PC3193 summary X-ray Crystallography of sample 5

PC3193 summary 1: X-ray Crystallography of sample 5

Lim Zheng Liang

A0137567U/E0001040

The crystal structure of sample 5 was analysed by investigating the X-ray diffraction spectrum
produced from irradiation of the sample with the Kα x-ray of a copper source. The lattice structure
was found to be face-centered cubic and has a lattice constant of (3.6160 ± 0.0006)Å. Upon close
inspection, the data seems to suggest that the sample is copper.

I. INTRODUCTION

The smallest group of particles in the material that

constitutes the repeating pattern is the unit cell of the
structure. The unit cell completely defines the symme-
try and structure of the entire crystal lattice. The unit
cells stacked in three-dimensional space describe the bulk
arrangement of atoms of the crystal. The unit cell is
represented in terms of lattice parameters or the lattice
constant. The crystal planes is described by the Miller
indices; introduced by William Miller.
In this experiment, we want to determine the crystal
structure the sample by investigating its X-ray spectrum
and working out the Miller indices for the three cubic
structure; simple cubic (SC), face-centered cubic (FCC)
and body-centered cubic (BCC). In addition, we seek to
qualify the lattice parameter and identify the element of
the sample.

FIG. 1. A schematic diagram of the de-excitation of elec-

II. THEORY trons from the 2P3/2 , 2P1/2 and 3P orbital, to the ground
state, producing the Kα1 , Kα2 and Kβ radiation respectively.
A. X-rays and Kα radiation Adapted from [1].

When high energy electrons bombard onto the metal

anode, it produces bremsstrahlung, or braking radiation
and the characteristic radiation; where the latter has a
much higher intensity than the former. The character-
isti x-ray emission ccur when vacancies are produced in
the n=1 or the K-shell of the atom and electrons de-
excites to fill the gap. In particular, the Kα radiation is
emitted by the transition from the L(n = 2) shell to the
K(n = 1) shell. However, due to spin orbit coupling, the
2P3/2 orbital has a higher energy than the 2P1/2 orbital FIG. 2. A Schematic diagram of X-ray diffraction by a crystal
and hence, two different Kα radiaiton can be produced, where 2θ is the scattering angle. Adapted from [4].
namely Kα1 and Kα2 as shown in figure 1.

where θ is half of the scattering angle, d is the distance

B. Diffraction and crystal structures
Diffraction occurs when the incident X-rays which has
a wavelength that is larger than the lattice spacing, in-
teracts with the electron density distribution of the crys-
tal lattice structure upon reaching its surface. Complete
constructive interference pattern occurs when,
between the crystal planes and λ is the wavelength of the
incident X-ray. This is known as the Bragg’s law. On the
other hand, complete destructive interference occurs if n
is half of odd integers. In general, for a plane with Miller
indices (h,k,l), the planes are spaced by an amount given
by,

a
d= √ (2)
2dsinθ = nλ, n ∈ Z (1) h2 + k 2 + l2

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PC3193 summary X-ray Crystallography of sample 5

Here, a is the lattice parameter. Intensity of x-ray

that scatters from planes with lower Miiler indices is
greater as they have a higher density of atoms. In
solid state physics, there are three conventional cubic
crystal strucutre, namely the simple cubic (SC), the
face-centered cubic (FCC) and the body-centered cubic
(BCC) [2]. Their sequential values of (h2 + k 2 + l2 ) are
given by,

• SC: 1,2,3,4,5,6,8,...
• BCC: 2,4,6,8,10,12,14,...
• FCC: 3,4,8,11,12,16,19,... FIG. 3. Linear graph of X-ray diffraction spectrum of Inten-
sity (count per second; cps) vs 2θ for V=40kV.
Moreover, combining (1) and (2) yields,

λ2 2
sin2 θ = (h + k 2 + l2 ),
4a2√ (3)
λ h2 + k 2 + l2
a= .
2 sin θ
2
λ
Since 4a 2 is a constant for any crystal structure, one
can determine the crystal structure, by comparing the
ratios of the various sin2 θ values with respect to that
of the first peak and the ratios obtained from dividing
the the values of (h2 + k 2 + l2 ) for the respective cubic
structure.
III. METHODOLOGY
The x-ray diffraction spectrum of sample 5 was ob-
tained via the usage of the Philips Analytical X-ray ma-
chine. The machine was set to Gonio mode where the
source and detector are positioned and moved symmet-
rically throughout while the sample remains at a fixed
place. The scan was completed from an angle of 30o to
140o at an interval of 0.02o . The time per step is set
to 0.40s with a total steps of 5500 taken. A voltage of
40kV and a current of 30mA was used. The source of the
X-ray is copper whose characteristic wavelengths of the
Kα1 radiation and Kα2 radiation are given by 1.54056Å
and 1.54439Å respectively.
IV. RESULTS AND DISCUSSION
The raw X-ray diffraction spectrum of sample is shown
in figure 5 while figure 6 list down the various peaks, in-
tensities and angular position. For each peaks, the value
of sin2 θ was computed. A total of six resolvable peaks
with the same full width half maximum (FWHM) were
identified due to the difference in the wavelength of the
two Kα radiation. However, one of the peaks (peak 5)
appears to be not resolved. Hence, the weighted mean
wavelength was utilised in the computation instead. As
seen in [3], it can be read as,
FIG. 4. Table of linest function output in excel for graph
shown in figure 3.
2 1
λmean = λKα1 + λKα2 . (4)
3 3
To qualify the crystal structure of the sample, we have
compared the ratios r of the values of sin2 θ of the var-
ious intensity peaks with respect to the peak obtained
at the smallest angle. Expected ratios r(C) of the cubic
lattice structures were also computed by dividing the se-
quential values of (h2 + k 2 + l2 ) of each peak with respect
to their individual original number as demonstrated in
figure 7. A function G was introduced as G = |r − r(C)|,
where C can be FCC, BCC or SC, to obtain the mag-
nitude of the deviation of the ratio of the sample from
the possible listed cubic structure. A smaller G value
implies that, the sample concurs with a particular cubic
structure. Fortunately, the sample appears to be in close
agreement with the face-centered cubic structure with a
G value of 0.06 for all the peaks. Otherwise, we may
need to consider other more complicated structures like
hexagonal ones. After confirming the crystal structure of
the sample, the Miller indices for the various peaks were
listed and via equation (3), the lattice constant of the
peaks can be computed. One can deduce the uncertainty
of the lattice parameter using,
δa δd
= = −cotθδθ (5)
a d
which can be obtained by differentiating the Bragg’s
equation (1) with respect to θ. δθ holds a value of
0.00034907 rad since the step size of the machine is 0.02o .

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PC3193 summary
The accuracy of the lattice parameter measurement of
the sample may be undermined by various factors such
as the misalignment of the diffractometer parts, displace-
ment of the sample from the diffractometer axis, vertical
divergence of the incident X-ray beam, etc. These are the
main sources of errors. In addition, since the measure-
ment of the diffraction peak at 2θ = 180o is physically
impossible, the extrapolation of the lattice parametr ver-
sus certain functions that produces a straight line is gen-
erally employed. In our case, we will be using the method
of Nelson-Riley, which used the function given by,
cos2 θ cos2 θ
N (θ) = + . (6)
sinθ θ tained if the angles are increased at steps of 0.01o instead
where the first term accounts for displacement error
and the second to account for the effect due to the vertical
divergence of the X-ray beam [4]. The linear relationship
between the measured lattice constant and the Nelson
Riley function is written as,
a = c + mN (7)
where c is the y-intercept and m is the gradient.
Figure 4 shows the results of the linear regression of
a(Å) vs N (θ). The y-intercept a0 was found to by
(3.6160 ± 0.0006)Å and the gradient of the graph m is
given by (−0.0035 ± 0.0002)Å. Moreover, the linear cor-
relation coefficient of the graph (figure 3) is determined
as 0.9462, which is very close to one. This suggest that,
there is indeed a strong linear correlation between a(Å)
and N (θ). Thus, the true lattice constant is given by
[1] Pieter Kuiper (2006), “Siegbahn notation”,
https://en.wikipedia.org/wiki/Siegbahn notation.
[2] Gerald D. Mahan (2011), “Condensed Matter in a
Nutshell”, Princeton University Press.
[3] Myeongkyu Lee (2016), “X-RAY DIFFRACTION
FOR MATERIALS RESEARCH From Fundamentals to
Applications”, Apple Academic Press.
[4] Yoshio. W, Eiichiro.M, Kozo Shinoda (2011), “X-
Ray Diffraction Crystallography Introduction, Examples
and Solved Problems.”, Springer.
[5] Henry, N. F. M. (1974) “The Interpretation of
X-Ray Diffraction Photographs.”, University Microfilms.
[6] “Lattice Constants of the elements”,
http://periodictable.com/Properties/A/LatticeConstants.html
3
X-ray Crystallography of sample 5
(3.6160 ± 0.0006)Å. The relatively small gradient simply
means that the contributions due to systematic errors is
not significant. By comparing with known values of lat-
tice parameters [5,6], the crystallographic data of sam-
ple 5 closely resembles that of copper Cu which also has
a face-centered cubic structure and a lattice constant of
3.6149Å. Hence, the percentage discrepancy of our result
is 0.0304%, which indicates that the results are accurate
due to the effectiveness of the Nelson Riley extrapolation
method.
The accuracy and precision of the experimental results
could be enhanced by implementing a monochromatic
source of X-rays, as it makes the peaks easily resolvable.
In addition, a sharper, well defined peak could be ob-
of 0.02o .
V. CONCLUSION
In conclusion, we have examined the crystal structure
of sample 5 by analysing the X-ray spectrum of the sam-
ple. By computing the ratios of sin2 θ for each of the
intensity peaks and comparing it with the expected val-
ues of each cubic structures, it was found that the data
follows closely with that of a face-centered cubic struc-
ture. Moreover, to improve the accuracy of the lattice pa-
rameter measurements, we have implemented the Nelson-
Riley extrapolation scheme and found that the lattice
parameter of the crystal is given by (3.6160 ± 0.0006)Å
with a percentage discrepancy of 0.0304% in comparison
to the lattice parameter of copper. Therefore, our results
indicates that the unknown sample is the element copper
which also has a face-centered cubic structure.
PC3193 summary X-ray Crystallography of sample 5

APPENDIX

FIG. 5. X-ray diffraction spectrum of Intensity (counts per seconds; cps) vs 2θ of sample 5 for V = 40kV .

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PC3193 summary X-ray Crystallography of sample 5

FIG. 6. Table of angular position and the intensities of the various peaks identified in the X-ray spectrum of the sample. The
values of sin2 θ and the Nelson Riley function was computed.

FIG. 7. Table of ratios of the individual calculated values of sin2 θ with respect to the first peak. The expected ratio of the
three cubic structure were also computed by taking the ratios of the subsequent (h2 + k2 + l2 ) values with respect to their
individual first. The function G denotes the difference in the two different ratios; G = |r − r(C)| where C can be FCC, SC, or
BCC. It can be easily seen that the sample has a face-centered cubic structure since its difference or G values are the smallest.
By using equation (3), the lattice constant can be computed by listing the various Miller indices of the various peaks for a FCC
structure. The uncertainty of a; δa was calculated using equation (5).