BPT 602 Solid State Physics

Instructor: Dr. Jayeeta Lahiri

Assistant Professor
Department of Physics
Banaras Hindu University

14.03.2022
Topics
• Reciprocal space
• X-ray diffraction
• Bragg’s law
• Laue equation
• Qualitative determination of the crystal
structure
• Ewald's construction

2
Introduction
Crystals can’t be examined directly using optical microscopes;

How do you study crystal structure?

X ray scattering/Diffraction

• Diffraction is the constructive interference of the scattering from the very

large number of atomic scatterer’s of the crystal
• Crystals act as 3D diffraction grating
• We can represent the structure of the crystals in a virtual space, known as
reciprocal space, using the geometry of the different diffraction spot sites.
 Diffraction in crystals
• Crystals can be used as three-dimensional ‘diffraction gratings’
for x-rays.
• In 1912, Max von Laue, a German physicist, discovered that x-
rays could be diffracted, or scattered, in an orderly way by the
orderly array of atoms in a crystal.
• The phenomenon of x-ray diffraction from crystals is used both
to analyze x-rays of unknown wavelength using a crystal whose
atomic structure is known, and to determine, using x-rays of
known wavelength, the atomic structure of crystals.
• Diffraction maps the reciprocal lattice of the crystal.
• Crystal act as 3D grating where the atoms are the scatterers.

4
 Reciprocal Lattice vector
3D 2D
* * * * *
*
Ghkl  h b1  k b2  lb3 G*
hkl  h b1  k b2

 * 2   * 1 
b1  a2  a3  b1  a2  n 
V A

* 1 
 * 2  
b2  a3  a1  b2  n  a1 
V A
 
 * 2  
b3  a1  a2  A  a1  a2 
V
    
V  a1. a2  a3  ai . b j  2 ij
 Reciprocal space
• Reciprocal space is also called Fourier space, k- space, or
momentum space in contrast to real space or direct space.
• The reciprocal space lattice is a set of imaginary points
constructed in such a way that the direction of a vector from one
point to another coincides with the direction of a normal to the real
space planes and the separation of those points (absolute value of
the vector) is equal to the reciprocal of the real interplanar
distance.
• The things which are larger in real space are smaller in reciprocal
space by definition.

6
 Properties of Reciprocal lattice
• The reciprocal lattice of a Bravais lattice is again a Bravais lattice.
• The reciprocal lattice of a reciprocal lattice is the (original) direct
lattice.
• Consider a reciprocal lattice vector G such that:
 * * *
G  ha  kb  lc
• where h, k and l are both integers, and are the Miller Indices of a plane
in real space (h k l)
• This vector G has two important properties

  1
G  (hkl ) G
d hkl
 
 b a  c a
B   ;C  
k h l h
  
B  C  G (hkl )

 G (hkl )
n 
G (hkl )
  
a  a G (hkl )
d hkl  .n  . 
h h G (hkl )
 * * *
a ha  kb  lc 2
 .   
h G (hkl ) G (hkl )
 Construction of reciprocal lattice

Any plane can be represented by a vector perpendicular to it.

If we define 1/dhkl, as the length of the vector σhkl, the product of this vector, times
the dhkl spacing of the planes family is the unit.
If we take a vector 2 times longer than σhkl , the interplanar spacing of the
corresponding new family of planes would be a half.

http://www.xtal.iqfr.csic.es/Cristalografia/parte_04-en.html
The moduli (lengths) of the perpendicular vectors (σhkl) are reciprocal to the
interplanar spacings. The end points of these vectors (blue arrows in figure) also
produce a periodic lattice that, due to this reciprocal property, is known as the
reciprocal lattice of the original direct lattice. The reciprocal points obtained in this
way (green points) are identified with the same numerical triplets hkl (Miller
indices) which represent the corresponding plane family.
Crystal X-ray diffraction
• Diffraction occurs when each object in a periodic array scatters
radiation coherently, producing concerted constructive interference at
specific angles.
• The electrons in an atom coherently scatter X-rays. The electrons
interact with the oscillating electric field of the X-ray.
• The atoms in a crystal are a periodic array of coherent scatterers and
thus can diffract X-rays.
• Diffraction from different planes of atoms produces a diffraction
pattern, which contains information about the atomic arrangement
within the crystal
• X-Rays are also reflected, scattered incoherently, absorbed, refracted,
and transmitted when they interact with matter.

11
Scattering
• X-rays, Electrons, Neutrons
• X-rays scatter from the electrons X-rays are scattered by the electrons in a
material through an interaction between the negatively charged electrons
and the electromagnetic field of the incoming X-rays.
• respond to the applied field of the X-ray flux, oscillating with the period of
the X-ray beam. These accelerated charged particles then emit their own
electromagnetic field, identical in wavelength and phase to the incident X-
rays. The resultant field, which propagates radially from every scattering
source, is called the scattered wave.
• Intensity proportional to the density n(r) - Mainly the core electrons
around the nucleus
• Similarly for high energy electrons. Electrons are scattered much more
strongly than X-rays as electrons are scattered both by the electron cloud
and by the nucleus of an atom.
• Neutrons scatter from the nuclei (and electron magnetic moment)
X-ray scattering

Incident X-ray photons hν0 Coherent Scattering XRD

hν0
hν1 Incoherent scattering
hν2 Fluorescence XRF
e- Photoelectron
XPS
e- Auger Electron

Penetration
depth Interaction Volume
1 mm

Excitation area diameter

1 mm-1 cm Sample

13
X-ray scattering

14
Braggs Law

Bragg’s equation
2dsinθ=nλ
n=order of diffraction
λ=X-ray wavelength,
d=distance between lattice planes,
θ=angle of incidence of the radiation

• Diffraction occurs ONLY when the path difference between the parallel X-
rays are an integer of the wavelength.
• Additionally, the plane normal [hkl] must be parallel to the diffraction
vector s where diffraction vector s: the vector that bisects the angle
between the incident and diffracted beam

15
Bragg’s equation tells us about the position of the diffraction peaks (in terms of ) but tells
us nothing about the intensities.
Diffraction: single crystal
A single crystal specimen in a Bragg-Brentano diffractometer would produce only one
family of peaks in the diffraction pattern.

s is the diffraction vector

s is normal to the Bragg
planes (and thus is fixed
wrt the crystal)

17
Sample rotation
• Diffraction from a single crystal will
[400]
produce a diffraction point for each set
s of planes. Therefore need to rotate
sample to see different planes
2

[220] [220]
s s
The sample can be tilted to measure
Bragg peaks with different crystallographic
directions

18
Diffraction: polycrystalline
A polycrystalline sample should contain thousands of crystallites. Therefore, all possible
diffraction peaks should be observed.

19
 Diffraction from single crystal

(a) X-ray diffraction photograph for a single crystal of magnesium.

(b) Schematic diagram illustrating how the spots (i.e., the diffraction pattern) in (a) are produced.
The lead screen blocks out all beams generated from the x-ray source, except for a narrow beam traveling in a single
direction. This incident beam is diffracted by individual crystallographic planes in the single crystal (having different
orientations), which gives rise to the various diffracted beams that impinge on the photographic plate. Intersections
of these beams with the plate appear as spots when the film is developed.

20
 Diffraction from single crystal
• The diffraction pattern of a single crystal
consists of spots whose distance from the
center depends on the interplanar(d) spacing of
the crystallographic planes which generated the
diffraction effect.
• The closer the spots to the center, the lower the
θ angle at which diffraction occurs, the larger
the interplanar(d) spacing.
• Every family of crystallographic planes generates
a group of spots at the same distance from the
center i.e. these spots will lie on a circle.
• The number of these spots depends on the
symmetry of the crystal.

http://www.vanbokhoven.ethz.ch/education
Diffraction pattern (Example)

Single crystal Single crystal Powder or polycrystalline

+ Diffraction rings
Polycrystalline

22
Single Crystal 4 Crystallites rotated w.r.t each other
 Polycrystalline

If the sample is composed of

a large number of crystals
oriented in all of the possible
directions ( polycrystalline
sample), the spots belonging
to each crystal will sum up to
produce continuous circular
lines, the diffraction rings.
By cutting the diffraction lines in a radial manner and representing
this section as a plot of the intensity as a function of the distance
from the center (normally expressed as 2θ), we get the typical
powder X-ray diffraction (PXRD) pattern of a polycrystalline solid.
Diffraction from (a) an oriented single crystal, (b) a collection of four crystals and (c) from
a polycrystalline material, with (d) the cross-section of the Debye-Scherrer rings

Water 2010, 2
Diffraction spectra

27
Information from Diffraction spectra
1) Peak positions:
- refer to geometrical parameters: (unit cell, space group)
- influenced by stresses
2) Peak intensities:
- refer to electron density distribution within the unit cell
- influenced by preferred orientation / texture in thin films and
manufactured materials (rolling processes,…)
3) Peak shape:
- refers to the quality (defects) in single crystal materials (broadness)
- refers to the crystallite size in polycrystalline materials (broadness)
- strain (asymmetry)
- (influenced by diffractometer setup)

28
Peak shape(Broadening)
Origin of Line Broadening

• Instrumental
– The radiation is not perfectly monochromatic(finite width of Kα line)
– Unresolved Kα and Kβ line
– Beam divergence
– Non ideal optics
• Imperfect crystal
– crystallite size (smaller the crystallite size, fewer lattice planes,
broader the peak)
– crystal lattice distortion (micro-strain) due to dislocations and
concentration gradients
– Structural defects like stacking faults, twin faults and more
– concentration gradients in non-stoichiometric compounds
Diffraction spectra
• With modern X-ray diffractometers the signals are converted into peaks
• The angular positions (2q) and intensities of the diffracted peaks of radiation(reflections
or peaks) produce a two dimensional pattern
• This pattern is characteristic of the material analysed (fingerprint)

2θ
44.48
51.83
76.35
92.90
98.40
121.87
144.54
155.51

PH 354 Basics of Condensed Matter Physics (Spring 2014) University of Hyderabad 30

 Laue Experiment
• In the Laue method, a stationary single crystal is bathed in a beam of ‘white’ radiation.
• In the experimental arrangement, either a transmission photograph or a back-reflection
photograph may be taken, and the pattern of spots which are produced lie on ellipses in
the transmission case or hyperbolae in the back-reflection case.
• All spots on any ellipse or hyperbola are reflections from planes of a single zone (i.e.
where all the lattice planes are parallel to a common direction, the zone axis) and,
consequently, the Laue pattern is able to indicate the symmetry of the crystal.

https://doi.org/10.1016/B978-0-08-098204-5.00005-5
 Equivalence of the Bragg and Laue formulations

where 𝐺⃗ is the shortest wave vector

parallel to 𝐺⃗

• A Laue diffraction peak corresponding to a change in the wave vector given by the reciprocal lattice
vector corresponds to a Bragg reflection from the family of direct lattice planes perpendicular to 𝐺⃗ .
• The order, n, of the Bragg reflection is just the length of divided by the length of the shortest
reciprocal lattice vector parallel to 𝐺⃗ .
• (222) diffraction peak is the 2nd order (n=2) diffraction peak of the (111) plane.
 Ewald sphere
Diffraction can be represented graphically using the Ewald construction as follows
• Construct the reciprocal lattice of the crystal
• Draw the incidence wave vector k0 with the origin chosen such that k0
terminates at the reciprocal lattice point.
• Draw a sphere of radius centered at the origin k0.
• Find the reciprocal lattice points lying on the surface of the surface and draw
the scattered vectors k to these points.
• Only the points lying on the Ewald sphere surface will give rise diffraction.

Here is the incidence wave vector

is the scattered wave vector
is the reciprocal lattice vector
Top view
“A Valt” not “E Walled”
 Ewald Sphere for 3D lattice

Coherent X-ray diffraction uses a monochromatic beam. With monochromatic X-rays the
Ewald sphere passes only through a limited number of reciprocal lattice points making it
necessary to rotate the sample to measure different Bragg reflections.
• Laue diffraction is based on polychromatic X-ray beams covering a large energy range.
• When employing a broad spectrum of X-rays, a large number of reciprocal lattice points
are accessible simultaneously.
• The two circles indicate the respective Ewald sphere for the X-rays with the largest
energy (shortest wavelength) and the lowest energy (longest wavelength) within the
spectrum of the polychromatic X-ray beam.
• All reciprocal lattice points which are in between these two circles (indicated by the
shaded area) are measured simultaneously without any rotation of the crystal.
• This technique using a white (or polychromatic) X-ray beam is known as Laue diffraction
which is historically the very first diffraction technique that has been employed in fact by
Max von Laue.
 Ewald sphere for 2D lattice
• A 2D lattice can be thought as a 3D lattice with infinite Dotted horizontal line: Sample
periodicity in the normal direction 𝑐⃗ → ∞.
• This leads to the reciprocal lattice vector 𝑐 ∗ → 0. So
the reciprocal lattice points along the normal direction
is very closely spaced (i.e. they are infinitely dense)
forming rods.
• In contrast to 3D lattice, the 2D lattice has reciprocal
lattice rods associated with every 2D reciprocal lattice
points in the plane.
• The Ewald sphere will intersect the reciprocal lattice
rods.
• The incidence wave vector k0 that terminates at the
reciprocal lattice rod will give rise to diffraction.
• The wave vector component normal to the surface is
not conserved in this process.
• The law of conservation of momentum concerns with
∥ ∥
only the wave vector components parallel to the
surface.
• Tip of the incidence vector is the origin (00).
 Ewald Sphere for 2D lattice

• The radius of the Ewald sphere is defined by the incident radiation energy and its center by the
wave vector of the incident beam.
• Spots are observed whenever the Ewald sphere intersects with reciprocal lattice rods of the surface.
• Accordingly, a one-dimensional scan through the LEED pattern corresponds to a line along the circle,
and the measured distances between LEED spots reflect the perimeter of the arc between
reciprocal lattice rods.
• Ideally Surface is one atomic layer.
• The mean free path of the of low-energy electrons (20–200 eV) is 5– 10 Å .
• If the interlayer spacing is ~ 2.5 Å, then LEED beam will see 4 layers (i.e. more than
one layer).
• Thus in reality the reciprocal lattice seen by LEED is a mixture between continuous
rods and discrete points.
• Energy conservation demands that the length of the k-vector is the same, for
both the incoming and the elastically scattered electron wave.
• and
ℏ ℏ
• ∥

• ℏ ∥
• There is no Laue-condition for the z-component of ko. The only condition for
diffraction into a spot is that kz,o has a real value.
• This condition is synonymous with the obvious fact that the length of the parallel
component of k cannot be greater than the length of the entire vector, but it
also limits the number of observable LEED spots.
• The number of observable spots increases With increasing electron energy while
the polar emission angle with respect to the specular spot (0,0) decreases for
each spot.

for normal incidence

 Ewald sphere
3D surface lattice 2D surface lattice