Thin Solid Films 649 (2018) 147–153

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Thin Solid Films

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Effect of F and Nb co-doping on structural, electrical and optical properties T

of spray deposited tin oxide thin films
Likun Wanga, Jianyuan Yua,c, Xiaoyou Niua, Li Wanga, Chen Fua, Rumeng Qiua, Weijing Yana,
⁎ ⁎
Hongli Zhaoa,b, , Jingkai Yangd,
a
College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004, China
b
State Key Laboratory of Metastable Materials Science and Technology, Qinhuangdao 066004, China
c
Department of environmental and chemical engineering, Tangshan University, Tangshan 063000, China
d
National Defense Science and Technology, Yanshan University, Qinhuangdao 066004, China

A R T I C L E I N F O A B S T R A C T

Keywords: F and Nb co-doped tin oxide films were deposited from monobutyltin trichloride (C4H9SnCl3) on glass substrates
Tin oxide at 470 °C by spray pyrolysis. The evolution of the film structure and morphology was investigated by X-ray
Co-doping diffraction and scanning electron microscopy, respectively. All the films were a single phase with polycrystalline,
Spray pyrolysis exhibiting a tetragonal cassiterite structure with (200) orientation. The introduction of F and Nb contributed to
Electrical and optical properties
the growth of the films towards (200) crystal orientation and the formation of pyramidal shape particles with
(101) twin planes. Resistivity, carrier concentration, and Hall mobility values of 3.62 × 10−4 Ω cm,
7.463 × 1020 cm−3, and 27.8 cm2 V−1 s−1, respectively, were achieved in the films for a dopant concentration
of 20 at.% F and 1 at.% Nb in the precursor solution. Also, the transmittance of all the films in the visible range
reached about 80% and the infrared reflectivity was oscillated between 92 and 96%.

1. Introduction
In recent years, transparent conductive oxide (TCO) films exhibit a
growing demand and play an integral role in various opto-electronic
applications and energy-related technologies, such as display devices,
light-emitting diodes, architectural windows and solar cells [1–5]. In
particular, among the family of TCO, tin oxide (SnO2) has become one
of the most studied semiconductor materials due to its wide direct
optical band gap (> 3.6 eV), excellent mechanical hardness, chemical
stability, inexpensive and capability for large-area deposition. All of
these properties make it to be a promising candidate for practical ap-
plications, such as gas sensors, low-e window glazing and solar cells
windows [6,7].
However, the un-doped SnO2 films present high resistivity due to
the limited oxygen vacancies, low intrinsic carrier density and mobility
[8,9]. Through extensive theoretical and experimental validation, re-
searchers have found that doping can improve the film conductivity
effectively. The doping of SnO2 is mainly achieved by replacing Sn4+ or
O2– ions with dopant ions, which can provide extra carriers (free
electrons or holes) in SnO2 lattice and cause an increase in electrical
conductivity. Antimony (Sb) is one of the typical cation dopants to
substitute for Sn4+ ions in SnO2 host lattice to obtain good quality films
for device applications, but Sb-doped SnO2 film usually involves both of
Sb3+ and Sb5+ ions in SnO2 lattice and Sb3+ ions is supposed to act as
an electron trap which will have an opposite effect on doping efficiency
in the films [10,11]. In the case of F-doped SnO2 (FTO) films, F− ions
are use as anionic dopants to replace O2– ions in SnO2 lattice to increase
the carrier concentration. However, because of its small ion radius, it is
easy to enter the grain boundary and increase the grain boundary
barrier as an interstitial impurity, which will decrease the Hall mobility
of carriers and affect the optical properties of the film, especially when
the doping concentration of F− is relatively high [12]. Therefore, the
opto-electronic properties of FTO films are constrained and there is an
urgent need to find a way to further improve it.
Fortunately, there are many reports about Nb-doped SnO2 films by
Rf magnetron sputtering [13], pulsed laser deposition [7,14] and spray
pyrolysis [15,16]. These researches have proved that Nb is an excellent
dopant since the radius of Nb5+ (0.064 nm) is nearly equal to that of
Sn4+ (0.069 nm) [17], which facilitates the substitution of Nb5+ for
Sn4+ in SnO2 crystal lattice. It can be inferred that if SnO2 were doped
with F and Nb simultaneously, the positions of O2– and Sn4+ in SnO2
lattice would be replaced together, and the carrier generation and Hall
mobility would be further enhanced. Furthermore, the introduction of
Nb5+, by contrast, affects the nanostructure of the films and the

⁎
Corresponding authors at: State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, China.
E-mail addresses: zhaohongli@ysu.edu.cn (H. Zhao), yangjk@ysu.edu.cn (J. Yang).

https://doi.org/10.1016/j.tsf.2018.01.035
Received 5 June 2017; Received in revised form 17 January 2018; Accepted 21 January 2018
0040-6090/ © 2018 Elsevier B.V. All rights reserved.
L. Wang et al. Thin Solid Films 649 (2018) 147–153

Fig. 1. The schematic of the spray pyrolysis unit

of in-house design.

incorporation of F−, which may be helpful to improve the film per- sodium silicate glass substrates, the compressed air was used as carrier
formance. But to date, most of the studies have focused on finding novel gas. The substrates were fixed and the distance between the nozzle to
and effective dopants for SnO2 [18–21], there is few report on F and Nb substrate was maintained at 3 cm. The substrates were ultrasonically
co-doped SnO2 films deposited from monobutyltin trichloride cleaned using acetone, distilled water and ethanol separately for 5 min,
(C4H9SnCl3, MBTC) by spray pyrolysis. and then dried in hot oven prior to be used. The substrate surface
In this study, F and Nb co-doped SnO2 films with high transmittance temperature was kept at 470 ( ± 5) °C, measured by a k-thermocouple
and electrical conductivity were deposited from MBTC on glass sub- and controlled electronically. Each film was sprayed for 2 min and kept
strates at 470 °C by spray pyrolysis, the structural, morphological, in hot plate for 1 min, subsequently cooled down to room temperature
electrical and optical properties were investigated. Particularly, the naturally. Each coating process was repeated at least 3 times to ensure
evolution of microstructures was discussed by using the periodic bond reproducibility and one of the samples was selected for performance
chain (PBC) theory, and the mean free path was calculated to study the characterization.
electrical properties in detail. The crystal structure was characterized by X-ray diffraction (Rigaku
D/MAX-rB) with a Cu Kα radiation (λ = 0.15406 nm). The morpholo-
2. Experimental details gical characterization was performed on a Hitachi S4800 scanning
electron microscopy (SEM). The film thickness was estimated by cross-
The un-doped, Nb-doped, F-doped and Nb + F co-doped SnO2 films sectional SEM images to be used for necessary calculations. The sheet
were deposited using a spray pyrolysis unit of in-house design. (Fig. 1). resistance was evaluated by a four-point probe, the carrier concentra-
Starting solution of SnO2 was prepared by dissolving 0.5 M MBTC in tion and mobility of the samples were confirmed by Hall effect mea-
6 ml concentrated hydrochloric acid (HCl) and diluted with methyl surement system (HMS) ECOPIA-3000 with a 0.55 T magnetic induc-
alcohol (CH3OH). Necessary amounts of ammonium fluoride (NH4F) tion. UV–Vis spectroscopy was employed to investigate the optical
and niobium pentachloride (NbCl5) have been dissolved in deionized transmission spectra and the average transmittance values in the
water and methyl alcohol, respectively. For F-doped and Nb + F co- spectral region of 380–780 nm were calculated.
doped SnO2 films, the concentration of the dopant F/Sn in the solution
was 20 at.%, and the concentrations of the dopants Nb/Sn in the solu-
tion were 0.5 at.%, 1 at.%, 2 at.% and 4 at.% (the films were named 3. Results and discussion
NFTO-0.5, NFTO-1, NFTO-2, NFTO-4, respectively). For Nb-doped SnO2
film, the Nb/Sn was kept in 1 at.% (the film was named NTO-1). The 3.1. Structural properties
detailed amount of chemicals used for each sample type was listed in
Table 1. In order to obtain homogeneous spray solutions, all solutions The typical X-ray diffraction patterns of the as-deposited films are
were stirred at room temperature for 5 h and aged at room temperature shown in Fig. 2 (a) and (b). It can be observed that the as-deposited
for 24 h. The coating solutions were sprayed onto 30 × 25 × 1 mm3 films are polycrystalline with SnO2 tetragonal cassiterite structure,
corresponding to the space group D144h (P42/mnm). Other phases be-
Table 1
longing to SnF2, SnO, Sn2O3, and metallic Nb are not observed in the
The detailed amount of chemicals used for each sample type. deposited films. One interesting fact highlighted by X-ray diffraction
patterns is that all the films exhibit an obviously preferred orientation
Samples NH4F/g NbCl5/g MBTC/g CH3OH/ml H2O/ml HCl/ml with (200) plane, which is significantly increased in NTO-1, FTO and
SnO2 – – 14.1 84 10 6
NFTO-1 films than that in un-doped SnO2 film, while the introduction
NTO-1 – 0.1350 14.1 84 10 6 of dopants inhibits the growth of (301) plane. From Fig. 2 (b), it can be
FTO 0.37 – 14.1 84 10 6 seen that the (200) orientation increases with the increase of Nb con-
NFTO-0.5 0.37 0.0675 14.1 84 10 6 centration in co-doped SnO2 films, NFTO-1 film possesses the highest
NFTO-1 0.37 0.1350 14.1 84 10 6
intensity of (200) orientation, and then decreases while Nb con-
NFTO-2 0.37 0.2700 14.1 84 10 6
NFTO-4 0.37 0.5400 14.1 84 10 6 centration is above 1 at.%. These results confirm that the preferred
orientation and the crystallinity of the films are affected by the dopants

148
L. Wang et al. Thin Solid Films 649 (2018) 147–153

Fig. 2. XRD patterns of (a) SnO2, NTO-1, FTO, NFTO-1 thin films and (b) the as-deposited films as a function of Nb concentration form 0 to 4 at.%. (c) Evolution of the texture coefficients
and (b) the degree of preferred orientation as a function of different types of doped SnO2 thin films.

and the doping concentration. Similar experimental results have been 0.9λ
D=
observed in other studies [22,23]. β cos θ (3)
The preferential orientation of crystallographic planes can be
where D is the grain size, λ is the X-ray wave-length (1.5406 Å), β is the
quantitatively estimated from the calculation of texture coefficient
full width at half-maximum (FWHM) of the most intense diffraction
(Chkl). The Chkl and the degree of preferred orientation (σ) were defined
peak, θ is the Bragg angle. As shown in Table 2, the grain size increases
respectively as follows [24,25]:
from 25.2 nm to 35.0 nm after doping with 1 at.% Nb in the solution of
Ihkl FTO film, and then it decreases to 30.4 nm in NFTO-4 film. This in-
I0, hkl dicates that the excessive Nb concentration will suppress the increase of
Chkl =
( )∑
1
N
Ihkl
I0, hkl (1)
grain size.
In order to make a further investigation on the film microstructure,
the lattice parameters (ɑ and c) were calculated from the following
∑ (Chkl − 1)2 relation [29]
σ=
N (2) 1 h2 + k 2 l2
= + 2
d2 a2 c (4)
where N = 6 is the number of peaks, Ihkl is the measured intensity of
(hkl) Bragg reflection and I0,hkl is the standard intensity given in JCPDS in which d is the interplanar distance, a and c are lattice parameters, h,
card No. 41-1445. In theory, for randomly oriented crystallites, the Chkl k, and l are miller indices. The calculated values of lattice parameters
and σ of samples are equal to 1 and 0, respectively. But Chkl is equal to N (Table 2) are slightly shifted compared with the standard SnO2 (JCPDS,
or 0 and σ equals N − 1 when the samples have perfectly oriented No. 41-1445). The variation of lattice parameters may be related to the
grains [26]. From Fig. 2(c) and (d), It can be seen that all the films doping. Since the radius of F− (0.133 nm) is bigger than that of O2–
exhibit an obviously preferred orientation with (200) plane. The
highest value of Chkl of 5.36 is obtained in NFTO-1 film but then de- Table 2
Grain sizes and lattice parameters of as-deposited films.
creases to 4.90 in NFTO-4 film. The degree of preferred orientation
increases from 1.64 to 1.95 after doping 1 at.% Nb in FTO film, the Samples Grain size Lattice parameters
addition of Nb can significantly increase the preferred orientation of D (nm)
(200) plane. Belanger et al. [27] have found that the deep lying trap- ɑ (Å) c (Å) V (Å3)
ping centers appear only on the surface of crystallites with (110), (211), SnO2 20.4 4.7415 3.2058 72.07
and (301) planes, the (200) plane is predicted to have no deep lying NTO-1 38.0 4.7381 3.2293 72.50
trap levels at grain boundary surfaces correlating to a higher degree of FTO 25.2 4.7450 3.1909 71.84
conductivity. It indicates that the addition of Nb is helpful for the im- NFTO-0.5 33.7 4.7515 3.2281 72.88
NFTO-1 35.0 4.7501 3.2137 72.51
provement of the film conductivity.
NFTO-2 31.6 4.7474 3.2194 72.56
The grain sizes (D) of the films were calculated using the Scherrer's NFTO-4 30.4 4.7467 3.2156 72.45
formula [28]

149
L. Wang et al.
Fig. 3. SEM images of films deposited from MBTC by spray pyrolysis at 470 °C: (a) SnO2, (b) NTO-1, (c) FTO, (d) NFTO-0.5, (e) NFTO-1, (f) NFTO-2, (g) NFTO-4. (h) Morphological
simulation of SnO2 crystal made of K-(111)-type faces.
(0.132 nm), it can be speculated that when F− incorporate into SnO2
lattice, the values of lattice parameters will be slightly enlarged. On the
contrary, the radius of Nb5+ (0.064 nm) is smaller than that of Sn4+
(0.069 nm), when Sn4+ ions are substituted by Nb5+ ions ideally, the
solubility of F− will be increased, there will be a space compensation
effect to reduce the lattice distortion at the same time, so the decrease
in a with increasing Nb concentration is reasonable. It is necessary to
make a further study to evaluate the changing mechanism of crystal
lattice of NFTO films.
3.2. Morphological properties
Fig. 3 shows the evolution of the film morphology. It is observed
that the surface morphology of the un-doped SnO2 film is comprised of
pyramidal particles with about 120 nm diameter and prismatic particles
exist between them, of which the major axis and the minor axis are
300–500 nm and 100–200 nm, respectively. Interestingly, after doping
1 at.% Nb to form the NTO-1 film, the film morphology is significantly
ameliorated and the size of pyramidal particles is obviously increased.
For F-doped SnO2, the film is mainly comprised of pyramidal particles
and the needle-like particles exist between them. For F and Nb co-doped
SnO2, only pyramidal particles are observed in the films. When the Nb
concentration is no > 1 at.%, the film morphology is compact and
homogenous, and the size of the particles is drastically increased. But
when the Nb concentration is > 1 at.%, the film crystallinity is dete-
riorated, which has a detrimental effect on carrier mobility and hence
the film performance, the size of the particles is decreased. Ad-
ditionally, the statistical distribution of the particle size and the Gaus-
sian fitting were obtained by measuring the largest size of 100 particles
using Nano Measurer, the results were shown in Fig. 4(b). It can be
observed that the distribution of particle size is concentrated after
doping with F and Nb together. The evolution of the mean particle size
is in agreement with the variation of grain size as listed in Table 2.
The evolution of film morphology can be explained using the
150
Thin Solid Films 649 (2018) 147–153
concept of PBC according to Hartman [30]. The theory explores the
interface growth from the geometric characteristics of the crystal
structure and particle energy. There are a series of periodic repetition
strong bond chains in the crystal structure, and the repetitive features
are consistent with the periodic repetition of the particles in crystal. The
strong bond chains were called PBCs. The growth direction of crystal is
parallel to bond chains, and the morphologies of the crystal can be
classified into flat (F), stepped (S) and kinked (K) faces depending on
the crystal faces parallel to at least 2, 1 and none PBC, respectively
[31]. According to the polarity of crystal faces, the planes can also be
classified into polar faces and less-polar faces. The planes consisting of
only tin atoms or only oxygen atoms are polar faces, such as F-{101}
and K-{111}, while the planes containing both tin and oxygen atoms
are less-polar faces, such as F-{110} [32]. From the thermodynamic
equilibrium, it is known that F-faces are formed in initial stages of
crystal formation. However, (200) oriented SnO2 crystal is formed by
(111) K-faces, which can form pyramidal particles with (101) twin
planes (as shown in Fig. 3(h)). The suppression of F-faces by K-faces
may be caused by the presence of the polar halogen-rich gases as by-
products of pyrolysis of chlorine tin precursors [33]. Furthermore, the
(200) orientation gets stronger drastically and the films display pyr-
amidal particles after doping with F and Nb together. It can be specu-
lated that the dopants increase the polar halogen-rich gases, then slow
down the growth of (101) F-faces and lead SnO2 films to grow with
(200) orientation.
3.3. Electrical and optical properties
Sheet resistance (Rs), resistivity (ρ), carrier concentration (η) and
Hall mobility (μ) of the as-deposited films were evaluated and shown in
Fig. 5. The resistivity of the un-doped SnO2 film is 2.45 × 10−3 Ω cm
and then decreases to 1.72 × 10−3 Ω cm and 5.23 × 10−4 Ω cm after
doping with Nb and F, respectively. NFTO films exhibit better electrical
properties, the minimum resistivity of 3.71 × 10−4 Ω cm is obtained
L. Wang et al.
Fig. 4. (a) The statistical distribution and the Gaussian fitting of equivalent particle size
by measuring the largest size of 100 particles using Nano Measurer. (b) The evolution of
equivalent particle size as a function of different types of doped SnO2 thin films.
with Nb concentration of 1 at.%. Nevertheless, the resistivity increases
while the Nb concentration is > 1 at.%.
From Fig. 5(b), Hall measurement shows that all the films are n-type
conductivity, the carrier concentration increases obviously by doping a
little amount of Nb in FTO films due to the Nb5+ ions substitute the
Sn4+ ions and incorporate into the host lattices to create excess elec-
trons. But when the Nb concentration is > 1 at.%, the carrier con-
centration decreases, which is likely due to the valence of Nb changes
from positive pentavalent to trivalent, leading to the conversion of
donor impurities to acceptor impurities and compensating the donor
levels [34,35]. Furthermore, excess dopants may cause some Nb5+ ions
to enter the interstitial positions, and the Nb5+ ions at interstitial po-
sitions may act as electrons traps (shallow acceptors) and thus reduce
the carrier concentration. Finally, the highest carrier mobility of
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Thin Solid Films 649 (2018) 147–153
Fig. 5. (a) Variation of sheet resistance and resistivity as a function of different types of
doped SnO2 thin films. (b) Carrier concentration and Hall mobility change with the dif-
ferent types of doped SnO2 thin films.
33.5 cm2 V−1 s−1 is obtained in NFTO-0.5 film and decreases when the
Nb concentration is > 1 at.%. It can be inferred that the mobility in-
creases with the increase of crystallinity. However, in TCO films, the
carriers are affected by scattering centers, such as lattice thermal vi-
bration, ion and neutron impurities and grain boundary. Hall mobility
in doped SnO2 thin films is limited by ionized impurity scattering and
grain boundary scattering [35]. When the mean free path (l) of carriers
is much smaller than grain size, the effect of boundary scattering is
small and negligible. When l is close to the grain size, grain boundary
scattering is a major role. The value of l can be calculated from the
formula [36]
h 3n 1/3
l= ⎛ ⎞ μ
2e ⎝ π ⎠ (5)
where h is the Plank's constant (6.626 × 10−34 J·s), e is the electron
charge, n is the carrier concentration and μ is the Hall mobility. The
mean free paths of the free carriers are in range of 1.57–5.26 nm
(Table 3), which are much smaller than grain size in the films. This
indicates that the impact of grain boundary scattering is minimal, while
the mobility of the films is mainly affected by ionized impurity scat-
tering. Thangaraju [35] and Lee [37] found the similar results when
studying Sb-doped SnO2 films.
L. Wang et al. Thin Solid Films 649 (2018) 147–153

Table 3
Electrical and optical parameters of as-deposited films.

Sample Rs ρ η μ l (nm) ϕ RIR ε

(Ω sq.−1) (×10−4 Ω cm) (×1020 cm−3) (cm2 V−1 s−1) (×10−2 Ω−1) (%)

SnO2 30 24.5 1.914 15.6 1.57 0.49 74.4 0.327

NTO-1 21 17.2 2.087 17.5 2.12 0.47 80.9 0.241
FTO 5.5 5.21 3.839 28.6 4.18 1.76 94.4 0.069
NFTO-0.5 4.6 4.37 4.556 33.5 5.26 2.50 95.3 0.058
NFTO-1 3.9 3.62 7.463 27.8 5.14 2.20 96.0 0.049
NFTO-2 5.2 5.00 4.350 29.3 4.53 1.94 94.7 0.065
NFTO-4 7.5 7.03 3.611 25.2 3.66 0.93 92.5 0.093

ε = 0.0129Rs − 6.7 × 10−5Rs 2 (8)

The calculated values of RIR and ε were presented in Table 3. It can
be observed that NFTO-1 film has higher reflectivity and lower emis-
sivity. This means that the F and Nb co-doped SnO2 film obtains ex-
cellent optical and electrical properties, and is an attractive candidate
for solar cells and building energy efficiency applications.

4. Conclusion

Transparent conductive F and Nb co-doped SnO2 films were de-

Fig. 6. Transmittance spectra as a function of different types of doped SnO2 thin films.
It is well known that the resistivity and transmittance interact with
each other and are subject to various factors such as coating para-
meters, doping elements, film thickness and microstructure. The optical
transmittance spectra of the films as a function of wavelength are
shown in Fig. 6. The absorption edge appears red-shifted and the
average transmittance of films is in the range of 76%–80%, which is
affected by the dopants. The film transmittance at 550 nm decreases
from 83% in SnO2 film to 77% in NFTO-4 film. The red-shifted may be
related to the doping, which can modify the band structure and shift the
absorption edge to lower photon energy. The transmittance exhibits a
decreasing tendency with the increase of doping concentration in
visible and NIR ranges. This is may be due to the increase in the con-
centration of the dopant, the film structure and morphology are dete-
riorated, thereby the impurities locate in defects centers cause the
scattering of incident photon, and then lead to a transmittance decay. In
addition, the doped SnO2 films exhibit a pronounced free-carrier ab-
sorption in visible and NIR ranges, whereas for the un-doped SnO2 film,
the free-carrier absorption is much less, thereby the transmittance of
the film decreases with doping.
In order to define a criterion of reference value to describe in-
tegrated photoelectric performance of the films, figure of merit was
introduced and calculated by the formula [38]
T10
ϕ=
Rs (6)
where ϕ is the figure of merit, T is the value of transmittance at 550 nm,
and Rs is the sheet resistance of the film. The highest value of figure of
merit 2.5 × 10−2 Ω−1 is obtained in NFTO-0.5 film.
It is further shown the relationship between sheet resistance (Rs),
infrared reflectivity (RIR) and emissivity (ε) of the as-deposited films as
follows [39,40]
RIR = (1 + 0.0053Rs )−2 (7)
posited on glass substrates at 470 °C by spray pyrolysis from MBTC
precursor solutions. The film structure and morphology reveal that the
addition of F and Nb can improve film crystallinity, increase grain size
and contribute the films to grow with (200) orientation while Nb
concentration is no > 1 at.%. The carrier concentration and Hall mo-
bility are enhanced by doping with F and Nb, together. Ionized impurity
scattering is the dominant mechanism to affect Hall mobility. In par-
ticular, the NFTO-1 film possesses the highest carrier concentration of
7.463 × 1020 cm−3 and obtains the lowest resistivity of
3.71 × 10−4 Ω cm, while the NFTO-0.5 film obtains the highest mobi-
lity of 33.5 cm2 V−1 s−1 and the highest value of figure of merit
2.5 × 10−2 Ω−1. The transmittance of the NFTO films in the visible
range can reach about 80% and the IR reflectivity oscillates between 92
and 96%. In summary, the F and Nb co-doped SnO2 films have better
opto-electronic properties compared to F or Nb doped tin oxide films,
which may be due to the synergistic enhancement effect caused by co-
doping, it is necessary and important to make a further study about this.
Acknowledgements
This work has been financially supported by the National Key
Research and Development Program of China (No. 2016YFB0303902),
the National Natural Science Foundation of China (No. 51602278), Key
Basic Research Project of Hebei Province (No. 17961109D), and the
Natural Science Foundation of Hebei Province (No. E2016203149).
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