Effect of Substrate Surface on the Wide Bandgap

SnO2 Thin Films Grown by Spin Coating

Md. Nur Amin Bitu *†, Nazmul Islam Tanvir*§†, Suravi Islam*†, Md. Saidul Islam*†, and Syed Farid Uddin Farhad*§†
*
Energy Conversion and Storage Research, Industrial Physics Division, BCSIR Labs, Dhaka 1205, Bangladesh
§
Central Analytical and Research Facilities (CARF), Dhaka 1205, Bangladesh
†
Bangladesh Council of Scientific and Industrial Research (BCSIR), Bangladesh
Email: [email protected]

Abstract— Tin (IV) oxide (SnO2) sols have been synthesized growth that dictate their overall surface roughness and
from SnCl2.2H2O precursor solution by applying two different morphology, resulting in their optoelectronic properties. To
processing conditions. The prepared sols were then deposited on this end, we choose the two most popular non-conducting
UV-Ozone treated quartz and soda lime glass (SLG) substrates substrates, namely SLG and Quartz, to investigate their effect
by spin coating. The as-synthesized film was soft-baked at about on the growth of SnO2 films and their physical properties.
100 C for 10 min. This process was repeated five times to get a
compact film, followed by air-annealing at 250 C for 2 h. The This paper describes the synthesis and characterization of
pristine and annealed films were characterized by UV–Vis-NIR SnO2 thin films annealed at a low processing temperature of
spectroscopy, Grazing Incident X-Ray Diffraction (GIXRD), 250 °C. The annealing temperature of 250 °C was chosen to
and Field Emission Scanning Electron Microscope (FESEM). prevent the cracking of both deposited layers on the substrate
The effect of substrate surface was investigated by measuring surface as well as the SLG substrate itself (glass softening
the contact angles with De-Ionized (DI) water. UV-Ozone temperature is ~300 °C) ([6] and refs. therein).
treatment of substrate provides a cleaner surface to grow a
homogeneous film. The electrical resistivity of annealed thin II. EXPERIMENTAL SECTION
films was carried out by a four-point-collinear probe employing
A. Substrate Preparation
the current reversal technique and found in the range of ~2×103
to 3×103 Ω.cm. Film thickness was found in the range of ~137 - Before thin film deposition, soda lime glass (SLG)
285 nm, measured by a stylus profilometer. UV-VIs-NIR substrate and quartz substrate (12×12×1) mm3 were initially
Transmission data revealed that all the thin film samples scrubbed with detergent soap in clean tap water and then
showed maximum (82-89) % transmission in the visible range. immersed into a hot water-filled beaker for ultrasonic cleaning.
The optical bandgap of the thin films was estimated to be ~3.75 To remove the grease and other stubborn dirt from the surface
- 4.00 eV and ~3.78 to 4.35 eV for the films grown on SLG and of the substrate, they were further subjected to ultrasonic
quartz substrates, respectively. cleaning sequentially in toluene, acetone, isopropanol, and
Keywords— Wide bandgap semiconductor, Tin (IV) oxide finally in deionized (DI) water at 40 ○C, each step for 15 min.
(SnO2), Spin coating, UV-Ozone treatment, Contact angle Then, to eliminate moisture from the substrate's surface, they
measurement. were dried by a compressed air blower and air-annealed at 100
○
C for 5 min. Finally, the substrates were subjected to UV-
I. INTRODUCTION ozone treatment for 20 min just before the spin coating.
Metal oxide semiconductors are intriguing because of B. Thin Film Fabrication
their tunable optical bandgap, variable physicochemical Tin (II) chloride di-hydrate (SnCl2.2H2O, purity ∼98 %,
properties, nature of conductivity, excellent mechanical and Alfa Aesar) was used as a starting material for preparing the
chemical stability [1-3], etc. With the help of advanced precursor solution. Briefly, tin (II) chloride di-hydrate (molar
technology, as it is possible to produce metal oxides as thin mass: 225.65 g/mol) of 0.5641 g was dissolved with 25 ml
films [4], nanoparticles [5], nanowires, and nanorods [6], ethanol (C2H5OH, purity ∼99.9 %, Merck Germany) to
their application in semiconductor electronics and energy prepare 0.1 M precursor solutions. Then the solution was
conversion and storage devices has increased over time. Thin stirred at 500 rpm with a magnetic stirrer coupled hotplate
films of such metal oxides are desirable as electrodes for under two conditions (80 ○C for 2 h and 60 ○C for 5 h) to
optoelectronic devices that need materials that can be synthesize SnO2 Sols. The solution was then filtered using a
transparent to light and conduct electricity. These thin films 0.20 μm polytetrafluoroethylene (PTFE) filter before coating
enable light to flow through with minimum absorption, which the substrates. Spin-coating was carried out using a
led to the development of transparent conductive oxide commercial spin coater (Polos-SPIN150i-NPP, Germany)
(TCO) [7]. Due to their conducive electro-optical properties, with two steps (500 rpm, 5 s, and 2000 rpm, 25 s). The
highly transparent and conductive oxide thin films are prepared film was soft-baked at about 100 oC for 10 min. This
extensively used materials, especially in solar cells. TCOs process was repeated five times to get five layers for each
such as tin (IV) dioxide (SnO2) thin films with wide bandgap sample to achieve the desired film thicknesses. After
energies (Eg >3.4 eV) have a prominent interest in transparent deposition, SnO2 thin films were air-annealed at 250 oC for 2
conducting electrodes for displays, n-type transport layer for h in a furnace (model: Nabertherm P-310, Germany) with a
high-efficiency perovskite solar cells, as well as other heating rate of 5 ○C/min. The SnO2 thin films grown using the
optoelectronic devices [8,9,10]. solution synthesized at 80 ○C for 2 h and 60 ○C for 5 h on
The surface nature of substrates plays a critical role in glass substrates were abbreviated as G-1 & G-2, and those on
nucleation, coalescence of islands, and subsequent film quartz are abbreviated as Q-1 & Q-2, respectively.

Page 1 of 4
C. Thin Film Characterizations (a) (d)
The optical transmission and absorption data were
recorded at room temperature by a UV–Vis–NIR
spectrophotometer (SHIMADZU 2600, Japan) in the
wavelength range of 220–1400 nm. The structural
characterization of the deposited thin films was performed by
the grazing incident x-ray diffraction (GIXRD) technique
using a Thermo Scientific ARL EQUINOX 1000 X-Ray
Diffractometer (USA) with a monochromatic copper anode
source of Cu-Kα radiation, λ = 1.5406 Å in out-of-plane (b) (c)
geometry. The film thickness was measured by an Alpha-
Step D-500 stylus profilometer. The electrical resistivity of
the films was measured using a four-point collinear probe
(Ossila, UK) coupled with a Keithley 2450 Source Measure
Unit (SMU). The surface morphology of the deposited films
was investigated using a Field Emission Scanning Electron
Microscope (FESEM) (JEOL, JSM-IT800). A contact angle
goniometer, coupled with a high-resolution video camera
Fig. 1. Water contact angle (WCA) measurements to show the hydrophilic
(Ossila, UK), was used to measure the blank substrates' water nature of cleaned Glass and Quartz substrates’ surface.
contact angle (WCA) before and after cleaning with different
solvents and UV-Ozone treatment. B. Optical Properties
The absorption spectra of the synthesized SnO2 sols are
III. RESULTS AND DISCUSSION
shown in Fig. 2. A strong absorption peak that appeared near
A. Effect of Substrate Cleaning by Water Contact Angle about 244 nm and 249 nm confirms the formation of SnO2 sols
Measurement [12].
A properly cleaned substrate surface is the prerequisite for o
homogenous and compact thin film growth. To assess the SnO2 (80 C for 2 h)
249 nm
degree of cleanliness of substrate surfaces by the procedure 3 244 nm o
SnO2 (60 C for 5 h)
described in subsection A of experimental section II, all the
cleaning steps were systematically investigated by the water
Absorbance (a. u.)

contact angle (WCA) measurements (Fig. 1). The experiment

shows that the WCA of quartz without cleaning decreases a 2
little from 24.15  1.55 deg. to 16.35  1.43 deg. within 6 s
(Fig. 1b). In contrast, after sonication with different solvents,
WCA decreases from 9.60  0.37 deg. to 5.06  0.11 deg.
within 200 ms. When the substrate was further subjected to 1
UV-ozone treatment, the 185 nm radiation generated from the
UV-Ozone cleaner reacted with oxygen (O2) in the air to
produce ozone (O3), which decomposed and transformed
organic pollutants on the surface of the substrate into volatile 0
substances, which can easily remove [11]. After UV-Ozone 250 300 350 400 450 500
cleaning WCA of quartz decreases significantly from 7.14  Wavelength (nm)
0.12 deg. to 1.82 deg. within 100 ms (Fig. 1c). In the case of a
glass substrate, the WCA remains almost constant or Fig. 2. Absorption spectra of the synthesized SnO2 sols
decreases very slowly (Fig. 1d). From this observation, we can
conclude that UV-Ozone treatment offers better cleaning The optical transmission spectra of all the thin films,
results on quartz than on the SLG substrate, which may be along with the blank quartz and SLG substrate, are shown in
beneficial for producing a homogeneous thin film. Fig. 3. The transmission data revealed that all the films are
highly transparent (82-89 % transmission near 535 nm) in the
visible region. It is worth noting that the same sols were
deposited on quartz and SLG substrates. Here, we observed
that the SLG substrate absorbs light near about 300-350 nm
range, but quartz doesn't, which facilitates finding the actual
transmission spectra and the absorption edge of SnO2 thin
films.

Page 2 of 4
 100
Blank quartz
TABLE I. OPTICAL PROPERTIES OF SnO2 THIN FILMS
80
Parameter G-1 G-2 Q-1 Q-2
Transmission (%)

Before After Before After Before After Before After

G-1 Before Ann. Ann. Ann. Ann. Ann. Ann. Ann. Ann. Ann.
60 G-1 After Ann. Bandgap, 3.80 3.77 4.00 3.75 4.20 4.03 4.35 3.78
G-2 Before Ann. Eg (eV)
G-2 After Ann. T (%) at 85 83 86 83 89 82 85 83
40 Q-1 Before Ann. 535 nm
Q-1 After Ann.
Q-2 Before Ann.
20
Q-2 After Ann. C. Structural Properties
Blank glass (SLG)
0
The crystalline phase and structure of the synthesized
SnO2 thin films were confirmed by GIXRD (Fig. 6). The
250 300 350 400 450 500 550 600 650 700 750 800
angle of incidence was set as a program of two steps; one is
Wavelength (nm)
0.1 to 0.5 deg., and another is 0.5 to 4.5 deg. with an
Fig. 3. Optical transmission spectra of SnO2 thin films before and after
increment of 0.1 deg. and 0.5 deg., respectively. Fig. 6
annealing shows GIXRD patterns of SnO2 thin film (Q-1) and
exhibited a better XRD pattern from 0.3 deg. to 2.0 deg. of
The direct bandgap of the SnO2 thin films was found by incident angle. From the GIXRD pattern, observed (110),
extrapolating the linear portion of the graph of (αhv)2 versus (101), (211), and (112) planes indicate the characteristic
photon energy (hv) as shown in Fig. 4 and Fig. 5 for before peaks of tetragonal SnO2 [14].
and after annealing, respectively. The results reported in
Table I show that the bandgap of SnO2 films was found

(110)

(101)
1600
around (3.75 to 4.00) eV and (3.78 to 4.35) eV for thin film

(211)

(112)
Q1- 0.1 deg 600 s
grown on SLG and quartz substrates, respectively. Since Q1- 0.2 deg 600 s
1400
quartz does not absorb UV light up to 350 nm like SLG, Q1- 0.3 deg 600 s
Q1- 0.4 deg 600 s
therefore, quartz substrates allowed us to observe the actual 1200 Q1- 0.5 deg 600 s
wide bandgap (3.78 to 4.35) eV of our synthesized SnO2 thin
Intensity (a.u.)

Q1- 0.5 deg 600 s

Q1- 1.0 deg 600 s
films [12, 13]. 1000 Q1- 1.5 deg 600 s
Q1- 2.0 deg 600 s
Q1- 2.5 deg 600 s
7x1010 800 Q1- 3.0 deg 600 s
G-1 (Eg= 3.80 eV) Q1- 3.5 deg 600 s
6x1010 Q-1 (Eg= 4.20 eV) 600
Q1- 4.0 deg 600 s
Q1- 4.5 deg 600 s
G-2 (Eg= 4.00 eV)
(h)^2 (eV/cm)2

5x1010 Q-2 (Eg= 4.35 eV) 400

4x1010 200

10
3x10 0
10 20 30 40 50 60 70 80 90 100
2x10 10 Eg= 4.00 eV Eg= 4.20 eV 2 (deg.)

1x1010 Eg= 3.80 eV Eg= 4.35 eV Fig. 6. GIXRD patterns of SnO2 thin film (Q-1) after annealing

0 D. Electrical Properties and Thickness measurement

1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 The stylus profilometer measured thin film thicknesses
Energy (eV) ranging from 137 nm to 285 nm (Table II). The observed
electrical resistivity of the thin films grown on both SLG and
Fig. 4. Estimated direct bandgap of SnO2 thin films before annealing
quartz substrates was between 2.01×103 to 2.96×103 -cm.
Note that the electrical resistivities of thin films produced on
7x1010
G-1 (Eg= 3.77 eV) quartz are lower than those grown on SLG substrates. This
10 G-2 (Eg= 3.75 eV) presumably is due to more compact film from easy nucleation
6x10 Q-1 (Eg= 4.03 eV)
(h)^2 (eV/cm)2

Q-2 (Eg= 3.78 eV)

on the cleaner quartz substrate surface. The results of
5x1010 thickness and electrical resistivity are shown in Table II.
4x1010 TABLE II. THICKNESS and ELECTRICAL RESISTIVITY OF SnO2
FILMS
3x1010
SnO2 Thickness (nm) Electrical resistivity,
2x1010 Films ×103 /(-cm)
Eg= 3.77 eV Eg= 3.78 eV
1x1010 G-1 285 2.957
Eg= 3.75 eV Eg= 4.03 eV
G-2 238 2.245
0

1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 Q-1 276 2.092
Energy (eV) Q-2 137 2.013
Fig. 5. Estimated direct bandgap of SnO2 thin films after annealing

Page 3 of 4
 support of TWAS grant # 20-143 RG/PHYS/AS_I for ECSR,
IPD.
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