Review……Crystallography

• Crystallography is the study of atomic

arrangements in crystalline materials or
crystal shapes based on symmetry
• atoms combine to form geometric shapes on
smallest scale-- these in turn combine to form
seeable crystal shapes.
• This orderly arrangement in a crystalline
material is known as the crystal structure.
• X-ray crystallography is concerned with
discovering and describing this structure
(using diffraction as a tool).
 The Lattice
• Lattice is “an imaginary pattern of points (or nodes) in
which every point (node) has an environment that is
identical to that of any other point (node) in the
pattern. A lattice has no specific origin, as it can be
shifted parallel to itself.” (Klein, 2002)

• The lattice must be described in terms of 3-

dimensional coordinates related to the translation
directions. Lattice points, Miller indices, Lattice
planes (and the “d-spacings” between them) are
conventions that facilitate description of the lattice.

• Lattice parameter is used to describe the structure of

real materials.
1

Symmetry Operations

• Crystal structure is “created” by replicating a 3-d motif

with a variety of operations:
– Rotation (symbols: 1,2,3,4,6 = # of times form is
repeated in a 360º rotation)
– Reflection (symbol: m or ♦, Form replicated across
a mirror plane)
– Inversion (symbol: i. Form replicated by projection
through a point of inversion) 1
– Rotation-inversion (symbol: ī for single rotation
with inversion.  for 3-fold rotation w. inversion at
each rotation)
 Symmetry Symbols
• Reflection (m)- produced by a mirror plane
that passes through a crystal structure so the
pattern on one side is a mirror image of the
pattern on the other. (symmetry over a plane)

– How many mirror planes

do these crystals have?

Both have 3!
So notation is 3m
• Rotation (A)- rotational symmetry involves repeating
a motif by a set of uniform rotations around an axis.
(symmetry about an axis)
– Repeating the pattern every 120° of rotation means 3-fold
symmetry.
– Every 60° = 6-fold symmetry
– Denoted as #Ax where x=x fold rotational symmetry

Orthorhombic- 3 axes of 2-fold symmetry, so notation is 3A2

• Inversion (i)- also known as center symmetry.
Any line drawn through the origin will find
identical features equidistant from the origin
on the opposite side.

Both of these crystals have center symmetry (i)

• Rotoinversion (Āx) - involves a rotation and
inversion to repeat a pattern
– Denoted as #Āx where x=x fold rotational
symmetry
– Note Ā1 = i and Ā2 = m
i

m 3Ā3
• The 32 crystal classes represent the 32
possible combinations of symmetry
operations.
• Each crystal class will have crystal faces that
uniquely define the symmetry of the class.
• These faces, or groups of faces are called
crystal forms.
• Note that the 32 crystal classes are divided
into 6 crystal systems.
• The Triclinic System has only 1-fold or 1-fold
rotoinversion axes.
• The Monoclinic System has only mirror
plane(s) or a single 2-fold axis.
• The Orthorhombic System has only two fold
axes or a 2-fold axis and 2 mirror planes.
• The Tetragonal System has either a single 4-
fold or 4-fold rotoinversion axis.
• The Hexagonal System has no 4-fold axes, but
has at least 1 6-fold or 3-fold axis.
• The Isometric System has either 4 3-fold axes
or 4 3-fold rotoinversion axes.
 Symmetry Operation Symmetry Symbol Hermann-Mauguin Symbol

Mirror m m

Rotation A1,A2,A3,A4,A6 1,2,3,4,6

Axis

- - - - -
Rotoinversion Ā1=i, Ā2,Ā3,Ā4,Ā6 1,2,3,4,6
Axis
 Lattice Notation
• Origin chosen as 000
• Axis directions a, b, c
and unit measurements
defined by particular
crystal system
• Axes are shown with
brackets, i.e., [001]
• Lattice points are
defined in 3-dimesions
as units along the axes,
without brackets (i.e.,
111, 101, 021, etc.)

 Lattice planes are defined using Miller indices, calculated as

the reciprocals of the intercepts of the planes on the coordinate
axes (the plane above containing 100, 010, and 002).
 Spacing of Lattice Planes
• Miller indices define a
family of parallel planes
• The distance between
these planes is defined as
“d” and referred to as the
“d-spacing”.
• Determination of the unit
cell parameters from
diffraction data is called
indexing the unit cell
• These calculations are
usually done by computer

“Crysfire” is a widely used

free system for indexing
• h, k, l are
Miller indices
• a, b, c are
unit cell
distances
• , ,  are
angles
between the
lattice
directions

Complexity of
calculations is
dependent on
the symmetry
of the crystal
system.
 Lattices and Crystal Systems
There are 5 possible planar (2-d) lattices in the different
coordinate systems:

Translating these lattices into the 3rd dimension generates the

14 unique Bravais Lattices
Unit cell of 14 Types of Bravais Lattice
 System Type Edge - Angle Relations Symmetry

The Six Crystal Systems

Triclinic P abc Ī

Monoclinic P (b = twofold axis) abc
C  =  = 90   2/m

P (c = twofold axis) abc

C    = 90  

Orthorhombic P
C (or A, B) abc mmm
I  =  =  = 90
F
Tetragonal P a1 = a2  c 4/mmm
I  =  =  = 90

Hexagonal R a1 = a2  c m
P  =  = 90,  = 120 6/mmm

Cubic P a1 = a2 = a3
I  =  =  = 90 m3m
F

P=Primitive F=Face Centered I=Body Centered C=Centered on opposing faces

 The 32 Point Groups
• Operation of translation-free symmetry
operations on the 14 Bravais lattices
produces the 32 Point Groups
• These are also known as the “Crystal
Classes”
The Point
Groups
(Part 1)
The Point
Groups
(Part 2)
 The 230 Space Groups
• Operation of the translation operations on the 32
point groups produces the (somewhat intimidating)
space groups (listed on following slides).
• Screw Axes combine rotation about an axis with
translation parallel to it. Rotations can be 180º, 120º,
90º or 60º defining 2-, 3-, 4- and 6-fold axes
respectively.
• Glide Planes combine reflection across a plane
combined with translation parallel to it. Glides are
expressed as a direction (a,b,c) with a subscript
indicating how many glides occur in one unit
distance.
 The 230 Space Groups (pt. 1)
Crystal Class Space Group
 The 230 Space Groups (pt. 2)
Crystal Class Space Group
Direction in a crystal

25
Fraction

26
27
 Detector
X-ray
tube

w q 2q

2q 2q 2q

A polycrystalline sample should contain thousands of crystallites.

28
Therefore, all possible diffraction peaks should be observed.
• Each peak in a diffraction pattern arises from a
unique set of repeating planes in the structure.

• These sets of planes are oriented in all different

directions in three-dimensional space.

• However, in order to see diffraction from a

specific set, the planes must be oriented relative
to the incident X-ray beam.

• Therefore, X-ray powder diffraction relies on a

large number of crystallites in random
orientations in order to observe the most
diffraction peaks.
29
 Principles
Relationship between d-value and the lattice constants

Bragg´s law =2dsinq Equation for the determination

of the d-value of a tetragonal
elementary cell
1/d2= (h2 + k2)/a2 + l2/c2
• The wavelength is known
• Theta is the half value of • h,k and l are the Miller indices
the peak position of the peaks
• d will be calculated • a and c are lattice parameters
of the elementary cell

If a and c are known it is possible to calculate the peak position

If the peak position is known it is possible to calculate the lattice
parameter
Hands-On XRD Workshop 30
 Principles
Another view on the Bragg´s law

n = 2d sinq
 XRD Pattern for NaCl

18-19/05/2017 Hands-On XRD Workshop 32

Advanced XRD Analysis

Dr. Banjuraizah Johar

33
 Learning outcomes
• Students shall be able to model and quantify
phases in the XRD pattern using the Rietveld
method - lab
• Students shall able determine and understand
each of the refinement parameters.
• Students shall be able to recognize factors that
effect the intensity and positions of peaks.
• Students shall be able to calculate the crystallite
size and measure the amorphous content.
• Student shall understand and able to interpret
the XRD pattern.
34
Overview on the Diffraction Pattern

• Diffraction pattern
– Peak position
– Intensity
– Background
– Peak profile

35
36
37
 Single Peak
Summary
A peak may be described by the following peak
parameters:
• background (if yid(2q) instead of ybragg(2q) is
used),
• position,
• intensity,
• line width,
• shape factor and,
• asymmetry.

38
 Background
• Why we have background?
– Due to
• scattering by air,
• detector noise
• fluorescence radiation,
• diffuse scattering (TDS) or
• long tails of neighbouring peaks the measured
intensity will show not only coherently scattered
intensity (the Bragg peak itself) ybragg(2q) (light
green),
• background radiation yb(2q) (green).
• Unknown radiation
– Background radiation is often estimated to be linear
within the actual region of interest.

39
 Principles
Crystal and Unit Cell
• An ideal crystal is formed by unit cells
of the same size consisting of atoms
arranged in an identical manner.

• The size and shape of a unit cell are

described by the lattice parameters,
which are the length of the edges
and the angles between them.

40
 Principles
Another view on the Bragg´s law

n = 2d sinq
41
 Principles
Reflection planes in a cubic lattice

42
Direction in a crystal

43
Direction in a crystal

44
Fraction

45
 Principles
Miller’s indices and Pattern

• Each peak of a pattern of a crystalline phase may be described by

its Miller's indices.
• Some peaks will have an identical or nearly identical position in the
pattern. In cubic crystals this happens for the (333) and (511) peak.
Peaks like this are named multiple indexed.

46
 TiN and NaCl

Different atoms cause (normally) different scattering factors

47
 a=b=c=5.62A

atom x y z
Na/K 0 0 0
Cl 0.5 0.5 0.5

Sodium ion is smaller than potasium ion

a=b=c=6.309A

48
 KCl
a=b=c=6.309A
In the NaCl trace, the (111) peak is clearly
visible. In the KCl trace, the same reflection is
effectively absent.

NaCl
a=b=c=5.62A

Peak position is closely link to size of unit cell

49
 NaCl a=b=c=5.62A
No of electrons determines the intensity
Heavier atoms scatter more effectively

NaBr
a=b=c=6.0A

50
51
 Principles
Relationship between d-value and the lattice constants

Bragg´s law Equation for the determination

of the d-value of a tetragonal
elementary cell

=2dsinq 1/d2= (h2 + k2)/a2 + l2/c2

• h,k and l are the Miller indices of the

• The wavelength is known peaks
• Theta is the value of the peak • a and c are lattice parameters of the
position elementary cell
• d will be calculated • if a and c are known it is possible to
calculate the peak position
• if the peak position is known it is
possible to calculate the lattice
parameter

52
 Overview
• Space group (symmetry group of a conf in space)
and lattice parameter determine the position
peak in 2 theta region.
• Position of atom, type of atom, its occupancy
determine its intensity ratio.
• Concentration of unit cell in the sample
determine its scale factor.
• Peak shape – instrumental broadening, particle
size
• Background – air scattering, amorphos /
disordered structure/ temperature factor
53
 Methods
What information contains a Powder Diagram?

• peak position  dimension of the

elementary cell

• peak intensity  content of the elementary cell

• peak broadening  strain/crystallite size

• scaling factor  quantitative phase amount

• diffuse background  false order

• modulated background  close order

54
 Methods
Powder Diagram and Structure

• The d-spacings of lattice planes depend on the size of the elementary cell which determine
the position of the peaks.

• The intensity of each peak is caused by the crystallographic structure, the position of the
atoms within the elementary cell and their thermal vibration.

• The line width and shape of the peaks may be derived from conditions of measuring and
properties - like particle size - of the sample material.

55
Basic principles of Rietveld
method

56
 Rietveld method-Introduction
• The Rietveld method was developed by Hugo
M. Rietveld 1967/1969.

• The basic principle of these method is a

description of all data points of a powder
pattern using analytical functions.

57
 Rietveld Method-Purpose
• Structure refinement
– (lattice change/distortion, position of atoms ,
occupancy, thermal parameter, crystal density,
volume)
• Quantitative phase analysis
– (Amount of phase, crystallite size, lattice strain,
amorphous content)

58
 Rietveld method-Basic principle
• Modeled the profile pattern (calculated
pattern) Using crystal structure of all phase
present -– obtained quantitative result
(phase wt%, crystallite size, lattice strain)

59
 Basic principle
• Fitting the whole profile pattern
– Fitting the background
– Scale factor
– Peak shape
• Correction
– Shift or displacement of peak
– Intensity
– Preferred orientation

60
 Rietveld method-The model
The starting model consists of:
– structure parameters: (describe the
crystallographic parameters)
– global parameters: (affect the entire pattern,
regardless of phase(s))
– profile parameters: (describe the width and shape
of diffracted peaks)
– miscellaneous parameters: (affect the intensity of
a phase)

61
 General requirement
• Sample preparation
• Data collection (high quality)
• Phase identification (Qualitative analysis)
• Crystal structure data
• Model the diffraction pattern (instrument,
sample, peak profile, background, preferred
orientation, correction)

62
 Preparing a powder specimen
• An ideal powder sample should have many crystallites in random
orientations
– the distribution of orientations should be smooth and equally distributed
amongst all orientations
• If the crystallites in a sample are very large, there will not be a smooth
distribution of crystal orientations. You will not get a powder average
diffraction pattern.
– Particle size should be < 10mm in size to get good powder statistics
• Large crystallite sizes and non-random crystallite orientations both lead to
peak intensity variation
– the measured diffraction pattern will not agree with that expected from an
ideal powder
– the measured diffraction pattern will not agree with reference patterns in the
Powder Diffraction File (PDF) database

63
 Preferred orientation
• If the crystallites in a powder sample have plate
or needle like shapes it can be very difficult to get
them to adopt random orientations
– top-loading, where you press the powder into a
holder, can cause problems with preferred orientation
• In samples such as metal sheets or wires there is
almost always preferred orientation due to the
manufacturing process
• For samples with systematic orientation, XRD can
be used to quantify the texture in the specimen

64
Data collection strategy

65
 Rietveld method-Data collection
• Scan time – (minimum intensity > 10,000 counts on the highest
peak
• Counting errors are related to the square root of the intensity. If u
have 10,000 counts, then the error is 100 (1% as percentage error)
• ∆2θ < + 0.02o (for indexing)
• ICDD PDF: a pattern is considered to be a high quality pattern if
differences between measured and theoretical peak positions: Δ2θ
≤ ±0.04o
• Fixed Divergence slit
• Infinitively thick sample for reflection geometry
• To compare- measure all scans with the same optics, instrument
condition and treats all scans in the same way. E.g the step time,
step size, divergence slit, sample length,

66
Accuracy and precision of the
measurement

67
 Phase identification
• All phase although minor phase should be accurately
identified.

• Know the background of the samples (elements and

chemistry)

• If necessary, conduct XRF analysis for the unknown samples.

• Aware of overlapping peaks

68
Rietveld method requires –Correction
on shifted of diffraction pattern
• Zero shift (possible error that come from
instrument allignment)

• Sample displacement (occurs when sample at

wrong height- it will effect the position of peak)

• Refine either zero shift or sample displacement

69
 Rietveld method requires - crystal
structure data
• Lattice parameter
• Space group
• Position of atoms in (x, y, z direction)
• Occupancy
• Temperature factor

70
 Lattice parameter
• It is important not to let the cell dimensions
change too much from their original starting
value. This may happen in cases when the phase
is quite low in abundance or when there is
particularly high peak overlap.

• To prevent this, it is a good idea to put limits

(minimum and maximum values) on the values
for each of the refinable cell dimensions. (1 - 2 %
range for the cell dimension is a common value).
71
 Space group
• The space group and crystal system impose restrictions on
how these can vary; e.g. for a cubic cell, the angles must
always be at 90 degrees and all dimensions must be the same.

• When refining cell dimensions for a phase, refine all possible

values at the same time. For example, never refine just the a
parameter of a tetragonal cell, refine a and c at the same
time.

• Positions of peak (2q) for each plane can be identified if the

space group and lattice parameter are known.

• d-spacing represent a family of lattice plane

72
 Peak intensity

• Three coordinates, x, y and z, indicating the position of

a specific atom in the three dimensional space of the
unit cell.

• X-ray are scattered by an electron of atoms in each

plane. Thus, the intensity of peaks depends on what
type of atoms at that particular plane.

• To model the intensity of the peaks, we need to know

the location of the atoms within the crystal structure.
To do this, we must define atoms and its positions.
73
 Site Occupation Factors
• In some crystal structures, a location may be
shared by two or more atoms of different kinds.
• Phases that exhibit this effect are normally
referred to as solid solutions.
• Full occupancy of a particular site is given the
number 1. If two atoms are sharing a site with a
50/50 % distribution, say for instance Fe and Al,
each atom would have the same coordinates and
each would have an occupancy factor of 0.5.
74
75
 Temperature factor/displacement factor
• X-rays are scattered by electrons. When we define the
position of the atom, we define a single point in space.
However, this is really the location of the nucleus of the
atom. The electrons are distributed in the space around the
nucleus.

• The shape and the size of the electron cloud has an effect on
our diffraction pattern.

• Additionally, we must consider that the atoms in our

structure are able to vibrate. The hotter the sample, the
more the atoms will vibrate, hence this factor is commonly
referred to as a Temperature factor.

• The temperature factor is indicated by the symbol B

(sometimes by the symbol U - in that case, another definition
of the vibration is used). 76
 Temperature factor/displacement factor
• The effect that the temperature factors have on the
diffraction pattern is reducing the intensity at the higher
diffraction angles, as illustrated in the schematic diagram.

• In our imaginary diffraction pattern with no distribution of

the electrons, we have three peaks with approximately equal
intensity. By including the thermal vibration into the model,
the peaks get progressively less intense.

77
 Temperature factor/displacement factor

• There are three possible ways to refine the

temperature factors:
– B overall is a factor that is applied to all atoms for a
particular phase.
– B isotropic is applied to an individual atom. Isotropic
means that it is the same in all directions. This
assumes that the atom is spherical in shape.
– B Anisotropic is where you allow the atom to have a
shape other than spherical. You need to be able to
refine up to 6 separate factors to give its shape.

78
 Background determination
• To distinguished between peak intensity and
background intensity
• Background intensity – air scattering,
flourescense, amorphous etc

79
80
 Fluoresced X-rays
• The increased background noise from fluoresced X-rays can
be removed by using:
– a diffracted-beam monochromator
– an energy sensitive detector

• The diffracted beam signal can only be increased by using a

different wavelength of radiation

• The most problematic materials are those two and three

below the target material:
• For Cu, the elements that fluoresce the most are Fe and Co

81
 Refine the background
• Polynomial
• Chebychev
• Shifted Chebyshev
• Amorphous sinc funtion
• Damped amorphous sinc fuction
• Available background

Not important to know how they differ from each

other- as far the background gradually improve.

82
 Rietveld method- Model the peak
Profile
• Peak profile parameter
– Peak shape
– Peak width
– Peak asymmetry

The profile of peak is the combination of three

separate profile parameters.

83
 Refinement parameter-Peak shape
function
• Pseodo voight
• Pearson
• Voight and Pseodo voight 3
• Gaussion and Lorentzian

The choice of peak profile function should be made at the start of

the refinement.

Pseuodovoight function – the most common and

best to describe peak profile.

If u have long tail peak – use lorentzian

84
 Peak shape function-Gaussion
• Broad tip and short tail

85
 Peak shape function-Lorentzian
• Narrow peak tip and has quite long tales

86
 Refinement parameter - Peak width
• Must also be accurately match.
• Peak width parameter: u, V, W
• Full Width at Half Maximum
• It depends on θ
• Cagliotti function
– H2=U tan 2θ + V tanθ + W
• Often sufficient just to refine W

87
Peak width resolution

88
Refinement parameter-peak width
• FWHM are not consistent across the measurement range.

• It will gradually increased as u go to higher angle. To model

this we need cagliotti function.

• W is independent of 2 theta. So if u refine W alone, we are

using constant value for all peak.

• For quantitative analysis, do measurement at much lower

angle.

• If u measure at higher angle refine the fist parameter W,

followed with V and if necessary U
89
 Refinement parameter - Peak
asymmetry
• Not all peak have the ideal symmetrical shape.

• Peak asymmetry is caused by axial divergence.

• Axial divergence cause an increase in peak tail on the low

angle side.

• This can be controlled by using soller slits.

• If soller slits are not use, u have to refine peak asymmetry

90
 Miscellaneous parameters
• Scale factor
• Preferred orientation

91
 Scale factor
•The scale factor is a number that adjusts the overall
intensity of all peaks of a phase.

•The scale factor is always the first parameter that is to

be refined and it is always refined throughout the
refinement process.

•When a scale factor refines close to zero (or even to

slightly negative values) it usually means that the phase
is not present in the actual sample.

92
 Preferred Orientation
• General assumption in powder diffraction that the particles are randomly
orientated.

• Measurement done in Bragg-Brentano geometry, only measures the crystal

planes that are orientated approximately parallel to the sample surface.

• Plane at an incline to the sample surface are not measured.

• Therefore if we assume that the particles belonging to one phase are

randomly orientated, the planes measure are a true representative of all
particles of this phase in the material.

• If the particles are not randomly orientated, we will measure more crystal
than average for certain crystal planes. Consequently, we will see some peaks
that are more intense than expected.
93
 Preferred Orientation
• Results from crystallites lining up.

• May also results from crystal growth mechanism

or special cleavage planes.

• Use backloading or special sample preparation

techniques and spin sample.

• Watch out if symmetry related peaks are all

higher/lower in intensity than expected.

94
 Preferred Orientation
• Can be refined when necessary.
• Corrected using March Dollas function.
• Each reflection is corrected for intensity
according to the angle α between the plane of
the reflection and the main direction of the
preferred orientation.
• The preferred orientation direction should be
selected by the user.

95
 Microabsorption
• Arise when a sample contain phases that have
differences in linear absorption coefficients, μ

• The linear absorption coefficient is a measure

of the amount of radiation absorbed by a
species.

96
 Microabsorption
• If we have 2 phases, “a” and “b” and μa >> μb or
particles of “a” much larger than particles b, the
diffracted intensity of “a” crystal will be much less than
the calculated intensity.

• Therefore, accuracy of intensity measurements can be

greatly affected by microabsorption.

• Problems associated with microabsorption effects are

negligible if, i)μa = μb ii) Both phases have the same
particle size or both phases consist extremely fine
particle

97
 Absorption due to surface roughness
• When the surface is rough, some particles are exposed
directly to full X-ray beam, while other are exposed to
the X-ray beam after some absorption has taken place.

• This absorption of X-rays prior to diffraction has the

effect of changing the relative intensities of certain
analytes due to the difference in the mean linear
absorption coefficient.

• This effect are more pronounced at low angles where

the path lengths in the sample are greatest
98
99
100
The classical Rietveld Method

101
The classical Rietveld Method

102
 Structure Factor
• The structure factor is a means of grouping the atoms in the unit cell
into planar elements, developing the diffraction intensities from each
of those elements and integrating the results into the total diffraction
intensity from each dhkl plane in the structure.

• It describes total scattering intensity

F (hkl )  ( f N ,  N )
N
Where F(hkl) is the structure factor for the hkl reflection of the unit cell,
f is the atomic scattering factor for each of N atomic planes and
 is the repeat distance between atomic planes measured from a common
origin (called the phase factor)

103
 Multiplicity of Bragg Planes
• The number of identically spaced plane cutting a unit cell in a
particular hkl family is call the multiplicity factor.

• For a low symetry system, the multiplicity will always be low.

• For high symmetry system, a single family of planes may be

duplicate many times by symmetry operation, and each
duplicate will add to the intensity of the diffraction.

104
ATOMIC SCATTERING FACTOR AND
DEBYE-WALLER

105
THE CLASSICAL RIETVELD METHOD

106
THE CLASSICAL RIETVELD METHOD

107
THE CLASSICAL RIETVELD METHOD

108
THE CLASSICAL RIETVELD METHOD

109
QUALITY OF THE REFINEMENT

110
The R indices

111
WSS AND GOFF (OR SIGMA)

112
RIETVELD PROCEDURE

113
STARTING POINT: DEFINING THE
PHASES

114
ADJUSTING MANUALLY: CELL
PARAMETERS, INTENSITIES

115
STEP 1: REFINING SCALE FACTORS AND
BACKGROUND

116
STEP 2: PEAKS POSITIONS

117
STEP 3: PEAKS SHAPES

118
STEP 4: CRYSTAL STRUCTURE
REFINEMENT

119
Instrument

120
HIGH RESOLUTION INSTRUMENTS

121
LOW RESOLUTION INSTRUMENTS

122
Instrument assessment

123
The step size

124
Sample characteristics (1)

125
 Atomic scattering factor
• Scattering of X-rays mainly caused by the electrons.
• Ions, which have more or less electrons in the valence orbitals, have
different atomic scattering factors compared with neutral atoms,
which is significant especially at small scattering angles.
• The X-ray scattering power of an atom decreases with increasing
scattering angle and is higher for heavier atoms.
• The atomic scattering factor for the jth atom is the atomic
scattering factor for the jth point atom multiplied by an exponential
function of the atomic temperature factor:

where:
– fj is the atomic scattering factor for the jth atom
– f0j is the atomic scattering factor for the jth atom at rest
– B is the atomic temperature factor

126
Temperature factor

sin 2 q k
B j
Fk   N j  f j  e 2
 e i k
j

 B: The atoms slightly move around their ideal

position.

 The shift from the ideal position is given by

the parameter u, which is temperature
dependent.

 The weakening of peak intensity due to

delocalisation of the scattering center often
given by an isotropic thermal vibration
parameter B, which holds the equation

B  8  u
2 2
 Anisotropic parametrisations also exist.
127
 A good fit refinement

A correct (quantitative result)

128
 Refinement parameter
• The number of refinables nmax depends on the
model used.

• The greater n is, the more flexible the

analytical function is and the better the fit may
be, but also the higher correlations will be.

129
 Peak Profile
• The width of the divergence slit (primary beam)
and detector slit (secondary beam) also cause
broadening.

• The length of the target and the receiving slit

also influences peak shape.

• Therefore put correct instrument set up

130
 Rietveld method- General Procedure
• Phase identification
• Obtain crystal structure data
– Directly insert if available
– Find from free online structure data base and fed into TOPAS and
develop the ‘str. file’
• Define Global Parameter
– Emission profile
– Background
– Insert instrument set up during XRD measurement.
• Sample length, Gonoimeter radius……….
– Correction : surface roughness, micro-absorbtion, polarization.
– Refine the background, zero shift, lattice parameter,
• Scale factor
• Correct the intensity – preferred orientation,
• Refine the atomic position, temperature factor and occupancy
• Observe the refinement result.
131
 How good is the model
- Agreement indices
To judge the quality of refinement

Goodness of fit

132
 Crystallite size
• Crystallite size determination is one of the
most important applications in powder
diffractometry for materials characterisation.

133
Basic principle of crystallite measurement
• Therefore to calculate Bc, the instrument broadening, Bi must be
known. It must be measured using a reliable standard with very
good quality of data (30,000 counts)
• After subtraction the instrument broadening,
→ BR=Bc + Bs
• Substitution the equations:
k
BR    tan q
L cos q
k
BR cos q    sin q
L

• This eq. is linear if we plot a graph of BRcosθ against sinθ.

• A straight line is obtained, where the intercept can be used for
obtaining the crystallite size L and the slope for the strain, η
134
 Instrument and Sample Contributions to
the Peak Profile must be Deconvoluted
• In order to analyze crystallite size, we must deconvolute:
– Instrumental Broadening FW(I)
• also referred to as the Instrumental Profile,
Instrumental FWHM Curve, Instrumental Peak Profile
– Specimen Broadening FW(S)
• also referred to as the Sample Profile, Specimen
Profile

• We must then separate the different contributions to

specimen broadening
– Crystallite size and microstrain broadening of diffraction
peaks 135
 The Scherrer Constant, K
K 0.94
B2q   B2q  
L cos q L cos q
• The constant of proportionality, K (the Scherrer
constant) depends on the how the width is
determined, the shape of the crystal, and the size
distribution
– the most common values for K are:
• 0.94 for FWHM of spherical crystals with cubic
symmetry
• 0.89 for integral breadth of spherical crystals w/
cubic symmetry
• 1, because 0.94 and 0.89 both round up to 1
– K actually varies from 0.62 to 2.08
Crystallite Size & Strain Information
• Scherrer formula (average size, neglects strain)
• Integral breadth methods (provide avg values
of size and strain
• Peak shape methods (provide size and strain
distributions)

137
 Size Broadening
• SCHERRER (1918) first observed the crystallite
size could give rise to line broadening.
• Scherrer formula

138
 Lattice Strain (Microstrain)
• Strain is defined as the deformation of an object divided by
it’s ideal length, d/d
• 2 types of strain: uniform strain and Non-uniform strain.
• Uniform strain causes the unit cell to expand/contract in an
isotropic way. This simply leads to a change in a unit cell
parameters and shift of the peaks (No broadening
associated with this type of strain.
• Non-uniform strain leads to systematic shift of atoms from
their ideal positions and to peak broadening. This type of
strain arises from the following sources: point defect,
plastic deformation and poor crystallinity
139
Strain Broadening

140
 William-Hall Analysis
Simplified Integral Breadth Methods

141
 Methods used in Jade to Define Peak
Width
• Full Width at Half Maximum (FWHM)
FWHM
– the width of the diffraction peak,
in radians, at a height half-way

Intensity (a.u.)
between background and the
peak maximum

• Integral Breadth
46.746.846.947.047.147.247.347.447.547.647.747.847.9
– the total area under the peak 2q(deg.)

divided by the peak height

– the width of a rectangle having
Intensity (a.u.)
the same area and the same
height as the peak
– requires very careful evaluation
of the tails of the peak and the 46.7 46.8 46.9 47.0 47.1 47.2 47.3
2q (deg.)
47.4 47.5 47.6 47.7 47.8 47.9

background 143
 Integral Breadth

 2q  
L cos q
• Warren suggests that the Stokes and Wilson method of using
integral breadths gives an evaluation that is independent of
the distribution in size and shape
– L is a volume average of the crystal thickness in the
direction normal to the reflecting planes
– The Scherrer constant K can be assumed to be 1

• Langford and Wilson suggest that even when using the

integral breadth, there is a Scherrer constant K that varies
with the shape of the crystallites
144
 How is Crystallite Size Defined
• Usually taken as the cube root of the volume of a crystallite
– assumes that all crystallites have the same size and shape
• For a distribution of sizes, the mean size can be defined as
– the mean value of the cube roots of the individual crystallite
volumes
– the cube root of the mean value of the volumes of the individual
crystallites

• Scherrer method (using FWHM) gives the ratio of the root-mean-

fourth-power to the root-mean-square value of the thickness
• Stokes and Wilson method (using integral breadth) determines the
volume average of the thickness of the crystallites measured
perpendicular to the reflecting plane
• The variance methods give the ratio of the total volume of the
crystallites to the total area of their projection on a plane parallel to
the reflecting planes Hands-On XRD Workshop 145
 Anistropic Size Broadening
• The broadening of a single diffraction peak is the product of
the crystallite dimensions in the direction perpendicular to
the planes that produced the diffraction peak.

18-19/05/2017 Hands-On XRD Workshop 146

 Crystallite Size and Microstrain
• Crystallites smaller than ~120nm create broadening of diffraction peaks
– this peak broadening can be used to quantify the average crystallite size
of nanoparticles using the Scherrer equation
– must know the contribution of peak width from the instrument by using a
calibration curve
• microstrain may also create peak broadening
– analyzing the peak widths over a long range of 2theta using a Williamson-
Hull plot can let you separate microstrain and crystallite size
00-043-1002> Cerianite- - CeO2

K
B2q  
Intensity (a.u.)

L cos q

23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41
2q (deg.)
 Size/Strain Analysis
• The analysis of crystallite size and/or micro strain by the Rietveld
method is based on the change of the profile parameters, compared
to a standard sample.
• The profile parameters are, of course, depending on the instrument
settings used for data collection and on the profile function used for
the refinement.

Size-strain standard:
• The first thing is to measure a size-strain standard. This should be a
material with no micro strain and no size broadening. Often the NIST
SRM674 CeO2 is used for this purpose. It has a very limited amount of
size broadening, which does not substantially influence the results.
• You need a high quality scan up to at least 140 degrees 2θ, performed
with optics tuned for resolution. 148
 Refinement The Profile Function
• Open the file CEO2-NBS.RD from the tutorial
folder. Insert the structure of cerianite (the
mineral name of cerium oxide) from the
Standard.CRY structures file from the tutorial
folder.
• Now start an automatic Rietveld refinement
using the parameter set Size-Strain Analysis.

149
• Select the cerianite phase node and click on Take as
Size-Strain Standard. This copies the refined profile
and shape parameters from the phase to the
standard values of the global parameters section.

• Delete the cerianite phase from the refinement

control.

• Now you have a diffraction document containing no

structures and no scans anymore, but it contains the
refined standard data. Store the document with a
meaningful name like PseudoVoigtStandard.HPF

150
 The results obtained
The global agreement indices:
• R expected = 5.04721
• R profile = 12.46318
• Weighted R profile = 17.41862
• D-statistics = 0.37421
• Weighted D-statistics = 0.36507
• Goodness of Fit = 11.91036

The phase Bragg R-value and profile parameters:

• Cerianite R Bragg = 4.25
• Cerianite U = 0.00843
• Cerianite V = -0.00853
• Cerianite W = 0.01164
• Cerianite Peak Shape 1 = 0.32851
• Cerianite Peak Shape 2 = 0.00318

151
 Measurement of size and strain
• Start a Rietveld refinement with the Size-Strain
Analysis parameter set.
• Observe the quality of the fit and note the
calculated values for size and strain.
• Change the phase analysis mode to size only and
re-start the refinement. Note the crystallite size
result.
• Change the phase analysis mode to strain only
and re-start the refinement. Note the micro strain
result
152
 Crystallite size and
strain measurement

CEO2-NBS.RD, CAF2-RAW.RD.CAF2-
PseudoVoigtStandar 400.RD, CAF2-500.RD
d.HPF ,Standard.CRY CAF2-600.R

153
Results

154
 AMORPHOUS MEASUREMENT
• Degree of crystallinity calculations require the
definition of at least two phases in order to
describe the intensity contributions coming from
the crystalline and the amorphous parts of the
sample.

Examples
• Sample A, sample B, sample C, sample D
• Cryst.50.RD – constant background /intensity
ratio method

155
 Amorphous
content

Intensity ratio
Spiking method
method

Sample A, Sample
Cryst50+.RD Standard.CRY B, Sample C,
Sample D

156
 Basic principle
• Same chemistry
– No need to involve internal and external standard
– Measurements are performed under identical
condition (don’t change instrument setting)

157
 Degree of crystalinity
• Determine the background using automatic
mode
• Separate the crystalline peaks from the
amorphous hump and the background
• It is better to calibrate using the known value
with the same instrument setting, and enter
the calibration value for the constant
background before the measurement.

158
 Crystallinity Algorithm
• Amorphous substance- Amorphous hump

• Crystallinity (%) = intensity ratio of diffraction peak

and of the sum of all measured intensity

• High crystalline sample also has background which

arise from imperfection of sample, X-rays optic, sample
fluorescence and scatter.

• Therefore this constant background need to be

substracted from total intensity

159
 Crystallinity Determination
• Used standard sample – crystalline: amorphous 1:1
(amorphous 50%)
• Determine the background. Choose the background.
• Select the scan and double click to open object
inspector pane. Open scan statistic node
• Enter a value into the constant background replacing -
1.
• Change constant b/g until you get 50% crystallinity.
• Load cryst10.RD. Repeat b/g determination and enter
calibration value of const b/g

160
161
 Intensity ratio method
• Sample A – 100% crystalline
• Sample B- 100% amorphous
• Insert sample D-take as new anchor scan data
• Start autoscale-using default parameter
• Watch the sum profile and the difference plot
in Analyze view
• The autoscale values is displayed in the
Analyze view.
162
The solutions:

Sample Crystalline Amorphous

D 4.3 95.7
E 10.5 89.5

163
Measurement of amorphous phase
by spiking method using Rietveld

164
 Objective
• To determine the amorphous content of a
sample with Rietveld refinement by addition
of crystalline standard phase.
• Important when amorphous and multiphases
with different linear attenuation coefficient
exist in the sample.
• Small amount of standard e.g alumina, rutile
or silicon was used and mixed with the sample

165
 Spiking method-Cryst.50+.RD

• The following weight percentages for Quartz are shown:

• Weight percentage: 68.1%
• Recalculated weight percentage: 42.7%
• As received weight percentage: 53.4% (50.0% true weight)

• The true weight percentage of Quartz in this ample is 50%. The other
50% is made up of completely amorphous Quartz glass. (For a more
accurate result you need to calibrate the Rietveld analysis by tuning
the Boverall parameter of the standard phase.)
166