Journal of Alloys and Compounds 696 (2017) 1314e1322

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Determination of the optimum annealing temperature and time for

Indium-doped SnO2 films to achieve the best p-type conductive
property
Tran Le a, Huu Phuc Dang b, c, *, Van Hieu Le d
a
Faculty of Physics & Engineering Physics, HCMC University of Science e VNU, 227 Nguyen Van Cu St., Ward 4, District 5, Ho Chi Minh City, Viet Nam
b
Theoretical Physics Research Group, Ton Duc Thang University, Ho Chi Minh City, Viet Nam
c
Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Viet Nam
d
Faculty of Material Science, HCMC University of Science e VNU, 227 Nguyen Van Cu St., Ward 4, District 5, Ho Chi Minh City, Viet Nam

a r t i c l e i n f o a b s t r a c t

Article history: This report focuses on studying and fabricating In-doped SnO2 (TIO) films following various depositing
Received 4 August 2016 and annealing temperatures. TIO films were deposited on quartz glass substrates using a direct current
Received in revised form (DC) magnetron sputtering method. These preferred SnO2 (101) and (211) reflections became dominant
12 October 2016
due to the substitution of Sn by In in the SnO2 host lattice. The valence state of In existing in TIO film was
Accepted 19 November 2016
Available online 21 November 2016
recorded using X-ray photoelectron spectroscopy (XPS). The p-type conductive property was found at a
minimum temperature of 400
C, and the best conductivity was achieved at the optimum annealing
temperature of 550
C for 2 h with resistivity, hole concentration, and mobility of 0.68 U cm,
Keywords:
p-type transparent conducting oxide
1.13  1018 cm3, and 8.13 cm2V1s1, respectively. Furthermore, the average transmittance of the films
In-doped SnO2 film was above 85%. Grain shape and size were observed by scanning electron microscopy (SEM). The exis-
DC magnetron sputtering tence of the In3þ state in the band gap was identified using photoluminescence spectra at room tem-
X-ray diffraction perature. The rectified characterisation revealed the behaviour of a p-TIO/n-Si heterojunction diode.
Photoluminescence © 2016 Elsevier B.V. All rights reserved.
X-ray photoelectron spectroscopy

1. Introduction
SnO2 films, as n-type semiconductors with a direct optical band
gap of about 3.87e4.3 eV [1,2], have high transparency, excellent
electrical conductivity, mechanical hardness, and heat- and
chemical-treatment stability. Among the transparent conductive
oxides (TCOs), SnO2 is a promising candidate owing to its various
potential uses in a wide variety of applications, such as TCOs for
liquid crystal displays, flat panel displays, plasma displays, touch
panels, electronic ink applications, organic light-emitting diodes,
solar cells, and antistatic coatings. However, there have been few
reports to date of doping tin oxide to make it a p-type semi-
conductor. In fact, SnO2 film doping III group metals such as Al [3,4],
Ga [5e8], In Refs. [9,10], and Sb [11e14] serve as p-type TCOs. In
addition, dopants such as N [15,16] and Zn [17e21] also contribute a
hole when doped into the SnO2 film. Among the above possible
* Corresponding author.
E-mail addresses: ltran@hcmus.edu.vn (T. Le), danghuuphuc@tdt.edu.vn
(H.P. Dang).
dopants, N has been hard to replace at Sn sites because the for-
mation energy of SneN is higher than that of SneO, and dopants,
which have a smaller [3,8] or larger [16,17,21,22] ion radius than the
Sn4þ ion radius, cause a lattice distortion when used as a substitute
for Sn. This is due to a broadening or narrowing of the unit cell
volume, and the lattice distortion rule is not an exception also for In
Refs. [9,23]. Furthermore, non-stoichiometric SnO2 film, containing
more oxygen vacancy, causes broadening of unit cells and thus
causes lattice distortion [24]. However, no reports have mentioned
distortion suppression from a balancing between oxygen vacancy
and substitute dopants which have an ion radius larger than that of
Sn. Indium is a potential candidate because its ionic radius (0.81 Å)
[25] is greater than that of Sn4þ (0.71 Å). Therefore, the balance of
lattice distortion between In dopants and the existing oxygen va-
cancies in the SnO2 host lattice is possible when substituting Sn by
In, and this possibly leads to crystalline improvement and thus
increases hole mobility.
Recently, there have been two reports of the synthesis of In-
doped SnO2 films (TIO) using a Sol-gel dip-coating method [9,10].
One report did not pay attention to the electrical properties, and the
other revealed that p-type TIO films were obtained at an annealing

http://dx.doi.org/10.1016/j.jallcom.2016.11.276
0925-8388/© 2016 Elsevier B.V. All rights reserved.
 T. Le et al. / Journal of Alloys and Compounds 696 (2017) 1314e1322
temperature of 550
C but had low hole concentration of
1.14  1015 cm3. Both reports showed poor crystalline results. For
this reason, in this paper, we systematically studied and investi-
gated the structural, optical and electrical properties of p-type TIO
films deposited on quartz substrates by a DC magnetron sputtering
method in which the deposition and annealing temperature played
a major role in improving the crystalline and electrical properties as
well as optical properties.
2. Experiment
The SnO2 and TIO films were deposited on the quartz substrates
by Leybold Univex 450 DC magnetron sputtering system in ambient
Ar gas at a working pressure of 4.103 torr from a ceramic target
(SnO2 and 10% wt In2O3). A ceramic plate that was sintered at
1400
C for 4 h with a mixed powder of SnO2 (99.99% purity, Merck)
and In2O3 (99.99% purity, Merck) was used as the sputtering target
with a diameter of 7.5 cm. The quartz glass substrates were ultra-
sonically cleaned in NaOH 10%, acetone and deionized water for
35 min, and the target was pre-sputtered for 15 min to remove any
contaminant from the target surface before films were deposited on
the substrate. The sputtering parameters of power, target to sample
distance were 15 W, 7 cm.
The substrate temperature was investigated in the range of
room temperature (rt) to 500
C, and the films were annealed at
temperatures of 550 and 600
C after being deposited at 500
C. By
controlling the deposition time, the thickness of the SnO2 and TIO
films, which were measured using the SCOUT program to fit the
modelled spectrum with the experimental spectrum, was about
400 nm. The structure of the TIO films was studied using an X-ray
diffractometer (D8-ADVANCE) operated at 40 kV and 40 mA with
CueKa radiation. The chemical state of the elements was identified
using X-ray photoelectron spectroscopy (XPS) on an ESCALAB 250
measured at room temperature. The optical transmittance was
measured within the wavelength range of 200e1100 nm using
UVeVis Jasco V-530. A Hall measurement system (HMS 3000) was
used to measure carrier concentration and mobility at room tem-
perature. The surface morphology was observed with a field-
emission scanning electron microscope manufactured by the
Hitachi Company (S-4800). IeV characteristics were measured
using a semiconductor testing system (Keithley 2400). The PL
spectra were acquired after excitation by a Xenon lamp (Horiba
NanoLog).
3. Results and discussion
3.1. Crystal structure of TIO films with varying deposition and
annealing temperature
To study the effect of In3þ doping on the host lattice further, the
crystal structure of TIO films should be investigated with varying
deposition and annealing temperatures.
3.1.1. Crystal structure of TIO films with varying deposition
Fig. 1 shows the X-ray Diffraction (XRD) patterns of TIO films
deposited at the following temperatures. The results showed the
TIO film deposited at room temperature (rt ¼ 27
C) was amor-
phous because the thermal energy was insufficient to provide the
film to achieve the crystal. The film became crystal at the deposition
temperature of 200
C with a tetragonal rutile structure of the SnO2
(JCPDS No. 41-14445) in which the preferred (101) SnO2 plane was
dominant, the intensity of this peak heightened with an increase of
the deposition temperature above 200
C, and reached the highest
value at 500
C. The appearance of the (101) SnO2 plane, which is a
so-called reduced plane as explained in the report [7], was the
1315
Fig. 1. The X-ray diffraction patterns of TIO films deposited at different temperatures.
cause of a replacing Sn4þ by In3þ, accompanied with the formation
of an oxygen vacancy (VO) and the appearance of Sn2þ at lattice
points. However, the so-called oxidized (110) SnO2 reflection, as
mentioned in the report [7], existed and was preferred at the
deposition temperature of 400
C, indicating that the growth of the
(101) and (211) SnO2 planes was proceeding, or the substitution of
Sn by In was not sufficient. Furthermore, the (101) SnO2 reflection
became more dominant at 500
C, but the most preferred plane was
(211), and the (110) plane degraded significantly. This result can be
explained as follows, the (101) SnO2 surface was dominant caused
by the replacing of In at Sn lattice points as mentioned in the report
[7]. Also, the (211) reflection growth is due to not only the attri-
bution of the substitution of Sn4þ by In3þ but also the oxygen
deficiency in the ambient gas medium as observed for Tantalum-
doped SnO2 [26] and ATO [27]. In summary, the higher the depo-
sition temperature is, the more the substitution of Sn by In takes
place. However, the evaporation speed of the material vapor from
the substrate is larger than the condensation speed on the substrate
at temperatures above 500
C so that the formation of films could
not occur at this temperature. For the substitution of Sn by In to
proceed, the post annealing process is necessary after the films are
deposited at 500
C.
3.1.2. Crystal structure of SnO2 and TIO films with varying
annealing temperatures
Fig. 2 describes the XRD patterns of TIO films annealed at 550
C
and 600
C for 1 h after being deposited at 500
C. The results
indicated that TIO films annealed at 500
C had a tetragonal rutile
structure of SnO2 (JCPDS No. 41-14445), including the two
preferred planes (101) and (211) and one Sn2O3 phase (030). While
the intensity of the two (101) and (211) peaks degraded remarkably
and they broadened compared to those of the film annealed at
550
C; moreover, the Sn2O3 phase did not exist but the (110) SnO2
appeared at the annealing temperature of 600
C. It is understood
that the reflections (211) and (101) of the film annealed at 550
C
grew sharply due to the substitution of Sn by In which was
considerable, and the Sn2O3 phase appeared because the film ob-
tained energy released from that substitution as explained in the
previous papers [7,11]. In contrast, the crystal degradation rule was
the cause of the crystal reorganization similar to that of the SnO2
1316 T. Le et al. / Journal of Alloys and Compounds 696 (2017) 1314e1322
Fig. 2. The X-ray diffraction patterns of TIO films annealed at 550 and 600
C for 1 h
after being deposited at 500
C.
films mentioned in the report [28] and the possibility of existing
In2O3 clusters alternating in the host lattice. In short, the crystalline
of the TIO film grew completely at the optimum annealing tem-
perature of 550
C and the possibility of the substitution of Sn by In
was most efficient at this temperature. Furthermore, the annealing
time was also a factor that caused the effect on the crystal growth.
In fact, Fig. 3 shows XRD patterns of TIO films annealed at 550
C for
1, 2 and 3 h after being deposited at 500
C. The data showed the
TIO film had two preferred (101) and (211) SnO2 planes that were
the most dominant for the annealing time of 2 h and especially the
(030) Sn2O3 phase, which is semi-stable, and disappeared for the
annealing time of 2 h. However, the crystalline of the film degraded
Fig. 3. The X-ray diffraction patterns of TIO films annealed at 550
C for 1, 2 and 3 h
after being deposited at 500
C.
significantly for the annealing time of 3 h, being similar to the
crystal degradation rule for the TIO film annealed at 600
C. These
results indicate that the substitution of Sn by In was the most useful
at the optimum annealing time of 2 h.
The previous paper [11] was studied in the crystal growth rules
of SnO2 films versus deposition temperature so it was not
mentioned in this report. However, the crystal growth rules for
SnO2 films at optimum annealing temperature and time need to be
considered to understand more clearly the influence of In doping in
the host lattice on the crystal structure of TIO films.
Fig. 4 exhibits the XRD patterns for SnO2 and TIO films annealed
550
C for 2 h after being deposited at 500
C. These analysis results
revealed that the intensity of the peak (110) of the post-annealed
SnO2 film was higher than that of the as-deposited one, as refer-
enced in the paper [11]. Moreover, two peaks, (200) and (211),
appeared simultaneously, but their intensity was lower than that of
the peak (110). The crystal growth rule of the post-annealed SnO2
film could be due to the increase in the oxygen quantity released
from the vacuum chamber that was in agreement with the report
[29] that concluded the SnO2 (110) plane grew with rising partial
oxygen pressure. In comparison with the SnO2 film, the crystal
growth rule of the (101) and (211) planes for the post-annealed TIO
film was similar to that of (110) and the reflection of the post-
annealed SnO2. The conclusion is that the possibility of substitut-
ing Sn with In was available for TIO film regardless of the desorp-
tion of oxygen from the chamber wall. Furthermore, the
substitution of Sn by In dopants improved the crystalline of the TIO
films compared to SnO2 films because of the distortion balance
between the broadening of the unit cell volume caused by In
replacing Sn and its narrowing caused by the existing oxygen va-
cancy. As a matter of fact, the data from Table 1 shows that the
lattice constants a and c and the volume of the unit cell for the TIO
film were larger than those of the SnO2. However, they only were
somewhat greater than standard values while the work [23] sup-
ported that they were considerably larger than standard values,
indicating that the substitution of Sn by In did not broaden the unit
cell volume so significantly that lattice distortion could occur.
Fig. 4. The X-ray diffraction patterns of A) SnO2 and B) TIO films annealed at 550
C for
2 h after being deposited at a 500
C.
 T. Le et al. / Journal of Alloys and Compounds 696 (2017) 1314e1322 1317

Table 1
Lattice constants of SnO2 and TIO annealed at 550
C for 2 h after being deposited at 500
C.

Sample a¼b [Å] c [Å] The volume of a unit cell [Å]3

SnO2 4.7391 3.1709 71.2876

TIO 4.7484 3.1889 71.9019
Standard value (JCPDS, 00-041-1445) 4.7403 3.1885 71.6470

3.2. Surface morphology
To modify these crystal structure results, the surface
morphology (SEM images) of TIO films were investigated at the
same conditions as that of the XRD patterns of TIO films. SEM im-
ages in Fig. 5 showed that TIO film deposited at rt had small grain
size and an unidentified shape, being in agreement with the
amorphous structure as explained in the XRD patterns (Fig. 1).
Grain size became larger within the range of 200e300
C and the
distribution of grain was homogenous, but some voids existed
within the grains. At the deposition temperature of 400
C, the
grain had a polyhedron-like shape along with the existence of
many voids or porous holes among the boundaries and distributed
homogenously, indicating that the initial process of crystallization
was reasonable as mentioned in XRD patterns (Fig. 1). At the
deposition temperature of 500
C, the majority of grains were huge
and the films became compacted, but an alternation of a minority of
small grains and large grains appeared and voids did not exist
within the boundaries. It was revealed that the spreading out of the
agglomeration of small grains was possible when the thermal

Fig. 5. SEM images of TIO films deposited at different substrate temperatures.

1318 T. Le et al. / Journal of Alloys and Compounds 696 (2017) 1314e1322
Fig. 6. SEM images of TIO films annealed at (A) 550
C and (B) 600
C after being deposited at 500
C.
energy that provided the film was high enough, that is the cause of
the transformation for the preferred crystal direction as shown in
the XRD patterns (Fig. 1). It is interesting that the number of small
grains decreased enormously, and the majority of the grains
became huge at the annealing temperature of 550
C for 1 h as seen
in Fig. 5. This proved that the spreading out of the agglomeration of
small grains was complete, relevant to the best crystalline as
explained in the crystal structure section (Section 3.1). However,
the grain size was significantly reduced as the film annealed at
600
C for 1 h (see Fig. 6) due to crystal degradation as mentioned
in the structural property section (Section 3.1). Moreover, the
annealing time is also a factor that causes an effect on grain size. In
fact, the grain size was the largest and the grain distribution was
homogenous for the film annealing time of 2 h at 550
C as seen in
Fig. 7 similar to the crystal growth rule as explained in Fig. 4 of
Section 3.1. In summary, the grains had a huge size or decreasing
boundaries and were homogenously distributed as the film
annealed at the optimum temperature of 550
C for 2 h. Further-
more, the substitution of Sn by In dopants improved the crystalline
in TIO films compared to SnO2 films because of the balance of the
unit cell volume broadening caused by the In replacing the Sn and
its narrowing caused by the existing oxygen vacancy. In fact, Fig. 8
showed that the grain size of TIO annealed at 550
C for 2 h was
larger than that of the SnO2 film at the same annealing temperature
and time. This result contrasted to that of the previous reports
[9,23], proving that the DC sputtering method is possible.
3.3. The optical property of TIO films
The UVevisible transmittance spectra of TIO films are recorded
Fig. 7. SEM images of TIO films annealed at 550
C for (A) 2 h and (B) 3 h after being deposited at 500
C.
within a range of 200 nm ÷ 1100 nm.
3.3.1. The optical property of TIO films versus deposition
temperature
Fig. 9 presents the UVevisible transmittance spectra in the
range of 200 nm ÷ 1100 nm of the TIO films deposited following a
substrate temperature in Ar ambient gas. The results showed that
TIO film, deposited at rt, had an absorption edge at 405 nm wave-
length equivalent to a band gap energy of 3.06 eV while that of
SnO2 film was 2.87 eV as indicated in the report [7]. This can be due
to the substitution of Sn with In in the SnO2 host lattice, causing a
release of energy for supporting oxidization of some of the Sn2þ
states to Sn4þ states as studied for p-type ATO films [11]; and the
absorption edge is still due to the transition electron absorption
from the Sn2þ level to the conductive band. This effect of an ab-
sorption edge shift to a shorter wavelength was more clear for the
films deposited in the range of 200 to 300
C, i.e., the quantity of In
replacing Sn increased with the rising deposition temperature.
However, the absorption edge stopped shifting at a temperature
above 400
C, proving that the phase transformation from SnO to
SnO2 was complete and confirming that the band gap energy for
TIO is also the exciton absorption energy of SnO2 (4.2 eV) as
mentioned in Ref. [7].
3.3.2. The optical property of films versus annealing temperature
Fig. 10 depicts the UVevisible transmittance spectra of TIO films
annealed following various temperature in Ar ambient gas for 1 h
after being deposited at 500
C within the range of 200÷1100 nm.
The results indicated that annealed films had an absorption edge
which was located in the same position as that of the film deposited
 T. Le et al. / Journal of Alloys and Compounds 696 (2017) 1314e1322
Fig. 8. SEM images of (A) SnO2 films (B) TIO films annealed at 550
C for 2 h after being deposited at 500
C.
Fig. 9. The UVevisible transmittance spectra of TIO films were deposited at the
following substrate temperatures.
at 500
C, asserting that the SnO phase did not exist in TIO films. In
addition, the transmittance of all the annealed films was a little
higher than the as-posited film at 500
C and the average trans-
mission achieved was above 80%.
3.3.3. The optical property of annealed film at 550
C with different
times
Fig. 11 plots the UVevisible transmittance spectra of TIO films
annealed at the optimum temperature of 550
C for 1, 2 and 3 h
after deposition at 500
C within the range of 200 nm ÷ 1100 nm. It
is observed that the absorption edge of the films annealed at the
optimum temperature was the same site as that of the as-deposited
films. Furthermore, the transmittance of all the annealed films was
approximately equal to one another and higher than 80%, abso-
lutely asserting that Sn2þ did not exist in the TiO films at the
annealing temperature of 550
C regardless of the annealing time.
3.4. Investigation of photoluminescence spectra of as-deposited and
annealed TIO films with various temperatures
To prove the existence of the acceptor In3þ in the host lattice and
where its location in the band gap is, photoluminescence (PL)
spectra in the range of 350 ÷ 600 nm of as-deposited and annealed
1319
Fig. 10. The UVevisible transmittance spectra of TIO films annealed at 550
C and
600
C for 1 h after being deposited at 500
C.
TIO films with various temperature were investigated. Fig. 12 ex-
hibits PL spectra of all TIO films deposited following substrate
temperatures. All films were excited by a light source of 285 nm
wavelength at rt (27
C). It was observed that there existed two PL
peaks, B1 (395 nm, 3.14 eV), B2 (505 nm, 2.46 eV), and a no peak,
which is the exciton emission peak located at 295 nm or 4.2 eV,
caused by electron transition from the conductive to the valence
band. The report [7] indicated that SnO2 film deposited at rt had
two PL peaks where one peak was located at 408 nm, where the
electron transition was from the Voþ level to the Sn3þ acceptor, and
another at 431 nm where the electron emission transition was
between a conductive band and the Sn2þ acceptor level. However,
PL spectra of TIO films showed only one peak, B1 (3.14 eV), which is
greater than the band gap energy (3.06 eV) of TIO film deposited at
rt and is less than the exciton absorption energy of SnO2. Thus, the
B1 emission peak was not an electron emission transition between
the conductive band and the In3þ acceptor level but an electron
mission transition from the Voþ level to the In3þ acceptor level
which is 0.11 eV higher than the valence top. More clearly, the
absorption edge shifted toward a shorter wavelength with
increasing deposition temperature (Fig. 9), asserting that the Sn2þ
valence state gradually transformed to that of Sn4þ but the B1
emission peak did not shift. Furthermore, the B1 PL peak intensity
gradually rose as the deposition temperature increased within the
1320 T. Le et al. / Journal of Alloys and Compounds 696 (2017) 1314e1322

Table 2
The results of the Hall effect measurements of TIO films that were deposited at
different temperatures.

T (oC) r (Ucm) m (cm2/Vs) n/p (cm3) Type

rt ∞ e e e
200 ∞ e e e
300 136 2.89 1.59  1016 p
400 60.3 4.03 2.57  1016 p
500 20.7 4.33 6.97  1016 p

of TIO film such as hole concentration, mobility and resistivity are

Fig. 11. The UVevisible transmittance spectra of TIO films annealed at 550 for 1, 2, and
3 h after being deposited at 500
C.
Fig. 12. PL emission spectra of TIO samples.
range of 200oCe500
C and reached the highest value at 500
C,
indicating that the quantity of acceptor In3þ increased following
deposition temperature. The other B2 PL peak may be attributed to
the electron transition from the conduction band to the deep center
Voþþ donor, which is formed by Voþ capturing an active hole in the
valence band (Voþþ donor level is 2.46 eV below the conduction
band bottom). Fig. 12 also shows that TIO films annealed at 550 and
600
C had a PL intensity of B1 peak which was higher than that of
the as-deposited films at 500
C, especially, films annealed at
550
C had the highest B1 peak intensity relevant to the greatest
hole concentration. In addition, the B1 intensity of the films
annealed at 600
C was lower than that of films annealed at 550
C,
that can be due to acceptors compensated with donors. These re-
sults were in agreement with those of the structural and optical
properties as presented in Sections 3.1 and 3.2.
also factors to determine the contribution of In dopants as
acceptors.
Table 2 presents the electrical property of TIO films deposited at
different temperatures. According to the previous report [11], all
SnO2 films supported negative-charged carriers or electrons as
deposited at the temperature within the range of rt - 500
C. While,
TIO films were nonconductive at rt and 200
C temperature, which
is explained as follows: at below 200
C, there exist both holes,
created from the acceptor Sn2þ [11], and In3þ and donors, formed
from native defects such as oxygen vacancies (VO ; Vþ þþ 4þ
O ; VO ) or Sn
interstitials [11], compensating in the TIO film. However, TIO films
serve as p-type TCOs with an increase in hole concentration as
deposited in the range of 300e500
C and the highest concentra-
tion of 6.97  1016 cm3 at 500
C, equivalent to the lowest re-
sistivity of 20.7 U cm. The number of In3þ increased from
supporting thermal energy to films and was dominant compared to
that of the native oxygen vacancies, creating a p-type electrical
property. These results were in agreement with that of the previous
sections.
Table 3 shows the electrical property of TIO film annealed at
different temperatures for 1 h after being deposited at 500
C. The
data indicates that the resistivity of all annealed films decreased,
and hole concentration increased, asserting that the substitution of
Sn by In proceeded. However, the electrical property was optimum
as the film annealed at 550
C and degraded at an annealing tem-
perature above 550
C due to the crystal degradation and the cre-
ation of an In2O3 cluster as well as oxygen vacancies, which is
reasonable for these results as in the previous sections.
Table 4 shows the results of the Hall measurement of TIO films
annealed at 550
C for 1, 2 and 3 h after being deposited at 500
C.
The results revealed that the hole concentration and mobility of the
films achieved the highest value at an annealing time of 2 h with
the resistivity, Hall mobility, and hole concentration of 0.68 Ucm,
8.13 cm2/V, and 1.13  1018 cm3, respectively. These results were in
good agreement with the structural analysis (Section 3.1).
Table 3
The results of the Hall measurement of TIO films deposited at 500
C and annealed at
550 and 600
C.
Temperature r (U cm) m (cm2V1s1) n/p (cm3) Type
Annealed 550
C 0.85 7.86 9.36  1017 p
Annealed 600
C 4.15 3.41 4.42  1017 p
Table 4
The results of the Hall measurement of TIO films deposited at 500
C and annealed at
550
C for 1, 2 and 3 h.

3.5. Electrical property of TIO films Time (h) r (U.cm) m (cm2V1s1) n/p (cm3) Type
17
1 0.85 7.86 9.36  10 p
TIO films serve as a hole conductive material owing to the 2 0.68 8.13 1.13  1018 p
3 6.00 3.10 3.36  1017 p
replacing of In at lattice points of Sn. Thus, the electrical parameters
 T. Le et al. / Journal of Alloys and Compounds 696 (2017) 1314e1322 1321

Fig. 15. The In 3d5/2 and 3d3/2 XPS spectra (segment circles) and fit results (red line) of
Fig. 13. XPS wide spectra of TIO film annealed at 550
C for 2 h after being deposited at
TIO film annealed at 550
C for 2 h after being deposited at 500
C. (For interpretation
500
C.
of the references to colour in this figure legend, the reader is referred to the web
version of this article.)

3.6. XPS analysis

Table 5
The valence state of ions such as Sn4þ, In3þ, and O2 existing in XPS results of the atomic percentage ratio in TIO film annealed at 550
C for 2 h after
the TIO film annealed at 550
C for 2 h was determined using XPS being deposited at 500
C.

measurements. Fig. 13 presents a photoelectron double peak of Sn [In 3d5/2] [Sn 3d5/2] [In 3d5/2]/[Sn 3d5/2]
at positions of 486.6 eV (Sn 3d5/2 core-level) and 495 eV (Sn 3d3/2 Annealed for 2 h TIO film 21757.28 447215.60 0.05
core-level). It also shows the O 1s peak, which is located at 530,
6 eV, was the result of overlapping three peaks, including the
attribution to O2 ions in the rutile structure of the Sn4þ ion array
indicated that the substitution of Sn by In confirmed the reasonable
[30]; O2 ions in the oxygen-deficient regions [31]; and the
above explanation for structural, optical and electrical properties.
adsorbed oxygen species [32]. In addition, the positions of the In
double peak of 444.7 eV (In 3d5/2 core-level) and 452.3 eV (In 3d3/2
core-level) was also seen in Fig. 13. All peak positions were cali- 3.7. Properties of p-type TIO/n-type Si heterojunction
brated based on C 1s peak at 284.5 eV as a reference [33] and were
fit using the XPSEAK41 software. These peaks of Sn 3d5/2 and In 3d5/ To confirm p-type conduction in the TIO films, a simple heter-
2 core-levels were fit as shown in Figs. 14 and 15. Table 5 shows the ojunction diode was designed by depositing p-type TIO film on an
atomic percentage ratio of In and Sn, which as a ratio of the inte- n-type Si wafer as seen in Fig. 16. Indium electrodes are placed both
gration area of In 3d5/2 and Sn 3d5/2 peaks. This ratio which was 5% on the p-type and the n-type layers as shown in the upper left inset

Fig. 14. The Sn 3d5/2 and 3d3/2 XPS spectra (segment circles) and fit results (red line) of
TIO film annealed at 550
C for 2 h after being deposited at 500
C. (For interpretation
of the references to colour in this figure legend, the reader is referred to the web Fig. 16. The I-V characteristics of the p-type TIO/n-Si heterojunction. The insets show a
version of this article.) schematic diagram of the p-n heterojunction (upper left).
1322 T. Le et al. / Journal of Alloys and Compounds 696 (2017) 1314e1322
of Fig. 16, revealing that the linear IeV characteristics showed good
ohmic contact behaviour. The rectified characteristics of the p-type
TIO/n-type Si structure with a forward turn-on voltage of 1.74 V,
also indicated that the p-n junction was formed at the interface.
4. Conclusion
This paper showed that depositing and annealing temperatures
were parameters that influenced the structural, optical, and elec-
trical properties of TIO films. The p-type conductivity was found at
the deposition temperature of 300
C, and the best p-type electrical
properties were achieved for film annealed at 550
C for 2 h after
being deposited at 500
C with the lowest resistivity, the highest
hole concentration, and the greatest hole mobility of 0.68 U cm
1.13  1018 cm3 and 8.13 cm2V1s1, respectively. Furthermore, an
average optical transmittance of the films in the visible region
(400e760 nm) was about 85%, and the preferred orientation of the
(101), (211) planes was dominant as the number of In dopants
incorporated in the SnO2 host lattice was the most as well as the
grain size was the largest. The XPS and PL measurements indicated
that In replaced Sn at lattice points and acted as an acceptor. The p-
TIO/n-Si heterojunction diode exhibited rectified characteristics,
supporting that a p-type TIO film could be a promising candidate
for practical applications.
Acknowledgements
We wish to express to our late Professor Nguyen Huu Chi, who
was the first Professor to establish a thin films technology and
material sciences field at VietNam National University of Ho Chi
Minh City - HCMC University of Science, an especially grateful
thanks from the bottom our hearts. His unlimited scientific indul-
gence, motivation, and friendship have been essential to our
development as researchers.
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