Ceramics International 45 (2019) 9147–9156

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Studying the influence of deposition temperature and nitrogen contents on T

the structural, optical, and electrical properties of N-doped SnO2 films
prepared by direct current magnetron sputtering
Thanh Tung Nguyena,b,1, Huu Phuc Dangc,1, Quang Ho Lucd, Tran Lea,∗
a
Faculty of Physics & Engineering Physics, HCMC University of Science, VNU-HCM, 227 Nguyen Van Cu St, Ward 4, District 5, Ho Chi Minh City, Viet Nam
b
Thu Dau Mot University, Number 6, Tran Van On Street, Phu Hoa Ward, Thu Dau Mot City, Binh Duong Province, Viet Nam
c
Faculty of Fundamental Science, Industrial University of Ho Chi Minh City, No. 12 Nguyen Van Bao, Ward 4, Go Vap District, Ho Chi Minh City, Viet Nam
d
Faculty of Applied 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

A R T I C LE I N FO A B S T R A C T

Keywords: This report focuses on studying and investigating in detail the structural, electrical, and optical properties of p-
p-type N-doped SnO2 thin film type N-doped SnO2 (NTO) versus the deposition temperature and nitrogen content. P-type transparent con-
DC magnetron sputtering ductive NTO films were deposited on quartz glass substrates using a direct current (DC) magnetron sputtering
Deposition temperature method. The substitution of oxygen by nitrogen in the SnO2 host lattice was verified using measurements such as
Nitrogen content
X-ray photoelectron spectroscopy. The position of the N3− defect state in the band gap was determined using
X-ray diffraction
X-ray photoelectron spectroscopy
photoluminescence and ultra-violet-visible spectroscopy measurements. The data for the (110) to (101) rutile
lattice planes changed, and the rutile (plane (101)) to cubic (plane (111)) SnO2 phase transition indicated the
substitution of oxygen by nitrogen in the SnO2 host lattice. The best p-type conductive properties achieved were
8 × 10−2 Ω cm, 1.36 × 1019 cm−3, and 6.75 cm2 V−1 s−1 for the resistivity, hole concentration, and hole mo-
bility, respectively, for film deposited at the optimum substrate temperature of 300 °C in a gas mixture of Ar and
50% N2.

1. Introduction aim in the field of transparent electronics.

At present, transparent conducting oxides (TCOs) that possess a
combination of high electrical conductivity and optical transparency
are available for optoelectronic applications including for use in flat
panel displays [1], touch screens [2], dye-sensitized and perovskite
solar cells [3,4], light emitting diodes (LEDs) [5], organic LEDs [6], and
transparent thin film transistors [7,8]. Most TCOs serve as n-type con-
ducting transparent semiconductors known as indium tin oxide (ITO)
[9], doped zinc oxide (Al-, Ga-, and In- doped ZnO, which are com-
monly abbreviated as AZO, GZO, and IZO, respectively) [10–12], and
fluorine tin oxide [12]. Among these TCOs, only ITO functions as a hole
collecting electrode in organic optoelectronic devices [13]; however,
ITO has a high indium concentration, and indium is rare and therefore
expensive. Thus, replacements for ITO are required in the form of al-
ternative hole conducting oxides (that is, p-type TCOs).
Furthermore, p-type TCOs can be combined with n-type TCOs to
form transparent p-n junctions in fully transparent optoelectronic de-
vices [7,8,14,15]; achieving such devices is considered of the primary
Over the last few decades, many p-type TCOs have been developed
such as materials with delafossite [16-18] and perovskite groups [17]
or As-, P-, and N-doped ZnO [19–21]. SnO2 is also a promising TCO
with mechanical, thermal, and chemical stability and serves as a hole
conducting material.
In recent years, p-type SnO2 films doped with metals such as Al
[22], Ga [23,24], Zn [25,26], B [27], and In Ref. [28] have been re-
ported to have good properties. However, an unwanted charge com-
pensation effect occurs between the oxygen vacancies (VO) and metal
acceptors that exist in p-type metal-doped SnO2 [23]; to eliminate this
effect, N atoms are the most suitable dopants for replacing O in the
SnO2 host lattice, where the NO site acts as an acceptor. However, some
published research about N-doped SnO2 thin films [29–32] has not
indicated that they serve as p-type electrical conductive TCO and have
not yet investigated the structural, optical, and electrical properties of
N-doped SnO2 films in detail and wholly.
To date, few studies have reported on N-doped SnO2 films dis-
playing p-type conductive properties [33–36]; however, they report

∗
Corresponding author.
E-mail address: ltran@hcmus.edu.vn (T. Le).
1
Both authors contributed equally to this work.

https://doi.org/10.1016/j.ceramint.2019.01.255
Received 3 October 2018; Received in revised form 24 January 2019; Accepted 30 January 2019
Available online 31 January 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
T.T. Nguyen et al.
very low hole concentrations of approximately 1014 cm−3 [33]. Also,
higher hole concentrations of 1019 cm−3 for a p-type N-doped SnO2 film
were obtained via the oxidation of SnN and Sn3N4 films at high tem-
peratures [34,35]; however, this makes it difficult to eliminate in-
evitable SnxNy clusters in the SnO2 lattice. Furthermore, the atomic N
concentration in the SnO2 lattice and the energy levels of the defects
located in the forbidden band have not been described in detail. It is
also worth noting that the existence of more lattice planes can also
affect the crystal quality of SnO2 films.
In this study, N-doped SnO2 was deposited on quartz substrates via
direct current (DC) magnetron sputtering using a SnO2 ceramic target
under an Ar and N2 mixed gas atmosphere. The electrical conductivity,
optical transmittance, and crystal structures were investigated as
functions of both the percentage of N2 gas in the sputtering gas mixture
and the substrate temperature. In particular, we analyzed the sites of
the defect states in the forbidden band using photoluminescence (PL)
spectra. Moreover, the relationship of the concentration of N atoms in
the films and the films' electrical, optical, and structural properties were
systematically studied by X-ray photoelectron spectroscopy (XPS).
2. Experiment
N-doped SnO2 (NTO) films were fabricated on quartz substrates by
DC magnetron sputtering from a SnO2 ceramic target in a mixed N2 and
Ar atmosphere using a Leybold Uvinex 450 system (Germany). A SnO2
ceramic target with a diameter of 7.5 cm was used; the target was
fabricated by sintering SnO2 powder (99.99% purity, Merck) at 1500 °C
for four hours and by pressing the material into a circular disc using a
hydraulic press. The quartz substrates were cleaned in 10% NaOH and
acetone and then deionized water to remove any surface contamina-
tions; they were subsequently dried in a nitrogen atmosphere. Before
depositing the films on the substrates, the target was pre-sputtered for
15 min in Ar gas at a pressure of 10−3 Torr. The sputtering power and
the distance from the target to the substrate were 15 W and 7 cm, re-
spectively. The sputtering gases consisted of a mixture of high-purity Ar
(99.999%) and x% (x = 0, 10, 20, 30, 40, 50, and 60) of N2 gas. This
gas mixture was introduced into the vacuum chamber at a flow rate of
up to 20 sccm with a working pressure of 4 × 10−3 Torr. The samples
fabricated at room temperature (RT), 200, 300, 400, and 500 °C in
ambient Ar gas are denoted as S-T (where T = RT, 200, 300, 400, and
500). Additionally, those fabricated at T (where T = RT, 200, 300, 400,
and 500) in a mixture of Ar and x % (x = 0, 10, 20, 30, 40, 50, and 60)
N2 gas are denoted as NTO-T-x. The thicknesses of the films were ap-
proximately 340 nm and were identified by fitting the modeled spectra
to the experimental ultra-violet-visible (UV–vis) spectra using Scout
software (W. Theiss Hard- and Software, Germany). The structures of
Fig. 1. a) Sn3d and b) No XPS spectra of NTO films deposited at different temperatures with 20% N2 in the sputtering gas.
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the NTO and SnO2 films were studied using an X-ray diffractometer
(D8-ADVANCE, Bruker, Germany) operated at 40 kV and 40 mA with
Cu-Kα radiation. The optical transmittance was measured in the wa-
velength range of 200–1100 nm using a UV–vis spectrometer (JascosV-
530, Japan). A Hall measurement system in a Van de Pauw config-
uration (HL5500PC, Nanometrics Incorporated, USA) was used to
measure the hole concentration and mobility at RT. X-ray photoelectron
spectroscopy (XPS) was conducted at room temperature on an
ESCALAB, and the PL spectra were obtained after excitation using a
xenon lamp (Horiba Nanolog, Japan). The surface morphology was
observed using a field-emission scanning electron microscope (FESEM)
manufactured by Hitachi (S-4800, Japan) and via atomic force micro-
scopy (AFM, Bruker Dimension Edge).
3. Results and discussion
3.1. XPS spectra
Thin film SnO2 is a native n-type semiconductor due to its intrinsic
defects such as oxygen vacancies (VO) and interstitial tin (Sni). To
achieve p-type conductivity, we introduced N into SnO2 films using DC
magnetron sputtering. In addition to the thermal energy from the
substrate, the contribution of the kinetic energy of the N+ ions born in
the plasma also enhances the incorporation of N atoms into the film
surface, that is, the occupation of the O sites by the N atoms in the SnO2
host lattice. However, if the temperature is too high, the N+ ions will
return immediately to the plasma after reaching the substrate.
Additionally, the N2 mixing ratio determines the amount of N+ in the
plasma. With that in mind, the optimum substrate temperature and the
N2 gas ratio in the sputtering gas were determined so that the sub-
stitution of O by N in the SnO2 films was as great as possible.
Accordingly, the atomic composition of the films was determined using
XPS (based on the chemical states of the N, O, and Sn elements, which
were monitored via the N1s, Sn3d, and O1s core-level peaks) to verify
the N3−-O2− substitution (NO). The binding energies were fitted using
XPSPEAK 4.1 software (Raymund Kwok, The Chinese University of
Hong Kong), and the peak positions were calibrated using the C1s peak
as a reference at 284.8 eV to eliminate any deviations caused by charge
accumulation at the film's surface.
3.1.1. The atomic contents depend on the deposition temperature at 20% N2
in the gas mixture
Fig. 1a and b shows the XPS spectra of the NTO films deposited as a
function of the substrate temperature at a working pressure of
4 × 10−3 Torr in a mixture of Ar and 20% N2 gas. The result shows the
N1s core-level peak at 397.2–397.5 eV (deconvoluted from the XPS
T.T. Nguyen et al. Ceramics International 45 (2019) 9147–9156

Table 1 Table 2
XPS results of the atomic concentrations in the NTO films deposited at different XPS results of the atomic concentrations in the NTO films deposited at 300 °C
temperatures with 20% N2 in the sputtering gas. with different percentages of N2 in the sputtering gas mixtures.
RT 200 °C 300 °C 400 °C 500 °C 10% N2 20% N2 30% N2 40% N2 50% N2 60% N2

Sn 81.98% 80.85% 80.59% 80.28% 80.33% Sn 80.97% 80.59% 80.29% 80.02% 78.10% 79.98%
O531.5 4.03% 5.19% 5.68% 4.96% 3.17% O531.5 5.28% 5.68% 5.91% 6.08% 8.06% 6.1%
O530 13.69% 13.33% 13.06% 14.16% 15.97% O530 13.19% 13.06% 13.03% 12.95% 11.70% 13.08%
No 0% 0.31% 0.35% 0.27% 0.20% No 0.24% 0.35% 0.47% 0.63% 1.78% 0.51%
Ni 0.29% 0.30% 0.30% 0.30% 0.30% Ni 0.30% 0.30% 0.30% 0.30% 0.30% 0.30%

[34,37]; however, the amount of Ni changed negligibly and was much

Fig. 2. N1s XPS spectra (black line) and simulated results (dashed, colored
lines) for NTO films deposited at 300 °C with 20% N2 in the sputtering gas. (For
interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
Fig. 3. O1s XPS spectra (black line) and simulated results (dashed, colored
lines) of NTO films deposited at 300 °C with 20% N2 in the sputtering gas. (For
interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
less abundant than the NO in all of the films, as shown in Table 1.
Additionally, the Sn3d XPS spectra include two peaks located at
487.6–487.9 eV and 496.1–495.3 eV corresponding to the Sn3d5/2 and
Sn3d3/2 states, respectively. The difference between the Sn3d5/2 and
Sn3d3/2 levels (8.5 eV) is the same as that in the standard spectrum [38]
of Sn, which indicates that the chemical state of tin is 4+. It is worth
noting that the Sn3d doublet peak of the NTO films deposited above
200 °C shifted to higher energies compared with the RT-fabricated film
because the ionized N3− is more negative than the O2− as investigated
by Pan et al. [34,35], thus proving that NO is available in the SnO2
lattice. Interestingly, the largest shift of the Sn3d peak (0.3 eV) com-
pared with the film fabricated at RT was found in the film deposited at
300 °C, indicating that the amount of NO in the SnO2 lattice was highest
in that film. Along with the chemical states of N and Sn, we also con-
firmed the chemical states of O via the binding energy peaks of O1s (see
Ref. [23]) at 530, 531, and 532.5 eV (Fig. 3); those data were used to
help calculate the atomic composition of the films as shown in Table 1.
The results demonstrate that the NO concentration in the films was in
good agreement with the binding energy shift of Sn3d; in particular, the
highest NO concentration was found for the film deposited at 300 °C
with the largest shift of the Sn3d peak. At lower temperatures, the N
atoms did not have enough energy to replace the O atoms in the host
lattice. Conversely, at substrate temperatures over 300 °C, N+ ions in-
stantly returned to the plasma medium after reaching the substrate.
Thus, the N atoms did not have enough time to substitute into the O
sites in the host lattice.
In short, the aforementioned results can be explained as follows: at
the same nitrogen gas percentage in the sputtering gas mixture, the
quantity of formed N+ ions is the same in the plasma medium, leading
to the same kinetic energies of the N+ ions transferred to the substrate.
Therefore, the substitution of O by N in the SnO2 host lattice depends
only on the substrate temperature that supplies kinetic energy to the N
adatoms on the substrate. In fact, below the 300 °C substrate tempera-
tures, the N+ ions reach and then absorb on the surface of the substrate
as N adatoms, but they are not mobile enough to find and incorporate at
the O sites in the SnO2 host lattice. Also, above the 300 °C substrate
temperatures, N adatoms are supplied a high enough kinetic energy,
and some are released from the surface of the substrate, leading to the
decrease of N incorporating into the SnO2 host lattice. Only at the
substrate temperature of 300 °C do the N adatoms incorporate at the O
sites, reaching the greatest quantity, which is consistent with the
highest NO concentration or the largest shift of the Sn3d peak as pre-
viously analyzed.

spectra), which can be assigned to the Sn-N chemical bond as indicated
by the literature [33,34]. Furthermore, the intensity of the N1s peak
varies versus the deposition temperatures and reaches a maximum
value at a temperature of 300 °C, proving that N3−-O2− substitution
can occur. This is consistent with the high amount of NO sites in the
film, as shown in Fig. 1b and Table 1. Moreover, the N1s binding energy
peak is located at 399.9 eV; the peak is present in all of the NTO films
and is denoted as Ni (Fig. 2). Its presence could be caused by con-
tributions from the Sn-N-O or Sn-O-N bonds as described in Refs.
3.1.2. The atomic contents depend on the N2 percentage in the gas mixture
As mentioned in the introduction, at the same substrate temperature
of 300 °C, the N2 mixing ratio in the sputtering gas can be used to in-
crease or decrease the NO concentration in the films because the
quantity of N+ ions formed in the plasma medium increased following
the N2 percentage in the gas mixture, leading to the increase in the N
adatoms on the surface of the substrate. Thus, we studied the optimum
NO concentration in the SnO2 lattice for different N2 gas mixing ratios at
the optimum temperature of 300 °C. Consequently, the NO concentra-
tion in the films was found to be the highest at the N2 mixing ratio of

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Fig. 4. a) Sn3d and b) No XPS results for the NTO films deposited at 300 °C with different percentages of N2 in the sputtering gas mixture.

Fig. 5. PL emission spectra of NTO films deposited at different temperatures

with 20% N2 in the sputtering gas and of SnO2 films deposited at both RT and at Fig. 7. PL emission of NTO films deposited at 300 °C with different percentages
300 °C. of N2 in the sputtering gas mixture.

50% based on this concentration, leading to the largest shift to the
higher binding energy for the Sn3d peak as recorded in Table 2 and
Fig. 4. This result could be interpreted as follows: below an N2 per-
centage of 50%, the amount of N+ ions in the plasma is not at its
maximum, and thus the substitution of N3− for O2− also does not
achieve a maximum value. Conversely, above 50% N2, the nitrogenated
process from the reactively absorbed or implanted N atoms on the
target occurs as described in References [39,40] because the nitridation
rate is much faster than the sputtering rate [39]. This causes highly
energic N+, N+2 ions, or SnxNy neutral species to be available. They are

Fig. 6. PL emission mechanism of NTO films.

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Fig. 8. UV–vis spectra of SnO2 films deposited at different temperatures.
released from the bombarded target surface, knocking the films and
causing a reduction in the NO in the SnO2 lattice.
4. Photoluminescence spectra
4.1. Photoluminescence spectra of undoped and N-doped SnO2 films as a
function of the deposition temperature
We analyzed the positions of acceptor N3− in the forbidden band via
their PL spectra to prove the existence of NO in the host lattice. We
measured the PL spectra of NTO films deposited at various tempera-
tures (solid lines) and those of SnO2 films deposited at RT and 300 °C
(Fig. 5).
The PL spectra of all of the films contained the B1 peak at a wa-
velength of 387 nm (or energy of 3.26 eV); it refers to the electron
transition from the Vo+ donor level to the valence band maximum as
described in Reference [23]. Furthermore, the PL spectra of NTO films
fabricated at 200 and 300 °C additionally showed B2, B3, B4, and B5
peaks, where the B2 peak at 408 nm (3.03 eV) is considered to indicate
the electron transition to the acceptor Sn3+ level from the Vo+ level.
The B4 peak at 461 nm (2.69 eV) indicates an electron transition from
the conduction band minimum (CBM) downward to the Vo++ level as
mentioned in Ref. [23]. Additionally, the B3 peak at 431 nm (2.88 eV)
indicates a transition between the Vo+ and N3− levels, reflecting the
N3−-O2− substitution; these results agree with the density function
Fig. 9. UV–vis spectra of NTO films deposited at different temperatures with 20% N2 in the sputtering gas; and the inset shows the spectral range from 250 to 450 nm.
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theory calculation [36], indicating that the N3−-O2− substitution in the
SnO2 lattice formed N2p defects or acceptor states in the band gap.
Furthermore, the B4 peak at 464 nm (2.67 eV) represents the CBM-
Vo++ transition [23]. Finally, the B5 peak at 500 nm (2.48 eV) char-
acterizes the Vo+-Ni (interstitial N) level transition, which exists only in
NTO films without SnO2 as indicated in the XPS spectra; the intensity of
this peak was approximately equal for all of the films and agrees with
the XPS results. The intensities of the B3, B4, and B5 peaks achieved
their highest values in the film deposited at 300 °C (as they logically
should); in this film, we expect the maximum amount of NO in the SnO2
host lattice as previously discussed in relation to the XPS spectra. It is
obvious that the intensities of the B3 and B5 peaks were reduced for the
films deposited at temperatures above 300 °C; this reveals that the
amount of NO in the host lattice was significantly decreased. To analyze
this, we studied the electron transitions in the PL spectra; the sites of
the defect states previously discussed are illustrated in Fig. 6, in which
the emission at 295 nm (4.2 eV) refers to the CBM to valence band
maximum transition (this is in agreement with the optical band gap of
the SnO2 film deposited at 300 °C in an Ar atmosphere).
4.2. PL spectra of N-doped SnO2 films as a function of the N2 percentage in
the sputtering gas for a substrate temperature of 300 °C
As discussed in the section regarding the XPS spectra, the N2 mixing
ratio in the sputtering gas had an impact on the substitution of N for O
in the host lattice. Therefore, the PL spectra could be useful to quali-
tatively determine the amount of NO in NTO films fabricated with dif-
ferent N2 mixing ratios in the sputtering gas. Consistent with the results
of the XPS spectra, the PL spectra show that the intensity of the B3 peak
(Fig. 7) were highest for the NTO film deposited at a N2 percentage of
50% in the sputtering gas—a gas mixing percentage that also yields the
highest amount of NO in the SnO2 lattice. Additionally, the B2 peak
intensity also was largest for this N2 percentage, supporting the increase
in the hole concentration in these films as mentioned in Reference [23].
5. UV–vis transmittance spectra
To further confirm the substitution of N for O as seen in the XPS and
PL spectra, we also investigated the UV–vis transmittance spectra of
undoped and N-doped SnO2 deposited at different temperatures at 20%
N2 in the sputtering gas. The results shown in Fig. 8 indicate that the
absorption edge shifted differently than expected. Specifically, the ab-
sorption edge of the SnO2 moved to shorter wavelengths for higher
deposition temperatures, which is in agreement with the results re-
ported in Reference [23] in which the sublattice SnO phase disappeared
gradually as the deposition temperature increased. In contrast, except
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Fig. 10. UV–vis spectra of NTO films deposited at 300 °C with different percentages of N2 in the sputtering gas mixture; the inset shows the spectral range from 250 to
450 nm.
Fig. 11. X-ray diffraction patterns of SnO2 films deposited at different tem-
peratures.
Fig. 12. X-ray diffraction patterns of NTO films deposited at different tem-
peratures with 20% N2 in the sputtering gas.
for the NTO film deposited at RT under the same conditions as the SnO2
film, the absorption edge of the NTO film deposited at 300 °C was
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Fig. 13. X-ray diffraction patterns of NTO films deposited at 300 °C with dif-
ferent percentages of N2 in the sputtering gas.
located at the longest wavelength in comparison with the NTO films
fabricated at the other temperatures. This behavior is shown in Fig. 9
and its inset and is caused by the presence of the gap N3− acceptor
state, which results in a band to gap state transition as explained in
Reference [41]. More precisely, the red shift of the absorption edge was
caused by the increase of NO in the SnO2 lattice; in particular, the NTO
film deposited at 50% N2 (Fig. 10) shows an absorption edge located
furthest away on the long wavelength side. Additionally, both the SnO2
and NTO films achieved transmittances above 80% (when taking into
account the transmittances of the substrates).
6. XRD patterns
6.1. XRD patterns of the undoped and N-doped SnO2 films as a function of
the deposition temperature
Apart from using XPS, PL, and UV–vis spectra to verify the N3−-O2−
substitution, XRD patterns were also used to qualitatively determine
this replacement by studying changes in the lattice plane of the crystal
phase or the crystal phase transformation. Figs. 11 and 12 show the
crystal evolution rule of undoped and (20% N2 gas) N-doped SnO2 films
fabricated at various substrate temperatures. The XRD patterns of both
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Fig. 14. SEM images of the NTO films deposited at 300 °C with different percentages of N2 in the sputtering gas mixture.

indicate a tetragonal rutile structure (JCPDS No. 41-14445) with a ru- substitution was optimum for the NTO film deposited at 300 °C, which
tile (110) peak as the preferred peak; the crystallization of this peak was showed the highest intensity of the rutile (101) peak.
improved by increasing the deposition temperature. However, an ad-
ditional rutile (101) plane appeared for the NTO films deposited at
6.2. XRD patterns of N-doped SnO2 films deposited as a function of the N2
substrate temperatures above 300 °C, indicating the presence of the
percentage in the sputtering gas at a substrate temperature of 300 °C
N3−-O2− substitution reaction, which can be expressed using equation
1
(1) (2NOX + Olatt
X
→ 2NO− + VO++ + 2 O2 (1) ) [42], which can be found in
The rutile (101) peak evolution rule was enhanced in the range of
Reference [38], where NO denotes the N3−-O2− substitution. It is clear
−
10–30% N2 in the sputtering gas, but the rutile to cubic phase trans-
that the substitution of N3− for O2− formed an oxygen vacancy, which
formation suddenly occurred at a N2 gas ratio of 40–50% (Fig. 13),
was the cause of the rutile (101) peak appearance; this is similar to the
showing that the cubic (111) plane (JCPDS No. 50-1429) and its lattice
replacement of Sn by Ga [23], Zn [26], and In Ref. [28]. The N3−-O2−
parameter (5.10 ± 0.01 Å) are well-matched with that of the cubic

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Fig. 15. Three dimensional AFM images of NTO films deposited at 300 °C with different percentages of N2 in the sputtering gas.

Table 3 Table 5
The results of the Hall effect measurements of the SnO2 films deposited at The results of the Hall effect measurements of NTO films were deposited at
various temperatures. 300 °C with different percentage of N2.
Sample T [°C] ρ [Ω cm] μ [cm2 V−1 s−1] n/p [cm−3] Type Sample N2 [%] ρ [Ω cm] μ [cm2 V−1 s−1] n/p [cm−3] Type

S-RT RT ∞ Non-conductive NTO-300-0 0 32.00 3.67 −5.32 × 10 16

n
S-200 200 710.88 1.39 −6.33 × 1015 n NTO-300-10 10 4.70 3.52 3.78 × 1017 p
S-300 300 293.28 0.51 −4.18 × 1016 n NTO-300-20 20 1.02 4.05 1.51 × 1018 p
S-400 400 6.11 2.21 −4.63 × 1017 n NTO-300-30 30 0.24 4.5 5.79 × 1018 p
S-500 500 8.10 3.90 −1.98 × 1017 n NTO-300-40 40 0.19 4.95 6.65 × 1018 p
NTO-300-50 50 0.08 6.75 1.16 × 1019 p
NTO-300-60 60 0.23 4.75 5.72 × 1018 p
Table 4
The results of the Hall effect measurements of the NTO films deposited at dif-
ferent temperatures with 20% N2 in the sputtering gas. lattice has a similar effect on the film as when it is placed under a high
−3
compressive stress (which was shown to cause a phase transformation
Sample T [°C] ρ [Ω cm] μ [cm 2
n/p [cm ] Type
in Ref. [43]); thus, we propose that a crystal phase transformation
V−1 s−1]
reasonably explains the data.
NTO-RT-20 RT ∞ Non-
conductive
NTO-200-20 200 7.13 2.90 3.02 × 1017 p 7. The FESEM morphology evolution of N-doped SnO2 films
NTO-300-20 300 1.03 4.50 1.35 × 1018 p deposited at the different N2 gas ratios
NTO-400-20 400 1.95 3.80 8.43 × 1017 p
NTO-500-20 500 1.96 4.20 7.59 × 1017 p
The influence of the substitution for O by N in the structure also was
verified through the top view of the field emission scanning electron
SnO2 phase mentioned in Ref. [43], which is considered to match the microscopy images. Surface images of films deposited at 300 °C with the
high-pressure, cubic phase of SnO2. However, the disappearance of the different N2 gas mixing ratios are shown in Fig. 14. The results indicate
cubic phase instead of the reappearance of the rutile phase with only large and uniform grains for the film deposited with 0% N2 in the
the rutile (101) peak was caused by a reduction in the amount of NO in sputtering gas. Additionally, for N2 mixing percentages under 30%,
the host lattice, which was caused by the film bombardment from the both small and large grains were present in the mix; the grain shapes
N+, N+2 ions, or SnxNy neutral species released from the target as pre- were poorly defined. However, for a 30-40% N2 gas ratio, the grains
viously mentioned. We conclude that the amount of NO in the host SnO2 clearly started to adopt a polyhedron shape, but the various sizes were
still mixed with one another; in particular, the grains overlapped one

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another, and some large grains consisted of many smaller ones. Sur-
prisingly, the films deposited with 50% N2 in the sputtering gas had
grains with similar sizes that did not overlap one another. However, the
film structure was broken when the N2 percentage in the sputtering gas
was 60%, as shown in Fig. 14. In summary, the grain sizes and shapes
change when the films are deposited at the different N2 gas mixing
ratios, which substantiates the proposal of N being able to replace O.
8. The AFM surface morphology
Fig. 15 shows the AFM images of the films deposited at 300 °C with
different N2 percentages in the sputtering gas. The results show large
grains are the result of combinations of smaller grains for the films
fabricated at low N2 mixing ratios, while the small grains regularly split
from the larger ones as the N2 gas mixing ratio was increased. In par-
ticular, the splitting of the large grains into smaller grains was optimum
for the film fabricated with a sputter gas N2 mixing ratio of 50%.
However, etching was present for the films deposited with 60% N2, as
highly energetic N+, N+2 ions, or SnxNy neutral species bombarded the
surface, as discussed in Section 3. Furthermore, the root mean square
roughness decreased as the N2 gas percentage was increased, as shown
in Fig. 15.
9. The electrical properties
The electrical properties (for example, the resistivity ρ, carrier
concentration n, and carrier mobility) of the undoped and N-doped
SnO2 films were determined by Hall measurements; the results are
summarized in Tables 3–5. Table 3 shows the conductive properties of
the undoped SnO2 films as a function of the deposition temperature; the
results indicate that all of the films had n-type properties with in-
creasing electron concentrations for increasing deposition tempera-
tures. P-type properties were found for all of the NTO films except the
film deposited at RT, as shown in Table 4. The hole concentration of
NTO increased with respect to the increase of the substitution for O by
N; the hole concentration was highest at 1.36 × 1019 cm−3 for the NTO
films deposited at 300 °C with 50% N2 in the sputtering gas (Table 5),
which is consistent with the XPS analysis results in Section 1a. This
demonstrates the native behavior of the n-type undoped SnO2 films and
the p-type properties of the NTO films caused by the substitution of N
for O.
Furthermore, the substitution by N for O increased with the in-
creasing N2 gas mixing ratio in the sputtering gas (Table 5), except for a
N2 percentage of 60% because of the bombardment of the N+, N+2 ions,
or SnxNy neutral species (as previously discussed).
10. Conclusions
This work demonstrates via measurements such as XPS, PL, and
UV–vis spectra that the substitution of O by N in a host SnO2 lattice is
plausible. The interesting consequence of the N3−-O2− substitution was
the evidence of rutile (110) to (101) plane transitions and rutile (101)
to cubic (111) SnO2 phase transitions in the XRD patterns. The positions
of N3− acceptor in a forbidden gap coincided. In particular, N-doped
SnO2 thin film deposited at the optimum substrate temperature of
300 °C in a gas mixture of Ar and 50% N2 had the best electrical
properties when the resistivity, hole concentrations, and hole mobility
achieved optimum values of 8 × 10−2 Ω cm, 1.36 × 1019 cm−3, and
6.75 cm2 V−1 s−1, respectively.
Acknowledgments
This research is funded by Vietnam National Foundation for Science
and Technology Development (NAFOSTED) under grant number
103.03-2017.302.
9155
Ceramics International 45 (2019) 9147–9156
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