Journal of Sol-Gel Science and Technology (2021) 99:636–649

https://doi.org/10.1007/s10971-021-05599-7

O R I G I N A L P A P E R : S O L - G E L A N D H Y B R I D M A T E R I A L S F O R O P T I CA L ,
PHOTONIC AND OPTOELECTRONIC APPLICATIONS

Conductivity type inversion and optical properties of aluminium

doped SnO2 thin films prepared by sol-gel spin coating technique
S. S. Soumya1 R. Vinodkumar
●
1 ●
N. V. Unnikrishnan2

Received: 15 February 2021 / Accepted: 16 July 2021 / Published online: 11 August 2021
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2021

Abstract
This paper discuss the structural, optical and electrical properties of aluminium doped tin oxide thin films prepared by sol-gel
spin coating technique. The tetragonal rutile structure of SnO2 was confirmed from the XRD measurements and having a
preferential orientation along (1 1 0) plane. FESEM analysis reveals that the particles were uniformly distributed in the film
and they are in the range of 10.15–39.58 nm. UV-Vis spectroscopy studies shows that the films were highly transparent and
the band gap values are ranging from 3.30 to 3.57 eV. FTIR study reveals that the prepared films contain Sn–O–Sn, Sn–O,
1234567890();,:
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H–O–H, C–O and Sn–OH vibrations. Hall measurement analysis shows that the conductivity type was reversed from n-type
to p-type at higher doping concentration of aluminium. The calculated values of mean free path were ranging from 0.6052 to
5.3732 A0. The Figure Of Merit (FOM) values were calculated and are ranging from 5.58 × 10−7 Ω−1 to 1.74 × 10−5 Ω−1.

Graphical Abstract
The conductivity type was changed from n-type to p-type by doping tin oxide with 15 wt% aluminium.

Keywords Spin coating Aluminium doped tin oxide thin films Electrical properties and conductivity type inversion
● ●

* R. Vinodkumar
vinodkopto@gmail.com
1
Department of Physics, University college,
Thiruvananthapuram, Kerala, India
2
School of Pure and Applied Physics, Mahatma Gandhi University,
Kottayam, Kerala, India
Journal of Sol-Gel Science and Technology (2021) 99:636–649
Highlights
● XRD confirms the tetragonal rutile structure of SnO2 thin films.
● FESEM shows the agglomerated network like structures for 10 wt% aluminium doped tin oxide.
● The charge carrier concentration of the sample first decreases with increase in alumnium doping concentration up to
10 wt% aluminium doping and it decreases for 15 wt% aluminium doped tin oxide thin films.
● Conductivity type was inverted from n-type to p-type at 15 wt% aluminium doping.
1 Introduction
Materials in the form of thin films represent the key con-
stituent of advanced electronics, photovoltaic technology,
protective coatings technology and functional nano devices
[1]. In recent years so many studies focuses on thin films
made from transparent conducting oxide materials. Trans-
parent conducting oxides received considerable attention
because of their applications in optoelectronics and optical
and electrical devices. A good TCO must have low resis-
tivity, high transmittance in the visible region
(400–800 nm), and high chemical stability. TCO films have
high optical transmittance and low electrical resistivity,
which are the key elements for transparent electrodes in
solar cell [2]. SnO2 is an n-type semiconductor with wide
band gap of 3.8 eV [3]. Besides the other transparent con-
ducting oxides, doped SnO2 is the best known representa-
tive of the class of transparent conducting oxide and find
use in the form of polycrystalline thin films [4]. Transparent
conducting oxide thin films with large band gap energy
exhibit high electrical conductivity and high optical trans-
mittance in the visible region and high reflectance in the IR
region [5]. Tin oxide has so many applications in the nano
structured form. It is used in optoelectronic devices [6, 7],
solar cells [8], gas sensors [9, 10], lithium ion batteries [11],
thin film transistors [12, 13], substrates for electro deposi-
tion [14], aerogels [15] and for humidity sensing purposes
[16, 17].
SnO2 thin films can be prepared by using a number of
methods. They are Sol-gel Dip coating technique [18, 19],
Sol-gel Spin coating technique [20], Ultrasonic Spray pyr-
olysis [21], Co-precipitation method, Ball milling method,
Solvothermal method and pulsed laser deposition method
[22]. In this paper sol-gel spin coating technique was used
to synthesis tin oxide thin films. It is a chemical and low
cost method used for preparing uniformly coated thin films.
We can control the preparation parameters (such as con-
centration, viscosity, etc) easily by this method. Doping
enhances the electrical and optical properties of tin oxide
thin films and its applications. In this paper our aim is to
fabricate a p-type tin oxide thin film using the n-type tin
oxide material by doping it with aluminium. Aluminium is
an extrinsic p-type dopant used in the thin film technology
[23]. So we choose aluminium as dopant for the preparation
of p-type tin oxide thin film. P-type Transparent conducting
637
oxide materials were used for thin film transistor applica-
tions, gas sensing [24], functional windows, photovoltaic
industry [4] and optoelectronic applications. In this work we
studied the structural, optical and electrical properties of
aluminium doped tin oxide thin films deposited on glass
substrate by using sol-gel spin coating technique.
2 Experiment
The starting materials were Tin(II) chloride dehydrate,
SnCl2.2H2O (Purified by Merck), Aluminium nitrate
nonahydrate, Al(NO3)3.9H2O and absolute ethanol.
1.128 gm of SnCl2.2H2O was dissolved in 10 ml of abso-
lute ethanol and add 0.0937 gm, 0.1875 gm and 0.2813 gm
of Al(NO3)3.9H2O into this solution. So we get undoped,
5 wt%, 10 wt% and 15 wt% Aluminium doped SnO2
solutions. Then the solution was stirred for 1 h at 323 K
using a magnetic stirrer to get the homogeneous solution.
The resulting solution was kept 24 h under room tem-
perature for gelation. The glass substrates of dimension
2.5 cm × 2.5 cm were cleaned and were dried using a drier
at 80 °C. The gelated solution was coated on the pre-
cleaned glass plate using a spin coating machine
(SpinNXG-P1A). The spinning was done at 1500 rpm for
30 s to get uniform coating. The coated glass plates were
heated at 100 °C for 15 min using a hot plate to remove the
volatile solvents present in the films. Thus we get the
required SnO2 thin films. Undoped, 5 wt%, 10 wt% and
15 wt% Aluminium doped SnO2 thin films were named as
0AlSn, 5AlSn, 10AlSn and 15AlSn. All the films were
annealed at 600 °C in a muffle furnace for 1 h to increase
the crystalline nature. Ensure slow cooling of the samples
in the muffle furnace for the better oxidation of SnO
phases to SnO2. The softening temperature of the soda
lime glass substrate is 700 °C and its melting point is 1000
°
C. Gokçen Gokçeli et al. reported that they annealed the
indium tin oxide thin films from 450 °C to 650 °C for
studying the optoelectronic properties [25]. So in this work
we choose the annealing temperature as 600 °C.
The structural analysis of the films were characterised by
using XRD (BRUKER D8 ADVANCE) measurements in
2θ angle from 20 to 80° using CuKα radiation. Surface
morphology of the films was studied using FESEM (NOVA
NANOSEM 450) analysis and the film compositions were
638
Fig. 1 XRD spectra of undoped and aluminium doped tin oxide thin films by sol-gel spin coating technique
determined by using Energy dispersive X-ray analysis
(EDAX METEK Materials Analysis Division). The thick-
ness of all the prepared films was measured using Dektak
Stylus Profilometer. Optical studies of all the films were
done by using a UV—Vis Double beam spectrophotometer
(JASCO V-730) in the spectral range of 300–900 nm.
Fourier Transform Infrared spectroscopy was done by using
IRPrestige-21 Fourier Transform Infrared spectro-
photometer (SHIMADZU). Electrical study was done at
room temperature using Hall measurement apparatus
(Ecopia HMS 3000).
3 Results and discussions
3.1 XRD analysis
Figure 1 shows the XRD spectrum of undoped and alumi-
nium doped SnO2 thin films on glass substrates and post
annealed at 600 °C. The XRD patterns of 0AlSn, 5AlSn,
Journal of Sol-Gel Science and Technology (2021) 99:636–649
10AlSn and 15AlSn shows intense peaks suggesting the
good crystalline nature of the films. The peaks present in all
the films shows that they crystallise in tetragonal rutile
structure (JCPDS No.41-1445). The undoped SnO2 films
shows peaks corresponding to the lattice reflections (1 1 0),
(1 0 1), (2 1 1) and (1 1 2) with a preferential orientation
along (1 1 0) plane. All the aluminium doped films also
shows preferential orientation along (1 1 0) plane and all
other lattice reflection peaks were shown in Fig. 1. No
residual peaks of any other impurities and secondary phase
were found here, that confirms the proper phase formation
of the material [4]. No diffraction peaks corresponding to
aluminium were found in the aluminium doped tin oxide
thin films, that means aluminium gets properly incorporated
into the tin oxide lattice. The ionic radius of Al3+ ion is
0.53 A0, Sn4+ is 0.71 A0 and for O2− is 1.4 A0. So the Al3+
ions can properly incorporated into the Sn4+ sites in the tin
oxide lattice.
The texture coefficient (TC) represents the texture of a
particular plane, whose deviation from unity implies the
Journal of Sol-Gel Science and Technology (2021) 99:636–649 639

preferred growth [26]. The texture coefficient, TC(h k l) is

given by the equation [27].
(dislocations/nm2) × 10−3
Iðh k lÞ =I0ðh k lÞ
TCðh k lÞ ¼
Strain (×10−3) Dislocation density

ðN ÞΣfIðh k lÞ =I0ðh k lÞ g
1

Where I(h k l) and Io(h k l) are the measured and standard

2.25 intensities of (h k l) plane and N is the number of reflections
1.60
2.00
32.94

observed in the XRD pattern [27]. A sample with randomly

oriented crystallites presents TC(hkl) = 1, the larger the TC
value, the larger will be the abundance of crystallites
0.7097
0.6432
1.550
−17.99

oriented in that (hkl) direction [28]. For the calculation of

texture coefficient (1 1 0), (1 0 1) and (2 1 1) planes were
considered and are shown in Table 1. This shows that all the
films have preferential orientation along the (1 1 0) plane as
Average particle size from

shown in the XRD pattern. If TC(hkl) = 1 for all the (hkl)

planes considered, then the nanoparticles are with randomly
SEM Analysis (nm)

oriented crystallite similar to the JCPDS reference, while

Table 1 Structural parameters of undoped and aluminium doped tin oxide thin films prepared by sol-gel spin coating technique

values higher than 1 indicate the abundance of grains in a

given (hkl) direction [29].
The lattice constants, lattice distortion and cell volume
10.15
38.62
39.58
37.26

for all the films were calculated and were in good agreement
with the reported values. These values were shown in Table
W–H plot
Average crystallite size

1. The equation for calculating the lattice constants for

3.09
32.42
36.23
28.15

tetragonal lattice was

1 h2 þ k 2 l 2
2
¼ þ 2
d a2 c
Scherrer
method

6.15
21.09
24.99
22.35

Where h, k and l are the Miller indices and ‘a’ and ‘c’ are
(nm)

lattice constants and ‘d’ is the inter planar spacing of the

tetragonal lattice. The ‘c’ value decreases with increase in
Lattice volume

aluminium concentration in the tin oxide thin films.

The lattice distortion and lattice volume were calculated
V=a2c

73.86
70.92
70.40
70.70
(A0)3

using the equation

Lattice distortion U ¼ a=c

distortion

Lattice volume V ¼ a2 c
Lattice

U=a/c

1.5507 0.5011 0.9486 4.853 3.173 1.54

1.2309 0.9707 0.7984 4.733 3.172 1.49
10AlSn 1.4087 0.8620 0.7293 4.717 3.165 1.49
15AlSn 1.8464 0.5214 0.6322 4.734 3.161 1.50

The lattice volume of the tin oxide thin films decreases

with increase in aluminium doping concentration in the tin
constants

oxide thin films up to 10AlSn and for 15AlSn it increases

Lattice

(A0)
(1 10) (1 0 1) (2 1 1) a=b

because the lattice constant ‘a’ increases up to 10AlSn and

decreases for 15AlSn.
Sample Texture coefficient(TC)

The crystallite size was calculated using Scherrer equa-

tion [30] D ¼ βcosθ
kλ
Where k is the shape factor and is taken
as 0.9, λ is the wavelength of CuKα rays, β is the full width
half maximum (FWHM) and θ is the Bragg angle. The
average crystallite size calculated from XRD data were
shown in Table 1. The value of crystallite size ranges from
6.15 to 24.99 nm. The XRD peak broadening is mainly due
0AlSn
5AlSn

to instrumental broadening, Crystallite size, internal stress,

strain, lattice distortion and defects in the films. So the
640
Fig. 2 W–H plots of undoped and aluminium doped tin oxide thin films by sol-gel spin coating technique
crystallite size calculated by Debye-Scherrer formula may
not be the actual crystallite size [31]. So we use
Williamson–Hall plot for the calculation of crystallite size
and the study of FWHM (β), of the XRD peak. Depending
on different θ positions the separation of size, the strain
broadening analysis is done using Williamson and Hall plot
using the equation [32].
kλ
β cos θ ¼ þ 4ε sin θ
D undoped sample has the dislocation density 32.94 × 10−3
Where D is the actual particle size, k is the correction factor
which can be taken as unity, ε is the strain in the film and θ
is the Bragg angle. Strains in the films were calculated from
the slope and the actual particle sizes were calculated from
the y intercept of W–H plot and were shown in Table 1.
Figure 2 shows the W–H plot of all the samples. The
particle size calculated by W–H plot were ranging from
3.09 to 36.23 nm and these values did not vary extensively
from the values of crystallite size calculated by Debye-
Scherrer method, which indicate that the strain in the films
were less [33]. The instrumental broadening is corrected
Journal of Sol-Gel Science and Technology (2021) 99:636–649
using a standard material (silicon) for taking XRD and
subtracting that broadening from the sample [32]. Thus the
actual particle size D can be calculated.
The dislocation density, δ, is inversely proportional to
the square of the crystallite size according to Williamson
and Smallman’s relation. For the minimum dislocation
density, the proportionality constant is equal to unity [28].
The dislocation density is calculated by the equation δ ¼ D12 .
The calculated values were shown in the Table 1. The
dislocations/nm2 but the aluminium doping lowers the dis-
location density to 1.60 × 10−3 dislocations/nm2. This
means that aluminium incorporation reduces the disloca-
tions in the prepared thin films because these aluminium
ions occupies the lattice and the interstitial sites of tin oxide
thin films.
The crystallite size calculated by Scherrer method and
the crystallite size obtained by W–H plot were plotted
against the doping concentration of aluminium and were
shown in Fig. 3. From this we can understand that the
crystallite size increases with doping concentration up to
Journal of Sol-Gel Science and Technology (2021) 99:636–649
Fig. 3 Variation of grain size with Aluminium doping concentration in
SnO2 thin films by Scherrer method and W–H Plot
Fig. 4 Variation of strain with Aluminium doping concentration in
SnO2 thin films prepared by sol-gel spin coating technique
10AlSn and then it decreases for further increase of Alu-
minium doping concentration. This result was also sup-
ported by the particle size calculated by FESEM analysis.
After 10 wt% aluminium doping the grain size decreases
because it decreases the crystallanity of tin oxide and it act
as a grain growth inhibitor for higher concentrations [4].
Strains (ε) of all the samples were calculated using W–H
plot and were plotted against the doping concentration of
aluminium and were shown in Fig. 4. From this it was clear
that the strains of aluminium doped tin oxide thin films were
very high compared to the undoped sample. That means
Aluminium ions enters the crystal lattice of tin oxide
material and occupy the Sn4+ sites with Al3+ ions produce
strain in the crystal lattice. The strain of 5AlSn was higher
than 0AlSn means that aluminium incorporation in the tin
641
oxide lattice produces strain in the lattice. The doping
concentration of aluminium in the tin oxide films increases,
the strain in the tin oxide lattice decreases because the
excess Al3+ ions occupies the interstitial sites of the tin
oxide lattice. So for 10AlSn and 15AlSn the strain decreases
and is shown in the Table 1.
3.2 FESEM and EDAX analysis
FESEM analysis gives the information about the surface
topography and uniformity of the samples. The analysis of the
undoped and aluminium doped tin oxide thin films reveals that
the particles were uniformly distributed in the films and were
almost spherical in shape. The average particle size ranging
from 10.15 to 39.58 nm and are shown in Fig. 5. These were
in agreement with crystallite size obtained from XRD pattern.
The particles were spherical in shape for undoped tin oxide
thin films and the aluminium doping deviate the shape of the
particles from spherical nature. But for higher concentration of
aluminium doping (15AlSn), again the particles attain the
spherical nature. The particle sizes obtained from SEM ana-
lysis were shown in Table 1. The particles obtained in SEM
analysis were the aggregates of crystallites. So the particle size
was greater than the crystallite size. At higher concentrations
of aluminium doping, particle size decreases because the
aluminium ions act as grain growth inhibitor [34]. The net-
work like structures were formed due to the agglomeration of
nanoparticles in 10 wt% aluminium doped tin oxide thin films.
These network like structures facilitate the fast charge-
discharge characteristics [35] and were shown in Fig. 6 at
two different magnifications. The images of 10AlSn in Fig. 5c
and in Fig. 6 shows different morphology because in Fig. 6 the
images were at 5 µm and 10 µm magnifications but in Fig. 5c
the same sample was magnified to 500 nm.
EDAX analysis gives the quantitative analysis and che-
mical composition of the elements present in the sample. The
results reveal that tin, oxygen and Aluminium were present in
the sample and were shown in Fig. 7. The quantitative ana-
lysis reveals that there was a slight variation in the weight
percentage of aluminium in the tin oxide thin films and were
shown in the Table 2. Silicon was also present in the EDAX
spectrum because the films were coated on glass substrates.
The oxygen content of the glass substrate was registered
along with the oxygen content of the sample.
3.3 Optical studies
The transmittance spectra of glass substrate and all the
samples were shown in Fig. 8. Undoped tin oxide thin films
show the highest transparency (~80%) and all the alumi-
nium doped tin oxide thin films have transparency lower
than the undoped tin oxide thin films. Because aluminium
incorporation into the tin oxide lattice decrease the
642 Journal of Sol-Gel Science and Technology (2021) 99:636–649

Fig. 5 SEM images of (a) 0AlSn, (b) 5AlSn, (c) 10AlSn and (d) 15AlSn thin films by sol-gel spin coating technique

Fig. 6 FESEM images of 10AlSn at two different magnifications

transparency of the tin oxide thin films. The 5 wt% alumi- aluminium in the tin oxide thin films. 15 wt% aluminium
nim doped tin oxide thin films shows the lowest transpar- doped tin oxide thin films shows 72% transparency in the
ency in the lower wavelength region and the transparency wavelength range 400–900 nm and was steady in the visible
increases with increase in the doping concentration of range. The absorbance spectra of glass substrate and all the
Journal of Sol-Gel Science and Technology (2021) 99:636–649 643

Fig. 7 EDAX spectra of (a) 0AlSn, (b) 5AlSn, (c) 10AlSn and (d) 15AlSn thin films

Table 2 Weight percentage of the undoped and aluminium doped tin

oxide thin films obtained from EDAX analysis
Sample Weight (%)
Sn O Al

0AlSn 74.80 25.20 0

5AlSn 73.41 23.76 2.83
10AlSn 72.02 21.86 6.12
15AlSn 70.50 18.47 11.03

samples were shown in Fig. 9. The absorption coefficient α

of the films can be calculated using the equation α =
2.303 A/t
Where A is the absorbance and t is the thickness of the
films. The thickness of 0AlSn, 5AlSn, 10AlSn and 15AlSn
tin oxide thin films were measured using Dektak Stylus
Profilometer and the obtained values are 180 nm, 190 nm,
215 nm and 247 nm.
The optical band gap Eg of all the films were calculated
using Tauc
n plot [5] using the relationðαhν Þ ¼
A hν  Eg Where α is the absorption coefficient, h is the
Planck’s constant, ν is the transition frequency, A is a
constant, Eg is the band gap corresponding to a particular
transition occurring in the film and n gives transition type. n
= 1/2 for direct allowed, n = 2 for indirect allowed, n = 3/2
for direct forbidden and n = 3 for indirect forbidden. The
fundamental absorption which corresponds to the electron
Fig. 8 Transmittance spectra of Glass substrate, 0AlSn, 5AlSn,
10AlSn and 15AlSn SnO2 thin films by sol-gel spin coating technique
excitation from the valence band to the conduction band can
be used to determine the value of optical band gap [6]. The
values of direct optical band gap calculated for undoped and
Aluminium doped samples were shown in the Fig. 10. The
obtained values of optical band gap were ranging from 3.30
to 3.57 eV and are shown in Table 3. This value is in
agreement with the previously reported band gap values of
Aluminium doped SnO2 [23]. The variation of optical band
gap versus Aluminium doping concentrations were shown
644 Journal of Sol-Gel Science and Technology (2021) 99:636–649

Merit, φ (Ω−1)

1.74 × 10−5
2.91 × 10−6
5.58 × 10−7
2.83 × 10−6
Figure Of
Transmittance at
550 nm

79.82
67.32
65.14
71.90
sheet resistance,
Rs (KΩ)

6.0379
6.5691
24.6223
13.0557
Fig. 9 Absorption spectra of Glass substrate, 0AlSn, 5AlSn, 10AlSn
and 15AlSn thin films by sol-gel spin coating technique

path, L (A0)
Type Band gap Mean free

0.6052
3.9829
5.3732
2.5447
(eV)

3.50
3.57
3.52
3.30
n
n
n
p
σ (×103 Ω−1m−1)
Conductivity
Table 3 Hall measurement data of undoped and aluminium doped tin oxide thin films

0.9201
0.8012
0.1889
0.3101

Fig. 10 Direct optical band gap of 0AlSn, 5AlSn, 10AlSn and 15AlSn
thin films by sol-gel spin coating technique
ρ (×10−3 Ωm)
Resistivity

in Fig. 11. The optical band gap value of 5AlSn was higher
1.087
1.248
5.293
3.220

than the other undoped and aluminium doped films, because

5AlSn has the lowest value of transmittance in the lower
wavelength region.
(cm2/Vs)
Mobility

0.6758
12.220
39.460
3.172

3.4 FTIR analysis

FTIR spectroscopic technique was used as a fingerprint for the

concentration (cm−3)

identification and characterisation of the sample. Figure 12

shows the FTIR spectra of pure and aluminium doped tin oxide
SAMPLE Charge carrier

−8.498 × 1019
18

17

6.111 × 1018

thin films recorded between 400 and 4000 cm−1. The absorp-
−4.098 × 10
−2.988 × 10

tion peaks between 400 and 700 cm−1 are assigned to Sn–O &
Sn–O–Sn vibrations of tin oxide molecule [36]. The minimum
transmittance at 616 cm−1 and 622 cm−1 corresponds to
O–Sn–O bridge functional group, which clearly indicates the
10AlSn
15AlSn
0AlSn
5AlSn

formation of SnO2 phase [37]. The minimum transmittance in

the range of 1200–1300 cm−1 corresponds to the stretching
Journal of Sol-Gel Science and Technology (2021) 99:636–649
Fig. 11 Variation of Band gap with aluminium doping concentration in
the aluminium doped tin oxide thin films
Fig. 12 FTIR spectra of 0AlSn, 5AlSn, 10AlSn and 15AlSn thin films
by sol-gel spin coating technique
vibrations of O–H bond [38] or the in plane deformations of
O–H bond [39]. The absorption peaks between 1400 and
1700 cm−1 corresponds to Sn–OH vibrations because the pre-
cursor solution contain water [34]. The minimum transmittance
between the range of 2500–3600 cm−1 corresponds to the
bending mode of the H–O–H bond groups of adsorbed water
molecules and the stretching vibrations of the hydroxyl groups
present in the sample [16]. There was no peak corresponding to
the vibrations of Al–O bond. This means that aluminium gets
incorporated into the tin oxide lattice.
3.5 Electrical properties
Hall effect measurements were done for all the samples at
room temperature using Ecopia HMS 3000 and the results
reveals that at low doping concentration of aluminium the
645
SnO2 films shows n-type conductivity but at higher doping
concentration of aluminium (>10 wt%) the tin oxide films
shows p-type conductivity. Resistivity, conductivity, charge
carrier concentration and mobility were obtained from hall
measurement data and are shown in the Table 3. The n-type
conductivity of SnO2 films were attributed to the formation
of shallow donor levels occurring due to the presence of
oxygen vacancies and interstitial tin in the SnO2 lattice [40].
The conductivity of the films decreases with increase in the
aluminium doping concentration up to 10AlSn. But for
15AlSn the conductivity starts to increase. Deyu et al.
reported that the conductivity of aluminium doped SnO2
decreases consistently with increasing Al content due to the
presence of compensating holes up to 5.2 wt% [41]. In the
n-type SnO2 films the doped Al3+ ions replaces some of the
Sn4+ ions, there was a net decrease in charge carrier con-
centration [4]. Aluminium has one electron less than Sn and
were compensated by the conduction band electrons from
the SnO2 lattice [4]. So conductivity decreases for Alumi-
nium doped Tin oxide thin films up to 10 wt% of aluminium
doping. In 15 wt% aluminium doped tin oxide thin films the
conductivity starts to increases because all the Sn sites were
occupied by aluminium ions and all the conduction band
electrons were used for recombination with holes produced
by the doping of aluminium. Then the doping concentration
of aluminium increases the electron vacancies (holes) exist
as such and were responsible for the p-type conduction. The
increasing concentration of aluminium gradually changes
the conductivity from n-type to p-type [42]. The optical
band gap values decreases with increase in doping con-
centration of aluminium in the tin oxide thin films. This
shift in optical band gap of the aluminium doped films
depends on the free charge carrier concentration [42].
The charge carrier concentration increases, the mobility
of the ions decreases. This decrease in carrier mobility is
attributed to the increase in ionised acceptors [43]. A higher
n value usually creates more scattering centers that leads to
the reduction in the value of mobility [21]. The Hall
mobility in doped semiconductors is usually limited by two
major scattering mechanisms: grain boundary scattering and
ionised impurity scattering [44, 45]. The variation of charge
carrier concentration and mobility with doping concentra-
tion of aluminium in the tin oxide thin films was shown in
Fig. 13. The increase in charge carrier concentration of the
aluminium doped tin oxide thin films decreases the resis-
tivity of the films. Up to 10AlSn Charge carrier con-
centration decreases with increase in aluminium
concentration in the tin oxide thin films. For 15AlSn the
charge carrier concentration increases because of the con-
ductivity type inversion happens in the films. This change in
conductivity type from n to p type at higher doping con-
centration of aluminium was reported by Ahmed et al. [34].
The variation of resistivity and conductivity along with
646
Fig. 13 Variation of Carrier concentration and mobility with alumi-
nium doping concentration in the aluminium doped tin oxide thin films
Fig. 14 Variation of resistivity and conductivity with aluminium
doping concentration
doping concentration is shown in Fig. 14. The electrical
conductivity obtained in our samples were higher than the
reported values [4, 46]. Deyu et al. reported that the elec-
trical conductivity were lower than the conductivity
obtained in our work [41].
Mean free path is the average distance of the ions
between two successive collisions. The mean free path (L)
is calculated by using the following relation [44],
 
h 3n 1=3
L¼ μ
2e π
Where h is the Planck’s constant, e is the charge of the
electron, n is the carrier concentration and µ is the hall
mobility. The value of L was calculated for all the samples
and is shown in Table 3. The calculated values of L were
Journal of Sol-Gel Science and Technology (2021) 99:636–649
ranging from 0.6052 to 5.3732 A0. These values were
comparable with the previously reported values [21]. The
value of mean free path increases with increase in
aluminium concentration up to 10 wt% and it decreases
for higher doping concentration of aluminium in the tin
oxide thin films. Baber et al. reported that Antimony doped
tin oxide thin films also shows the comparable values for
the mean free path [44]. The mean free path obtained here
was considerably less than the grain size [45, 47].
The mobility, μ, is described by Matthiessen’s rule
[22, 46] by using the following equation
1 1 1 1 1
¼ þ þ þ þ¼
μ μimpurity μgb μphonon μhopping
where μimpurity, μgb, μphonon, and μhopping are factors that
influence mobility from impurity scattering, grain boundary
scattering, phonon scattering and retardation by hopping
transport, and phonon scattering respectively. In TCO thin
films, the ionised impurities and grain boundaries are found
to be the main scattering mechanisms [21]. Since the L
values are considerably shorter than the grain size, the Hall
mobility is limited by the ionised impurity scattering rather
than the grain boundary scattering [48]. Matthiessen’s rule
indicates that the inverse relationship between dopant
concentration and mobility fundamentally limits conductiv-
ity in TCO films [49].
The sheet resistance, Rs of a thin film is given by the
equation [50]
Rs ¼ 1=σ t
Where σ is the conductivity of the film and t is the
thickness of the film. The calculated value of sheet
resistance was shown in Table 3. Sheet resistance of the
aluminium doped tin oxide thin films increases with
increase in aluminium doping concentration up to 10AlSn
because the carrier concentration decreases up to 10AlSn.
For 15AlSn the Sheet resistance decreases because the
p-type carrier concentration increases. Sk F Ahmed et al.
reported that for aluminium doped tin oxide thin films
conductivity decreases first and then increases with
doping concentration of aluminium [34]. At first the
doping concentration of aluminium increases the genera-
tion of holes, but they recombine with the free carrier
electrons present in the tin oxide lattice. So conductivity
decreases [34]. On exceeding a critical percentage of
aluminium doping (12.5%) conductivity increases with
the increase of Al doping due to the generation of more
number of free carrier holes and there is no extra electrons
for recombination [34].
The figure of merit (FOM) of all the films were calcu-
lated using the Haacke’s relations [51, 52]
φ ¼ T10 =Rs
Journal of Sol-Gel Science and Technology (2021) 99:636–649
Where T is the transmittance at 550 nm and Rs is the sheet
resistance. Analogously to the procedure we did for the
electrical to optical conductivity ratio, we determined a model
for the FOM [53]. Figure of merit (FOM) is an important
parameter for evaluating the transparent conducting oxide thin
films for solar cell applications [51]. Higher the value of FOM,
the quality of the thin films increases [52–54]. FOM values of
all the samples were calculated and are shown in Table 3. The
calculated FOM values were ranging from 5.58 × 10−7 Ω−1 to
1.74 × 10−5 Ω−1. These values were comparable with the
reported values [21, 51, 55]. The highest value of FOM was
shown by 0AlSn films because its transparency is high.
Aluminium doping first decreases the FOM value up to 10%
aluminium doped tin oxide thin films and for 15% aluminium
doping FOM value increases. Here we successfully prepared
the p-type conducting tin oxide thin films from n-type tin oxide
material by using aluminium as the dopant. It was used in
optoelectronic devices, thin film transistors and in solar cell
technologies.
4 Conclusions
Tin oxide thin films with different aluminium concentra-
tions were prepared successfully by sol-gel spin coating
technique and were post annealed at 600 °C. XRD pattern
reveals that all the films were polycrystalline in nature with
tetragonal rutile structure. The average crystallite size varies
from 6.15 to 24.99 nm. The crystallite size calculated from
W–H analysis and XRD pattern were comparable and
showing less strain broadening in the films. FESEM ana-
lysis clarify that the particles were almost spherical in shape
and the spherical nature increases with increase in higher
doping concentration of aluminium. The average particle
size calculated from FESEM analysis varies from 10.15 to
39.58 nm. The transmittance spectra reveal that all the films
were transparent and the transparency lies in between 60%
and 80%. The band gap energy varies from 3.30 to 3.57 eV.
The FTIR spectrum shows that all the samples contain
Sn–O, Sn–O–Sn, O–Sn–O, C–O, Sn–OH and H–O–H bond
vibrations. Hall measurement study reveals that the alumi-
nium doping concentration change the conductivity from n
to p-type at 15 wt% aluminium doped tin oxide thin films.
So we successfully prepared p-type transparent conducting
tin oxide thin film from n-type tin oxide material by using
aluminium as the dopant with FOM value 2.83 × 10−6 Ω−1.
Acknowledgements Authors acknowledge RUSA for providing spin
coating unit and UV-Visible spectrophotometer.
Compliance with ethical standards
Conflict of interest The authors declare no competing interests.
647
Publisher’s note Springer Nature remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.
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