Reciprocal Lattice & Ewald sphere

Presented by- Mohammad Rameez & Santhosh Kumar

Unit Cells
Crystals consist of repeating asymmetric
units which may be atoms, ions or molecules.
The space lattice is the pattern formed by the
points that represent these repeating
structural units.

Unit Cells
A unit cell of the crystal is an imaginary
parallel-sided region from which the entire
crystal can be built up.
Usually the smallest unit cell which
exhibits the greatest symmetry is chosen. If
repeated (translated) in 3 dimensions, the
entire crystal is recreated.

Lattice the underlying periodicity of the crystal
Basis Entity associated with each lattice points
Lattice how to repeat
Motif what to repeat
Crystal = Lattice + Motif
Motif or Basis:
typically an atom or a group of atoms associated with each lattice point
Translationally periodic
arrangement of motifs
Crystal
Translationally periodic
arrangement of points
Lattice
Crystal =
Lattice (Where to repeat)
+
Motif (What to repeat)
=
+
a
a
2
a
Lattice
Motif
Motifs are associated with lattice points
they need NOT sit physically at the lattice point

Note: all parts of the motif do not sit on the lattice point
Crystal
An array of points such that every point has identical
surroundings

In Euclidean space infinite array

We can have 1D, 2D or 3D arrays (lattices)
Space Lattice
Translationally periodic arrangement of points in space is called a lattice
or
A lattice is also called a Space Lattice
Crystal Planes
7
Family of planes
Miller index
8
a
3

a
1

a
2

2
3
3
a
1
intercept is 2
a
2
intercept is 3
a
3
intercept is 3
Calculate reciprocal of these intercepts and
reduce them to smallest three integers
having same ratio.
Reciprocal
1/2
1/3
1/3
Hence Miller indices
are 3,2,2 and are
depicted by
( hkl ) = (322)
Inter-planer Distance
9
(hkl) represent a family of planes. All parallel
crystal planes have the same Miller index.
These planes are equally spaced at distance
d
hkl
. This distance is defined as:

h
2
+ k
2
+ l
2

a
d
hkl
=

a
b
Green
a b c
Intercept 3 2
Inverse 1/3 1/2 1/
Multiply
through
2 3 0
Crystal planes in
a cubic unit cell
12
(100)
d
hkl
= a
a
1

a
2

a
3

(110)
d
hkl
= a/2

(111)
d
hkl
= a/3

What is Real Space and Reciprocal Space?
Diffraction Techniques
Reciprocal-Space (i.e. spacing of diffraction spots in nm
1
)
Real Space (i.e. spacing of surface atoms in nm)
larger real-space smaller reciprocal-space
a
2
G
a
t
=
Reciprocal Space
A Bravais lattice is an infinite array of discrete points
with an arrangement an orientation which appears
exactly the same, from whichever of the points the
array is viewed.
There are 14 Bravais lattices with primitive vectors
a1, a2, and a3.
The set of all wave vectors k that yield plane waves
with the periodicity of a given Bravais lattice is
known as the reciprocal lattice.
The primitive vectors of the reciprocal lattice are
found from:
Where cyclic permutations of i, j, and k generate
the three primitive vector components.
Ref: Ashcroft and Mermin, Solid State Physics (1976).
( )
k j i
k j
i
a a a
a a
b

-

= t 2
REAL
RECIPROCAL
a
1

a
2

b
1
=2t/a
1

b
2
=2t/a
2

The Reciprocal Lattice of a 3D Array of Scattering Centres
Scattering centres in a real
space crystal lattice
Reciprocal Lattice
Fourier transform
Scattering centres in a
random group (e.g.
amorphous material)
Fourier transform
The reciprocal of any
repeated length scales give
reciprocal lattice features
1/L
L
The reciprocal lattice
A diffraction pattern is not a direct
representation of the crystal lattice
The diffraction pattern is a representation of
the reciprocal lattice
We have already considered some
reciprocal features -
Miller indices were derived as the
reciprocal (or inverse) of unit cell
intercepts.
Reciprocal Lattice vectors
Any set of planes can be defined by:
(1) their orientation in the crystal (hkl)
(2) their d-spacing
The orientation of a plane is
defined by the direction of a
normal (vector product)
Defining the reciprocal
Take two sets of planes:
Draw directions normal:
These lines define the orientation but
not the length
We use
1
d
to define the lengths
These are called reciprocal lattice
vectors G
1
and G
2

G
1

G
2

Dimensions = 1/length
Properties Of Reciprocal Lattice
Direct lattice is a lattice in ordinary space whereas the reciprocal lattice is a
lattice in the Fourier space.
The vectors in reciprocal lattice has the dimensions of (length)
-1
whereas the
primitive vectors of the direct lattice have the dimensions of length
A diffraction pattern of a crystal is a map of the reciprocal lattice of the crystal
whereas a microscopic image is a map of direct lattice

When we rotate a crystal, both direct and reciprocal lattice rotates
Each point in the reciprocal lattice represents a set of parallel planes of the
crystal lattice
If the coordinates of reciprocal vector G have no common factor, then G is
inversely proportional to the spacing of the lattice planes normal to G

The volume of unit cell of the reciprocal lattice is inversely proportional to the
volume of unit cell of the direct lattice

The direct lattice is the reciprocal of its own reciprocal lattice
The unit cell of the reciprocal lattice need not be parallelopiped
Reciprocal Lattice In Two
Dimensions
Construction of Reciprocal Lattice
1. Identify the basic planes in the direct space lattice, i.e.
(001), (010), and (001).
2. Draw normals to these planes from the origin.
3. Mark distances from the origin along these normals
proportional to the inverse of the distance from the
origin to the direct space planes
Above a monoclinic direct space lattice is transformed (the b-
axis is perpendicular to the page). Note that the reciprocal
lattice in the last panel is also monoclinic with |* equal to
180|.
The symmetry system of the reciprocal
lattice is the same as the direct lattice.
23
BCC Lattice

1 1
1 2 2 2
1
3 2

a ( x y z) a (x y z)

a (x y z)
a a
a
= + + = +
= +
1 2 3
2 2 2
y z x z x y
t t t
= + = + = + G G G
a a a
The reciprocal lattice is represented by
the primitive vectors of an FCC lattice.
Reciprocal Lattices
3
1
0 1 2 3 2
a a a O = = a
24
FCC Lattice

1 1
1 2
2 2
1
3
2
( x y z) (x y z)
(x y z)
= + + = +
= +
G a G a
G a
1 2 3
2 2 2

a y z a x z a x y
a a a
t t t
= + = + = +
The reciprocal lattice is represented by
the primitive vectors of an BCC lattice.
Reciprocal Lattices
3
0 1 2 3
a a a O = = a
25
Drawing Brillouin Zones
WignerSeitz cell
The BZ is the
fundamental unit cell
in the space defined
by reciprocal lattice
vectors.
26
Drawing Brillouin Zones
Direct Space to Reciprocal Space
Reciprocal Space to Direct Space
Reciprocal Lattice for Aluminium
30
Diffraction from a particle and solid
Single particle
To understand diffraction we also have to
consider what happens when a wave
interacts with a single particle. The
particle scatters the incident beam
uniformly in all directions
Solid material
What happens if the beam is incident on
solid material? If we consider a
crystalline material, the scattered beams
may add together in a few directions and
reinforce each other to give diffracted
beams
Theories: Common Names
Maxwell
Equations describing interactions of electromagnetic waves (X-rays)
Laue
Interference from 3D array of scattering centres in crystals
Ewald
Worked with on general solution for 3D array
Bragg
Simplified equation based on planes of scattering centres
Fresnel
Optical model based on uniform refractive index of a material (reflectivity)
Dynamical Diffraction (Darwin, Prins, James)
Theory for scattering from perfect single crystals including multiple scattering events
within the crystal
Kinematical Theory
Simplified theory for small crystals not including multiple scattering

Scattering by a crystals
For a general unit cell in a crystal, the structure factor is:
The total wave scattered by the crystal is:
A crystal contains a
large number of unit
cells
Scattering by a crystals
A crystal does not diffract X-ray unless
This is the famous Laue condition
Not constructive interference
unless all waves have the same
phase
Laue conditions specify scattering conditions
S is perpendicular to the imaginary reflecting plane
What is S???
a, b, c are unit vectors of crystal unit cell axes

For a particular crystal unit, X-ray will only be
scattered along discrete directions
What does Laue condition mean???
What does this mean?!
Laue assumed that each set of atoms could
radiate the incident radiation in all directions
Constructive interference only
occurs when the scattering vector,
K, coincides with a reciprocal
lattice vector, G
This naturally leads to the Ewald
Sphere construction
The Ewald Sphere
We have constructed the reciprocal lattice (RL) in terms of the reciprocal d-
spacings, 1/d
hkl
, another utility of this lattice in terms of crystallography is
made apparent by the Ewald sphere, which tells us the angle at which each
family of planes will diffract!

Consider a circle of radius r, with points X and Y lying on the circumference.
If the angle XAY is defined as u, then the angle XOY will be 2u by geometry and
sin(u) = XY/2r
If this geometry is constructed in reciprocal space, then it has some important
implications.
The radius can be set to 1/, where is the wavelength of the X-ray beam.
If Y is the 000 reciprocal lattice point, and X is a general point hkl, then the distance XY
is 1/d
hkl

Thus: sin(u) = (1/d
hkl
)/(2/) or, rearranged: = 2 d
hkl
sin(u) , and Braggs law is satisfied!
Ewald Sphere
We superimpose the imaginary sphere of
radiated radiation upon the reciprocal lattice
For a fixed direction and wavelength of incident
radiation, we draw -k
o
(=1/) e.g. along a*
Draw sphere of radius 1/
centred on end of k
o

Reflection is only observed
if sphere intersects a point
i.e. where K=G
Laue Condition Satisfied
In this case, the incident
wavevector angle is adjusted
such that two points lie on the
surface of the sphere.
The diffraction angle is then
half the angle between the
incident and diffracted
wavevectors.
Generally, only a few angles will
yield the proper conditions for
diffraction.
k
k'
K
2O
O
What does this actually mean?!
Relate to a real diffraction experiment with crystal at O
K=G so scattered beam
at angle 2u
Geometry:
tan tan 2 2
1
u u = =

x
R
x
R
but K
hkl
=
2sinu

so K
x
R
=
|
\

|
.
|

2 1
2
1

sin tan
Practicalities
This allows us to convert distances on the film to
lengths of reciprocal lattice vectors.
Indexing the pattern (I.e. assigning (hkl) values to
each spot) allows us to deduce the dimensions
of the reciprocal lattice (and hence real lattice)
In single crystal methods, the crystal is rotated or
moved so that each G is brought to the surface
of the Ewald sphere
In powder methods, we assume that the random
orientation of the crystallites means that G takes
up all orientations at once.
The Ewald Sphere
is defined as the sphere of radius 1/ that is the locus of possible scattering
vectors (S) when the beam (s
0
) is fixed.
s
0

x
y
z
Crystal position
defines the
coordinate axes.
This sphere is in scattering space
(reciprocal space).
If a scattered wave has S on the Ewald sphere,
it is visible on the film/detector.
Moving the beam moves the Ewald Sphere
For a given direction of the incoming x-
rays, the set of possible scattering
vectors S is the surface of a sphere of
radius 1/, passing through the
crystallographic origin.
s
0

Keeping the crystal fixed, we rotate the X-ray
source. The Ewald Sphere moves in parallel
with the X-ray source. The new set of S vectors
describe the phase vs. direction of scatter for
that position of the source.
x
y
z
x
y
z
By moving the X-ray source relative to
the crystal, we can sample every possible
S
Moving the beam. Crystal fixed.
The visible part of reciprocal space
Remember: in this view, the crystal is fixed (center of image, where
the X-rays are pointed). In real life, we find it easier to move the
crystal, not the source. It doesnt matter which one you move, the
crystal or the source. The results are the same.
limit = 2/
(u=180)
The set of all vectors S (red), given
all possible directions of the beam
(black arrows), is called reciprocal
space.
The Ewald Sphere
If one rotates the Ewald sphere completely about the (000) reciprocal lattice
point in all three dimensions, the larger sphere (of radius 2/) contains all of
the reflections that it is possible to collect using that wavelength of X-rays.
This construction is known as the Limiting sphere and it defines the
complete data set. Any reciprocal lattice points outside of this sphere can
not be observed. Note that the shorter the wavelength of the X-radiation, the
larger the Ewald sphere and the more reflections may be seen (in theory).
The limiting sphere will hold roughly (4/3tr
3
/ V*) lattice points. Since r = 2/, this equates to
around (33.5/ V*
3
) or (33.5 V/
3
) reflections. For an orthorhombic cell with a volume of 1600
3
,
this means CuKo can give around 14,700 reflections while MoKo would give 152,000
reflections.

u
2
1 2
hkl
hkl
hkl
d
d
Sin = =
Radiation related information is present in the Ewald Sphere
Crystal related information is present in the reciprocal crystal
The Ewald sphere construction generates the diffraction pattern
The Ewald Sphere construction
Which leads to spheres for various hkl reflections
Ewald Sphere for LEED
In low energy electron diffraction,
the electrons interact mainly with
the surface atoms so the
reciprocal lattice becomes
regularly spaced rods
perpendicular to the surface
plane.
The Ewald construction gives the
spot locations on the screen and
hence the in-plane lattice vectors.
Intensity of the spots versus
electron energy gives the d-
spacing.
k
k'
K
Ewald Construction for RHEED
In RHEED, High energy
electrons are incident at
grazing incidence.
The Ewald construction
illustrated why straks
are observed rather
than spots--the
reciprocal lattice rods
intersect the Ewald
sphere nearly
tangentially.
Ewald Sphere
Construction for
RHEED
= 2a/(h
2
+k
2
)
1/2
sinu
As u is very small in REED,

a = (h
2
+k
2
)
1/2
L/t

t is the distance between the streaks
Intensity
Measurement
by LEED
Interpretation of LEED patterns
a) Sharpness of LEED patterns:
Well ordered surfaces exhibit sharp bright spots and low background intensity.
The presence of surface defects and crystallographic imperfection results in
broadening and wakening of the spots and increased background

b) LEED spot geometry:
This yields information on the surface geometry, i.e. symmetry and lattice constants.
Furthermore one can deduce information on possible reconstructions or
superstructures caused by adsorbates
To produce diffraction patterns
the surface area has to be at least
the length of the coherence
length (typically several 100 ).

Therefore sometimes
superposition of several domains
leads to new diffraction patterns

eg. 2x2 superstructure on
hexagonal lattice leads to the
same pattern as three domains of
(2x1) superstructures
c) LEED spot profile:
The spot profile is determined by the perfectness of the surface. Any imperfections
broaden the spot. Reducing the domain size broadens the spot too. Even for a perfect
crystal surface there is some finite spot widths due to the finite coherence length,
determined by the energy distribution and the angular spread of the electron beam.
Regularly stepped surfaces lead to split spots. In this case the diffraction conditions are
given by two regularities, the terraces and the atomic arrangement in the terraces.

d) LEED I-V analysis:
The spot geometry gives only information on the regular arrangement on a surface. No
information can be obtained for the local arrangement of the surface atoms
(adsorbates) to the underlying array. However, due to multiple scattering the local
arrangement of the scatterer within the surface unit cell influences the scattering. This
shows up in special modulations of the spot intensities as function of the electron
beam: Therefore I-V curves have to be measured. On the other hand, I-V curves can be
calculated by assuming a special atomic arrangement.
Usually, by a trial and error method the best fit between
experimental and theoretical I-V curves yields then the most
probable atomic positions within the unit cell.

Substrate & over layer LEED pattern
Only Substrate
Substrate +Adsorbate