Thin Solid Films 495 (2006) 316 – 320

www.elsevier.com/locate/tsf

Investigation of properties of thin oxide films SnOx

annealed in various atmospheres
D.M. Mukhamedshina *, N.B. Beisenkhanov, K.A. Mit’, I.V. Valitova, V.A. Botvin
Institute of Physics and Technology of the MES RK, Ibragimova Street 11, Almaty 050032, Kazakhstan
Available online 3 October 2005

Abstract

The influence of annealing in various atmospheres on properties of the undoped SnOx thin films has been studied. The films with
thickness of ¨400 nm have been deposited on glass substrate by a method of magnetron sputtering in argon – oxygen atmosphere at the
pressure inside the chamber 0.9 and 2.7 Pa. The dependences of structural and optical properties of SnOx films from temperature of annealing
in air, vacuum and atmosphere hydrogen have been investigated. Correlations between the structural and optical properties of tin oxide films
were found.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Tin dioxide; Magnetron sputtering method; Various atmospheres; Annealing

1. Introduction 2. Experimental details

Various specific and unique properties of SnO2 make the
material useful for many applications. SnO2 is one of the few
electrical conductors that are optically transparent in the visible
range of wavelengths. It is often applied to fabricate
transparent conductive coatings for solar cells and opto-electric
devices. The gas sensitive layers of SnO2 are widely used in
making sensors for control of poisonous and combustible gas
leakage [1 –4].
The purpose of this work is to study an influence of heat
treatments of SnOx films in hydrogen gas, vacuum and air on
optical and structural properties. It is interesting to explore
some details of occurring phenomena connected with struc-
tural changes and phase composition of film, using various
regimes of deposition, and also thermal treatment by the steps
at various temperatures and atmosphere compositions.
The observed dependence of optical parameters of film from
the atmosphere composition, in which the annealing of films
was carried out, permits to make the conclusions concerning
dynamics of the occurring processes.
* Corresponding author. Tel.: +7 3272 545367; fax: +7 3272 545224.
E-mail address: dmm@sci.kz (D.M. Mukhamedshina).
0040-6090/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2005.08.293
The SnOx thin films were obtained by a method of reactive
magnetron sputtering in high-vacuum deposition chamber
made by TORR INTERNATIONAL (USA) corporation, in
which by usage of a combination of mechanical and turbo-
molecular pumps the ultimate vacuum of 10 4 Pa was
reached. High purity (99.99%) tin targets with the diameter
of ¨50 mm and thickness of 3 mm were used. The magnetron
sputtering mode parameters were: the cathode voltage
U c = 470 V, the ion beam current I ion = 35 mA and the
argon– oxygen mixture pressure inside the chamber 0.9; 2.7
Pa. The oxygen concentration was approximately 10%; the
growth rate of the films did not exceed 0.05 nm/s.
Temperature of the substrate was 200 -C. SnOx films were
deposited on microscopy glass slides located on a stage
rotation, the temperature of which could be supported in a
range from room temperature up to 450 -C. The thickness
monitor (model MCM-160, McVac Corporation) was located
near a stage rotation. The thickness of deposited films was
¨400 nm.
Isochronous annealing of tin oxide films was carried out in
air, in vacuum (6.6  10 4 Pa) and in flowing hydrogen at
pressure 6.6 Pa. The films deposited on the surface of
microscopy glass slides were annealed at temperatures 200,
300, 400, 500, 550 -C for 1 h.
 D.M. Mukhamedshina et al. / Thin Solid Films 495 (2006) 316 – 320
The optical transmittance spectra for the SnOx were
measured in the wavelength range from 190 to 1100 nm by
means of the SF-256 UVI and from 1100 to 2500 nm by means
of the SF-256 NIR spectrophotometers. Optical constants
(refractive index, optical band gap, thickness, extinction
coefficient) for the tin oxide films were estimated from the
transmittance spectra [4].
The film structures were investigated by X-ray diffraction
using a narrow collimated (0.05  1.5) mm2 monochromatic
(CuKa) X-ray beam directed at an angle of 5- to the sample
surface. The intensity of X-ray radiation along the diffraction
patterns was measured after each 2h = 0.05- using an MD-100
microdensitometer. The average size of crystallites was
estimated from the half width of X-ray diffraction lines
according to Jones’ method [5].
3. Results and discussion
As shown in works [6,7] the quality of tin oxide films
obtained by reactive magnetron sputtering depends on such
conditions of deposition as temperature of substrate, pressure
inside the chamber, the concentration of oxygen in an argon–
oxygen mixture and others.
In our experiments, both the concentration of oxygen and
temperature of the substrate was identical during deposition of
tin oxide films, but the pressure in the chamber was 0.9 and 2.7
Pa. The films obtained have mirror smooth surface and just
after deposition were yellowish in the first case (0.9 Pa), and
white color in the second case (2.7 Pa).
Both sets of films were isochronously annealed at tempera-
tures 200, 300, 400, 500, 550 -C in air, vacuum and in
hydrogen atmosphere for 1 h. Optical transmission spectra
were measured. The structure properties of films were
investigated by X-ray diffraction at annealing stages where
optical parameters have shown unusual properties.
3.1. Optical properties
The optical constants of the tin oxide films were calculated
by the envelope method from the transmittance data [4].
According to the envelope method the optical constants of a
thin film can be determined from measurement of optical
100
a)
80 5 1
Transmittance (%)
60
40
20
0 0
200
Fig. 1. The transmission spectra of SnOx films deposited on glass substrate with the pressure inside the chamber at 0.9 Pa and annealed at temperatures of (a) 200 -C
and (b) 550 -C for 1 h in various atmospheres: 1—air, 2—vacuum; 3—hydrogen. 4—SnOx film as-deposited, 5—substrate (glass).
317
transmittance alone when the film has a low absorption
coefficient and optical thickness. The maximum and mini-
mum transmittances appear when optical thickness is in the
multiple of quarter and half wavelength, so it can be used to
calculate refractive index (n) and film thickness (d) from
envelope curves at maximum and minimum transmittances,
respectively.
The transmittance spectra in UV region show that the
transition corresponding to the fundamental absorption falls in
this region of the electromagnetic spectrum. Then, the
absorption coefficient was evaluated from [4].
In Fig. 1a,b the transmission spectra of SnOx films
deposited on glass substrate with the pressure inside the
chamber at 0.9 Pa and annealed at temperatures of 200 and
550 -C for 1 h in air, vacuum and hydrogen atmosphere are
presented.
As can be seen from Fig. 1, the film shows higher
transparency after annealing in air than in vacuum or in
atmosphere of hydrogen. It can be caused by absorption of
oxygen and the best stoichiometry of the film composition. The
increase in transparency and enlightenment in regions of short
wavelengths after annealing at 550 -C indicate the formation of
polycrystalline SnO2 phase [8].
In Fig. 2a – c the transmission spectra of SnOx films
deposited on glass substrate with the pressure inside the
chamber at 2.7 Pa, are presented. The films were annealed at
temperatures ranging from 200 up to 550 -C for 1 h in various
atmospheres: (a) air, (b) vacuum and (c) hydrogen.
As can be seen from Fig. 2, just after deposition the film
with a high transparency in all intervals of considered
wavelengths (200 –2500 nm) is obtained. Comparing these
spectra similar to Fig. 1, it is possible to assume that conditions
of deposition (pressure 2.7 Pa, etc. [7]) are optimal for the
preparation of transparent SnOx films. Further annealing in air
(Fig. 2a) does not result the essential change of film
transparency, except for temperature 200 -C where the
transparency decreases with growth of the wavelength. A
similar effect is also found for annealing in vacuum and in
atmosphere of hydrogen. It is possible to assume that the
reason for this phenomenon is not connected with atoms of
oxygen, hydrogen and their compounds. It is more probable to
assume that this phenomenon is connected with atoms of tin.
100
b)
1
80 5
2
3 2
60
4 4
40
3
20
400 600 800 1000 200 400 600 800 1000
Wavelength (nm) Wavelength (nm)
318 D.M. Mukhamedshina et al. / Thin Solid Films 495 (2006) 316 – 320

100 100 100

a) 1 7 6 4 b) 1 2 c) 1 2

80 580 80
3 3 5 4 4
5
2 6
Transmittance (%)

4
60 60 4 6
60 4
3 7
glass (1) 3
glass+film (2)
40 40
200˚C (3) 7
300˚C (4)
400˚C (5)
20 500˚C (6) 20 20
550˚C (7)

0 0 0
200 800 1400 2000 200 800 1400 2000 200 800 1400 2000
Wavelength (nm) Wavelength (nm) Wavelength (nm)

Fig. 2. The transmission spectra of SnOx films deposited on glass substrate at the pressure inside the chamber 2.7 Pa and annealed at temperatures of 200, 300, 400,
500 and 550 -C for 1 h in various atmospheres: (a) air, (b) vacuum; (c) hydrogen.

Taking into account that the melting point of tin is 231.9 -C,
one can expect that during improvement of SnOx layer
structure and crystallization process, the formation of metal
microparticles from tin atoms at 200 -C is taking place. As it
has been reported in [9], that electron – electron interaction for
metal microparticles leads to increasing absorption in the infra-
red region. Really, the absorption in infra-red region is weakly
observed after annealing at 300 -C, i.e. at a higher temperature
than the melting point of tin.
It can seen from Fig. 2b,c that the increase in temperature of
the annealing in vacuum or in atmosphere of hydrogen results
in a decrease in transparency. It can take place due to
desorption of oxygen from a film in vacuum, or due to the
formation of water molecules in the film in the case of
annealing in hydrogen atmosphere. All these results lead to
stoichiometry breaking in SnO2 film and, accordingly, to
reduction of a transparency.
In Table 1 optical parameters for SnOx films prepared at
pressure in the chamber of 2.7 Pa are presented.
In Fig. 3 optical parameters of SnOx films deposited on
glass with the pressure inside the chamber at 0.9 and 2.7 Pa
and annealed at temperatures within 200 –550 -C for 1 h in
air, vacuum or atmosphere of hydrogen, are presented. As
can be seen from Fig. 3a, the optical band gap E g of as-
deposited films obtained at 2.7 Pa significantly exceeds the
one obtained at 0.9 Pa. The isochronous annealing over the
temperature range of 200– 550 -C has not resulted in the
increase of E g. Moreover, the annealing in vacuum or in
hydrogen atmosphere results in the decrease of E g. On the
contrary, the films obtained at 0.9 Pa increased their E g after
annealing at 500 –550 -C up to the values comparable with
the ones for films obtained at 2.7 Pa. Seemingly, that is a
result of the formation of SnO2 polycrystalline phase at these
temperatures. One can conclude that after deposition at 2.7

Table 1
Optical parameters of SnOx films deposited on glass at the pressure inside the chamber 2.7 Pa and annealed at temperatures within 200 – 550 -C for 1 h in air,
vacuum or hydrogen
Optical parameters Atmosphere Temperature
As-deposited 200 -C 300 -C 400 -C 500 -C 550 -C
Thickness d (nm) Air 453 446 447 452 445 446
Vacuum 491 493 488 519 – –
Hydrogen 487 491 491 514 – –
Refractive index (n) Air 1.81 1.79 1.79 1.73 1.75 1.77
Vacuum 1.81 1.85 1.99 1.91 1.68 –
Hydrogen 1.89 1.89 1.93 1.87 – –
3 3 3 3 3 3
Extinction coefficient Air 6.5  10 6.1 10 5.5  10 6.6  10 5.6  10 5.6  10
3 3 3 2 2
Vacuum 6.2  10 8.8  10 8.5  10 1.5  10 4.4  10 –
3 3 3 2
Hydrogen 5.7  10 9.2  10 8.7  10 1.2  10 – –
Optical band gap E g (eV) Air 4.04 4.00 4.00 4.00 4.00 4.00
Vacuum 4.00 3.95 3.75 3.70 3.65 –
Hydrogen 4.00 3.95 3.85 3.75 – –
 D.M. Mukhamedshina et al. / Thin Solid Films 495 (2006) 316 – 320 319

a) air 2.6
4.0
b)vac
air

Optical band gap Eg (eV)

H2
2.4 H2

Refractive index n
vac
3.5 vac 2.2
vac
H2
air 2.0
3.0
1.8
H2
air
2.5 1.6
0 200 400 600 0 200 400 600
T (˚C) T (˚C)

550 40
c) vac d)

Extinction coefficient
500
H2 30
Thickness (nm)

H2
450
air 20 vac
400 vac
vac air
10
350 H2
air H2
0 air
300
0 200 400 600 0 200 400 600
T (˚C) T (˚C)

Fig. 3. Optical parameters of SnOx films deposited on glass with pressure inside the chamber at 0.9 and 2.7 Pa and annealed at temperatures within 200 – 550 -C
for 1 h in air, vacuum or hydrogen. 2.7 Pa: ?—air, h—vacuum, r—hydrogen. 0.9 Pa: >—air, g—vacuum, q—hydrogen.

Pa the films with the highest E g were obtained without post- was close to SnO2. The thickness of these films (Fig. 3c) was
annealing. greater. Extinction coefficient of these films is smaller due to
One can see from Fig. 3b that the refractive index (n) of their high transparency (Fig. 3d).
films obtained at 0.9 Pa decreased after isochronous annealing In Table 1 the film parameters are not specified for
from ¨2.5 up to ¨1.9. The decrease is more intensive during temperatures 500 and 550 -C in cases of annealing in vacuum
annealing in air than in vacuum or hydrogen atmosphere. It can and hydrogen atmosphere. In Fig. 3 some parameters are not
be related with more intensive formation of polycrystalline specified after deposition. It is caused by difficulties of
SnO2 phase. As it is seen from Fig. 3b, the refractive index of definition of optical parameters (n, d, k) on the basis of the
films obtained at 2.7 Pa is small (¨1.8) and it did not envelope method, connected with the form of the transmission
significantly change during annealing. One can conclude that spectra curves, on which it is impossible to determine the
immediately after deposition at 2.7 Pa, the composition of films points of extrema with a sufficient degree of accuracy.

a) b) c)

1.8 1.5 1.9

SnO2(110)
SnO2(101)
SnO2(200)

SnO2(211)
SnO2(112)
SnO2(110)
SnO2(101)
SnO2(200)

SnO2(211)
SnO2(112)
SnO2(110)
SnO2(101)
SnO2(200)

SnO2(211)
SnO2(112)

1.6 1.3 1.7

I (arb. units)

1.4 1.1 1.5

1.2 0.9 1.3

1.0 0.7 1.1

0.8 0.5 0.9

10 15 20 25 30 35 10 15 20 25 30 35 10 15 20 25 30 35
θ (degree) θ (degree) θ (degree)
(

Fig. 4. X-ray diffraction pattern and microdensitometric intensity curve of X-ray radiation for the thin SnO2 film deposited on the glass substrate after deposition (a),
after annealing at 200 -C (b) and 300 -C (c).
320
10
9 - (110)
- (101)
Crystallite size (nm)
- (211)
Iint (arb.units)
8
7 0.020
6
5 conditions of a deficit of oxygen. In this investigation, for films
4 obtained at pressure 2.7 Pa, there is enough oxygen for the
3 0.005
0 100 200 300
Temperature (oC)
Fig. 5. Average size of crystallites (a) and integrated intensity (b) for the SnO2
films after deposition and annealing at 200 -C and 300 -C.
3.2. Structural properties
Structural investigation by X-ray diffraction of film obtained
with pressure in the chamber at 2.7 Pa shows that film structure
immediately after deposition is polycrystalline, consisting of
SnO2 crystallites (Fig. 4a). Sn and SnO phases have not been
found. Calculation of crystallite sizes (Fig. 5a) by Jones
method for SnO2 lines with Miller’s indexes (110), (101) and
(211) shows, that the average size of crystallites in these planes
are ¨3.8, 3.8 and 4.1 nm, accordingly.
After annealing at 200 -C, the phase composition of films
has not changed. The crystallite sizes of SnO2 grew up to
values of 4.4, 6.2 and 6.9 nm for the above-stated planes (Fig.
5a). Integrated intensity of lines also grew for all three lines
(Fig. 5b). It follows that growth of quantity of polycrystalline
phase of SnO2 takes place at the expense of amorphous phase.
After annealing at 300 -C, the crystallite sizes continue to grow
(7.1, 6.8, 8.9 nm) whereas the integrated intensity of lines
decreases. In this case, one can explain the increase of
crystallite sizes by their joining during annealing. Joining can
occur as a result of partial or full destruction of imperfect
crystallites during annealing following integration of their
atoms to more perfect crystallites. The decrease of phase
volume can be caused by evaporation of Sn atoms during
annealing [10].
The X-ray data explain the results presented in Fig. 3a,
where it has been shown that the optical band gap E g reaches
high values about 4 eV not only after annealing, but also after
deposition. Obviously, it is caused by the formation of
polycrystalline phase of SnO2 during deposition. By the same
factor it is possible to explain the low values of refractive index
(n) for films obtained at 2.7 Pa just after deposition.
The lines of h-Sn polycrystalline phase on the diffraction
patterns are not observed after annealing at 200 -C, though the
decrease of film transparency with increasing of wavelength
takes place. In papers [11,12] a relation of electrical and optical
properties of films with segregation of tin was shown. After
deposition and heat treatment [11] or plasma treatment [12] at
temperatures lower than the melting point of tin (231.9 -C) the
formation of h-Sn crystal grains in the film volume was
observed. As a consequence of this, the decrease of film
resistance [11] and transparence [12] had been observed. The
following annealing at temperatures higher than the melting
D.M. Mukhamedshina et al. / Thin Solid Films 495 (2006) 316 – 320
0.030 point of tin leads to the decay of h-Sn crystal grains in the film
volume. Tin excess is segregated on the film – substrate
0.025
- (110) boundary as h-Sn large aggregates, which are isolated from
- (101)
- (211) each other by crystal grains of SnO [11]. The increase of film
resistance [11] and transparence [12] at these temperatures are
0.015 observed. However, all this was shown for films obtained in
0.010
formation of SnO2 during deposition. Therefore, in the case of
0 100 200 300 inappreciable excess of tin atoms, the segregation of tin can
Temperature (oC)
cause a formation of fine tin particles, of which sizes can be
insufficient for formation of h-Sn crystal grains and
corresponding lines on the diffraction patterns, but are sufficient
for increase of IR-absorption. However, we believe that for a
more detailed analysis of the reasons of increase of IR absorption
after annealing at 200 -C, additional investigations are required.
4. Conclusion
After film deposition at pressure 2.7 Pa of oxygen – argon
mixture in the chamber, the polycrystalline SnO2 films with
high transparency and high optical band gap without post-
annealing were obtained. The growth of absorption in infra-red
region of wavelength for films annealed at 200 -C in various
atmospheres is found. It is assumed that this phenomenon is
caused by the presence of metal nanoparticles of tin. The
increase of temperature of annealing in vacuum or in hydrogen
atmosphere results in the reduction of the film’s transparency
due to breaking of stoichiometry of the film composition. The
annealing in air results in the growth of SnO2 crystallite sizes,
but the optical parameters have not significantly changed.
The decrease of pressure of oxygen– argon mixture up to 0.9
Pa leads to the significant decrease of optical band gap and
transparency and an increase of the refractive index of films.
The annealing at 550 -C is necessary to improve the optical
parameters of these films.
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