 0.49708 Rh 0.5339

Birkholz, M. «Thin Film Analysis by X-ray Scattering», Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2006.

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Summary: Kβ Filter

Kβ Filter:
- Mostly eliminates Kβ
- Does not eliminate Kα2
- Moderate loss of intensity of Kα1 and Kα2
- Leaves an absorption edge in the foot of the diffraction peaks
- Attenuation of Kβ depends on thickness of filter foil
- Can be placed in the primary or secondary beam

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Monochromator Crystal

Kβ and most of the Bremsstrahlung (BS)

are not in diffraction condition Extinction

θ = 13.3°
2θ = 26.6°

Graphite
single crystal

d (002) = 0.3352 nm

n · λ = 2 · d · sin(θ)
Emission Line Wavelength (nm) 2θ Bragg Diffraction
Condition (°)
CuKα1 0.154059 26.57
CuKα2 0.154441 26.64
CuKβ 0.139225 23.97

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Monochromator Crystal

Graphite Graphite Crystal

monochromator
BS
Kβ

Kα2
Kα1

High-resolution Si / Ge Crystals Kα1 Kα2

monochromator

Kα1

37
Graphite Monochromator

10000
CuKα1
9000

8000

7000

6000
Intensity

5000 CuKα2

4000

3000

2000

1000

0
27 28 29 30 31 32
Diffraction Angle (°2θ)

38
Graphite Monochromator

CuKα1 & CuKα2 duplet

500

400

300
Intensity

200 CuKα Satellites

(= CuKα3)

100

0
27 28 29 30 31 32
Diffraction Angle (°2θ)

39
Monochromator Crystal

Monochromator Crystal:
- Completely eliminates Kβ
- Reduces background intensity
- Si / Ge eliminate Kα2, Graphite does not eliminate Kα2
- Severe loss of intensity of Kα1 (and Kα2)
- Graphite crystal can be placed in primary or secondary beam
- Si / Ge crystals are usually placed in the primary beam
- Monochromatic beam is polarized

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Energy-Dispersive Detector

Detector

Detector’s energy window

is set to Kα1/2, other
wavelengths are ignored
(«digital filtering»)

BS Kβ Kα1 Kα2

Powder Sample

41
Energy-Dispersive Detector

Energy-dispersive Detector:
- Completely eliminates Kβ
- Reduces background intensity
- Does not eliminate Kα2
- No loss of intensity of Kα1 and Kα2

42
Summary: Monochromators

• Monochromatic X-radiation is required for powder XRD

• Bremsstrahlung and Kβ must be eliminated from the

tube’s spectrum

• 3 different types of monochromators:

• Kβ filter (Cu tube + Ni filter, Mo tube + Zr filter)
• Monochromator crystal
• Energy-dispersive detector

• Most systems do not eliminate Kα2!

43
Overview of Instruments

Lab Instrument Monochromator

Uppsala Uni Bruker D8 Ni-Filter
RMS (Uni Bern) Panalytical X’Pert Ni-Filter
RMS (Uni Bern) Panalytical CubiX Graphite
Monochromator

Bruker D8 Panalytical X’Pert Panalytical CubiX

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