Current Applied Physics 12 (2012) 307e312

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Current Applied Physics

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Characteristics of high sensitivity ethanol gas sensors based on nanostructured

spinel Zn1
xCoxAl2O4
S.D. Kapse a, F.C. Raghuwanshi b, V.D. Kapse c, *, D.R. Patil d
a
Department of Physics, G. S. College, Khamgaon 444303, Maharashtra, India
b
P.G. Department of Physics, Vidyabharati Mahavidyalaya, Amravati 444604, Maharashtra, India
c
Department of Physics, Arts, Science and Commerce College, Chikhaldara 444807, Maharashtra, India
d
Department of Physics, R.L. College, Parola 425111, Maharashtra, India

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

Article history: Nanocrystalline powders of Zn1
xCoxAl2O4 (x ¼ 0, 0.2, 0.4, 0.6, 0.8, 1.0) mixed oxides, with cubic spinel
Received 30 April 2011 structure were successfully prepared by the ethylene glycol mediated citrate sol-gel method. The
Received in revised form structure and crystal phase of the powders were characterized by X-ray diffraction (XRD) and micro-
25 June 2011
structure by transmission electron microscopy (TEM). X-ray diffraction results showed that the samples
Accepted 27 June 2011
Available online 27 July 2011
were in single phase with the space group Fd-3m. TEM analysis showed that the powders with spherical
shape were uniform in particle size of about 17e24 nm with mesoporous in nature. Further investiga-
tions were carried out by FT-IR. Thick films of as-prepared Zn1
xCoxAl2O4 powders were fabricated using
Keywords:
Nanostructured
screen-printing technique. The response of Zn1
xCoxAl2O4 based thick films towards different reducing
Crystallite size gases (liquefied petroleum gas, hydrogen, hydrogen sulfide, ethanol gas and ammonia) was investigated.
Ethanol gas The sensor response largely depends on the composition, temperature and the test gas species. The Co
Selectivity (cobalt) content has a considerable influence on the gas-sensing properties of Zn1
xCoxAl2O4. Especially,
Response time Zn0.4Co0.6Al2O4 composition exhibited high response with better selectivity to 100 ppm C2H5OH gas at
150  C. The instant response (w7 s) and fast recovery (w16 s) are the main features of this sensor.
Ó 2011 Elsevier B.V. All rights reserved.

1. Introduction concentration in the blood and to monitor the alcohol vapors in air.
It is also known that ethanol interacts sharply with the semi-
Semiconducting oxides like ZnO, Al2O3, TiO2, etc. have been conducting materials. Several semi-conducting oxides like SnO2,
studied extensively and have emerged as economical sensors for ZnO, g-Fe2O3, a-Fe2O3, NiFe2O4 have been reported for the alcohol
monitoring toxic gases and vapors than the other available organic sensors [5e9].
and polymeric material comparatively [1,2]. The sensitivity of these Metal oxides having the spinel-type structure attracted a great
sensors to gases depends on the microstructure, which can be deal of attention from scientists and industry leaders because of
attained by adopting special techniques of preparation or by doping their relevant magnetic, refractory and semi-conducting properties
impurities [3,4]. A semiconductor gas sensor exhibits the property [10,11]. ZnAl2O4 has been reported as a new gas sensitive material
of changing the resistivity of the sensing material when it is for detecting organic vapors. The normal spinel ZnAl2O4 is a typical
exposed to different gas atmospheres. The gas-sensing mechanism example of the general formula (A)[B]2O4, where A and B stands for
usually depends on the operating temperature. divalent and trivalent ions, respectively, and the ( ) and [ ] refer to 8
Alcohols broadly fall under the category of volatile organic tetrahedrally coordinated A sites and 16 octahedrally coordinated B
compounds, which usually have very low boiling point, and highly sites within the close-packed face-centered cubic unit cell with
reactive. Moreover, detection of alcohol vapor is one of the most Fd3m space group symmetry. In normal spinel ZnAl2O4 structure,
popular needs in our everyday life. The more common application the divalent cations Zn2þ are at the A sites and the trivalent cations
of an alcohol sensor is as a breath checker and to detect ethanol Al3þ at the B sites. ZnAl2O4 is a well-known wide-bandgap semi-
vapor in human breaths that is correlated with the alcohol conductor [12e14]. It is worth mentioning here that there are no
reports on the ethanol gas sensing performance of nanocrystalline
* Corresponding author. Tel.: þ91 9422157790.
ZnAl2O4. So, it is especially valuable and practical to study the
E-mail addresses: vdk_research@yahoo.com, vdk.nano@gmail.com, ath135@ ethanol gas sensing behavior of ZnAl2O4 and also by doping it with
rediffmail.com (V.D. Kapse). other additive.

1567-1739/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2011.06.030
308 S.D. Kapse et al. / Current Applied Physics 12 (2012) 307e312

The experimental conditions used in the preparation of nano- binder as a mixture of organic solvents to form pastes. The ratio of
materials play a vital role in the particle size of the product. inorganic to organic part was kept as 75:25 in formulating the
Consequently, a great variety of experimental methods have been paste. The paste was then used to prepare thick films. The thixo-
used in the preparation of nanoparticles of simple oxides or oxide- tropic paste was screen printed on a glass substrate in desired
based systems. The most common methods are: solid-state reac- patterns. The films prepared were fired at 500  C for 2 h. Silver
tion [15], solegel [16], micro-emulsion [17], co-precipitation [18], contacts were made by vacuum evaporation for electrical
hydrothermal [19] and polymeric precursor method [20e22]. The measurements. The thicknesses of the films were observed to be in
solegel technique is considered as the most promising technique the range from 25 to 30 mm. The reproducibility of the film thick-
for the preparation of metal oxides [23,24] as it allows for high ness was achieved by maintaining the proper rheology and thix-
purity ceramics with homogeneous distribution of components on otropy of the paste.
the atomic scale, lower crystallization temperature and economy. The sensing performance of the sensors was examined using
The main objective of the present investigation is to fabricate a ‘static gas-sensing system’. There were electrical feeds through
nanocrystalline Zn1
xCoxAl2O4 based ethanol sensor, having higher the base plate. The heater was fixed on the base plate to heat the
sensitivity along with optimization of selectivity, operable at lower sample under test up to required operating temperatures. The
operating temperature. In this work, pure and Co-doped ZnAl2O4 current passing through the heating element was monitored using
powders were prepared by the citrate sol-gel method and used for a relay with adjustable ON and OFF time intervals. A CreAl ther-
the fabrication of thick films. The electrical and gas-sensing prop- mocouple was used to sense the operating temperature of the
erties of thick films to different reducing gases, namely ammonia, sensor. The output of the thermocouple was connected to a digital
ethanol, LPG, hydrogen and hydrogen sulfide, were studied. temperature indicator. A gas inlet valve was fitted at one of the
ports of the base plate. The required gas concentration inside the
2. Experimental static system was achieved by injecting a known volume of test gas
using a gas-injecting syringe. To obtain the desired concentration of
2.1. Preparation of nanocrystalline Zn1
xCoxAl2O4 powders volatile organic compounds, the volume of liquid needed to achieve
a specific vapor concentration (in the test chamber) was calculated
Because of high chemical homogeneity, the polymeric precursor using following equation [25]:
method constitutes an interesting approach to prepare complex
oxides, such as spinels. In this method an aqueous solution of citric Cppm Va M
V ¼
acid and metal ions is polymerized by ethylene glycol to form 24:5  109 D
a polyester-type resin. The metal ions are immobilized and, Where V is the required liquid volume, D is the density of the liquid,
therefore, the segregation of a particular metal during the pro- Va is the volume of the air (equal to the volume of test chamber) and
cessing is strongly reduced. M is the molecular weight of the liquid - all units used are in
In the beginning, the stoichiometric molar amounts of analyti- milliliters, cubic centimeters and grams.
cally pure grade [Al(NO3)3.9H2O], [Zn(NO3)2$6H2O], [Co(NO3)3. A constant voltage was applied to the sensor, and current was
H2O] and citric acid were weighed and dissolved in ethylene glycol measured by a digital picoammeter. Air was allowed to pass into
and subsequently stirred at 80  C for 2 h to obtain a homogeneous the glass dome after every target gas exposure cycle.
and stable sol. The solution was further heated in pressure vessel at Sensor response (S) is defined as the ratio of change in
about 130  C for 12 h. During this reaction transparent solution was conductance of the sensor on exposure to the target gas to the
transform into a gel state with very high viscosity. The gel precursor original conductance in air medium. The relation for S is as [26]:
was then heated in a furnace at 350  C for 4 h. During the heating,
 
a violent combustion occurs that spontaneously propagates until all S ¼ Gg
Ga Ga
the gel was burnt out to form a loose powder. The powders were
then calcinated at 700  C for 6 h to improve the crystallinity of Where Ga and Gg are the conductance of a sensor in air and in
material. gaseous medium, respectively.
Selectivity is the ability of a sensor element to respond to certain
2.2. Characterization of Zn1
xCoxAl2O4 powders target gas in the presence of other gases. The time taken for the
sensor to attain the maximum (90%) change in conductance on
The crystal phases of calcined samples were analyzed using X- exposure to the target gas is measured as the response time. The
ray diffractometer (model: Philips X’pert) with Cu Ka radiation time taken by the sensor to get back 90% of the original conduc-
(l ¼ 1.54059 Å). The average grain size (D) was calculated according tance is measured as the recovery time.
to the Debye-Scherrer formula D ¼ K l=B:Cos q; where B is the full
width at half-maximum intensity (in radians) of a peak at an angle 3. Results and discussion
q; K is a constant, depending on the line shape profile; l is the
wavelength of the X-ray source. The lattice parameters of the 3.1. Material characterizations
prepared powder samples were calculated from the XRD peaks by
indexing corresponding peaks in a cubic space group Fd-3m, using When the obtained dried gel heated to 700  C, the color changed
least square refinement. The structure, morphology and grain size from pink to blue. This color change is possibly attributable to the
of the samples were observed using transmission electron coordination number of the Co2þ ions in the samples. The dried gels
microscopy along with electron diffraction patterns (TEM-ED). contain much water and Co2þ ions are coordinated with six water
Further studies by Fourier transform infrared spectroscopy (Model: molecules, so they exhibit a pink color. The blue color of the cal-
Magna 550) were also carried out. cinated samples is because of the tetrahedrally coordinated Co2þ
ions in the ZnAl2O4 nanocrystallites. With the increase in Co
2.3. Sensor fabrication and measurement of gas-sensing properties concentration, the blue color deepened, which indicated that there
are more Co2þ ions located in the tetrahedral sites.
For gas-sensing properties, the calcined materials were groun- Fig. 1 shows the X-ray powder diffraction patterns of
ded into fine powders, sieved and dispersed with a temporary Zn1
xCoxAl2O4 (x ¼ 0, 0.2, 0.4, 0.6, 0.8 and 1.0) powder samples
 S.D. Kapse et al. / Current Applied Physics 12 (2012) 307e312 309

(220)

(311)

(440)
(511)
(422)
(400)

(331)
(f)

(e)
Intensity (a.u.)

(d)

(c)

(b)

(a)

20 30 40 50 60 70
Two Theta (Degree)

Fig. 1. XRD diffraction patterns of (a) ZnAl2O4, (b) Zn0.8Co0.2Al2O4, (c) Zn0.6Co0.4Al2O4,
(d) Zn0.4Co0.6Al2O4, (e) Zn0.2Co0.8Al2O4 and (f) CoAl2O4 powder samples calcinated at
700  C.

calcinated at 700  C. The analysis of XRD patterns of all the samples

confirmed the formation of cubic spinel structure. All XRD peaks
are correspondent with the JCPDS card no. 01-074-1136 (ZnAl2O4)
and 00-044-0160 (CoAl2O4). No other phases were detected in the
calcinated samples. In all cases, the characteristic peaks for spinel
structure are broad with maximum at 2q (o) ¼ 31.2, 36.8, 44.8, 49.1,
55.6, 59.3 and 65.2 which can be indexed as (2 2 0), (3 1 1), (4 0 0), (3
3 1), (4 2 2), (5 1 1) and (4 4 0) diffraction planes, respectively. The
average crystallite size has been calculated from the XRD peaks
using Debye-Scherrer formula. Further, the lattice parameters of
the prepared powder samples were calculated from the XRD peaks
by indexing corresponding peaks in a cubic space group Fd-3m,
using least square refinement. The calculated cell parameters are
listed in Table 1. It can be seen that the experimental values of
Fig. 2. TEM images of Zn1
xCoxAl2O4 powders with (a) x ¼ 0 and (b) x ¼ 0.6.
lattice parameters and unit cell volume were found to increase with
the increase in Co content. Furthermore, lattice parameters were
found to be within the range of that of ZnAl2O4 (8.084 Å) and due to physically adsorbed water, potentially also present as a result
CoAl2O4 (8.101 Å). of the use of hygroscopic KBr during sample preparation for IR
The average crystallite size estimated from XRD data agree with study.
the TEM investigations. The TEM images of Zn1
xCoxAl2O4 (x ¼ 0
and 0.6) powders calcinated at 700  C are provided in Fig. 2(a and 3.2. Gas sensing studies of nanocrystalline Zn1
xCoxAl2O4
b). The small amount of agglomerations is observed in the micro-
graphs. The selected area electron diffraction (SAED) patterns, When semiconductor metal oxide-based sensors are exposed to
presented in the Fig. 3(a and b), correspond to that of a spinel reducing gases, a chemical reaction between gas molecules and
phase, agreeing with the results obtained from powder XRD negatively charged adsorbed oxygen species on the sensor surface
analysis. of the semiconductors plays a vital role in the electrical transport
Fig. 4 shows FT-IR spectra of all samples recorded in the properties and the electrical resistance of the semiconductor oxide
4000e400 cm
1 range. These spectra shows the presence of three material will change with respect to the operating temperature
bands at w690, 550 and 500 cm
1, respectively. These bands can be [29]. Thus, the reaction of the surface chemisorbed species with the
attributed, in accordance with literature data [27,28], to zinc surrounding gases is critical in the sensing mechanism of the
aluminate spinel structure. The bands at 3440 and 1635 cm
1 are sensor. Furthermore, gas-sensing properties of semiconductor
metal oxides are generally concerned with the changes in the
Table 1
operating temperatures because of the concentration changes of
Cell parameters and average crystallite size of samples obtained from XRD data. the surface oxygen adsorbates. The gas-sensing responses of
Zn1
xCoxAl2O4 with x ¼ 0 towards various reducing gases like liq-
Sample Average Lattice parameters (Å) a¼b¼g Cell
crystallite [o] Volume
uefied petroleum gas (LPG), ammonia (NH3), ethanol gas (C2H5OH),
a¼b¼c hydrogen (H2) and hydrogen sulfide (H2S) are illustrated as
size (nm) Å3
ZnAl2O4 24.6 8.0747 (8) 90 526.47 a function of operating temperature in Fig. 5. The concentrations
Zn0.8Co0.2Al2O4 20.8 8.0752 (9) 90 526.58 are 100 ppm for C2H5OH and 1000 ppm for all other the tested
Zn0.6Co0.4Al2O4 17.6 8.084 (8) 90 528.35 gases. Each curve shows a maximum response value corresponding
Zn0.4Co0.6Al2O4 17 8.0916 (6) 90 529.80 to an optimum heating temperature. Various gas-sensing responses
Zn0.2Co0.8Al2O4 22.5 8.0961 (4) 90 530.67
CoAl2O4 22.4 8.1011 (9) 90 531.65
to different gases may be due to the adsorption of the reducing
gases and reaction between the gases and the adsorbed oxygen.
310 S.D. Kapse et al. / Current Applied Physics 12 (2012) 307e312

30
LPG
H2
25 NH3
C2H5OH
H2S
20

Sensor Response
15

10

0
0 50 100 150 200 250 300 350
0
Operating Temperature ( C )

Fig. 5. Sensor response of Zn1
xCoxAl2O4 with x ¼ 0 towards different reducing gases

as a function of operating temperature.

response to ethanol increases with increasing the Co2þ-doping

amount till x ¼ 0.6, where it reaches the highest value, then
gradually decreases, and Zn0.4Co0.6Al2O4 has the maximum
response to 100 ppm ethanol at 150  C. It is evident that the sensor
elements fabricated from Zn1
xCoxAl2O4 nanoparticles exhibit
a typical n-type semi-conducting behavior, as there is increase in
the conductance on exposure to the reducing gases. Fig. 7
demonstrates the relationship between the response and the
concentration of ethanol vapors at the optimum working temper-
ature. The linear relationship between the response and the gas
concentrations suggests that the sensor response exhibits a good
dependence on the gas concentrations.
Fig. 3. Selected area diffraction pattern of Zn1
xCoxAl2O4 powders with (a) x ¼ 0 and For metal-oxide semiconductor based sensors, the change in
(b) x ¼ 0.6.
resistance is mainly caused by the adsorption and desorption of
oxygen on the surface of sensing materials. When the Zn1
xCox-
The sensing characteristics indicate that the sensor element Al2O4 sensing material is exposed to air, it interacts with the oxygen
exhibited the better response to 100 ppm C2H5OH at 175  C as by transferring the electrons from the valence band to adsorbed
compared to other tested reducing gases. The effect of Co addition
on gas-sensing properties of Zn1
xCoxAl2O4 towards 100 ppm
30
C2H5OH is shown in Fig. 6. The results demonstrate that the sensor ZnAl2O4
Zn0.8Co0.2Al2O4
(f) 25 Zn0.6Co0.4Al2O4
Zn0.4Co0.6Al2O4
Zn0.2Co0.8Al2O4
(e) 20
CoAl2O4
Sensor Response
Transmittance (%)

(d)
15

(c)
10

(b)

5
(a)

0
0 50 100 150 200 250 300 350
4000 3500 3000 2500 2000 1500 1000 500
0
wavenumber cm Operating Temperature ( C )

Fig. 4. FT-IR spectra of (a) ZnAl2O4, (b) Zn0.8Co0.2Al2O4, (c) Zn0.6Co0.4Al2O4, (d) Fig. 6. Sensor response of Zn1
xCoxAl2O4 (x ¼ 0, 0.2, 0.4, 0.6, 0.8 and 1.0) to 100 ppm
Zn0.4Co0.6Al2O4, (e) Zn0.2Co0.8Al2O4 and (f) CoAl2O4 samples calcinated at 700  C. C2H5OH as a function of operating temperature.
 S.D. Kapse et al. / Current Applied Physics 12 (2012) 307e312 311

35 Alcohols are easily oxidized to aldehyde and when the alcohol

vapors comes into contact with the surface oxygen ions of the
30 oxide surface, it reacts with either O
or O
2 ions and gets oxidized
to aldehyde and water and liberates electrons which actually
25
causes the conductivity to increase, and desorption of weakly
bound RCHO from the surface provides a new vacant sites for the
Sensor Response

surface approaching alcohol molecules. Furthermore, we know

20
that the properties of gas-sensing materials are related to their
grain size, and nano-material shows a high sensitivity because of
15
its small grain size, high specific surface area, high surface atomic
activity, and so on. Therefore, Zn0.4Co0.6Al2O4 exhibited grater
10 response to ethanol vapors owing to smaller grain size, lower
activation energy and larger surface area that results in greater
5 oxygen adsorption and higher sensitivity than the other tested
composites.
0 For the reaction to proceed to the right hand side, some amount
0 50 100 150 200 250 300 of activation energy has to be supplied thermally. An increase in
C2H5OH Concentration (ppm) operating temperature increases the thermal energy and the
reducing gas like ethanol vapors donates electrons to the
Fig. 7. The response vs. C2H5OH concentration of Zn0.4Co0.6Al2O4 sensor element at composite. Therefore the resistance decreases and the gas response
150  C. increases with operating temperature. The point at which the gas
response reaches maximum is the actual thermal energy needed
for the reaction to proceed. However, the response decreases at
oxygen atoms, forming ionic species such as O


2 , O or O
2

as higher operating temperatures, as the oxygen adsorbates are des-
illustrated below. orbed from the surface of the sensor. Also, at higher temperatures,
the carrier concentration increases due to intrinsic thermal exci-
O2 ðgasÞ4O2 ðadsÞ (1)
tation. This is possibly one of the reasons for the decreased gas
response at high temperatures [26]. As the species are desorbed
O2 ðadsÞ þ e
4O

2 ðadsÞ (2) from the oxide surface, oxygen is adsorbed again at the vacant sites
as shown in Equation (9).
O



2 ðadsÞ þ e 42O ðadsÞ (3) Furthermore, the response of Zn0.4Co0.6Al2O4 was tested
towards LPG, NH3, H2, C2H5OH and H2S at optimal operating

temperature. It can be seen from Fig. 8 that the Zn0.4Co0.6Al2O4
O
ðadsÞ þ e
4O2 ðadsÞ (4)
based sensor elements exhibits maximum response to C2H5OH gas
The more the oxygen ions are on the surface, the higher the at 150  C. The sensors demonstrated good selectivity for C2H5OH
potential barrier and therefore the higher the resistance [30]. among all other tested gases.
However, when the sensors are exposed to reducing gas, the It is well known that the sensing mechanism of semiconductor
depleted electrons are released back to conduction band, which gas sensor materials is a surface controlled process. The adsorption
results in a sharp change in the resistance of the sensors. Thus, the of test gases, which depends on the type of gas and the sensor
sensors exhibit high response. At relatively low operating temper- material, might affect both response and recovery characteristics.
ature, the sensing layer surface preferentially adsorbs O
2 and as The response and recovery times are the important parameters of
a result of that the sensitivity of the material is little. As the oper- gas sensors. To obtain the response and recovery time, the requisite
ating temperature increases the adsorption of O
become the amount of gas was injected in the test chamber keeping the sensor
dominant process and consequently the sensitivity of the material at the optimal operating temperature. The Fig. 9 demonstrated the
increases [31,32]. response and recovery characteristics for Zn0.4Co0.6Al2O4 (the
The reducing gas R acting on the Zn1
xCoxAl2O4 surface can be
described as: 30

RðgasÞ4RðadsÞ (5)
25

O



2 ðadsÞ þ e 42O ðadsÞ (6)
20
RðgasÞ þ O
ðadsÞ4RðadsÞ þ e

Sensor response

(7)
The improved response towards ethanol can be explained by the 15
involvement of the OH
hydroxyl group. When the aluminate
sensor is exposed to ethanol vapor, the OH
group reacts with
10
chemisorbed oxygen on the sensor surface, generating free elec-
trons, which decrease the resistance of the aluminate. The reactions
involved during the ethanol vapor sensing are summarised below 5
(taking O
and C2H5O for example) [33]:

C2 H5 OHðgÞ þ O
ðadsÞ/CH3 CHOðadsÞ þ H2 OðgÞ þ e
(8) 0

LPG H2 NH3 C2H5OH H2S


CH3 CHO ðadsÞ/CH3 CHOðgÞ þ vacant sites (9) Fig. 8. Sensor response of Zn0.4Co0.6Al2O4to different reducing gases at 150  C.
312 S.D. Kapse et al. / Current Applied Physics 12 (2012) 307e312

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