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Sımple Method For The Determınatıon of Band Gap of a Nanopowdered

Sample Usıng Kubelka Munk Theory

Article · May 2016

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 Journal of the Nigerian Association of Mathematical Physics
Volume 35, (May, 2016), pp 241-246
© J. of NAMP

Sımple Method For The Determınatıon of Band Gap of a

Nanopowdered Sample Usıng Kubelka Munk Theory

Sabiu Said Abdullahi1, Sadik Güner2, Yuksel Koseoglu3 Ibrahim Murtala Musa4,
Bala Ismail Adamu5, and Mahmud I Abdulhamid6
1,4,5
Physics Department, Federal University Dutse, P.M.B 7156, Dutse, Jigawa State, Nigeria.
2
Department of Physics, Fatih University, 34500 Buyukcekmece, Istanbul-Turkey.
3
Department of Primary Education, Faculty of Education, Suleyman Demirel University,
32260 Cunur, Isparta-Turkey
6
Department of General Studies , Audu bako College of Agriculture Danbatta Kano.
PMB3159

Abstract
Diffuse reflectant spectra (DR) is used to present a simple method for the determination of
band gap of the synthesized MnxCo0.1Zn0.9-xO nanopowdered samples prepared with
different doping concentration (x=0.0, 0.05, 0.1, 0.15, and 0.2).The idea was originated from
Kubelka-Munk theory which describes the behavior of light travelling inside a light scattering
sample. The band gap is calculated by plotting the graph of the square product of the
absorption coefficient and energy (αE)2 versus energy E, ((αE)2 vs E). The band gap can be
obtained by extending the straight line from the straight segment of the graph touching the E
axis, the band gap of the sample was found to have decreasing values of 3.24, 3.21, 3.17, 3.16,
and 3.02 eV values with respect to Mn content of x=0, 0.05, 0.10, 0.15, 0.20 at. %,
respectively.

1.0 Introduction
Semiconductor nanoparticles have attracted great attention decades ago, where most of the
devices with semiconductor nanoparticles were found to possess novel optical and electronic
properties that are potentially useful for technological applications [1]. Optical semiconductor
devices are mainly luminescent devices (light-emitting diodes and laser diodes), or light-
receiving devices (solar cells and photo-detectors), therefore the wavelengths of the light
depend on the optical semiconductor materials used [2]. Optical band gap is a significant
factor for semiconducting materials. The term “band gap” refers to the energy difference
between the top of the valence band and the bottom of the conduction band, electrons are able
to jump from the valence band to the conduction band. In order for an electron to jump from
the valence band to the conduction band, it requires a specific minimum amount of energy for

1
Corresponding author1:E-mail address: [email protected],+2348137883843.
 Journal of the Nigerian Association of Mathematical Physics
Volume 35, (May, 2016), pp 241-246
© J. of NAMP

the transition [3]. The band gap can be classified as direct or indirect, a band gap is said to be
``direct'' when the energy minimum (the bottom) of the conduction band lies directly above
the energy maximum (the top) of the valence band that is they are at the same crystal
momentum (k-Vector). Otherwise, it is called an ``indirect'' band gap [4]. Moreover, a wide
band gap is one of the novel properties of semiconductor [5]. A diagram illustrating the band
gap is shown in Figure 1.

Figure 1 Energy band gap of a semiconductor.

2.0 Methodology
UV-vis spectrometer is used to measure the optical properties of the sample. It consists of a
light source for the spectral range and a tungsten lamp for the visible and IR spectra, having a
monochromator for the selection of a single frequency (wave-length) from all those provided
by the lamp source to scan over a desired frequency. Moreover a sample holder and a detector
is used to measure the intensity of each monochromatic beam after traversing the sample
which is finally displayed and the spectra is recorded. For the powdered crystalline materials,
diffuse reflectance is an excellent method for analyzing the optical properties of the sample
[6,7].

2
Corresponding author1:E-mail address: [email protected],+2348137883843.
 Journal of the Nigerian Association of Mathematical Physics
Volume 35, (May, 2016), pp 241-246
© J. of NAMP

Figure 2: Illustration of a High performance Reliable UV-Vis spectrometer Evolution 300

3.0 Diffuse Reflectance Spectroscopy

When an electromagnetic radiation is directed on to the surface of solid powder, two types of
reflection occurs: specular reflection and diffuse reflection (DR). The specular reflection is the
direct radiation from the powder sample surface and according to the Snell’s reflection law;
the angle of incidence is equal to the angle of reflection. The diffuse reflection (DR) is the
radiation that penetrates into the powder sample and undergoes scattering (it follows many
reflections, refractions and diffraction at all directions due to nanostructured mass) and
wavelength dependent absorption within the nanomaterial. Some part of this radiation
ultimately leaves the bulk sample in all directions. A DR accessory is designed to collect the
diffused reflection rather than specular component and directs it into a photo detector.
Commonly, the accessory has a spherical surface (integrating sphere) or any other suitable
geometry that is coated with a white standard reflecting thin film as illustrated in Fig 3.

3
Corresponding author1:E-mail address: [email protected],+2348137883843.
 Journal of the Nigerian Association of Mathematical Physics
Volume 35, (May, 2016), pp 241-246
© J. of NAMP

Integrating
sphere

I S
D
D D

I: Incident ray
S: Specular reflectance
D: Diffuse reflectance

Fig.3. A configuration used to record the DR spectra for powder samples.

The measurement of diffuse reflection (DR) with a UV-Vis spectrophotometer is a standard

method to determine the optical properties of powder nanomaterials [8, 9]. In the case of
semiconducting powder nanomaterials, these properties are potentially the absorption
coefficient (K) and band-gap energy (or band gap, Eg) [8]. Especially, the Eg is an important
feature for semiconducting nanopowders which specifies the ability for use in optoelectronic
applications. There is no standard method of powder sample preparation in DR spectroscopy.
Usually, powder samples are filled into a rectangular or cylindrical sample holder with a
surface of a few ten square millimeters to several square centimeters. The powder
nanoparticles should form a 1-3 mm thick layer for all incidents light to be absorbed or
scattered before reaching the back surface of the sample [9, 10].

4
Corresponding author1:E-mail address: [email protected],+2348137883843.
 Journal of the Nigerian Association of Mathematical Physics
Volume 35, (May, 2016), pp 241-246
© J. of NAMP

The original idea to use the DR spectra recorded from semiconducting nanostructures to
calculate the Eg was proposed by Kubelka-Munk theory in 1931 [11, 12]. Originally, the
theory describes the behavior of light travelling inside a light scattering sample and based on
two differential equations:

−𝑑𝑖 = −(𝑆 + 𝐾)𝑖𝑑𝑥 + 𝑆𝑗𝑑x

𝑑𝑗 = −(𝑆 + 𝐾)𝑗𝑑𝑥 + 𝑆𝑖𝑑𝑥 …………………… .(1)

Here i and j are the intensities of light travelling inside the sample towards its un illuminated
and illuminated surfaces, respectively; dx is the differential part along the light path; S and K
are the scattering and absorption coefficients, respectively. The Kubelka-Munk theory holds
for a particle size that is comparable or smaller than the wavelength of incident light and DR
no longer permits the secondary contributions of reflection, refraction, and diffraction.

When the thickness of sample is in the relevant limitation then it has no influence on the
reflectance. Hence, the Kubelka-Munk equation at any wavelength can be written as

𝐾 (1−𝑅∞ )2
= ≡ 𝐹(𝑅∞ ) …………………………………(2)
𝑆 2𝑅∞

where 𝑅∞ is the diffuse reflectance and 𝐹(𝑅∞ ) is called the Kubelka-Munk function. In the
parabolic band structure, the Eg and absorption coefficient are related through the well known
Tauc relation [13, 14]. The Tauc relation for a direct band gap material is given by the
expression

𝛼ℎ𝜐 = 𝐴 (ℎ𝜐 − 𝐸𝑔 )𝑛 ……………………………………(3)

where α is linear absorption coefficient, υ is light frequency, and A is the proportionality

constant. The power of the parenthesis, n is taken equal to the 1/2 for direct band gap
materials. When incident radiation scatters in a perfectly diffuse manner, the absorption
coefficient K becomes equal to 2α. In this case, considering the scattering coefficient S as
constant with respect to wavelength, the kubelka munk function is proportional to the
absorption coefficient α [15], applying eq.(2) we obtain the relation:

[𝐹(𝑅∞ )ℎ𝜐]2 = 𝐴(ℎ𝜐 − 𝐸𝑔 ) ………………………………………(4)

5
Corresponding author1:E-mail address: [email protected],+2348137883843.
 Journal of the Nigerian Association of Mathematical Physics
Volume 35, (May, 2016), pp 241-246
© J. of NAMP

The (αhυ)2 vs. hυ graph is plotted and the energy-band gap of the powder sample is extracted
easily.

4.0 Results and Discussion

The Diffuse reflectant spectra (DR) recorded from the synthesized MnxCo0.1Zn0.9-xO
nanoparticles with different doping concentration (x=0.0, 0.05, 0.1, 0.15, and 0.2) by
microwave assisted combustion synthesis method using urea as a fuel. The Mn and Co
coordinated zinc oxide powder samples in the (300-1100) nm wavelength region are given in
Fig.4. Since the Co ratio is constant (0.1 at. %) the percent reflectance decreases with
increasing Mn concentration.
The pure ZnO samples have an absorption band edge at 372 nm indicating a direct band gap
of 3.33 eV which compares favorably with the room temperature value of 3.37 eV [16,17].
However this band edge is not so sharp like detected ones from many ZnO specimens in the
literature [18-21]. In the case of metal doped nanopowders, there are three more absorption
bands observed at 566 (2.19 eV), 613 (2.02 eV), and 656 nm (1.89 eV). These three
absorption bands are due to interatomic d-d transitions in tetrahedrally coordinated Co2+ ions
[22]. The 3-d levels in the Co2+ ions undergo splitting due to tetrahedral crystal field formed
by O ions. These transitions denoted as 1,2, and 3 in the Fig.4 correspond to
4
A2 (F)→ 2A1(G),

4
A2 (F)→ 4T1 (P), and

4
A2 (F)→ 2E(G) respectively, in high spin Co2+ [23]. Although, all metal doped ZnO
nanoparticles have the same magnitude of Co content, the intensity of these peaks are seem to
be comparable just for Mn0.05Co0.10Zn85O and Mn0.10Co0.10Zn80O samples

6
Corresponding author1:E-mail address: [email protected],+2348137883843.
 Journal of the Nigerian Association of Mathematical Physics
Volume 35, (May, 2016), pp 241-246
© J. of NAMP

35
ZnO
30 Mn0.05Co0.10Zn0.85O
Mn0.100Co0.10Zn0.80O
25
Mn0.15Co0.10Zn0.75O
20 Mn0.20Co0.10Zn0.70O
DR %

15

10
1 2 3
5

300 400 500 600 700 800 900 1000 1100

Wavelength (nm)
Fig4. Diffuse Reflectance spectra of MnxCo0.10Zn1-xO powder
samples.

7
Corresponding author1:E-mail address: [email protected],+2348137883843.
 Journal of the Nigerian Association of Mathematical Physics
Volume 35, (May, 2016), pp 241-246
© J. of NAMP

ZnO
linear fit

(h) (a.u.)
2

Eg=3.24 eV
1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5
h (eV)

Mn0.05Co0.10Zn0.85O Mn0.10Co0.10Zn0.80O
linear fit linear fit
(h) (a.u.)

(h) (a.u.)
2

Eg=3.21 eV Eg=3.17 eV

1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 1,5 2,0 2,5 3,0 3,5 4,0 4,5

h (eV) h (eV)

Mn0.15Co0.10Zn0.75O Mn0.20Co0.10Zn0.7O
linear fit linear fit
(h) (a.u.)

(h) (a.u.)
2

Eg=3.16 eV Eg=3.02 eV
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5
h (eV) h (eV)

Fig.5. Tauc plots for ZnO and MnxCo0.10Zn1-xO powder

8
samples.
Corresponding author1:E-mail address: [email protected],+2348137883843.
 Journal of the Nigerian Association of Mathematical Physics
Volume 35, (May, 2016), pp 241-246
© J. of NAMP

The band gap Eg of the samples were calculated from the Tauc relation given in equation (3).
The (αE)2 vs E graphs were plotted. In the graphs, a straight line is fitted for the straight
segment. The extrapolation of this straight line to the axis of abscissa (E axis) gives the band
gap values. The Tauc plots of ZnO and MnxCo0.10Zn1-xO powder samples are shown in the
Fig.5. Eg values were obtained by extrapolating the line to the E axis The band gap of the
samples was found to have decreasing magnitude of 3.24, 3.21, 3.17, 3.16, and 3.02 eV
values with respect to Mn content of x=0, 0.05, 0.10, 0.15, 0.20 respectively. The decrease in
the band gap is expected due to increase of carrier concentration.

5.0 Conclusion
We have presented a simple method for the determination of band gap energy of the
synthesized MnxCo0.1Zn0.9-xO nano powdered samples prepared with different doping
concentration (x=0.0, 0.05, 0.1, 0.15, and 0.2) by Diffuse reflectant spectra (DR) using
Kubelka-Munk theory. The theory describes the behavior of light travelling inside a light
scattering sample. The band gap is calculated by plotting the graph of the square product of
the absorption coefficient and energy (αE)2 versus energy E, ((αE)2 vs E) where the straight
line touching the E axis from the straight segment of the graph gives the band gap. The band
gap of the samples was ranged between 3.24 to 3.02 eV, with an increase in Mn content from
x = 0, to 0.20.

9
Corresponding author1:E-mail address: [email protected],+2348137883843.
 Journal of the Nigerian Association of Mathematical Physics
Volume 35, (May, 2016), pp 241-246
© J. of NAMP

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Corresponding author1:E-mail address: [email protected],+2348137883843.
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Volume 35, (May, 2016), pp 241-246
© J. of NAMP

[11] Kubelka, P. and Munk, F. Z. (1931). Tech. Phys. 12, 593.

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Volume 35, (May, 2016), pp 241-246
© J. of NAMP

[23] Koidl, P., (1977). Optical absorption of Co2+ in ZnO’’ Physical Review. B 15, 2493.

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