European Scientific Journal September 2016 edition vol.12, No.

27 ISSN: 1857 – 7881 (Print) e - ISSN 1857- 7431

Structure, Morphology and Opto-Electrical

Properties of Nanostructured Indium Doped SnO2
Thin Films Deposited by Thermal Evaporation

Md. Mahafuzur Rahaman

University of Dhaka, Dhaka, Bangladesh
Kazi Md. Amjad Hussain
Atomic Energy Center, Dhaka, Bangladesh
Mehnaz Sharmin
Bangladesh University of Engineering and Technology, Dhaka, Bangladesh
Chitra Das
BRAC University, Dhaka, Bangladesh
Shamima Choudhury, Prof.
University of Dhaka, Dhaka, Bangladesh

doi: 10.19044/esj.2016.v12n27p263 URL:[Link]

Abstract
Indium doped Tin oxide (SnO2: In) thin films of various thicknesses
(200-600 nm) with fixed 2% indium (In) concentration were prepared by
thermal evaporation method onto glass substrates under high vacuum (10-6
Torr). As deposited films were vacuum annealed at 200o C for 60 minutes.
The structure, optical, electrical and morphology properties of SnO2: In thin
films were investigated as a function of film thickness. The XRD analysis
revealed that films were polycrystalline in nature with a tetragonal structure
having (110) plane as the preferred orientation. The average crystalline size
increased from 34.8 to 51.25 nm with increase of film thicknesses. The
surface morphology of the doped films was obtained by Atomic Force
Microscopy (AFM) and Field Emission Scanning Electron Microscopy
(FESEM). Optical transmittance was obtained from a double beam UV-Vis-
NIR spectrophotometer. Maximum transmittance varied from 65-76% in the
visible range of the spectrum. Optical band gap (Eg) varied between 2.89 and
3.20 eV. The resistivity of SnO2: In thin films was as high as 105 Ω-cm.
Activation energy of the films were found to be 0.18 to 0.47 eV for 300-600
nm film thicknesses. Due to high optical band gap and high electrical
resistivity, these nanostructured films can be used in optoelectronic devices
especially as opto-isolator.

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Keywords: Nanostructured films, XRD, AFM, FESEM, Band gap

Introduction
Tin oxide (SnO2) is a wide band gap (3.6 eV) n-type semiconductor
where oxygen vacancies act as n-type dopants (Batzil, 2005). SnO2 films
have attractive properties like high transmittance in the visible range, low
resistivity and thermal stability (Zadsar, 2012) for which it has immense
applications such as gas sensing material for photovoltaic cell (Cachet,
1997), gas sensors devices (Galdikas, 1997), window materials in solar cells
(Roy, 2010), transparent conductive electrode for solar cells (Mohammadi-
Gheidani, 2005) and so on. Pure and doped-SnO2 thin films can be prepared
by various techniques, such as sol-gel (Banerjee, 2003), spray pyrolysis
(Gokulakrisshan, 2011), electron beam evaporation (Shamala, 2004),
electrostatic spray deposition (Joshi, 2013), RF sputtering (Tuna, 2010) and
thermal evaporation (Chuhan, 2012). Among these methods, vacuum
evaporation has the advantages of depositing high purity crystalline and
uniform films in a single step. This method is substrate friendly and
materials can be deposited in short time.
P-type SnO2 can be fabricated with effective substitution of Sn with
group III-family elements such as aluminum (Al), gallium (Ga), indium (In).
Recently there have been a number of studies on group III elements doped
SnO2 thin films such as Al doped SnO2 (Ahmed, 2006; Bagheri-
Mohagheghi, 2004), Ga doped SnO2 (Yang, 2010), SnO2: In (Chowdhury,
2011; Ji, 2006). We had investigated the optical properties of Indium doped
tin oxide thin films with various concentration of indium at a fixed thickness
of 200 nm by thermal evaporation method (Chowdhury, 2011).
In this present work, indium doped tin oxide thin films were prepared
with varying thicknesses (200-600 nm) and the prepared thin films were
vacuum annealed at 200°C for 60 minutes. The effects of film thickness on
the structure, optical, electrical and morphology properties were investigated.

Experimental
SnO2: In thin films were deposited on to glass substrates by thermal
evaporation method using a vacuum evaporation unit (EU-300), in high
vacuum (~10-6Torr). Two molybdenum boats- one for Indium and another
for SnO2- were used as a resistively heated source for the evaporation. The
substrate was placed at a distance 6.4 cm above the source materials. Before
deposition, glass substrates were cleaned chemically and ultrasonically. The
rate of evaporation was 0.2 nm/sec measured in situ by the FTM5 quartz
crystal thickness monitor (Edwards, UK). Thin films of various thicknesses
(200, 300, 400, 500 and 600 nm) were prepared keeping substrate
temperature constant at 100°C. As deposited films were vacuum annealed at

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200°C for 60 minutes. The structure of the SnO2: In thin films was examined
by X-Ray diffraction (XRD) measurements using PHILIPS PW 3040 X’ Pert
PRO system. The surface morphology of the films was performed using
Atomic Force Microscope (AFM) (Nano Surf) and Field Emission Scanning
Electron Microscope (FESEM) of model JEOL JSM-7600F. A double beam
UV-VIS-NIR recording spectrophotometer (Shimadzu, UV-3100) was used
to measure optical transmittance (T%) and reflectance (R%) of the SnO2: In
thin films. The resistivity of the films was measured by locally fabricated
four point probe method. Resistivity of the films were studied in the
temperature range 25°C-100°C and activation energy was calculated from
the obtained data.

Results and Discussion

Structural Analysis
Typical XRD patterns of the annealed indium doped tin oxide thin
films of different thicknesses are shown in Figure 1. All the films are
oriented along (110) direction and the peak position is consistent with the
JCPDS file card No. 41-1445, which is in agreement with the other workers
(Gurakar, 2014). The intensity of the (110) diffraction peak increases with
film thickness. Thin film of 200 nm is less crystalline due to the effect of
amorphous glass substrate. The effect of the glass substrate decreases with
the increase of film thickness. The crystallinity of the films increases with
film thickness up to 500 nm.
There is no peak for indium oxide, indicating that indium
incorporates into SnO2 lattice. Form Table 1 it can be shown that diffraction
angle decreases with the increase of film thicknesses. The decrease in
diffraction angle results in increase of the lattice constants due to the larger
size of In3+ (0.81 Å) compared to Sn4+ (0.71 Å). This is an indication of
increase of substitution of Sn4+ by In3+with the film thickness (Ji, 2006).
The average size of the crystallites (D) corresponding to (110)
direction was calculated using the Scherrer’s formula (Cullity, 1972)
0.9𝜆
𝐷= (1)
𝛽 cos𝜃
Where, λ is the wavelength of the X-rays, β is the full width at half
maxima (FWHM) of the peak which has maximum intensity, and θ is the
Bragg’s angle. The variation of crystallite size with film thickness is shown
in Table. 1. It is clear from the table that crystallite size increases with
increasing film thickness.

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Figure 1: XRD patterns of SnO2: In thin films of different thicknesses.

The dislocation density (δ) and the strain (ε) of the films were
determined with the use of the following formula (Jassim, 2013)
𝛿 = 1⁄𝐷2 (2)
𝛽 cos 𝜃
𝜖= (3)
4
Where, δ is defined as the length of dislocation lines per unit volume.
It is the measure of the amount of defects in a crystal. The dependence of the
strain and dislocation density of SnO2: In thin films on thickness is shown in
Table 1.
It is seen from Table. 1, that strain and dislocation density decrease
with the increase of film thickness. This decrease in strain and dislocation
density indicates a decrease in the concentration of lattice imperfection.
Table 1: Structural properties of SnO2: In thin films of different thicknesses
Distance
Thickness Position between Cryst- Dislocation Microstrain
(nm) Plane 2θo crystal allite Density, δ ε
plane, d Size, D (cm-2)
(Å) (nm)
200 29.55 3.0205 34.80 8.26 x 1010 9.97 x 10-5
10
300 29.53 3.0225 45.83 4.76 x 10 7.56 x 10-5
10
400 (110) 29.51 3.0245 47.03 4.52 x 10 7.37 x 10-5
10
500 29.38 3.0376 51.25 3.81 x 10 6.54 x 10-4

Optical Properties
The variation of optical transmittance (T %) and reflectance (R %) of
the indium doped tin oxide thin films were measured with photon
wavelength in the range of 300-2500 nm. Figure 2 shows T% and R%
spectra of the films at different film thicknesses. The spectra shows

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interference pattern with a sudden fall of transmittance near the band edge.
The maximum transmittance of the films varies from 65% to 76% in the
visible range of spectrum. All the films show maximum transmittance in NIR
region and peaks of transmittance spectrum shift towards the higher
wavelength with film thicknesses. The 300nm doped film shows maximum
transmission (85%) in NIR region. Das et al. found similar results for
vacuum evaporated GaAs thin films. The reflectance spectra shows
interference pattern with distinct peaks and valleys.
Extinction coefficient (k) was obtained from Transmission (T%) and
Reflection (R%) measurements (Heavens, 1955 and Tomlin, 1968). For a
film of thickness d which has a complex refractive index, n1-ik1, the relevant
equations are
1 (1 + n12 + k12 ){(n12 + n22 + k12 )cosh2α1 + 2n1 n2 sinh2α1 } +
[ ]−
2 2
4n2 (n1 +k1 ) (1 − n12 − k12 ){(n12 − n22 + k12 )cos2γ1 − 2n2 k1 sin2γ1 }
1+R
= f1 (n1 , k1 ) = 0 (4)
T

1 n1 {(n12 + n22 + k12 )sinh2α1 + 2n1 n2 cosh2α1 } + 1−R

(n2 +k2 )
[ 2 2 2 ] − =
2n2 1 1 k1 {(n1 − n2 + k1 )sin2γ1 + 2n2 k1 cos2γ1 } T
f2 (n1 , k1 ) = 0 (5)
Where, n1=2.006 and n2=1.45 are refractive indices of the films and
substrate, respectively. k1 is the extinction-coefficient of the films. α1 =
2πk1 d (2πn1 d)
and γ1 = , where λ is the wavelength of light. For each value of
λ λ
n1, a value of k1 is computed from Eq. (5). This value is then fed into Eq. (6)
to determine the condition f2 (n1 , k1 ) ≅ 0. The procedure is repeated until the
best solution is found.

Figure 2: Optical transmittance T (%) and reflectance R (%) versus wavelength (λ) of SnO 2:
In films at different thicknesses.

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Dependence of extinction coefficient with wavelength is represented

in Figure 3. Extinction co-efficient exhibits very high value near UV region
indicating high absorption in that wavelength region and begins to decrease
as the wavelength increases and seems to be saturated in the visible and
infrared region. It is also observed that the highest value of the extinction co-
efficient decreases with the increase of film thickness. Similar results was
observed for vacuum evaporated CdTe thin films (Mousumi, 2014).

Figure 3: Variation of extinction co-efficient (k) with wavelength (λ) for SnO2:In thin films
of different thicknesses.

Figure 4: Dependence of (αhν)2 on incident photon energy (hν) for SnO2: In thin films for
different thicknesses.

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Figure 4 shows a plot of (αhν)2versus photon energy (hν) for SnO2:

In thin films of different thickness. The values of the direct optical band gap
Eg were determined by extrapolations of the linear regions of the plots to
zero absorption (αhν = 0).
Optical band gap of films is depicted in Figure 5. The 300nm film
shows minimum band gap. A shift in optical band gap is observed from 2.89
eV to 3.20 eV as the film thickness increases from 300 nm to 400 nm. The
shift of band gap towards higher energy can be explained by the Burstein-
Moss shift. The dependence of B-M shift with thickness was observed by
Kim et al. for the thickness varying indium-tin-oxide thin films. These band
gap values are in agreement with the band gap values of concentration
varying Indium doped SnO2 films (2.77 - 2.98 eV) deposited on glass
substrate using thermal evaporation method (Chowdhury, 2011).

Figure 5: Dependence of optical band gap (Eg) on film thickness of SnO2: In thin films.

Electrical Properties
Figure 6 shows plot of resistivity as a function of film thickness for
SnO2: In films. The films reveal a high resistivity which varies in between
1.5 x 105 and 3.6 x 105 Ω-cm. These results are in agreement with the works
reported by (Benouis, 2011 and Ji, 2003). Substitution of tin (Sn4+)
tetravalent by trivalent indium (In3+) may cause a deficiency of one electron
or creation of a hole which results in increasing the resistivity of films.
The resistivity of the SnO2: In films increases with the film thickness
upto 500 nm. There are may be two reasons for the increase of resistivity. (i)
From XRD spectra it is observed that, the substitution of Sn4+ by In3+
increases with the film thickness which decreases the n-type carrier
concentration. (ii) The increase in resistivity may be due to the increase in
grain size with film thickness. Because the incorporation of indium may take

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place at the grain boundary which can decrease the carrier concentration
resulting in increasing the resistivity (Pe Waal, 1981).

Figure 6: Dependence of electrical resistivity (ρ) as a function of film thickness for SnO 2: In
films deposited at Ts= 100 oC.

The electrical conductivity(σ) against temperature is expressed as

follows (Chopra, 1969),
∆E
σ = σ0 exp (− ) (7)
2kT
Where, ∆E is the thermal activation energy, σ0 is the conductivity at T
= 0 K, k is the Boltzmann constant.
The inset of Figure 7 shows the dependence of thermal activation
energy ∆E (eV) on the thickness of SnO2: In thin films. The straight line
nature of Arrhenius plot indicates the thermally activated conduction which
often found in doped semiconductors. ∆E varies between 0.18 to 0.47 eV
with film thickness which is larger than those found by (Benouis, 2011) for
spray pyrolysis SnO2: In thin films. The inset of Figure 7 shows that 500 nm
thin film has maximum activation energy. As 500 nm SnO2: In film has the
largest grain size, maximum energy is needed to transfer a charge from one
grain to another grain.

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Figure 7: Semi-log plot of electrical conductivity (σ), inset shows profile of activation
energy (∆E) dependence on film thickness.

Surface Morphology and Elemental Analysis

(a) (b)
Figure 8: Atomic Force Micrograph (AFM) of the surface of SnO 2: In film of thickness 300
nm deposited by thermal evaporation method (a) 2D view, (b) 3D view.

Figure 8 shows AFM image (1µm x 1µm) of SnO2: In thin film with
thickness 300 nm. It is observed that the distribution of grains is uniform on
the surface. The root-mean-square (rms) surface roughness of the film is 2.98
nm. Average crystallite size of the film is 42.87 nm which is in consistence
with the XRD data of the film.

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Figure 9: SEM image (x 30K) shows the surface morphology of the SnO 2: In film of
thickness 300 nm.
Counts

KeV

Figure 10: EDX image of SnO2: In thin film of thickness 300 nm.

The SEM surface view of the SnO2: In film of thickness 300 nm is

shown in Figure 9. The SEM micrograph shows small crystallites and
agglomeration of the grain particles for the film. Energy Dispersive X-ray
(EDX) spectra of indium doped tin oxide thin film shows that the grains are
comprised of O, Sn and In. EDX spectrum is shown in Figure 10. Atomic%
of Sn, O and In were found as 13.27, 85.23 and 1.50 respectively.
Stoichiometry of this film is confirmed by EDX data.

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Conclusion
The role of film thickness on structure, optical, electrical and
morphology properties of vacuum evaporated In doped SnO2 thin films were
studied in this present research work. XRD measurement reveals the
tetragonal structure with the dominant peak (110). Here crystallinity
increases with film thicknesses up to 500 nm. These thin films are highly
transparent in NIR region. Maximum transmittance (85%), lowest optical
band gap (2.89 eV) is obtained for the film of thickness 300 nm. High
electrical resistivity is observed for SnO2: In thin films and least value of
resistivity is found for 300 nm thickness. SEM and AFM micrographs
reveals homogeneous surface of the film with rms surface roughness 2.98
nm. Due to high optical band gap and high resistivity, SnO2: In thin films
can be used in different optoelectronic devices especially as opto-isolator.

Acknowledgements
Laboratory facilities of Experimental Physics Division, Atomic
Energy Centre, Dhaka; Department of Physics, University of Dhaka; Centre
for Advanced Research in Sciences (CARS), University of Dhaka;
Department of Physics, Bangladesh University of Engineering &Technology
(BUET); Department of Glass & Ceramics, BUET; are acknowledged.

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