XRD
Unit cell: the building block of crystalline solids
z
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,
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?
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
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
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.
1 1 1
The Miller indices are defined by h= ,k = ,l =
X Y Z
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
Distances between planes defined by the same set of Miller indices are
unique for each material
dhkl
2D
d'h’k’l’
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
Thus for each possible diffraction angle there are crystals oriented correctly for
Bragg 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
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
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)
(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
Powder diffraction data from known compounds have been compiled into a
database (PDF) by the Joint Committee on Powder Diffraction Standard,
(JCPDS)
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
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
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).
? ?
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 )
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
F (h )( )( )
+ k 2 , h 2 + l 2 , k 2 + l 2 = 2n (even number)
2
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
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