ZnO-TiO2 Nanocomposite: Characterization and Moisture Sensing Studies

Narendra Kumar Pandey*, Karunesh. Tiwari, Akash Roy Sensors and Materials Research Laboratory, Department of Physics, University of Lucknow, U.P., Pin-226007, India Phone: +91-9415003998, Fax: +91 522 2740462 * Corresponding Author E-mail: nkp1371965@gmail.com

Abstract
ZnO-TiO2 nanocomposite powder pellets have been obtained through solid-state reaction route. When exposed to humidity, resistance of pellets decreases with increase in relative humidity from 10 to 90%. Sensing element with 15 weight % of TiO2 in ZnO shows best results with maximum sensitivity of 9.08 M/%RH in 10-90% relative humidity range. This sensing element manifests smallest crystallite size of 71 nm as measured from XRD and lowest grain size of 207 nm calculated from SEM micrograph. Smaller crystallites are getting agglomerated to make larger grains, leading to exposure of more surface area which increases sensitivity. Sensitivity is further enhanced due to porous structure of the sensing elements as manifested by the SEM micrographs. This sensing element manifests low hysteresis, less effect of ageing and good reproducibility.

1. Introduction
Control and monitoring of environmental humidity has become an essential condition for comfortable life and industrial process. Lately the use of humidity control systems has greatly increased in the quality control of production processes and products in a wide range of industries, such as production of electronic devices, precision instruments, textiles and foodstuffs. Many domestic applications, such as air conditioning, microwave ovens and intelligent control of living environment in the buildings also need efficient control and monitoring of humidity to comfortable levels. 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. The materials used in humidity sensing exploiting variations of electrical parameters are roughly classified into three groups: electrolytes, organic polymers and ceramics. The electrolyte humidity sensors show are unable to operate in very humid environment or in the presence of ammonia or organic solvents. Polymer films cannot operate at high temperature and high humidity, and show hysteresis, long-term drift and degradation upon exposure to some solvents. Ceramic humidity sensors, particularly those based on porous and sintered metal oxides, have been attracting attention due to their chemical and physical stability and 1

mechanical strength. The problems for ceramic humidity sensors are mainly related to the need for periodic regeneration by heat cleaning to recover their humidity-sensitive properties; prolonged exposure to humidity environments leads to ageing problems due to the gradual formation of stable chemisorbed OH- on the surface. Contaminant like dust, dirt, oil, smoke, alcohol, solvents, etc. act in the same way as chemisorbed water to further the ageing problem1-4. In consideration of quality and cost, resistive type ceramic humidity sensors are becoming more prevalent than capacitance5-7, fieldeffect transistor8, and fiber-optic sensors9-11. Furthermore, thin film or pellet type humidity sensors having nanosize grains and nanoporous structures have drawn interest because of the high surface exposure for adsorption of water molecules. ZnO is an attractive semiconductor oxide having a wide band gap and is known for its n-type conduction due to the presence of oxygen12-14. Mixing or doping is an effective method for manipulating semiconductors for different applications15-17. Doped ZnO or ZnO mixed with other oxides exhibits various properties, different types of morphologies and has many applications18. TiO2 is one of the most extensively studied metal oxides because of its remarkable optical and electrical properties. Zinc titanate is a promising candidate as dielectric material19-21. It is reported that three compounds exist in ZnO-TiO2 system viz. Zn2TiO4 (cubic), ZnTiO3 (hexagonal) and Zn2Ti3O8 (cubic)22-24. Among these compounds ilmenite-type hexagonal ZnTiO3 compound has been reported to have superior electrical properties21, 25-26. Zinc orthotitanate Zn2TiO4 can be prepared easily via the conventional solid state reaction of ZnO-TiO2. Li et al. have obtained ZnTiO3 phase as precipitate inside the Zn2TiO4 matrix having the same structure and lattice parameter as Zn2TiO4 phase27. T. Ivetic et al. have reported results with compositions of ZnO and SnO 2 powders with molar ratio of 2:1 and discussed photo acoustic investigation of thermal and transport properties of bulk zinc stannate synthesized by the reaction sintering method28. Raid et al. have reported results with dopants of 1 , 2 and 3 % weight of (Al, Cu, I) powder with ZnO and discussed the micro structural, optical and electrical properties of ZnO by chemical spray pyrolysis29. Yavale et al. have studied the effect of humidity on the pure and doped SnO2 and ZnO thick films30. M. A. Marigiote et al. have reported results with the compositions of 0.5 and 1 % mol of WO3 and 1 and 2 % mol of ZnO powder with SnO2 and discussed their micro structural, ohmic characteristic and densification31. Kenan Yildiz et al. have reported results of ZnO-TiO2 compositions having 1, 2, 3 and 4 % weight of TiO2 powder in ZnO and discussed their microstructure properties and densification32. In our earlier works, we have reported morphological and humidity sensing studies of WO3 mixed with ZnO and TiO2 powders and 2

optical humidity sensor based on titania films fabricated by sol gel and thermal evaporation 33-34. We have also reported humidity sensing studies of WO3 mixed with ZnO35 and ZnO doped with Cu2O36. We report here morphological and humidity sensing studies of ZnO-TiO2 nanocomposites prepared by solid state reaction route. The compositions are having 10, 15 and 20 % weight of TiO2 in ZnO. The sensitivity in the present case is found to become nearly two fold as compared to the work reported on Cu2O doped ZnO as moisture sensor36.

2. Principle of Operation of Sensor

ZnO and TiO2 both are n-type semiconductors, hence sensitivity to humidity is a result of electronic conduction37-38. As semiconducting dry oxides of ZnO-TiO2 nanocomposite are brought in contact with humid air, water molecules chemisorb on the available sites of the oxide surface. The adsorption of water molecules on the surface takes place via a dissociative chemisorption process which may be described in a two-step process as given below: (i) Water molecules adsorbed on grain surface reacts with the lattice A (A Zn or Ti) as H2O + Oo + A 2OHA + Vo + 2e reaction. Oo O2 + Vo (2) (ii) Doubly ionized oxygen, displaced from the lattice, reacts with the H+ coming from the dissociation of water molecules to form a hydroxyl group as given below: H+ +O2 OH (3) ZnO and TiO2 both have electron vacancies. Hence. because of this reaction, the electrons are accumulated at the ZnO/TiO2 surface and consequently, the resistance of the sensing element decreases with increase in relative humidity. 3. Sample Preparation and Experimental Process 10, 15 and 20 % weight of TiO2 powder (Qualigens, 99.9 % pure) in ZnO (Qualigens, 99.9 % pure) have been mixed uniformly for half an hour. 10 % weight of glass powder has been added as binder to increase the strength of the sample. The powders have been pressed in pellet shape by uniaxially applying pressure of 260 M Pa in hydraulic press machine at room temperature. The samples have been labeled S-10, S-15 and S-20 respectively. The samples are having diameter of 8 mm and thickness 4 mm. The samples have been sintered in air at temperature of 300C, 400C and 500C for 3 hours in an electric muffle furnace (Ambassador, India). 3 (1) here Oo is the lattice oxygen and Vo the vacancy created at the oxygen site according to the

After sintering, the samples have been exposed to humidity in a humidity control chamber. 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 the pellet has been recorded using a resistance meter (sino meter, 1 M, model: VC-9808). Copper electrode has been used to measure the resistance of the pellet. The resistance of the pellet has been measured normal to the cylindrical surface of the pellet. The electrical resistance at different relative humidity levels of the sensing elements in the form of pellets has been determined by a two-probe method, as the present work is to measure the changes in surface conductivity as a function of applied field. The electrical contacts have been made on the surface of pellet by means of two thin copper sheets. Given the high resistivity of the materials under consideration, the potential inaccuracy due to contact resistance is assumed negligible. 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 mm 2. These values have been kept constant for all the sensing elements. The experimental sample has been electrically connected to a dc power supply and sinometer (VC 9808) in series. 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 control chamber after six months. 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.

4. Result and Discussion 4.1 Humidification and Desiccation Graphs

Figure 1 shows graphs between resistance of the sensing elements with the change in relative humidity (% RH); a, b and c are the curves for the sensing elements S-10, S-15 and S-20 respectively. We observe continuous decrease in the value of resistance of all the sensing elements with increase in % RH. All graphs in figures 1 show that from 10 to 40 % RH there is a rapid change in resistance while in 40 to 90 % RH range the fall in resistance is slow; it indicates that in 10 to 40 % RH range sensitivity of the sample is high whereas in 40 to 90 % RH range sensitivity is low. It is understood that the increase in the conductivity of the sample with relative humidity in the lower range (<40 % 4

RH) 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 enhances diffusion rate of water into or out-off the porous structure; and thus, helps in getting good sensitivity. At high relative humidity (>40% RH), liquid water condenses in the capillary like pores, forming a liquid like layer. Sensitivity of humidity sensor is defined as the change in resistance (R) of sensing element per unit change in relative humidity (RH %). For calculation of sensitivity, the humidity from 10 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. Formula for calculation of sensitivity of the sensing elements may be written as given below: Sensitivity = (R)/(%RH) (4) Values of sensitivity calculated for sensing elements S-10, S-15 and S-20 for annealing temperatures 300C, 400C and 500C are shown in table I. Column a in table I represents values of sensitivity for increasing cycle of relative humidity (humidification). It can be seen from table I that the sensing element S-15 annealed at 500C shows the value of maximum sensitivity of 9.08 M/ %RH. Variation of resistance of the sensing elements has been recorded both for increasing and decreasing cycles of % RH for all sensing elements S-10, S-15 and S-20 for annealing temperatures 300C, 400C and 500C. All the sensing elements manifest hysteresis for all the annealing temperatures. For the annealing temperature 500C, it has been observed that all the sensing elements show lower hysteresis. In figure 2 we present variation of resistance with % RH of the best sensing element S-15 for annealing temperature of 500C. Graph a in figure 2 is for increasing cycle of % RH and graph b for decreasing cycle of % RH. Column b in table I depicts values of sensitivity for decreasing cycle of % RH. 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. To determine the hysteresis effect in the ZnO-TiO2 sensing elements annealed at 500C, the humidity in the chamber has been increased from 10 % RH to 90 % RH and then cycled down to 10 % RH. It has been observed that all sensing elements have acceptable hysteresis values; sample S-10 has a hysteresis of 4.11 %, sample S-15 has a hysteresis of 1.90 % and sample S-20 has a hysteresis of 5

7.59 %. The data sheets of some commercially available humidity sensors have indicated hysteresis values in the range from 1.20-5.00 %39-40. Our best sensing element S-15 has shown small value of hysteresis of 1.90 %. 4.2 X-Ray Diffraction Analysis X-Ray diffraction has been studied using XPERT PRO-Analytical XRD system (Netherlands). The wavelength of the Cu-K radiation used is 1.54060. Figure 3 shows X-ray pattern for the sensing element S-15 annealed at 500C. The pattern shows extent of crystallization of the sensing element in the form of powder. The average crystalline size of the samples has been calculated using Scherers formula D= K /Bcos (5)

Here D is the crystallite size, K is a fixed number of 0.9, is the X-ray wavelength, is the Bragg angle and B is the full width at half maximum of the peak. The average crystallite size measured for sensing elements S-10, S-15 and S-20 are 89 nm, 71 nm and 80 nm respectively. XRD pattern shows peaks of ZnO-TiO2 binary system. In addition to these peaks, the pattern also manifests presence of peaks of cubic Zn2TiO4 (zinc orthotitanate), cubic Zn2Ti3O8 and hexagonal ZnTiO3 formed due to solid state reaction between TiO2 and ZnO. It may be mentioned here that in addition to the distinct peaks, the XRD pattern manifests some not very clear peaks at [110] [111] [210] etc. These peaks have been observed only at high resolution. 4.3 Scanning Electron Microscopic (SEM) Study The study of surface morphology of sensing elements has been carried out using Scanning Electron Microscope (LEO-430, Cambridge, England). SEM micrographs show flakes of TiO2 scattered throughout ZnO substrate forming a network of pores that are expected to provide sites for humidity adsorption. It has been observed that the particle density was getting increased with increase in the % weight of TiO 2 in ZnO. It seems as if the grain size of ZnO were getting inhibited with increasing composition of TiO2. The particle size for the sensing elements S-10, S-15 and S-20 calculated from SEM micrographs are 300 nm, 207 nm and 236 nm respectively. Here we observe that both the crystallite size and the grain size are the minimum for sensing element S-15. SEM micrographs show that the sensing elements manifest porous structure having granulation and tendency to agglomerate. 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 area of the sensing elements are exposed leading to more adsorption of water molecules. This

increases the sensitivity of the sensing elements. In figure 4 we present SEM micrograph of nanocomposite of the best sensing element S-15 annealed at temperature 500C. 4.4 Problem of Ageing in Humidity Sensors Metal oxide sensors suffer from the problem of ageing. Aging 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. This is a significant problem in sensing devices41. To see the effect of ageing, the sensing elements have again been exposed to humidity in the chamber after six months and variation of resistance with % RH recorded. Corresponding values of sensitivity after six months for these sensing elements are depicted in column c of table I. Sensing element S-15 shows the best reproducible results. In figure 5 we present the repeatability graph for the best sensing element S-15. In this figure a represents initial increasing cycle of % RH and c represents increasing cycle after six months. It may be observed from table I that the repeatability in the value of sensitivity is within 0.33 % of the measured value after six months for sensing element S-15 where as repeatability is within 1.29 % for sensing element S-10 and a very high value of nearly 20 % for S-20. Thus sensing element S-15 shows good reproducibility and low hysteresis for annealing temperature 500C. Sensing element S-15 shows good reproducibility and lower hysteresis for annealing temperatures 300C and 400C as well. However, the results of highest sensitivity and very low hysteresis are best obtained for the sensing element annealed at 500C. Figure 6 shows the graph between the sensitivity and the annealing temperature for the sensing element S-15. It is seen that for sensing element S-15, the sensitivity increases with increase in the annealing temperature. Figure 7 shows the graph between the sensitivity and % weight of TiO2 in ZnO for annealing temperature 500C. The graph shows the maximum value of sensitivity for sensing element S-15 having 15 % weight of TiO2 in ZnO. 5. Conclusions As relative humidity increases, there is decrease in the resistance of pellets in the range 10 to 90 % RH. Sensing element with 15 weight % of TiO2 in ZnO shows best results in 10 to 90 % relative humidity range. The sensitivity of this sensing element is 9.08 M/%RH. This sensing element shows good reproducibility, low hysteresis and less effect of aging. XRD pattern of this sensing element 7

shows peaks of cubic Zn2TiO4, cubic Zn2Ti3O8 and ZnTiO3 formed due to solid state reaction between TiO2 and ZnO. SEM micrographs show that the sensing elements manifest porous structure. Acknowledgement Authors would like to thank the University Grants Commission, India for providing the Financial Support for carrying out the research work [(File No.33-23-2007 (SR)]. We would also like to thank the Geological Survey of India, Lucknow for providing XRD and SEM facilities. References [1]. [2] [3]. [4]. [5]. [6]. [7]. [8]. Traversa E, Sens. & Act. B (1995) 135-156. Shimizu Y, Shimabukuro M, Arai H and Seiyama T, Chem. Lett. 14 (7) (1985) 917-920. Fagan J G, and Amarakoon V R W, Am. Ceram. Soc. Bull., 72 (1993) 119-30. Yarkin D G, Sens. and Act., 107 (2003) 16. Gu L, Huang Q A, and Qin M, Sens: and Act. B, 99 (2/3) (2004) 491-98. Cantalini C, and Pelino M, J. Am. Ceram. Soc., 75 (3) (1992) 546-51. Wang W S and Virkar A V, Sens. and Act. B, 98 (2004) 282-90. Lee S P, and Park K J, Sens. and Act. B, Proc. of the 6th Int. Meet on Chem. Sensors, 35(1-3) (1996) 80-84. [9]. [10]. [11]. [12]. Kronenberg P, Rastogi P K , Giaccari P and Limberger H G, Opt. Lett., 27 (2002) 1385-87. Xu L, Fanguy J C, Soni K and Tao S, Opt. Lett., 29 (2004) 1191-93. Yeo T L, Sun T, Grattan K T V et al., Sens. and Act. B, 110 (1) (2005) 148-156. Kishimoto Yamamoto and Y. Nakagawa Y, Superlattices Microstruct., 39 (1-4) (2006) 306313. [13]. [14]. Sahu D R and Huang J L, Mater. Sci. Eng., B 130 (2006) 295-99. Yogeeswaran G, Chenthamarakshan C R, de Tacconi N R and K. Rajeshwar K, Mater. Res. Soc., 21 (2006) 3234-41. [15]. Gosh M, Seshadri R and Rao C N R, J. Nanosci. Nanotechnol., 4 (2004) 136-140. 8

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Table I
Sensitivity (M/%RH) of Sensing Elements for different annealing temperatures

S-10 Temp. 300C 400C 500C

a

S-15 c a b c a b

S-20 c

increasing cycle; b decreasing cycle; c repeatability

10

Figure 1 Humidification graphs; variation of resistance with % RH. a. sensing element S-10; b. sensing element S-15; c. sensing element S-20.

11

Figure 2 Variation of resistance with % RH for sensing element S-15; a. humidification process, b. desiccation process.

Figure 3 XRD Pattern for Sensing Element S-15.

12

Figure 4 XRD Pattern for Sensing Element S-15.

Figure Variation of Resistance with % RH for Sensing Element S-15. a. increasing cycle; b. repeat cycle after six months.

13

Figure 6 Variation of sensitivity with temperature for sensing element S-15.

Figure 7 Variation of sensitivity with % composition.

14

15