Journal of Alloys and Compounds 807 (2019) 151650

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Journal of Alloys and Compounds

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

Optimization NH3 sensing performance manifested by gas sensor

based on Pr-SnS2/ZnS hierarchical nanoflowers
Qixian Zhang, Shuyi Ma*, Rong Zhang, Kaiming Zhu, Yue Tie, Shitu Pei
Key Laboratory of Atomic and Molecular Physic & Functional Materials of Gansu Province, College of Physics and Electronic Engineering, Northwest Normal
University, Lanzhou, 730070, China

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

Article history: Pure and Pr doped 3D SnS2/ZnS hierarchical nanoflowers were prepared by two-step hydrothermal
Received 8 April 2019 method. The as-prepared samples were characterized by various techniques. For the Pr-SnS2/ZnS sam-
Received in revised form ples, XPS results confirmed that Pr3þ/Pr4þ ions were successfully doped into the samples. Pr doping led to
15 July 2019
lattice distortion, inhibiting grain growth and reducing grain size. Compared with sensors based on SnS2/
Accepted 30 July 2019
Available online 30 July 2019
ZnS nanoflowers, Pr doped SnS2/ZnS samples exhibited better gas sensing performance to 50 ppm
ammonia gas at 160  C, including higher response (14.03) and ultrafast responding and recovering time
(6 s/13 s). The excellent gas sensing performance may be attributed to more free electrons generated by
Keywords:
Pr-SnS2/ZnS
Pr doping, SnS2/ZnS heterojunction and the high specific surface area of such unique hierarchical flower-
Ammonia like structure. In addition, the gas sensing mechanism of Pr-SnS2/ZnS sensor was also analyzed.
Hydrothermal © 2019 Elsevier B.V. All rights reserved.
Nanoflowers
Sensing performance

1. Introduction
Ammonia (NH3) is a commonly used chemical agent in our lives.
In addition, it is harmful to human body and can lead to vomiting,
diarrhea, pulmonaryedema [1]. According to the OSHA standard
issued by the Occupational Safety and Health Administration, the
threshold for ammonia in the workplace is 50 ppm [2]. Thus, it is
particularly urgent to monitor low concentrations of ammonia gas
in the environment. In the past few decades, most sensitive ma-
terials based on metal oxides semiconductor have been studied,
including ZnO [3], SnO2 [4] and WO3 [5] et al. Although they have
promoted the development of gas sensors, they still have high
optimal operating temperatures and poor selectivity.
Tin sulfide (SnS2) is an IV-VI compound, n-type semiconductor
material with a band gap of approximately 2.1 eV. It belongs to a
typical layered hexagonal CdI2 type crystal. Its atoms are combined
into an “SeSneS” structure by means of covalent bond, and a
layered structure is formed in a hexagonal close-packed manner
[6]. Due to its excellent physical and chemical properties, it is used
in lithium ion batteries [7], photocatalysis [8], and gas sensor [9]. In
our previous work, 3D SnS2 hierarchical micro-flowers for ultra-
sensitive NH3 gas sensor have been reported [10]. In the recent
years, multicomponent heterojunction semiconductor has caused
extensive attention. The construction of heterojunction facilitates
the transmission of electrons and formation of an interfacial
depletion region. It will eventually lead to enhanced sensor per-
formance [11e13]. Meanwhile, rare earth element doping will
improve the sensing performance of gas sensing materials. For
example, Tie et al. [14] have reported that the formaldehyde gas
sensing of ZTO/SnO2 gas sensor has been significantly improved by
Y-doped ZTO/SnO2. Chen et al. [15]. have proved that the ethanol
sensing performance has been enhanced by Pr and Ce co-doped
ZnSn(OH)6.
In this paper, we successfully synthesized Pr doped 3D SnS2/ZnS
nanoflowers by using two-step hydrothermal method. In particular,
the structure, morphology and specific surface area were investi-
gated. Moreover, the gas sensing performance of pure SnS2/ZnS and
Pr-doped SnS2/ZnS materials were studied. Compared with pure
sample, Pr-doped 3D SnS2/ZnS nanoflowers exhibited better
sensing performance to ammonia.
2. Experiments

2.1. Chemical reagent

* Corresponding author.
E-mail address: zhangqixian1992@163.com (S. Ma). All chemicals reagents in our experiments were analytical grade

https://doi.org/10.1016/j.jallcom.2019.151650
0925-8388/© 2019 Elsevier B.V. All rights reserved.
2 Q. Zhang et al. / Journal of Alloys and Compounds 807 (2019) 151650
and no need for purification, including Sodium stannate (Na2S-
nO3$3H2O), Zinc acetate ((CH3COO)2Zn$2H2O), ammonia aqueous
solution (NH3$H2O, 25%), Thioacetamide (CH3CSNH2), Sodium
alginate ((C6H7NaO6)n), and Acetic acid glacial (CH3COOH).
2.2. Preparation of ZnSn(OH)6 hollow nanospheres
Firstly, 5 mmol Na2SnO3$3H2O was fully dissolved in 15 ml of
deionized water, and 0.02 g sodium alginate was dissolved in 5 ml
of deionized water. Subsequently, 5 mmol Zn (CH3COO)2$2H2O was
fully dissolved in 10 ml of deionized water, and 5 ml of ammonia
aqueous solution was added. Then, after the two above solutions
were fully mixed, reacted at 160  C for 10 h. To be cooled to room
temperature, white precipitates were obtained by centrifugation
and washed with deionized water and ethanol for several times,
dried at 80  C for 10 h.
2.3. Preparation of Pr-SnS2/ZnS nanoflowers
In this process, 0.286 g ZnSn(OH)6 samples were completely
dispersed in 20 ml of deionized water with magnetic stirring.
Meanwhile, 5 mmol thioacetamide (TAA) and a certain amount of
PrN3O9$6H2O (0 wt % and 3 wt %) were dissolved in 10 ml of
deionized water, and 5 ml acetic acid glacial was added. The above
solutions were mixed together with stirring until well mixed. Then,
the mixture kept at 160  C for 8 h. After cooling to room tempera-
ture, yellow precipitates were collected by cleaned with deionized
water and ethanol for several times. It was dried at 80  C for 12 h.
2.4. Preparation and measurement of sensors
The sensor was prepared as follows: (1) The SnS2/ZnS and
Pr  SnS2/ZnS samples were mixed with deionized water in weight
ratio of 4:1 and form a slurry; (2) As shown in Fig. 1(a), the slurry is
uniformly coated on the surface of the ceramic tube with a thick-
ness. (3) As shown in Fig. 1(b), ceramic tube is soldered with the
pedestal, the sensor was kept at 200  C for 48 h to enhance its
stability. In order to study the gas sensing performance, the cor-
responding test circuit schematic is shown in Fig. 1(c). The gas
sensing measurement system has been in Ref. [16]. In the experi-
ment, the response was defined as S]Ra/Rg (Ra is the resistance of
gas sensor in air and Rg is the resistance of gas sensor in a test gas).
When the test gas is injected/extracted, the time for getting 90% of
Fig. 1. (a) The structure diagram of gas sensor configuration, (b) Sensor diagram, (c)
measurement circuit.
the total resistance change is defined as the response/recovery time
[16].
3. Results and discussion
3.1. Samples structure characterization
Fig. 2(a) displays the XRD pattern for the ZnSn(OH)6 samples. It
can be seen from the figure, all the diffraction peaks are well cor-
responding to the standard spectrum (JCPDS NO. 73e2384). There
are no observed other impurities peaks, which indicates the high
purity of the samples. Fig. 2(b) displays two sets of diffraction peaks
corresponding from SnS2 (JCPDS NO. 89e2358) and ZnS (JCPDS No.
65e0309), respectively. Nevertheless, due to the low content of Pr
element, diffraction peaks of Pr element are not detected in Pr-
SnS2/ZnS samples. In Fig. 2(c), it shows a large enlarged view of the
(100) and (011) diffraction peaks in the SnS2/ZnS and Pr-SnS2/ZnS
XRD pattern. It displays that the (100) and (011) peaks of Pr-SnS2/
ZnS compared with pure SnS2/ZnS have obviously right shift of
 
0:06 and 0:07 , respectively. It may be due to the large ionic radius
of Pr (0.099 nm)/Pr4þ (0.085 nm) than that of Sn4þ (0.071 nm)
3þ
[15,17]. When the Pr3þ/Pr4þ ions substitute for Sn4þ ions, due to the
different valence states of them, more S vacancies are generated
based on the charge compensation effect, leading lattice distortion
[17]. Besides, the crystallite size D of the SnS2/ZnS and Pr-SnS2/ZnS
samples are calculated through the XRD data and the Scherrer
formula (Eq. (1) [18,19]), corresponding results are displayed in
Table 1. Compared with pure SnS2/ZnS, the crystallite size of Pr-
SnS2/ZnS decreased. However, it is known that the width of the
diffraction peak depends on the size of the particles, ambient
temperature and lattice strain. The Williamson-Hall approach
claims that the grain size and lattice strain are two principal factors
affecting the FWHM of X-ray diffraction peaks at a constant tem-
perature [20]. Lattice strain is a measure of the distribution of lat-
tice constants arising from crystal imperfections, such as lattice
disruption, in which crystallite size reduction can induces a large
amount of strain. Thus, the grain size DW-H and εWH of pure and Pr
doped SnS2/ZnS samples are identified by the Williamson-Hall
approach (Eq. (2) [20e23]). Where D is the Scherrer's crystallite
size, k ¼ 0.89, linc ¼ 1:5406 Å is the X-ray incident wavelength and
qhkl is the diffraction angle, bhkl is full width at half maximum of
intensity, DW-H and εWH is the size of the nanocrystals and lattice
strain in the Williamson-Hall method, respectively.
D ¼ klinc =ðcosqhkl bhkl Þ (1)
bhkl cosqhkl ¼ 4 εWH sinqhkl þ klinc =DWH (2)
Fig. 2 (d-e) show the Williamson-Hall plots of pure and Pr doped
SnS2/ZnS samples. DW-H can be calculated from the y-axis intercept.
The DW-H and εWH of the pure and Pr doped SnS2/ZnS samples are
22.663372 and 19.756974 nm, 0.0004125 and 0.0002075,
respectively. From the results of Scherrer's and Williamson-Hall
outputs, implying on the same trends of the grain size in two ap-
proaches, which has proved that Pr doping can lead to lattice
distortion and suppress the growth of crystallite [14,24].
3.2. XPS analysis
As shown in Fig. 3, the Pr-SnS2/ZnS hierarchical nanoflowers are
analyzed by XPS. In Fig. 3(a), the survey spectrum of the sample
displays that it is composed of Sn, Zn, S, Pr, C and O elements, where
C and O elements may come from XPS system and O2 adsorption on
the surface of materials [15]. The peaks located at 495.3 eV and
486.8 eV are well corresponding to Sn 3d5/2 and Sn 3d3/2 for Sn4þ
 Q. Zhang et al. / Journal of Alloys and Compounds 807 (2019) 151650 3

Fig. 2. XRD patterns of the synthesized samples: (a) ZnSn(OH)6; (b) SnS2/ZnS and Pr-SnS2/ZnS; (c) Comparison the shift of (100) and (011) peaks of SnS2/ZnS and Pr-SnS2/ZnS;
Williamson-Hall plots (d) pure SnS2/ZnS, (e) Pr doped SnS2/ZnS.

Table 1 3.3. Morphological analysis

Parameters of the (100) and (011) diffraction peaks of undoped SnS2/ZnS and Pr-
SnS2/ZnS.
The morphology of the ZnSn(OH)6 samples was firstly tested by
Materials Planes (h k l) 2q ( ) FWHM ( ) D (nm) SEM. Fig. 4(a) shows that ZnSn(OH)6 samples exhibit regular
0 wt% Pr-SnS2/ZnS 100 28.243 0.378 21.457 spherical architecture and good dispersity. These nanospheres have
011 32.137 0.399 20.515 an average size of about 800 nm. Fig. 4(b) clearly displays the sur-
3 wt% Pr  SnS2/ZnS 100 28.304 0.473 17.150 face of these nanospheres have rough surface and some apparent
011 32.211 0.411 19.920
pores. It indicates that these nanospheres may have hollow nano-
structure. As shown in Fig. 4(c), there is a bright center and a much
darker edge in TEM image, demonstrating these nanospheres are
states in Fig. 3(b) [25], respectively. In Fig. 3(c), the peaks located at hollow.
1022.9 eV and 1045.9 eV are corresponding to Zn 2p3/2 and Zn 2p1/2 Fig. 4(d) and (e) show that the typical SEM images of pure SnS2/
for Zn2þ states [26], respectively. In Fig. 3(d), the peaks centered at ZnS nanoflowers samples. There are a lot of nanoflowers self-
161.62 eV and 162.90 eV are well corresponding to S 2p3/2 and S assembled by nanosheets. And there are no other morphologies,
2p3/2 for S2 states [17], respectively. As seen from Fig. 3(e), the indicating a high yield of SnS2/ZnS nanoflowers. The typical TEM
spectrum can be resolved into 5 peaks at s (929.5 eV), s’ (949.8 eV), image (Fig. 4(f)) displays a similar result to SEM images. And the 3D
m (933.5 eV), m’ (953.9 eV) and t’ (955.8 eV) [27], respectively. The SnS2/ZnS hierarchical nanoflowers are composed of uniform
peaks marked with s and s’ are corresponding to Pr4þ states, those nanosheets, the thickness of which is about 30 nm. As shown in
marked with m and m’ are corresponding to Pr3þ states, and the Fig. 4 (g-i), compared with the pure SnS2/ZnS, the morphology and
peak marked with t’ only exists in 3d3/2 part [28,29]. The corre- size of 3 wt % Pr-SnS2/ZnS samples have no obvious change.The
sponding element atomic concentration is shown in Table 2. The individual elemental mappings of Zn, Sn, S and Pr are shown in
XPS results show that Pr element exist in Pr-SnS2/ZnS with Pr3þ and Fig. 4(jen), indicating the homogenous distribution for the
Pr4þ. mentioned elements on the surface of Pr doped SnS2/ZnS
4 Q. Zhang et al. / Journal of Alloys and Compounds 807 (2019) 151650

Fig. 3. XPS spectra of the Pr-SnS2/ZnS hierarchical nanoflowers: (a) a survey spectrum, (b) Sn 3d, (c) Zn 2p, (d) S 2p, (e) Pr 3d.

Table 2 target gas and improve gas sensing performance of the sensing
The atomic concentration of the Pr doped SnS2/ZnS. materials.
Element C 1s O 1s S 2p Zn 2p3 Sn 3d5 Pr 3d

At/% 69.15 9.48 10.90 1.24 9.17 0.06 3.4. Gas sensing performance

The optimal operating temperature and selectivity are critical

nanoflowers.
As shown in Fig. 5, the isotherms are identified as type IV ac-
cording to the IUPAC classification, which indicates pure SnS2/ZnS
and Pr-SnS2/ZnS samples belong to mesoporous materials [29]. The
specific surface area of the synthesized samples is 21.4228 m2/g for
pure SnS2/ZnS, 24.8033 m2/g for 3 wt % Pr doped SnS2/ZnS nano-
flowers. Obviously, the Pr-SnS2/ZnS nanoflowers samples provide
larger specific surface area which can promote the adsorption of
for semiconductor gas sensors. In this paper, the optimal operating
temperature was firstly tested. Moreover, the gas sensing perfor-
mance of pure SnS2/ZnS and Pr-SnS2/ZnS are studied for getting
compared. In Fig. 6(a), the responses of the gas sensors of pure
SnS2/ZnS and Pr-SnS2/ZnS to 50 ppm ammonia are tested at the
range of 100  Ce240  C. It is obviously observed that the response
of two gas sensors first increases and then decreases, reaching their
maximum response at 160  C. It demonstrates that the optimal
operating temperature of two sensors is 160  C. The relationship
 Q. Zhang et al. / Journal of Alloys and Compounds 807 (2019) 151650 5

Fig. 4. SEM and TEM images of samples: (a) and (b) SEM of ZnSn(OH)6, (c) TEM of ZnSn(OH)6 hollow nanospheres; (d) and (e) SEM of SnS2/ZnS, (f) TEM of pure SnS2/ZnS
nanoflowers; (g) and (h) SEM of 3 wt % Pr-SnS2/ZnS nanoflowers, (i) TEM of Pr-SnS2/ZnS, (jen) SEM images of Pr-SnS2/ZnS and its elemental mapping images of Zn, Sn, S and Pr,
respectively.

Fig. 5. N2 adsorption-desorption isotherm of samples: (a) pure SnS2/ZnS, (b) 3 wt % Pr-SnS2/ZnS.

6 Q. Zhang et al. / Journal of Alloys and Compounds 807 (2019) 151650
Fig. 6. (a) The response of the synthesized samples to 50 ppm ammonia under different operating temperatures; (b) The response of the synthesized samples to 50 ppm various test
gases at 160  C.
between temperature and response is also studied. Firstly, when
the operating temperature is too slow, the chemical reaction rate is
slow due to the temperature, resulting in a lower response. Sub-
sequently, with the operating temperature increasing, the
ammonia gas obtains a certain energy to promote the reaction, so
the response is correspondingly increasing. However, when the
operating temperature is too high, the ammonia molecules will
escape, resulting in a downturn response. Therefore, the semi-
conductor gas sensor can effectively monitor ammonia at the op-
timum operating temperature. As shown in Fig. 6(b), the response
of the sensors is tested at 160  C to 50 ppm of various testing gases.
It can be clearly observed that both sensors of SnS2/ZnS and Pr-
SnS2/ZnS have excellent gas sensing performance to ammonia gas,
and the response of Pr-SnS2/ZnS to ammonia gas is higher than
SnS2/ZnS. Therefore, the sensor based on Pr-SnS2/ZnS samples has a
better selectivity than SnS2/ZnS to ammonia gas.
In Fig. 7(a), the dynamic response variation of SnS2/ZnS and Pr-
SnS2/ZnS sensors to 5e500 ppm concentrations of ammonia at
160  C is tested. When the ammonia gas is injected, the response of
two sensors firstly increases. When the ammonia gas took away,
the response of two sensors decreases. Moreover, when the Pr
doped SnS2/ZnS sensors are exposed to 5 ppm ammonia at 160  C, it
can still deliver a response value of 3.06, which indicates the
detection minimum limit of such gas sensor is 5 ppm as well as high
sensitivity to ammonia. In Fig. 7(b), a relationship image about the
response and gas concentration, the response rises with increasing
of ammonia concentration. If the concentration is too high, the gas
concentration will reach a saturated state with a certain response
[16]. The response of Pr-SnS2/ZnS to 50 ppm ammonia is 14.03,
which is 1.7 times higher than the SnS2/ZnS sample. Usually, in the
range of relatively low concentration, the response is satisfied with
a functional relationship which already reported in Ref. [16].
Therefore, as shown in Fig. 7(c), in the range of 5e100 ppm
ammonia, the linear fitting relationship of SnS2/ZnS is Ln (S-
1) ¼ 1.004 Ln (C) - 1.6934, correlation coefficient R2 ¼ 0.97562.
Meanwhile, the linear fitting relationship of Pr-SnS2/ZnS is Ln (S-
1) ¼ 0.81825 Ln (C) - 0.78269, correlation coefficient R2 ¼ 0.97922.
It can be seen that the correlation coefficient of Pr-SnS2/ZnS is
closest to 1, which proves that the Pr-SnS2/ZnS gas sensor can
accurately predict the response of ammonia in the range of
5e100 ppm. Compared with SnS2/ZnS, the sensor of Pr-SnS2/ZnS is
more suitable for monitoring ammonia in the range of low
concentration.
Fig. 8 shows the resistance change of SnS2/ZnS and Pr-SnS2/ZnS
to 50 ppm ammonia at 160  C. It can be seen that the response/
recovery time are 11/22 s and 6/13 s for the sensors of SnS2/ZnS and
Pr-SnS2/ZnS, respectively. Therefore, the Pr-SnS2/ZnS sensor pos-
sesses a faster response and recovery speed for detecting ammonia
than pure SnS2/ZnS sensor.
Therefore, the sensor of Pr-SnS2/ZnS has better gas sensing
performance to ammonia than pure SnS2/ZnS at 160  C. Compared
with pure 3D SnS2/ZnS hierarchical nanoflowers, Pr doped SnS2/
ZnS effectively improves the gas sensing performance to detect low
concentration of ammonia.
In addition, as depicted in Table 3, we have made a comparison
concerning ammonia sensing properties of Pr doped SnS2/ZnS
nanoflowers and other SnS2 based materials. The Pr doped SnS2/
ZnS sensor possesses a relatively higher response value and faster
response/recovery time in detecting low concentration of ammonia
[2,6,30e33]. Therefore, the sensor based on Pr-SnS2/ZnS materials
has potential applications in monitoring low concentrations of
ammonia.
3.5. Sensing mechanism
As well known, SnS2 and ZnS are both n-type semiconductors,
the gas sensing mechanism of gas sensor is based on the gas/
semiconductor surface interaction [16,34,35] (as shown in
Fig. 9(a)).
In the air atmosphere, the oxygen molecules adsorb on the
surfaces of the materials and obtain electrons from the conduction
band, forming the chemisorbed oxygen species (such as O 
2, O ,
2
O ) through equations (1)e(4):
O2ðgasÞ /O2ðadsÞ (3)
O2ðadsÞ þ e /O
2ðadsÞ (4)
O  
2ðadsÞ þ e / 2OðadsÞ (5)
O  2
ðadsÞ þ e /OðadsÞ (6)
In this process, oxygen is adsorbed on the semiconductor metal
oxide surface which forms a potential barrier at the grain boundary.
And an electron depletion layer is formed on the surface of the
material and increase the potential barrier at the grain boundaries.
The layer restricts the flow of electrons, corresponding resulting a
relatively higher resistance [34,36].
When the sensors are exposed to ammonia gas atmosphere, it
involves the electrochemical oxidation reaction of ammonia (Eq. (7)
and (8)) [34,37,38]:
 Q. Zhang et al. / Journal of Alloys and Compounds 807 (2019) 151650 7

Fig. 7. (a) The dynamic response change of the synthesized samples toward 5e500 ppm ammonia at 160  C; (b) The response of the synthesized samples to different ammonia
concentrations ranging from 5 to 2000 ppm; (c) Plot of ln (S-1) and ln C for all samples toward 5e100 ppm ammonia at 160  C.

Fig. 8. The resistance change of the sensors to 50 ppm ammonia at operating temperature of 160  C: (a) SnS2/ZnS, (b) Pr-SnS2/ZnS.

Table 3
A comparision of the performance of ammonia sensors based on various SnS2 structures.

Sensing materials Concentration Topt ( C) Response Response/Recovery Time (s) Ref.

Flower-shaped SnS2 100 ppm 200 7.4 50.6/624 [2]

2D SnS2 500 ppm RT 4.2 16/450 [6]
SnO2/SnS2 nanotubes 100 ppm RT 2.48 21/110 [30]
SnO2eSnS2 hybrids 500 ppm RT 2.3 11/NA [31]
SnS2 nanosheets 50 ppm RT 2.04 16/NA [32]
Sn/SnO2/N doped carbon nanocomposite 300 ppm 65 172.70 60/55 [33]
Pr-SnS2/ZnS nanoflowers 50 ppm 160 14.03 6/13 This work

RT denotes room temperature, NA denotes no specific data are available.

8 Q. Zhang et al. / Journal of Alloys and Compounds 807 (2019) 151650
Fig. 9. Schematic illustration of the sensing mechanism.
4NH3 þ O
2 ðadsÞ ¼ 2N2 þ 6H2 O þ 6e

2 
2 = 3 NH3 þ O / 1=3 N2 þ H2 O þ 2 e
In this process, the electron concentration of the system
increased, leading to reduction of the sensor resistance and
increased conductivity [39e41]. Moreover, the corresponding
response value of the material can be obtained by using R ¼ Ra/Rg.
To comprehensively understand the enhancement gas sensing
property of Pr doped SnS2/ZnS nanoflowers to ammonia, we pre-
sent qualitative explanation of the possible mechanisms:
Firstly, the SnS2/ZnS heterojunction is beneficial to improve gas
sensing performance. The energy band structures of SnS2 and ZnS
are shown in Fig. 9(b). The bandgap energies of SnS2 and ZnS are
2.11 and 3.7 eV, respectively [42,43]. It is easily found that the
conduction band (CB) of ZnS is higher than that of SnS2, the elec-
trons on the CB of ZnS can transfer toward the CB of SnS2 [44].
Meanwhile, the SnS2/ZnS n-n heterojunction could reduce the
recombination probability of electron-hole pairs and improve the
electrons transmission efficiency [45]. Consequently, the absorbed
oxygen molecules will capture the additional electron which can
further increase and decrease the sensor's resistance in air or
ammonia, respectively. Therefore, the SnS2/ZnS heterojunction
plays an important modulating role in electrical conductivity for Pr-
SnS2/ZnS sensor.
Secondly, the improvement of gas sensing performance is
closely related to the doping of Pr3þ and Pr4þ ions. On the one hand,
the growth of SnS2/ZnS crystallites can be restrained by Pr doping,
which leads to crystallite sizes of Pr doped SnS2/ZnS samples
smaller than in SnS2/ZnS ones. It has been reported in the relevant
literature that reducing the crystallite size can significantly
enhance gas sensing [46]. On the other hand, Pr3þ may give an
electron to O2 adsorbed on the surface of Pr doped SnS2/ZnS to form
O 4þ
2 by transforming into Pr . In contrast, the Pr
4þ
species may
capture electrons to form Pr3þ, it may include the following reac-
tion of Eq. (9) and (10) [47]. Moreover, when Pr3þ/Pr4þ ions were
doped into SnS2 lattice, they will substitute Sn site to form the
electron-donor defects. In order to maintain electronic neutrality,
Pr ions will liberate small amount of free electrons [25]. Therefore,
Pr doping can increase the concentration of free electrons, which
produce more O and O2 on the sample's surface through Eq. (5)
and (6). When ammonia molecules reacting with those O and O2 ,
there will be more free electrons released back to the conduction
band on the basis of Eq. (7) and (8). The process will increase the
concentration of free electron. Hence, the more transport of free
electrons results in excellent gas sensing performance.
Pr 3þ þ O2 / Pr 4þ þ O (9)
(7) 2
Pr 4þ þ e / Pr 3þ (10)
(8) Finally, the excellent gas sensing performance of Pr doped SnS2/
ZnS sensor are also related to hierarchical flower-like structure. The
distinctive three-dimensional hierarchical flower-like nano-struc-
tures are composed of numerous thin nanosheets, which increases
effective specific surface area and provides more convenient
channels for adsorption and desorption of oxygen and target gases.
4. Conclusion
In summary, the Pr doped 3D SnS2/SnS2 hierarchical nano-
flowers are successfully prepared by using ZnSn(OH)6 as precursor.
Due to the right shift of the diffraction peak and the presence of the
Pr element in the XPS patterns, it proved that Pr is doped into SnS2/
ZnS. Pr doping led to the lattice distortion inhibit grain growth and
reduce grain size. The specific surface area of SnS2/ZnS and Pr-SnS2/
ZnS samples is 21.4228 m2/g and 24.8033 m2/g, respectively. The
sensor based on Pr doped SnS2/ZnS hierarchical nanoflowers
effectively improved gas sensing performance to ammonia
including higher response and quicker responding and recovering
speed. The response of Pr-SnS2/ZnS to 50 ppm ammonia is 14.03 at
160  C, which is 1.7 times higher than the SnS2/ZnS sample. At the
same time, the Pr doped SnS2/ZnS sample has a faster response/
recovery time (6s/13s). Apart from the increase in specific surface
area, the SnS2/ZnS heterojunction and Pr3þ/Pr4þ doping improve
the electrons transmission efficiency, which is the main reason for
the improvement of gas sensitivity.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (Grant No. 11864034 and 51562035), the Sci-
entific Research Project of Gansu Province (Grant No. 18JR3RA089
and 17JR5RA072).
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