Thin Solid Films 437 (2003) 34–44

Properties of spray deposited tin oxide thin films derived from tri-n-
butyltin acetate
P.S. Patila,*, R.K. Kawarc, S.B. Sadalea, P.S. Chigareb
a
Thin Film Physics Laboratory, Department of Physics, Shivaji University, Kolhapur 416 004, India
b
Department of Physics, Shivraj College, Gadhinglaj, Kolhapur 416 004, India
c
Department of Physics, S.G.M College, Karad, Satara, India

Received 21 July 2002; received in revised form 18 March 2003; accepted 8 April 2003

Abstract

The thin films of undoped tin oxide were deposited using organotin compound tri-n-butyltin acetate onto the amorphous glass
substrates at 673 K by spray pyrolysis technique. The spraying solution concentration of tri-n-butyltin acetate was varied from
12.5 to 100 mM to deposit thin films of tin oxide and their structural, electrical and optical properties have been studied, which
were found to be solution concentration dependent. The thermal decomposition behaviour of the tri-n-butyltin acetate salt was
studied using differential thermal analysis and thermal gravimetric analysis techniques. The preferred orientation of the film along
(110) plane prevails upto 50 mM concentration, which shifts to (200) plane for higher concentrations. The values of room
temperature electrical resistivity, carrier concentration and mobility of charge carrier were improved with rise in solution
concentration. The samples deposited at 100 mM concentration exhibit better results than any other studied sample. The possible
explanation for this is given in the present investigation.
䊚 2003 Elsevier Science B.V. All rights reserved.

Keywords: Tin oxide; X-Ray diffraction; Optical properties; Structural properties

1. Introduction lating phases like bSnO, aSnO, Sn2O3 and SnO2

Tin oxide (SnO2) is a multifaceted material having
diverse uses in optical technology w1x, consequently
leading to almost inexhaustible literature w2x. Tin oxide
thin films have been successfully demonstrated as trans-
parent conductors, optical windows for the solar spec-
trum, stability resistors, touch-sensitive switches, digital
displays and electrochromic displays w3–5x, due to their
outstanding properties.
A survey of the literature shows that a variety of
methods of preparation led to the layers having different
structural, optical and electrical properties, which evoked
critical influence of oxygen vacancies, serving as donors
in tin oxide films w6,7x. In principle physical methods
viz. sputtering w1,5x, thermal evaporation w8x, chemical
vapour deposition w9,10x, etc., led to weakly non-
stoichiometric tin oxide with co-existence of other insu-
*Corresponding author. Tel.: q91-231-693-579; fax: q91-231-
691-533.
E-mail address: patilps_2000@yahoo.com (P.S. Patil).
resulting into relatively highly resistive films. However,
chemical methods especially spray pyrolysis technique,
led to strongly non- stoichiometric tin oxide films
without co-existence of other insulating phases, resulting
into films with relatively low resistivity w11–24x. The
properties of spray deposited SnO2 thin films were found
to be dependent on the processing conditions and the
nature of precursors. The precursors play a key role in
the formation of film structure, morphology of the films,
growth of the films and electrical and optical properties
of the deposited material w11–17x. So far a few pre-
cursors such as SnCl4.5H2O, SnCl2.3H2O, SnBr4,
(NH4)2SnCl6, (CH3COO)2SnCl2, (C4H9)4Sn (TBT),
(C4H9)2Sn(OOCCH3)2 (DBTDA) and (C4H9)3Sn
(OOCCH3) (TBTA) have been reported w17x. As per
our knowledge, no reports are available on precursors
like Sn(NO3)4 and Sn(SO4)2.2H2O, probably because
of explosiveness of the former and hygroscopicness of
the latter. We are interested in SnOx films in connection
with their electrochromism. Electrochromic tin oxide

0040-6090/03/$ - see front matter 䊚 2003 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 0 - 6 0 9 0 Ž 0 3 . 0 0 6 8 0 - 1
 P.S. Patil et al. / Thin Solid Films 437 (2003) 34–44
films have been described recently by Orel et al. w25x
and Olivi et al. w26x, who have prepared samples by dip
coating and Isidorosson et al. w1x have prepared samples
by sputtering and they have emphasized the importance
of various properties that SnOx should exhibit for attain-
ing pronounced electrochromism. In this investigation,
we have employed spray pyrolysis technique for SnOx
thin film deposition and discussed their structural, elec-
trical and optical properties. The deposition of the films
has been carried out from organotin compound, viz. tri-
n-butyl-tin acetate (TBTA), which has three butyl
groups and one acetoxy group in a molecule, dissolved
in methanolic solvent.
2. Experimental
The tin oxide films were prepared by using methanolic
tributyl tin acetate (TBTA) solution as a precursor.
Methanolic TBTA solution of various molar concentra-
tions (12.5–100 mM) was sprayed through a specially
designed glass nozzle of 0.5 mm inner diameter onto
the ultrasonically cleaned amorphous glass substrates.
The deposition parameters like substrate temperature
(Tss673 K), rate of spraying solution (5 cc miny1),
nozzle to substrate distance (28 cm), quantity of the
solution sprayed (30 cc), pressure of carrier gas (1 kg
cmy2), and to and fro frequency of the nozzle (15
cycles miny1) were kept constant at the optimized
values indicated in brackets. The substrate temperature
was kept constant using electronic temperature control-
ler, model 9601 (Aplab make) with an accuracy of "5
8C. The Chromel-Alumel thermocouple was used to
measure the temperature of the hot plate.
The as-deposited films were characterized by means
of structural, electrical and optical techniques. The
thermogravimetric and differential thermal analyses of
the precursor salts were carried out using TA instrument
(USA) STD 2960 (simultaneous DSC-TGA). The pow-
der scratched from the deposited films was characterized
by infrared (IR) spectroscopy using a Perkin-Elmer IR
spectrophotometer (model 783) in the spectral range
200–4000 cmy1. To record IR patterns, the pellets were
prepared by mixing KBr with tin oxide powder collected
by scratching thin films from glass substrates in the
ratio 300:1 and then pressing the powder between two
pieces of polished steel.
The structural properties of the films were studied by
a Philips PW 3710 X-ray diffractometer using CuKa
radiation of wavelength (l), 1.5405 A ˚ operated at 25
kV, 20 mA, in the range of 2u between 10 and 808. The
scanning electron micrographs (SEMs) have been car-
ried out by Philips Make XL series, XL 30. The room
temperature dc-electrical resistivity was measured by
means of two-point probe method in the temperature
range of 298–548 K with "5 K accuracy. The current
and voltage were measured with a 5.5 digit digital
35
Fig. 1. Thermal gravimetric analysis (a) and differential thermal anal-
ysis (b) of the precursor powder of tri-n-butyltin acetate in the tem-
perature range 25–850 8C.
multimeter (ESCORT Make). The area (1 cm2) of the
film was defined and silver paste applied to ensure good
ohmic contacts. Hall measurements were carried out
using ‘Hall effect setup’ (model DHE-21- scientific
instrument, Roorkee). The Seebeck measurements were
carried out with the help of a thermo electrical power
(TEP) unit in the temperature range of 298–548 K with
"5 K accuracy using a chromel–alumel thermocouple.
The optical absorption and transmittance were studied
with a UV-VIS-NIR spectrophotometer Hitachi model
330, in the wavelength range of 300–850 nm at room
temperature. The optical interference patterns observed
in optical transmittance spectrum were used to measure
the thickness of the films and their refractive indices
w5 x .
3. Results and discussion
3.1. Thermal decomposition characteristics of tri-n-
butyltin acetate (TBTA)
The thermal decomposition behavior of the precursor,
TBTA,(C4H9)3SnOOCCH3 powder was studied using
TG and DT analyses techniques. TGA and DTA were
performed from 45 to 800 8C with alumina as a reference
material at the scan rate of 10 8Cymin. The DTA
chamber was purged with ambient oxygen at the flow
rate of 100 cm3 ymin.
The TGA and DTA thermograms obtained for TBTA
are shown in Fig. 1a,b. The thermal evolution in oxygen
atmosphere takes place in two consecutive stages with
weight loss for which the inflection points coincide with
temperature. The DTA curve comprises of one exother-
mic and one endothermic peak. The weight loss of the
precursor begins at 90 8C. The existence of the endo-
thermic peak at 100 8C clearly depicts the loss of
physisorbed water from the precursor. The profound
weight loss of the precursor in the temperature range
36 P.S. Patil et al. / Thin Solid Films 437 (2003) 34–44

(C4H9)3SnOOCCH3q3CH3OH
™(CH3O)3SnOOCCH3
q3CH3–CH2–CH2–CH3 (1)

This solution is then atomized by compressed air at

the pressure of 1 kgycm2 on to the ultrasonically cleaned
glass substrates maintained at 673 K, through the glass
nozzle with inner diameter 0.5 mm. The sprayed droplets
undergo solvent evaporation, solute condensation and
thermal decomposition, thereby resulting in the forma-
tion of tin oxide thin films. The chemical reaction that
takes place is given by Eq. (2),

Fig. 2. The variation of transmittance (T%) vs. wavelength (l) of all
the samples.
from 100 to 190 8C can be assigned to the decomposition
of three butyl groups and one acetate group from the
precursor, leading to the formation of a-SnO phase. The
reaction is exothermic, showing a major peak at 190 8C.
Increase in the temperature range from 200 to 400 8C
results in further oxidation by decomposing acetate
group at 300 8C, which is accompanied by a weak
exothermic peak leading to a non-stoichiometric SnOx
phase. Weight loss calculation ascertains formation of
a-SnO phase at 190 8C and formation of SnOx at
approximately 400 8C. Beyond 400 8C weight loss is
unnoticeably slow. The presence of a weak endothermic
shoulder at 590 8C may be due to expulsion of residual
carbon from the precursor. From 590 to 850 8C the
thermogram shows no changes and is devoid of shoulder
peaks, inferring that at 590 8C SnO2 is formed, which
remains stable upto 850 8C.
3.2. Film formation
The appropriate quantity of precursor powder
(TBTA), when dissolved in methanol at room tempera-
ture forms trimethoxy tin acetate, accompanied with n-
butane according to the Eq. (1),
(CH3O)3SnOOCCH3
air at 673 K
q3CH3–CH2–CH2–CH3 ™ SnO2
q 17 CO2
≠ q 21 H2O ≠ (2)
All the films were transparent, adherent to the sub-
strates and stable for a long period, when kept in the
ambient atmosphere.
3.3. Transmittance and thickness measurement
3.3.1. Transmittance
Fig. 2 shows the interference modulation of transmit-
tance spectra of all the samples in the wavelength range
340–850 nm. From the plot it is observed that the
transmittance at 340 nm decreases with increase in the
solution concentration as evidenced from the Table 1.
The transmittance at 630 nm wavelength was varied
from 77% for the sample deposited at 100 mM to the
highest value 88% for the sample deposited at 12.5 mM.
Interference modulation of the transmittance decays
more rapidly with the wave number, which suggests that
with increasing wave number, a large amount of light
does not participate in the interference. The number of
charge carriers ascends with increase in solution concen-
tration and becomes the maximum for the sample
deposited at 100 mM. As the carrier concentration is
maximum in this sample, absorption of light by the
carriers is higher leading to higher absorption coefficient
and consequently lower transmittance. Similar results

Table 1
Structural, optical and electrical properties of SnO2 thin films prepared by SPT at various solution concentrations

Solution concentration Thickness Grain TC (hkl) rRT NH mH Ea rH TEP Eg (NH)2y3 R.I. T%

(mM) (nm) size (110) (Vcm (cmy3 (cm2 (eV) (Vcm (mVyK) (eV) (cmy3 at 630
˚
(A) plane =10y2) =1019) Vy1 sy1) =10y2) =1019) nm
12.5 175 165 9.09 17.67 10.08 1.55 0.125 3.96 48.2 3.5 33.33 1.56 88
25 245 183 6.69 6.14 10.48 1.99 0.092 2.99 51.4 3.4 38.25 1.59 84
50 376 236 6.81 3.6 11.09 2.2 0.06 2.56 56.5 3.35 40.99 1.62 82
75 445 285 2.95 2.8 12.09 2.39 0.075 2.16 80.9 3.3 48.72 1.78 80
100 521 328 6.485 2.1 14.09 2.82 0.045 1.57 99.8 3.2 66.18 1.85 77
 P.S. Patil et al. / Thin Solid Films 437 (2003) 34–44
Fig. 3. Thickness of all the samples vs. TBTA solution concentration.
are reported in the literature w6,22x. Transmittance data
were further analyzed for determination of refractive
indices (n f ) using Eq. (3) w5,18x;
4 nanf
Tls
(naqnf)2
where, Tl is the transmittance at a particular wavelength,
nf is the refractive index (RI) of the film and na is the
RI of air. The calculated refractive indices of all the
samples are listed in Table 1, which lie in the range
1.56–1.85. Spray deposited SnO2 thin film prepared
from SnCl4.5H2O exhibit same values of refractive
indices w12x.
3.3.2. Thickness measurement
Optical interferometric method was used to measure
the thickness of the as-deposited tin oxide thin films.
The spectrum shows maxima and minima for the con-
tinuous scan of all the samples in the wavelength range
350–850 nm, due to optical interference between film
Fig. 4. The IR spectrum of the sample deposited at 50 mM (a) and the same film annealed at 550 8C (b) of the tin oxide thin film.
37
layer and surface of the substrate. The thickness (t) of
the films can be determined from any two maxima (or
two minima) using Eq. (4) w5,18x
Ml1l2
ts (4)
2wnf(l1)l2ynf(l2)l1x
where, M is the number of oscillations between two
extrema occurring for l1 and l2, n f (l1) and n f (l2)
are the corresponding refractive indices.
The thickness calculated by this method for all the
samples are listed in Table 1. The variation of film
thickness (t) vs. the change in solution concentration of
the methanolic TBTA is shown in Fig. 3. From the plot,
it is noted that the film thickness linearly increases as
the concentration of precursor solution is varied from
12.5 to 50 mM. The thickness of the samples varies
from 175 to 376 nm. After 50 mM solution concentra-
tion, slope of the plot changes and thickness variation
is relatively slower upto 100 mM solution concentration,
which may be due to the change in deposition efficiency
of the technique, resulting in low yield.
3.4. Infrared spectroscopy (IR)
(3)
The IR transmittance spectrum presents information
about phase composition as well as the way oxygen is
bound to the metal ions (M-O structure). IR transmit-
tance spectra of the powder scratched from sample
deposited at 50 mM solution concentration and the same
sample annealed at 823 K for an hour, in the wave
number range 200–4000 cmy1 are shown in Fig. 4a,b.
From Fig. 4a, it is observed that the spectrum com-
prises four IR transmission bands centered at 620
cmy1 (n1), 1360 cmy1(n2), 1600 cmy1(n3), 3460
cmy1(n4). The n1 band corresponds to Sn–O2 stretching.
The n2 band can be assigned to carbon ions retained in
the film, since the film under investigation is prepared
at 673 K. Transmission bands n3 and n4 correspond to
OHy vibrations at 1600 cmy1 and at 3460 cmy1,
respectively, due to surface hydration and physisorbed
38 P.S. Patil et al. / Thin Solid Films 437 (2003) 34–44

water bending. Fig. 4b shows the IR transmission

spectrum of the annealed sample, which comprises one
major broad band centered at 620 cmy1(n1) and a very
weak peak at 1600 cmy1(n3). The transmission bands
(n2) and (n4) corresponding to 1360 cmy1 and 3460
cmy1 due to carbon and surface hydration disappeared,
when annealed at 823 K. However, a weak shoulder at
3460 cmy1 remained, may be due to a small amount of
surface hydration, during mixing of the scratched pow-
der and pelleting with KBr. The sol–gel deposited
SnO2 samples processed at 40 8C exhibit similar bands,
corresponding to SnO2 and deformed water. However,
with rise in processing temperature a band corresponding
to water completely disappeared at 200 8C and at 450
8C, formation of both Sn–O and Sn–O2 bands are
reported w27x.

3.5. Structural properties

3.5.1. X-Ray diffraction studies

Fig. 5a–e shows XRD patterns of all the samples.
All the patterns consist of multiple X-ray reflection
peaks inferring polycrystallinity of the samples. How-
ever, the number of peaks and their orientations are
changed with solution concentrations used for the dep-
osition of thin films. At the lowest (12.5 mM) solution
concentration, the major orientation of (110) plane,
which is assigned to tetragonal SnO2, is observed. This
peak is accompanied with other minor peaks as shown
in Table 2. After matching corresponding phases to the
joint committee for powder diffraction standards
(JCPDS) data, it is noticed that the sample consists of
three types of SnO2 (tetragonal, orthorhombic and
cubic), and Sn2O3 (triclinic). By increasing solution
concentration to 25 mM, slight improvement in the
crystallinity was observed. A new plane (200) emerged
and number of other minor peaks waned. The peaks
related to Sn2O3 phases are suppressed and can be Fig. 5. XRD patterns of the SnO2 thin film samples deposited at var-
neglected. The hetero-phase structure has changed to ious solution concentrations.
single-phase structure of tetragonal SnO2. At 50 mM
solution concentration, overall crystallinity of the sample This resulted in the formation of bi-structural (tetragonal
ameliorates drastically, retaining the orientations along and orthorhombic) SnO2 films.
the same planes (110) and (200). The number of minor The three different stages of growth of SnO2 thin
peaks further wanes. It was interesting to note that, the films are: (1) nucleation; (2) crystal growth; and (3)
orientation wwhich was along (110) planex of the sample further crystal growth with preferred orientation. At
deposited at 75 mM solution concentration shifted along lower solution concentration (12.5 mM) and at pyrolysis
(200) plane by retrenching (110) plane. Nevertheless, temperature of 673 K (which was kept constant through
the crystallite orientations along (211) and (310) are out the experiment), large number of small nuclei might
relatively improved. have formed. The growth of each nucleus has taken
At 100 mM solution concentration, again a peak place separately with different orientations and finally
corresponding to (200) plane reduces and that the two the crystal growth along (110) plane is dominant. With
planes (110) and (211) ameliorate, (211) being the increasing solution concentration (25 mM and 50 mM),
most intense. Moreover, some new planes corresponding initially formed large number of small nuclei might have
to orthorhombic SnO2 along (110) and tetragonal agglomerated (coalescence) and relatively small number
SnO2 along (101), (210), (220) and (310) emerged. of large nuclei might have formed, which may have
 P.S. Patil et al. / Thin Solid Films 437 (2003) 34–44 39

Table 2
Comparison of observed and standard ‘d’ values of tin oxide thin films prepared at various solution concentrations

Std. ‘d’ values ˚

Observed ‘d’ values for samples (A) JCPDS data file number
˚
(A) Samples deposited at (hkl) plane Identification of phase
12.5 mM 25 mM 50 mM 75 mM 100 mM

8.20 8.22 – – – – (010) Triclinic-Sn2O3 25-1259

4.08 4.09 – – – – (020) Triclinic-Sn2O3 25-1259
3.71 3.75 – – – – (001) Triclinic-Sn2O3 25-1259
3.64 – – – – 3.63 (110) Orthorhombic-SnO2 41-1445
3.34 3.34 3.34 3.34 3.34 3.33 (110) Tetragonal-SnO2 41-1445
2.64 – – – – 2.64 (101) Tetragonal-SnO2 41-1445
2.36 – 2.36 2.36 2.36 2.36 (200) Tetragonal-SnO2 41-1445
2.12 2.15 – – – – (112) Orthorhombic-SnO2 29-1484
1.76 1.76 1.76 1.76 1.76 1.76 (211) Tetragonal-SnO2 41-1445
1.68 1.68 – – – – (220) Tetragonal SnO2 41-1445
1.49 1.49 1.49 1.49 1.49 1.49 (310) Tetragonal-SnO2 41-1445
1.48 1.48 – – – – (311) Cubic-SnO2 33-1374
1.44 – – 1.44 – – (222) Orthorhombic-SnO2 29-1484
1.41 – 1.41 – 1.41 1.41 (301) Tetragonal-SnO2 41-1445
1.21 – 1.21 – – 1.21 (321) Tetragonal-SnO2 41-1445
1.01 – 1.06 – – – (312) Tetragonal-SnO2 41-1445

caused minor peaks to suppress or disappear and crystal
growth along (110) plane is further dominated. At 75
mM solution concentration preferred orientation is
changed and lies along (200) plane. This might be due
to saturation of growth of nuclei and crystallites, which
enforces gradual incorporation of ‘Sn’ atoms at the
interstitial sites w11x. Similar process might have taken
place at different sites with further increase in the
solution concentration (100 mM), which favoured
growth along (211) plane.
Formation of SnO2 thin film from SnCl4.5H2O pre-
cursor by spray pyrolysis technique is well known. The
existence of preferred orientations of SnO2 thin films by
SPT and CVD are briefly discussed here for comparison.
Agashe et al. have demonstrated that the preferential
growth changed from (110) to (200) plane as the
solution concentration increases. This change was
ascribed to gradual increase in ‘Sn’ incorporation at
interstitial sites in the SnO2 lattice w11x. The orientation
and growth of CVD SnO2 thin film in a particular plane
found to depend on Tpyr. as well. The preferred orien-
tation was changed from (110) to (200) as pyrolytic
temperature, Tpyr. was increased from 573 to 673 K
and finally at 673 K, two peaks along (200) and (301)
were found to be predominant w9x. It has also been
reported that the existence of prominent plane depends
on amount of doping w15x. Some anomaly was observed
in case of dependency on Tpyr. Vasu et al. w24x reported
that the preferred orientation along (211) plane remains
unchanged as Tpyr. was varied between 360 and 440
8C. Thickness dependent preferred growth was examined
by Yoshida et al. w21x and demonstrated that the plane
(110) was predominant irrespective of the film thickness
in the range of 220–690 nm, although at 560 nm and
690 nm relatively low intense (211) plane exists. Bru-
neaux et al. w14x have reported that the films prepared
from concentrated stannic chloride solution showed
preferred orientation, along (110) plane and those pre-
pared from diluted stannic chloride solution presented
different orientations.
The growth of SnO2 thin film along preferred direc-
tion was also found to depend on nature of the precursor,
e.g. for organotin compound, dibutyltin diacetate
(DBTDA), (200) plane was dominant, whereas for
tetra-n-butyltin (TBT), (110) plane was predominant
w17x. TBTA derived SnO2 film exhibits preferred orien-
tation along (200) and (211) at Tpyr.s450 8C w16x.
The (111) reflection peak is not practically observed for
cassiterite planes due to the low atom density for this
plane family, and thus the low scattering factor. It is
therefore, concluded that the planes (110) and (200) are
predominant in most of the cases irrespective of depo-
sition conditions and precursors.
The SnO2 film with a growth along (110) plane
showed higher gas sensitivity and those with preferred
orientation along (200) plane exhibited higher electrical
conductivity w17x. In the present study we have dem-
onstrated that the SnO2 film could be grown along (110)
or (200) plane merely by adjusting the solution
concentration.
3.5.2. Crystallite size
In order to determine the crystallite size, slow scans
of XRD patterns were carried out with the step of 0.028y
40 P.S. Patil et al. / Thin Solid Films 437 (2003) 34–44

Fig. 6. Variation of the texture coefficient of the SnO2 films with the
TBTA solution concentration.

min between the angle of diffraction 26–27.58 for the

(110) plane. The size of the crystallites oriented along
the plane is deduced using Scherrer’s formula (5), w28x;

0.9l
D(110)s (5)
b cos u

where, D(110) is the average size of crystallites oriented

along (110) plane, b is the broadening of diffraction
line measured at half its maximum intensity in radians
and l is the wavelength of X-rays (1.5406 A) ˚ used.
Here, we presume that the values of angle u, b and
instrumental error are common for all the samples. The
calculated average crystallite size for all the samples are
given in Table 1. From the values of crystallite size, it
is found that the size increases from 165 to 328 A, ˚ as
solution concentration increases. The preferred growth
orientation was determined using texture coefficient
{TC(hkl)}, which is described by Eq. (6) w17x,

I(hkl) yIo(hkl)
TC(hkl) s (6)
1yN w8(I(hkl) yIo(hkl))x

where, TC(hkl) is the texture coefficient of the (hkl)

plane, I(hkl) is the measured intensity of (hkl) plane,
Io(hkl) is the corresponding recorded intensity in JCPDS
data file and N is the number of preferred direction of
the growth. The values of TC are listed in Table 1 and
it is found that the TC(200) for the sample deposited at
100 mM solution concentration showed maximum devi-
ation from unity. This indicates that the film prepared
at 100 mM solution concentration has strong reflex
along (200) plane.
Fig. 6 shows the variation in the texture coefficients
(TC) of the planes (110) and (200) with change in the
solution concentration. The texture coefficient of (110)
Fig. 7. SEM micrographs of SnO2 thin films prepared using TBTA
solution concentration of (a) 12.5, (b) 25, (c) 50 and (d) 75 mM.
plane was maximum at 12.5 mM solution concentration
and decreases gradually up to 25 mM, beyond which it
remains almost constant at 6.5 throughout the solution
concentration range, whereas the TC of (200) plane
increases with solution concentration upto 25 mM. Upon
further rise in solution concentration TC (200) decreas-
es, followed by an instant hike at 100 mM solution
concentration.
 P.S. Patil et al. / Thin Solid Films 437 (2003) 34–44
3.6. Scanning electron microscopy (SEM)
Fig. 7a–d shows SEM micrographs of the samples
deposited at 12.5 mM (a), 25 mM (b), 50 mM (c), 75
mM (d), respectively, with =10 000 magnification. It
is observed that the sample deposited at 12.5 mM
exhibits a very smooth surface, devoid of asperity (rough
surface morphology) and pin-holes than other samples
and no-well defined crystallites can be seen. This evinc-
es that the film is appreciably uniform and forces to
believe on the uniform distribution of larger number of
small nuclei. Further rise in solution concentration
resulted in agglomeration of these (initially formed)
nuclei to form cluster. In Fig. 7b, larger clusters (of
approx. 1 mm size) with blurred boundaries can be
clearly seen. These clusters grow larger with increase in
solution concentration (50 mM) and their boundaries
have started sharpening. Some spherically shaped grains
can be seen which are as if imbedded in the clusters, a
step towards formation of individual grains. Finally, at
75 mM, formation of independent spherical grains is
clearly depicted. The average grain size was approxi-
mately 250 nm. Considering above results the growth
process of SnO2 films from TBTA solution by SPT can
be sequenced in four steps:
1. Formation of large number of smaller nuclei.
2. Agglomeration of these nuclei to form cluster.
3. Growth of cluster and onset of grain formation.
4. Formation of well defined grains.
3.7. Electrical properties
Temperature dependence of electrical resistivity is an
important aspect to explore. Fig. 8 shows variation of
log r vs. temperature (1yT) for all the samples. The
sample deposited at 12.5 mM exhibits higher room
temperature dc electrical resistivity, rRTs17.6=10y2
V cm, which may be due to: (1) co-existence of
insulating triclinic Sn2O3 phase along with tetragonal
SnO2, as evidenced by XRD; and (2) small degree of
oxygen vacancies.
For the sample deposited at 25 mM, room temperature
dc resistivity, (rRTs6.1=10y2 V cm), decreases appre-
ciably and the values of resistivity (rRT) throughout the
temperature range are lower than the sample deposited
at 12.5 mM. This may be due to increment in oxygen
deficiencies, as the sample is devoid of insulating SnO
phase. With further increase in solution concentration
the resistivity values decrease from 3.6=10y2 to
2.1=10y2 V cm monotonically, which can be ascribed
mainly to increasingly larger extent of oxygen deficien-
cy, induced in the samples deposited above 25 mM
solution concentration. From Fig. 8, it is also seen that
there are two distinct regions (I and II) having different
slopes, corresponding to low temperature region, region-
I (298–358 K) and high temperature region, region-II
41
Fig. 8. The variation of log r vs. (1000yT) for all the samples of tin
oxide thin films.
(358–548 K). In region-I, the resistivity (r) is almost
constant upto 358 K, after which it rapidly decreases
with rise in temperature up to 548 K. The existence of
two regions are also reported by others w9x for CVD
films. The donor activation energy values are shown in
Table 1. The activation energy values decrease with
increasing solution concentration from 0.125 to 0.044
eV, at 100 mM being minimum. This indicates creation
of shallow donor levels near the conduction band for
higher solution concentration, which may engender low-
er resistivity in the sample deposited at 100 mM solution
concentration.
Hall effect measurements were carried out for all the
samples at room temperature and the values of Hall
resistivity (rH), carrier concentration (NH ) and mobility
of charge carriers (mH) are calculated w29x. Their vari-
ation with solution concentration is shown in Fig. 9.
The values are calculated and given in Table 1. From
the Fig. 9, it is seen that as solution concentration
increases, resistivity decreases. The decrement in resis-
tivity is due to increase in carrier concentration, which
stem from ionization of gradual increment in oxygen
vacancies. The gradual hike in mobility of charge
carriers may be due to decrement in grain boundary
concentration, which minimizes grain boundary scatter-
ing. Typical values of rRT for spray deposited and
SnCl4.5H2O derived SnO2 films are reported to be in
the range of 2.7=10y1 w20x to 3.1=10y2 V cm w23x,
with a exception of 5=10y3 V cm for the films
annealed at 400 8C in argon w3x. The carrier concentra-
tion NH and mobility mH values lie in the range
6.6=1018 cmy3 to 25=1019 cmy3 w12x and 2 cm2 yVs
w13x to 16 cm2 yVs w20x, respectively. The values report-
42 P.S. Patil et al. / Thin Solid Films 437 (2003) 34–44
Fig. 9. The variation of rH, NH and mH of SnO2 thin films prepared
using TBTA solution concentration of (a) 12.5, (b) 25, (c) 50, (d)
75 and (e) 100 mM.
ed in this invention are in consistency with the reported
values. No reports are available on these parameters for
spray deposited SnO2 films derived from TBTA solution.
3.8. Seebeck (thermo electric power) measurement
Thermo electric power (TEP) is the ratio of thermally
generated voltage to the temperature difference across
the semiconductor. It gives information about the type
of charge carriers in the samples. For tin oxide material,
conduction electrons originate from ionized defects such
as oxygen vacancies. TEP of all the samples was studied
in the temperature range 298–548 K using TEP unit
with chromel–alumel thermocouple with "5 K accura-
cy. In this effect thermally generated electrons in the
semiconductor always migrate from hot end to cold end.
The polarity of thermally generated voltage at the hot
end was positive indicating that the films exhibit n-type
conductivity. Fig. 10 shows the variation of the thermo-
emf (DE) with temperature difference (DT) for all the
samples. From the plot, it is observed that the thermo-
emf increases almost linearly with increase in the tem-
perature difference. This may be attributed to increase
in the mobility of charge carriers and carrier concentra-
tion with rise in temperature.
The average values of thermo electrical power (S),
can be calculated from the plots of (DE) vs. (DT) using
the Eq. (7)w30x,
NSMs0.5=8dj NSjM (7)
where, Sj is given by the relation (DE)y(DT) between
two consecutive points of the jth interval, NSjM is the
average of TEP in each of the jth segments, dj is a
factor defined as: djsNjyN, where, Nj is the number of
points in the jth interval and N is the total number of
points. The plot of (DE) vs. (DT) is further subdivided
in six segments, which contain points equally spaced in
the selected temperature range. The values of TEP
calculated for all the samples using above relation are
listed in Table 1. From the values of TEP it is observed
that the magnitude of TEP increases with increase in
solution concentration. The calculated values of TEP lie
in the range of 48.2–99.8 mVyK. It is a proliferation
that as the film thickness varies with solution concentra-
tion, TEP increases and it continues to increase with
increasing the temperature w9x. The trend observed in
TEP in this investigation confirms that the conduction
mechanism in the samples is due to polaron hopping
due to localized electronic state for the oxides.
3.9. Optical properties
Fig. 11 shows variation of (ahn)2 vs. hn for all the
samples. The nature of the plots indicates the existence
of direct optical transitions. The band gap is determined
by extrapolating the straight line portion of the plot to
the energy axis. The intercept on energy axis gives the
value of band gap energy ‘Eg’ for all the samples and
the values lie in the range of 3.2–3.5 eV, which are
listed in Table 1. Similar results are given in the literature
for spray deposited SnO2 thin films w3,12,13x. It may
be noted that the fundamental absorption edge shifts
from 3.2 eV from the sample deposited at 100 mM to
3.5 eV for the sample deposited at 12.5 mM. The shift
in the fundamental absorption can be attributed to the
Fig. 10. The variation of thermo-emf (mV) vs. temperature difference
(DT) (K) for all the samples of tin oxide thin films.
 P.S. Patil et al. / Thin Solid Films 437 (2003) 34–44
Fig. 11. The variation of (ahn)2 vs. hn for all the samples of tin oxide
thin films.
Moss–Burstein effect w3,13x, which occurs owing to
filling up of low lying energy levels by the conduction
electrons. Due to such a large shift in the absorption
edge, tin oxide is termed as a broad band semiconductor.
It is well known that SnO2 is a degenerate semiconductor
with a band gap energy in the range of 3.4–4.6 eV
w6,19x. This scatter in band gap energy of SnO2 may be
due to varied extent of non-stoichiometry of the depos-
ited layers. The dependency of the band gap energy on
the carrier concentration has been explicitly given in the
literature w19x. It has been apprehended that the values
of band gap energy varies linearly with the carrier
concentration (NH) to the power 2y3, which is shown
in Table 1.
4. Conclusion
The simple and inexpensive spray pyrolysis technique
was used to prepare thin films of tin oxide on amorphous
glass substrates using non-aqueous solution of tri-n-
butyltin acetate (TBTA) at 673 K. The effect of solution
concentration on thin film properties was studied. It is
observed from DTA and TGA studies that the complete
pyrolytic decomposition of the precursor takes place at
approximately 590 8C (863 K) and SnO2 forms, below
which incomplete pyrolytic decomposition led to the
formation of non-stoichiometric, SnOx. The existence of
Sn–O and Sn–O2 bands were confirmed from IR Spec-
tra. The films deposited at different solution concentra-
tions exhibit polycrystallinity, the grain size ameliorates
(165–328 A) ˚ with increasing solution concentrations.
The preferred orientation is along (110) plane for low
solution concentration (below 50 mM), which changes
to (200) and (211) for higher solution concentrations.
The room temperature electrical resistivity decreases
43
with increase in solution concentration, thicker sample
deposited at 100 mM being more conducting. The n-
type conductivity was confirmed from the thermo elec-
tric power measurements. The optical direct band gap
energy lies in the range of 3.2–3.5 eV with visible
transmittance, 77–88% at 630 nm. The refractive index
varies from 1.56–1.85. The above properties were com-
pared with the films prepared by using other precursors,
mainly SnCl4. It is concluded that the properties of
SnO2 films prepared by TBTA and SnCl4 are
comparable.
Acknowledgments
The authors (P.S.C., R.K.K.) gratefully acknowledge
U.G.C., New Delhi, India for the award of Teacher
Fellowship under IXth Plan. The authors acknowledge
financial support from U.G.C.-D.R.S. (S.A.P.) project.
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