27-05-2022

Solid State:
Crystallography
The Insight of Solids: How close, how far…

X-Ray Diffraction

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Laue Spots: X-Ray Diffraction

❏ Diffracting X-rays from a NaCl
crystal and collecting the image
on photographic film
❏ The resulting negative shows
dark spots on a lighter
background

X-Ray Diffraction
❏ Max von Laue, a German
physicist,
first to suggest the use of X-
rays for the determination of
crystal structure
❏ In 1913, the British
physicists William Bragg and
his son Lawrence Bragg
developed the method on
which modern crystal-
structure determination is
based…

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X-Ray Diffraction: Bragg & Bragg

❏ “Atoms in a crystal form reflecting
planes” for x rays
❏ Fundamental equation of crystal-
structure determination:
n l = 2 d sin q [where, n = 1, 2,
3…]
Bragg equation
l = the wavelength of X-rays
d = distance between atomic planes
q = angle of reflection
❏ Reflections occur at several angles,
corresponding to different integer
values of n (called nth order of
reflection)

Wave interference
❏(A) Two waves constructively
interfere: in phase (when their peaks
and troughs match)
❏ Waves add to give a resultant wave
with higher peaks and deeper troughs
than either wave
❏(B) Two waves destructively
interfere: out of phase (when the
peaks of one wave match the troughs
of the other wave)
❏ The two waves subtract to give a
resultant wave with lower peaks and
more shallow troughs than either
wave.
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Diffraction of X-rays from Crystal Planes

❏At most
angles ,
reflected waves
are
out of phase
and
destructively
interfere
❏ At certain
angles ,
however,
reflected waves
are in phase
and
constructively
interfere

Diffraction of X-rays from Crystal Planes

❏Condition of
Constructive
interfere:
For phase difference to be zero,
Path difference=n l
In OGH:
GH GH
sin q= =
OG d
GH=d sin q
For a given plane (e.g., HCP layers in CCP):
Path difference=GH+FG
d fixed, θ changed to get the maxima (Crystallography)
n l=2d sin q

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Diffraction of X-rays from Crystal Planes

❏Condition of
Constructive
interfere

Bragg Spectrometer
❏ Moving detector
along a radial path for
determination of
maximum density

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Automatic X-Ray Diffractometer

Outline of Diffractometer: The schematic diagram shows the
diffracted rays being detected by a photograph

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Automatic X-Ray Diffractometer

❏ The single-crystal specimen is
mounted on a glass fiber, which is
placed on a spindle within the
circular assembly of the
diffractometer
❏ A new data collection system
(left of specimen) reduces data
collection time from several days
to several hours

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Bragg’s Intensity vs, 2q

❏Identification
of purity of
sample & its
crystal structure

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Bragg’s Intensity vs, 2q

❏ General expression for the spacing
of the planes (hkl) in a cubic lattice,

❏ Combined with the Bragg

equation,
)

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Crystal Axis
❏ 3 axes: lengths a, b, and c
❏ Cut by the plane ABC, making
intercepts OA, OB, and OC
❏ Lengths of the intercepts may be
expressed as OA/a, OB/h, OC/c
❏ The reciprocals of these lengths:
a/OA, b/OB, c/OC
❏ Set of axes on which the
reciprocal intercepts of crystal
faces are small whole numbers

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Miller Indices
❏ Set of axes on which the
reciprocal intercepts of crystal
faces are small whole numbers
❏ h, k, l are small integers:

❏ If a face is parallel to an axis,

the intercept is at , and the
Miller index becomes l/ or 0

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Miller Indices

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Finding Miller Indices for a Plane

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Interfacial Spacing in SC

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Interfacial Spacing in SC

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Interfacial Spacing in SC

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Interfacial Spacing in BCC

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Interfacial Spacing in BCC

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Interfacial Spacing in BCC

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Interfacial Spacing in FCC

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Interfacial Spacing in FCC

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Interfacial Spacing in FCC

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Nearest Neighbours
& Next Nearest
Neighbours

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Simple Cubic
❏Nearest Neighbours (First Nearest
Neighbour, i.e., Coordination Number)
6
❏Second Nearest Neighbours (NN2)
12
❏Third Nearest Neighbour (NN3)
8

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Body Centred Cubic

❏Nearest Neighbours (First Nearest
Neighbour, i.e., Coordination Number)
8
❏Second Nearest Neighbours (NN2)
6
❏Third Nearest Neighbour (NN3)
12

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Face Centred Cubic

❏Nearest Neighbours (First Nearest
Neighbour, i.e., Coordination
Number)
12
❏Second Nearest Neighbours
(NN2)
6
❏Third Nearest Neighbour (NN3)
24

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neighbor no. distance

a
no. of neighbors
Neighbours in NaCl
1 6
2
a
2 12
2
3 3a 8
2
4 a 6

5 5a 24
2

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