Article Type : Research Article
Authors : Zuhoor Elahi* and Wafa Gull
Keywords : Nanoparticles; Crystallite size; Bandgap; Annealing; Calcination
The Zinc Oxide (ZnO) nanoparticles were successfully synthesized by solgel method using Zinc nitrate hexahydrate and sodium hydroxide. Obtained nanoparticles were successfully analyzed for structural, optical, morphological, and compositional studies using XRD, UV-VIS, SEM, and EDX analysis techniques respectively. The structure of ZnO was found to be hexagonal wurtzite. The crystallite sizes of the three sets of nanoparticles samples were successfully calculated using the Scherrer formula and found the dependence on the growth temperature, annealing temperature, and calcination temperature. The bandgaps of the particles were also determined from the UV-VIS spectra. UV-VIS spectroscopy reveals that UV absorption characteristics can be tuned by varying the annealing and calcination temperatures. The SEM images show that most of the samples consist of spherical nanoparticles. UV-Visible spectroscopy reveals that UV absorption characteristics can be tuned by varying the calcination temperature.
Band gap engineering is becoming an effective tool for
tailoring the properties of materials [1]. At nanoscale quantum confinement
effects become dominant which derives the material to show different properties
as they show in bulk [2]. There are a lot of methods to synthesize the desired
nanoparticles (ZnO), but we are choosing one of the low-cost methods, the
Sol-gel method. Several studies have shown that ZnO is proven to be non-toxic
for human cells and toxic for bacteria. This property made it biocompatible
[3]. Semiconductor NPs possess wide bandgaps and therefore showed significant
alteration in their properties with bandgap tuning. Therefore, they are very
important materials in photocatalysis, photo-optics and electronic devices [4].
As an example, variety of semiconductor nanoparticles are found exceptionally
efficient in water splitting applications, due to their suitable bandgap and
bandgap positions [5]. The various properties of nanoparticles such as
physical, optical, etc. can be tailored by varying temperature at the time of
their growth, annealing, and calcination etc. Annealing help to improving the
crystallinity of ZnO nanoparticles [6,7]. It can take place in air or in
neutral or reducing atmospheres, but usually is done in air. A terminology used
both in metallurgy and in the case of thin films, referring to a heat treatment
process that helps to reduce residual stress and hence decrease defects in any
structure [8]. The idea is to give the atoms some mobility through thermal
energy, such that they can diffuse to the lower energy (more stable) position.
Calcination is used to increase crystallinity of material [9]. In case of any
impurities present on the surface is also removed and calcination temperature utilized
to prepared material converted one phase to other [10]. Calcination temperature
generally favors crystal growth [11]. In this paper we discussed the effects of
temperature at the time of growth, annealing, and calcination on crystallite
size and bandgap of the synthesized ZnO nanoparticles. The obtained results are
then compared to see the effects of different synthesis conditions.
Zinc oxide nanoparticles were synthesized by wet
chemical method using zinc nitrate and sodium hydroxide precursors. A 0.5M
aqueous ethanol solution
of zinc nitrate hexahydrate(Zn(NO3)2·6H2O),
and a 0.9M aqueous ethanol solution of sodium hydroxide (NaOH) were kept under
constant stirring using magnetic stirrer to completely dissolve the zinc
nitrate for one hour. The 0.9M NaOH aqueous solution was added under high-speed
constant stirring, drop by drop (slowly for one hour) touching the walls of the
vessel. The stirring continued for two more hours, and the beaker was sealed at
this condition. The solution was allowed to settle for overnight and further,
the supernatant solution was separated carefully. The remaining solution was
centrifuged for 10 min, and the precipitates were removed. The precipitated ZnO
NPs were cleaned three times with deionized water and ethanol to remove the by products,
and then dried in furnace at about 60oC for 48 hours (2 days). The first set of
five samples are grown at different temperatures, that is at RT (room
temperature), 30oC, 40oC, 50oC, and 60oC.
The second set of five dried samples (grown at room temperature) are annealed
at 200oC, 300oC, 400oC, 500oC, and
600oC in a furnace. The third set of samples was calcined at 450oC,
500oC, 550oC, 600oC, and 650oC. The
process is shown schematically in (Figure 1).
Structural analysis
The
XRD patterns of the samples grown, annealed, and calcined at different
temperatures are shown in (Figures 2-4), respectively which show that the ZnO
nanoparticles have hexagonal wurtzite structure. The crystallite sizes and
lattice constants are found by applying Gaussian fit in the Origin lab (Origin
2023b), and, using the Scherrer formula. The calculated values are plotted
against the growth, annealing, and calcination temperatures in (Figures 5-7)
respectively, and listed in (Tables 1-3) respectively. Figure 5 shows that the crystallite
size increases as we increase the growth temperature. The value of the lattice
constant has an average value of 3.2542? for the first four data points, and decreased
in the fifth point, but that change is at the third decimal place which is not
a significant change. In the case of annealing temperature, Figure 6 shows that
the crystallite is again increased with increasing temperatures, as was the
case of increasing growth temperatures, while the lattice constant oscillates
between 3.2505? and 3.2661?. In contrast to previous cases, Figure 7 shows that
the crystallite size decreases with the increase in calcination temperature.
The crystallite sizes are observed to be decreased from 26.84nm to 25.25nm for
the temperatures range of 450oC to 650oC. The lattice
constant also follows a path like that of the crystallite size having values
ranging 20 from 3.2571? to 3.2529?.
Figure
1:
Experimental setup.
Figure
2:
XRD patterns of the samples grown at different temperatures.?
Figure
3:
XRD patterns of the samples annealed at different temperatures.
Figure 4: XRD patterns of the samples calcined at different
temperatures.
Figure 5: Crystallite size (blue) and lattice constant (red) for the samples grown at different temperatures.
Figure 6: Crystallite size (blue) and lattice constant (red) and lattice constant
for the samples annealed at different temperatures.
Figure 7: Crystallite size (blue) and lattice constant (red) and lattice constant for the samples calcined at different temperatures.
Figure
8:
Absorption spectrum for the samples annealed at different temperatures.
Figure 9: Absorption spectrum for the samples calcined at different temperatures.
Figure 10: Optical absorption against photon energy is plotted
to find the bandgap by drawing the slopes (broken lines) for the samples
annealed at different temperatures.
Figure 11: Optical absorption against photon energy is plotted to find the bandgap by drawing the slopes (broken lines) for the samples calcined at different temperatures.
Figure 12: Peak wavelengths, absorption coefficients, and the bandgap
energy as functions
of annealing temperatures.
Figure 13: Peak wavelengths, absorption coefficients, and the bandgap energy as functions of calcination temperatures.
Figure 14: SEM images of samples for growth temp. (a) Room Temperature, (b) 30oC,
(c) 40oC, (d) 50oC, and (e) 60oC
Figure 15: SEM images of samples
for Annealing temperatures (a) 200oC, (b) 300oC, (c) 400oC,
(d) 500oC, and (e) 600oC
Figure 16: SEM images of samples
for Calcination temperatures (a) 450oC, (b) 500oC, (c) 550oC,
(d) 600oC, and (e) 650oC
Absorption spectrum
The effects of annealing and calcination temperatures on the optical properties of the ZnO nanoparticles were studied by UV-VIS absorption spectroscopy. Graph of Figure 8 shows the optical absorption spectra of ZnO nanoparticles annealed at different temperatures. The absorption peaks are observed to increase from 301.52 nm to 308.75 nm for the annealing temperatures of 200oC to 600oC respectively. A slight redshift in absorption peak for the samples annealed at different temperatures was noticed. It is known that the ZnO particles which have absorption at higher wavelength in the UV-visible spectrum have higher particles size. With increasing temperature, the particle size increases, and the peak absorbance wavelength becomes redshifted due to decreasing quantum confinement. The graph of Figure 9 shows the optical absorption spectra of ZnO nanoparticles calcined at different temperatures. In contrast to the previous case a blueshift was observed in the case of increasing calcination temperatures.
Bandgap
The
optical bandgaps of the prepared samples are estimated by plotting (?h?)2
against h? and using the Tauc relation given below, and extrapolation procedure
as shown in Figure 10 and Figure 11. ????????? = (????? ? ????????)½ where,
? is the optical absorption coefficient, h? is the photon energy, Eg is the
direct band gap, and A is a constant. The bandgap energy was observed to be
decreased with the increasing annealing temperature due to quantum confinement.
The results support our structural analysis discussed in section 3.2.
Figure 17: EDX spectrum, and the
qualitative analysis of the samples grown at (a) 30oC, (b) 40oC,
(c) 50oC, and (d) 60oC.
Whereas the bandgap was increased with the increase in calcination temperature. The peak wavelengths, absorption coefficients, and the bandgaps are plotted in Figure 12 and Figure 13 and listed in Table 4 and Table 5, for the annealing and calcination temperatures respectively. These results indicate that the band gap energy can be tuned by varying the annealing and/or calcination temperature for different applications.
Morphology and Composition
The
morphological studies of synthesized nanoparticles were carried out by scanning
electron microscopy (SEM). (Figures 14-16) represent SEM images of the three
sets of ZnO nanoparticles samples that are prepared at different growth
temperatures, annealing temperatures, and calcination temperatures
respectively. In most of the images, it can be seen that the ZnO samples have
spherical nanoparticles with random orientation. However, some of the samples
are non-spherical such as in the case of Figure 14 (a) and (e) which look more
like nanoflakes instead of spherical particles. Some of the samples such as in
the Figure 15(e) and Figure16 (e) few nanotubes can also be seen. Elemental
analysis was done by the energy dispersive x-ray spectroscopy (EDX) for the
first set of samples which differ in the growth temperature. The EDX spectra of
the four samples grown at 30oC, 40oC, 50oC,
and 60oC are shown in Figure 17 (a) to (d) respectively. The EDX spectra
confirm the existence of zinc (Zn), and O (oxygen), in ZnO matrix. A
predominant peak corresponds to Zn. However, significantly small peaks of C in
all the four samples, and the peaks Na in the last two samples also appeared
which might be due to some of the biproducts.
Table 1: Crystallite size and lattice constant for the samples Grown at different temperatures.
Growth Temperature
oC |
Crystallite size
nm |
Lattice constant ? |
20 |
28.76 |
3.2542 |
30 |
29.35 |
3.2541 |
40 |
32.68 |
3.2544 |
50 |
36.31 |
3.2543 |
60 |
38.70 |
3.2529 |
Table 2: Crystallite size and lattice constant for the samples Annealed at different temperatures.
Annealing Temperature oC |
Crystallite size
nm |
Lattice constant ? |
200 |
17.41 |
3.2540 |
300 |
17.50 |
3.2505 |
400 |
19.01 |
3.2661 |
500 |
19.67 |
3.2528 |
600 |
23.40 |
3.2565 |
Table 3: Crystallite size and lattice constant for the samples Calcined at different temperatures.
Calcination
Temperature oC |
Crystallite size nm |
Lattice constant ? |
450 |
26.55 |
3.2559 |
500 |
26.84 |
3.2571 |
550 |
26.33 |
3.2554 |
600 |
25.26 |
3.2534 |
The XRD patterns of the synthesized nanoparticles are shown in (Figures 2-4) which show that the particles are of hexagonal wurtzite structure. As discussed in section-3.1 the crystallite sizes are observed to be varied for varying temperatures at the time of growth, annealing, and calcination. The crystallite sizes are observed to range from 28.76nm to 38.70nm, 17.41nm to 23.40, and 26.84nm to 25.25nm for temperatures ranging from 20oC to 60oC growth temperatures, 200oC to 600oC annealing temperatures, and 450oC to 650oC calcination temperatures, respectively. It is observed that increasing the growth and annealing temperatures the crystallite size also increases, whereas the increase in calcination temperature leads to the decrease in the crystallite size of the ZnO nanoparticles.
Table 4: Peak wavelengths, absorption coefficients, and the bandgap energy for annealing temperature found from the Figure 8 & Figure 10, and plotted in Figure 12.
Annealing |
Peak Wavelengths (nm) |
Absorption Coefficient
(cm-1) |
Band Gap Energy (eV) |
200 |
301.52 |
1.07 |
3.45 |
300 |
304.44 |
1.96 |
3.15 |
400 |
305.54 |
3.22 |
3 |
500 |
307.72 |
4.16 |
2.75 |
600 |
308.75 |
4.89 |
2.57 |
Table 5: Peak wavelengths, absorption coefficients, and the bandgap energy for calcination temperature found from the Figure 9 & Figure 11, and plotted in Figure 13.
Calcination
Temperature |
Peak Wavelengths (nm) |
Absorption Coefficient
(cm-1) |
Band Gap Energy (eV) |
450 |
262.69 |
2.71 |
3.94 |
500 |
260.85 |
2.18 |
4.19 |
550 |
260.53 |
1.98 |
4.31 |
600 |
258.7 |
1.64 |
4.5 |
650 |
257.66 |
1.35 |
4.63 |
The
UV-VIS analysis discussed in section-3.2 shows that the bandgap of the ZnO
nanoparticles can be tuned by varying the annealing or calcination temperatures.
The bandgap of the ZnO samples annealed at temperatures 200oC to 600oC
decreased from 3.45eV to 2.57eV, while in the case of varying calcination
temperatures the bandgap increased from 3.94eV to 4.63eV. The morphological
studies show that most samples have nanoparticles that are of spherical shape, while
nanoflakes and nanotubes were also seen in few samples. The elemental studies
were also done using the EDX analysis technique, and the results can be seen in
Figure 17 above.
The
Zinc Oxide (ZnO) nanoparticles were successfully synthesized by the solgel
method, which is a time taking, but a low-cost synthesis technique. Obtained nanoparticles
were successfully analyzed for structural, optical, morphological, and compositional
studies. The dependencies of the crystallite size and the bandgap of the ZnO
particles on the growth temperature, annealing temperature, and calcination
temperature were successfully studied. The comparison of the above-said cases
is successfully presented.
We
are heartly thankful to our mentor, Dr. Shahid Mahmood, Professor, Department
of Physics, University of Karachi, who provided us the opportunity to work at his
great Spectroscopy research laboratory where we performed most of the work in a
peaceful and calm environment.