Journal of Alloys and Compounds 687 (2016) 1012e1020

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Journal of Alloys and Compounds

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

The influence of deposition temperature and annealing temperature

on Ga-doped SnO2 films prepared by direct current magnetron
sputtering
Huu Phuc Dang a, Quang Ho Luc b, Van Hieu Le c, Tran Le d, *
a
Industrial University of HCMC, Ho Chi Minh City, No. 12 Nguyen Van Bao, Ward 4, Go Vap District, Ho Chi Minh City, Viet Nam
b
Faculty of Foundation Sciences, HCMC University of Technology and Education, No. 1 Vo Van Ngan Street, Linh Chieu Ward, Thu Duc District, Ho Chi Minh
City, Viet Nam
c
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
d
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

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

Article history: Transparent Ga-doped tin oxide (GTO) thin films were fabricated on quartz glass from a (SnO2 þ Ga2O3)
Received 29 April 2016 mixture ceramic target by direct current (DC) magnetron sputtering in Ar ambient gas at a working
Received in revised form pressure of 4.103 torr. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Hall-effect
8 June 2016
and UVevis spectral measurements were performed to characterize the deposited films. The films could
Accepted 23 June 2016
Available online 1 July 2016
be given p-type electrical properties by supplying energy, such as kinetic (by controlling pressure) or
thermal (by controlling temperature substrate) energy. However, kinetic energy caused film stress;
therefore, we investigated the substrate temperature of the films in two ways. In the first method, films
Keywords:
p-type transparent conducting oxide
were deposited directly with different temperatures; in the second method, post-deposition annealing in
Ga-doped SnO2 thin film Ar ambient gas after deposition at 400  C was used. The deposited films showed p-type conduction,
DC magnetron sputtering polycrystalline tetragonal rutile structure, and the average transmittance was above 80% in the visible
X-ray diffraction light range after annealing at the optimum temperature of 550  C for 2 h. The results for the best
Photoluminescence conductive film showed a low resistivity of 0.63 Ucm and a sheet resistance of 15.7 kU/sq, a hole con-
centration of 3.3  1018 cm3, and a Hall mobility of 3.01 cm2 V1 s1 with thickness is about 400 nm. In
addition, p-type conductivity was also confirmed by the non-linear characteristics of a p-type GTO/n Si
heterojunction.
© 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction Therefore, p-type TCOs are considered important by researchers

Tin oxide, which is a transparent conductive oxide (TCO), has a
wide band gap (3.6e4 eV) and high exciton binding energy
(60 meV), is abundant and non-toxic and has high thermal and
chemical stability.
SnO2, which can serve as a good n-type semiconductor by
doping elements such Sb [1], Ta [2], and F [3], has been widely
studied, with reports of good results such as a resistivity of
103e104 Ucm and high transparency of approximately 80%e90%.
As such, SnO2 has been applied to an electrode in solar cells, LEDs,
laser diodes, sensors, and optoelectronic devices. To date, n-type
TCOs have served as positive electrodes for optoelectronic devices.
* Corresponding author.
E-mail address: ltran@hcmus.edu.vn (T. Le).
because of the potential for them to replace n-type TCOs. However,
research on p-type SnO2 is still in its infancy. There have been a few
reports regarding films prepared using spray pyrolysis, sputtering,
and solegel methods, and elements such as In [4e6], Ga [7e10], Al
[11,12], Sb [13e15], Zn [16e18], Fe [19], Cu [20], N [21,22], or In-Ga
co-doping [23] used as acceptor dopants. Among these dopants, Ga
seems to be the most effective p-type dopant for SnO2, as its ionic
radius (0.62 Å) is nearly equal to that of Sn4þ (0.69 Å). However,
these studies on p-type Ga-doped SnO2 (GTO) [7e10] have not
systematically investigated fabrication parameters and have not
explained the relationship between preferred crystal orientation
and substituted dopant clearly. With respect to the synthesis
methods mentioned above, solegel and spray pyrolysis methods
give porous films that recrystallize after being annealed, and the
radio-frequency sputtering method is expensive and difficult to

http://dx.doi.org/10.1016/j.jallcom.2016.06.236
0925-8388/© 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 H.P. Dang et al. / Journal of Alloys and Compounds 687 (2016) 1012e1020 1013

apply at an industrial scale. Meanwhile, direct current (DC) in Table 1, the resistivity of the GTO films increases with increasing
magnetron sputtering is inexpensive, and fabricating large-scale temperature, and they are nonconductive above 400  C. Noncon-
films is easy. ductive GTO films were formed because of a compensation effect of
In this paper, p-type GTO thin films were deposited on quartz donor electrons as neutral oxygen vacancy V0 and localized holes as
substrates by direct current (DC) magnetron sputtering and their acceptor Ga3þ and Sn3þ at 400  C. Compensation was perfect at
electrical and optical properties as well as crystal structures were 400  C, the so-called “critical temperature”. The compensation
systematically investigated. In detail, the effects of substrate tem- mechanism may be explained as follows: replacing Sn with Ga,
perature, annealing temperature, and annealing time on the which creates acceptor Ga3þ and adjacent Vo (Fig. 1) causes high
structural, electrical, and optical properties of GTO films were electronegativity for oxygen and interaction between Vo and Sn2þ is
studied. less than that between Sn4þ and O2. Thus, one or two free elec-
trons of Vo were associated with or captured into the localized
acceptor states [24].
2. Materials and methods
Table 2 summarizes the electrical properties of SnO2 and GTO
films annealed at various temperatures. SnO2 films annealed at
SnO2: Ga (GTO) thin films were deposited on quartz from a
500e550  C showed n-type conductivity, and their resistivity
ceramic target by DC magnetron sputtering in ambient Ar gas using
increased from 19.5 to 56.2 Ucm because of the decrease in carrier
a Univex 450 system. Ar gas was introduced into the vacuum
concentration. The decrease in SnO2 carrier concentration occurred
chamber through a high-resolution needle valve during the sput-
because of compensation between Vo and acceptor Sn3þ (the Sn2O3
tering process with a working pressure of 2  103 torr. A ceramic
phase appeared at this condition, Fig. 3A). GTO films annealed at
plate that was sintered at 1400  C for 4 h with mixed powders of
500e550  C showed p-type conductivity, and their resistivity
85% wt SnO2 (99.99% purity, Merck) and 15% wt Ga2O3 (99.99%
decreased from 40.9 to 9.0 Ucm because of the increase in positive
purity, Merck) with a diameter of 7.5 cm was used as the sputtering
carrier concentration. The increased resistivity of GTO films can be
target. The quartz glass substrates were ultrasonically cleaned in
donor Vo compensated with acceptor Ga3þ at 600  C. This is in
10% NaOH, acetone, and deionized water for 35 min. Before depo-
agreement with the increasing native donors of SnO2.
sition, the target was pre-sputtered for 15 min to remove any
The results in Table 3 show that the carrier concentration and
contaminants on the target surface. The sputtering parameters
mobility increase with annealing time from 1 to 2 h. Increasing the
power and target to sample distance were 15 W and 7 cm,
annealing time causes more Ga3þ to replace Sn4þ in the lattice and
respectively.
more Sn3þ to replace Sn4þ from the dissociation of SnO2 in Sn2O3.
The substrate temperature of films was investigated in two
These replacements contribute a positive concentration so that the
steps. Films were deposited directly with different temperatures to
resistivity of GTO films decreases from 9 to 0.63 Ucm. However, the
determine the optimum temperature. In the next step, they were
resistivity of GTO films annealed for 3 h increase significantly from
annealed in Ar ambient gas after being deposited at the optimum
0.63 to 31 Ucm. It can be explained that donor concentration
temperature. By controlling the deposition time, the thickness of
increased from these increase of intrinsic defects, so the measured
SnO2 and GTO films were kept at approximately 400 nm. The
hole concentration decreased due to self-compensation.
thicknesses of the thin films were measured using the SCOUT
program by fitting the modeled spectrum with the experimental
spectrum. The structures of SnO2 and GTO films were studied using
3.1. Structural properties
an X-ray diffractometer (D8eADVANCE) operated at 40 kV and
40 mA with CueKa radiation. The optical transmittance was
Fig. 2 shows XRD patterns of GTO films deposited directly on a
measured in the wavelength range from 200 to 1100 nm using a quartz substrate at different temperatures. The result shows that
UVeVis Jasco V-530. A Hall measurement system (HMS 3000),
the GTO films had an amorphous structure at room temperature
operated at room temperature, was used to measure carrier con- and started to crystallize at 200  C with a SnO2 tetragonal rutile
centration and mobility. X-ray photoelectron spectroscopy (XPS)
structure (JCPDS No. 41-14445) with a (200) peak as the preferred
was conducted at room temperature on an ESCALAB. Current- peak; those grown at 300e500  C exhibit gradually increasing
voltage (I-V) characteristics were measured using a semi-
crystallinity. The best crystallinity was obtained at 500  C, at which
conductor characteristic analyzer system (Keithley 2400). The PL the preferred orientation plane was (101). This can be explained
spectra were acquired after excitation by a Xeon lamp (Horiba
according to [25,26]: the (101) surface, which is rich in Sn2þ atoms
Nanolog). (rich in oxygen vacancies), increased sharply corresponding to a
substitution of Sn4þ by Sn2þ. This effect is similar to the substitution
3. Results and discussion of Sn4þ by Ga3þ in this report.
Fig. 3A shows the XRD pattern of SnO2 films deposited at 400  C
Because the deposition temperature plays an important role in
the electrical, structural, and optical properties, GTO films need to
be investigated according to their substrate temperatures. As seen

Table 1
Results of Hall measurement of GTO films deposited at various temperatures.

T ( C) GTO films

r (Ucm) m (cm2V1 s1) n/p (cm3) Type

RT 2.40 2.62 1.0  1018 n

200 0.52 4.66 2.6  1018 n
300 0.70 2.94 2.1  1018 n
400 ∞
500 ∞
Fig. 1. Charge carrier compensation due to Ga3þ doping.
1014 H.P. Dang et al. / Journal of Alloys and Compounds 687 (2016) 1012e1020

Table 2
Results of Hall measurement of SnO2 and GTO films deposited at 400  C and annealed at various temperatures in Ar.

T ( C) SnO2 films GTO films

r (Ucm) m (cm2V1 s1) n/p (cm3) Type r (Ucm) m (cm2V1 s1) n/p (cm3) Type
17 16
500 19.5 1.78 1.86  10 n 40.9 3.82 3.69  10 p
550 56.2 1.84 6.05  1016 n 9.0 0.43 1.60  1018 p
600 7.06 1.91 4.63  1017 n 3.3 3.01 6.33  1017 p

Table 3 and annealed at different temperatures. All the patterns of thin

Results of Hall measurement of GTO films deposited at 400  C and annealed at
550  C for 2 h in Ar.
Time (h) r (Ucm)
1 9.0
2 0.63
3 31
films were SnO2 with a tetragonal rutile structure (JCPDS No. 41-
14445); the peak intensities of the (110) and (211) planes increased
m (cm2V1 s1) n/p (cm3) Type with annealing temperature because of oxidation of Sn2þ to Sn4þ,
0.43 1.6  1018 p as mentioned in Refs. [18,19]. At 550  C, the (231) Sn2O3 phase
3.01 3.3  1018 p appeared because of the dissociation of SnO2. Conversely, Fig. 3B
0.35 5.7  1017 p shows that the XRD patterns of GTO films show strong (101) and
relatively weaker (211) SnO2 reflections at 500  C and 550  C. In
addition, the (021) Sn2O3 phase appears at 500  C and the (030)
phase appears at 550  C. This indicates that Ga3þ continues to
replace Sn4þ, which leaves many oxygen vacancies, leading the
intensity of the (101) orientation to increase. When annealed above
500  C, Ga3þ is markedly activated to substitute for Sn4þ, which
provides the energy to dissociate SnO2 to form Sn2O3. The energy
released from the replacement of Sn4þ by Ga3þ also contributes to
the oxygenation of Sn2O3 to SnO2 during annealing at 600  C.
Fig. 4 shows XRD patterns of GTO films deposited at 400  C and
annealed at 550  C for 1, 2 and 3 h. The results indicate the crys-
tallinity of 2-h GTO films is better than that of 1-h films; the in-
tensities of the (101) SnO2 and (030) Sn2O3 reflections increase
slightly versus the temperature. This proves that Ga3þ continues to
replace Sn4þ as annealing time increases. However, the intensity of
the (101) SnO2 reflection decrease significantly and the (030) Sn203
reflection disappear when GTO films annealed for 3 h.

3.2. Optical properties

Fig. 5 presents the transmittance spectra of GTO films deposited

at different temperatures and SnO2 deposited at rt. The results
show that at room temperature, the SnO phase exists in SnO2 films,
i.e., the acceptor Sn2þ level is deep so that it absorbs a part of visible
light at wavelengths below 450 nm, as mentioned in Refs. [27,28].
Therefore, the UV absorption edge shifts to long wavelengths while
GTO films have absorption edges that shift to the shorter wave-
length side, indicating that energy released from the possible
Fig. 2. XRD spectra of GTO films deposited at different temperatures.
replacement of Ga3þ at Sn4þ sites can be attributed to the trans-
formation of Sn2þ to Sn4þ. At above 200  C, the increase in the

A B

Fig. 3. A. XRD spectra of SnO2 films deposited at 400  C and annealed at 500  C, 550  C, and 600  C. B. XRD spectra of GTO films deposited at 400  C and annealed at 500  C, 550  C,
and 600  C.
 H.P. Dang et al. / Journal of Alloys and Compounds 687 (2016) 1012e1020
Fig. 4. XRD spectra of GTO films deposited at 400  C and annealed at 550  C for 1, 2
and 3 h.
Fig. 5. The UVeVisible transmission spectra of GTO films prepared at different
deposition temperatures and SnO2 film prepared at rt.
average transmission of GTO films in the visible region can be
associated with the disappearance of the SnO phase.
Fig. 6A and B presents the transmittance spectra of SnO2 and
GTO thin films deposited at 400  C and annealed at 500  C, 550  C,
and 600  C. The average transmittance of all SnO2 films in the
visible region (300e800 nm) is above 80%. However, the trans-
mission of GTO films decreases with increasing annealing tem-
perature because the crystalline of the GTO films increases, in
agreement with the structural properties of GTO mentioned above.
Fig. 7 presents the transmittance spectra of GTO films annealed
at 550  C for 1, 2 and 3 h. It is shown that the transmission of films
annealed at 550  C for 1 and 2 h are lower than that of 3 h. This is
due to the crystalline degree of film annealed for 3 h decrease
sharply as mentioned in Fig. 4. The average transmittance of all
films in the visible region (300e800 nm) is above 80%.
The transmittance spectra were used to determine the optical
constants such as refraction index (n), extinction (k) coefficient and
thickness of the GTO films, and the effects of deposition and
annealing temperature on the optical properties were investigated.
The optical transmittance spectra data in Figs. 5, 6B and 7 are fitted
with a computer model using SCOUT 98 software [29], simulations
1015
of transmittance data essentially base on Drude [30] and O’Lear-
yeJohnsoneLim (OJL) [31] models to determine the corresponding
optical constants of GTO films.
Figs. 8A and 9A present dispersion spectra of n and k coefficients
in the wavelength range of 300e1100 nm, evaluated from simu-
lating of optical transmittance spectra data of as-deposited films in
Fig. 5. It was observed that the refractive indices and extinction
coefficients of all the films decrease with the wavelength range of
300e400 nm and then vary slightly towards longer wavelengths.
This increasing is attributed to the increase of the absorption co-
efficient due to the direct electronic transitions at the absorption
edge region. It is also seen that the refractive indices of the films
increase as a result of increasing deposition temperature while the
extinction coefficients decrease. The increase in refractive indices
can be attributed to the increase of the degree of homogeneity and
the packing density of films in which the velocity of light in films
would decrease, this can be explained by the Lorentz-Lorenz rela-
tion (equivalent to Clausius-Mossotti relation) as mentioned in
reports [32e35]. The decrease in extinction coefficients can be
correlated to the decrease of defects and absorption centers in
films. It is interesting to see that the transmittance increases with
increasing deposition temperature, this is due to extinction co-
efficients decrease much compared to the increase of refractive
indices.
Figs. 8B and 9B show a variation of n and k coefficients with the
wavelength range of 300e1100 nm, fitted from simulating of op-
tical transmittance spectra data of annealing films in Figs. 6B and 7.
It is obvious that refractive indices of films annealed at 600 and
550  C for 1 and 2 h nearly are the same values and higher than
those of films annealed at 500  C for 1 h and 550  C for 3 h while
variation rule of the extinction coefficients is opposite. The varia-
tion rule of refractive index and extinction coefficient can be
attributed to the increase in the degree of crystalline of films. It is
noted that the transmittance of films annealed at 600 and 550  C
for 1 and 2 h decreases compared to that of films annealed at 500  C
for 1 h due to their refractive indices increase more than the
decrease of extinction coefficients. However, the transmittance of
films annealed at 550  C for 3 h increases again compared to that of
1 and 2 h due to the crystalline degree of films decrease sharply.
Table 4 shows the calculated results of refractive indices,
extinction coefficients and film thicknesses (d) versus annealing
temperatures at 550 nm wavelength in which the refractive index
and extinction coefficient of GTO film annealed at 550  C for 2 h was
found to be around 1.9727 and 0.0022, respectively. This result
shows that GTO film can be applied for anti-reflective coating onto
Silicon solar cells [32].
3.3. XPS spectra
Figs. 10e12 show the XPS spectra of the Ga 2p3/2, Sn 3d5/2, and O
1s core-level of the GTO films deposited at 400  C and GTO films
annealed at 500  C for 2 h after being deposited at 400  C. All peak
positions were corrected for surface charge by the C 1s peak at
284.5 eV. The O 1s spectrum can be deconvoluted into three peaks
for SnO2 (530, 531.5, and 532.5 eV) using XPSEAK41 software, and
the profile of each peak was taken as a Lorentzian-Gaussian mixed
function. Deconvolutions obtained the three peaks of O 1s at 530,
531, and 532.5 eV (Fig. 12). The two peaks at 530 and 531.5 eV can
be attributed to O2 ions in the rutile structure of the Sn4þ ion array
[36] and the O2 ions in oxygen-deficient regions [37]. The peak at
532.5 eV can be assigned to the adsorbed oxygen species [38]. The
peaks of Ga 2p3/2 are located at 1117.8 eV (Fig. 10), which corre-
sponds to the situation of pure Ga2O3 [39]. In addition, Table 5
shows the existence of Ga in films, which proves a complete
compensation effect at 400  C, as mentioned previously.
1016 H.P. Dang et al. / Journal of Alloys and Compounds 687 (2016) 1012e1020

A 100 B
100

Transmittance (T%)
Transmittance (T%)

500oC
500oC 50
50 550oC
550oC
600oC
600oC

0 0
200 400 600 800 1000 200 400 600 800 1000
Wavelength (nm) Wavelength (nm)

Fig. 6. A. The UVeVisible spectra of SnO2 films prepared at 400  C and annealed at 500  C, 550  C, and 600  C. B. The UVeVisible spectra of GTO films prepared at 400  C and
annealed at 500  C, 550  C, and 600  C.

Additionally, the compensation elimination effect was calculated

using the ratio of the integrated area of [O532.5] to [O531.5]. The re-
sults show that the ratio increases when the films were annealed.
This can be explained as follows: oxygen that exists in the ambient
gas is absorbed in the Voþ site and takes one or two electrons to
leave holes on the acceptor Ga3þ and Sn3þ. This will be discussed
clearly regarding the PL spectrum.

3.4. Photoluminescence spectra

The photoluminescence (PL) emission spectra of the SnO2 and

Fig. 7. The UVeVisible spectra of GTO films annealed at 550  C for 1, 2 and 3 h.
GTO films excited at a wavelength of 285 nm at room temperature
are shown in Fig. 13. The results show four emission peaks, at
381 nm (3.25 eV, peak B1), 408 nm (3.03 eV, peak B2), 431 nm
(2.87 eV, peak B3), and 464 nm (2.67 eV, peak B4). None of the
peaks was electron transition emission from the conduction band
to the valence band corresponding to 295 nm (4.2 eV) because this
emission energy is equal to the energy that supports electron
transition from the valence band to the conduction band. The
electron transition emission is equal to the band gap energy given

A B

Fig. 8. The change on refractive index of GTO films A) deposited various temperature B) annealed at 500, 550, 600  C for 1 h and 550  C for 2 and 3 h after being deposited at 400  C.
 H.P. Dang et al. / Journal of Alloys and Compounds 687 (2016) 1012e1020 1017

A B

Fig. 9. The variations in extinction coefficient of GTO films A) deposited various temperature and B) annealed at 500, 550, 600  C for 1 h and 550  C for 2 and 3 h after being
deposited at 400  C.

Table 4
Refractive index, extinction coefficient and thickness of GTO films at 550 nm wavelength.

T C Annealed at 500  C for 1 h Annealed at 550  C for 1 h Annealed at 600  C for 1 h Annealed at 550  C for 2 h Annealed at 550  C for 3 h

(n) 1.9616 1.9712 1.9715 1.9727 1.9386

(k) 0.004 0.0042 0.0032 0.0022 0.0044
d (nm) 413 383 418 393 392

Fig. 10. XPS Ga2p3/2 spectra of a) non-annealed 15% GTO and b) annealed GTO.

Fig. 11. XPS Sn3d5/2 spectra of a) non-annealed GTO films and b) annealed 15% GTO films.
1018 H.P. Dang et al. / Journal of Alloys and Compounds 687 (2016) 1012e1020

Fig. 12. The XPS O 1S spectra (segment circles) and simulated results (red line) of a) non-annealed GTO films and b) annealed GTO films. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)

Table 5 transition from the interstitial Vþ

o donor level to the valence band.
XPS results of percent concentration in non-annealed and annealed GTO films. The B4 peak may be attributed to the electron transition from the
Sample %O531.5 %Sn %Ga %O530 [O532.5]/[O531.5] conduction band to the deep center Vþþ o donor, which is formed by
Non-annealed GTO films 0.28 0.38 0.05 0.26 0.47
Vþ þþ
o capturing an active hole in the valence band (Vo donor level is
Annealed GTO films 0.16 0.66 0.07 0.10 1.13 2.67 eV below the conduction band bottom). However, the electron
transition mechanism of the B3 peak, which was a transition from
the Vþo donor to the Ga
3þ
acceptor (Ga3þ acceptor level is 0.379 eV
above the top of the valence band) differs from the electron tran-
sition mechanism of sample A. This is because the electron tran-
sition absorption energy of the sample B is 4.2 eV (Fig. 5), which
does not equal that of sample A (Fig. 5). The intensities of the B2 and
B3 peaks of the GTO films increase at 200  C (sample C). This is due
to the increasing quality of Ga3þ acceptors. Additionally, the in-
tensity of the B1 peak decreases but that of the B4 peak increases
because Vþ o captures an active hole in the valence band. At 300 C


(sample D), the intensities of the B2 and B3 peaks decrease

significantly. This can be explained as follows: a compensation ef-
fect appears because of the interaction between Vo and Ga3þ and
Sn3þ acceptors. This phenomenon occurs because of electron
transition from Vo or association with acceptors. In addition, the
intensities of the B1 and B4 peaks disappear because the electrons

35000 Peak
Peak
B2
B3
30000
sample F
sample G
Fig. 13. PL emission spectra of sample A, B, C, D and E. 25000
sample H
Intensity a.u

20000
in the UVeVis spectrum (Fig. 5). The PL spectra of SnO2 films
deposited at room temperature (sample A) have two B2 and B3
emission peaks; the B2 peak can be assigned to the electron tran- 15000
sition in the Vþ þ
o donor (the Vo donor level, which is formed by the
Vo state giving an electron to the conduction band, is 0.95 eV below
10000
the bottom of the conduction band) to the Sn3þ acceptor (Sn3þ
acceptor level is 0.2 eV above the top of the valence band). The
other peak is attributed to electron transition from the conduction 5000
band to a Sn2þ acceptor (Sn2þ acceptor level is 1.32 eV above the top
of the valence band), and this matches the electron transition ab-
0
sorption from the Sn2þ acceptor up to the conduction band, as seen 300 350 400 450 500 550 600
in the UVeVis spectra given in Fig. 5. Conversely, the PL spectra of
GTO films deposited at room temperature (sample B) have four B1, Wavelength (nm)
B2, B3, and B4 peaks. The B1 peak can be attributed to the electron
Fig. 14. PL emission spectra of sample F, G and H.
 H.P. Dang et al. / Journal of Alloys and Compounds 687 (2016) 1012e1020 1019

Fig. 15. Mechanism of photoluminescence emission from A) GTO films and B) SnO2 films.

completely transition from Vþ o to Ga

3þ
and Sn3þ acceptors. At
400  C (sample E), the B1 peak appears again because the quality of
Vo increases by replacing Sn4þ by Ga3þ, and all the electrons of Vo
play only a part in the compensation process but do not contribute
electrons to the conduction band. Thus, the resistivity of sample E
was indefinite, indicating that the results agree with the electrical
properties mentioned above. Furthermore, the quality of Vþ o was
such that its one electron recombined with active holes in the
valence band to create the B4 peak.
The emission patterns of GTO films annealed at various tem-
perature after deposition at 400  C are shown in Fig. 14. The B2 and
B3 peaks appear again when the GTO films are annealed above
500  C for 1 h. These peaks have the highest intensities at 550  C
(sample G), indicating the compensation effect was eliminated
completely, while this effect was not perfect at 500  C (sample F) or
600  C (sample H). The above mentioned defect energy levels are
illustrated in Fig. 15.
3.5. Properties of p-type GTO/n-type si heterojunction
To confirm p-type conduction in the GTO films, a simple p-n
heterojunction diode was fabricated by growing p-type GTO films
on n-type Si glass at 550  C. Fig. 16A shows the typical I-V rectifying
characteristics of the resultant p-n junction. The results show that
the leakage current under reverse bias is very low, and the forward
turn on voltage is 1.84 V. Fig. 16B shows the double logarithmic
curve. The forward bias characteristics show three distinct linear
regions with different slopes. Region I (IeV3.2) suggests the possi-
bility of the space charge limited current mechanism (SCLC) with
the presence of traps. Region II (IeV2.4) indicates that the device
approaches the trap-filled limit. Region III has a slope value of 1.9
(IeV1.9), indicating that the majority of charge carriers diffused to
the p-n junction.
4. Conclusions
In summary, this report indicates the effects of temperature on
the electrical, optical, and structural properties of GTO thin films.
Considering Hall-effect measurements and XRD results, the authors
explain that the preferred orientation of the (101) plane favors the
formation of p-type conductivity. The XPS and PL measurements
indicate that gallium exists in the form of Ga3þ in the films and acts
as an acceptor. These results also explain the compensation effect
and decompensation effect. Highly transparent, p-type conducting

Fig. 16. A) I-V data B) The log-log plot for the I-V data of P-type GTO/n-Si heterojunction.
1020 H.P. Dang et al. / Journal of Alloys and Compounds 687 (2016) 1012e1020
GTO films were prepared by DC magnetron sputtering. Hall-effect
measurements indicated that the deposition and annealing tem-
peratures are critical for preparing these p-type conducting GTO
films. It was found that a substrate temperature of 400  C and an
annealing temperature of 550  C for 2 h was necessary for high p-
type conductivity, to obtain p-type GTO films with the highest hole
concentration (3.3  1018 cm3). The average transmission of p-
type GTO films in the visible region was approximately 80%,
refractive index and extinction coefficient was 1.9727 and 0.0022,
respectively. In addition, p-type conductivity was also confirmed by
the non-linear characteristics of the p-type GTO/n-type Si structure.
Acknowledgments
This research was supported by Vietnam National University
(VNU-HCM), Ho Chi Minh City, [grant number C2014-18-27].
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