X-Ray Diffraction (XRD)

Laura Holz
lauraholz@ua.pt
2023
What is an X-ray?

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How are X-ray produced

Target bombarded by accelerated

electrons (30kV)

Electrons ionize some of the inner orbital

electrons in target

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How are X-ray produced

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Bragg’s Law

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Bragg’s Law

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Bragg’s Law

x z

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 Fundamentals
} X-Ray Diffraction on Crystals

v Bragg’s Law

2 dhkl sin q = n l
dhkl - interplanar spacing of the crystal
q - angle of incidence
l - wavelength of the incident X-RAY
n - order of reflection (integer)

v For parallel planes of atoms with a dhkl between the planes, constructive interference only
occurs when Bragg’s law is satisfied
• In most diffractometers, the X-ray wavelength l is fixed
• A family of planes production a diffraction peak only at a specific angle q

v Additionally, the plane normal [hkl] must be parallel to the diffraction vector
• Plane normal [hkl]: the direction perpendicular to a plane of atoms
• Diffraction vector s: the vector that bisects the angle between the incident and diffracted beam
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 X-Ray Diffractometer
} Bragg-Brentano configuration (reflection)

Primary Optics Secondary Optics

v The incident angle w is defined between the X-ray source and the sample.

v The diffraction angle 2q is defined beween the incident beam and the detector
• In a q: 2q instrument (e.g. Rigaku H3R) the tube is fixed, the sample rotates at q°/min and the
detector rotate at 2q°/min
• In a q: q instrument (e.g. PANanalytical X’Pert Pro) the sample is fixed and the tube rotates at a
rate -q °/min and the detector rotates at a rate of q °/mi

v The diffraction vector s is always normal to the surface of the sample

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Primary Optics

1)Soller Slits
• Corrects Angular Divergence

2) Divergence Slits
• Controls beam spread

3) Monochromator
• Absorbs Kβ radiation and white radiation
• Allows Kα1 and Kα2 through

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Secondary Optics
1)Selection Slit
• Reduce scattering of x-rays amorphous or
air scattering

2) Height Limiting Slit (Soller Slit)

• Reduce axial diversions, limit beam height

3) Receiving Slit
• Remove diffuse scattered x-rays

4) Secondary Monochromator
• Absorbs Kβ radiation and white radiation
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 X-Ray Diffractometer
} Bragg-Brentano configuration (reflection)
v A polycrystalline sample should contain thousands of crystallites. Therefore, all possible
diffraction peaks should be observed

v For every set of planes, there will be a small percentage of crystallites that are properly oriented to
diffract (the plane perpendicular bisects the incident and difracted beams)

v Basic assumptions of powder difrfraction are that for every set of planes there are an equal number of
crystallies that will diffract and that there is a statistically relevant number of crystallites
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 X-Ray Powder Diffraction
} Samples
v Samples can be powders, sintered pellets, metal foils, coatings on substrates

v The ideal powder sample contains tens of thousands of randomly oriented crystallites
• Every diffraction peak is the product of X-rays scattering from an equal number of crystallites
• Only a small fraction of the crystallites in the specimen actually contribute to the measured diffraction pattern
v Irradiating a larger volume of material can help ensure that a statistically relevant number of grains
contribute to the diffraction pattern

v Small sample quantities should be avoid because the sample size limits the number of crystallites that
can contribute to the measurement

v If the crystallites in a sample are very large there will not be a smooth distribution of crystal
orientations. Crystallites should be < 10 µm in size to get good powder statistics

v Exensive dry grinding may lead to amorphization. Wet grinding is preferable

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 X-Ray Powder Diffraction
} Difractogram: powder diffraction data are collected as Absolute Intensity vs 2q
v The peak position as 2q depends on instrumental characteristic such as wavelength, l
• The peak position as dhkl is an intrinsic, instrument-independent, material property.
® Bragg’s Law is used to convert observed 2q to dhkl

v The absolute intensity, i.e, number of X-rays observed in a given peak, can vary due to instrumental and
experimental parameters
• The relative intensities of the difraction peaks should be instrument independent
® To calculate relative intensity, divide the absolute intensity of every peak by the absolute intensity of the most intense peak,
and then convert to a percentage. The most intense peak of a phase is therefore called the “100 % peak”
® Peak areas are much more reliable than peaks heights as a measure of intensity.
Raw Data Peak List and Parameters
Position Intensity
(2-theta) (counts) No Pos. d-spacing Rel. Int. FWHM Area Backgr. Height
10 154 . [°2Th.] [Å] [%] [°2Th.] [cts*°2Th.] [cts] [cts]
10.02 144 1 21.2986 4.1718 1.21 0.1574 13.9 139 89.51
10.04 149 2 30.2359 2.95597 100 0.1968 1436.41 169 7399.07
10.06 144 3 37.1856 2.41794 6.74 0.1574 77.5 164 499
10.08 154 4 43.2608 2.09143 32.64 0.1771 421.93 178 2414.87
10.1 114 5 48.6052 1.87323 0.75 0.2362 12.85 170 55.15
10.12 125 6 53.595 1.71001 38.99 0.1378 392.03 185 2884.81
10.14 121 7 62.681 1.48099 15.64 0.096 148.1 178 1157.07
10.16 149 8 67.1279 1.39443 0.22 0.9446 15.24 169.4 16.36
10.18 149 9 71.1381 1.32426 14.25 0.168 236.1 174 1054.02
10.2 135 10 75.1653 1.26298 1.33 0.192 25.26 173 98.68
······· ······ 11 79.1815 1.20869 4.02 0.24 95.28 174 297.74
······· ······· 12 79.4331 1.20849 2.33 0.144 33.16 174 172.73
Difractogram of a powder sample of BaZrO3
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 X-Ray Powder Diffraction
Peak Position
Determined by size and symmetry of unit
} Information Provided From the Difractogram cell

Peak Width
Influenced by size/strain of crystallites – the
microstruture

Peak Intensities:
Determined by the position of the atoms in
the unit cell; influenced by preferred
orientation

Peak Tails
Diffuse scattering, point defects

Background
Amorphous contents

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 X-Ray Powder Diffraction
} Information Provided From the Difractogram
v Identification of phases
• Unit cell latice parameters and Bravais lattice symmetry
® Index peak positions
® Lattice parameters can vary as a function of, and therefore give you information about alloying,
doping, solid solutions, strains

v Crystallite Size and Microstrain

• Estimating by peak broadening

v Quantitative phase analysis

• Determines the relative amounts of phases in a mixture by refering the relative peak intesities
• Determination of amorphous content

v Crystal Structure
• By Rietveld refinement of the entuire diffraction pattern. Determines the relative amounts of phases in a mixture by
refering the relative peak intesities

v Residual Strain (macrostrain)

v Other defects (e.g. stacking faults) can be measured by analysis of peak shape and peak width

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 X-Ray Powder Diffraction
} Phase identification
v The diffraction pattern for every phase is as unique as your fingerprint
• Phases with the same chemical composition can have different diffraction patterns
• The position and relative intensity of a series of peaks to match experimental data to the reference
patterns in the database

monoclinic
tetragonal

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 X-Ray Powder Diffraction
} Phase identification Same element. Different allotropes

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Crystal structure determination

Simple Cubic (SC) Body Centred Cubic (BCC) Face Centred Cubic (FCC)

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Crystal Structure determination
Selection rules
(hkl) (h2+k2+l2) SC BCC FCC
100 1 ü û h+k+l = û h,k,l all
110 2 ü ü even û even or
111 3 ü û ü all odd
200 4 ü ü ü
210 5 ü û û
211 6 ü ü û
220 8 ü ü ü
300 9 ü û û
310 10 ü ü û
311 11 ü û ü
222 12 ü ü ü
320 13 ü û û
321 14 ü ü û
400 16 ü ü ü
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Crystal Structure determination

2q

44.48
51.83
76.35
92.90
98.40
121.87
144.54
155.51

What’s the structure?

What is the lattice parameter?

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How to guide!

l= 2dsinq (1)

d = a / (h2 + k2 + l2)½ , where a = lattice parameter (2)

Combine (1) and (2)

l2/4a2 = sin2q/(h2+k2+l2)

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How to guide! l2/4a2 = sin2q/(h2+k2+l2)

} 1) Start 2q values and generate set of sin2q

} 2) Normalize sin2q values by dividing sin2qi/ sin2q1
} 3) Convert to Integers
} 4) Speculate h2+k2+l2 values that would equal integers

2q sin2q sin2qi/ sin2q1 Integer (x3) (h k l)

44.48 0.143 1 3 111

51.83 0.191 1.34 4 200
76.35 0.382 2.67 8 220
92.90 0.525 3.67 11 311
98.40 0.573 4.01 12 222
121.87 0.764 5.34 16 400
144.54 0.907 6.34 19 331
155.51 0.955 6.68 20 420
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Crystal Structure determination

Systematic absences?

SC will have (001)

BCC = h+k+l = even

ü
FCC = hkl all odd or all even

What’s the structure?

What is the lattice parameter?
l2/4a2 = sin2q/(h2+k2+l2)

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How to guide!

} 1) Start 2q values and generate set of sin2q

} 2) Normalize sin2q values by dividing sin2qi/ sin2q1
} 3) Convert to Integers
} 4) Speculate h2+k2+l2 values that would equal integers
l2/4a2 = sin2q/(h2+k2+l2)
2q sin2q sin2qi/ sin2q1 Integer (x3) (h k l) sin2q/ l = 1.542Å
h2+k2+l2 a = 3.53Å
44.48 0.143 1 3 111 0.00477
FCC
51.83 0.191 1.34 4 200 0.00477
76.35 0.382 2.67 8 220 0.00477
92.90 0.525 3.67 11 311 0.00477
Ni
98.40 0.573 4.01 12 222 0.00477 metal!!!
121.87 0.764 5.34 16 400 0.00477
144.54 0.907 6.34 19 331 0.00477
155.51 0.955 6.68 20 420 0.00477
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Crystal structure determination

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 X-Ray Powder Diffraction
} Estimation of Crystallite Size and Microstrain

v Contributions to Peak Broadening

• Specimen broadening (also referred as Sample Profile, Specimen Profile)

® Crystallite Size

® Microstrain
o Non-uniform Lattice Distortions
o Faulting
o Dislocations
o Antiphase Domain Boundaries
o Grain Surface Relaxation
® Solid Solution Inhomogeneity
® Temperature Factors

• Instrumental broadening (also referred as the Instrumental Profile, Instrumental Peak Profile)
® depend on source and equipment

Calibration is required to calculate accurate crystallites sizes and microstrain

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 X-Ray Powder Diffraction
} Estimation of Crystallite Size
v Scherrer Equation
K – Scherrer constant
B – peak width due to crystallite size
L – crystallite size
l - wavelength
q - Bragg angle

• Peak width (B) is inversely proportional to crystallite size and cos (q)
® As the crystallite size gets smaller, the peak gets broader

® The crystallite size broadening is most pronounced at large angles 2q

Ä however the instrumental profile width and microstrain broadening are also largest at large
angles 2q
® If using a single peak, often get better results from using diffraction peaks, 2q = 30° - 50°
Ä below 2theta = 30°, peak asymmetry compromises profile analysis

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 X-Ray Powder Diffraction
} Estimation of Crystallite Size
v Scherrer Equation

• Determination of Peak Width: FWHM vs Integral Breadth

® Full Width at Half Maximum (FWHM)

Ä the width of the diffraction peak, in radians, at a height half-way
between background and the peak maximum
Ä It is easier to calculate

® Integral Breadth (b)

Ä the total area under the peak divided by the peak height
!"#$%&'($
Ä the width of a rectangle having the same area and the same b)
*($+ ,(-./#
height as the peak
Ä requires very careful evaluation of the tails of the peak and the
background

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 X-Ray Powder Diffraction
} Estimation of Crystallite Size
v Scherrer Equation

• Scherrer Constant, K
® depends on the how the width is determined, the shape of the crystal and the size
distribution
Ä K actually varies from 0.62 to 2.08

Ä The most common values for K are:

o 0.94 for FWHM of spherical crystals with cubic symmetry
o 0.89 for integral breadth of spherical crystals wih cubic symmetry
o1, because 0.94 and 0.89 both round up to 1

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 X-Ray Powder Diffraction
} Estimation of Crystallite Size
v Scherrer Equation

• Determination of Peak Width: Peak Profile Analysis

Ä Peak Profile Analysis

Information
Peak Fit Functions
from fit:
• Position • Gaussian
• Width
• Height • Lorentzian
• Area
• Pearson-VII
• Deconvolution
• Skewness (sharp peaks)
• Pseudo-Voight
(round peaks)

measurement fit background

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 X-Ray Powder Diffraction
} Estimation of Crystallite Size
v Scherrer Equation

• Limits for Crystallite Size Analysis

® There is only broadening due to crystallite size when the crystallite is too small to be

considered infinitely large

Ä above a certain size, there is no peak broadening
Ä in practice, the maximum observed size for a standard laboratory
diffractometer is 80 to 120 nm

® The minimum size requires enough repeating atomic planes to produce the

diffraction phenomenon
Ä this depends on the size of the unit cell
Ä the minimum size is typically between 3 to 10 nm, depending on the material

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X-ray Powder Diffraction

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 X-Ray Powder Diffraction
} Estimation of Crystallite Size and Microstrain
v Williamson-Hall Plot

• Microstrain Broadening

® Lattice strains from displacements of the unit cell about their normal
positions
® Microstrains are very comon in nanoparticles materials

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 X-Ray Powder Diffraction
} Estimation of Crystallite Size and Microstrain
v Williamson-Hall Plot

• Microstrain Broadening
distortion
® Contributions to Microstrain Broadening planes

Ä Non uniform lattice distortions

Ä Structural defects (e.g. site vacancies,
distortion
intersticials defects, stacking faults) planes

Ä Dislocations
Ä Antiphase Domain Boundaries
Ä Grain Surface Relaxation
® The peak broadening due to microstrain will
vary as:

- strain

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 X-Ray Powder Diffraction
} Estimation of Crystallite Size and Microstrain
v Williamson-Hall Plot

• When both crystallite size and microstrain are present, a Williamson-Hall Plot is used

Size Broadening

Microstrain Broadening

! l " e #sinq L – crystallite size

Bspecimen = +
L cosq cosq e - strain

! l
Bspecimen cosq = + " e #sinq
L
slope
y-intercept
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 X-Ray Powder Diffraction
} Estimation of Crystallite Size and Microstrain
v Williamson-Hall Plot

! l
Bspecimen cosq = + " e #sinq
L
slope
y-intercept

Peak Fitting
0.003
Pos. [°2Th.] d-spacing [Å] Rel. Int. [%] FWHM [°2Th.] L = 96 nm
30.1938 2.95755 100 0.1903 e = 0.03

FWHMspecimen . cos q (rad)

37.1889 2.41573 6.82 0.2089
43.2019 2.09241 33.67 0.1881
53.5746 1.70919 37.9 0.2089 0.002

62.7045 1.4805 16.92 0.2275

y = 0.001x + 0.0015
71.1296 1.3244 14.09 0.2305 R² = 0.8325

0.001
38 0.2 0.3 0.4 0.5 0.6 0.7
sinq
 X-Ray Powder Diffraction
} Advantages
v Only a small quantity of material is required, particularly if the camera method is used.

v The method is non destructive

v The actual chemical compounds are determined. Most methods of analysis only give the
elements present, so it is not always possible to state the compounds present.

v Can distinguish different polimorphic forms of the same material

v Simple analysis of data.

v Analysis of difractograms of the sample can also information about the presence of
amorphous materials or the existence of prefered orientation

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 X-Ray Powder Diffraction
} Limitations
v It is not possible to identify:
• Non crystalline (amorphous) materials
• Components in a mixture ocurring bellow about 0.5% by weight since there would be
insufficient of the materials present to give measurable diffraction lines.

v Difficulty may be experience in identifying the following materials

• Multi-component mixtures due to overlapping reflections, and phases occurring in low
concentrations
• Patterns containing strong very low angle reflections which have not been recorded
• Materials exhibiting preferred orientation

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 End

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