XRD Basics and Applications

Introduction to X-ray Powder Diffraction Mangesh Mahajan, Ph.D.

and Applications PANalytical, India

1
Outline

• Description of crystals
• Principles of diffraction
• XRD Applications

Basic XRD Course 2

The Crystalline State

Atoms, ions, molecules

Matter

Gaseous Liquid
State State

Solid
State
Amorphous Crystalline
(disordered) (ordered)

Basic XRD Course 3

States of matter

SOLID LIQUID GAS

Matter in solid state
Crystalline Amorphous

Single crystal Polycrystalline

5
The Crystalline State
A crystal is constructed by the ‘infinite’ repetition in
space of identical ‘building blocks’.
b
a

Grid Building
+ Crystal
system block

Basic XRD Course 6

The Crystalline State
Building block describes arrangement of
groups of atoms

Grid system describes how building block

repeat in space

The lattice parameters describe the

‘infinite repetition’ unit. A volume element whose
edges are successive grid lines.

Basic XRD Course 7

The Crystalline State
Lattice parameters

c a b c - sides
b    - angles

Basic XRD Course 8

Crystals - lattices
Ionic: Molecular:

9
The 14 Bravais Lattices

10
Space Groups

32 crystallographic point groups

+
14 Bravais lattices (7 crystal classes)

230 space groups

Basic XRD Course 11

Interaction of X-rays with matter
X-ray Scattering X-ray Diffraction
Counts

15000

10000

5000

26 28 30 32

Position [°2Theta]

12
Diffraction

Diffraction is an ‘interference’ phenomenon

Waves interact with an object

Simple example: optical diffraction

Basic XRD Course 13

Diffraction

Placing an atom on a lattice (i.e. a crystal) gives a regular

array of scatters. The (X-ray) waves scattered by these
atoms can interfere in the same way as the (light) waves
from the array ‘scatters’ in a diffraction grating.

Basic XRD Course 14

Superposition of Waves
A1 A1

A2
A2

A1+A2
A1+A2

Basic XRD Course 15

Diffraction

A  C
A' C'
A" C"
B

B'
3  d
 2 B"
First order Second order Third order

A D

A’
 C 
n = 2d sin
d
B’

Basic XRD Course 16

X-ray diffraction experiment
Basic set-up

Bragg’s law:
n=2dsin
Constructive interference is
detected when the path-length
difference is equal to an
integer number of wavelengths

17
Diffraction
For a crystal the beam is reflected only when the crystal
is correctly oriented.

2
 No reflection

 2 Reflection

18
Single crystal vs. powder diffraction

•A single crystal •Powder Diffraction gives

scatters at discrete cones of intensity.
angles.

19
Classical Powder Diffractometer
Goniometer

Detector

X-ray tube Monochr.

Soller slit
Soller slit
Receiving slit
Divergence slit
Anti-scatter
Mask slit

Sample stage
20
 Powder diffraction pattern
Peak position  Structure
Intensity (Height)  Quantity
FWHM  Crystallite size
Counts
Alpha1.RD FWHM
100000

Integrated peak
Intensity
50000

0
10 15 20 25 30

Position [°2Theta]
Angular peak position

21
XRD Pattern components Counts

10000

Grains of multi-phase sample

5000

15 20 25 30

Position [°2Theta]

Counts

4000

2000

10 15 20 25 30

Position [°2Theta]

22
Information in XRD powder pattern
• Crystal structure is most precise analysis of certain solid
material
• Powder pattern is unique 1D “picture” of 3D structure
• Powder pattern characterizes material by it’s
structure, so it can be used for IDENTIFICATION
• Intensities in XRD pattern are in relation with quantity of
analyzed material, so it can be used to determine
quantitative ratio of phases in mixture

23
Why XRD?

24
Why is XRPD important
• Properties of crystalline material depend on crystal
structure.
• Crystal structure describes atomic positions and regularity
(symmetry) of atoms in space (unit cell).
• Diffraction patterns are defined by crystal structure.
• Powder (polycrystalline) diffraction is used for
determination of structure itself, or for determination of
structure related properties (phase identification, residual
stress, texture,…).
• The phases (not the elemental composition) determine the
mechanical and many other properties of crystalline
materials.
25
 The Bragg-Brentano Diffractometer
Counts
Asp.ASC
Receiving slit
20000

10000
2
0
10 20 30
Position [°2Theta]

Peak List

acetylsalicylic acid

Goniometer axis

Sample
X-ray tube
: angle between incident beam and sample
2: angle between incident and diffracted beam
26
X’Pert PRO: X-ray diffraction for today
What can X-ray diffractometer do?

Flat samples Stress

Non-ambient

Phase analysis/ Rough samples

Crystallography
Diffractometer
Texture
Small amounts
Thin Films/
SAXS, PDF Reflectivity

27
 The second wave: detectors

Advances in Detection

• From end-90’s: electronic 1- or 2-dimensional

detectors with sufficient linearity
• Now, a big leap in recording speed can be gained
– 2-dimensional detector: spot analysis and texture
– 1 dimensional detector: rapid collection of diffraction
patterns with excellent angular resolution

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Real Time Multiple Strip Detection Technology

Part of a diffractogram recorded

from 20° to 80° 2Theta, Cu radiation
0.1 mm Receiving Slit:
2 hours and 56 minutes
X’Celerator:
1 minute and 51 seconds

Raw data
29
New generation of pixel detectors

30
Resolution, Range, and Background
Counts

•Better than 0.028 degrees 8000

➢Measured on NIST660a LaB6 powder with 6000

LaB6
MPD system 4000

•0.5 degrees (or lower with good sample 2000

alignment) to 160 or higher depending on

types of stages 0
29 30 31 32

Position [°2Theta]

•Very careful control of scatter through fixed or Counts

programmable diffracted slits produces

300

refineable background shapes

200

•Programmable incident and diffracted slits

allows wide ranging scans with no compromise 100

data quality at either ends of the scan

0
130 131 132

Position [°2Theta]

31
Exceptional Low Limits of Detection

3 microgram/m3 respirable quartz sample on

silver membrane

0.1% of Form II azithromycin spiked into Form I

0.05% quartz in amorphous silica
32
Studying Chocolate using transmission XRD
• Chocolate
consists mainly
of sucrose and
cocoa butter
reflection
• Cocoa butter
transmission
has reflections
at low 2Theta
angles
• Difficult to
observe in
reflection
geometry

33
Non-Ambient Experimental setup

Special interface reduces

the sample-detector distance

34
Application example: phase transition of CsCl

CsCl changes from Counts

3 613.738

P m -3 m to F m -3 m 3 510.406
3 407.074
3 303.742

near 476 °C 3 200.41

3 097.078
2 993.746
2 890.414
2 787.082
2 683.75
2 580.418
2 477.086
Snapshots can be taken 42
44
2 373.754
2 270.422
2 167.09
while ramping up the 3 600
3 400
3 200
40
38
2 063.758
1 960.426
36 1 857.094
temperature
3 000
2 800 34 1 753.762
2 600 1 650.43
32
2 400
Count s

30 1 547.098
2 200
1 443.766
2 000 28
1 800
1 340.433
26
1 600 1 237.101
24 1 133.769
1 400

Automatic sample 1 200

1 000
800
22
20
Scan number
1 030.437
927.105
823.773
height compensation
18
600
16
720.441
41.5 617.109
14
42 513.777
can be used 42.5
43
43.5
44
12
10
410.445

44.5 8
Position [°2Theta] (Copper (Cu))
45
45.5 6
46 4
46.5
47 2
47.5

35
From high to low temperature

38 K
36 K
34 K
32 K
30 K
28 K

48 50 52
Position [°2Theta]

36
Industrial process control - Examples
• Cement industry (clinker, cement, …)
• Pharmaceuticals (batch control: polymorphs, API)
• Metal processing
• Semiconductors & TF based new materials
• Component inspection

37
Cement industry
Standardless Quantitative Rietveld Analysis
Counts

C3S 51.50 %
Brownmillerite 9.82 %
C3A - Na-Aluminate ortho, NIST 6.16 %
Calcium sulfate hemihydrate - Bassanite 1.71 %
Calcium sulfate dihydrate - Gypsum 4.42 %
15000 Magnesium oxide - Periclase 3.02 %
C2S - beta - Belite 19.92 %
Anhydrite 3.05 %
Calcium oxide - Lime 0.08 %
Calcium hydroxide - Portlandite 0.32 %

10000

5000

0
10 20 30 40 50 60 70

Position [°2Theta]

5000
0
38
-5000
Pharmaceutical industry II
• Final dosage form control

Conc=Slope*Intensity+Intercept

LLD=0.09%
(50s measurement
time)

Ventolin (Salbutamol) aerosol delivered by pressurized metered dose inhaler (pMDI)

100 g of active substance delivered per actuation 450

400
350
300

Mass (mkg)
250
200
150
100
50
0
0 20 40 60 80
Intensity (kcounts/s)

39
Metal processing
Galvannealed steel
production process
Before Annealing Galvannealed
Layer
Air cooling

Zinc Layer
After Annealing

Steel Sheet Annealing

furnace

Steel Sheet

Air knife

Data courtesy of
ThyssenKrupp Steel Zinc pot

40
Semiconductors & thin films
Wafer mapping

SiGe 5x
Strained Si
Si0.8Ge0.2
Graded SiGe to 20%(relaxed)

Si substrate

Qy*10000(rlu) #1_M1.A00

1.6
5740 3.0
5.4

5720 9.8
17.9
32.5
5700
59.0
107.3

Fast reciprocal 5680

5660
195.0
354.5
644.5
1171.6

space mapping
2129.6
5640 3871.2
7037.1
12792.0
5620
23253.1
42269.2
5600 76836.5
139672.5
-100 -50 0 50 100 253895.1
Qx*10000(rlu)

41
Component inspection - Micro-diffraction
Cu plating
Cu(111)

0.4 mm

x
x
Sample with small area
of interest Mono-cap

X’Celerator = 0.3°

X-ray tube
(point focus)

42
Texture Measurement
• Materials

• Metals
• Alloys
• Ceramics
• Polymers
• Rocks

43
Pole Figures and ODF calculation
• Crystal symmetry
• Must be known from
phase identification
• Sample symmetry
• Triclinic or orthorhombic
• Determined
from pole
figure
inspection

44
Line Profile Analysis – crystallite size / lattice strain

• Analysis of profile widths and shapes

– broadening due to small particle size (size)

• 1 nm < D < 1 m

– broadening due to lattice distortion (strain)

• 0.005 % < e < 5 %

45
Final Conclusion
• The optimal choice of your diffractometer configuration
strongly depends on your sample and your problem
• With the easy exchange of all relevant modules you can
address a broad range of applications
• With PreFIX you can tune your configuration to just the one
you need at any time
• Modern software enables in-depth manual or fully
automated analysis
• System can be configured to perform also non-diffraction
experiments (XRR, SAXS, PDF)

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 Thank You

The Analytical X-ray Company

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