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Accuracy-in-XRD.1, A. Kern© 1999 BRUKER AXS All Rights Reserved
Accuracy and Precisionin Powder Diffractometry
A. Kern
Bruker AXS GmbHÖstliche Rheinbrückenstraße 50
D-76187 Karlsruhe
Accuracy-in-XRD.2, A. Kern© 1999 BRUKER AXS All Rights Reserved
Topics to be covered
Accuracy and Precision in Powder DiffractometryDefinition
Optimized Measurement and Evaluation Strategies: Early Decisions
Sample
Instrument
Data Colletion Strategies
Optimized Evaluation Procedures
Accuracy-in-XRD.3, A. Kern© 1999 BRUKER AXS All Rights Reserved
Definition of Terms:“Accuracy” - “Precision”
Legend:
Z : Measurand = “true” value
A : Measurement result
AS : Accuracy
AR : Precision = standard
deviation
R
Z
|A -Z | = AA
A
Accuracy-in-XRD.4, A. Kern© 1999 BRUKER AXS All Rights Reserved
Accurate Powder Diffractometry Precise or Accurate Results?
Tissue, 1996
High AccuracyHigh Precision
Low AccuracyLow Precision
Low AccuracyHigh Precision
High AccuracyLow Precision
Accuracy-in-XRD.5, A. Kern© 1999 BRUKER AXS All Rights Reserved
Any diffraction experiment ca be devided in 5 parts:
Without a close consideration of each part, which must be repeated for each different experiment, one will most unlikely obtain an optimum analytical outcome
The Experiment:Overview
EarlyDecisions Sample Instrument Data
Collection Evaluation
Accuracy-in-XRD.6, A. Kern© 1999 BRUKER AXS All Rights Reserved
Early Decisions: Step by Step
What is the aim of the experiment?
What accuracy and precision is necessary?
What are the sample properties?
What instrument and measurement parameters to use?
What evaluation methods and models to use?
By answering all these questions before executing any experiment on can save a whole lot of time as well as protect himself against erroneous results and frustration!
Accuracy-in-XRD.7, A. Kern© 1999 BRUKER AXS All Rights Reserved
Early Decisions:General Conditions
What is the form of the sample?
How much sample is there?
What instruments are available?
Waht instrument setup are available?
Primary optics?
Sample holders?
Detectors?
What intensity / resolution is required?
...
Accuracy-in-XRD.8, A. Kern© 1999 BRUKER AXS All Rights Reserved
Early Decisions: Accuracy / Precision needed
Methodical limits•Peak overlap•Scattering factors•Speed of analysis
Evaluation errors•Software errors•User errors•Quality of methods
Calibration errors•Uncalibratable errors•Use of standards•Quality of calibration
Measurement errors•Physical effects•Geometric effects•Alignment errors•Others...
Accuracy and precision
of results
Accuracy-in-XRD.9, A. Kern© 1999 BRUKER AXS All Rights Reserved
Early Decisions:“Fitting the Experiment to the Need”
Identification and quantification of errors
Correction of errors by means of calibration
Minimizing of errors using optimized measurement and evaluation strategies
Checking of results
Accuracy-in-XRD.10, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Sample:General Considerations
One of the most important steps before data collection is the minimisation of systematic sample related effects. This is as important as the minimisation of instrumental aberations!
Avoid persisting with poor data - if possible
Re-prepare or remake the sample
Find a better sample
Change instrument or instrument setup
Improve instrument and measurement parameters
Accuracy-in-XRD.11, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Sample:Typical sample related problems
Not enough scattering particles (spotiness)
Sample not representative for the bulk
Bad sampling / particle heterogeneity / phase separation
Preferred orientation
Extinction
Microabsortion (multiphase samples)
“Sample problems” can also provide important informations:
preferred orientation degree of orientation
peak broadening crystallite size and strain
Accuracy-in-XRD.12, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Sample:Preparation
Back pressing, side drifting not effective on preferred
orientation in all cases
Use of capillary techniques most effective
intensity and resolution losses
not automatable
Addition of diluents contamination
enhanced transparency
amorphous scatter /additional peaks
Spray drying expensive equipment
large sample amount needed
lavish cleaning of equipment
Sample motion motion should be 90° to the
diffraction vector
improves particle statistics
no effect on preferred orientation in Bragg-Brentano reflection geometry
The grains in a powder should be randomly oriented:
Accuracy-in-XRD.13, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Sample:Number of Crystallites needed
Peak intensities for structure refinement required to be accurate to ±2%
Accurate, reproducible diffraction intensities require small crystallite size
typical intensity reproducibility for Quartz (113) reflection with CuK: is
15-20 m 5-50 m 5-15 m <5 m
18.2% 10.1% 2.1% 1.2%
The number of crystallites diffracting is related to size
diameter 40 m 10 m 1 m
crystallites / 20mm3 597.000 38.000.000 3.820.000.000
number diffracting 12 760 38.000
Smith, 1992
Accuracy-in-XRD.14, A. Kern© 1999 BRUKER AXS All Rights Reserved
Non-Random Specimens:Particle Size or “Spotiness” Effect
Accuracy-in-XRD.15, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Sample:Sample Motion - Two Examples
Bragg-Brentano Reflection Debye-Scherrer Capillary
Rotation parallel to the scattering vector does not minimize preferred orientation effects!
Accuracy-in-XRD.16, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Instrument:General Considerations
The choice of the optimum instrument must consider the aim of the experiment as well as specific sample properties.
Whats the aim of the experiment
Radiation?
Geometry?
Instrumental setup (optics, sample carriers, detectors)?
Accuracy-in-XRD.17, A. Kern© 1999 BRUKER AXS All Rights Reserved
Welches Instrument:Was ist das Ziel des Experiments?
Qualitative AnalyseQualitative Analyse
Quantitative AnalyseQuantitative Analyse
IndexingIndexing
22 IntensitätIntensität
AuflösungAuflösung
Struktur LösungStruktur Lösung Rietveld AnalyseRietveld Analyse
Wann werden folgende Profilparameter benötigt:
Accuracy-in-XRD.18, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Instrument:What Radiation to use?
X-Ray Laboratory
X-Ray Laboratory
X-RaySynchrotron
X-RaySynchrotron NeutronsNeutrons
IntensityIntensity
ResolutionResolution
Absorption problemsAbsorption problems
Atom discriminationAtom discrimination
Light atomsLight atoms
small / reflection
small / reflection
small / reflection
small / reflection
Small samplesSmall samples
AvailabilityAvailability
Accuracy-in-XRD.19, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Instrument:What Geometry to use?
BBBB DSGöbel Optics
DSGöbel Optics
DSConventional
DSConventional
IntensityIntensity
ResolutionResolution
P/BP/B
AbsorptionAbsorption
Preferred orientationPreferred orientation
reflectionreflection
reflectionreflection
reflectionreflection
reflection / -2reflection / -2
capillarycapillary Sample amountSample amount capillarycapillary
Non ambientNon ambient
Weak scatteringWeak scattering reflectionreflection
Accuracy-in-XRD.20, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Instrument:Debye-Scherrer / Bragg-Brentano
Bragg-BrentanoReflection
Debye-ScherrerCapillary
Accuracy-in-XRD.21, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Instrument:Effect of Absorption
Bragg-Brentano Absorption is independent of 2:
Constant diffraction volume
Transparency effect may cause problems High absorption : Use reflection geometry
Low absorption : Use transmission geometry
Debye-Scherrer Absorption is 2-dependent:
Variable diffraction volume
An intensity correction (effR) is crucial, if accurate intensities are needed
Accuracy-in-XRD.22, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Instrument:Fixed or variable Divergence Slits (I)
FixedFixed VariableVariable
Beam divergenceBeam divergence FixedFixed VariableVariable
Diffraction volumeDiffraction volume ConstantConstant VariableVariable
Illuminated sample length Illuminated sample length FixedFixed VariableVariable
Never use variable divergence slits for structure analysis!
Fix them always to constant beam divergence!
Accuracy-in-XRD.23, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Instrument:Fixed or variable Divergence Slits (II)
Fixed divergence slits Variable divergence slits
Accuracy-in-XRD.24, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Instrument:Point-, Line- and Area-Detectors
Scintillation detector
small spot measured scan necessary long measuring time
PSD
large 2range measured simultaneously
medium measuring time
HI-STAR / CDD
large 2 and chi range measured simultaneously
very short measuring times measurement of oriented
samples and very small sample amounts
Accuracy-in-XRD.25, A. Kern© 1999 BRUKER AXS All Rights Reserved
The Instrument:Powder Diffraction using 2-D Detectors
Amorphous Sample Crystalline Sample Heavily oriented crystalline sample with amorphous content
Accuracy-in-XRD.26, A. Kern© 1999 BRUKER AXS All Rights Reserved
Data Collection:General Considerations
A very crucial step in each experiment is the choice of optimum instrument and measurement parameters. Important examples are:Sample carrier material
Receiving slit
Divergence and anti-scatter slits
Soller slit(s)
Accuracy-in-XRD.27, A. Kern© 1999 BRUKER AXS All Rights Reserved
Data Collection:Sample Carrier Material
0 .0 0 5 .0 0 1 0 .0 0 1 5 .0 0 2 0 .0 0 2 5 .0 0 3 0 .0 0
0
1 0 0
2 0 0
3 0 0
4 0 0
In te n s ity[cp s]
Plastic
S ingle crysta l (S i)
Accuracy-in-XRD.28, A. Kern© 1999 BRUKER AXS All Rights Reserved
Data Collection:Counting Statistics - Detection Limit
20
40
60
80
100
t = 1 0 s2 = ±4,5c/s
t = 5 s2 = ±6,3c/s
t = 1 s2 = ±14,1c/s
t = 0 ,5 s2 = ±20c/s
Av e ra g e b a c k g ro u n d le v e l= 5 0 c/s;
Jenkins, 1989
Accuracy-in-XRD.29, A. Kern© 1999 BRUKER AXS All Rights Reserved
Data Collection:Influence of Divergence Slit
2 6 .3 0 2 6 .4 0 2 6 .5 0 2 6 .6 0 2 6 .7 0 2 6 .8 0 2 6 .9 0
0
2 0
4 0
6 0
8 0
1 0 0
IR e l
Q u a rz , 10 1
R ec e iv in g S lit: 0 .0 5 °
D iv e rg e n c e S lit:
1 °
0 .3 °
Accuracy-in-XRD.30, A. Kern© 1999 BRUKER AXS All Rights Reserved
Data Collection:Flat Specimen Error
Accuracy-in-XRD.31, A. Kern© 1999 BRUKER AXS All Rights Reserved
Data Collection:Influence of Receiving Slit
2 8 .0 0 2 8 .2 0 2 8 .4 0 2 8 .6 0 2 8 .8 0 2 9 .0 0
0
2 0
4 0
6 0
8 0
1 0 0
I re l
Si, 111 Receiving slit:
0.015°0.05°0.15°0.6°
Accuracy-in-XRD.32, A. Kern© 1999 BRUKER AXS All Rights Reserved
Instrument Resolution (I):D500 with Ge-Primary Monochromator
Scintillation counter
FWHM = 0.038° 2
Position sensitive detector
FWHM = 0.046° 2
2 5 .0 0 2 5 .2 0 2 5 .4 0 2 5 .6 0 2 5 .8 0 2 6 .0 0
0
2 0
4 0
6 0
8 0
1 0 0
IR e l
D 5 0 0 S ZS R M 1 9 7 6 , 0 1 2
F W H M : 0 ,0 3 8 ° 2
2 5 .0 0 2 5 .2 0 2 5 .4 0 2 5 .6 0 2 5 .8 0 2 6 .0 0
0
2 0
4 0
6 0
8 0
1 0 0
IR e l
D 5 0 0 O E DS R M 1 9 7 6 , 0 1 2
F W H M : 0 ,0 4 6 ° 2
Accuracy-in-XRD.33, A. Kern© 1999 BRUKER AXS All Rights Reserved
Instrument Resolution (II):D8 ADVANCE
Scintillation counter
FWHM = 0.030° 2
2 4 .7 5 2 5 .0 0 2 5 .2 5 2 5 .5 0 2 5 .7 5 2 6 .0 0 2 6 .2 5 2 6 .5 0
0
1 0 0 0
2 0 0 0
3 0 0 0
In te n s ity[c o u n ts ]
D 8 A D V A N C E S ZS R M 1 9 7 6 , 0 1 2
FW H M = 0.030° 2
Accuracy-in-XRD.34, A. Kern© 1999 BRUKER AXS All Rights Reserved
Evaluation:
Most important Errors
Software errors
User errors, e.g. Smoothing
Background subtraction
Quality of methods, e.g. 2-Determination
2nd derivative
Profile fitting
Accuracy-in-XRD.35, A. Kern© 1999 BRUKER AXS All Rights Reserved
Evaluation:Errors due to smoothing
2 8 .0 0 2 8 .2 0 2 8 .4 0 2 8 .6 0 2 8 .8 0 2 9 .0 0
0
2 0
4 0
6 0
8 0
1 0 0
I re l
Si, 111
R AW data5 poin t sm ooth ing9 poin t sm ooth ing17 point sm ooth ing
Accuracy-in-XRD.36, A. Kern© 1999 BRUKER AXS All Rights Reserved
Evaluation:Gaussian and Lorentzian Function
28.00 28.20 28.40 28.60 28.80 29.00
0
20
40
60
80
100
IRel
GaussianSi 111
28.00 28.20 28.40 28.60 28.80 29.00
0
20
40
60
80
100
IRel
LorentzianSi 111
Accuracy-in-XRD.37, A. Kern© 1999 BRUKER AXS All Rights Reserved
Evaluation:Split-PearsonVII Function
28.00 28.20 28.40 28.60 28.80 29.00
0
20
40
60
80
100
IRel
Split-PearsonVIISi 111
Accuracy-in-XRD.38, A. Kern© 1999 BRUKER AXS All Rights Reserved
Evaluation:Comparison of Peak Profile Functions
2 0 .0 0 2 0 .0 5 2 0 .1 0 2 0 .1 5 2 0 .2 0 2 0 .2 5 2 0 .3 0
0
2 0
4 0
6 0
8 0
1 0 0
IR e l
(L o re n tz )m = 1m = 1 .5m = 2m = 1 0G a u ß
(M o d ifiz ie rte L o re n tz )(M ittle re L o re n tz )
Accuracy-in-XRD.39, A. Kern© 1999 BRUKER AXS All Rights Reserved
Evaluation:Calibration
Instrument alignment Crucial for alignment checking and alignment. Use always the
same sample!
Internal calibration Standard added to the sample. Almost all errors can be
corrected
External calibration Standard used external to the sample. Does not correct for
important errors like sample displacement and transparency!
Accuracy-in-XRD.40, A. Kern© 1999 BRUKER AXS All Rights Reserved
Evaluation:List of recent NIST XRD Standards
Material SRM Number Certified forSilicon SRM 640b d-value calibration
Fluoro-Phlogopite SRM 675 d-value calibration
-Al2O3 SRM 1976 intensity calibration,instrument alignment
LaB6 SRM 660 profile analysis
-Al2O3 SRM 676 quantitative analysis
-Si3N4, -Si3N4 SRM 656 quantitative analysis
-Quartz SRM 1978a quantitative analysis
Cristobalite SRM 1979a quantitative analysis
-Al2O3, ZnO, TiO2, SRM 674a quantitative analysis
Cr2O3, CeO2
Accuracy-in-XRD.41, A. Kern© 1999 BRUKER AXS All Rights Reserved
Evaluation:Typical Intensity Calibration Function
2 0 .0 0 4 0 .0 0 6 0 .0 0 8 0 .0 0 1 0 0 .0 0 1 2 0 .0 0 1 4 0 .0 0 1 6 0 .0 0
0 .7 0
0 .8 0
0 .9 0
1 .0 0
1 .1 0
1 .2 0
1 .3 0
IA / I B
In s tru m e n t R esp o n se F u n c tio nS R M 1 9 7 6
S Z
Accuracy-in-XRD.42, A. Kern© 1999 BRUKER AXS All Rights Reserved
Evaluation:Typical Angle Calibration Function
2 0 .0 0 4 0 .0 0 6 0 .0 0 8 0 .0 0 1 0 0 .0 0 1 2 0 .0 0 1 4 0 .0 0 1 6 0 .0 0
-0 .0 3
-0 .0 2
-0 .0 1
0 .0 0
0 .0 1
0 .0 2
0 .0 3
A n g le C a lib ra tio n F u n c tio nS R M 1 9 7 6
S Z
Accuracy-in-XRD.43, A. Kern© 1999 BRUKER AXS All Rights Reserved
Evaluation:Accuracy of XRD results
Lattice parameters : ~ 0.001% 2 ~ 0.003° 2
Thermal expansion L/L : < 3%
Atom coordinates : < ± 1 Temperature factors : < 50%
Accuracy-in-XRD.44, A. Kern© 1999 BRUKER AXS All Rights Reserved
Bruker AXS:Diffraction Solutions
Diffraction solutions is our comprehensive, application oriented package consisting of
High-precision, fast and innovative analysis technology for all your needs
Hardware Software
Supply of analytical and technical expertise - knowledge transfer between customer and supplier
Application support, consulting User trainings Workshops User meetings