Diffraction Theory Introduction

Zhao Wang
January 31, 2013

Part I

Crystallography
Crystallography is the subject which studies the geometrical arrangement of
atoms in the crystal. Before crystallography was incorporated in the field of
solid state physics, it has been intensively studied through various means for
hundreds of years. However, Most of the studies had focused on the macroscopic vision of crystal until the famous physicists W.L Bragg discovered
Braggs Law, studying the X-ray diffracted pattern to reveal microscopic or
atomic structure of the crystal. Therefore, crystallography has been brought
into a new era and often was called X-ray crystallography. X-ray diffraction
technique have made big contribution to a variety of scientific research such
as physics,chemistry, material science, biology, mineralogy and so on. Newer
1

technologies such as electron and neutron diffraction is also based on X-ray

diffraction theory. Therefore, in this report, we are going to first review the
basic knowledge of crystallography and explain why X-ray is a unparalleled
way to study the structure of crystal. Then, modern techniques LEED and
RHEED will be briefly discussed.

Bravais Lattice

Bravais lattice is an important concept in crystalline solid. It forms a geometrical picture in which a identical unit is so constructed that it repeats
itself into infinite 3-D space. This identical unit could be an single atom or
a cluster of atoms. This unit is defined as basis. Two definitions of Bravais
lattice could be made, one of which is more related to its geometry and the
other of which is more explicit in mathematics. They are stated as [1]:

1. A Bravais lattice is constructed in a way that the geometrical arrangement and symmetry of atoms are exactly identical no matter from
which lattice point is viewed.
2. All the points in a (3-D)Bravais lattice can be reached by the vector

~ = u1
translational operation expressed as R
a1 + u2
a2 + u3
a3 , provided
that u1 , u2 , u3 are integers.

Figure 1: Primitive vectors in a 2-D Bravais lattice

a1 ,
a2 ,
a3 are called primitive vectors in lattice and are not all in the same
plane. A primitive cell that is constructed by primitive vectors will repeat
itself in an infinite space neither overlapping with neighbor cells nor leaving
a void between neighbor cells. Therefore, a primitive cell is a minimumvolume cell and serves as the smallest building block. Equivalently speaking,
one can say that a primitive cell contains only one lattice point. It is worth
mentioning that the choices of primitive vectors is not unique, some choices
are preferred due to the simpler symmetry. See an example [3] in Fig.1 where
we have many choices of primitive vectors for a 2-D Bravais lattice excepted
the vectors in the red circle . The Bravais lattice point can be invariant with
respect to other points by translation or point symmetrical operation such
as rotations about certain axis or reflection about a certain plane. Some
rotations by 2, 22 , 23 , 42 , 26 are noted as one-, two-, three-, four- and sixfold rotation. One would ask if there is other rotational symmetry found
in natural crystal such as fivefold rotation[3]. The answer is no. Imagine
we have a pentagon shape as a primitive cell in 2-D space. It is impossible

Figure 2: An example of non-existed fivefold symmetry of crystal lattice

for us to construct a Bravais lattice with such a primitive cell because these
primitive cells can not fill in all the space, as shown in Fig.2 [3]. However,
not only can the primitive cell repeat itself in space without leaving a void
or overlapping but also some non-primitive cells can do so as well although
these non-primitive cells are not minimum-volume cells. These non-primitive
cell are often preferred due to advantage in point symmetry (rotation and
reflection) and they are called as unit cell. There are only 14 lattices based on
the distinctive unit cell in 3-D for the point symmetry group, shown in Fig.3
Keep in mind that only simple cubic is primitive cell while the other unit cells
are non-primitive cells, such as face centered cubic (fcc) and volume-centered
or body-centered cubic (bcc). However, the primitive cell can be found by
vector translation . Take a bcc unit cell as an example[3] shown in Fig.4 .The
primitive vectors can be contructed through vector operation

x +
y
z ), b = 21 a(
x +
y +
z ),
c = 21 a(
x
y +
z)
a = 12 a(
with a being the lattice constant in x, y, z direcctions in a rectangular coor4

Figure 3: 14 distinctive lattices in three dimensional

Figure 4: Primitive vectors of the volume-centered cubic cell being constructed

dinate system . For the other lattices, the primitive cells can be constructed
in a similar fashion.

Miller Indices

A notation system should be first established in order to study crystal structure more functionally. In a crystal structure, a specific plane will intercept
with three axes at position u1 , u2 , u3. Thus the coordinates of intercepts
(u1 u2 u3 ) can be used to specify a plane. However, it is more often interesting
to know the orientation of a plane for the structural analysis. Consequently,
Miller indices has been used. To form a Miller indices, one needs to do the
following steps:[3]

Find the intercepts (u1 u2 u3 )

Take the reciprocals of (u1 u2 u3 ) and then it gives ( u11 u12 u13 )
Let (hjk) = ( u11 u12 u13 ), find then convert (hjk) to three smallest integers
which have the same ratio. Thus, Miller indices is founded.

For example, in a cubic lattice, if a plane intercepts with three axes at (213),
the reciprocal values would be 21 ,1, 31 and then multiply these three values
6

by 6. The smallest integers thus can be obtained as (hjk) = (362). It

is noted that Miller indices can indicate a family of parallel planes or a
single plane. For instance, if two parallel planes intercept with three axes
at (213) and (426), respectively. The Miller indices of both plane is (326).
Besides, (200) plane is parallel to (100) plane but cutting x axis at

u1
.
2

If

the intercept position is in the negative side of origin, a little bar above the
number indicates negative like (hjk). If under certain condition of symmetry
a set of planes are equivalent, then {hkj}are used. For instance, in cubic
lattice, (100), (010), (001), (100), (010), (001) planes are all identical so that
the set of all these planes are denoted as {100}. Since we are generally
interested in a set of parallel planes, the inter-planar spacing for different sets
of parallel planes is a very important parameter. It can be indeed obtained
from the analysis of geometry which we will give full detail in this report.
In general, the inter-planar spacing formula of simple lattices is given in the
Table.1. a, b, c are the lattice constants on x, y, z axes which has occurred in
Fig.2 as a1 , a2 , a3 and h, j, k are Miller indices.

Reciprocal Lattice

At beginning, one may think why we would even bother defining a reciprocal
space if the crystal structure is perfectly defined in space domain. In compar-

Table 1: Inter-planar spacing of simple lattices

ison, electrical engineer often look at problem in frequency domain besides
time domain. It is natural to analyze problem in its Fourier domain as the
reciprocal lattice plays an important role in study of periodic structures such
as Bravais lattice. In fact, it also leads us to study the theory of diffraction
in crystal on which we focus.

A plane wave can form in the Bravais lattice, defined as ei K r . Generally

speaking, the wave vector K could be any value. Most of plane waves which
have random wave vectors would destructively interfere among each other
and vanish eventually but some plane waves will constructively interfere as
long as its wave vector fulfill the requirement of periodicity in Bravais lattice,
defined as:[1]

ei K ( r + R ) = ei K r
8

(1)

R is the periodicity of Bravais lattice, defined as a primitive vector in the

first section. we can say that such a wave vector K belongs to the reciprocal

lattice of such a Bravais lattice. Factoring out the common term ei K r , we

can get [1]

ei K R = 1

(2)

Therefore, for each Bravais lattice system indicated by R , there is a cor

respondent reciprocal lattice system indicated by K . Let b1 , b2 , b3 be the

primitive vectors in the reciprocal lattice and

a1 ,
a2 ,
a3 be the primitive vec

tors in the corresponding Bravais lattice. We get b1 , b2 , b3 as

a2
a3
b1 = 2

a1 ( a2
a3 )

a
3
1
b2 = 2

a1 (
a2
a3 )

a
1
2
b3 = 2

a1 (
a2
a3 )

(3)

As a result, the reciprocal lattice translational vector K = v1 b +v2 b2 +v3 b3 .

v1 , v2 , v3 are nothing but Miller indices h, j, k. Therefore, it can be rewritten

as K = h b + j b2 + k b3 .

Braggs Law

The crystal structure in atomic level is studied through the diffraction of

X-ray, electrons and neutrons. W.L. Bragg first presented X-ray diffraction
9

Figure 5: Bragg equation derivation

theory which gives the constructive diffraction condition for a beam of X-ray
diffracted by crystal, show in Fig.5 . When X-ray beam is incident on a set of
parallel lattice planes which has an interval d, it will be elastically scattered
by the electron of the atoms. The zero order scattering beam that is the also
the direct reflection with respect to the planes will take up most of the power
and the higher order parts are not considered in this case. Its diffracted angle
is thus equal to incident angle. Therefore, the optical path difference (OPD)
of diffracted beams can be calculated. In Fig.5, we can tell that the OPD
between diffracted beam 1 and 2 is ABC = 2dsin and the OPD between
diffracted beam 1 and 3 is A B C = 4dsin = 2ABC. We can imagine
that the OPD between diffracted beam 1 and n+1 is n ABC. In order
to constructively interference between diffracted beam 1 and all the other
diffracted beams. the OPD between diffracted beam 1 and 2 ABC must be
multiple numbers of wavelength and consequently the OPD between other
beams are also multiple numbers of wavelength . The equation is given as[1]
2dsin = n
10

(4)

The radiation of diffracted beam is a collection of reflection from all the parallel planes. Each plane reflects about 103 to 105 of the incident radiation
(give a citation). Despite of straightforwardness of this expression, X-ray
diffraction has become the most powerful tool for studying crystal structure.
Since the typical unit cell parameter (it is d in this case ) of most crystal is
In the above equation , the maximum
on the order of several angstroms (A).
value of sin is 1 and n is integer. It is apparent that in order to make
diffraction occur, must be on the order of around 10 A or below. Consequently, the X-ray is chosen or other particle source like electron beam or
neutron beam as their wavelengths are even smaller. Besides, this is also the
reason that we can not observe the diffraction from visible light. However,
one must notice that the X-ray diffraction does not give the information of
basis such as which kinds of atom a basis has.

Laue Condition and Ewald Sphere

Braggs law basically states a condition under which the diffracted beams by
a set of parallel planes will constructively interfere. A set of parallel planes
needs to be singled out so as to observe the diffracted radiation. Max Von
Laues method differs from Braggs but eventually approaches the same goal
which is to find the condition for constructive interference. Instead of forming parallel planes, the crystal is constructed by identical microscopic objects
such as atoms and irons attached to the Bravais lattice points . Each micro11

Figure 6: Illustration model of Laue condition

scopic object can been seen as scatterer. The scattering by these microscopic
objects is illustrated in Fig.6. An incoming parallel beam with wave vector

k in is incident on the objects and changes direction as outgoing parallel

holds due to
beam with wave vector k out . The relation | k in | = | k out | = 2

elastically scattering characteristic. Constructive interference will occur only

if[1]
OP D = dcos () + dcos () = m

(5)

Convert it into the phase difference between incoming beam and outgoing
beam so that we can obtain

2
2
cos () + d cos () = 2m

(6)

From Fig.6, we can easily impose a vector operation

a b = |a||b|cos on

Eq.8. Moreover, notice that the angle between d and k in is and the angle

between d and k out is 180o so that we can get

d k in d k out = 2m
12

(7)

d is translation vector between two points in Bravais lattice. To consider all

the scattering points in space, d could be replaced by Bravais lattice vector

R . Therefore, the above equation can be rearranged to

R ( k in k out ) = 2m

(8)

This equation can be re-written in an equivalent form as

ei R ( k in k out ) = 1

(9)

Comparing the Eq.11 with Eq.4 which we have obtained the previous chapter,we get

( k in k out ) = K

(10)

Therefore, the Laue condition states that constructive interference only occur

if ( k in k out ) is a vector in the reciprocal plane.

We have already come up with the truth that Braggs Law and Laue condition must be equivalent criterions for forming a constructive interference in
the lattice. To prove such an equivalency[3], we can make some redundant

operations on the Laue condition ( k in k out ) = K . Due to elastically

scattering, we can obtain

| k in | = | k out | = | k in K |

13

(11)

Squaring both sides, we get

| k in |2 = | k in | 2 k in K + | K |2

(12)

Rearrange the equation and we can get

k in K = |K|2
2

(13)

We assume we are dealing with cubic lattice and the similar analysis can
be applied to the other cubic systems but with more complicated mathematic deduction (citation here). The reciprocal lattice of a cubic lattice is

still a cubic lattice. With K = h b1 + j b2 + k b3 , the spacing of a certain

2
set of parallel planes dhjk = |K|
and k in K = 2
|K|cos. Seeing the geo
metrical arrangement of Bragg condition and Laue condition in Fig.5 and
Fig.6 respectively, we shall notice that is the angle between incident beam

and reciprocal vector d which is normal to crystalline planes while is the

angle between incident beam and crystalline planes. Thus, =

and

cos = sin. Plug all terms into Eq. 13, we obtain

1 (2)2
2 2
sin =
dhjk
2 d2hjk
dhjk may have contain a common factor n so that dhjk =

(14)
d
n

for a cubic lattice

. Thus rearranging the above function ,we can obtain

2dsin = n

14

(15)

Figure 7: Ewald construction

Therefore, the equivalency is proved in an oversimplified but applicable way.

Ewald Construction

Ewald construction is a simple geometric illustration of Laue condition to

understand the occurrence of the diffraction. It also gives the guideline for a
practical X-ray diffraction experiment. The general picture is given by Fig.7

[1] . The incident beam and outgoing beam wave vectors are k and k ,
respectively. The Ewald construction is to draw a sphere, centered on the

tip of k with radius | k | in the reciprocal lattice. Since we know from Eq.11

that | k | = | k |, the only possible positions which K can point to are on

the surface of such a sphere. Fig.7 only gives a cross section of 3-D sphere
but one can imagine a Ewald sphere is formed in 3-D space. Apparently, any
point which lies on such a surface will satisfy the Laue condition in which
case there will be a Bragg diffraction from a certain set of parallel planes
15

correspondent to this reciprocal lattice point. This sphere is called Ewald

sphere.
Ewald sphere is the most useful tool to guide a practical experiment.It can
be seen that generally there would be no Bragg diffraction peak observed if
the wave vector of the incident beam is not wisely picked up so that there
is no reciprocal lattice points intersecting with the surface of Ewald sphere.
To ensure that the Bragg diffraction peak can be observed during the experiment, several techniques are proposed based on the Ewald construction.
There are 3 general schemes to make use of Ewald construction, which will
be given below.

The Laue Method

The crystal under test is fixed in a certain axis and instead of a monochromatic X-ray beam, a range X-ray beam (1 0 ) is used in order to make
sure the occurrence of diffraction. The Ewald construction is shown in Fig.8
[1]. It is noticed that for the reciprocal lattice points which locate in the

shadow region between Ewald sphere of radius k 0 and Ewald sphere of ra

dius k 1 , they will satisfy Laue condition and thus there will be Bragg
diffraction for them. The Laue method is suitable to study one single bulk
sample with a known structure. For example, if the direction of the incident
beam is same as the symmetry axis of the crystal, the diffraction pattern will
have the same symmetry.
16

Figure 8: Ewald construction for the Laue method

The Rotating-Crystal Method

For this method, a monochromatic X-ray beam is used while the bulk crystal
under test is rotated around the rotation axis and the orientation of rotation
axis is varied several times. When the crystal is rotating, its correspondent
reciprocal lattice will rotate about the same angle as in the space domain.
Therefore, it could be imagined that the Ewald sphere is fixed in the reciprocal lattice space while the entire reciprocal lattice points will rotate about
the same rotation axis. If any reciprocal lattice point hits the surface of the
Ewald sphere, there will be a consequent Bragg diffraction observed. This

17

Figure 9: Ewald construction for the rotating-crystal method

method is illustrated in the Fig.9 . [1]

The Debye-Scherrer Method

The Debye-Scherrer Method is often referred as the powder method. The
crystal will be first made into powder. As a result, the crystal axes of the
powder elements will be randomly oriented. When the powder sample is
rotating, it means rotating about all possible rotation axes. It is similar to
the rotating-crystal method whose orientation of rotation axis is only varied
several times. The resulted diffraction pattern of the Debye-Scherrer method
is the the accumulated diffraction from all possible orientations of a single
bulk crystal. When a reciprocal point is rotating about all possible axes, it

will construct a 3-D sphere with radius K . When it extends to all the lattice

18

Figure 10: Ewald construction for the Debye-Scherrer method. (a) 3-D model

indicating that the possible reciprocal vector K for the occurrence of Bragg
diffraction. (b) a plane section of (a) and is the diffracted angle.
points, the results will be a series of concentric spheres with different radii
defined in the reciprocal lattice. The Ewald construction is shown in Fig.10

(a) [1]. The smaller sphere is Ewald sphere with radius k while the larger

sphere is rotating reciprocal lattice plane with radius K . These two spheres

will intersect in a ellipse, provided that | K | is less than 2| k |. Otherwise, the

Ewald sphere will totally immerse inside the bigger sphere and thus there
wont be intersection. It is obvious to see that each reciprocal lattice vector

of length less than 2| k | will generate a cone of Bragg diffraction at an angle

with respect to the forward direction. The relation among K , k and is

illustrated in Fig.10 (b) when a cross section is singled out. The triangle is
isosceles and applying the sine rules in triangle, we get

|k|
|K |
=
sin
sin(
)
2
19

(16)

Figure 11: Experiment setup on Debye-Scherrer method

Manipulate it with sin = 2cossin, we can rearrange the equation as
1

| K | = 2| k |sin
2

(17)

The above equation tells that when the Bragg diffraction is observed at

diffracted angle . the corresponding reciprocal lattice vector K can be

calculated with monochromatic X-ray wave vector | k |. This analysis indeed

provides a guideline for the experimental setup. Fig.11 gives a model of X-ray
diffraction setup based on the Debye-Scherrer method . In the Figure, the
red and green cones represent the Bragg diffraction radiation with different
reciprocal lattice vectors. The yellow cone represents the backscattered radiation. All the radiations are recorded on a circular film so that the diffraction
angles can be obtained.

20

Some Important Parameters

There are some interesting parameters which are particularly helpful to understand the structure of crystal. to summarize them, they include atomic
scattering factor, structure factor and shape factor.

Structure Factor and Forbidden Reflection

First , we are assuming that a monochromatic X-ray wave,traveling inside
the crystal with monoatomic lattice, has a complex amplitude electric field
defined as[1]

E in = A0 ei k in r

Similarly,the scattered wave is defined as

E out = A0 ei k out r

(18)

(19)

As we have concluded that the scattered wave will only constructively interfere when it satisfies Eq.12. Insert Eq.12 into the above Equation we can
get

E out = A0 ei( k in K ) r

(20)

Rearrange the equation to get

E out = E in ei K r

(21)

It can be seen that the complex amplitude of electric field between outgoing
21

wave and incident wave has a ratio ei K r . The crystal is consist of many
identical atoms so that we give j to index each scatterer. A little tweak is
made on above equation and we can get

E out = E in ei K rj

(22)

If there are n atoms in the lattice. Accordingly, the electric field of outgoing
beam will be the sum of the electric fields of all the scattered wave from n
scatterers. Then we can get the electric field of outgoing beam
n

j i

E in e K rj
E out =

(23)

j=1

E in is a constant complex number because of identical atoms so that it can

be factored out. Then we can get
n

ei K rj
E out = E in

(24)

j=1

The structure factor SK is then defined as

n

ei K rj
SK =

(25)

j=1

What information does the structure factor tell us? It is better to answer this
question by looking some examples. We are going to calculate the structures
factors of a bcc lattice to see the importance of the structure factor.[3]

Structure factor of the bcc lattice

The bcc cubic cell has identical atoms at position

r 1 = 0
x +0
y +0
z
22

Table 2: Forbidden reflection in Miller indices

and
r 2 = 21
x + 21
y + 21
z . insert them into Eq.27 and it becomes
SK = 1 + exp[i(h + j + k)]

(26)

Provided that K = h b + j b2 + k b3 . Furthermore, we could get

SK = 0 when h + j + k = odd number
SK = 2 when h + j + k = even number
Notice that when S = 0, the electrical field of outgoing beam is zero.
This means there is no diffraction on plane (hjk) if h + j + k =
odd number. This is called forbidden reflection condition.

Generally, to apply such a analysis to the other lattice types. We can get the
forbidden reflections for them. They are included in Table.2 The forbidden
reflection is very useful for analyzing the crystal structure as it can tell the
crystal type from the X-ray diffraction experimental results

23

Atomic Form Factor

In the previous section , one of the important assumption we made is that
the crystal has a monochromatic lattice with identical points everywhere. If
the lattice points are not identical with different atoms attached, then the
electric field of the diffracted wave will be different for different point due to
different scattering power. Therefore, the structure factor has to be modified
as[3]
SK =

n
X

fj ( K )ei K rj

(27)

j=1

fj is called the atomic form factor. Without detailed prove, It can be calculated through
1

fj ( K ) =
e

d
r ei K r j (
r)

(28)

The atomic form factor is said to be proportional to the Fourier transform

of the charge distribution of the corresponding ion (the basis attached to the
lattice point). The X-ray diffraction experimental results (give a citation)
between powder KCl (Potassium Chloride) and KBr (Potassium Bromide)
give the best visual illustration to explain the structure factor and the atomic
form factor. First of all, KCl and KBr both have the same crystal structure,
which is given in Fig. 12 [3]. In the picture, the iron with larger mass is
assigned to a larger atom. Thus, for KCl, the green atom is K+ and the blue
one is Cl- while for KBr, such an assignment is just opposite. Now, if we
discard the blue atoms, then the rest green atoms form a perfect fcc lattice.
24

Figure 12: Crystal structure of KCL and KBr

Then, if we discard the green atoms, then the red atoms form a fcc lattice as
well. Assume the lattice constant of fcc it is a. Then, the structure can be
considered as two fcc lattice interlacing with each other by a translation of
a
.
2

The X-ray experimental result is show in Fig.13 [3]. Two comments can

be made by this comparison of the result.

In KCl, the density of electrons of K+ and Cl- are equal and the atomic
form factor fK + fCl . Therefore, it looks like a sc lattice of lattice
constant

a
2

which has identical atom everywhere. Therefore, the X-

ray diffraction result is similar to the result from a sc lattice while only
even integers appears because the actual lattice constant is a.
On the viewpoint of forbidden reflection given in Table.2, Bragg reflec25

Figure 13: Comparison of X-ray reflections from KCl and KBr

tion can not arise in a fcc lattice if the indices are mixed with odd and
even number. In KBr, the atomic factors of K+ and Br- are quit different. The result shows that the indices only contain all odd numbers or
even numbers, implying that this is actually a fcc lattice.

Therefore, the comparison of experiments qualitatively explains the structure

factor and atomic form factor. Basically, for the material with unknown crystal structure, its lattice type can also be told by matching the experimental
X-ray to the experimental results of the typical lattice types.

26

Shape Factor
Ideally, the Bragg diffraction should reflect as a delta peak in the experiment
result only of the crystal is infinitely large. However, in realistic experiment
based on Debye-Scherrer method, the Bragg diffraction peak is broadened.
This is mainly due to the smaller crystal size. Therefore, the Bragg equation
must be modified in order to deal with this finite size effects. Therefore,the
Scherrer Formula is given as a modified formula in X-ray science:[7]
Dhjk =

W
Bhjk cos(hjk )

(29)

Dimensionless W is the shape factor , B is the line broadening at half the

maximum intensity (FWHM ) in radian and is the Bragg angle. Therefore,
we get a mean size of crystalline distance D. In the original paper written by
Schnerrer, the shape factor W is approximately equal to 0.93. The Schnerrer
equation also has it limitation. Mainly, they are

Schnerrer equation is only applicable for the crystallite size short than
0.1um.
It does not include the other effects which may broaden the line-width
of the peak as well,such as inhomogeneous strain or instrument effects.

27

Part II

Electron Diffraction Technique

Apart from the traditional X-ray diffraction, the particle such as electron
can also exhibit wave-like behavior, so called particle-wave duality. The
application of the electron diffraction was first sparked by the famous the
Debrogie hypothesis:
=

h
p

(30)

where h is the Planck constant and p is linear momentum. Therefore, when

comes to crystallography, the electron diffraction theory should be very close
to the X-ray diffraction theory and this means that the general rules such as
Bragg law, Laue condition can apply for both of techniques. However, it is
also worth mentioning the differences between them in order to understand
how the electron diffraction technique evolved from the X-ray diffraction one.
These differences can be concluded as:

The wavelength of electrons (e.g. 2pm for 300keV electron, obtained

by the above equation)is much shorter than that of X-rays (typical
value around 100pm). Therefore, the electron diffraction Technique
can complement X-ray diffraction for studying even smaller objects

28

 The X-ray is scattered by the electrons in the material under test to

yield the information of atomic structure. On the other hand, the
electron is primarily scattered by the nuclei, which carry the direct
information of atom location. The interaction strength of the latter
technique is dramatically larger (> 105 ) than that of the former one.
Therefore, the diffracted electron beam has much higher intensity than
diffracted X-rays which allow us observe better experimental results.
However, one should also notice that not only the stronger elastic scattering presents in the electron diffraction but also does the inelastic
scattering due to phonon, plasmon excitation as well as Coulomb interaction. The deeper the electron beam travels through the material, the more inelastic scattering it produces. Therefore, The electron
diffraction is very used to study the structure of the surface, another
advantage over X-ray diffraction because X-ray will most of time penetrate through a thin layer without strong interaction. The inelastic
process in the electron diffraction can be quantitatively described by
the penetration depth equation which is given by

I(d) = I0 exp(

d
)
(E)

(31)

I is the intensity with respect to the propagation distance d.(E) is

the penetration depth, defined as the distance an electron can travel
before its intensity has decreased by the factor 1e .
29

Figure 14: Bragg condition for electron beam diffraction

Mainly, there are two popular techniques associated with the electron diffraction. One is called low-energy electron diffraction (LEED) and the other one
is called reflection high-energy electron diffraction (RHEED). Before we introduce them, a simple theoretical background of surface science is given.
The Bragg condition is basically no different from X-ray diffraction except
that we are more concerned about the surface structure instead of a set of
parallel planes. The Bragg condition is illustrated in Fig.14 [5].The only
change is that d is the interval of a set of points instead of parallel planes (a
citation here). Second, as we did not mention in the previous, the Bravais
lattice is not only defined in 3-D but also in 2-D. There are five distinctive
types of Bravais lattice, Listed in Table.3 [8].To name the planes, the Miller
indices (hjk) is still used,shown in Fig.15 [8]. In Fig.5, fcc(100) is the (100)
face of an fcc structure and fcc(111) is the (111) face. (1 1) is the primitive
mesh of the substrate layer (shown as green atoms) while (2 2) are the
30

Table 3: 2-D Bravais lattice

Figure 15: Notation of 2-D Bravais planes

31

primitive mesh of red atoms with doubled magnitude. c(2 2) is centered

mesh. R300 denotes a rotation of 30 degree. A compact notation is written
as X(hjk)m nR.

Surface Reconstruction

In the surface science, one usually is involved with growing a single layer with
one type of lattice on top of a substrate layer with another type of lattice.
For example, Molecular beam epitaxy (MBE) is the method to deposit layer
by layer to make a semiconductor device. Surface reconstruction happens
when the newly deposited layer has a different structure as shown in Fig.15
where deposited layer (red atoms) has a different lattice compared to the
substrate (green atoms). Therefore, the rearrangement of the atoms will
introduce a new set of primitive vectors. Finding the new set of primitive
vectors with respect to the reference plane is called surface reconstruction.
Typically, the reference plane is the substrate. For example, if the primitive
mesh of substrate is a1 a2 and the primitive mesh of new layer on top is
b1 b2 shown in Fig.16[8], then we can find a matrix G satisfy
(

a1
a2

)=(

G11 G12
G21 G22

)(

b1

b2

Therefore, the surface reconstruction is described by matrix G.

32

(32)

Figure 16: Surface reconstruction

LEED

Indicated by its name, LEED is diffraction method to determine the surface structure with low energy electrons (typically from 20 to 200eV). The
schematically experimental setup is illustrated in Fig.17 [2] .

1. The experiment is conducted in a ultra-high-vacuum (UHV) chamber

in order to avoid the unwanted absorption and diffraction by the atoms
in the air.
2. The sample must be well prepared,more specifically, to form a clean
surface. The containments on the surface can be removed by ion sputtering or by chemical process [2].
3. Electrons are emitted from a electron gun and then accelerated by
the external electrical field created by a series of electrodes. These
electrodes are not drawn in the picture. The energy of electrons can be
tuned by these electrodes. Thus, through a hole which has normally
33

Figure 17: Schematic of LEED

has the same size as the samples, the electron beam impinges on the
surface and the diffracted electron beam is detected by the florescent
screen for direct eye viewing. A demonstration of such a screen is given
in Fig.18.
4. Before collecting the diffracted beam, a LEED system normally contains several hemispherical concentric grids. These grids play an important role on receiving clean image by blocking the inelastically scattered electrons. The first grid, closest to the sample, is used to filter out
the non-spherical field from the retarding field. the second and third
grids(drawn as one grid as they are very close to each other), known
as suppressor grids is for blocking the low-energy electron in order to
34

Figure 18: An example of LEED pattern of Si(100)

make the diffracted electrons more homogeneous. The fourth grid(not
drawn in this picture as it is attached to the screen is for electronically
reading out the signal[2].
5. The screen directly reveals the result through the fluorescence effect.

The Ewald construction for LEED method is given in Fig.19 [10].

10

RHEED

Differing from LEED, RHEED typically operates with much higher-energy

electrons (>1keV) so that it can cause more inelastic reflection. It is necessary to work in grazing incident angle to avoid vertical penetration. The
35

Figure 19: Ewald construction for LEED method in one dimension

experimental setup is shown in Fig.20 [9]. A electron gun shoots high-energy
electron beam in a grazing angle (about 1 degree). Also same as LEED, a
fluorescent screen is set up for recording the diffracted electron beam. Ideally, if the sample has a perfect flat surface, the diffracted electron beams
should be reflected as an array of bright spots on the screen. However, due
to irregularity and defect on the surface, the received electron beams become
so-called streak pattern, an array of elongated spots. A real case of streak
pattern as an example is give in Fig.21 This streak can be also explained by
Ewald construction. An ideal Ewald construction is shown in Fig.22 . Therefore, we can see that the reciprocal lattice vector intercept with Ewald sphere
about a point. However, for a rough surface, the Ewald sphere is broadened

36

Figure 20: Schematic experimental setup of RHEED

Figure 21: Real case streak pattern of TiO2

37

Figure 22: Ewald construction of RHEED method

so that the resulted interception becomes a elongated lines instead of points.
This is the reason for the formation of streak pattern.
One of the biggest breakthrough of RHEED is the capability of real-time
monitor for crystal layer growth in molecular beam expitaxy (MBE). It refers
to the oscillation of the specular beam intensity as a function of time during
MBE growth. The reason for the occurrence of the oscillation is given in
Fig.23 [4]. Ideally, we have a clean and smooth surface so that the we get
maximum intensity of the diffracted beam. Then the new layer starts growing
in MBE. When = 0.25, a few atoms land or become localized on the surface
so that the electron beam is defocused due to the imperfection of the layer.
Therefore, the intensity of the diffracted beam drops as shown in the figure.
When = 0.5, the new layer become half-complete and most imperfect so
that the intensity drops down to the valley. However, when the new layer
keep growing, the surface becomes more complete so that the electron beam

38

Figure 23: Formation of a single compete monolayer and intensity oscillation

of the diffracted electon beam where is monolayer completion fraction

39

Figure 24: Typical RHEED oscillation during the deposition of GaAs on a

GaAs(001) substrate
becomes more focused until the entire monolayer is finished and the intensity
recover back to the maximum. As a result, one can say that the oscillation
period (one cycle) is equal to the time required to deposit one monolayer. An
experimental result of a RHEED oscillation is given in Fig.24 [6]. One can
notice that a damping occurs to the oscillation. From the previous analysis,
we assume a perfect monolayer is formed. However, in Fig.24, When growing
GaAs, the newly deposited layer becomes rougher and rougher as the grows
continue. This is normally associated with the defect on the surface such as

40

a void, missing atoms, mismatch and so on.

Part III

Conclusion
In this report,we give an introduction to the diffraction theory and its applications: X-ray diffraction, LEED and RHEED. This review is by no means
complete. However, one should learn that the diffraction technique is a powerful method to study the periodic structure. The geometrical structure of a
crystal may seem to be very complicated but its reciprocal space is straightforward when it deals with diffraction theory.Besides, lots of mathematical
prove in this report is oversimplified and lack of auxiliary diagrams due to
the scope of discussion. One should look up other literature about solid-state
physics in order to gain deeper insight on this topic. At last, thanks for Prof.
R. Lapierre for his kind help.

References
[1] Neil W. Ashcroft and N. David Mermin. Solid State Physics. Brooks
Cole, 1976.
[2] California Institute of Technology. Surface Science Laboratory : Low
Energy Electron Diffraction. 2009.
41

[3] Charles Kittel. Introduction to Solid State Physics. Wiley, 1995.

[4] Milton Ohring. Materials Science of Thin Films, Second Edition. Academic Press, 2001.
[5] Dirk Rosenthal. Surface crystallography. 214(1991), 2008.
[6] S. Martini,Quivy A. A. In-situ determination of indium segregation in
InGaAs/GaAs quantum wells grown by molecular beam epitaxy. Brazilian Journal of Physics, 2002.
[7] Detlef-M Smilgies. Scherrer grain-size analysis adapted to grazingincidence scattering with area detectors. Journal of applied crystallography, 42(Pt 6):10301034, December 2009.
[8] Lund University. Surface crystallography.
[9] B. K. Vajn. Structure analysis by electron diffraction. Nuovo Cimento
(Italy) Divided into Nuovo Cimento A . . . , 3(S4):773797, April 1956.
[10] MA VanHove, WH Weinberg, and CM Chan.
diffraction, volume 214. 1986.

42

Low-energy electron