Notice that we only got certain planes (0 0 1)

Finding Lattice
Parameters
You’ve just joined a research
group and been asked to
determine the lattice parameters
of a film your groupmate (or
you) just made. Is this a good
film?
Diffraction pattern for a film on a substrate. Both the STO substrate and LSAT
film are perovskites. Calculate the lattice parameters of both (a STO and a LSAT)
using all three peaks (why?). Find the strain mismatch of the film and compare it
to what you would expect if it matched the STO lattice parameter exactly. The
bulk lattice parameter for LSAT is about 0.387 nm.
For more about LSAT, see https://en.wikipedia.org/wiki/LSAT_(oxide)
A single crystal specimen in a Bragg-Brentano diffractometer (θin=θout)
would produce only one family of peaks in the diffraction pattern.

Why might
you use this
technique?
2q

The (110) planes would diffract at

At 20.6° (2q), 29.3 °2q; however, the detector is The (200) planes are parallel to
Bragg’s law fulfilled not at that position (the the (100) planes. Therefore,
for the (100) planes, perpendicular to those planes does they also diffract for this crystal.
producing a not bisect the incident and Since d200 is ½ d100, they appear
diffraction peak. diffracted beams). Only background at 42° (2q).
is observed.
 THE EWALD SPHERE (Will show a few ways)
Consider an arbitrary sphere
passing through the reciprocal lattice (which we will define soon),
with the crystal arranged in the center of the sphere.
We specify two conditions:
(1) the sphere radius is 2 / - the inverse wavelength of X-ray radiation
(2) the origin of the reciprocal lattice lies on the surface of the sphere

diffracted
X-rays are ON ray

2q
O
2/

The diffraction spot will be observed when a

reciprocal lattice point crosses the Ewald sphere
1. Longitudinal or θ-2θ scan
Sample moves as θ, Detector follows as 2θ

k0 k’

0 10 20 30 40
1. Longitudinal or θ-2θ scan
Sample moves on θ, Detector follows on 2θ

G
k0 k’

0 10 20 30 40

Reciprocal lattice
rotates by θ during
scan
1. Longitudinal or θ-2θ scan
Sample moves on θ, Detector follows on 2θ

G
k0 k’ 2q

0 10 20 30 40
1. Longitudinal or θ-2θ scan
Sample moves on θ, Detector follows on 2θ

G
k0 k’ 2q

0 10 20 30 40
1. Longitudinal or θ-2θ scan
Sample moves on θ, Detector follows on 2θ

G
k0 2q
k’

0 10 20 30 40
1. Longitudinal or θ-2θ scan
Sample moves on θ, Detector follows on 2θ

G
k0 2qk’

0 10 20 30 40
 1. Longitudinal or θ-2θ scan
Sample moves on θ, Detector follows on 2θ

k’
G
k0 2q

0 10 20 30 40

•Provides information about relative arrangements,

angles, and spacings between crystal planes.
 3 COMMON X-RAY DIFFRACTION
METHODS

X-Ray Diffraction
Method

Laue Rotating Crystal Powder

Orientation Lattice constant or Lattice Parameters

Single Crystal Secondary Phases Polycrystal/Powder
Polychromatic Beam Single Crystal Monochromatic Beam
Fixed Angle Monochromatic Beam Fixed Angle
Variable Angle
 Zoom in
Back-reflection vs. Transmission
Laue Methods
In the back-reflection method, the film
is placed between the x-ray source and
the crystal. The beams which are
diffracted backward are recorded.
Which is this?

X-rays have wide

wavelength range
(called whiteSingle
beam).
Crystal

X-Ray Film
Single Film
X-Ray Crystal
The diffraction spots generally lay on:
a hyperbola an ellipse
 LAUE METHOD
The diffracted beams form arrays of
spots, that lie on curves on the film.
The symmetry of the pattern reflects the
symmetry of the crystal when viewed along
the direction of the incident beam.

Each set of planes in the

crystal picks out and
diffracts a particular
wavelength from the
white radiation that
satisfies the Bragg law
for the values of d and θ
involved. 13
 Crystal structure
determination by
Laue method?

• Although the Laue method can be used,

several wavelengths can reflect in different
orders from the same set of planes, making
structure determination difficult (use when
structure known for orientation or strain).
• Rotating crystal method overcomes this
problem. How?
 ROTATING CRYSTAL
METHOD
A single crystal is mounted
with a rotation axis
perpendicular to a
monochromatic x-ray
beam.

A cylindrical film is placed

around it and the crystal is
rotated and/or a detector is
rotated.
Sets of lattice planes will at some point make the
correct Bragg angle, and at that point a diffracted
beam will be formed.
 Rotating Crystal Method
Reflected beams are located on imaginary cones.

By recording the diffraction

patterns (both angles and
intensities), one can determine
the shape and size of unit cell as
well as arrangement of atoms
inside the cell.
But around what axis should you rotate?

Film
 THE POWDER METHOD
Least crystal information needed ahead of time
If a powder is used, instead of a single crystal,
then there is no need to rotate the sample,
because there will always be some crystals at an
orientation for which diffraction is permitted.
A monochromatic X-ray beam is incident on a
powdered or polycrystalline sample.
 The Powder Method

• A
 If the
asample
monochromatic
sample of consists
some x-ray
of some
beam
hundreds tens
is
of
directed
of randomly
crystals at aa single
(i.e. orientated
powderedcrystal, single
then
sample)
only one
crystals,
show the
thator the
two
diffracted
diffracted
beams
diffracted beamsare
may result.
seen
form to lie oncones.
continuous the surface of
Aseveral
circle cones.
of film is used to record the
 diffraction
The cones may point
pattern as both forwards
shown.
 Each
and backwards.
cone intersects the film giving
diffraction arcs.

18
 Powder diffraction film

When the film is removed from the camera,

flattened and processed, it shows the diffraction lines
and the holes for the incident and transmitted beams.
Likewise, detectors can show the same thing.

19
K
 Useful for Phase Identification
The diffraction pattern for every phase is as unique as your
fingerprint
– Phases with the same element composition can have drastically
different diffraction patterns.
– Use the position and relative intensity of a series of peaks to match
experimental data to the reference patterns in the database
 Databases such as the Powder Diffraction File (PDF)
contain dI lists for thousands of crystalline phases.
• The PDF contains over 200,000 diffraction patterns.
• Modern computer programs can help you determine
what phases are present in your sample by quickly
comparing your diffraction data to all of the patterns in
the database.
 The Reciprocal Lattice
• Is a useful tool to handle the diffraction of waves
• Used to describe all things of “wavy nature”
including electrons and lattice vibrations
• Is used to represent band structure
• Is the collection of all wave vectors G that yield
plane waves with a period of the Bravias lattice
(note: any R= u1 a1+u2 a2+u3 a3 vectors is a possible
period of the Bravais lattice)
• It can be shown that G = K (Laue condition). I’ll use
both.
 Reciprocal Space =
Fourier transform of the real crystal lattice.
Also called Fourier space, k (wavevector)-space, or
momentum space in contrast to real space or direct space.

https://www.youtube.com/watch?v=DFFU39A3fPY

This abstraction seems unnecessary. Why do we care?

1. The reciprocal lattice simplifies the interpretation of

x-ray diffraction from crystals
2. The reciprocal lattice facilitates the calculation of
wave propagation in crystals (lattice vibrations,
electron waves, etc.)
 Simple proof
The derivation of reciprocal lattice vectors in terms of the direct
space lattice vectors starts by expanding a translationally invariant
lattice function f(R + r) in plane waves fk eiG⋅R eiG⋅r.

R= u1 a1+u2 a2+u3 a3 is some crystal translation vector

Again G is all wave vectors that yield plane waves with period R
and G = v1 b1+v2 b2+v3 b3 , where b’s define reciprocal lattice vectors

Then by the translational invariance eiG⋅R must equal 1.

From which we have G⋅R=2πN, where N is an integer.

From this the next step in most derivations says that

bi⋅aj=2πδi,j
Consider what this means for b in the case of simple cubic.
 The Reciprocal Lattice
Crystal planes (hkl) in the real-space (or the direct lattice) are
characterized by the normal vector 𝑛ොℎ𝑘𝑙 and dhkl interplanar spacing
z

y
[hkl]
𝑛ො ℎ𝑘𝑙

x
𝑑ℎ𝑘𝑙

Practice has shown the usefulness of defining a different lattice in

reciprocal space whose points lie at positions given by the vectors
2𝜋𝑛ො ℎ𝑘𝑙
𝐾ℎ𝑘𝑙 ≡ This vector has magnitude
𝑑ℎ𝑘𝑙
2/dhkl, which is a
reciprocal distance
A point in the reciprocal lattice corresponds to a set of planes (hkl) in
the real-space lattice.
 Definition of the Real/Reciprocal Lattice
Rn = n1 a1 + n2 a2 + n3 a3 (real lattice vectors a1,a2,a3) (h, k, l integers)
Suppose K can be decomposed into reciprocal lattice vectors: 𝐾 = ℎ𝑏1 + 𝑘𝑏2 + 𝑙𝑏3

b’s are defined such that: bi a j  2ij Note: a has dimensions of length, b has
dimensions of length -1

Implication: b1 is always perpendicular to a2 and a3

The basis vectors bi define a reciprocal lattice:

- for every real lattice there’s a reciprocal lattice
𝐚2 × 𝐚3
𝑏1 = 2𝜋
𝐚1 ⋅ 𝐚2 × 𝐚3 + cyclic permutations

𝐚1 ⋅ 𝐚2 × 𝐚3
is volume of unit cell

Definition of a’s are not unique, but the primitive volume is.
 2D Reciprocal Lattice
A point in the reciprocal lattice corresponds to a set of
planes (hkl) in the real-space lattice.

Identify
these
a2
planes
a1

Real lattice planes (hk0) K in reciprocal space

Khkl is perpendicular to (hkl) plane
Magnitude of K is inversely proportional to distance between (hkl) planes
 Another Similar View: Lattice waves
real space reciprocal space

2π/a

(0,0)
2π/b

There is always a (0,0) point in reciprocal space.

How do you expect the reciprocal lattice to look?
 Lattice waves
real space reciprocal space

2π/a

(0,0)
2π/b

Red and blue represent different phases of the waves.

 Lattice waves
real space reciprocal space

2π/a

(0,0)
2π/b

Note that the vertical planes in real space correspond to

points along the horizontal axis in reciprocal space.
 Lattice waves
real space reciprocal space

2π/a

(0,0)
2π/b
 Lattice waves
real space reciprocal space

2π/a

(0,0)
2π/b

The real horizontal planes relate to points along R.S. vertical.

In 2D, a reciprocal lattice vector is  to opposite R.S. axis.
 Lattice waves
real space reciprocal space

2π/a

(0,0)
2π/b

(11) plane
 Group: What happens if the lattice is
not rectangular?

• Determine the reciprocal lattice for:

a2
b2
a1
b1

Real space Fourier

(reciprocal)
In 2D, reciprocal vectors are space
perpendicular to opposite axis.
Group: Find the reciprocal A D BF–EC
B E DC–AF
lattice vectors of BCC C F AE–BC
a 2  a3
• The primitive lattice vectors for BCC are: b1  2
a1  a 2  a 3 )

• The volume of the primitive cell is ½ a3(2 pts./unit cell)

• So, the primitive translation vectors in reciprocal space
are:
Look familiar?
Good websites:
http://newton.umsl.edu/run//nano/reltutor2.html
http://matter.org.uk/diffraction/geometry/plane_reciprocal_lattices.htm
Reciprocal Lattices to SC, FCC and BCC
Primitive Direct lattice Reciprocal lattice Volume of RL
2𝜋/𝑎 3
𝑎 = 𝑎x b1 = 2𝜋/𝑎 x
SC ቐ𝑏 = 𝑎y ൞b2 = 2𝜋/𝑎 y
𝑐 = 𝑎z b3 = 2𝜋/𝑎 z Direct Reciprocal
Simple cubic Simple cubic
bcc fcc
1 2𝜋 fcc bcc
a1 = 𝑎 x + y − z b1 = y+z
BCC 1
2 𝑎
2𝜋
2 2𝜋/𝑎 3
a2 = 𝑎 −x + y + z b2 = x+z
2 𝑎
1 2𝜋
a3 = 𝑎 x − y + z
2
b3 =
𝑎
x+y We will come
1 2𝜋
back to this if
a1 = 𝑎 x + y b1 = −x + y − z
FCC
2
1
a2 = 𝑎 y + z b2 =
𝑎
2𝜋
x−y+z
time.
2 𝑎
1 2𝜋 3
a3 = 𝑎 z + x b3 = x+y−z 4 2𝜋/𝑎
2 𝑎
Volume of the Brillouin Zone (BZ)
In general the volume of the BZ is equal to

(2 )3
Volume of real space primitive lattice

Real lattice Real BZ Volume

Volume
Simple a3 8 3/a3
cubic
bcc a3/2 16 3/a3
fcc a3/4 32 3/a3
 The reciprocal lattice in one dimension
a
Real lattice x

-/a /a What is the range of

Reciprocal lattice unique environments?

k
-6/a -4/a -2/a 0 2/a 4/a

Weigner Seitz Cell: Smallest space enclosed when

intersecting the midpoint to the neighboring lattice points.

Why don’t we include second neighbors here (do in 2D/3D)?

 The Brillouin Zone
-/a /a
Reciprocal lattice

k
-6/a -4/a -2/a 0 2/a 4/a

• Is defined as the Wigner-Seitz primitive cell in

the reciprocal lattice (smallest unique set of
distance/area/volume in reciprocal space)
• Its construction exhibits all the wavevectors k
which can be Bragg-reflected by the crystal
• Also critical for understanding energy diagrams
Group: Determine the shape of the BZ
of the FCC Lattice

How many sides will

it have and along
what directions?

SC BCC FCC
FCC Primitive and
# of nearest Unit
Conventional neighbors
Cells 6 8 12
Nearest-neighbor distance a ½ a 3 a/2
# of second neighbors 12 6 6
Second neighbor distance a2 a a
 WS zone and BZ
Lattice Real Space Lattice K-space

bcc WS cell Bcc BZ (fcc lattice in K-space)

fcc WS cell fcc BZ (bcc lattice in K-space)

The WS cell of bcc lattice in real space transforms to a Brillouin zone

in a fcc lattice in reciprocal space while the WS cell of a fcc lattice
transforms to a Brillouin zone of a bcc lattice in reciprocal space.
 Usually, it is sufficient to know the
Nomenclature
energy En(k) curves - the dispersion
relations - along the major directions.

Directions are chosen that lead aong

special symmetry points. These
points are labeled according to the
following rules:
Direction along BZ

Energy or Frequency
• Points (and lines) inside the Brillouin zone are denoted with Greek letters.
• Points on the surface of the Brillouin zone with Roman letters.
• The center of the Wigner-Seitz cell is always denoted by a G
 Brillouin Zones in 3D
fcc
bcc Note: bcc lattice in reciprocal
space is a fcc lattice

Note: fcc lattice in reciprocal hcp

space is a bcc lattice

•The BZ reflects lattice symmetry (future class)

•Construction leads to primitive unit cell in rec. space
 Brillouin
Zone of
Silicon
Points of symmetry on the BZ are
important (e.g. determining
bandstructure).
Electrons in semiconductors are
perturbed by the potential of the
crystal, which varies across unit cell.
Symbol Description
Γ Center of the Brillouin zone
Simple Cubic
M Center of an edge
R Corner point
X Center of a face
FCC
Middle of an edge joining
K
two hexagonal faces
L Center of a hexagonal face C6
Middle of an edge joining a
U
hexagonal and a square face
W Corner point
X Center of a square face C4
BCC
H Corner point joining 4 edges
N Center of a face
P Corner point joining 3 edges
 Group: Polonium
Consider simple cubic polonium, Po, which is the
closest thing we can get to a 1D chain in 3 dimensions.

(a) Taking a Po atom as a lattice point, construct the

Wigner-Seitz cell of polonium in real space. What is
it’s volume?

(b) Work out the lengths and directions of the lattice

translation vectors for the lattice which is reciprocal
to the real-space Po lattice.

(c) The first Brillouin Zone is defined to be the Wigner-

Seitz primitive cell of the reciprocal lattice. Sketch
the first Brillouin Zone of Po.
 Square Lattice
(on board)

Introduction of Higher Order BZs

(these will make more sense when we
get to energy band diagrams)
 Extra Slides
Alternative Approaches and Other
Stuff for which we ran out of time

If you already understand reciprocal

lattices, these slides might just confuse
you. But, they can help if you are lost.
Group: Draw the 1st Brillouin Zone of a sheet of graphene
(atoms at corners)

a1*
a1

a2 a2*

Real Space

2-atom basis
(many ways to define vectors)
Wigner-Seitz Unit Cell of Reciprocal Lattice
The same perpendicular = First Brillouin zone
bisector logic applies in 3D
 Dirac cones

Brillouin zone
representations of
graphene Real space
 Quantitative Phase Analysis
• With high quality data, you can Reference Intensity Ratio Method
determine how much of each phase 60

I(phase a)/I(phase b) ..
is present 50
• The ratio of peak intensities varies 40
linearly as a function of weight
30
fractions for any two phases in a
mixture 20

• RIR method is fast and gives semi- 10

quantitative results 0
• Whole pattern fitting/Rietveld 0 0.2 0.4 0.6 0.8 1
refinement is a more accurate but X(phase a)/X(phase b)
more complicated analysis
Examples of Image Fourier Transforms
Real Image

Fourier Transform

Brightest side points relating to

the frequency of the stripes
Examples of Image Fourier Transforms

http://www.users.csbsju.edu/~frioux/diffraction/crystal-rot.pdf
 Construction of the 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. Note that distances from the origin along these
normals proportional to the inverse of the distance
from the origin to the direct space planes
Real space Fourier (reciprocal) space

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.
 Reciprocal lattice (Similar)

Consider the two dimensional

direct lattice shown below. It
The reciprocal lattice has reciprocal vectors a*
is defined by the real vectors
and b*, separated by the angle g*. a* will be
a and b, and the angle g. The
perpendicular to the (100) planes, and equal in
spacings of the (100) and
magnitude to the inverse of d100. Similarly, b* will
(010) planes (i.e. d100 and d010)
be perpendicular to the (010) planes and equal in
are shown.
magnitude to the inverse of d010. Hence g and g*
will sum to 180º.
 Reciprocal Lattice
02 12 22
(01)

𝑎Ԧ 2 (11) 01 11
(10) 21
∗ ∗
(21) 𝑏2∗
𝑔11 𝑔21

𝑎Ԧ1
𝑎1 10 20
00 𝑏1∗ 1ൗ
𝑎1

The reciprocal lattice has an origin!

 22
(01) 12
02

(11) 21
(10) 11
𝑎Ԧ 2
(21) 01
𝑎Ԧ1 𝑏2∗ 20
𝑎1 10
𝑏1∗
22
12
00
02
(01)
21
11
01 (11)
(10)
20
(21) 10 Note perpendicularity of various vectors
00
 More on Nomenclature
We use the following nomenclature: (red for fcc, blue for bcc):
The intersection point with the [100] direction is called X
(H). The line G—X is called D.

The intersection point with the [110] direction is called K

(N). The line G—K is called S.

The intersection point with the [111] direction is called L

(P). The line G—L is called L.

Brillouin Zone for fcc is bcc

and vice versa.
 Why Use
Sample
Reciprocal Space?
X-rays

Many different
types of XRD
A diffraction pattern
Purpose of this
(the interference of
one?
waves) is not a direct
representation of the
crystal lattice
b2
 The diffraction pattern Is this what you think of
is a representation of b1 when you hear diffraction?
the reciprocal lattice