T3 – Structure Factor, X-Ray Diffraction

1. Structure factor
One can think of scattering from a crystal as scattering from a periodic potential:

𝑉 (𝑥) = ∑ 𝑓𝑗 𝛿(𝑥 − 𝑥𝑗 ) [1.1]

𝑎𝑡𝑜𝑚𝑠 𝑗

Where 𝑥𝑗 is the position of the j th atom in the unit cell and 𝑓𝑗 is the atomic form factor which
represents the different scattering amplitude.

The Fourier transform yields the structure factor:

−
𝑆(𝐺) = ∫ 𝑑𝑥𝑒 𝑖𝐺·𝑥 𝑉(𝑥) [1.2]
𝑢𝑛𝑖𝑡 −𝑐𝑒𝑙𝑙

Where G is a reciprocal lattice vector.

Plugging the potential from [1.1] into [1.2] reads:

𝑆(𝐺) ≈ ∑ 𝑓𝑗 𝑒 𝑖𝐺·𝑥𝑗 [1.3]

𝑎𝑡𝑜𝑚 𝑗 𝑖𝑛 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

or in a more explicit way:

𝑆(ℎ𝑘𝑙) = ∑ 𝑓𝑗 𝑒 2𝜋𝑖(ℎ𝑥𝑗+𝑘𝑦𝑗 +𝑙𝑧𝑗 ) [1.4]

𝑎𝑡𝑜𝑚 𝑗 𝑖𝑛 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

As already discussed in the course, the scattering from a lattice is strongly related to its
Fourier transform. The intensity of scattering will be proportional to the structure factor:

2
𝐼ℎ𝑘𝑙 ∝ |𝑆(ℎ𝑘𝑙) | [1.5]

For example, let's say that we wish to calculate the x-ray diffraction, specifically for the
family of planes defined by Miller indices (00𝑙).

For (00l) we have h = k = 0 so we obtain:

𝑆(00𝑙) = ∑ 𝑓𝑗 𝑒 2𝜋𝑖(𝑙𝑧𝑗) [1.6]

𝑎𝑡𝑜𝑚 𝑗 𝑖𝑛 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

And:

𝐼ℎ𝑘𝑙 ∝ | ∑ 𝑓𝑗 𝑒 2𝜋𝑖(𝑙𝑧𝑗 ) | [1.7]

𝑎𝑡𝑜𝑚 𝑗 𝑖𝑛 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

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In order to be more concrete, let's talk about specific lattices:

Structure factor of cubic structures (SC/FCC/BCC)

Previously, we saw that the reciprocal lattice of FCC is BCC and vice versa. This result is
valid, but in finding the structure factors of cubic lattices we will have to take a slightly
different approach. Remember that we described the FCC/BCC using a convenient unit cell
that has more than one lattice point (BCC has 2, FCC has 4). When calculating the structure
factor, we don’t want to miss atoms. Here, we will decompose the FCC/BCC convenient unit
cell to consider all atoms in the unit cell. Each lattice (SC/FCC/BCC) will be characterized
using SC lattice+basis.

SC

In this approach, the SC has 1 atom at (0,0,0). The potential:

𝑉 (𝑥) = ∑ 𝑓𝑗 𝛿(𝑥 ) [1.8]

𝑎𝑡𝑜𝑚𝑠 𝑗

And the structure factor:

𝑆(ℎ𝑘𝑙) = 𝑓 [1.9]

For the SC lattice we have the same scattering intensity for every (ℎ𝑘𝑙) plane!

BCC

Figure 1 - BCC

The bcc structure can be generated using a SC lattice with a two-atom basis.

1 1 1
First atom at (0,0,0) and the second atom at (2 , 2 , 2). Both atoms are identical so they have

the same scattering factor, 𝑓.

The structure factor:

2
 1 1 1
2𝜋𝑖(ℎ +𝑘 +𝑙 )
𝑆(ℎ𝑘𝑙) = 𝑓𝑒 2𝜋𝑖(ℎ0+𝑘0+𝑙0) + 𝑓𝑒 2 2 2 = 𝑓(1 + 𝑒 𝜋𝑖(ℎ+𝑘+𝑙) ) [1.10]

For the lattice plane (00l) we have h = k = 0 so we obtain:

𝑆(00𝑙) = 𝑓(1 + 𝑒 𝜋𝑖(𝑙) ) [1.11]

And we got:

2𝑓 ; 𝑙 = 𝑒𝑣𝑒𝑛
𝑆(00𝑙) = { [1.12]
0 ; 𝑙 = 𝑜𝑑𝑑

This result, of course, can be generalized:

2𝑓 ; ℎ + 𝑘 + 𝑙 = 𝑒𝑣𝑒𝑛
𝑆(ℎ𝑘𝑙) = { [1.13]
0 ; ℎ + 𝑘 + 𝑙 = 𝑜𝑑𝑑

FCC

Figure 2 – FCC

The FCC structure can be generated from a SC lattice with a four-atom basis.

1 1 1 1 1 1
First atom at (0,0,0), second atom at (0, 2 , 2), third at (2 , 0, 2) and fourth at (2 , 2 , 0). All

atoms are identical so they have the same scattering factor, 𝑓.

The structure factor:

𝑆(ℎ𝑘𝑙) = 𝑓(1 + 𝑒 𝜋𝑖(ℎ+𝑘) + 𝑒 𝜋𝑖(𝑘+𝑙) + 𝑒 𝜋𝑖(ℎ+𝑙) ) [1.14]

So:

4𝑓 ; ℎ, 𝑘, 𝑙 𝑎𝑙𝑙 𝑒𝑣𝑒𝑛/𝑜𝑑𝑑
𝑆(ℎ𝑘𝑙) = { [1.15]
0 ; ℎ, 𝑘, 𝑙 = 𝑚𝑖𝑥𝑒𝑑 𝑒𝑣𝑒𝑛/𝑜𝑑𝑑

2. X-Ray diffraction
Ex1 (from exam):

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 Figure 3- X-Ray Diffraction Results. Intensity as function of illumination angle.

The above measurements are the results of an x-ray experiment at a wavelength of 1.54A (2𝜃
is the scattering angle). The sampled structure is cubic. Determine which structure is it
(SC/FCC/BCC) and decide whether the sample is Tantalum (Ta) or Tungsten (W).
*The lattice constant of Ta is 3.3A and the lattice constant of W is 3.15A.
** Use the following relation (Miller indices and lattice planes in cubic structures) –

1 ℎ2 + 𝑘 2 + 𝑙 2
= [2.1]
𝑑2 𝑎2

Where 𝑎 is the lattice constant, 𝑑 is the distance between lattice planes, ℎ, 𝑘, 𝑙 are the Miller
indices of this plane.

Solution:

From Bragg law:

𝑛𝜆
𝑠𝑖𝑛𝜃 = [2.2]
2𝑑

So:

𝑛2 𝜆2
sin2 𝜃 = [2.3]
4𝑑2

From the given relation [2.1]:

𝑛2 𝜆2 ℎ2 + 𝑘 2 + 𝑙 2
sin2 𝜃 = [2.4]
4 𝑎2

The ratio between 2 scattering angles, 𝜃1 𝑎𝑛𝑑 𝜃2 , is given by:

sin2 𝜃2 ℎ2 2 + 𝑘22 + 𝑙22

= 2 [2.5]
sin2 𝜃1 ℎ1 + 𝑘12 + 𝑙12

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We know that not all h,k,l values are acceptable for every lattice type. For BCC, the sum
h+k+l must be even, and for FCC, hkl must all have the same parity. The following table
counts all the possible states:

Figure 4- Possible hkl values

Now, let's go back to the XRD results. [2.4] gives us the relation between the scattering
angles and the Miller indices whereas [2.5] gives us the relation between two measured
angles. Figure 5 holds together all the measured 2𝜃 values together with the squared sine
value of each angle.

Figure 5 – XRD results

0.1085 is the smallest value measured (ratio=1). Every other value, is an integer multiple of
this value (ratio =2,3,4...). The rightmost column shows the (ℎ, 𝑘, 𝑙) values corresponding to
each measurement so that the ratios are obtained according to [2.5].

Note that we assumed that the first peak is given for (1,1,0) and not for (1,0,0). If (1,0,0) is
indeed the first peak, we must have another peak for (hkl) indices satisfy:
ℎ2 + 𝑘 2 + 𝑙 2
= 7 → ℎ2 + 𝑘 2 + 𝑙 2 = 7 [2.6]
12 + 02 + 02

Which is impossible! Hence, there is no peak for (100) which means that SC is no longer an
option.
From figure 5, it's clear that the measured crystal is BCC (compare to figure 4 and see that
FCC is impossible as well).

Now we have to calculate 𝑎 –

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We can use [2.1] again:

𝑎2 = 𝑑2 (ℎ2 + 𝑘 2 + 𝑙 2 ) [2.7]

From Bragg term:

𝜆
𝑑= [2.8]
2𝑠𝑖𝑛𝜃

Figure 5 holds combinations of (hkl) and the corresponding 𝜃. Let's choose (1,1,0) and
2𝜃 = 38.46 and plug these values into [2.7] and [2.8]:
From [2.8]:
𝑑 = 2.33𝐴 [2.9]

And into [2.7]:

𝑎2 = 2.322 (1 + 1) → 𝑎 = 3.3𝐴 [2.10]

This 𝑎 values matches the given value of Ta!