Professional Documents
Culture Documents
XRD Basics and Applications NEW
XRD Basics and Applications NEW
1
Outline
• Description of crystals
• Principles of diffraction
• XRD Applications
Matter
Gaseous Liquid
State State
Solid
State
Amorphous Crystalline
(disordered) (ordered)
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
c a b c - sides
b - angles
9
The 14 Bravais Lattices
10
Space Groups
15000
10000
5000
26 28 30 32
Position [°2Theta]
12
Diffraction
A2
A2
A1+A2
A1+A2
B'
3 d
2 B"
First order Second order Third order
A D
A’
C
n = 2d sin
d
B’
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
19
Classical Powder Diffractometer
Goniometer
Detector
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
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?
27
The second wave: detectors
Advances in Detection
28
Real Time Multiple Strip Detection Technology
Raw data
29
New generation of pixel detectors
30
Resolution, Range, and Background
Counts
LaB6
MPD system 4000
Position [°2Theta]
Position [°2Theta]
31
Exceptional Low Limits of Detection
33
Non-Ambient Experimental setup
34
Application example: phase transition of CsCl
P m -3 m to F m -3 m 3 510.406
3 407.074
3 303.742
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
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)
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
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
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
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
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)
46
Thank You