Fundamentals of diffraction

Geometry of crystal lattices

The crystalline lattice is a periodic arrangement of atom or molecules. In the crystals the most
important symmetry element is the translation symmetry. The vector connecting two
points of the lattice is called lattice vector. All lattice vectors can be expressed as the whole
number linear combination of the elemental lattice vectors (fig.1):

where the n1,n2,n3 coefficients are whole numbers.

The parallelepiped determined by the elemental lattice vectors is the unit cell of the crystal.

   
R1  a1  a2  2a3

a3


a2    

a1
R2  a1  2a 2  a3

Fig.1.

The unit cells shifted by lattice vectors fill the space wholly. This is called as Bravais lattice.
The V0 volume of the unit cell is determined by the following expression:

To this real physical lattice we can order a mathematical lattice, the so called reciprocal
lattice. The definition of the elemental reciprocal lattice vectors is the following:

The formulas are symmetric, we can express similarly the elemental lattice vectors of the real
lattice by the elemental reciprocal lattice vectors:
where the volume of the reciprocal unit cell is:

In case of an orthorhombic lattice determined by the elemental lattice vectors the

volume of the unit cell is . (Orthorombic lattice: the elemental lattice vectors are
perpendicular to each other, their lengths are different.)
The lengths of the elemental reciprocal lattice vectors:


a3


 b3
a2

  
a1 b1 b2
Fig.2.

This is the origin of the reciprocal lattice appellation.

The following relation is generally valid for the scalar products of the elemental lattice
vectors and the corresponding elemental reciprocal lattice vectors:

It can be verified in the following way:

Here we used the rule for the triple product:

The vector connecting two arbitrary lattice points of the reciprocal lattice is called as
reciprocal lattice vector. The reciprocal lattice vectors can be expressed as whole number
linear combination of elemental reciprocal lattice vectors:

where are whole numbers.

Properties of reciprocal lattice vectors

Planes in the crystal consisting of lattice points are called lattice planes.
A lattice plane with normal vector can be represented in the coordinate system
with the c1,c2,c3 distances at which the plane crosses the axis of the coordinate system.

c3


n

a3

a2
 c2
a1

c1

Fig.3.

The numbers are whole numbers because the lattice plane has to cross the axis
at lattice points. In that case if the lattice plane is parallel to axis the corresponding c crossing
point is in the infinity. The handling of this quantity is mathematically difficult, so in the
practice we use the reciprocal value of the former expression. The planes parallel to the axis
are characterized by 0 in this case, but the other planes are characterized not whole numbers.
Multplying the numbers with an appropriate Z whole number we get the h,k,l
whole numbers. We have to choose that Z value which results the lowest possible h,k,l whole
numbers.
The h,k,l numbers are called as Miller-indices.
In the following calculations is more convenient to use K1,K2,K3 instead of the conventional
h,k,l notation:
Let’s see the reciprocal lattice vector. There are two important thesis connecting
to this:

a) is perpendicular to the planes characterized by the K1,K2,K3 Miller-indices.

b) The d distance between the parallel K1,K2,K3 planes is equal to the reciprok absolute value
of :
We can justify statement a) if we show that the dot products of and two linearly
independent vectors in the K1,K2,K3 plane are 0.

The odds of és a vectors is in the K1,K2,K3 plane:

vector is linearly independent of and laying in plane K1,K2,K3. This vector is

also perpendicular to as we can justify similarly.

To justify statement b) let’s see the dot product of the normal vector of the K1,K2,K3 plane
and the above mentioned vector.


n


a3 
a1

c1
Fig.4
According to fig.4 this dot product is equal to the d lattice plane distance.

We can use the above relation for the case of the orthorhombic lattice:

In case of cubic lattice:

In the crystallography we use the following notations:

the assembly of planes characterized by all possible permutations (sequence and

sign) of Miller indices.
a specific plane characterized by the h,k,l Miller-indices
the assembly of directions characterized by all possible permutations (sequence and
sign) of Miller indices.
a specific direction characterized by the h,k,l Miller-indices

Diffraction in crystallographic lattices

The incoming wave is characterized by the complex wave function. In

the following we take into account only the space variable dependent part ( )

of the wave function because our detectors are producing the time average of the I intensity,
which is the perceptible quantity of the wave. It is proportional to the square of the A
amplitude, and can be calculated for complex wave functions in the following way:

The incoming wave characterized by the wave is scattered elastically on the scattering
centres placing at the positions in the material. The elastic scattering means

that the energy (and the wavelength) of the scattered wave is not changed : .
  
R  Rj
λ
P
λ
 
R1 k

 Ri
k0

 R
R2


R3
Fig.5.

The incoming wave excites the scattering centres (atoms) and the amplitude at the i-th centre
is:

where fi is the atomic scattering factor, a material dependent quantity which shows the
scattering ability of the atom.
In the P observation site this results a wave:

The amplitude of the above wave is:

The whole group of N atoms results a scattered wave at P with amplitude:

The scattering vector has 1/m dimension so we can represent it in the reciprocal
space as a linear combination of the elemental reciprocal lattice vectors:

In this case the ci coefficients are not inevitably whole numbers.

If the incoming wave scatters on a crystal the scattering centres are in lattice points. in this
case the vectors are lattice vectors and can be produced as whole number linear
combinations of the elemental lattice vectors:

where the coefficients are whole numbers.

In case of primitive lattices the scattering centres are individual atoms in the lattice points.
The above expression has a maximum (and real) value if the expression is a whole

number. In general will be whole number if all of the ci coefficients are whole
numbers.
This means that the scattering vector has to be equal to a reciprocal lattice vector:

This is the Bragg equation in the reciprocal space.


k

θ   
k0  k  g
d


k0

Fig.6.

According to fig.6 :
Using the following relations: we get the well-known form of the Bragg-
equation in the direct space:

In case of non-primitive (centred) crystals the unit cell contains more (Z) atoms. The position
of the m-th atom in the i-th unit cell is given by the vector. The amplitude of the
scattered wave:

If the Bragg condition is satisfied then

The expression is the scattering factor of the unit cell.
As an example calculate the scattering factor of the face centered cubic (f.c.c.) unit cell. The
unit cell contains 4 atoms (fig.7). In the coordinate system of the elemental lattice
vectors the positions of the atoms:


r2

r3

r4

r1

Fig.7.
Supposing that the atoms in the unit cell are identical (the atomic scattering factors are equal
f1=f2=f3=f4=f) the scattering factor of the unit cell:

The maximum value of the scattered amplitude will be observed if all h, k, l indices are odd or
all h, k, l indices are even. These reflexions are the allowed reflexions.
If the Miller-indices are mixed (there are odd and even numbers between them) the resultant
amplitude will be 0 even in that case if the Bragg condition is satisfied. These are the
forbidden reflexions.
These are the so called selection rules. Similar selection rules can be derived for all centered
lattices.

The Ewald construction

In case of elastic scattering k=ko =1/λ. The directions of the maximum intensity waves
can be determined by graphical representation of the Bragg equation. This is the
Ewald construction.
Plot the reciprocal lattice of the investigated material as the first step. One end of the
incoming wave vector is placed into a reciprocal lattice point (fig.8). Around the other
end of we construct a sphere with ko radius. Where this sphere crosses a reciprocal
lattice point in that directions the Bragg-law satisfies and maximum intensity can be
observed.
 Fig.8.

In case of electron diffraction the wavelength is very short and the length of wave vector is
very long. At 100kV accelerating voltage the wavelength is 0,04Å and the usual values of
lattice plane distances are few Å. This means that in the reciprocal space the radius of the
Ewald sphere is very long relative to the reciprocal lattice distances. At the usual small
observation angles the curvature of the Ewald sphere is negligible and the Bragg condition is
satisfied in a plane of the reciprocal lattice. This plane is perpendicular to .

Polikristályos anyag esetében a beeső elektronhullám nem egy egykristályon hanem

egymáshoz képest véletlenszerű (random) kristálytani irányokban elhelyezkedő krisztallitok
sokaságán szóródik. Egy ilyen random polikristályos anyag reciprokrácsát ugy
szerkeszthetjük meg, hogy az anyag kristályrendszerének megfelelő reciprokrácsot annak egy
pontja körül a tér minden irányába megforgatjuk. Ekkor a reciprokrácspontok koncentrikus
gömbfelületeket írnak le a térben. Ezeknek a koncentrikus gömböknek a halmazát tekintjük a
random polikristályos anyag reciprokrácsának. A beeső ko hullámszámvektort úgy vesszük
fel, hogy az végpontjával a gömbhalmaz középpontjába mutasson. A korábbiak alapján
tudjuk, hogy a diffrakciós kép a reciprokrács egy síkmetszete lesz, ami jelen esetben
koncentrikus körök formájában jelenik meg a mikroszkóp megfigyelőernyőjén.
Az elektrondiffrakciós képek gyakorlati kiértékelése az alábbi meggondolások alapján
történhet:
Mivel elektrondiffrakció esetén az igen rövid hullámhossz miatt a Bragg-egyenletben szereplő
θ szög igen kicsi (0,01rad) ezért a következő közelítés alkalmazható:

2dsinθ2dθ=λ

Az ábrán látható geometria szerint ez a λ=dR/L alakba írható ahol L a minta és a képernyő
távolsága, R pedig a mintán eltérülés nélkül áthaladó központi nyaláb és egy kiválasztott (hkl)
Miller-indexekkel jellemezhető reflexió ernyőn mért távolsága. Tekintettel arra, hogy az R
távolság a gyakorlatban nehezen mérhető kellő pontossággal (a központi nyaláb pontos
helyzetét nehéz meghatározni mert a nagy intenzitás miatt a fényképek közepe általában
túlexponált) célszerűbb helyette a (hkl) és a (-h-k-l) reflexiók D távolságával számolni, ami R
kétszerese. Ezt behelyettesítve az előbbi egyenletbe átrendezés után az elektrondiffrakció
gyakorlati alapegyenletéhez jutunk:

dD=2Lλ (8)
A jobboldali szorzat csak a mikroszkóp jellemző adatait tartalmazza és ezért célszerű egy
mennyiségként kezelni, amit a továbbiakban kamerakonstansnak vagy gépállandónak (K)
fogunk nevezni. Mivel L és λ értéke a mikroszkóp pillanatnyi állapotától függ ezért célszerű
K értékét hitelesítő méréssel meghatározni. Ennek során ismert kristályszerkezetű
polikristályos anyagról (legyakrabban Au, MgO vagy más egy kristálymódosulattal
rendelkező kémiailag stabil anyag) határolt területű diffrakciós képet készítünk, amelyen
megmérjük az egyes reflexiókhoz tartozó D távolságokat, vagyis a diffrakciós képen látható
körök átmérőit. Ezeket megszorozzuk a hozzájuk tartozó d rácssíktávolságokkal. Ekkor a
szorzatoknak mérési hibahatáron belül ugyanazokat a K értékeket kell szolgáltatni. A
továbbiakban ezek átlagát tekintjük a gépállandó értékének. A számításhoz szükséges d
értékeket pl. a röngendiffrakciós adatbázisból (ASTM) szerezhetjük be.

Valamely polikristályos anyag szerkezetének az azonosításához első lépésként meg kell

mérnünk a diffrakciós képen látható gyűrűk D átmérőit amelyekből a gépállandó ismeretében
kiszámíthatjuk az anyagra jellemző d rácssíktávolságokat. Ezeket irodalmi adatokkal
összehasonlítva lehetőségünk van az anyag azonosítására. Ha ez nem lehetséges, akkor meg
kell próbálkoznunk a kristályszerkezet meghatározásával illetve a rácsparaméterek
kiszámításával.