Professional Documents
Culture Documents
06 Diffraction Basics II
06 Diffraction Basics II
Intensities
EPS400-002
Introduction to X-ray Powder Diffraction
Jim Connolly, Spring 2012
Intensity variations in Diffraction Data
Locations of diffraction peaks are related to
d-spacings of families of lattice planes
Relative intensities of diffraction peaks can
yield information about the arrangement of
atoms in the crystal structure
Intensities may be measured as
Peak heights
Areas under peaks (minus background)
By convention, the strongest peak (in a
pattern or of a particular phase in a pattern) is
assigned an intensity of 100, and all others
are reported in proportion to it.
Intensity = the vector sum of all scattering
A peak is the result of lots of scattering
Electron Scattering intensity (Thompson Eq.):
2
IO e 1 cos 2 (2 )
2
I 2 2
r e
m c 2
Qualitatively, as
T increases, B
increases and
scattering
intensity
decreases
Shown for Cu at
right
Calculations are
very complex
and standard
values not well
agreed upon
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)
m/2
Fhkl 2f
j 1
n exp 2i (hx j ky j lz j
Key: P = primitive lattice; C, B, A = side-centered on c-, b-, a-face; I = body centered; F = face centered (001)
Factors affecting intensities of Bragg
Reflections: Calculation of the Diffraction
Pattern
Consideration of all factors contributing to
relative intensities of Bragg Reflections allows
calculation of theoretical diffraction pattern for
phases whose structures are well characterized
Calculated patterns in the ICDD Powder
Diffraction File are created from this information
A qualitative understanding of these factors is
very useful in interpreting your experimental
results
The Plane Multiplicity Factor
The number of identically spaced planes cutting a
unit cell in a particular hkl family is called the plane
multiplicity factor.
For high symmetry systems, the factor can be very high
For low symmetry systems, it is low
As an example, each cubic crystal face has a diagonal (110)
and an equivalent plane. With six faces, there are 12
crystallographic orientations. The (100) will similarly have 6
orientations. Thus, the (110) family will have twice the intensity
of the (100) family because of the multiplicity factor.
The Lorentz Factor
As each lattice point on the
reciprocal lattice intersects the
diffractometer circle, a diffraction
related to the plane represented
will occur.
As angles increase, the
intersection approaches a
tangent to the circle; thus at
higher angles, more time is spent
in the diffracting condition.
This increased time will be a function of the diffraction angle
and may be corrected by inserting the term I/(sin2 cos)
into the expression for calculating diffraction intensities.
This term is called the Lorentz factor. In practice, this is
usually combined with the atomic scattering polarization term
(Thompson equation) and called the Lorentz polarization
(Lp) correction.
Extinction from Strong Reflections
A phase-shifted reflection can occur from the
underside of very strongly reflecting planes. This will
be directed towards the incident beam but 180 out of
phase with it.
The net effect is to reduce the intensity of the incident
beam, and therefore the intensity of the diffraction
from that plane.
A similar phenomenon will reduce the penetration of
the beam into strongly diffracting planes by reducing
the primary beam energy.
Corrections are very difficult to calculate or estimate.
Careful sample preparation and a uniform small
crystallite size (~ 1 m) will reduce this effect.
This effect can still reduce the experimental
intensities of the strongest reflecting peaks by up to
25%.
Other Absorption Effects
Absorption
Related to Depth of Penetration: In a diffractometer, at low
2 values a larger area of sample is irradiated with less
depth of penetration. At higher 2 values, the irradiated area
is smaller, but depth of penetration greater. In general,
these tend to be offsetting effects as related to diffracted
intensity over the angular range of the data collection.
Linear Absorption: Calculated intensities include a term for
1/s where s is the linear absorption coefficient of the
specimen.
Microabsorption
Occurs in polyphase specimens when large crystals
preferentially interact with the beam causing both anomalous
absorption and intensities not representative of the
proportions of the phases.
The effect is minimized in diffraction experiments by
decreasing the crystallite size in the specimen
The Intensity Equation
The Intensity of diffraction peak from a flat rectangular sample of
phase in a diffractometer with a fixed receiving slit (neglecting air
absorption), may be described as:
K e K ( hkl ) v
I ( hkl )
s
Here Ke is a constant for a particular experimental system:
2
Io e 3 2
Ke
2
64r me c
where:
I0 = incident beam intensity
r = distance from the specimen to the detector
= wavelength of the X-radiation
(e2/mec2)2 is the square of the classical electron radius
s = linear attenuation coefficient of the specimen
v = volume fraction of phase in the specimen
The Intensity Equation (cont.)
where:
Mhkl multiplicity for reflection hkl of phase
V = volume of the unit cell of phase
the fraction in parentheses equals the Lorentz and polarization
corrections for the diffractometer (Lp)hkl, including a correction for the
diffracted beam monochromator
2m = the diffraction angle of the monochromator
F(hkl) = the structure factor for reflection hkl including anomalous
scattering and temperature effects
The Intensity Equation (cont.)
Putting it all together we get . . .
2
I 0 e M ( hkl )
3 2
2 1 cos 2 (2 ) cos 2 (2 m ) v
I ( hkl )
2
F( hkl )
64r me c V2
sin cos
2
hkl s
K
cos
Where
is the mean crystallite dimension,
K is the shape factor (typically about 0.9),
is the wavelength, and
is the line broadening (equal to the B b, B being the
breadth of the observed diffraction line at its half-intensity
maximum, and b the instrumental broadening)
Crystallite Size vs. Instrument Broadening
Instrument broadening
is the baseline line
width shown by any
diffraction peak
It is a characteristic of
the instrument and not
related to the
specimen
Crystallite or particle
size broadening is
related to deviation of
crystallite size from
ideality
Broadening related to
crystallite size is
measurable at <1m
and not significant for
larger sizes
Residual Stress and Strain
Strain in the crystal lattice will
produce a distortion of the diffraction
line
Macrostrain causes the lattice
parameters to change resulting in a
peak shift. Glycolation or heating of
clay minerals are examples of
induced macrostrains.
Tensile and compressive forces can
produce Microstrains resulting in a
broadening of the diffraction peaks or
peak asymetry in some cases.
Dislocations, vacancies, shear
planes, etc can produce Microstress.
The result can be a distribution of
peaks around the unstressed peak
location, appearing like a crude
broadening of the peak.
Mudmaster
An excellent tool for understanding particle size and
strain effects (and calculating them) in the diffraction
pattern is Mudmaster from Dennis Eberl
Reference: Mudmaster: A Program for Calculating
Crystallite Size from Distributions and Strain from the
Shapes of the Diffraction Peaks by Dennis Eberl, et
al., U.S. Geological Survey Open-File Report 96-171,
1996.
Program uses Microsoft Excel (with Solver and
Statistical add-on tools installed) to do calculations