Determination of The Structure of ZnO Powder

Experiment #3: Determinaton of the structure of ZnO Powder
Ahmad Moh. Awadallah -9100030 Advanced physics lab-0352712

1

Abstract
In this work, we had examined the structure of the ZnO powder sample. For this purpose, we
prepared our sample by grinding a small amount of ZnO via an agate mortar and pestle until
reaching to a very fine powder could be reached. Then we pressed a small amount of it into the
sample holder. The prepared sample then was studied through the XRD machine, where the used x-
rays are Cu-K (=1.5406) and Cu-K2 (=1.5444). The x-ray diffraction pattern was then
treated by the Origin 9 software, and the result was presented in this report. The figures of the fitted
peaks were sited at the appendix. By treating the data, we found that the structure of ZnO contains
two phases; the major one is the wurtzite phase which has a hexagonal structure with a lattice
parameters: = (3.24 0.03) and = (5.19 0.03) , in addition to a very small fcc cubic
phase with the lattice parameter = (3.59 0.03). We lost an amount of accuracy due to
ignoring the contribution of the oxygen ions through calculating the structure factor.

1. Introduction
The hexagonal system is one of the most important crystallite systems, it is a wide spread system in
the nature. A lot of crystals were composed from two or more basic structures. One example of this
composition is the Zinc oxide (ZnO); it is naturally composed from: wurtzite (B4) which is a
hexagonal structure, the zinc blende (B3) which form an fcc cubic structure, and the rocksalt (or
Rochelle salt) (B1) as demonstrated in fig.1. The main object in this job is to calculate the lattice
parameters (a) and (c) for the hexagonal structure, the crystallite size (D). They was calculated and
then compared with the Published ones. The intensities of the peaks were calculated and compared
with the experimental (fitted) ones. The differences were explained due to the texture of the cells,
they prefer to be ordered in a certain direction because of its cubic design. The collected XRD
peaks shall be divided into two categories: the 1
st
(main) one for the hexagonal structure, and the
other for the cubic one.
In general, the following formulae are used in such a study:
To calculate the d-spacing (d):
4sin
2
2
=
1
2

To find the lattice parameters (a) and (c):
1
=
4
3
(
2
++
2
2
) +
2

Which can be simplified to: log(
2
) = log(
2
) log [
4
3
(
2
+ +
2
) +
2
(
2
)
]

If we have (0,0, )peak, Eqn. (1.3) becomes: =

So we can calculate (c) directly.

If we have (, , 0)peak, Eqn. (1.3) becomes:
2
=
4
3
(
2
+ +
2
)
2

So we can calculate (a) directly.
Eqn. 1.1
Eqn. 1.2
Eqn. 1.3
Eqn. 1.4
Eqn. 1.5
2

To calculate the crystallite size (D): =
0.94
(2)cos ()

Where B (2): the full width at half maximum (FWHM).

To calculate the intensity of a peak:
= ||
2
()

Where F: structure factor
() =
[1 +
2(
+2
3
+
2
)
]

2
=
{
0 +2 = 3, =
4
2
+2 = 3, =
3
2
+2 = 3 1, =
2
+2 = 3 1, =

}

m: multiplicity of the indices.
LP (): Lorentz polarization factor () =
1+
2
2
.2

2. Experimental
ZnO was brought from our lab; it was prepared as a very fine powder. This fine powder then was
stuck into a sample holder stainless steel plate of 2cm diameter to fit inside the x-ray machine. The
thickness of the sample holder is about 2mm with a flat surface. The x-ray diffraction pattern was
obtained for an angular position (2) range 20.00
to 95.00
with 0.01
step between each two

succession channels. The x-ray machine does not contain a filter for Cu-K2, so it will be taken in
consideration that the peaks are formed from a super position from both Cu-K1 and Cu-K2 tell
reaching to high positions (2 60) where the peaks divided into two close peaks due to the
different wavelengths. Then these collected data had been analyzed. The diffraction pattern was
studied and the intensities of the peaks were analyzed using ORIGIN 9.0.0 software. I had fitted the
peaks using the Gaussian distribution function. The splitted peaks were fitted through a multipeaks
fitting routine to ensure taking in consideration the intensity of peak due to the Cu-K2 rays. Then I
had used the Xpert HighScore (virgin 2.0a) enhance the pattern picture and to get the recorded
value of(
). Microsoft excel was used to calculate and arrange our results. The Microsoft word
2010 then was used to prepare this report.

3. Results and Discussion
a. Fig.2 shows the XRD pattern for powdered ZnO, we can see clearly that there are 18 peaks
through the whole pattern, 4 of them are very small peaks. From the 8
th
peak and go on, the peaks
started to split into two close peaks because of the influence of Cu-K2 ray inside the XRD
machine because it appears at high positions. We can overlap this point by using Cu-K2 filter in
the XRD machine which not used in our one.

Eqn. 1.6
Eqn. 1.7
Eqn. 1.8
Eqn. 1.9
Eqn. 1.10
3

Fig.2: XRD paterns for the ZnO sample
Fig.1: diferent phases in ZnO
4

The peak positions were determined using the Gaussian fitting, and they were listed at table 3.1.
The d-spacing for the different reflections were calculated using Braggs law:
(2d sin =m) [m=1 for the first order reflection] [2dsin=]
The results were tabulated in the same table. In order to index the peaks, we calculated log () for
each (d), and then we used the Hull-Deavy chart to index the peaks. The values of h, k, and l that
obtained from the chart were inserted to the same table. From the rectangular strip of paper and the
Hull-Deavy chart which will be submitted with the report-, we found that the axial ratio (c/a) is
equal to:
(1.605 0.005)
and recorded at the same table. There are 4 peaks that did not fit with the chart. They did not match
with the lines that represent the hexagonal structure, which indicates for the existence of another
phase beside the hexagonal structure.
Using the (0,0, ) peaks, we calculated the value of (c) by eqn. (1.4), and with the assistance of the
(, , 0) peaks we calculated the value of (a) using eqn. (1.5), both were inserted into table 3.1.
We calculated () () to compare it with the recorded value.
Peak # Position (2) d+d() log(d) (, , ) () c()
1 31.900.01 2.800.03 0.4480.01 (1,0,0) 3.23 -
2 34.600.01 2.590.03 0.4140.01 (0,0,2) - 5.18
3 36.400.01 2.470.03 0.3920.01 (1,0,1) - -
4 43.600.01 2.080.03 0.3170.01 x - -
5 47.700.01 1.910.03 0.2800.01 (1,0,2) - -
6 50.800.01 1.800.03 0.2540.02 x - -
7 56.800.01 1.620.03 0.2100.02 (1,1,0) 3.24 -
8 63.000.01 1.470.03 0.1680.02 (1,0,3) - -
9 66.500.01 1.400.03 0.1470.02 (2,0,0) 3.23 -
10 68.100.01 1.380.03 0.1380.02 (1,1,2) - -
11 69.200.01 1.360.03 0.1320.02 (2,0,1) - -
12 72.700.01 1.300.03 0.1140.02 (0,0,4) - 5.20
13 74.580.01 1.270.02 0.1040.02 x - -
14 77.080.01 1.240.02 0.0920.02 (2,0,2) - -
15 81.500.01 1.180.02 0.0720.02 (1,0,4) - -
16 89.700.01 1.090.02 0.0380.02 (2,0,3) - -
17 90.500.01 1.080.02 0.0350.02 x - -
18 92.900.01 1.060.02 0.0260.02 (2,1,0) 3.24 -

3.24 0.03 5.19 0.03
To find the error in calculating (a) and (c):
=
sin
=
(sin)
2
2
=
)
So: = (
sin
) [ = 0.01]
Table 3.1: Position against d-spacing and Lattice parameters.
5

Was diverge between 0.02 and 0.03 depends on as recorded in table 3.1.
The error in log (d) is: log() =

To find the error in calculating (a):
2
=
4
3
(
2
+ +
2
)
2
=
To find the error in calculating (c): = =
Now, the calculated value of
is:
=
5.19
3.24
= 1.60 0.02
One now can compare between the experimental value and the calculated one of the axial ratio
:
(
= (1.605 0.005)
(
= (1.60 0.04)
(
=
5.18
3.24
= 1.60

This small value of P.E indicates how accurate our calculation of the lattice parameters is.
b. Using the Origin fitting routine, we found the B (2): Full widths at Half Maximum
(FWHM), these values were sited in table 3.2. The crystallite size (D) was calculated depending on
the value of B () through the equation:
=
0.94
(2)cos ()

They were tabulated in the same table against the position 2. I used the average value of for the
1
st
7 peaks where no splitting appears in them, while the value of
1
where used in calculation for
the rest peaks.
The crystallite size is very small; it is in the nano scale; the value of the crystallite size was of the
magnitude of 600. The uncertainty in calculating D was very small and could without loss of
accuracy- be ignored.
From fig.3, it is clear that the peaks #: (4, 6, 13, 17) are not go systematically with the other peaks.
In general, the FWHM are decreasing with increasing , while in the existence of the non-
hexagonal 4 peaks the relation becomes unstable as shown. The high values of the FWHM for the
cubic peaks lead to a small crystallite size among the big hexagonal crystallite.

(
) =
)
2
+(
)
2

. =
|
100% =
|1.61 1.60|
1.61
100% = 0.62%
. =
|
100%=
|1.60 1.60|
1.60
100% = 0%
Fig. 3a: FWHM & 2 with the non-hexagonal 4 peaks. Fig. 3b: FWHM & 2 without the non-hexagonal 4 peaks.
Peak #4
Peak #6
Peak #13
Peak #17
6

Eqn. 1.11
Peak # Position (2) FWHM (2)(rad) Crystal size (D)
1 31.90 0.00440 343
2 34.60 0.00412 368
3 36.40 0.00412 370
4 43.60 0.00407 384
5 47.70 0.00419 378
6 50.80 0.00559 287
7 56.80 0.00461 358
8 63.00 0.00290 586
9 66.50 0.00269 644
10 68.10 0.00267 654
11 69.20 0.00278 634
12 72.70 0.00210 858
13 74.58 0.00382 476
14 77.08 0.00208 891
15 81.50 0.00255 750
16 89.70 0.00267 765
17 90.50 0.00543 379
18 92.90 0.00278 757
D (average)=597

c. The last part of studying the hcp structure is to calculate the intensity. The intensity was
calculated from eqn.1.3. For this aim, we calculated the multiplicity (m) and put it in table 3.3, then
we found the value of the structure factor (F) for each peak using eqn.1.5, we used the standard
values of the constants a
i
, b
i
, and c from the tables at internet. The atomic form factor for Zn at each
position was calculated using the following formula:
(
) =
(/)
2
) 4
=1
+

The ZnO hcp structure (fig. 3b) contains Zn hexagonal structure bonded to the O ions hexagon. The
atomic form factor (f) should be calculated taking in consideration the two types of ions. This will
make calculating (f) more difficult. So I ignored the oxygen ions and do the job for the Zn ions
only. This will impart more inaccuracy to my calculations, but we can balance it by the time and
effort-saving.
The values of (F) were inserted into table 3.3 too. Then I had evaluated the Lorentz Polarization
Factor (LP) using eqn.1.10, I put these values at table 3.3 to complete the required parameters to
find the intensity.

Table 3.2: The values of FWHM and crystal size with position.

7

Peak # 2 f
Zn
|
2
| (, , ) m LP()

1 31.90 25.1 628 (1,0,0) 6 11.8 44629
2 34.60 24.5 2406 (0,0,2) 2 9.9 47772
3 36.40 24.2 1753 (1,0,1) 12 8.9 186893
4 43.60 x x x x x x
5 47.70 22.0 486 (1,0,2) 12 4.9 28314
6 50.80 x x x x x x
7 56.80 20.4 1671 (1,1,0) 6 3.3 32713
8 63.00 19.4 1128 (1,0,3) 12 2.6 35043
9 66.50 18.8 355 (2,0,0) 6 2.3 4901
10 68.10 18.6 1382 (1,1,2) 12 2.2 36322
11 69.20 18.4 1017 (2,0,1) 12 2.1 25880
12 72.70 17.9 1281 (0,0,4) 2 1.9 4924
13 74.58 x x x x x x
14 77.08 17.3 298 (2,0,2) 12 1.7 6187
15 81.50 16.7 278 (1,0,4) 12 1.6 5285
16 89.70 15.7 739 (2,0,3) 12 1.4 12563
17 90.50 x x x x x x
18 92.90 15.3 235 (2,1,0) 12 1.4 3909

The error in calculating structure Factor is coming only from reading the value of atomic form
factor (f) which is negligible. The error in calculating LP is also very small.
To compare our experimental values of intensity that obtained from the fitting routine with the
calculated ones, I normalized the calculated intensities to the second peak because it is the larger
one, and so I did for the experimental values of the intensity, then I put it in table 3.4.
The difference between the normalized calculated intensities and the experimental ones are large,
and that may be for several reasons. One of them is due to the hexagonal structure of our sample,
the cells prefer to stack on its faces rather than the other directions, so the texture make the intensity
for the some peaks be at a great difference from the calculated one.
Another reason that make this difference between calculated and experimental intensities is that the
error in reading the integrated intensity from the fitting routine. In addition, one can get very
different normalized intensities if he normalizes the peaks to another one than the second. Our
calculated intensities are close to some of the recorded patterns, fig.2 shows one of them. Ignoring
the oxygen atoms in calculating the atomic form factor added a non-small amount of inaccuracy to
my calculations.

Table 3.3: Calculated structure factor, Multiplicity, LP, and the corresponding Intensity.

8

Peak # 2 (, , )
()
()
Percentage error (P.E)
|
(
100%|
1 31.90 (1,0,0) 44629 24% 440 70% 0%
2 34.60 (0,0,2) 47772 26% 232 37% x
3 36.40 (1,0,1) 186893 100% 631 100% 13%
4 43.60 x x x x x x
5 47.70 (1,0,2) 28314 15% 108 17% 55%
6 50.80 x x x x x 4%
7 56.80 (1,1,0) 32713 18% 171 27% 21%
8 63.00 (1,0,3) 35043 19% 114 18% 21%
9 66.50 (2,0,0) 4901 3% 20 3% 42%
10 68.10 (1,1,2) 36322 19% 97 15% 62%
11 69.20 (2,0,1) 25880 14% 51 8% x
12 72.70 (0,0,4) 4924 3% 6 1% 25%
13 74.58 x x x x x 66%
14 77.08 (2,0,2) 6187 3% 16 2% 27%
15 81.50 (1,0,4) 5285 3% 6 1% x
16 89.70 (2,0,3) 12563 7% 31 5% 21%
17 90.50 x x x x x 0%
18 92.90 (2,1,0) 3909 2% 10 2% x

d. For the 4 unfitted peaks, I isolated them and inserted them into a new table (3.5); I used the
same procedure in the 1
st
two experiments to calculate the lattice parameter for this cubic structure.
It was found that this structure is an fcc cubic which mentioned in the introduction as the zinc
blende (B3) structure in fig.3.
Peak
#
Position (2) d()
(
sin
sin
)
2
3(
sin
sin
)
2

(, , ) +()
1 43.60 2.080.03 1.000 3.0 (1,1,1) 3.590.03
2 50.80 1.800.03 1.334 4.0 (2,0,0) 3.590.03
3 74.58 1.270.02 2.661 8.0 (2,2,0) 3.590.02
4 90.50 1.080.02 3.657 11.0 (3,1,1) 3.600.02

= 3.59 0.04

The recorded value of (a) at the literature was: = 4.63(). This difference is due to the error
sources in our experiments. The percentage error is:
. = |
(
100%| = |
4.63 5.59
4.63
100%| = 20.7%

Table 3.4: Calculated and Experimental Intensities.

Table 3.5 : Position against d-spacing and Lattice parameters for the cubic phase.
9

4. Conclusions
From the XRD pattern, we can decide that the structure of ZnO is a hexagonal structure because all
the peaks of the hcp were appeared. The lattice parameter were calculated and found to be: : =
(3.24 0.03) and = (5.19 0.03). The crystallite size was obtained and has the order of
600; it was increased when calculated from the last peaks due to the decrease in broadening of the
peaks. In addition, The ZnO structure includes another phase which is the zinc blende fcc structure
with a lattice parameter: = (3.59 0.04). The experimental intensities of the peaks were
calculated; they are compared closely to the calculated ones.

Fig.4: A recorded XRD pattern for ZnO powder

Fig.2: XRD paterns for the ZnO (REPEATED)
sample
10

Appendix: Fited peaks with their informaton

11

12

Determination of The Structure of ZnO Powder

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Experiment #3: Determinaton of the structure of ZnO Powder

Ahmad Moh. Awadallah -9100030 Advanced physics lab-0352712

step between each two

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