Please cite this article in press as: N. Van Hieu, et al., Gas-sensing properties of tin oxide doped with metal oxides and carbon nanotubes: A competitive sensor for ethanol and liquid petroleum gas, Sens. Actuators B: Chem. (2009), doi:10.1016/j.snb.2009.03.043 ARTICLE IN PRESS G Model SNB-11453; No.of Pages7 Sensors and Actuators B xxx (2009) xxx–xxx Contents lists available at ScienceDirect Sensors and Actuators B: Chemical journal homepage: www.elsevier.com/locate/snb Gas-sensing properties of tin oxide doped with metal oxides and carbon nanotubes: A competitive sensor for ethanol and liquid petroleum gas Nguyen Van Hieu a,∗ , Nguyen Anh Phuc Duc b , Tran Trung c , Mai Anh Tuan a , Nguyen Duc Chien b a International Training Institute for Materials Science (ITIMS), Hanoi University of Technology (HUT), No. 1 Dai Co Viet Road, Hanoi, Viet Nam b Institute of Engineering Physics, Hanoi University of Technology, Hanoi, Viet Nam c Faculty of Environment and Chemistry, Hung Yen University of Technology and Education, Hung Yen, Viet Nam article info Article history: Available online xxx Keywords: Gas sensor Tin oxide Carbon nanotubes abstract SnO 2 doped with metal oxides such as PtO 2 , PdO, La 2 O 3 CuO, and Fe 2 O 3 and multi-walled carbon nan- otubes (MWCNTs) thin films were prepared by the sol–gel method. Thin film gas sensors were fabricated by spin-coating the sol onto interdigitated microelectrodes. The microstructure and morphology of the materials were characterized by XRD, FE-SEM, and TEM. The results reveal that their SnO 2 particle size is lower than 10nm, and the MWCNTs doping is well embedded in the SnO 2 matrix. The response of all the sensors was studied for different concentrations of ethanol and liquid petroleum gases (LPG) and at different operating temperatures. Comparative results reveal that the (1 wt%) PtO 2 -doped SnO 2 sensor exhibits higher sensitivity to ethanol gas and LPG than the sensors doped with the other dopants. Espe- cially, the (1 wt%) PtO 2 -doped SnO 2 sensor shows higher selectivity to ethanol gas over LPG, while the (0.1wt%, 20 <d < 40 nm)-doped SnO 2 shows higher selectivity to LPG over ethanol gas in the same testing conditions. © 2009 Elsevier B.V. All rights reserved. 1. Introduction The hybrid materials made of semiconductor metal oxides (SMO) such as TiO 2 , SnO 2 and WO 3 and carbon nanotubes (CNTs) have been given much attention in recent year for their various applications such as photocatalysis, anode material for lithium- ion batteries and gas sensor [1–14]. The nanoarchitectures forming hybrid materials between SMO and CNTs have been conducted in different ways such as SMO/CNTs composite [1–5], SMO-coated CNTs [6–8], SMO-filled CNTs [9] and CNTs-doped SMO [10–14]. The special geometries and properties of the hybrid materials facilitate their great potential applications as high-performance gas sensors. Previous works have demonstrated that the hybrid materials can be used to detect various gases such as NH 3 ,NO 2 ,H 2 , CO, LPG, and ethanol [4–6,10–14]. These works also reported that the hybrid materials gas sensors have a better performance compared to the sensors used SMO as well as CNTs as sensing materials. Interest- ingly, the composite SnO 2 /CNTs and the CNTs-doped SnO 2 sensors respond to NH 3 and NO 2 at room temperature, respectively [4,10]. This would reduce considerably the power consumption of the ∗ Corresponding author. Tel.: +84 4 38680787; fax: +84 4 38692963. E-mail addresses: hieu@itims.edu.vn, hieunv-itims@mail.hut.edu.vn (N. Van Hieu). sensing-device. The CNTs are hollow nanotube and p-type semi- conductor, therefore the enhancement of the sensing performance of the sensors based on CNTs/SnO 2 hybrid materials in comparison with the sensorsbased on the separated materials was attributed to additional nanochannel for gas diffusion and p/n junctions formed by CNTs and SnO 2 . These mechanisms were previously represented in [4,5,10]. Ethanol gas sensors are extensively used for the control of drunken driving and monitoring of fermentation and other pro- cesses inchemical industries, whileLPG sensorsare frequently used in the detection of the gas leakages to prevent accidental explo- sion. The development of ethanol gas and LPG sensors based on SnO 2 thin film technology offers great advantages such as high sensitivity, fast response, and low cost. Therefore, much effort has been devoted to improve its sensitivity and selectivity by intro- ducing various dopants such as PtO 2 , CdO, La 2 O 3 , PdO, SiO 2 , and RuO 2 [16–31] or by mixing with other metal oxides such as Nb 2 O 3 , Fe 2 O 3 , andZrO 2 [23,32,33]. It was found thatamong additives, SnO 2 sensors doped with La 2 O 3 and CdO showed good performance to ethanol gas [17–19], while the Pd-, Pt- and RuO 2 -doped SnO 2 sen- sors showed good performance to LPG [20,24]. In this paper, for the first time, we study and compare the performance of various metal oxides-doped SnO 2 and MWCNTs-doped SnO 2 sensors for the detection of ethanol gas and LPG. In the later, the MWCNTs with different diameters were used for the doping. 0925-4005/$ – see front matter © 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.snb.2009.03.043 Please cite this article in press as: N. Van Hieu, et al., Gas-sensing properties of tin oxide doped with metal oxides and carbon nanotubes: A competitive sensor for ethanol and liquid petroleum gas, Sens. Actuators B: Chem. (2009), doi:10.1016/j.snb.2009.03.043 ARTICLE IN PRESS G Model SNB-11453; No.of Pages7 2 N. Van Hieu et al. / Sensors and Actuators B xxx (2009) xxx–xxx Fig. 1. XRD pattern of typical SnO 2 thin film heat-treated at 500 (a), 600 (b), and 700 ◦ C (c). 2. Experimental Stannic acid gel was synthesized by hydrolyzing 0.2 M solution of tin chloride (SnCl 4 ) with ammonia, using the following reaction at room temperature: SnCl 4 + 4NH 4 OH → SnO 2 ·nH 2 O + 4NH 4 Cl + (2 − n)H 2 O (1) The resulting precipitate was washed thoroughly by repeating the procedures of suspending the gel into deionized water and collect- ing it back by filtration to remove Cl − . The SnO 2 gel was suspended in an aqueous ammonia solution (pH 10.5) and followed by stir- ring for 2 h, with a calculated amount of SnO 2 gelinorderto achieve5 equivalent wt%SnO 2 sol–gel solution.The suspensionwas transferred to a Teflon-lined stainless steel autoclave and treated hydrothermally at 200 ◦ C for 10 h. The 1 equivalent wt% CuO-, Fe 2 O 3 -, La 2 O 3 -, and PtO 2 -99 wt% SnO 2 sols were prepared by mix- ing the required amount of dissolutions of Cu(NO 3 ) 2 , Fe(NO 3 ) 3 , La(NO 3 ) 3 and PtCl 4 (0.1M) to the pure SnO 2 sol. Functionalized MWCNTs with different diameters (d <10nm, d =20–40 nm, and d =60–100 nm) were used for the fabrication of the MWCNTs-doped SnO 2 sensors with a calculated amount of the MWCNTs in order to achieve 0.1 equivalent wt% MWCNTs–99.9 wt% SnO 2 sol. The MWCNTs were functionalized by using a typical pro- cedure described as follows: 200 mg MWCNTs were suspended in 35 mL concentrated nitric acid (15 M) and refluxed for 12 h in a silicone oil bath maintained at 140 ◦ C to modify the MWCNTs sur- face, they were then rinsed with distilled H 2 O until the pH of the solution was neutral, and finally they were dried at 80 ◦ C in vac- uum oven. The immersion-probe ultrasonic generator with a high power up to 500 W (Model VC-505, Sonics, US) was used for disper- sion of MWCNTs in SnO 2 sol. The morphology and the crystalline phase ofthe filmswerecharacterized byusing afield emissionscan- ning electron microscope (FE-SEM; 4800 Hitachi, Japan) and X-ray diffraction (XRD, Philips XPert Pro), respectively. The dispersion of the MWCNTs in theSnO 2 sol was characterized by TEM usinga JEM- 100cx instrument with an accelerating voltage of 80 kV. The details on the gas sensor fabrication and characterization were describe d in our previous works [4,14]. All sensors were tested with various concentrations of ethanol gas (100–1000 ppm) and LPG (0.1–1% or 1000–10,000 ppm), and with different operating temperatures Fig. 2. TEM image of SnO 2 nanoparticles (a); FE-SEM image of a SnO 2 thin film heat-treated at 500 ◦ C (b); TEM image of an MWCNTs-doped SnO 2 sol (c); FE-SEM image of an MWCNTs-doped SnO 2 (d). Please cite this article in press as: N. Van Hieu, et al., Gas-sensing properties of tin oxide doped with metal oxides and carbon nanotubes: A competitive sensor for ethanol and liquid petroleum gas, Sens. Actuators B: Chem. (2009), doi:10.1016/j.snb.2009.03.043 ARTICLE IN PRESS G Model SNB-11453; No.of Pages7 N. Van Hieu et al. / Sensors and Actuators B xxx (2009) xxx–xxx 3 Fig. 3. Response of PtO 2 ,Fe 2 O 3 ,La 2 O 3 , and CuO-doped SnO 2 sensors to 2500 ppm (0.25%) LPG in air (a) and 250 ppm ethanol gas in air (b); the response to ethanol gas (250 ppm) and LPG (2500 ppm) of (1 wt%) a PtO 2 -doped SnO 2 sensor (c); step wise decrease in electrical resistance obtained with a increase in ethanol concentration from air to 1000 ppm ethanol gas in air for (1wt%) PtO 2 -doped SnO 2 sensor operating at 240 ◦ C; (e) the sensor response versus ethanol gas concentration. (190, 220, 240, 260, 290, 320, 340, and 360 ◦ C). It should be noted that technological application requires the ethanol and LPG sensor to be able to detect at least 200 ppm alcohol (∼0.6g/L in the human blood) and 0.24% (2400 ppm) LPG (lowest explosive level). Hence, our gas-concentration range to be tested is within levels. 3. Results and discussion Fig. 1a–c shows the XRD patterns of the SnO 2 samples after the heat-treatment at temperatures of 500, 600, and 700 ◦ C, respec- tively. The XRD characterization was also carried out with the MWCNTs-doped SnO 2 samples (not shown), but we observed no differences. This is attributed to the use of very low doping con- tent of MWCNT and the well-embedded MWCNTs in SnO 2 matrix, which have already been reported in the literature [1,3,4,7].Itcan be seen that the heat-treated samples are well crystallized with all diffraction peaks which can be well indexed to the tetragonal rutile structure of SnO 2 . The broad and well-defined reflections were observed at 2Â =26.51, 33.67 and 51.78 corresponding to (11 0), (1 01) and (21 1) planes, respectively, in the XRD spectrum of the annealed SnO 2 thin films, which are in good agreement with the previously reported [20,21], confirmingthe formation ofa polycrys- talline SnO 2 thin film. The estimated value of the lattice constants were found to be a = b = 4.734Å and c = 3.185 Å (JCPDS 21-1250). The value of the crystallite size of the heat-treated SnO 2 thin film was estimated by fitting the width of (1 1 0) reflection using Scherrer formula d=K/ˇcos Â, where K is 0.94,  is the X-ray wavelength, ˇ the peak full width half maxima (FWHM) and, Â is the diffraction peak position. The roughly estimated values of crystallite size of the sam- ples heat-treated at 500, 600, and 700 ◦ C are found to be about 5.8, 6.2, and 7.1 nm, respectively. This indicated that the crystallite sizes do not significantly vary for heat-treating temperature rang- ing from 500 to 700 ◦ C. Actually, we have already investigated the gas-sensing properties of blank SnO 2 films heat-treated at these temperatures, and we have obtained similar responses to ethanol gas and LPG (not shown here). Therefore, these characterizations are in order to choose right heat-treated temperature for metal oxides- and MWCNTs-doped SnO 2 thin films. In addition, it is well known that MWCNTs materials can be burned out at heat-treated temperatures higher than 550 ◦ C. Fig. 4. Response as a function of operating temperature of the PtO 2 -doped SnO 2 sensors with varying PtO 2 doping content. Please cite this article in press as: N. Van Hieu, et al., Gas-sensing properties of tin oxide doped with metal oxides and carbon nanotubes: A competitive sensor for ethanol and liquid petroleum gas, Sens. Actuators B: Chem. (2009), doi:10.1016/j.snb.2009.03.043 ARTICLE IN PRESS G Model SNB-11453; No.of Pages7 4 N. Van Hieu et al. / Sensors and Actuators B xxx (2009) xxx–xxx Fig. 5. Response of (0.1wt%) MWCNTs (with d < 10 nm; 20 nm < d < 40 nm; 60 nm < d < 100 nm) -doped SnO 2 sensors to 2500 ppm (0.25%) LPG in air (a) and 250 ppm ethanol gas in air (b); response to ethanol gas (250 ppm) and LPG (2500 ppm) of (0.1 wt%, 10 nm < d < 20 nm) MWCNTs-doped SnO 2 sensor (c); step wise decrease in electrical resistance obtained with an increase in LPG concentration from air to 10000ppm (1%) LPG in air for (0.1wt%, 10 nm < d< 20 nm) MWCNTs-doped SnO 2 sensor operating at 240 ◦ C; (e) the sensor response versus LPG concentration. The particle size and morphology of the SnO 2 thin film charac- terized further by TEM and FE-SEM are shown in Fig. 2. The TEM image (Fig. 2a) shows that the particle size is quite homogenous in the range of 4–8 nm. The FE-SEM image (Fig. 2b) shows the mor- phology of the SnO 2 thin film treated at 500 ◦ C. It is shown that the particle size is smaller than 10 nm. The MWCNTs-doped SnO 2 sample was characterized by TEM and FE-SEM as shown in Fig. 2c and d, respectively. Fig. 2c shows the TEM image of the MWCNTs- dispersed SnO 2 sol in which the black materials absorbed onto the wall of the functionalized MWCNTs were believed to be SnO 2 nanoparticles from the SnO 2 sol. This is because it was recognized that the MWCNTs-SnO 2 bonding can be formed naturally through some physicochemical interactions such as Van der Waals force, H bonding and other bonds. For example, the OH group on SnO 2 may possibly react with the OH and COOH groups on the functional- ized MWCNTs in removing the H 2 O contained in the wet material, and thus the bonding C O Sn or O C O Sn might form through the dehydration reaction that happens among the groups on the two materials. However, this was not strongly explained and more intensive studies are needed to confirm this. The absorbed SnO 2 on the MWCNTs would grow up and enclose the MWCNTs during the heat-treatment. This observation was consistent with previous reports [1–3]. Fig. 2d shows the FE-SEM image of the MWCNTs- doped SnO 2 film after heat-treatment at 500 ◦ C. It can be seen that the MWCNTs are well encapsulated with a SnO 2 matrix and is still present after the heat-treatment at 500 ◦ C. The sensing characteristics of (1 wt%) metal oxides (PtO 2 ,Fe 2 O 3 , CuO, La 2 O 3 )-doped sensors to ethanol gas and LPG have indicated in Fig. 3. The sensor responses as a function of operating tempera- ture to LPG and ethanol gas are respectively shown in Fig. 3a and b. It seems that the optimized operating temperatures of the sensor to ethanol gas and LPG are around 350 and 250 ◦ C, respectively. It can be recognized that all the metal oxides-doped SnO 2 sen- sors show an improvement in their response to ethanol gas, while only CuO, PtO 2 , and La 2 O 3 -doped sensors show an improvement in the sensor response to LPG compared with undoped SnO 2 sen- sors. However, this also depends on the operating temperature to be selected. These observations are consistent and have been rea- sonably explained in the literature [30,31]. Our experimental data show that (1 wt%) the PtO 2 -doped sensor has a better sensitivity to ethanol gas and LPG as compared to that of the sensors doped with the other dopants. For instance, at the operating temperature of 240 ◦ C, the response to 250 ppm ethanol gas and 2500 ppm (0.25%) LPG is around 101.9 and 2.1, respectively. These values are compa- rable with the data reported in the literature [17–20,31].Wehave plotted the responses to ethanol gas (250 ppm) and LPG(2500 ppm) of the (1 wt%) PtO 2 -doped SnO 2 sensor as depicted in Fig. 3c. It can be seen that the sensor has relatively good selectivity to ethanol gas over LPG. Fig. 3d shows the electrical resistance variations obtained with several steps of different ethanol concentration from air to 1000 ppm ethanol in air for the (1 wt%) PtO 2 -doped SnO 2 sensor at an operating temperature of 240 ◦ C. As can be seen, upon switching on ethanol gas, the film reaches the saturated resistance R g in 50 s and at the end of the injection cycle, when dry air is introduced, its electrical resistance returns to the original value (R a ). This fact is a proof of the reversibilityof theprocess. Thestepwise decrease of the electrical resistance of the film is very consistent with an increas- ing amount of ethanol oxidation. Greater ethanol oxidation caused the introduction of more electrons into the SnO 2 surface and the film became less resistive. Fig. 3e depicts the correlation between the ethanol gas concentration and the response of the (1 wt%) PtO 2 - doped SnO 2 sensor.It seemsthat the correlation lines were not good linear for such broad ethanol concentration (100–1000 ppm). How- ever, for practical applications of this sensor, the linear fit can be Please cite this article in press as: N. Van Hieu, et al., Gas-sensing properties of tin oxide doped with metal oxides and carbon nanotubes: A competitive sensor for ethanol and liquid petroleum gas, Sens. Actuators B: Chem. (2009), doi:10.1016/j.snb.2009.03.043 ARTICLE IN PRESS G Model SNB-11453; No.of Pages7 N. Van Hieu et al. / Sensors and Actuators B xxx (2009) xxx–xxx 5 well made between the sensor response and ethanol concentration for narrower ethanol concentration ranges (e.g. 100–500 ppm and 500–1000 ppm). The linear dependent of the ethanol concentration on the sensor response of our PtO 2 -doped SnO 2 sensor for the nar- row ethanol concentration range is consistent with that previous reported [17,18]. Indeed, we have studied further the sensing properties of the PtO 2 -doped SnO 2 sensors, in which the PtO 2 doping content was varied from 0.2 to 2 wt% in comparison with SnO 2 weight. The sens- ing characteristics of these sensors were measured with 250 ppm ethanol at different operating temperatures, and the results are shown in Fig. 4. It can be seen that the (1 wt%) PtO 2 -doped SnO 2 sensor shows a higher response. From this, it can be concluded that the PtO 2 doping content of 1 wt% is the optimal value. The 90% response time for gas exposure (t 90%(air-to-gas) ) and that for recovery (t 90%(gas-to-air) ) were calculated from the resistance- time data shown in Fig. 3d. The t 90%(air-to-gas) values are around 23 s, while the t 90%(gas-to-air) value is around 46 s. These results are quite comparable with those of SnO 2 -based sensors reported previously [17–20]. Recently, hybrid CNTs/SnO 2 sensors have been extensively investigated. Therefore, for comparison with metal oxides-doped SnO 2 sensors, we have prepared and characterized MWCNTs-doped SnO 2 sensors in the same route as metal oxides-doped sensors in this work. Fig. 5 shows the sensing characteristics of SnO 2 sensors doped with different kinds of MWCNTs. It can be recognized that the responses to ethanol gas and LPG of all MWCNTs-doped SnO 2 sensors are improved at a low region of operating temperature. This observation is consistent with previously reported data for the hybrid sensors of CNTs/SMO [5,7,11,13,14]. To explain this, we speculate that it may result from the fact that the doping of MWC- NTs in the SnO 2 matrix can introduce nanochannels and additional hetero-junction between SnO 2 (n-type) and CNTs (p-type). Both these effects do not cause the response improvement of the hybrid MWCNTs-doped sensor athigh operatingtemperatures because the nanochannels formed by the MWCNTs may not play any role for gas diffusion into the SnO 2 matrix at a high operating temperature. Otherwise, we believe that SnO 2 (n-type)/MWCNTs (p-type) can not functionalize well at a temperature higher than 350 ◦ C due to the transition from semiconductor behavior to metallic one of the CNTs. More detail on this mechanism can be found further in recent worksby us andothers [4,5,10,14]. Additionally,it also observed that the effect of MWCNTs on the response of the MWCNTs-doped SnO 2 sensors is not significant in the detection of LPG and ethanol gas. It seems that (d = 10–20 nm) MWCNTs-doped SnO 2 sensors have bet- ter performance to LPG and ethanolgas atan operatingtemperature range of 280–350 ◦ C. The specific surface area (SSA) of MWCNTs with diameter of <10, 20-40 nm and 60–100 nm were 242.2, 112.2, and 45.2m 2 /g, respec- tively. In principle,the material with ahigher SSA would have better gas response. However, we have observed that the doping content is so small that it could not affect the SSA of the MWCNTs-doped SnO 2 materials. Thus, the SSA factor cannot be a piece of evidence on the difference in the sensor response. The observed effect can be explained by the fact that the MWCNTs embedded in SnO 2 behave as nanochannels for the gas diffusion in the SnO 2 bulk material. However, a larger diameter of MWCNTS (e.g. d = 60–100 nm) can result in the decrease of sensor response because such larger diam- eter of MWCNTs could not be well embedded in the SnO 2 matrix, and they begin to connect together, resulting in a shorter resistance path of the MWCNTs-doped SnO 2 sensors. From Fig. 5c, we can see that MWCNTs-doped SnO 2 sensors are more selective to LPG than to ethanol gas at an operating tem- perature range of 280–350 ◦ C. This effect is completely different with the metal oxides-doped SnO 2 sensors (see Fig. 3c) that will be discussed further in the next paragraph. Fig. 5d depicts the Fig. 6. Response of an undoped SnO 2 sensor to 250 ppm ethanol and 2500 ppm (0.25%) LPG in air operating at a temperature range from 190 to 360 ◦ C. electrical resistance variations obtained with several steps of dif- ferent LPG concentration from air to 1% LPG in air for the (0.1wt%, 20 < d < 40 nm) MWCNTs-doped SnO 2 sensor operating at 320 ◦ C. Similar to the PtO 2 -doped SnO 2 sensors in the detection of ethanol, the MWCNTs-doped SnO 2 sensors shows a good reversibility in the detection of LPG and the stepwise decrease of electrical resistiv- ity of the MWCNTs-doped SnO 2 film is very consistent with the increasing amount of LPG oxidation. More LPG oxidation caused the introduction of more electrons into the SnO 2 surface and the film became less resistive. Fig. 5e depicts the variation of response with LPG concentration in air for the MWCNTs-doped SnO 2 sensors at an operating temperature of 320 ◦ C. It can be observed that the response does not increase linearly for the concentration range of 0.1–0.6% (1000–6000 ppm). It seems that the response tends to sat- urate for an LPG concentration higher than 0.5% (5000 ppm). This can be attributed to the fact that there would be an insufficient number of oxygen anions available on the surface of the MWCNTs- doped SnO 2 materials for reaction with LPG. The 90% response time for gas exposure (t 90%(air-to-gas) ) and that for recovery (t 90%(gas-to-air) ) were calculated from the resistance- time data shown in Fig. 5d. The t 90%(air-to-gas) value is around 21 s, while the t 90%(gas-to-air) value is around 36 s. It can be seen that the response times of the Pt- and MWCNTs-doped SnO 2 sensors are similar, while the recovery time of the MWCNTs-doped sensor is relatively shorter than that of the PtO 2 -doped SnO 2 sensors. This could be attributed to the formation of the nanochannels in SnO 2 materials by doping CNTs that can enhance the diffusion in and out of the gas molecules. To study the effect of MWCNTs doping on the sensing proper- ties to ethanol gas and LPG, we plotted the response of undoped SnO 2 sensor to 250 ppm ethanol gas and 2500 ppm (0.25%) LPG as shown in Fig. 6. It is indicated that the response of undoped SnO 2 sensors to 250 ppm ethanol gas is higher than that to 2500 ppm (0.25%) LPG over an operating temperature range of 190–360 ◦ C. Therefore, this points out that the higher response of the MWCNTs- doped SnO 2 sensors to LPG than to ethanol can be attributed to the MWCNTs doping. This is an interesting finding that cannot yet be clearly explained as of now. The pure SnO 2 sensor is more sensitive to ethanol than LPG even though the ethanol gas concentration is about 10 times lower than the LPG concentration. This has alsobeen explored in previous works [15]. The sensing mechanism of the ethanol and LPG has long been known and widely adopted in pre- vious reports [24–30]. However, to explain why the ethanol is more sensitive than LPG, even though the former has a lower concentra- tion than the later, is still unclear. It has long been known that there Please cite this article in press as: N. Van Hieu, et al., Gas-sensing properties of tin oxide doped with metal oxides and carbon nanotubes: A competitive sensor for ethanol and liquid petroleum gas, Sens. Actuators B: Chem. (2009), doi:10.1016/j.snb.2009.03.043 ARTICLE IN PRESS G Model SNB-11453; No.of Pages7 6 N. Van Hieu et al. / Sensors and Actuators B xxx (2009) xxx–xxx is a dehydrogenation step in the reaction between ethanol/LPG and SnO 2 surface at elevated temperatures, and they can be described as [25,30]: Ethanol dehydrogenation 2CH 3 CH 2 OH + O 2 − → 2CH 3 CHO + H 2 O + e (2) LPG dehydrogenation 2CH 3 CH 2 CH 3 + O 2 − → 2CH 3 CH 2 CHO + H 2 O + e (3) 2CH 4 CH 2 CH 2 CH 3 + O 2 − → 2CH 4 CH 2 CH 2 CHO + H 2 O + e (4) 2CH 3 CHCH 2 + O 2 − → 2CH 3 CHCO + H 2 O + e (5) It should be noted that the main constituent of LPG is propane (∼85% by liquid volume), butane (∼2.5% by liquid volume) and propene (∼5% by liquid volume). Among these constituents, propane and butane are m ore stable than propene, which is an unsymmetrical alkene containing a double bond. Thus, propene is more prone to hydrogenation than to the dehydrogenation, which can be used to compare with the dehydrogenation of ethanol gas. For 2500 ppm LPG, the propene concentration can be estimated to be about 125 ppm. This is the reason why the response of the SnO 2 sensors to 2500 ppm LPG is lower than that of 250 ppm ethanol gas. It has been reported that the MWCNTs-doped SnO 2 sensors show a better performance compared with undoped SnO 2 sen- sor. In our case, for ethanol detection, the response of the (0.1 wt, 20 <d < 40 nm) MWCNTs-doped SnO 2 sensors (∼12.3 for 250ppm at 260 ◦ C, see Fig. 5b) is about three times higher than that of the undoped SnO 2 sensor (∼3.4 for 250 ppm at 260 ◦ C, see Fig. 5b). The reason for this was previously explained in detail [4,5,10,14]. The question to raise here is that why the MWCNTs-doped SnO 2 is more sensitive to 2500 ppm LPG than to 250 ppm ethanol as depicted in Fig. 5c. Further intensiveinvestigationshould be done to understand this phenomenonmore comprehensively.The plausible explanation for the observed effect can be based are as follows: (i) the MWCNTs are hollow nanotubes that gas absorption could occur in the inside andoutside of theMWCNTs[34], (ii) themethane (CH 4 ) molecules (e.g. propane and butane) can be physically adsorbed on the outgassed nanotubes (i.e., nanotube after oxygen exposure) [35], and (iii) the oxygen molecules are strongly adsorbed on the defective sites of MWCNTs (adsorption energy is about 0.32 eV) [36] that can serve as a reactive gas for the oxidation reactions of LPG. These reasons can enhance Reactions (3) and (4). Additionally, the consumption of the adsorbed oxygen can affect the electrical prop- erties of the MWCNTs [36,37], and the electrical resistance of the MWCNTs-doped SnO 2 film can be consequently changed. 4. Conclusion We have systematically investigated and compared the perfor- mance of metal oxide- and MWCNTs-doped SnO 2 thin film sensors to LPG andethanol gas.We have found that the SnO 2 doped withthe 1 wt% PtO 2 sensor shows the highest response to ethanol gas and LPG compared with that of SnO 2 doped with the other dopants. Among carbon nanotubes-doped SnO 2 sensors, the sensor doped with 0.1 wt% MWCNTs with a diameter ranging from 20 to 40 nm exhibits the highest response to ethanol gas and LPG. An interesting finding is that the PtO 2 -doped SnO 2 sensor shows good selectivity to ethanol gas over LPG, while, the MWCNTs-doped SnO 2 sensor shows good selectivity to LPG over ethanol gas, at the same testing conditions. The gas-sensing mechanism of the hybrid sensor has been discussed. However, further study is needed to understand better the selectivity of the hybrid sensor to ethanol gas and LPG. Acknowledgments The work was supported by the National Foundation for Sci- ence and Technology Development (NAFOSTED) of Vietnam (for Basic Research Project: 2009-2012), the National Key Research Pro- gram for Materials Technology (Project No. KC 02-05/06-10), the research projects of Vietnam Ministry of Education and Training (Code B2008-01-217 and B2008-21-09) and Key basic research pro- gram for application orientation (2009-2012). References [1] M.H. Chen, Z.C. Huang, G.T. Wu, G.M. Zhu, J.K. You,Z.G. Lin, Synthesis and charac- terization of SnO–carbon nanotube composite as anode material for lithium-ion batteries, Mater. Res. Bull. 38 (2003) 831–836. [2] W. Wang, P. Serp, P. Kalck, J.L. Faria, Photocatalytic degradation of phenol on MWCNT and titania composite catalysts prepared by a modified sol–gel method, Appl. Catal. B: Environ. 56 (2004) 301–308. [3] Xie, K. 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Zettl, Extreme oxygen sensitivity of electronic properties of carbon nanotubes, Science 187 (2000) 1801–1804. Biographies Nguyen Van Hieu received his MSc degree from the International Training Institute for Materials Science (ITIMS), Hanoi University of Technology (HUT) in 1997 and PhD degree from the Department of Electrical Engineering, University of Twente, Nether- lands in 2004. Since 2004, he has been a research lecturer at the ITIMS. In 2007, he worked as a post-doctoral fellow at Korea University. His current research inter- ests include nanomaterials nanofabrications, characterizations and applications to electronic devices, gas sensors and biosensors. Nguyen Anh Phuc Duc received the BS degree in Engineering Physics from Institute of Engineering in Physics, Hanoi University of Technology, Vietnam in 2005, his MSc degree in Materials Science from the International Training Institute for Materials Science (ITIMS), Hanoi University of Technology (HUT) in 2007, and he is currently working toward his PhD degree at Leuven University, Belgium. His current research interests include oxide semiconductors nanoparticle for gas-sensing applications. Tran Trung received his MSc degree in 1994 and his PhD degree in 1998 from the Department of Electrochemistry, Hanoi University of Technology. In 2000 and 2001, he worked as a post-doctoral fellow in Pusan National University, Korea. At present he is working as an Associate Professor at the Faculty of Environment and Chemistry, Hung-Yen University of Technology and Education. His research activities are related with the design, fabrication and characterization of organic–inorganic hybrids and nanomaterials for application to electronic devices and battery systems. Mai Anh Tuan received his MSc degree from the International Training Institute for Material Science (ITIMS), Hanoi University of Technology (HUT) in 1999. In 2004, he completed his PhD program at Universite Claude Bernard Lyon 1, France. Since 2000, he has been working as a lecturer at ITIMS, HUT. He is now biosensor group- leader at ITIMS. His current research interests include biosensors for bio-medical and environmental application, functional materials and IC packaging technology (materials consideration). Nguyen Duc Chien received the engineering degree in Electronic Engineering at Leningrad Electrotechnical University, Russian, in 1976, and the MSc and PhD in Microelectronics at Grenoble Polytechnique University, France, in 1985 and 1988, respectively. He has been working as Professor at the Institute of Engineering Physics (IEP), Hanoi University of Technology (HUT). From 1989 to 1990 he worked as a vis- iting professor at the Grenoble University, France. From 1992 to 2006 he was a vice director of the International Training Institute for Materials Science (ITIMS), HUT, where he established the Laboratory of Microelectronics and Sensors. Since 2003 he has been the Director of the IEP, HUT. His research interests include: characteriza- tions and modeling of MOS devices, nanomaterials for chemical sensor, biosensor, optoelectronic materials and devices, and MEMS devices. He has been the leader of many national research projects related to microelectronic devices and functional nanomaterials. Dr Nguyen Duc Chien is also a member of Physics Society of Vietnam and the Vietnamese Materials Research Society. . Van Hieu, et al., Gas-sensing properties of tin oxide doped with metal oxides and carbon nanotubes: A competitive sensor for ethanol and liquid petroleum. www.elsevier.com/locate/snb Gas-sensing properties of tin oxide doped with metal oxides and carbon nanotubes: A competitive sensor for ethanol and liquid petroleum