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INTRODUCTION TO

XRD
Unit cell: the building block of crystalline solids
z

The parameters that define a unit cell


are:
a, b, c = unit cell dimensions along x, y,
z respectively
α, β, γ = angles between b,c (α); a,c
(β); a,b (γ) x

y
Shapes of unit cells
All the possible shapes of a unit cell are defined by 7 crystal systems,
which are based on the relationship among a,b,c and α, β, γ,

a = b = c ; α = β = γ = 90° Cubic system

a = b ≠ c ; α = β = γ = 90° Tetragonal system

a ≠ b ≠ c ; α = β = γ = 90° Orthorhombic system

a = b = c ; α = β = γ ≠ 90° Rhombohedral system

a = b ≠ c ; α = β = 90°; γ = 120° Hexagonal system

a ≠ b ≠ c ; α = γ = 90° ≠ β Monoclinic system

a ≠ b ≠ c ; α ≠ β ≠ γ ≠ 90° Triclinic system


Types of Unit Cells

Primitive lattice: the unit cell has a lattice point at each


corner only (P)

Body centred lattice: the unit cell has a lattice point at


each corner and one in the centre (I)
Face-centred lattice: the unit cell has a lattice point at
each corner and one in the centre of one pair of
opposite faces (A), (B), (C)

All-face-centred lattice: the unit cell has a lattice point


at each corner and one in the centre of each face (F)
CHARACTERIZATION OF THE STRUCTURE OF SOLIDS

Three main techniques:

X-ray diffraction Electron diffraction Neutron diffraction


Single crystal
Powder

Principles of x-ray diffraction


X-rays are passed through a crystalline material and the patterns produced give
information of size and shape of the unit cell

X-rays passing through a crystal will be bent at various angles: this process is called
diffraction

X-rays interact with electrons in matter, i.e. are scattered by the electron clouds of
atoms
WHAT IS DIFFRACTION?

Diffraction – the spreading out


of waves as they encounter a
barrier.
What is a Diffraction pattern?

- an interference pattern that


results from the superposition
of waves.

- Mathematically, this process


can be described by Fourier
transform, if the diffraction is
kinematic (electron or X-ray has
been scatted only once inside
the object).

Laser diffraction pattern of a thin


grating films, where the size of
holes is closed to the
wavelength of the laser (Ruby
red light 594 um) .
Fourier transform of regular lattices:

Real space Reciprocal space


INTERACTION BETWEEN X-
RAY AND MATTER
d
incoherent scattering
λCo (Compton-Scattering)
coherent scattering
wavelength λPr
λPr(Bragg´s-scattering)
absorbtion
Beer´s law I = I0*e-µd
intensity Io
fluorescense
λ> λPr
photoelectrons
The angles at which x-rays are diffracted depends on the distance between adjacent
layers of atoms or ions. X-rays that hit adjacent layers can add their energies
constructively when they are “in phase”. This produces dark dots on a detector plate
Scattering of x-rays by crystallographic planes
We need to consider how x-rays are diffracted by parallel crystallographic planes

incident x-rays λ diffracted x-rays

lattice planes d

atoms on
lattice planes

X-rays diffracted in phase will give a signal. “In phase” means that the peak of one
wave matches the peak of the following wave
The angle of incidence of the
x-rays is is θ

θ C The angle at which the x-


rays are diffracted is equal to
θ θ the angle of incidence, θ
D F d The angle of diffraction is
the sum of these two angles,
E 2θ

The two x-ray beams travel at different distances. This difference is related to the
distance between parallel planes

We connect the two beams with perpendicular lines (CD and CF) and obtain two
equivalent right triangles. CE = d (interplanar distance)

DE
sin θ = d sin θ = DE DE = EF d sin θ = EF
d
2d sin θ = EF + DE = difference in path length
Reflection (signal) only occurs when conditions for constructive interference between
the beams are met
These conditions are met when the difference in path length equals an integral number
of wavelengths, n. The final equation is the BRAGG’S LAW

nλ = 2d sin θ
Data are collected by using x-rays of a known wavelength. The position of the sample
is varied so that the angle of diffraction changes

When the angle is correct for diffraction a signal is recorded

With modern x-ray diffractometers the signals are converted into peaks

(301)
Intensity (a.u.)

(310)

(611) (321)
(600) (411) (002)
(200) (110) (400)

2θ degrees
TEST
NaCl is used to test diffractometers. The distance between a set of planes in
NaCl is 564.02 pm. Using an x-ray source of 75 pm, at what diffraction angle
(2θ) should peaks be recorded for the first order of diffraction (n = 1) ?

Hint: To calculate the angle θ from sin θ, the sin-1 function on the calculator
must be used

nλ = 2d sin θ
1 × 75 pm = 2 × 564.02 pm × sin θ
75 pm
sin θ = = 0.066
2 × 564.02 pm
θ = 3.81 ; 2θ = 7.62 
Lattice Planes and Miller Indices
Atoms or ions in lattices can be thought of as being connected by lattice planes.
Each plane is a representative member of a parallel set of equally spaced planes.

A family of crystallographic planes is always uniquely defined by three indices, h, k, l,


(Miller indices) usually written (h, k, l)

1 1 1
The Miller indices are defined by h= ,k = ,l =
X Y Z

X, Y, Z are the intersections of one plane with on a, b, c respectively

Note ­ plane // to axis,
intercept = ∞ and 
1/∞ = 0
( 0kl ) x
( h0l ) family of lattice planes parallel to y
( hk 0 ) z
How to Determine Miller Indices
EXAMPLES OF CRYSTALLOGRAPHIC PLANES

c c
(111) (100)

b b

a a

c
(212)
0.5

a
Inter-Planar Spacing, dhkl, and Miller Indices

The inter-planar spacing (dhkl) between crystallographic planes belonging


to the same family (h,k,l) is denoted (dhkl)

Distances between planes defined by the same set of Miller indices are
unique for each material

dhkl

2D
d'h’k’l’

Inter-planar spacings can be measured by x-ray diffraction (Bragg’s Law)


The lattice parameters a, b, c of a unit cell can then be calculated

The relationship between d and the lattice parameters can be determined


geometrically and depends on the crystal system

Crystal system dhkl, lattice parameters


and Miller indices

Cubic
1 h2 + k 2 + l 2
2
=
d a2

Tetragonal
1 h2 + k 2 l 2
2
= 2
+ 2
d a c

Orthorhombic 1 h2 k 2 l 2
2
= 2 + 2 + 2
d a b c

The expressions for the remaining crystal systems are more complex
THE POWDER TECHNIQUE

An x-ray beam diffracted from a lattice plane can be detected when the x-ray source,
the sample and the detector are correctly oriented to give Bragg diffraction

A powder or polycrystalline sample contains an enormous number of small


crystallites, which will adopt all possible orientations randomly

Thus for each possible diffraction angle there are crystals oriented correctly for
Bragg diffraction

Each set of planes in a crystal


will give rise to a cone of diffraction

Each cone consists of a set of closely spaced dots each one of which represents a
diffraction from a single crystallite
FORMATION OF A POWDER PATTERN

Single set of planes

Powder sample
Experimental Methods
To obtain x-ray diffraction data, the diffraction angles of the various cones, 2θ,
must be determined
The main techniques are: Debye-Scherrer camera (photographic film) or
powder diffractometer

Debye Scherrer Camera


Powder Diffractometer
The detector records the angles at which the families of lattice planes scatter (diffract)
the x-ray beams and the intensities of the diffracted x-ray beams

The detector is scanned around the sample along a circle, in order to collect all the
diffracted x-ray beams

The angular positions (2θ) and intensities of the diffracted peaks of radiation
(reflections or peaks) produce a two dimensional pattern

Each reflection represents the x-ray beam diffracted by a family of lattice planes (hkl)

This pattern is characteristic of the material analysed (fingerprint)

(301)
(310)
Intensity

(611) (321)
(600) (411) (002)
(200) (110) (400)

2θ degrees
APPLICATIONS AND INTERPRETATION
OF X-RAY POWDER DIFFRACTION DATA
Information is gained from:
crystal class
Number and positions (2θ) of peaks lattice type
cell parameters
types of atoms
Intensity of peaks
position of atoms

Identification of unknown phases


Determination of phase purity
Determination and refinement of lattice parameters
Determination of crystallite size
Structure refinement
Investigation of phase changes
Identification of compounds

The powder diffractogram of a compound is its ‘fingerprint’ and can


be used to identify the compound

Powder diffraction data from known compounds have been compiled into a
database (PDF) by the Joint Committee on Powder Diffraction Standard,
(JCPDS)

‘Search-match’ programs are used to compare experimental diffractograms


with patterns of known compounds included in the database

This technique can be used in a variety of ways


PDF - Powder Diffraction File

A collection of patterns of inorganic and organic compounds

Data are added annually (2008 database contains 211,107 entries)


Example of Search-Match Routine
Outcomes of solid state reactions

SrCuO2
2SrCO3 + CuO
? Sr2CuO3

Product: SrCuO2?
Pattern for SrCuO2from database

Product: Sr2CuO3?
Pattern for Sr2CuO3from database
Phase purity
When a sample consists of a mixture of different compounds, the resultant
diffractogram shows reflections from all compounds (multiphase pattern)

Sr2CuO2F2+δ

Sr2CuO2F2+δ + impurity

*
Effect of defects

8 mol % Y2O3 in ZrO2 (cubic)

3 mol % Y2O3 in ZrO2 (tetragonal)

ZrO2 (monoclinic)

http://www.talmaterials.com/technew.htm
Determination of crystal class and lattice parameters

X-ray powder diffraction provides information on the crystal class of the unit cell
(cubic, tetragonal, etc) and its parameters (a, b, c) for unknown compounds

1 Crystal class comparison of the diffractogram of the unknown


compound with diffractograms of known compounds
(PDF database, calculated patterns)

2 Indexing Assigning Miller indices to peaks

3 Determination of Bragg equation and lattice parameters


lattice parameters

λ
sin 2 θ = 2 ( h 2 + k 2 + l 2 )
2
Cubic system
4a
PROBLEM

NaCl shows a cubic structure. Determine a (Å) and the missing Miller indices
(λ = 1.54056 Å).

? ?

Selected data from the NaCl diffractogram

2θ (°) h,k,l
27.47 111
31.82 ?

45.62 ?
λ
sin 2 θ = 2 ( h 2 + k 2 + l 2 )
2
56.47 222
4a
a (Å)
Use at least two reflections and then average the results

λ2 ( h 2 + k 2 + l 2 ) 1.5412 ×12
a= = = 5.638 Å (222)
4 sin θ
2
4 × sin 2
56.473
2

Miller Indices
λ2 2
sin θ = 2 ( h + k 2 + l 2 )
2

4a
A

(
sin 2 θ = A h 2 + k 2 + l 2 )
λ2 1.54056 2
A= 2 = = 0.01867
4 × ( 5.638)
2
4a

sin 2 θ
A
(
= h2 + k 2 + l 2 )

2θ = 31.82 sin 2 31.82


(h )

2 = 4.026 ≈ 4 2
+ k 2 + l 2 = 4 ∴ ( 200 )
0.01867

sin 2 45.62
2θ = 45.62 2 = 8.052 ≈ 8
(h )

2
+ k 2 + l 2 = 8 ∴ ( 220 )
0.01867
Systematic Absences
For body centred (I) and all-face centred (F) lattices restriction on reflections from
certain families of planes, (h,k,l) occur. This means that certain reflections do not
appear in diffractograms due to ‘out-of-phase” diffraction

This phenomenon is known as systematic absences and it is used to identify


the type of unit cell of the analysed solid. There are no systematic absences for
primitive lattices (P)

Conditions for reflection

F (h )( )( )
+ k 2 , h 2 + l 2 , k 2 + l 2 = 2n (even number)
2

i.e indices are all odd or all even

I (h 2
+ k + l ) = 2n
2 2

P No conditions
Considering systematic absences, assign the following sets of Miller indices
to either the correct lattice(s).

Lattice Type
Miller Indices P I F
100 Y N N
110 Y Y N
111 Y N Y
200 Y Y Y
210 Y N N
211 Y Y N
220 Y Y Y
310 Y Y N
311 y N Y
Autoindexing

Generally indexing is achieved using a computer program.


This process is called ‘autoindexing’

Input: •Peak positions (ideally 20-30 peaks)


•Wavelength (usually λ=1.54056 Å)
•The uncertainty in the peak positions
•Maximum allowable unit cell volume

Problems: •Impurities
•Sample displacement
•Peak overlap
λ2 2
Derivation of sin θ = 2 ( h + k 2 + l 2 )
2

4a

1 h2 + k 2 + l 2 λ = 2d sin θ
2
=
d a2
2
a 1
d = 2
2
; d =a 2
h + k +l
2 2
h + k2 + l2
1
λ = 2a 2 sin θ
h + k +l
2 2

λ
sin θ = h2 + k 2 + l 2
2a
λ 2
sin2θ = 2 h 2 + k 2 + l 2
4a

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