Structure elucidation from

XRD
X-rays are electromagnetic waves with a wavelength in the range of interatomic
distances (0.1-10 )

topics
Highlight on instrumentation
Crystallography
X-ray diffraction from polycrystalline
samples (powders);
XRD data interpretation

X-ray Powder Diffraction

Particle size
and defects

Peak shapes

Peak relative
intensities
Background
Peak
positions

10

20

30

40

Atomic
distribution in
the unit cell

Unit cell
Symmetry
and size

c
b
a

Diffuse scattering,
sample holder,
matrix, amorphous
phases, etc...

Instrumentation highlight
Details should be given in
Instrumentation lecture !

What is X-ray Diffraction?

Our powder diffractometers typically use the

Bragg-Brentano geometry.
Detector
X-ray
tube

The incident angle, , is defined between the X-ray source and the sample.
The diffracted angle, 2, is defined between the incident beam and the
detector angle.
The incident angle is always of the detector angle 2 .
In a :2 instrument (e.g. Rigaku RU300, our XRD), the tube is fixed, the
sample rotates at /min and the detector rotates at 2 /min.
In a : instrument (e.g. PANalytical XPert Pro, Bruker), the sample is fixed
and the tube rotates at a rate - /min and the detector rotates at a rate of
/min.

Braggs law is a simplistic model to understand

what conditions are required for diffraction.

For parallel planes of atoms, with a space dhkl between the planes, constructive
interference only occurs when Braggs law is satisfied.

In our diffractometers, the X-ray wavelength is fixed.

Consequently, a family of planes produces a diffraction peak only at a specific angle .
Additionally, the plane normal must be parallel to the diffraction vector

dhkl dhkl

= 2d hkl sin

Plane normal: the direction perpendicular to a plane of atoms

Diffraction vector: the vector that bisects the angle between the incident and diffracted beam

The space between diffracting planes of atoms determines peak positions.

The peak intensity is determined by what atoms are in the diffracting plane.

constructive interference results in diffraction line, but destructive interference does not

monochromatic/single wavelength
with highest intensity is used as
the X-ray source

- 2 Scan
The - 2 scan maintains these angles with the
sample, detector and X-ray source
Normal to surface

Only planes of atoms that share this normal will be seen in the - 2 Scan

Solid matter

The atoms are

arranged in a
regular pattern,
and there is as
smallest volume
element that by
repetition in three
dimensions
describes the
crystal (a unit
cell).
Long range order
(>103 molecules)

non-crystalline
(amorphous)
The atoms and
molecules are arranged
in a random way similar
to the disorder we find in
a liquid do not form
crystallites. Glasses are
amorphous materials.
Small particles with no
long-range order (100
)

polycrystalline

single crystal
Solid which contains
single crystallite

B
A [101]
A
A

Intensity (a.u)

crystalline

5h
Am
4h
3h
2h

10

20

30

40

50

60

70

80

90

2 ( )

Solids which contain

many small, randomly
oriented and joined
crystallites/grains

Quartz (SiO2), a crystalline solid and the

most abundant mineral in the earths crust)
Fig. 10.2: Crystalline solids are
characterized by highly ordered arrays of
atoms, ions or molecules and give distinct
X-ray diffraction patterns.
Amorphous solids have no long-range
ordering in their structures.
What type of attractive forces are most
important in the quartz structure?

Glass (SiO2), has the same chemical

composition as quartz but exhibits no
extensive, repeating organization.

Crystalline Versus Amorphous

Quartz

Obsidian

10

Crystalline materials are characterized by the

orderly periodic arrangements of atoms.
The (200) planes
of atoms in NaCl

The (220) planes

of atoms in NaCl

The unit cell is the basic repeating unit that defines a crystal.
Parallel planes of atoms intersecting the unit cell are used to define
directions and distances in the crystal.
These crystallographic planes are identified by Miller indices.

The atoms in a crystal are a periodic array of

coherent scatterers and thus can diffract light.
Diffraction occurs when each object in a periodic array scatters
radiation coherently, producing concerted constructive interference
at specific angles.
The electrons in an atom coherently scatter light.
The electrons interact with the oscillating electric field of the light wave.

Atoms in a crystal form a periodic array of coherent scatterers.

The wavelength of X rays are similar to the distance between atoms.
Diffraction from different planes of atoms produces a diffraction pattern,
which contains information about the atomic arrangement within the
crystal

X Rays are also reflected, scattered incoherently, absorbed,

refracted, and transmitted when they interact with matter.

11

X-Ray Powder Diffraction (XRPD) uses information about

the position, intensity, width, and shape of diffraction peaks
in a pattern from a polycrystalline sample.

The x-axis, 2theta, corresponds to the angular position of the detector

that rotates around the sample.

Peaks result from

constructive
interference for the
reflected X-rays

This is an example of an
XRD spectrum for quartz.

12

 Only crystallites having reflecting planes (h,k, l)

parallel to the specimen surface will contribute to
the reflected intensities.
If we have a truly random sample, each possible
reflection from a given set of h, k, l planes an
equal number of crystallites contributing to it.
We only have to rock the sample through the
glancing angle THETA in order to produce all
possible reflections.

13

Crystallography: reviews

14

There are seven

crystal systems
also knows as
Bravais
Structures.

In Chapter 11
we will cover
only the cubic
systems, sc,
fcc, and bcc.
Sides:
a=b=c
Angles
= = = 90

15

 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.

16

17

18

XRD for polycrystalline

samples

19

Powder diffraction data consists of a record of

photon intensity versus detector angle 2.

Diffraction data can be reduced to a list of peak positions and intensities

Each dhkl corresponds to a family of atomic planes {hkl}
individual planes cannot be resolved- this is a limitation of powder diffraction
versus single crystal diffraction
Raw Data
Reduced dI list

Position
[2]

Intensity
[cts]

25.2000

372.0000

25.2400

460.0000

25.2800

576.0000

25.3200

752.0000

25.3600

1088.0000

25.4000

1488.0000

25.4400

1892.0000

25.4800

2104.0000

25.5200

1720.0000

25.5600

1216.0000

25.6000

732.0000

25.6400

456.0000

25.6800

380.0000

25.7200

328.0000

hkl

dhkl ()

Relative
Intensity
(%)

{012} 3.4935

49.8

{104} 2.5583

85.8

{110} 2.3852

36.1

{006} 2.1701

1.9

{113} 2.0903

100.0

{202} 1.9680

1.4

A single crystal specimen in a Bragg-Brentano

diffractometer would produce only one family of peaks in
the diffraction pattern.

At 20.6 2, Braggs law

fulfilled for the (100) planes,
producing a diffraction peak.

The (110) planes would diffract at 29.3

2; however, they are not properly
aligned to produce a diffraction peak
(the perpendicular to those planes does
not bisect the incident and diffracted
beams). Only background is observed.

The (200) planes are parallel to the (100)

planes. Therefore, they also diffract for this
crystal. Since d200 is d100, they appear at
42 2.

20

A polycrystalline sample should contain thousands of

crystallites. Therefore, all possible diffraction peaks should
be observed.

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 diffracted beams).
Basic assumptions of powder diffraction are that for every set of planes there is an equal
number of crystallites that will diffract and that there is a statistically relevant number of
crystallites, not just one or two.

About 95% of all solid materials can be described as

crystalline
When X-rays interact with a crystalline substance
(phase) gets a diffraction pattern
In 1919 A.W.Hull gave a paper titled, A New Method of
Chemical Analysis. Here he pointed out that .every
crystalline substance gives a pattern; the same substance
always gives the same pattern; and in a mixture of
substances each produces its pattern independently of
the others.
The X-ray diffraction pattern of a pure substance a
fingerprint finger print identification

The powder diffraction method is thus ideally suited for

characterization and identification of
crystalline/polycrystalline phases

21

Today about 50,000 inorganic and 25,000 organic single

component, crystalline phases, diffraction patterns have
been collected and stored on magnetic or optical media as
standards
The main use of powder diffraction is to identify
components in a sample by a search/match procedure
The areas under the peak are related to the amount of
each phase present in the sample
For single-phase materials the crystal structure can be
obtained directly using X-Ray diffraction (XRD)
XRD can be used :
for phase identification (With the help of a database of
known structures)
to determine crystal size, strain and preferred
orientation of polycrystalline materials
the related technique of X-ray reflection enables
accurate determination of film thickness

XRD applications and

interpretation

22

You can use XRD to determine

Crystalline phase and sample identification

Phase Composition of a Sample
Quantitative Phase Analysis: determine the relative amounts of phases in a
mixture by referencing the relative peak intensities

Unit cell lattice 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, etc.

Residual Strain (macrostrain)

Crystal Structure

Epitaxy/Texture/Orientation
Crystallite Size and Microstrain

By Rietveld refinement of the entire diffraction pattern

Indicated by peak broadening

Other defects (stacking faults, etc.) can be measured by analysis of peak shapes
and peak width

in-situ studies (evaluate all properties above as a function of time,

temperature, and gas environment)

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Phase Identification
The diffraction pattern for every phase is as unique as your
fingerprint
Phases with the same chemical composition can have drastically
different diffraction patterns.
Use the position and relative intensity of a series of peaks to match
experimental data to the reference patterns in the database

Databases such as the Powder Diffraction File (PDF)

contain d-I lists for thousands of crystalline phases.
The PDF contains over 200,000 diffraction patterns.
Modern computer programs can help you determine what phases are
present in your sample by quickly comparing your diffraction data to
all of the patterns in the database database XRD pattern matching
The PDF card for an entry contains a lot of useful information,
including literature references.

24

25

26

XRD patterns of furnace materials and reference patterns of identified phases

27

28

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- - CeO
2

Intensity (a.u.)

D=

K
cos

23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41

2 (deg.)

29

D=

K
cos

Different crystallite sizes

30

Quantitative Phase Analysis

With high quality data, you can determine
how much of each phase is present
must meet the constant volume assumption
(see later slides)

The ratio of peak intensities varies linearly

as a function of weight fractions for any two
phases in a mixture
need to know the constant of proportionality

RIR method is fast and gives semiquantitative results

Whole pattern fitting/Rietveld refinement is
a more accurate but more complicated
analysis

60

I(p h a s e a )/I(p h a s e b ) ..

50
40
30
20
10
0
0

0.2

0.4

0.6

0.8

X(phase a)/X(phase b)

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Unit Cell Lattice Parameter Refinement

By accurately measuring peak positions over a long
range of 2theta, you can determine the unit cell lattice
parameters of the phases in your sample
alloying, substitutional doping, temperature and pressure, etc
can create changes in lattice parameters that you may want to
quantify
use many peaks over a long range of 2theta so that you can
identify and correct for systematic errors such as specimen
displacement and zero shift
measure peak positions with a peak search algorithm or profile
fitting
profile fitting is more accurate but more time consuming

then numerically refine the lattice parameters

determination and refinement of

lattice parameters (indexing)
relationship between Miller indices and diffraction angles

sin 2 =

2
4a

(h 2 + k 2 + l 2 )
2

sin 2 = C (h 2 + k 2 + l 2 )

dividing the above equation with the first reflection angle gives the ratio of hkl

sin 2
(h 2 + k 2 + l 2 )
=
sin 2 1 (h12 + k12 + l12 )
the ratio of hkl define the possible Miller indices: ratio = h2 + k2 + l2
if there are some possible hkl, the highest number comes first
After indexing, one of the peaks can be used to calculate the cell parameters.
As the error in measuring the diffraction angles is a systematic error, the last
reflection data will be used

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exercise 1: indexing XRD data (cubic)

2
19.213
27.302
33.602
38.995
43.830
48.266
56.331
60.093
63.705
67.213
70.634

sin2
0.0279

ratio
1

Miller indices
100

1. define the Miller

indices
2. calculate the
lattice
parameters

lattice type and systematic absences

on cubic system
destructive interferences occurring
between the diffracted waves intensity
cancels out
eg:

33

topics
Evaluation of the intensities of X-rays
diffracted from polycrystalline samples;

Evaluating crystallinity
taking the sum total of relative intensities of
ten individual characteristic peaks1 then
taking the ratio over the corresponding
relative intensities of standard materials
E.g.:
Comparing crystallinity of flyash-based
zeolite-A using XRD and IR spectroscopy

1CURRENT

SCIENCE, VOL. 89, NO. 12, 25 DECEMBER 2005

34

% crystallinity = (IR sample)/(IR standard)

% crystallinity =
(AD4R)/(ATO4)

72.8%

85%

98.6%
98.6%

98.6%

100%

35

83.2%
72.8%

92%

96.2%

93.3%

100%

Crystallinity = (A ratio of 560 over 464 cm-1 bands of sample/reference) x 100%

Preferred Orientation (texture)

Preferred orientation of crystallites can create a
systematic variation in diffraction peak intensities
can qualitatively analyze using a 1D diffraction pattern
a pole figure maps the intensity of a single peak as a function of
tilt and rotation of the sample
this can be used to quantify the texture
10.0

(111)

00-004-0784> Gold - Au

Intensity(Counts)

8.0

(311)
(200)

6.0

(220)
4.0

(222)

2.0

(400)
3

x10

40

50

60

70

80

90

100

Two-Theta (deg)

36

 For example MoO3 crystallizes in thin plates (like sheets

of paper) these crystals will pack with the flat surfaces
in a parallel orientation.
Comparing the intensity between a randomly oriented
diffraction pattern and a preferred oriented diffraction
pattern can look entirely different.
Quantitative analysis depend on intensity ratios which
are greatly distorted by preferred orientation.
Careful sample preparation is most important to deal
with preferred orientation samples
The following illustrations show the Mo O3 spectra's
collected by using transmission , Debye-Scherrer
capillary and reflection mode.

37

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