J Mater Sci: Mater Electron
DOI 10.1007/s10854-014-1781-x
Structural and optoelectronic properties of indium doped SnO2
thin films deposited by sol gel technique
S. Sujatha Lekshmy • K. Joy
Received: 25 September 2013 / Accepted: 31 January 2014
Ó Springer Science+Business Media New York 2014
Abstract Indium doped tin oxide (SnO2:In) thin films
were deposited on glass substrates by sol–gel dip coating
technique. X-ray diffraction pattern of SnO2:In thin films
annealed at 500 °C showed tetragonal phase with preferred
orientation in T (110) plane. The grain size of tin oxide
(SnO2) in SnO2:In thin films are found to be 6 nm which
makes them suitable for gas sensing applications. AFM
studies showed an inhibition of grain growth with increase
in indium concentration. The rms roughness value of
SnO2:In thin films are found to 1 % of film thickness which
makes them suitable for optoelectronic applications. The
film surface revealed a kurtosis values below 3 indicating
relatively flat surface which make them favorable for the
production of high-quality transparent conducting elec-
trodes for organic light-emitting diodes and flexible dis-
plays. X-ray photoelectron spectroscopy gives Sn 3d, In
3d and O 1s spectra on SnO2:In thin film which revealed
the presence of oxygen vacancies in the SnO2:In thin film.
These SnO2:In films acquire n-type conductivity for
0–3 mol% indium doping concentration and p type for 5
and 7 mol% indium doping concentration in SnO2 films.
An average transmittance of [80 % (in ultra-violet–Vis
region) was observed for all the SnO2:In films he In doped
SnO2 thin films demonstrated the tailoring of band gap
values. Photoluminescence spectra of the films exhibited an
increase in the emission intensity with increase in indium
doping concentration which may be due structural defects
or luminescent centers, such as nanocrystals and defects in
the SnO2.
S. Sujatha Lekshmy  K. Joy (&)
Thin Film Lab, Post Graduate and Research Department of
Physics, Mar Ivanios College, Thiruvananthapuram 695015,
India
e-mail: jolly2jolly@gmail.com
1 Introduction
Nanocrystalline tin dioxide (SnO2) is an important trans-
parent material due to its potential use in many techno-
logical applications. Recently, there has been much interest
in wide band gap transparent oxide semiconductors due to
the huge commercial desire for short-wavelength lumi-
nescent devices, such as blue and ultra-violet (UV) light-
emitting diodes and laser diodes. Among the various
semiconductor materials, SnO2 is an n-type wide band gap
semiconductor (3.6 eV) [1]. As a wide band gap semi-
conductor, SnO2 and doped SnO2 are known to have a wide
range of applications such as gas sensors, solar cells,
photovoltaic solar energy conversion devices, and trans-
parent electrodes [2, 3]. Oxide semiconductors occur in a
variety of crystal structures and exhibit diverse electronic
and optical properties. Controlling the electrical conduc-
tivity in oxide thin films is an important step towards their
application in electronics and optoelectronics. SnO2 has
n-type conductivity because of the intrinsic defects such as
oxygen vacancies and tin interstitials. It can be easily
doped with a wide variety of ions to meet the demands of
several application fields. SnO2 can exhibit n-type and
p-type conductivity behaviour depending on type of do-
pants. Theoretically, if SnO2 is substituted with III-family
elements, then p-type SnO2 can be fabricated. The ele-
ments used as dopants such as Li, Fe, Sb and In act as an
acceptor in SnO2 [4–9]. Among them, being noted for the
high conductivity and good optical transmittance is indium
doped SnO2 (SnO2:In) films, which have drawn consider-
able attention for transparent conducting electrodes [10].
Indium has one less valance electron than tin, so substi-
tutional doping; indium in SnO2 can act as an acceptor. In
general, the indium dopant can inhibit the growth of
crystallite and play an important role in the optical
123

properties including transmittance and luminescence. The
surface roughness of thin films has been reported to
influence the electrical and optical properties [11]. The rms
roughness values of range greater than 4 % of the film
thickness makes the films suitable for solar cell applica-
tions [6]. Also, the smooth films (approximately equal to
1 % of the film thickness) finds applications in optoelec-
tronics [12]. Thin films of indium tin oxide are widely used
as transparent and conductive oxide layers for many
microelectronics applications, such as transparent electrical
contacts in liquid crystal displays, organic light-emitting
diodes (OLEDs), plasma displays, thin film solar cells, etc.
[13].
SnO2:In films have been prepared by various techniques
such as chemical vapor deposition, spray pyrolysis, reac-
tive RF sputtering, sol–gel technique. Sol–gel fabrication
has gained much interest because of its simplicity, low
processing temperature, stoichiometry control and its
ability to produce uniform, chemically homogenous films
over large areas that can provide integration with other
circuit elements. The sol–gel method can be successfully
used for the preparation of pure oxide films applied in
electronics and optics [14]. The main advantage of the sol–
gel process is the ability to form inorganic structures at
relatively low temperature. Moreover, incorporation of
dopant is easier in this technique. Ji et al. [15] deposited p
type transparent SnO2 thin films by sol–gel dip coating
method and used indium as acceptor dopant.
In this study, SnO2:In films were deposited by sol–gel
dip coating method on corning glass substrate. We report
the effect of indium content on the structural, morpho-
logical, optical and electrical properties of the film.
Besides, X-ray photoelectron spectroscopy (XPS) studies
revealed the chemical composition, chemical state of the
surface species and different defect states in the SnO2:In
thin film.
2 Experimental Section
Undoped and In-doped SnO2 films were deposited on
corning glass substrate by sol–gel method using dip-coat-
ing technique. The indium doped SnO2 thin films were
prepared by using SnCl22H2O (Alfa Aesar, purity: 98 %)
as the source for tin and InCl34H2O (HPLC, purity: 97 %)
as the source for indium. A 6.8 g of SnCl22H2O was
dissolved in 85 ml of absolute ethanol, and different con-
centration (0–7 mol%) of InCl34H2O was added as dopant
source. To stabilize the solution, 15 ml of acetic acid
(Merck, purity: 99 %) was added as stabilizer. The solution
was stirred for approximately 2 h at 60 °C until a limpid
sol–gel was obtained. The prepared sol–gel was kept at
room temperature for 30 h [16].
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J Mater Sci: Mater Electron
The filtered precursor solution was deposited on clean
corning glass substrates using a locally fabricated dip
coating apparatus. The dip coating parameters were opti-
mized as 20 cm/min lifting speed and 90 ° vertical lifting,
depending on the viscosity and concentration of the pre-
cursor solution. The dip coated films were dried at room
temperature and pre-fired at 250 °C for 30 min. The doped
samples were annealed at 500 °C at the rate 4 °/min in air,
and held at this temperature for 120 min during the course
of annealing. The process of dipping, pre-firing and
annealing were repeated seven times, as seven coatings
were required for obtaining useful data from X-ray dif-
fraction characterization.
Crystallization phase of the SnO2:In films were char-
acterized by X-ray diffraction (XRD) using X-ray diffrac-
tometer (Model—PW 1710 PHILIPS).The XRD patterns of
the films were measured by Philips X’pert Materials
Research diffractometer operated at a voltage of 40 kV and
a current of 30 mA, using Cu Ka radiation
(k = 1.54 Å).The parameter setting for all XRD scans is
1.5 °/min and a step size of 0.016 ° in a 2 h range of
20–60. The surface morphology of the annealed films were
investigated by using atomic force microscopy, Bruker
Multimode III. AFM parameters details, such as roughness,
kurtosis and skewness were deduced from WSxM 5.0
Developer 5.3 data processing and analysis software.
XPS spectrum was recorded using a monochromatic Al
Ka (1,486.6 eV) source and a MAC-2 electron analyzer
(RIBER system model-FCX 700). The resistivity of
SnO2:In films was determined by four-point probe mea-
surements with a Keithley 6200 source meter and a cylin-
drical four-point probe head. The spectral transmittance of
the films were recorded as a function of wavelength, in the
range 300–900 nm, using JASCO V-550 UV–Vis spectro-
photometer. The film thickness and optical band gap values
were determined using Swanepoel’s envelope method [17].
The Photoluminescence spectra were recorded by using a
Perkin-Elmer fluorescence spectrometer (Model-LS55) with
a 40 W Xenon Lamp as the excitation source and 5 nm
excitation and emission slit width.
3 Results and discussion
3.1 X-ray diffraction studies
Figure 1 shows the XRD pattern of undoped and indium
doped SnO2 thin films for various doping concentrations of
indium. The XRD data of SnO2 films revealed peaks at
26.6 °, 33.83 °, 37.95 °, 51.8 ° and 54.76 ° corresponding
to the (110), (101), (200), (211) and (220) planes respec-
tively. All the prominent peaks in the pattern correspond to
the tetragonal structure of SnO2 and are indexed on the
J Mater Sci: Mater Electron

(110) 500 (110) Table 1 Crystallite size, FWHM and lattice parameters of SnO2:In
160
450 (101) films for various In doping concentrations

Intensity(a.u)
400
(101) (211)
In doping Crystallite size D FWHM b Lattice
350

300 (200)
(220)
concentration (nm) (rad) parameters
120 250 (mol%) (Å)
200
Intensity(a.u)

20 30 40 50 60
2Theta(degrees) a c
(211)
80 (220) (300) 0 11.38 ± 0.01 0.012 4.742 3.173
a 1 9.07 ± 0.03 0.015 4.754 3.188
3 6.02 ± 0.01 0.023 4.751 3.249
40 b 5 5.56 ± 0.14 0.026 4.736 3.212
7 4.74 ± 0.17 0.031 4.733 3.185
c
d
0
20 30 40 50 60 Table 2 RMS roughness, average roughness, kurtosis and skewness
2θ (degrees) of SnO2:In films for various In doping concentrations

Fig. 1 XRD patterns of SnO2:In films for a 1 mol% In, b 3 mol% In, In doping RMS Average Kurtosis Skewness
c 5 mol% In (Inset: XRD pattern of undoped SnO2) concentration roughness roughness
(mol%)

0 0.7681 0.6291 2.4726 0.037

1 1.7015 1.3424 2.9359 0.4188
basis of JCPDS file no. 41-1445. In XRD data of the SnO2 3 1.7139 1.3558 2.9183 0.4198
:In films, along with the SnO2 peaks, a low intense peak at 5 3.6995 3.0237 2.4877 0.3949
58.19 ° corresponding to (300) plane of In2O3, rhombo- 7 4.0081 3.0586 2.2013 0.2809
hedral structure was observed. Neither metallic tin nor high
intensity indium characteristic peaks were observed from
the XRD patterns, indicating that indium gets incorporated
into the tin oxide lattice. The (110) is the dominant crystal works, grain size effects on the sensitivity of gas sensor
structure of the low-index crystal faces for this material due devices have been reported [21]. The experimental studies
to its stability. This is the desired structure of SnO2 for revealed that the sensitivity is enhanced, when the grain
sensing applications since its prevalent (110) growth plane size is decreased. Also, Xu et al. [22] have observed that,
is extremely stable and can reject oxygen with little dis- by reducing the particle size (* 6 nm), high gas sensitivity
tortion [18]. and short response times can be achieved. In the present
The average crystallite size (D) of the SnO2 thin films study, the 3 and 5 mol% indium doped SnO2:In films sat-
were calculated using Scherrer’s equation [19] isfies (Table 1) this criteria and hence our SnO2:Sb thin
kk film is a potential material suitable for gas sensing
D¼ ð1Þ applications.
b cos h
XRD data was used to study the structural and lattice
where D is the grain size, K = 0.9, a correction factor, ‘b’ parameters of the deposited films. From the XRD spectra
the full width at half maximum (FWHM) of the most obtained, interplanar spacing was calculated. The lattice
intense diffraction peak, ‘k’ the wavelength of X-ray distortion of the crystal is caused by doping, due to the
(CuKa radiation k = 1.5405 Å) and ‘h’ the Bragg angle. difference between the dopant radius and base material. All
The grain size decreased with increasing In doping content. the d-values are slightly smaller or higher than those of the
It was observed that the FWHM increased with an increase bulk, which indicates a distortion in the unit cell structure
in indium content in the SnO2 thin films [20]. This suggests compared to that of bulk materials. The distortion in
that indium incorporation in the SnO2 lattice induced a samples [13] is evaluated as,
decrease of the grain size. In the case of gas sensor
d  d0
applications, a general strategy for tailoring materials for Dd ¼  100 ð2Þ
d0
the selective sensor response involves the modification of
the surface by the addition of dopants during sensor fab- where d and do are the d-spacing values of the film and
rication. The grain size of the SnO2:In films prepared is of bulk, respectively. This lattice distortion contributes to
the order of 11.38–4.74 nm with increase in doping con- lattice strain. The values of lattice distortion in the samples
centration (Table 1). In experimental and theoretical are given in Table 2.

123

Since it is a tetragonal system, the lattice constants a and
c were determined from the spectra using the equation
1 h2 þ k2 l2
2
¼ þ 2 ð3Þ
d a2 c
where ‘d’ is the interplanar distance, (hkl) are the miller
indices, a and c are the lattice constants. The lattice con-
stants for tetragonal SnO2 film are reported in standard data
a = 4.7382 Å and c = 3.1871 Å (JCPDS card no:
041-1445). In addition, the lattice constants for SnO2:In
films were larger than that of the SnO2 films. In3? substi-
tution for Sn4? leads to an increase in lattice constant due
to the difference between their ionic radii (Table 2). In3?
(0.84 Å) possesses a larger size than Sn4? (0.71 Å), which
in turn results in the slight shift of the diffraction peaks
[15], which is in good agreement with the XRD patterns
(Fig. 1). This is indication of In3? substitution Sn4?,
therefore, this result can be attributed to indium ions
substituting for the tin ions and suppressing the growth of
SnO2.
3.2 Surface morphological studies
The surface roughness plays a major role in optical and
electrical properties of thin films. The AFM images taken
for SnO2 and SnO2:In thin films for various indium con-
centrations are shown in Fig. 2 on a scanning area of
2.5 lm 9 2.5 lm. It can be seen that the surfaces of all
films are uniform and crack free. It is seen that the grains
appear to be less dense in nature with increase in indium
content (Fig. 2b–d). This shows that the grain growth is
inhibited at higher indium doping concentrations. This
observation agrees with the XRD results. The unique
properties of the semiconducting oxides are related to the
microstructural properties of the thin films. The micro-
structure depends on indium content, and the incorporation
of In into the SnO2 film causes change in morphology of the
film. The surfaces of SnO2:In films were found to be slightly
rough and displayed surface roughness values which ranges
from 0.7681 (0 mol%) to 4.0081 (7 mol%). Such roughness
values were comparable and even lower than those varying
from 10 to 40 nm reported in the other reports [23]. The
roughness of the SnO2:In films increased with increase in
indium doping content. The prepared SnO2:In films with
indium doping greater than 3 mol% posses rms roughness
values approximately equal to 1 % of the film thickness.
These films, although not very smooth,are promising, since
the control of film roughness would allow us to extend the
range of applications in optoelectronics. The two key
parameters used to characterize the asymmetry and the
flatness of the surface distribution is the skewness and
kurtosis. Skewness measures the symmetry of surface data
and kurtosis indicates the flatness of the surface. For the
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J Mater Sci: Mater Electron
Gaussian distribution, the skewness is equal to zero and the
kurtosis is equal to three. In this study, SnO2:In films pos-
ses’ kurtosis values below 3 indicating relatively flat sur-
face. The flat surface morphology of the films could protect
against cathode-to-anode electrical shorts in OLEDs [13].
Therefore, our SnO2:In films are the best candidate for the
production of high-quality transparent conducting elec-
trodes for OLEDs and flexible displays.
3.3 XPS studies on the film surface
XPS study was used to understand the surface chemical
changes in the SnO2:In film (1 mol%) through the study of
binding energy of core-level electrons. Figure 3 shows the
XPS survey scan spectrum and XPS core level spectra of
the film sample. The spectrum revealed the presence of
impurity, such as carbon, as well as the constituent ele-
ments of indium, oxygen and tin. The energy scale was
calibrated using C 1s peak position set at 284.4 eV of
carbon as a Ref. [24]. In the XPS spectra of Sn, the binding
energies of Sn 3d5/2 and Sn 3d3/2 were measured to be
488.8 and 497.2 eV respectively. The Sn 3d5/2 located at
about 488.8 eV, demonstrates that the chemical state of Sn
in the sample is ?4. The separation between Sn 3d5/2 and
Sn3d3/2 level (8.4 eV) is approximately the same as in the
standard spectrum of Sn and agrees well with other report
[25]. The O 1s peak observed at 532.8 eV can be attributed
to O2- state adsorbed at oxygen vacancies respectively due
to chemisorbed oxygen in non-stoichiometric oxides. This
value of binding energy agrees with reported results [26].
Reports suggest that, the indium core is orbit split to 3d5/2
and 3d3/2, with the 3d5/2 peak positioned at 446 eV and the
3d3/2 peak positioned at 453 eV [26]. The presence of the
peak 444.1, 446 and 453.9 eV in the In 3d spectrum shows
the presence of In 3d5/2 and In 3d3/2 in SnO2:In sample.
The In 3d5/2 located at about 446 eV, demonstrates that the
chemical state of In in the sample is ?3. The quantitative
analysis was done from the normalized areas of the Sn
3d and O 1s peaks, which shows a molar ratio of
O/Sn *1.61 for the sample which is smaller than the value
for stoichiometric SnO2, suggesting oxygen vacancies [27].
This oxygen vacancy contributes to the photoluminescence
(PL) in SnO2:In film.
3.4 Electrical studies
Figure 4 shows the variation in resistivity of SnO2:In films
for various indium doping concentrations. SnO2 has n-type
conductivity due to the intrinsic defects such as oxygen
vacancies and tin interstitials. In SnO2 films, Sn can exist in
two possible valence states, Sn2? and Sn4?. As seen in
Fig. 4, the resistivity of the SnO2:In (0–3 mol%) films
increases and then tends to decrease with an increase in In
J Mater Sci: Mater Electron
Fig. 2 AFM images of indium
doped SnO2 films a 0 mol% In,
b 1 mol% In, c 3 mol% In,
d 5 mol% In, e 7 mol% In
content (SnO2:In 5 mol%). But when the doping concen-
tration increased to 7 mol%, the resistivity started to
increase slightly. The nature of the semiconductor was
confirmed using hot probe method. The hot probe mea-
surements used to determine conductivity type of the films
showed that the SnO2:In (0–3 mol%) films exhibited
n-type conductivity, while the SnO2:In (5–7 mol%) films
exhibited p-type conductivity behavior. As already known,
undoped SnO2 reveals n-type conductivity due to oxygen
vacancies and interstitial tin atoms. It is believed that these
two contributions together produce electron concentrations
up to 1017 cm-3 [13]. In this study, SnO2:In (0–3 mol%)
films exhibited n-type conductivity,which may be due to
the low doping of indium in SnO2. This low doping of
indium atoms that incorporate to the lattice, may be
insufficient to switch them from n to p type film. Substi-
tution of tin (Sn4?) tetravalent by trivalent indium (In3?)
may cause a deficiency of one electron or creation of a
hole. Hence, the decrease in resistivity of the SnO2:In films
at 5 mol% indium contents, can be attributed to an increase
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 J Mater Sci: Mater Electron

a 300000 c 500000
Sn 3d Sn 3d Sn 3d
5/2
250000
400000
Sn 3d3/2

Intensity(a.u)
200000
Intensity(a.u)

O 1S 300000
150000
200000
100000

100000
50000 C 1S
In 3d
0 0
0 200 400 600 800 1000 1200 480 485 490 495 500
Binding Energy(eV)
Binding energy(eV)

O 1S
d 20000
b 220000 In 3d5/2 In 3d
19500
200000 O 1S
19000

Intensity(a.u)
180000 In 3d3/2
18500
Intensity(a.u)

160000
18000

In 3d5/2
140000
17500
120000
17000
100000
16500
80000
525 530 535 540 545 430 435 440 445 450 455 460

Binding energy(eV) Binding energy(eV)

Fig. 3 a XPS wide spectra of SnO2:In film(1 mol% In). b XPS wide spectrum of O 1S in SnO2:In film(1 mol% In). c XPS wide spectrum of Sn
3d in SnO2:In film(1 mol% In). d XPS wide spectrum of In 3d in SnO2:In film(1 mol% In)

400000 in the hole concentration with increasing the indium con-

350000 tent. This gives one extra charge carrier, giving rise to
increased conduction. At higher doping concentration
( Resisitivity*10^ -9 ) Ω-1 m-1

300000
(7 mol%), the grain size again became smaller and
250000
numerous grain boundaries are formed. Consequently grain
200000 boundary scattering disturbs movement of charge carriers.
150000 So this may cause slight increase in resistivity with higher
100000 indium doping concentrations.
50000
3.5 Optical studies
0

-50000 The optical transmission spectra of SnO2:In thin films for

0 1 2 3 4 5 6 7
various indium concentrations are shown in the Fig. 5. An
Indium Concentration(mol %)
average transmittance greater than 80 % was observed for
Fig. 4 Variation of resistivity with different indium concentrations in all the films in the visible region. The high average value of
SnO2:In films transmittance in the visible region is indicative of fairly

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J Mater Sci: Mater Electron

100 Table 3 Thickness and band gap value of SnO2:In films for various
b
a In doping concentrations
ce
80 In doping concentration (mol%) Thickness (nm) Band gap (eV)
d
Transmittance (%)

3.00E+013
0 405 ± 0.77 3.608 ± 0.002
60 1 408 ± 0.94 3.565 ± 0.003
d
2.00E+013 c 3 426 ± 0.59 3.530 ± 0.002
(αhυ)2(eV/cm)2

e
40 5 437 ± 0.89 3.503 ± 0.001
b
1.00E+013 a
7 458 ± 1.47 3.489 ± 0.005

20
0.00E+000
2.5 3.0 3.5 4.0
υ
Energy (hυ)
0 2.5
400 500 600 700 800 900
Wavelength (nm) 2.0

Fig. 5 Transmittance spectra of a 0 mol% In, b 1 mol% In,

c 3 mol% In, d 5 mol% In thin films. (Inset: hm vs. (ahm)2 graph) 1.5

Figure of merit
1.0
smooth surface and relatively good homogeneous films
were formed possesing nanometer-sized small grains. The 0.5
slight decrease of transmittance at higher doping concen-
trations may be due to the scattering of photons by crystal 0.0
defects created by doping. This is in agreement with the
AFM data, the roughness of the films are found to be -1 0 1 2 3 4 5 6 7 8
increasing. Indium doping Concentration(mol %)
The optical band gap of semi-conductor materials can be
deduced from transmission measurements using Wood– Fig. 6 Variation in figure of merit for SnO2:In films for different
Tauc relation [28]. indium doping concentrations

1=2
ðahmÞ ¼ A hm  Eg ð4Þ

where hm is the photon energy, a the absorption coefficient in the potential barrier required for charge movement in
corresponding to frequency m, A is a constant, Eg the band nanocrystalline SnO2:In films. In transparent conductor
gap energy. Eg values obtained by extrapolating the linear applications, electrical and optical coating parameter
portion of (ahm)2 versus hm plots to intercept the photon optimisation plays a key role. Both conductivity and
energy axis (inset–Fig. 5), the calculated Eg values are transmittance should be as high as possible for solar cell
given in the Table 3. In our films the plots of (ahm)2 as a applications. The definition of figure of merit of a
function of energy(hm) for SnO2:In films tend transparent conducting film was given by Haacke [29]
asymptotically towards a linear section,which shows that equation:
the investigated films have a direct optical band gap. The
T
incorporation of indium is accompanied by a systematic U¼ ð5Þ
RS
low energy shift of the band gap. Eg values of SnO2 films
decreased with In doping from 3.6 to 3.49 eV (inset where T is the transmittance at 550 nm and Rs is the sheet
Fig. 5). Presence of dopant, can introduce impurity band resistance. The calculated value of figure of merit as a
levels into the band gap of tin oxide. The narrowing band function of various In doping concentration is depicted in
gap energy is possibly due to the existence of indium Fig. 6. The Fig. 6 shows that the figure of merit decreasing
impurities in the SnO2 structure, which induce the and increasing nature depending on the indium doping
formation of new recombination centers with lower concentration. A higher figure of merit of the films suggests
emission energy. The lowering of the band gap gives an that the prepared SnO2:In films posses good optoelectrical
indication of the stoichiometric deviation and degeneracy properties. The 5 mol% SnO2:In films in this study posses
of the doped SnO2 and the increase in oxygen vacancies low sheet resistance, transmittance greater than 80 % and
within the lattice. Because of this reduction in band gap, high figure of merit. Hence, 5 mol% SnO2:In films are best
room temperature gas sensing is possible with a reduction suited for optoelectronic and gas sensing applications.

123

900
800
700
600
Intensity(a.u)
500
400
d
300
e
200 c decrease in grain size with increase in indium doping con-
100 a centration. With the decreasing grain size of SnO2:In films,
0 the oxygen vacancy concentration increases [30]. This
b
350 400 450 500 550
Wavelength(nm)
Fig. 7 PL spectra of a 0 mol% In, b 1 mol% In, c 3 mol% In,
d 5 mol% In in SnO2:In films
3.6 Photoluminescence study
Optical measurements such as photoluminescence is useful
in the determination of the structure, defects,and impurities
in nanostructures. Figure 7 shows PL emission spectra of
undoped and SnO2:In thin films for various indium con-
centrations. The excitation wavelength used in this study
for the PL measurement was 330 nm. The origin of the
peak at 392 nm (3.16 eV) in undoped SnO2 film is attrib-
uted to the electron transition from the donor level formed
by oxygen vacancies to the acceptor level formed by other
defects and impurities [30]. The defects like tin interstitials
and oxygen vacancies dominate in the structure of SnO2
due to the multivalence of tin. The energies of all the PL
peaks are smaller than the band gap of SnO2:In films which
lies in the range 3.6–3.48 eV, therefore, the electron does
not directly recombine to a hole in the valence band from
conduction band.
It is observed that the UV emission peak at 392 nm of
SnO2:In films shifted to lower wavelength (blue shift) along
with the appearance of shoulder peaks at 415 nm (2.98 eV)
and 482 nm (2.57 eV) with indium doping. The shoulder
peak at 415 nm corresponds to blue luminescence [13]. The
origin of the blue luminescence band seems to be related to
tin interstitials and non-stoichiometric oxide. The hole in
the valance band can trap at the oxygen vacancy sites. This
surface traps hole tunnels back into the particle to recom-
bine with an electron in a deep trap Voo center to form the
V?0 center at the surface of the particle. Then recombination
of a Vooo center with an electron in the conduction band
gives rise to trap emission in visible blue light. This emis-
sion is in the visible region. Previous reports suggest that the
major free carriers in sol–gel derived nanocrystalline
SnO2:In films are, in fact, monoionized oxygen vacancies
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J Mater Sci: Mater Electron
[31]. The peak at 482 nm which corresponds to green
luminescence, can be attributed to singly charged oxygen
vacancies in the material [32]. It was seen that with the
increase of indium concentration, the luminescent peak
intensity increases. Full doping of SnO2 with indium will
lead to substitution of In3? onto a Sn4? site and the creation
of oxygen vacancies to retain charge neutrality within the
cassiterite structure [33]. Also, the XRD results show
oxygen containing defects act as luminescence centers. The
combined effect of charge balance and decrease in grain
size increased the PL intensity in indium doped SnO2 films.
It is also noticed that the PL spectra is blue shifted with
increase in indium concentration. This shift has been
attributed to the strain and a reduced crystallite size in In
doped SnO2 films which is in agree with the XRD. Such
transparent oxide semiconductors are essential requisites
for short-wavelength luminescent devices, such as blue and
UV light-emitting diodes and laser diode.
4 Conclusions
Undoped and In-doped SnO2 films were deposited by sol–
gel dip-coating method onto corning glass substrates.
Effect of the indium content on the structural, morpho-
logical, optical and electrical properties of the SnO2 films
were investigated. XPS study confirmed the presence of
indium in the SnO2:In films.The hot probe measurements
of indium doped SnO2 films showed p-type conductivity
for 5–7 mol% SnO2:In films. The optical band gap values
decreased from 3.6 to 3.49 eV with increase in In doping.
The intensity of the PL emission peaks increased with
increase in indium concentration. The SnO2:In films in this
study posses low sheet resistance, roughness values
approximately equal to 1 % of the film thickness, trans-
mittance greater than 80 %, high figure of merit and grain
size 6 nm. Hence, the prepared SnO2:In films films are best
suited for optoelectronic and gas sensing applications.
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