Determination of Optical Constants and

Thickness of Nanostructured ZnO Film by Spin

Coating Technique

R. R. Ghimire, Y. P. Dahal, K. B. Rai and S. P. Gupta

Journal of Nepal Physical Society

Volume 7, Issue 2, June 2021
ISSN: 2392-473X (Print), 2738-9537 (Online)

Editors:
Dr. Binod Adhikari
Dr. Bhawani Joshi
Dr. Manoj Kumar Yadav
Dr. Krishna Rai
Dr. Rajendra Prasad Adhikari
Mr. Kiran Pudasainee

JNPS, 7 (2), 119-125 (2021)

DOI: https://doi.org/10.3126/jnphyssoc.v7i2.38632

Published by:
Nepal Physical Society
P.O. Box: 2934
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 JNPS 7 (2): 119-125 (2021) Research Article © Nepal Physical Society
ISSN: 2392-473X (Print), 2738-9537 (Online) DOI: https://doi.org/10.3126/jnphyssoc.v7i2.38632

Determination of Optical Constants and Thickness of

Nanostructured ZnO Film by Spin Coating Technique
R. R. Ghimire1, Y. P. Dahal2, K. B. Rai1 and S. P. Gupta1, *
1
Department of Physics, Patan Multiple Campus, Tribhuvan University, Lalitpur
2
Department of Physics Bhaktapur Multiple Campus, Tribhuvan University, Bhaktapur
*
Corresponding Email: suresh.gupta@pmc.edu.np

Received: 05 May, 2021; Revised: 13 June, 2021; Accepted: 25 June, 2021

ABSTRACT
In this report, we have investigated optical constants and thickness of nanostructured ZnO films
grown on a glass substrate by sol-gel spin coating technique using zinc acetate as
precursor. Optical constants such as complex refractive index and dielectric constant ϵ
determined from the transmittance spectrum in the ultraviolet, visible, near infrared (UV-VIS,
NIR) region by envelope method. The value of refractive index decreases from 2.34 to 1.86 and
extinction coefficient increases from 0.28 to 0.64 with increasing wavelength. The decreasing
behavior of refractive index is attributed due to the increase in transmission and decrease in
absorption coefficient with increasing wavelength. The film exhibits reasonably high
transmittance (>80%) in the visible region. Absorbance coefficient α and film thickness (d)
were calculated from the interference of fringes of transmittance spectrum. The band gap and
thickness of the film were found 3.02 eV and 275nm, respectively. The thickness of the film
measured by envelope method is validated with cross-section micrograph of SEM images
which is about 285 nm. The real part of the dielectric function of nanostructured ZnO decreases
with increasing wavelength where as the imaginary part of dielectric constant increases with
increasing wavelength. The observed high value of refractive index n and real part of dielectric
constant ϵ at lower wavelength is due to band edge absorption of carriers. The dispersion
relation shows the increase of complex refractive index and dielectric constant at the high
frequency regime is due to the discharging of defect levels using optical excitation of carriers in
the visible region.

Keywords: Transparent conducting oxide, Grain boundary, Dielectric constants, Scanning

electron microscope, UV-visible Spectroscopy.

1. INTRODUCTION region and electrical conductance at ambient

Recently, transparent conducting oxides (TCO) temperature make ZnO an important material for
have been widely studied because of its excellent possible application in blue and ultraviolet (UV)
optoelectronic applications. Among various TCOs, light emitters [1,2], photovoltaic devices [1,2],
ZnO is one of the most promising materials for the surface acoustic wave devices [1,2,3], gas sensors
fabrication of next generation optoelectronic [1,2,4,5], light emitting diode (LED) [4,5,6],
devices in the UV region and optical and display Varistors [1], heat mirrors, conducting coating in
devices. ZnO is a wide band gap (Eg=3.3eV) aircraft glass and transparent electrodes [3,4,5].
semiconductor with high exciton binding energy The various most intensively studied techniques to
(60meV). The devices based on ZnO nanostructure grow the semiconductor thin film are spin coating,
can operate at high temperature, high electric and spray pyrolysis, dip coating, and an electrochemical
magnetic field and also scale down to the nanoscale method using chemical route [6,7,8,9,10]. Beside this
regime with fascinating optoelectronic properties. some physical methods such as thermal evaporation,
The high value of optical transmittance in visible pulsed laser deposition and sputtering methods are

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Determination of Optical Constants and Thickness of Nanostructured ZnO Film by Spin Coat Technique

used to grow high quality ZnO films on different undoped nanostructured ZnO films in UV and
substrate even at low temperature flexible polyamide visible illumination region. The high transmission
or textile substrates [11]. Sol-gel spin coating and low absorption in visible and infrared (IR)
technique is an excellent method for the deposition of region urges to decrease the refractive index n and
nanostructured ZnO thin film using the acetate dielectric constant ϵ within this wavelength region.
precursor solution with a sol stabilizing agent like The critical role to modulate the optical constants
amine [1,4,5]. The spin speed and number of coatings under illumination is essentially by carrier
primarily controlled the film thickness and grain size, generation and discharging the grain boundary
which shows the possibility to tune the size dependent defect levels by optically excited carriers [9].
material properties.
The accurate knowledge of crystal structure, film 2. EXPERIMENT
thickness and some optical constants such as band Undoped ZnO thin films were prepared by sol-gel
gap, complex refractive index and dielectric spin coating method. Zinc acetate dihydrate,
constant is critically important for the fabrication of ethanol and diethanolamine (DEA) were used as
high quality optoelectronic devices. The optical starting material, solvent and stabilizer,
characterization of the films gives the physical respectively. Zinc acetate dihydrate was first
parameters such as band gap, refractive index, dissolved in a mixture of ethanol and DEA solution
dielectric constants and film thickness. The current at room temperature. The molar ratio of DEA to
methods for determining the optical constants of zinc acetate was maintained at approximately 1.0
transparent thin films usually based on highly and the molar concentration of zinc acetate was
advanced expensive computerized technique. In our fixed at 0.1M. The solution was stirred at 600C for
previous study [4,9] we have investigated the role 2 hrs to yield a clear and homogeneous solution,
of aluminium doping and controlled of defect states which served as the precursor solution. The
lying in visible region which enhanced the carrier precursor solution was filtered through filter paper
mobility as well as the photo response of and dropped onto glass substrates, which were
nanostructured ZnO film. On the other hand grain rotated at 3400 rpm for 30 s. The coated film is first
and grain boundaries have the major role in carrier dried at 1200C for 5 minutes and then heated to
generation, recombination and transport properties 4500C for 10 minutes. The process of coating and
of nanostructured films. drying is repeated several times to get the required
In this report, we employ a non destructive thickness. The experimental procedure is described
technique to determine optical constants and film in the flow chart shown in Fig. 1.
thickness, which is highly recommended in
scientific research and industrial production of
granular TCO. Here we have calculated film
thickness, absorption coefficient and optical
dispersion relation of pristine ZnO film grown on
glass substrate using the envelope method.
Transmittance spectra measured using for
spectrophotometer used to evaluate absorption
coefficient, optical band gap, complex refractive
index, dielectric constants and film thickness. There
are few papers which report the determination of
optical constants and film thickness using non
destructive Swanepoel envelope method
[8,12,14,15], but there is no report which compares
the film thickness obtained from scanning electron
micrograph with the thickness calculated from
transmittance spectra using envelope method.
Therefore, in this paper, we report a thickness
measurement using transmission spectra and
validated with a cross-section image of ZnO films.
We have also studied the wavelength dependent Fig. 1: Flow chart to deposit a ZnO film by spin coating.
complex refractive index and dielectric function of

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 R. R. Ghimire, Y. P. Dahal, K. B. Rai and S. P. Gupta

The optical properties of ZnO films were carried These optical constants are evaluated outside the
out with Ultraviolet–visible Spectrometer (Ocean region of fundamental band gap For
Insight model no: FLAME-T-UV-VIS). The optical this we have made envelope in the interference
transmittance at normal incidence was recorded in region (weak and medium absorption region) in the
the wavelength range of 375nm-1300. Swanepoel’s transmittance curve as shown in Fig. 2 (a).
envelope method [10,14,16,17] was employed to The absorption coefficient α and the extinction
evaluate the optical constants such as the refractive coefficient κ can be calculated as, [13, 16]
index n, extinction coefficient k and absorption
coefficient α from transmittance spectra. The
thickness of the ZnO films was determined from
interference fringes of transmittance data and ... (1)
validated with the cross-section SEM micrograph.

3. RESULTS AND DISCUSSION

... (2)
Determination of optical band gap and thickness
of ZnO film
Fig. 2 (a) depicts the variation of optical Where α is the absorbance coefficient and is the
transmittance (T%) of ZnO thin films in the film thickness and and are the wavelength at
wavelength region 375nm to 1300nm. The average two adjacent maxima or minima.
transmittance of the film, including substrate in the An optical band gap of nanostructured ZnO film is
visible range is observed over 84%. This high calculated from the fundamental absorption edge of
transmittance value suggests that the film is better the films which corresponds to the transition of
crystalline and can be used as a TCO and solar cell electrons from the valence band to the conduction
electrodes. An excellent surface quality and band.
homogeneity of the film is also confirmed by the Material like ZnO which has direct transition, the
appearance of interference fringes in the absorption gap (Eg) can be expressed by [2,3,4,12]
transmittance spectra which appears due to the
reflection from the film surface without much
... (3)
absorption and scattering in the bulk of the film
[16]. The value of transmittance is suddenly
dropped close to zero when the wavelength falls Where A is a constant, is the photon energy
below 400 nm because of band gap absorption of and Eg is the optical energy band of ZnO. Fig. 2
ZnO. The optical constants such as refractive index (b) depicts the plot of (αhν) 2 versus photon
n, absorption coefficient α, extinction coefficient k energy (hν) for ZnO sample. The values for
and band gap (Eg) and film thickness were (αhν)2 and (hν) were determined from
determined from the transmittance spectrum by transmittance data for different wavelength. The
envelope method [17]. optical band gap (E g) of the films was determined
by extrapolating the linear portion of (ahv)2
(a) (b) versus hν curve to (ahv)2 = 0. The calculated
value of the band gap in ZnO film was found to
be 3.02 eV, which is shown in table 1. The
obtained value of band gap is slightly less than
the most of reported value which may arise due
to the large grain size and impurities’ effect [4].
The thickness of the film was calculated using
following relation [13, 14]

... (4)

Fig. 2: (a) Transmittance spectrum of undoped ZnO films 1 11

O 2
annealed at 450 C (b) Plot of (αhν) as a function of Where, n1 and n2 are the refractive indices at
photon energy two adjacent maxima (or minima) corresponding to

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Determination of Optical Constants and Thickness of Nanostructured ZnO Film by Spin Coat Technique

the wavelengths λ1 and λ2. The thickness of the zinc be 275 nm. This is very close to the thickness
oxide film calculated by this method was found to measured from SEM image (290 nm).

Fig. 3: SEM Micrograph of undoped ZnO films annealed at 450ºC (a) Surface view of (b) cross-section view
B
Linear Fit of Sheet1
Fig. 3 (a) shows the surface view of the Scanning
Electron micrograph (SEM) of the ZnO films. 0.40
The film consists with large no. of grains and
grain boundaries. The porosity and voids of the 0.35
(n2-1)-1

films are clearly observed in this image. The

average grain size of the film is observed ~ 30 0.30
nm. Fig. 3 (b) shows the SEM image of a cross-
section of undoped ZnO film and the thickness of
the film is ~285 nm. This value of thickness is 0.25
very close to the thickness measured by envelope
method. 0.20
0 1 2 3 4 5 6 7
Determination of complex refractive index and 2 -2
Cauchy’s parameters of ZnO films 1/l (micron)
The variation of refractive index n and extinction
coefficient κ with wavelength in the region 400nm 2 -1
Fig. 5: Plot of (n -1) versus λ
-2

– 1100nm is shown in Fig. 4.

Imaginary part of dielectric constant

2.40 5.5 2.4

Extinction Coefficient (K)

Real part of dielectric constant

Extinction coefficientk(Experimental)
Refractive index n (Experimental) 0.64
2.32 2.2
Refractive index (n)

Refractive index n (Theoritical)

5.0
2.24 0.56
2.0
4.5
2.16 0.48 1.8
4.0
2.08 0.40 1.6
2.00 3.5 1.4
0.32
1.92 3.0 1.2
0.24
1.84 400 500 600 700 800 900 1000 1100
400 500 600 700 800 900 1000 1100
Wavelength (nm) Wavelength (nm)
Fig. 4: n and k versus λ of undoped ZnO film Fig. 6: λ versus n of nanostructured ZnO film

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 R. R. Ghimire, Y. P. Dahal, K. B. Rai and S. P. Gupta

The dispersion of refractive index ( ) of the film corresponding minimum (Tm) may be determined at
along the Cauchy’s constants was theoretically the same λ, and vice versa. Fig.4 shows the plot of
observed in ZnO by the following relation [10,12] complex refractive index of the film
with wavelength λ, where is the real part and
... (5) is the imaginary part (extinction coefficient)
of refractive index .
Where, and are Cauchy’s parameter and is The real part of complex refractive index varies
the wavelength of light interacted with the film. from a minimum of 1.86 to a maximum of 2.34.
The experimental graph is very closely matched The value of the real part of the refractive index
with simulated curve. Fig. 4 shows the refractive decreases with increasing the wavelength and the
index vs. wavelength (dispersion relation of imaginary part of complex refractive index i.e.
refractive index : solid black curve shows the Extinction coefficient is increasing with
theoretical and red dashed curve shows with increasing wavelength. The value of n is first
experimental plot). Experimentally the value of steeply down up to 600 nm and then gradually
refractive index is calculated using the fringe decreasing with wavelength. The higher value of
envelop method: refractive index in the UV and blue green region
is due to band gap and defect state absorption of
ZnO film [10]. The minimum value of extinction
... (6) coefficient indicates that the ZnO film has low
dielectric loss and this loss will increase with
increasing wavelength [10]. The dispersion
Where ... (7) parameter and are obtained using Sellmeier
equation as [10,19]

TM and Tm are maximum and minimum

... (8)
transmission respectively, on the envelope at a
certain λ, and refractive index ns of the substrate.
The envelopes connecting the interference maxima Where and are slope and intercept of the plot
and minima are considered to be continuous of vs. . The plot is shown in
functions of the wavelength λ. Therefore, for each Fig. 5 and least square fit of A and B are listed in
maximum of the transmission curves (TM) table 1.

Table 1: Values of ‘n’ Extinction coefficient, and least square fit of A and B
Thickness of sample (nm) Refractive index Extinction A(µm-2) B Band gap (eV)
(n) coefficient
~290nm (SEM Micrograph) 2.34-1.86 0.28-0.64 0.036 0.44 3.02
~280nm (Envelope method)

For , Determination of frequency dependence

complex dielectric functions of ZnO film
For longer wavelength, which gives
The dielectric function of bulk ZnO has been
. This value of B for the long wavelength region
intensively studied by various group using
is well matched with a fitted value as listed in the
Spectroscopic Ellipsometer and impedance
table.
analyzer [20,21,22]. It is known that the exciton
The value of n decreases slowly with increasing the created near band edge absorption significantly
wavelength beyond 600 nm. This phenomenon is influences the dielectric function of nanostructured
attributed due to the scattering of the light within ZnO. The dielectric properties of this material in
surface level defect states. The value of extinction visible region offer much information related to
coefficient is considerably low in comparison to the impurities, defects and space charge carrier
value of the refractive index n, which confirms the transport. Grain size and surface roughness have
ZnO film has a low dielectric loss. the critic role to tune the dielectric function of ZnO

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Determination of Optical Constants and Thickness of Nanostructured ZnO Film by Spin Coat Technique

films in visible regime. SEM micrograph shows the and the film thickness was measured 375 nm by
polycrystalline large number of nano grains with envelop method. Further the calculated thickness
sufficient voids and porosity. The dielectric was validated by a cross-section view of SEM
function of ZnO primarily depends on the dielectric image of nanostructured ZnO film. The measured
behavior of grain and grain boundary defect states. thickness using nondestructive envelope method is
The optical constants or dielectric function of nearly consistent with thickness measured from
nanostructured ZnO is essentially depends on the SEM micrograph image. The optical constant such
band gap of this material. The electronic excitation as complex refractive index and dielectric functions
spectrum of a thin film is generally described in were measured in the UV-visible region. The real
terms of complex electronic dielectric function part of the refractive index decreases with
given below [10,18]. increasing wavelength whereas the imaginary part
is increasing. The high value of refractive index at
... (9) lower wavelength and wavelength dependency
primarily depends on the absorption and scattering
due to deep levels and sallow level defect states.
The real part and imaginary part of the complex The visible illumination controls the midgap states
dielectric function contains the desired information by discharging the oxygen vacancies which reduced
of nanostructured films. The real part and the carrier scattering center. The complex dielectric
imaginary part of dielectric functions are associated function of this material is substantially dependent
with refractive index n and extinction coefficient k on the frequency of the light used. The exitonic
by the following formula. emission or carrier generation greatly enhanced the
real part of dielectric and low dielectric loss.
... (10)
ACKNOWLEDGEMENTS
... (11) Technology Innovation Center, Sungkyunkwan
University, Suwon 440-746, Korea is
Fig.6 depicts the real and imaginary part of the acknowledged for SEM micrograph. Prof. Shankar
complex dielectric function of nanostructured ZnO Prasad Shrestha is acknowledged for his valuable
film. The real part of dielectric function is higher suggestion and UV visible spectroscopy.
than the imaginary part which confirms the film has
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