Morphological and Moisture Sensing Studies of WO3-SnO2 Nanocomposites

N. K. Pandey1*, Akash Roy1, Karunesh Tiwari1, S .N. Pandey2, Anil Govindan3

Sensors and Materials Research Laboratory, Department of Physics, University of Lucknow, Lucknow-226007, Lucknow, Pin-226007, Uttar Pradesh, India. 2 Department of Physics, Motilal Nehru National Institute of Technology, Allahabad 211004, India 3 Department of Physics, Mahanand Mission Harijan (M.M.H.) College, Ghaziabad-201009, U.P., India. *Corresponding Author E-mail: nkp1371965@rediffmail.com;nkp1371965@gmail.com Phone:91-9415003998; fax:91-522-2740467
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Abstract This paper reports characterization and relative humidity sensing studies of WO3-SnO2 nanocomposite powder pellets obtained through solid-state reaction route. Resistance of the pellets is observed to decrease with increase in relative humidity in the 15 to 90% range. Sensing element with WO3-SnO2 weight % ratio 90:10 shows maximum value of sensitivity of 29.15 M/%RH in the 15 to 90% relative humidity range. The hysteresis is less than 1% for this sample. This sample shows the least ageing effect after 4 and 6 months. The response and recovery times of this sensing element are 86 s and 378 s respectively. Keywords: WO3, SnO2, nanocomposite, humidity sensor, activation energy.

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Introduction Research has been going on to find suitable materials that show good sensitivity over

large range of relative humidity (RH), low hysteresis and properties that are stable to thermal cycling and exposure to the various chemicals likely to be present in the environment. Ceramic humidity sensors, particularly those based on porous and sintered metal oxides have been attracting attention due to their chemical and physical stability and mechanical strength. These materials possess a unique structure consisting of grains, grain boundary surfaces and pores, which make them suitable for this kind of sensors [1-4]. Many oxides such as SnO2, ZnO, TiO2, ZrO2 and SiO2 are being studied for the development of humidity sensors. A. B. Glot et al have studied the electronic properties of SnO2based ceramics with double function of varistor and humidity sensor. In this work, the tin dioxide based varistor ceramics SnO2-Co3O4-Nb2O5-Cr2O3-xCuO (x=0; 0.05; 0.1 and 0.5) were made and their electrical properties studied. Observed varistor and humidity-sensitive properties are explained by grain-boundary barrier concept, as a decrease of the barrier height with electric field or relative humidity [5]. V. Jeseentharani et al have investigated humidity sensing

properties of the composites prepared by mixing 1:1 mole ratio of CuO-ZnO, CuO-NiO, and NiO-ZnO compound and sintered at 800C for 5 hours. Among the three composites, CuO-NiO compound possessed the highest humidity sensitivity. The response and recovery times of the CuO-NiO composites were 80 s and 650 s respectively [6]. S.P. Yawale et al have doped semiconducting materials SnO2 and ZnO with TiO2 and Al2O3 and screen printed them in the form of a film. DC-electrical resistance of the films has been measured in the presence of humidity. They have found SnO2 5 mol % Al2O3 and ZnO 5 mol % Al2O3 to be good sensing materials for humidity [7]. B.C. Yadav et al have reported moisture sensing properties of

niobium penta oxide, neodymium oxide and lanthanum oxides in the form of pellets for annealing temperatures 200C and 400C. Variation in DC-electrical resistance with the relative humidity was recorded for each annealing temperature. They have reported lanthanum oxide to have the highest sensitivity. They have reported results to be reproducible within 5% error under vigorous stirring [8]. B.C. Yadav et al have synthesized, pelletized and then annealed nanocomposite ZnOTiO2 for 3 h at 150C, 300C, 450C and 550C. The pellet sample has exhibited its highest average sensitivity of 18 M/%RH from 10 to 95% RH, at room temperature [9]. Weon-Pil Tai et al measured resistances of AZ/TiO2 and TiO2/AZ thin films for investigating humidity sensing property. Bilayered TiO2/AZ film showed low hysteresis and high sensitivity and three-orders change in the resistance during the relative humidity variation of 3090% [10]. Tungsten trioxide (WO3), which is a wide band-gap n-type semiconductor and considered as a promising sensing material of solid-state semiconductor gas sensors, has turned out to be an interesting material for humidity sensing applications. Suman Pokhrel et al have reported the electrical and humidity sensing properties of Cr2O3-WO3 composites. Cr2O3-WO3 composites were made by mixing Cr2O3 and WO3 in different molar ratio and pressed at 100 M Pa to form cylindrical pellets and sintered at temperature range 373673 K and then humidity sensing properties studied. Cr2O3-WO3 composite in 1:4 molar ratio showed sensitivity factor higher than 1.4104. With Cr2O3-WO3 sensor the response and recovery times are 7 min and 25 min respectively [11]. N. Parvatikar et al have presented humidity sensor based on polyaniline/WO3 composites by in situ polymerization. Composite with 50 weight % of WO3 showed better sensing properties and exhibited good linearity in sensing response curve [12]. Dewyani Patil et al have reported that the poly (2, 5-dimethoxyaniline)/WO3 (PDMA/WO3) composites show

better humidity sensing properties than pure PDMA, such as higher sensitivity, quicker response and small hysteresis. The resistance of the composite with 30 weight % of WO3 changed linearly over the humidity range (23 84% RH). Furthermore, it exhibited a maximum percentage response factor (~651 at 87% RH), narrow hysteresis (~5%) and good repeatability [13]. Morphological and humidity sensing studies of Ag loaded WO3, Cu2O loaded ZnO, ZnOTiO2 have been reported [14-16]. This paper reports comprehensive studies of characterization and moisture sensing properties of SnO2 loaded WO3 nanocomposites with various compositions by weight of WO3:SnO2 viz. 95:5, 92:8, 90:10, 88:12, 85:15, 80:20 and 70:30 prepared by solid state reaction route [17]. The sensitivity value for the best sample of WO3-SnO2 nanocomposite is 29.15 M /%RH which is much higher than the values reported in the case of ZnO-TiO2 (9.08 M /%RH), pure ZnO (12.89 M /%RH), ZnO-Cu2O (4.78 M /%RH) and WO3-Ag (2.11 M /%RH). The hysteresis for WO3-SnO2 is within 1.00% compared to 1.90% for ZnO-TiO2, 2.80% for pure ZnO, 2.30% for ZnO-Cu2O and within 1.00% for Ag loaded WO3. The response/recovery times and the repeatability after six months for WO3-SnO2 nanocomposite are comparable to above reported sensors. Thus, the best sensing element of WO3-SnO2

nanocomposite manifests better parameters (than others reported earlier) in terms of very high sensitivity, low hysteresis, comparable response and recovery times and good repeatability after six months. 2. Sample Preparation and Experimental Process Pellets of WO3-SnO2 nanocomposite have been made by taking WO3 (Loba Chemie99.9%) and SnO2 (Loba Chemie-99%) in weight % ratio of 95:5 (Sample WS-5), 92:8 (Sample WS-8), 90:10 (Sample WS-10), 88:12 (Sample WS-12), 85:15 (Sample WS-15), 80:20 (Sample WS-20) and 70:30 (Sample WS-30). The powder mixtures have been grinded in mortar and
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pestle for one hour to get uniformity. 10 weight % of glass powder has been added as binder to each of these powder mixtures as well. These powders have been given pellet shape in a hydraulic pressure machine (M.B. Instruments, Delhi, India) under uni-axial pressure of 260 M Pa at room temperature. The pellet samples are 12 mm in diameter and 3 mm in thickness. Samples have been annealed at 600C for 3 hours in muffle furnace (Ambassador, India). After annealing, samples have been exposed to humidity in a specially designed humidity chamber. Standard solution of potassium sulphate has been used as humidifier and potassium hydroxide as de-humidifier. Inside the humidity chamber, a thermometer (1C) and standard hygrometer (Huger, Germany, 1% RH) are placed for the purpose of calibration. Variation in resistance has been recorded with change in relative humidity at room temperature (27C). Relative humidity has been measured using the standard hygrometer. Variation in resistance of pellets has been recorded using a multi-meter (0.001 M, model: VC-9808). Resistance has been measured normal to the cylindrical surface of pellets. Copper electrodes have been used to measure resistance of the pellets. Electrical contacts have been made on the surface of pellets by means of two thin copper sheets. The surface contact area of all the sensing elements with the electrodes is 113.11 mm2 and the cylindrical surface area that has been exposed to the humidity in the chamber is also 113.11 mm2. These values have been kept constant for all the sensing elements. Given the high resistivity of the materials under consideration, the potential inaccuracy due to contact resistance is assumed negligible. The stability of the sensing elements has been checked by keeping the sensing element at fixed values of % RH in the chamber and the values of resistance recorded as a function of time. The values have been found to be stable within 3% of the measured values.

Comprehensive study has been undertaken of the humidity sensing properties of WO3SnO2 nanocomposites in different proportions. The aim of the work is to analyze the changes induced on the WO3 sensing element by different percentage of SnO2 loading. The nature of the changes analyzed is two-fold. On the one hand, activation energy, morphological and crystalline changes are studied with change in the percentage of loading and, on the other hand, changes in response to humidity are investigated. Activation energy has been measured from the Arrhenius plot. X-ray diffraction (XRD) has been used to look into the changes in the crystalline structure. X-ray diffraction pattern of the samples has been taken by X-Pert PRO XRD system (Netherland). The wavelength of the CuK source used is 1.54060 . Surface morphology of sensing elements has been studied using scanning electron microscope unit (SEM LEO-0430, Cambridge). Finally, humidity sensing studies of SnO2 loaded WO3 have been investigated. We have demonstrated the feasibility of the porous metal oxide SnO2 loaded WO3, prepared by solid state reaction route, as humidity sensor. The performance characteristics, such as sensitivity, reproducibility and response time, have been recorded and correlated to the microstructures. 3. 3.1 Results and Discussion Humidification Process Figure 1 shows the humidification graphs for the sensing elements WS-5, WS-8, WS-10, WS-12, WS-15, WS-20, WS-30. These are the graphs between the variation of resistance of the sensing elements with change in the value of the relative humidity. It is observed that there is a decrease in the value of resistance with increase in the value of % RH. All the graphs in figure 1 show that from 15 to 40% RH there is a rapid change in resistance while in 40 to 90% RH range, the variation of resistance is comparatively slow. This indicates that in the 15 to 40% RH range sensitivity of the sample is high whereas in 40 to 90% RH range sensitivity is comparatively low.
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Due to this reason, values of sensitivity have been calculated in the two ranges separately, viz. 15-40% RH and 40-90% RH and shown in columns (II) and (III) of table I. The values of sensitivity have also been calculated for the whole range of relative humidity 15-90% RH and shown in column (IV) of table I itself. Sensing element WS-10 shows maximum sensitivity of 29.15 M/%RH in the 15 to 90% relative humidity range. The following polynomial of degree 5 represents the variation of resistance with change in relative humidity for the sensing element WS-10 shown in figure 1: y = 19952 1511 x + 45.94 x2 - 0.694 x3 + 0.005 x4 - 2x10-5 x5 (1)

Here, y = resistance of the sensing element in M and x = % RH. For convenience, the trend line (the thin line superposed on the graph of WS-10 sensing element) of the polynomial and the polynomial equation have been shown in the figure 1 itself. At low humidity water vapor chemisorbs by a dissociation mechanism, forming hydroxyl ions at the surface. Hydroxyl group adsorbed on active surface dissociates easily, providing protons which move across the ceramic by hopping. At this stage, the electrical conductivity increases due to increased number of charge carriers. With increased humidity, subsequent layers of water molecules will be physically adsorbed on to hydroxyl group through hydrogen bonding. The Grotthuss proton transfer occurs among the hydronium ions (H3O+), resulting in relatively large increase in protonic conductivity. With a further increase in humidity, the multi-layers of physisorbed water molecules tend to condense in capillary pores. An electrolytic conduction in condensed water will take place in addition to protonic transport in physisorbed layers. On the whole, resistance of the ceramic decreases with increase in humidity [18]. The reduction of resistance or increase of conductance also occurs because of the variation of grain boundary

barrier height in ceramics. In this case, adsorption of water molecules at WO3 surface penetrated inside the sample can decrease the height of potential barriers at the surface of WO3 grains and at the surface of necks between WO3 grains. Therefore, the size of the depletion regions in the vicinity of the necks in the direction of electric field is lowered and conductance of ceramics is increased. Penetrated water molecules can promote the decrease in the barrier heights of grain boundary potential exponentially and even slight decrease of grain boundary barrier height due to relative humidity can cause substantial decrease of resistance (or increase of conductance) [19]. Figure 2 shows such schematic diagram for grain boundary potential barrier model. Sensitivity of the sample has been measured from the formula: Sensitivity= [Change in resistance]/[Change in % RH]; i.e.,

Sensitivity = [( R)/( % RH)]

(2)

For calculation of sensitivity, the humidity from 15 to 90% RH has been divided in equal intervals of 5% RH each. Difference in the value of the resistance for each of this interval has been calculated and then divided by 5. The average has been taken for all these calculated values. It can be seen from the table I that as doping % of SnO2 increases, sensitivity of sensing element increases up to 10 weight % and then decreases but for the sensing element WS-15. An observation of columns (IV) and (VIII) in table I would suggest that with reduction in grain size, the sensitivity of the sensing elements is generally increasing and vice versa. Variation of sensitivity with grain size has been depicted in figure 3. The following polynomial of degree 5 shown in the figure 3 along with the graph represents the mathematical correlation between the sensitivity of the sensing elements and the grain size:

y = 6 x 10-5 - 0.044 x4 + 14.04 x3 - 2204 x2 +17257x - 5 x 106 (3) It may be noted that this correlation works only up to the grain size of 165 nm. With decrease in the grain size, surface to volume ratio increases. This provides more sites for water vapor to be adsorbed on active sites leading to increase in the sensitivity of the sensing elements. Similarly, an increase in grain size should decrease the sensitivity due to decrease in surface to volume ratio. Thus, an inverse correlation between the sensitivity of the sensing elements and the weight % of SnO2 in WO3 is observed i.e. lesser the grain size in the sensing elements, greater the sensitivity. Following could be the plausible explanation for this trend. As SnO2 is doped in WO3, up to 10 weight % of loading, SnO2 arrests grain growth of WO3 and this decreases grain size. This leads to increase in the sensitivity of sensing elements [20]. When the doping of SnO2 increases above 10 weight %, effect of SnO2 dominates the sensing property of WO3. SnO2 is less humidity sensitive than WO3; hence increase of loading % of SnO2 in WO3 should decrease humidity sensitivity of sensing elements beyond 10%. 3.2 Humidification and Desiccation Process Metal oxides and binary systems of metal oxides show deviation in their behavior in the decreasing cycle of % RH from those in increasing cycle of % RH. Minimization of this hysteresis behavior is an important condition for sensor application. To determine the hysteresis effect in the sensing elements, the humidity in the chamber has been increased from 15 to 90% RH and then cycled down to 15% RH and the values of resistance of the sensing elements recorded with change in % RH. It is observed that all sensing elements have acceptable

hysteresis values. The percentage change in the value of sensitivity during desiccation cycle over that in humidification cycle are 0.3, 0.8, 0.6, 8.0, 0.8, 3.4, 2.0 for sensing elements WS-

5, WS-8, WS-10, WS-12, WS-15, WS-20, WS-30 respectively. Thus, the maximum change in the values of sensitivity for the decreasing cycles over increasing cycles is below 4% except for sample WS-12. The phenomenon of hysteresis may be attributed to the initial chemisorptions on the surface of the sensing elements. This chemisorbed layer, once formed is not further affected by exposure to or removal of humidity, it can be thermally desorbed only. Hence in the decreasing cycle of % RH, the initially adsorbed water is not removed fully leading to hysteresis. Figure 4 shows hysteresis graphs for the best sensing element WS-10. Sample WS-5 shows least hysteresis among all samples. Values of sensitivity for humidification and desiccation processes have been shown in columns (IV) and (V) in table I. 3.3 Problem of Ageing

Ageing is a significant problem in sensing devices based on metal oxides [4]. Ageing mechanisms in humidity sensors may be due either to prolonged exposure of surface to high humidity, adsorption of contaminants preferentially on the cation sites, loss of surface cations due to vaporization, solubility and diffusion, or annealing to a less reactive structure, migration of cations away from the surface due to thermal diffusion. Generally, the more sensitive a material is to humidity, the more it tends to be susceptible to ageing. After studying humidity sensing properties, sensing elements have been kept in laboratory environment and their humidity sensing characteristics regularly monitored. To see the effect of ageing, the sensing properties of these elements have been examined again in the humidity chamber after four and six months. Columns (VI) and (VII) in table I show that sensing element WS-10 shows the least ageing effect after four and six months which further increases the importance of WS-10 sample as humidity sensor. Figure 5 shows the aging graphs of sample WS-10 after four and six months.

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Of all the sensing elements, WS-10 shows maximum sensitivity of 107.47 M/% RH in the 15-40% RH range. In the 40-90% RH range, but for the sensing element WS-30, WS-10 again shows the maximum sensitivity of 5.66 M/% RH. In other parameters like response and recovery times, ageing, hysteresis, etc. sensing element WS-10 shows far better performance than the sensing element WS-30. For the sensing element WS-10, the average sensitivity in the overall 15-90% RH range is maximum at 29.15 M/% RH for the humidification cycle and 28.97 M/% RH for desiccation cycle. 3.4 Response and Recovery Time The time taken to accomplish 90% of the total resistance variation is defined as response/recovery time during the RH increasing and decreasing processes. Response and recovery times for all the sensing elements have been tabulated in columns (XII) and (XIII) of table I. Sample WS-10 shows the least values of response and recovery times which make this sample the most deserving candidate among all samples examined. Figure 6 shows the variation of resistance with time for the best sensing element WS-10. The response time and recovery times for the best sensing element i.e. WO3-SnO2 nanocomposite annealed at 600C (WS-10) are 86 s and 378 s respectively. Since desorption is an endothermic process, it takes longer time to desorb water vapor; therefore, the recovery time is always greater than the response time [21-23]. 4. 4.1 Sample Characterization Temperature-Resistance Measurement: Arrhenius Graph In order to measure the variation of resistance with temperature change, an indigenous laboratory made device has been used. In this device the temperature of the sample is increased, keeping the sample in a heating chamber and variation in resistance of the sample is measured by a multi-meter (0.001M, model: VC-9808) using two copper plates as electrodes and two thin
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copper wires as connecting leads at these temperatures. Activation energy for all the samples has been measured from the Arrhenius plot for resistance. Figure 7 shows the Arrhenius graph between logeR and 1000/T for the sensing element WS-10. The temperature dependence of the resistance has been shown from the relation [24]: R=R0 exp(Ea/kT) (4)

Here, Ea is the activation energy. Activation energy depends on various trapping levels in the sensing elements. It may have one or multiple values in different ranges of temperature. A lower value of activation energy indicates higher conductivity leading to better sensitivity. Our moisture sensing is at room temperature; hence, a lower value of activation energy in the temperature range from 50 C to 300 C implies good sensitivity for sensor. Activation energy measured from Arrhenius plot in 50 to 300C range and 300 to 600C range respectively have been shown in columns (X) and (XI) in table I. Activation energy for the sample WS-10 is found to be 0.15 eV and 0.80 eV in 50 to 300C and 300 to 600C temperature ranges respectively. 4.2 Crystalline Study: X-ray Diffraction Study X-ray diffraction pattern of the samples shows extent of crystallization in the WO3-SnO2 nanocomposite samples. The average crystallite size for the samples have been calculated using Scherers formula D= KP/ CosU (5)

Here, D is the crystallite size, K is a fixed number of 0.9, P is the X-ray wavelength, U is the Bragg angle and is the full width at half maximum of the peak. Column (IX) in table I shows

range of crystallite size for all samples. Figure 8 shows XRD pattern of sensing element WS-10. The XRD pattern has been indexed properly and different phases in the sensing materials have been shown in the pattern itself. The diffraction peaks of WO3 have been matched with JCPDS
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Card No. 01-083-0951 and that of SnO2 have been matched with JCPDS Card No. 00-041-1445. The XRD pattern shows the monoclinic structure of WO3 with space group P21/n and the tetragonal structure of SnO2 with space group P42/mnm. The crystallite size for WS-10 is in 17138 nm range. At 2 value 58.48, the crystallite size is 17 nm and at 2 value 55.92, the crystallite size is 138 nm for the sample WS-10. The XRD pattern shows presence of peaks of SnWO4 of hubnerite structure along with WO3 and SnO2 peaks. The high peaks of XRD pattern manifest high crystallinity of sensing elements. 4.3 Surface Morphology: Scanning Electron Microscope Study SEM micrographs show that sensing elements are porous in nature and grains as well as pores are of nanometer range. The bar intercept method taking the whole of the SEM micrographs has been used to calculate the grain size from the SEM micrographs. In the process, it is the average value of the grain size that is calculated. Values of grain size with change in doping % have been given in column (VIII) of table I. The average grain size for the sensing element WS-10 is found to be the least 141 nm among all samples. The morphology of the sensing element influences water vapor adsorption and de-adsorption. The condensation of water vapor occurs as a result of capillary action. It is understood that the large increase in the conductivity with relative humidity is due to the adsorption of the water molecules on the pellet surface with capillary nanopores. Higher porosity increases surface to volume ratio of the materials and therefore, helps in getting good sensitivity. It also helps in reducing response and recovery times because it enhance diffusion rate of water into or out-off the porous structure. An observation of the crystallite size and grain size would suggest that smaller crystallites are getting agglomerated to form larger grains. In this process, more of the surface areas of the sensing elements are exposed leading to more adsorption of water molecules. This increases the

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sensitivity of the sensing elements. Figure 9 shows the SEM micrograph of the best sensing element WS-10. 5. Conclusions Change in resistance with humidity is seen up to three orders. Polynomial of degree 5 represents the variation of resistance with change in relative humidity for the sensing element WS-10. As doping % of SnO2 is increased, sensitivity of the samples first increases up to 10% of SnO2 in WO3, then decreases. An inverse correlation represented by polynomial of degree 5 is observed between the sensitivity and the grain size. Sensing element WO3:SnO2 with weight % ratio of 90:10 shows maximum value of average sensitivity of 29.15 M/%RH in 15 to 90% RH range. The hysteresis is less than 1.00% for this sample. This sample shows the least ageing effect after 4 and 6 months. The response and recovery times of this sensing element are 86 seconds and 378 seconds respectively. Thus, the sensing element WS-10 manifests highest sensitivity, low hysteresis, least ageing effect and least response and recovery times. Acknowledgments Authors would like to thank the University Grants Commission, New Delhi for their financial support for the work [File 33-23 (2007)], Geological Survey of India, Lucknow for providing XRD facility and Birbal Sahani Institute of Paleobotany, Lucknow for providing SEM facility.

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References [1] Padmanathan Karthick Kannan, Ramiah Saraswathi, John Bosco Balaguru Rayappan, A highly sensitive humidity sensor based on DC reactive magnetron sputtered zinc oxide thin film, Sens. and Act. A: Physical, 164 (1-2) (Nov.-Dec. 2010) 8-14. [2] N. Yamazoe, Y. Shimizu, Humidity sensors: principles and applications, Sens. and Act., 10 (1986) 379-398. [3] E. Traversa, Ceramic sensors for humidity detection: the state-of-art and future developments, Sens. and Act. B, 23 (1995) 135-156. 8. [4] B. M. Kulwicki, Humidity sensors, Journal of the American Ceramic Society 74 (1991) 697- 708. [5] A. B. Glot, A. P. Sandoval-Garca, A.V. Gaponov, R. Bulpett, B.J. Jones, G. JimenezSantana, Electronic properties of SnO2-based ceramics with double function of varistor and humidity sensor, Azojomo-Journal of Materials Online, 5 (April 2009) 1-17. [6] V. Jeseentharani, B. Jeyaraj, J. Pragasam, A. Dayalan, K.S. Nagaraja, Humidity sensing properties of CuO, ZnO and NiO composites, Sens. and Trans. Journal, 113 (2) (Feb. 2010) 48-55. [7] S. P. Yawale, S. S. Yawale, G. T. Lamdhade, Tin oxide and zinc oxide based doped humidity sensors, Sens. and Act. A 135 (2007) 388 393. [8] B. C. Yadav, M. Singh, Morphological and humidity sensing investigations on niobium, neodymium, and lanthanum oxides, IEEE Sensors Journal, 10 Issue 11 (Nov. 2010) 175966.

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[9] B. C. Yadav, Richa Srivastava, C. D. Dwivedi, Synthesis and characterization of ZnO-TiO2 nanocomposite and its application as a humidity sensor, Philosophical Magazine, 88 (7) (2008) 1113-1124. [10] Weon-Pil Tai, Jun-Gyu Kim, Jae-Hee Oh, Humidity sensitive properties of nanostructured Al-doped ZnO:TiO2 thin films, Sens. and Act. B 96 (2003) 477 481. [11] Suman Pokhrel, K. S. Nagaraja, Electrical and humidity sensing properties of Chromium (III) oxide tungsten (VI) oxide composites, Sens. and Act. B 92 (2003) 144 150. [12] N. Parvatikar, S. Jain, S. Khasim, M. Revansiddappa, S.V. Bhoraskar, M.V.N. Ambika Prasad, Electrical and humidity sensing properties of polyaniline/WO3 composites, Sens. and Act. B 114 (2006) 599 603. [13] Dewyani Patil, You-Kyong Seo, Young Kyu Hwang, Jong-San Chang, Pradip Patil, Humidity sensitive poly (2,5-dimethoxyaniline) / WO3 composites, Sens. and Act. B 132 (2008) 116 124. [14] N. K. Pandey, Karunesh Tiwari, Akash Roy, Ag doped WO3 nanomaterials as moisture sensor, IEEE Sensors Journal (In Press, 2011). [15] N. K. Pandey, K. Tiwari, A. Roy, Moisture Sensing Application of Cu2O doped ZnO nanocomposites IEEE Sensors Journal, Volume: 11 Issue 9 pp.2142 2011. [16] N. K. Pandey, K. Tiwari, A. Roy, ZnO-TiO2 nanocomposite: characterization and moisture sensing studies, J. Bulletin of Materials Science (Accepted, September, 2011). [17] N. K. Pandey, A. Roy, Alok Kumar, characterization of WO3-SnO2 nanocomposites and application in humidity sensing, Sensors & Transducers Journal 125 (2) (2011) 89-99. [18] Wenmin Qu, Ray Green, Mike Austin, Development of multi-functional sensors in thick 2148, September

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film and thin film technology, Meas. Sci. Tech. 11 (2000) 1111. [19] I. Skuratovsky, A. Glot, E. Di Bartolomeo, E. Traversa, R. Polini, The effect of humidity on the voltage current characteristic of SnO2 based ceramic varistor, Journal of the European Ceramic Society 24 (2004) 2597 2604. [20] Hye-Kyung Kim, Shivaram Dattatraya Sathaye, Young Kyu Hwang, Sung Hwa Jhung, JinSoo Hwang, Soo Hwan Kwon, Sang-Eon Park, Jong-San Chang, Humidity sensing properties of nanoporous TiO2-SnO2 ceramic sensors, Bull. Korean Chem. Soc. 26 (11) (2005) 1881. [21] D. Saha, R. Giri, K.K. Mistry, K. Sengupta, Magnesium chromate TiO2 spinel tape cast thick film as humidity sensor, Sens. and Act. B 107 (2005) 323 33. [22] R. Sundaram, E.S. Raj, K.S. Nagaraja, Microwave assisted synthesis, characterization and humidity dependent electrical conductivity studies of perovskite oxides, Sm1 xSrxCrO3 (0 x 0.1), Sens. and Act. B 99 (2004) 350 354. [23] W. Qu, J.U. Meyer, A novel thick-film ceramic humidity sensor, Sens. and Act. B 40 (1997) I75-I82. [24] M. N. Rumyantseva, M.N. Bulova, T.A. Kuznetsova, L. I. Ryabova, A. M. Gaskov, G. Loucaseau, M. Labeau, Nanocrystalline metal oxides as promising materials for gas sensors for hydrogen sulfide, Russian Journal of Applied Chemistry, 74(3) (2001) 434-439.

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Figure Captions: Figure 1 Humidification graph for samples WS-5 to WS-30. Figure 2 Schematic diagram for grain boundary potential barrier model. Figure 3 Graph between sensitivity and grain size. Figure 4 Hysteresis graph for sample WS-10; h-humidification; d-desiccation. Figure 5 Repeatability graph for sample WS-10. a. an initial humidification cycle; b. humidification cycle after 4 months; c. humidification cycle after 6 months. Figure 6 Resistance time variation graph of sample WS-10.

Figure 7 Arrhenius graph for sample WS-10. Figure 8 X-ray Diffraction pattern of sensing element WS-10. Figure 9 SEM micrograph of sensing element WS-10.

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Authors Biography Dr. N. K. Pandey did his graduation with honors in physics in the year 1985 from prestigious St. Xaviers College, Ranchi. India. Dr. Pandey finished his post graduation and doctorate from Indian Institute of Technology, Delhi in 1995. Presently, Dr. Pandey is working as Associate Professor in the Department of Physics, University of Lucknow. Areas of interest of Dr. Pandey include humidity and gas sensing, nanotechnology, optical fiber sensors, fiber bragg grating sensors, etc. Dr. Akash Roy did his graduation from University of Lucknow, U.P., India in the year 1997. He did his M.Sc. in physics from Kanpur University in the year 2003. Dr. Roy has done his Ph.D. from the Department of Physics, University of Lucknow. His areas of interest include humidity and gas sensing. Dr. Roy has also taken up teaching assignments along with research. Dr. Karunesh Tiwari did his graduation from Avadh University, Faizabad, U.P., India in the year 2002. He did his M.Sc. in physics from the same University in the year 2004. Dr. Tiwari has completed his Ph.D. in the year 2010 from the University of Lucknow, India. Dr. Tiwari is presently taking up teaching and research assignments. His areas of interest include humidity and gas sensing. Dr. S. N. Pandey finished his M.Sc. in physics from University of Gorakhpur, Uttar Pradesh, India in the year 1986. He received his Ph.D. degree in Physics from Avadh University, Faizabad, India in 1992. His areas of interest are solid state devices, metal oxide thin films, humidity and gas sensors. He is presently Associate Professor in the Department of Physics, Motilal Nehru National Institute of Technology, Allahabad 211004, India.

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Dr. Anil Govindan did his M.Sc. in Physics (specialization: solid state physics) from Cochin University of Science and Technology, India. He did his Ph.D. from Indian Institute of Technology, Delhi in the year 1998. He is presently Associate Professor, Department of Physics, Mahanand Mission Harijan (M.M.H.) College, Ghaziabad-201009, U.P., India. His areas of interest include solid state materials, ceramics, electroceramics and composites.

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