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Diffraction Methods
Method
Laue variable fixed
Powder fixed variable
Principal Diffraction Methods
Single crystal diffractometer method: single crystal sample, thin film sample, rotating ,
w, and , fixed
used for determining complex crystal structures from single crystal and thin film
materials
Powder Diffraction
Understanding powder diffraction patterns
Pattern
Crystal structure Specimen property Instrumental parameter
component
a = 180o – 2
a a
2
P P
X-ray Powder Diffractometer
Bragg-Brentano geometry
Powder Diffraction
𝑙1 𝑅
𝜑 = 𝜑
sin sin 𝜃 +
2 2
Sample length 𝑙2
𝜑 =
𝑅
𝜑
Sample irradiated area sin
2 sin 𝜃 − 2
𝐿 = 𝑙1 + 𝑙2
Powder Diffraction
Sample length
Sample irradiated area
R = 320 mm
= 2o
= 1o
= 1/2o
= 1/4o
Powder Diffraction
Fixed Slits
Divergence Slit:
• Match the diffraction geometry and sample size L sin
• At any angle beam does not exceed sample size
a (rad)
R
Receiving Slit:
• As small as possible to improve the resolution
• Very small slit size reduces diffracted beam intensity
Powder Diffraction
Variable Slits
R = 320 mm
s = 0.15 mm
s = 0.10 mm
s = 0.05 mm
s = -0.05 mm
s = -0.10 mm
s = -0.15 mm
Powder Diffraction
Intensity scale:
Linear
Logarithmic
Square Root
Powder Diffraction
Horizontal scale:
2
1/d
1/d2
2d sin
Powder Diffraction
Ka 1 Ka 2
d
2 sin 1 2 sin 2
Peak shape
2 Ka1 Ka 2
Ka ave
3
X-ray Powder Diffractometer
Powder Diffraction of MgB2 sample.
Basic Principles of Crystal Structure Analysis
The angular positions of diffracted peaks gives information on the
properties (size and type) of the unit cell
The intensities of diffracted peaks gives information on the positions
and types of atoms within the unit cell
General procedure:
“index the pattern” assign hkl values to each peak
Indexing the pattern – an assumption is made as to which of the 7 crystal systems the
unknown structure belongs and then, on the basis of the assumption, the correct Miller
indices are assigned to each reflection.
Indexing of Cubic Patterns
4ao2
so Bragg’s law becomes: 4d sin 2
2 2 2
sin 2
h k l
2 2
constant for
sin
2
sin 2
2
a given crystal
so:
h2 k 2 l 2 s 4a02
because of restrictions
on h,k,l different cubic
crystal structures will
have characteristic
sequences of diffracted
always equal
peak positions
to an integer
Indexing of Cubic Patterns
measure sample
& list angles
calculate (sin2)/s
for three Bravais
lattices
If the observed lines are from a particular lattice type, the (sin2)/s values should be constant.
Indexing of non Cubic Patterns
1 h2 k 2 l 2
Cubic:
d2 a2
1 h2 k 2 l 2
Tetragonal: 2
d2 a 2
c
1 h2 k 2 l 2
Orthorhombic:
d2 a 2 b2 c2
Hexagonal:
1 4 h 2 hk k 2 l 2
2
d2 3 a2 c
Rhombohedral:
1
h 2 k 2 l 2 sin 2 a 2 hk kl hl cos 2 a cos a
d 2
a 2 1 3cos 2 a 2 cos3 a
1 1 h 2 k 2 sin 2 b l 2 2hl cos b
Monoclinic: 2
d 2 sin 2 b a 2 b2 c ac
Indexing of non Cubic Patterns
Tetragonal System:
The sin2 must obey relation:
sin 2 A h 2 k 2 Cl 2
2 2
where: A 2
and C 2
are constants for any pattern
4a 4c
sin 2 A h 2 k 2
(h 2 + k 2) are 1, 2, 4, 5, 8, …
then C can be found from other lines:
sin 2 A h 2 k 2 Cl 2
Indexing of non Cubic Patterns
Hexagonal System:
sin 2 A h 2 hk k 2 Cl 2
2 2
where: A 2
and C
3a 4c 2
Orthorhombic System:
sin 2 Ah 2 Bk 2 Cl 2
2 2 2
where: A 2
, B 2
,C
2a 2b 2c 2
The “trick” is to find values of the coefficients A, B and C that account for all the
observed sin2’s when h, k and l assume various integral values
Number of Atoms in the Unit Cell
After establishing shape and size we find the number of atoms in that
unit cell.
• Note that the “X-ray density” is almost always larger than the measured bulk
density
• We need to know the unit cell volume
• We need to index the powder pattern in order to obtain the unit cell parameters
Number of Atoms in the Unit Cell
V
A 1.66042
V – volume of the unit cell in Å3
For simple elements: An A 1 where n1 is number of atoms per unit cell
A is atomic weight of an element
I K F2
where:
N
F f n e 2i hun kvn lwn
i
Phase problem
Example CdTe
A
1.66042
945
F 16 f Cd2 f Te2
2
if (h+k+l) is odd
F 16 f Cd f Te
2 2
if (h+k+l) is even F 16 f Cd f Te
2 2
F 16 f Cd f Te
2 2
if (h+k+l) is odd
if (h+k+l) is even multiple of 2
Example CdTe
The Powder Diffraction File
Experience has shown that the ensemble of d-spacings (“d “ s) and
intensities (“I “ s) is sufficiently distinctive in order to identify phases
“garbage in, garbage out” -- poor quality data will usually give
a poor match
Schematic diagram of the CheMin instrument and resulting XRF and XRD data.
Bish et al.
Volume 1 | Part 6 | November 2014 | Pages 514–522 | 10.1107/S2052252514021150
XRD on Mars
XRD patterns of crushed and sieved (150 µm) NaCl measured on the CheMin III instrument,
(left) without and (right) with sonic vibration.
Bish et al.
Volume 1 | Part 6 | November 2014 | Pages 514–522 | 10.1107/S2052252514021150
XRD on Mars
XRD on Mars
Plagioclase 30
Forsterite-Fe 16
Augite 11
Pigeonite 10
Magnetite 1.5
Anhydrite 1.1
Quartz 1.0
Sanidine† 1.0
Hematite† 0.8
Ilmenite† 0.9
Amorphous 27
Observed (blue, integrated from the two-dimensional image in Fig.6) and calculated (red) plots
from Rietveld refinement using data for Rocknest (∼26.4 h integration, phases listed in Table1).
Bish et al.
Volume 1 | Part 6 | November 2014 | Pages 514–522 | 10.1107/S2052252514021150