Materials Chemistry and Physics 130 (2011) 13251328

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Materials Chemistry and Physics
j our nal home page: www. el sevi er . com/ l ocat e/ mat chemphys
Fast response detection of H
2
S by CuO-doped SnO
2
lms prepared by
electrodeposition and oxidization at low temperature
Shulan Wang
a
, Yang Xiao
a
, Dongqi Shi
b,
, Hua Kun Liu
b
, Shi Xue Dou
b
a
Department of Chemistry, School of Sciences, Northeastern University, Shenyang 110004, China
b
Institute for Superconducting and Electronic Materials, University of Wollongong, NSW2522, Australia
a r t i c l e i n f o
Article history:
Received 20 January 2011
Received in revised form30 July 2011
Accepted 10 September 2011
Keywords:
CuO-doped SnO
2
H
2
S detection
Selectivity
Electrodeposition
a b s t r a c t
Fast response detection of H
2
S by CuO-doped SnO
2
lms prepared was prepared by a simple two-step
process: electrodeposition from aqueous solutions of SnCl
2
and CuCl
2
, and oxidization at 600

C. The
phase constitution and morphology of the CuO-doped SnO
2
lms were characterized by X-ray diffraction
andscanning electron microscopy. In all cases, a polycrystalline porous lm of SnO
2
was the product, with
the CuO deposited on the individual SnO
2
particles. Two types of CuO-doped SnO
2
lms with different
microstructures were obtained via control of oxidation time: nanosized CuO dotted island doped SnO
2
and ultra-uniform, porous, and thin CuO lm coated SnO
2
. The sensor response of the CuO doped SnO
2
lms to H
2
S gas at 50300 ppm was investigated within the temperature range of 25125

C. Both of
the CuO-doped SnO
2
lms show fast response and recovery properties. The response time of the ultra-
uniform, porous, and thin CuO coated SnO
2
to H
2
S gas at 50ppm was 34 s at 100

C, and its corresponding

recovery time was about 1/3 of the response time.
2011 Published by Elsevier B.V.
1. Introduction
H
2
S, oneof thecombustionproducts of fuels, is ahighlytoxic and
ammablegas. Thefast monitoringof suchtoxic gases has therefore
become extremely important. CuO doped SnO
2
has been found to
bethemost sensitivematerial toH
2
Sgas [1]. Toimprovethesensing
properties of CuOdoped SnO
2
, various CuOSnO
2
materials in such
forms as thin/thick lms, bulk CuOSnO
2
[25], CuSnO
2
bilay-
ers and heterostructures [68], and nano-CuO doped SnO
2
[913]
have been prepared through different techniques, i.e., hydrother-
mal synthesis [1012], solgel synthesis [11,14], aerosol deposition
[15], thermal evaporation [5], sputtering [16], electrostatic spray-
ing [17,18], and screen printing [20]. Although the response time
of the CuO doped SnO
2
to the H
2
S gas at 20200ppm could be
decreased to less than 1min, the recovery time was still long, about
48min [2,17,1921]. Therefore, it is very attractive to prepare CuO
doped SnO
2
with fast response and recovery properties to H
2
S gas.
In the present work, CuO doped-SnO
2
porous and polycrys-
talline lms have been prepared by an electrodeposition and
oxidization method. It was grown different microstructures, like
nanosized CuO dotted island doped SnO
2
and ultra-uniform,
porous, and thin CuO lm coated SnO
2
. It has been made a sensor

Corresponding author. Tel.: +61 2 42215727; fax: +61 2 42215731.

E-mail address: dongqi@uow.edu.au (D. Shi).
structure and its gas response of the CuO doped SnO
2
lms was
found to be fast to H
2
S gas at the lowtemperature.
2. Experimental
The CuOdoped SnO
2
lms were prepared by an electrodeposition and oxidation
method. 1.75g SnCl
2
, 6.25g Na
3
C
6
H5O7, and balanced distilled water were com-
bined in a 250mL ask, labeled as solution a. Solution b was prepared by the same
method as solution a, except that the SnCl
2
was replaced by 0.1g CuCl
2
.
A piece of indium tin oxide (ITO) glass (10mm20mm) was dipped in 50mL
of solution a, and a 1mA current was passed through the ITO glass for 3600s using
an EG&G M273 potentiostat, a platinum counter electrode (1cm
2
in area), and a
saturated camel reference electrode, with the electrodes placed near the ITO glass.
The same ITOglass was also dipped in 50mL of solution b, and a 0.7mA current was
passed through it for 600s using the same method. Tin and copper were nominally
deposited on the ITO glass in the atomic ratio of 8.6:1, which was estimated from
the electric charge passed.
After the electrodeposition, the ITO glass pieces were red in air for 810h
at 500

C and 600

C and the copper and tin on the ITO glass were oxidized dur-
ing the ring. X-ray diffraction (XRD) patterns of the oxidized lms were collected
using a Philips PW3040/60 diffractometer at a scanning rate of 0.03

min
1
for
2

C in the range of 1080

. Scanning electron microscope (SEM) images of the as-

electrodepositedlmandtheoxidizedlms werecapturedusingascanningelectron
microscope (SSX-550) operated at an acceleration voltage of 30kV.
Two platinumwires (0.5mmin diameter) at a distance of 10mmwere xed on
the ITOglass. The platinumwires were xed onto the ITOglass by a clamp to make a
good electric connection. This assembly was then put in the bottomof a one ended
and air-tight quartz tube (60mmin inner diameter, 65mmin outdiameter, 600mm
in height) and the quartz tube was heated in a vertical furnace. The H
2
S gas was
diluted in a container. According to the designed detection concentration, a certain
amount of the diluted H
2
S gas was taken and injected into the quartz tube. The
resistance of the oxidized lms was recorded by a multimeter (Aglient A34401) and
a computer. The sensor response of the oxidized lms to the H
2
S gas at 50300ppm
0254-0584/$ see front matter 2011 Published by Elsevier B.V.
doi:10.1016/j.matchemphys.2011.09.023
1326 S. Wang et al. / Materials Chemistry and Physics 130 (2011) 13251328
70 60 50 40 30 20
+ + + +
+
+
+
+
+
#
#
^
^
(d)
(c)
(b)
(a)
+ SnO
2
^ CuO
* In
2
O
3
# Sn
3
O
4
1
1
1
*
*
*
*
*
*
*
*
*
1
1
0
1
0
1
2
0
0
3
0
1
1
1
2
3
1
0
0
0
2
2
2
0
2
1
1
I
n
t
e
n
s
i
t
y
(
a
.
u
)
2(deg)
0
0
2
1
1
1
-
2
0
2
^
2
2
2
4
0
0
4
4
0
6
2
2
#
+
Fig. 1. XRD patterns of the ITO glass substrate and the oxidized lms: (a) the ITO
glass substrate, (b) tin oxide lm red at 500

C for 8h, (c) tin oxide lm red at

600

C for 8h, and (d) CuO doped SnO

2
lmred at 600

C for 8h.
was tested. When the response remained constant at a xed operating tempera-
ture, air was let in immediately. The temperature of the furnace was controlled at
25, 50, 75, 100 and 120

C, respectively, by a type N thermocouple and a DTC-2B

temperature controller.
3. Results and discussion
The phase and purity of the oxidized lms were determined by
X-ray diffraction (XRD), and the diffraction patterns are shown in
Fig. 1. The diffraction patterns of the ITO glass (In
2
O
3
JCPDS card
number 03-065-3170) were also collected for comparison. After
8h ring at 500

C and 600

C in air, tin oxide lms and CuO doped

SnO
2
lms were obtained. All the patterns of SnO
2
could be readily
indexed to the tetragonal phase of SnO
2
(JCPDS card number 01-
077-0447). However, the X-ray diffractionpatterns of tinoxide lm
red at 500

C also showpeaks corresponding to the triclinic phase

of Sn
3
O
4
(JCPDS card number 16-0737). With increasing tempera-
ture (from Fig. 1(b) and (c)) the intensity of the tetragonal SnO
2
phase increases signicantly, while the intensity of the triclinic
Sn
3
O
4
phase is reduced. In the patterns of CuO doped SnO
2
lm
red at 600

C for 8h, the diffraction peaks of CuO emerge (JCPDS

card number 03-065-2309) (Fig. 1(d)).
Scanning electron microscope (SEM) images of the as-
electrodeposited lm and the oxidized lms are shown in Fig. 2.
As can be seen from Fig. 2(a), the as-electrodeposited lm con-
sisted of uniformly distributed irregular crystals, some of them
presenting rectangular section. Both the average size of the crystals
and the average size of the spaces between the crystals are about
3mm. However, after the as-electrodeposited lm was red for
8h at 600

C in air, the as-electrodeposited irregular crystals was

destroyed and instead consisted of porous, nanosized, CuO dotted
islands on the SnO
2
particles in the lm(Fig. 2(b)). The space that
existedbetweenthe crystals inFig. 2(a) was largely occupiedby the
growth of oxide particles. After further ring for 2h at 600

C, the
nanosized CuO particles were transformed into an ultra-uniform,
porous, and thin CuO lm coating on the top of the porous SnO
2
particles (Fig. 2(c)).
Sensors wereassembledbytheCuOdopedSnO
2
lms connected
separately with two platinum wires. The resistances of the sen-
sors in air were rst recorded in a few minutes and the H
2
S gas at
50300ppm was ejected gradually after the resistances are con-
stants and the sensing properties of the CuO doped SnO
2
lms
to the H
2
S gas were measured within the temperature range of
Fig. 2. SEM images of the as electrodeposited lm and the oxidized lms: (a) as-
electrodeposited lm with rectangular-shaped crystals, (b) nanosized CuO dotted
island doped SnO
2
red at 600

C for 8h, and (c) ultra-uniform, porous, and thin CuO

lmcoated SnO
2
red at 600

C for 10h.
25125

C. The sensitivity is dened as R

a
/R
g
, where R
a
and R
g
are
the resistances in air and in the detected atmosphere, respectively.
Fig. 3shows the baseline andsensitivities of the CuOdopedSnO
2
lmas functions of the concentration of H
2
S gas and the operating
temperature. The sensor resistance is stable before and after the
ejection of 100ppmH
2
S gas. The ratio of the resistance before and
after the gas ejection is around 3. The sensor response started at
room temperature and reached maximum value at 100

C. With
increasing operating temperature, the response times of both the
S. Wang et al. / Materials Chemistry and Physics 130 (2011) 13251328 1327
350 300 250 200 150 100 50 0 -50
-10
0
10
20
30
40
50
60
70
300 ppm
200 ppm
100 ppm
50 ppm
25
o
C
S
e
n
s
i
t
i
v
i
t
y
350 300 250 200 150 100 50 0 -50
-10
0
10
20
30
40
50
60
70
50
o
C
350 300 250 200 150 100 50 0 -50
-10
0
10
20
30
40
50
60
70
75
o
C
S
e
n
s
i
t
i
v
i
t
y
Time(s)
350 300 250 200 150 100 50 0 -50
-10
0
10
20
30
40
50
60
70
100
o
C
Time(s)
500 400 300 200 100 0
5000
10000
15000
20000
25000
R
,

t, s
225 200 175 150 125 100 75 50 25 0 -25
-2
0
2
4
6
8
10
12
14
16
18
20
22
24
26
S
e
n
s
i
t
i
v
i
t
y
Time(s)
25
o
C
50
o
C
75
o
C
100
o
C
125
o
C
a
b
c
Fig. 3. Baseline and sensitivity versus response time curve of CuOdoped SnO
2
lms
to H
2
S gas: (a) the baseline of nanosized CuO dotted island doped SnO
2
to 100ppm
H
2
S at 25

C; (b) the sensitivity of the nanosized CuO dotted island doped SnO
2
to 100ppm H
2
S at operating temperatures of 25125

C; (c) the sensitivity of the

ultra-uniform, porous, and thin CuO lmcoated SnO
2
to H
2
S gas at 50300ppmat
operating temperatures of 25100

C.
CuO doped SnO
2
lms decreased. At 125

C, the response values

decreased to one (Fig. 3(a)). The response time of the nano-sized
CuO dotted island doped SnO
2
to 100ppmH
2
S ranged from160 to
100s within the temperature range of 25100

C (Fig. 3(a)). How-

ever, this range was decreased to 6646s for the ultra-uniform,
porous, and thin CuO lm coated SnO
2
(Fig. 3(b)). A further 2h
ring at 600

C greatly decreased the response time of the CuO

doped SnO
2
lms to the H
2
S gas. However, the response time was
increased by increasing the concentration of H
2
S gas. At 100

C, the
response time of the CuO lmcoated SnO
2
to 50ppmH
2
S gas was
34s, and this increased to 50s for 300ppm H
2
S (Fig. 3(b)). This
indicates that we were successful in fabricating CuO doped SnO
2
lmwith a short response time of 34s to H
2
S gas at 50ppmat the
low operating temperature of 100

C by an electrodeposition and
oxidation method.
Another important feature of the CuO doped SnO
2
lms is their
fast recovery property. This can also be seen fromFig. 3. The recov-
ery time of the nanosized CuO dotted island doped SnO
2
from
100ppm H
2
S gas within the temperature range of 25100

C is
4030s, andthis range decreasedto1510s for the CuOlmcoated
SnO
2
. The recovery times for both the CuO doped SnO
2
lms were
about 1/3 of their corresponding response times, which is much
shorter than the reported results in the literature [24,9,17,18].
The ultra-uniform, porous, and thin CuO coated SnO
2
had a larger
sensing area and higher sensitivity to H
2
S gas than the nanosized
CuO dotted island doped SnO
2
. The fast recovery property of CuO
lm coated SnO
2
is mainly attributed to the more uniform distri-
bution of CuO on the surface of the SnO
2
than in the case of the
nanosized CuO dotted island doped SnO
2
and to the transitional
layer at the CuOSnO
2
interface due to interdiffusion processes [3],
as well as the n-SnO
2
/p-CuO heterojunctions formed in the CuO
doped SnO
2
lms [4]. The ultra uniform, porous, and thin CuO lm
coated SnO
2
has advantages over the nano-sized CuOdotted island
doped SnO
2
in the speeds of both response and recovery, and in the
sensitivity. It is a promising material for fast sensing of H
2
S at low
temperature.
4. Conclusions
We prepared fast response detection of H
2
S by CuO-doped SnO
2
lms prepared by an electrodeposition and oxidization method.
We designed a sensor assemble and tested the sensor response
of the CuO-doped SnO
2
lms. By controlling the oxidization time
of the electrodeposited lms, two types of CuO doped SnO
2
lms
were prepared: ultra-uniform, porous, and thin CuO lm coated
SnO
2
and nano-sized CuO dotted island doped SnO
2
. Both the CuO
doped SnO
2
lms response to the H
2
S gas at 50300ppm from
room temperature and show the maximum sensitivity. The ultra-
uniform, porous, and thin CuO lmcoated SnO
2
is better in terms
of response and recovery properties than the nano-sized CuO dot-
ted island doped SnO
2
lm. The response time of the ultra-uniform,
porous, and thin CuO lm coated SnO
2
to H
2
S gas at 50ppm was
34s at 100

C, and its corresponding recovery time was about 1/3

of the response time.
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