Materials Chemistry and Physics 72 (2001) 320–325

Structural and optical properties of sprayed In2−2x Al2x S3−3y O3y alloys
L. Bhira a , T. Ben Nasrallah a , J.C. Bernède b , S. Belgacem a,∗
a Laboratoire de Physique de la Matière Condensée, Faculté des Sciences de Tunis, Campus Universitaire, 2092 Tunis, Tunisia
b Equipe de Physique des Solides pour l’Electronique, Faculté des Sciences et des Techniques, Université de Nantes,

2 Rue de la Houssinière, BP 92208, 44322 Nantes, France

Received 17 May 2000; received in revised form 21 July 2000; accepted 16 September 2000

Abstract
Structural and optical properties of In2−2x Al2x S3−3y O3y alloys obtained by the spray pyrolysis technique have been studied. X-ray
diffraction (XRD) shows for low compositions (x ≤ 0.2) well crystallized films preferentially oriented towards (4 0 0) direction cor-
responding to ␤-In2 S3 phase; for x > 0.2, the structure becomes amorphous as confirmed by scanning electron microscopy (SEM).
Moreover, microanalysis and X-ray photoelectron spectroscopy (XPS) measurements have detected oxygen in the films present in Al2 O3
and In2 O3 oxides and Al(OH)3 hydroxides form. On the other hand, from the optical transmission T(λ) and reflection R(λ) curves, the
study of the absorption coefficient of thin layers versus incident light energy revealed that the value of the band gap energy increases with
the composition x according to a parabolic profile. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: In2−2x Al2x S3−3y O3y ; Spray pyrolysis; X-ray photoelectron spectroscopy (XPS); Optical properties

1. Introduction was varied in solution from 0 to 1. Solution and gas flow

In2−2x Al2x S3−3y O3y alloys are attractive materials as ac-
tive semiconductors in optoelectronic applications. Indeed
these compounds offer the possibility to cover a large band
gap and were not been studied up to now.
In this work, the spray pyrolysis technique is selected to
prepare In2−2x Al2x S3−3y O3y thin layers [1] which were an-
alyzed by X-ray diffraction (XRD) and scanning electron
microscopy (SEM). In the same way, thin layers of this ma-
terial have been examined by microprobe analysis and X-ray
photoelectron spectroscopy (XPS). We have also deduced
the band gap energies for different compositions from spec-
trophotometric measurements.
2. Experimental
In2−2x Al2x S3−3y O3y thin films were obtained by spraying
an aqueous solution containing indium chloride (10−3 M),
aluminum chloride and thiourea 2 × 10−3 M as starting ma-
terials. The value of the ratio concentration x = [Al]/[In]
∗ Corresponding author. Tel.: +216-1-872600, ext: 496;
fax: +216-1-885073.
E-mail address: said.belgacem@fst.rnu.tn (S. Belgacem).
rates were kept constant at 2 cm3 min−1 and 4 l min−1 , re-
spectively, corresponding to a mini spray pyrolysis. Nitro-
gen was used as carrier gas. The substrate temperature Ts
was adjusted to 340 ◦ C.
The crystallinity and the orientation of the studied com-
pounds were obtained by means of a Philips (PW 1729)
system using Cu K␣ monochromatic radiation (wavelength
λ = 1.5405 Å). The morphology of the film surface was
visualized by SEM using a 6400 F JEOL field emission ap-
paratus. The optical transmission and reflection of the films
were determined in the wavelength range 0.3–2.4 ␮m by a
Shumadu UV 3100 F spectrophotometer equipped with an
LISR 3200 integrating sphere.
The samples have been characterized by electron mi-
croprobe analysis (EMPA). A software program (PGI —
IMIX PTS) did the background correction and gave the
percentage of the elements. XPS measurements were per-
formed with a magnesium X-ray source (1253 eV) oper-
ating at 10 kV and 10 mA. An in-depth study was done
by recording XPS spectra after ion etching using an ion
gun. Sputtering was accomplished at pressures of less than
5 × 10−4 Pa with a 10 mA emission current and 5 kV beam
energy. The quantitative studies have been based on the de-
termination of the In 3d5/2 , Al 2p, Cl 2p, C 1s and O 1s
peak areas.

0254-0584/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 2 5 4 - 0 5 8 4 ( 0 1 ) 0 0 3 3 3 - 9
 L. Bhira et al. / Materials Chemistry and Physics 72 (2001) 320–325 321

Table 2
Structural parameters of In2−2x Al2x S3−3y O3y thin layers

x e (␮m) ∆ (◦ ) D (nm) Fo

0.00 0.8 0.34 40 0.82

0.05 1.0 0.46 28 0.76
0.10 1.2 0.33 30 0.81
0.15 1.2 0.63 18 0.60

observations are coherent with the decrease of the average

grain size D (Table 2) deduced from Scherrer formula [2]
kλ
D=
cos θ(∆2 − ∆20 )1/2
where k = 1.05 and ∆0 = 0.22◦ . When x increases (x ≥
0.2), the structure becomes amorphous.

3.2. Morphology

Fig. 2 shows the surface micrographs of thin films corre-

sponding to x = 0, 0.1, 0.3, 0.5 and 0.8. It can be seen from
these images that the samples corresponding to low compo-
sitions are continuous, fairly homogeneous and with little
surface roughness. For x > 0.1, the films exhibit the pres-
Fig. 1. XRD pattern of sprayed In2−2x Al2x S3−3y O3y alloys deposited on
pyrex glass at 340 ◦ C.
ence of rounded small clusters less than 1 ␮m onto a homo-
geneous fond. In the same line, we observe an increase of
the density of circled filaments located around these clusters.
3. Results and discussion
3.3. Microanalysis
3.1. Structure

For compositions x ≤ 0.15, the X-ray diffraction spectra
of In2−2x Al2x S3−3y O3y alloys show well-defined peaks of
(3 1 1), (4 0 0) and (5 1 1) principal orientations correspond-
ing to ␤-In2 S3 (Fig. 1). The (4 0 0) orientation is privileged
in all cases (Table 1).
On the other hand, we establish a decrease in the orien-
tation coefficient Fo defined by
I(h k l) /I0(h k l)
Fo (h k l) =

I(h k l) /I0(h k l)
indicating that the films having weak compositions are rel-
atively better crystallized than the others (Table 2). These
The microprobe analysis results of the thin layers are re-
grouped in Fig. 3. We point out the presence of oxygen in
the samples besides In, Al, S and C elements. Its proportion
increases from 11 to 65% with the detriment of the sulfur
when x varies from 0 to 1. Indeed, this rate is complemen-
tary to that of the sulfur and is necessary for a stoichio-
metric composition (theoretically 60% of sulfur and 40%
of In–Al). The increase of the oxygen proportion with the
composition x in the films can be attributed to the aluminum
oxide Al2 O3 phase which becomes abundant and gives an
amorphous structure for the film having high composition.
3.4. XPS measurements

Table 1 The XPS analysis of the alloys for 0 ≤ x ≤ 0.4 compo-

Orientation of the (3 1 1) and (4 0 0) planes of In2−2x Al2x S3−3y O3y sitions have been done at the surface and in the volume in
sprayed alloys
order to identify the different phases present in the films.
Composition x Orientation Surface analysis shows that all the films are contaminated
I4 0 0 /I5 1 1 I3 1 1 /I5 1 1 with carbon. After etching, the intensity of the carbon peaks
(ASTMa : 0.66) (ASTMa : 0.86) decrease strongly (Fig. 4) which shows that the main part
0.00 7.20 1.26 of the contamination is only a surface effect. Chlorine in
0.05 6.65 1.81 the films is mainly present in the form of chlorine anion
0.10 8.80 1.40 which corresponds to the starting solution (InCl3 , AlCl3 ),
0.15 4.60 3.25
this means that there is some contamination of the films by
a Values corresponding to ␤-In2 S3 phase. the starting solution.
322 L. Bhira et al. / Materials Chemistry and Physics 72 (2001) 320–325

Fig. 2. SEM micrographs of In2−2x Al2x S3−3y O3y thin layers: (a) x = 0; (b) x = 0.1; (c) x = 0.3; (d) x = 0.5; (e) x = 0.8.

On the other hand, the S 2p and In 3d peaks (Figs. 5 and
6) decrease after etching for low compositions showing that
the films are sulfur and indium deficient at the surface. This
deficiency increases progressively when x increases.
Moreover, these analysis pointed out the oxygen contam-
ination for all the films, especially for high compositions.
For x = 0, before etching, the O 1s peak shows that there
are two components (Fig. 7). The first one situated at about
532 eV can be attributed to air contamination during sam-
ple elaboration. The second contribution situated at about
530.4 eV corresponds to the binding energy of oxygen in in-
dium oxide In2 O3 [3]. Since first minute of etching, the last
contribution becomes dominant indicating that the totality
of the oxygen present in the film is bounded to indium.
For higher compositions (x = 0.4), the oxygen peak has
been decomposed in order to determine its nature. Fig. 8
shows that the oxygen peak exhibits clearly three max-
ima. The first O 1s peak is situated at a binding energy of
530.4 eV, the second at 532.4 eV and the third at 534.1 eV
which can be attributed, respectively, to indium oxide In2 O3 ,
aluminum oxide Al2 O3 and hydroxyl aluminum Al(OH)3
compounds with 5, 76 and 19%, respectively.
The decomposition of the Al 2s peak corresponding to
x = 0.4 shows two peaks situated at 121 and 125.2 eV
(Fig. 9), which corresponds to the phases Al2 O3 and
Al(OH)3 with approximate percentages of 84 and 16%,
respectively. This result confirms the O 1s peak decomposi-
tion described below. For x = 0.2, the Al 2s peak situated
 L. Bhira et al. / Materials Chemistry and Physics 72 (2001) 320–325
Fig. 3. Variation of the atomic percentages of Al, O, S and In elements
as a function of the composition x of the In2−2x Al2x S3−3y O3y alloys.
Fig. 4. XPS spectra of C 1s line of sprayed In2−2x Al2x S3−3y O3y thin
films: (a) before etching and after etching of (b) 1 min; (c) 3 min; (d)
6 min.
Fig. 5. XPS spectra of S 2p line of sprayed In2−2x Al2x S3−3y O3y thin
films: (a) before etching and after etching of (b) 1 min; (c) 3 min; (d)
6 min.
323
Fig. 6. XPS spectra of In 3d line of sprayed In2−2x Al2x S3−3y O3y thin
films: (a) before etching and after etching of (b) 1 min; (c) 3 min; (d)
6 min.
Fig. 7. XPS spectrum of O 1s line of sprayed In2−2x Al2x S3−3y O3y thin
film for x = 0: (a) after etching of 1 min; (b) before etching; (c) after
etching of 3 min.
Fig. 8. Decomposition of the O 1s peak of In2−2x Al2x S3−3y O3y thin
film (x = 0.4) after etching of 1 min: (– – –) experimental spectrum; (—)
decomposed spectrum.
324 L. Bhira et al. / Materials Chemistry and Physics 72 (2001) 320–325

Fig. 9. Decomposition of the Al 2s peak of In2−2x Al2x S3−3y O3y thin

film (x = 0.4) after etching of 6 min: (– – –) experimental spectrum; (—)
decomposed spectrum.

Fig. 12. Reflection spectra of sprayed In2−2x Al2x S3−3y O3y thin films:
(a) x = 0; (b) x = 0.05; (c) x = 0.10; (d) x = 0.15; (e) x = 0.30; (f)
x = 0.70.

at 119.8 eV shows the existence of pure aluminum, while

the other one situated at 124.3 eV can be attributed to the
Al2 O3 phase (Fig. 10).

3.5. Optical measurements

The optical transmission T(λ) and reflection R(λ) spectra

for films deposited on pyrex substrate are shown in Figs. 11
and 12, respectively. For low compositions, we point out
the presence of the interference fringes due to the multitude
Fig. 10. Decomposition of the Al 2s peak of In2−2x Al2x S3−3y O3y thin
film (x = 0.2) after etching of 6 min.

Fig. 11. Transmission spectra of sprayed In2−2x Al2x S3−3y O3y thin films: Fig. 13. Variation of the absorption (αhν)2 as a function of the light
(a) x = 0; (b) x = 0.05; (c) x = 0.10; (d) x = 0.15; (e) x = 0.30; (f) energy hν of In2−2x Al2x S3−3y O3y thin films: (a) x = 0.30; (b) x = 0.40;
x = 0.70. (c) x = 0.50; (d) x = 0.70; (e) x = 0.80.
 L. Bhira et al. / Materials Chemistry and Physics 72 (2001) 320–325
Fig. 14. Evolution of the band gap energy Eg of the In2−2x Al2x S3−3y O3y
alloys versus the composition.
reflection phenomenon showing fairly homogeneous films.
Moreover, these films exhibit a good transparency in the
visible and infrared regions. For higher compositions, these
interferences disappear; this is probably due to the inhomo-
geneities present in the volume and the perturbed relief at
the surface as shown in the SEM micrographs. On the other
hand, these spectra shows that for an approximately same
thickness (e ≈ 1 ␮m) (Table 1), the transmission decreases
as a function of the composition.
The exploitation of the T(λ) and R(λ) spectra in the fun-
damental absorption zone allowed us to determine the ab-
sorption coefficient α according to the approximate relation
T = (1 − R)2 exp(−αe)
We have thus studied the absorption (αhν)2 as a function of
the photon energy hν (Fig. 13). These quasi-linear variations
325
show in fact that the transitions are direct as seen in the
relation
(αhν)2 = A(hν − Eg ), A = cte
The intersection with the hν axis gives the band gap energy
values 2.08 ≤ Eg ≤ 2.95 eV for 0 ≤ x ≤ 0.8 according to
a parabolic profile (Fig. 14).
4. Conclusions
In2−2x Al2x S3−3y O3y alloys have been deposited by the
spray technique, showing well-crystallized films for low
compositions as confirmed by XRD and SEM analysis. A
detailed study of the composition of these layers by means of
microprobe and XPS analysis permitted to identify ␤-In2 S3 ,
Al2 O3 , In2 O3 and Al(OH)3 phases present in the layers.
The optical study shows an increase in the band gap energy
when the composition increases as hoped, giving for such
materials the possibility to be used in several optoelectronic
applications.
Acknowledgements
This work was supported by a cooperation contract
between LPMC (Tunis–Tunisia) and EPSE (Nantes–France)
laboratories (contract CMCU No. 98/F 1304).
References
[1] L. Bhira, M. Amlouk, S. Belgacem, R. Bennaceur, D. Barjon, Phys.
Stat. Sol. (a) 165 (1998) 141.
[2] E.F. Kaeble, Handbook of X-ray, McGraw-Hill, New York, 1967.
[3] L. Bhira, H. Essaidi, S. Belgacem, G. Couturier, J. Salardenne, N.
Barreaux, J.C. Bernède, Phy. Stat. Sol. (a) 181 (2000) 427.