Research article

Ultrasonically synthesized nanocrystalline ZnO powder-based thick lm sensor for ammonia sensing
L.A. Patil, A.R. Bari, M.D. Shinde and Vinita Deo
Nanomaterials Research Laboratory, Department of Physics, Pratap College, Amalner, India
Abstract Purpose The purpose of this paper is to show how to obtain better response, selectivity and fast response and recovery from nanocrystalline ZnO-based gas sensors as compared to conventional materials. Design/methodology/approach Nanocrystalline ZnO powders were prepared from the ultrasonic spray pyrolysis method. Aqueous solution of zinc acetate was atomized using ultrasonic atomizer. The aerosol generated was fed to the reaction furnace for pyrolysis. Nanocrystalline ZnO crystallites were collected using simple but novel trapping system. Thick lm resistors of this powder were fabricated using screen printing technique. Findings As-prepared powder was studied using X-ray diffraction, transmission electron microscopy and scanning electron microscopy to know structure, size of nanocrystallites and microtopography, respectively. Absorption spectroscopy is used to determine the band gap energy. The gas-sensing performance of this lm was tested. Originality/value The sensor was found to be the most sensitive to NH3. It gives better response, selectivity and fast response and recovery as compared to conventional materials-based thick lms. Keywords Powders, Chemical elements and inorganic compounds, Ammonia, Sensors, Nanotechnology Paper type Research paper

Introduction
In the last few decades, study of nanostructured zinc oxide has attracted much interest due to its important applications for fabricating piezoelectricity, optoelectronics, photocatalysis, photovoltaic conversion and gas-sensing devices (Carotta et al., 2005; Hsueh and Hsu, 2008). Many techniques have been used to prepare ZnO nanostructures: like metal organic chemical vapour deposition (Ohya et al., 2001), sol-gel (Kim et al., 2004; Bari et al., 2009; Ryu et al., 2003), DC magnetron sputtering (Chou et al., 2006; Chawla et al., 2007) and spray pyrolysis (Suh and Suslick, 2005; Shinde et al., 2007). Compared with these methods, ultrasonic spray pyrolysis (USP) is convenient and simple, which is a versatile technique widely used for the preparation of a variety of inorganic and organic materials (Rao, 2000; Gandhi et al., 2001). In USP, the precursor solution was rst atomized by ultrasonic transducer; the resulting droplets were then transported by the carrier gas to a heated tubular furnace, where several reactions, such as solvent evaporation and atomic rearrangement, take place in a continuous ow process.
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Gas-monitoring devices are in demand for a rapidly growing range of applications. Metal oxide-based chemical sensors have been used for the detection of toxic-pollutant gases, combustible gases and organic vapours. The main advantage of chemical sensors is long life, small in size, low power consumption and easy fabrication. Many reports have demonstrated that the gas-sensing properties of the semiconducting sensors are greatly affected by the addition of noble metals (Huang et al., 2009). As ammonia is utilized extensively in many chemical industries, fertilizer factories, refrigeration systems, etc. a leak in the system can result the health hazards. Ammonia is harmful and toxic (Close et al., 1980; Hoz et al., 1996; Michaels, 1999; Narasimhan et al., 2001) in nature. The exposure of ammonia causes chronic lung disease, irritating and even burning the respiratory track, etc. It is therefore needed to monitor ammonia gas and to develop the ammonia gas sensor. In this paper, we have developed USP technique to prepare nanocrystalline ZnO powder. Structural properties were studied from X-ray diffraction (XRD); surface topography was studied using scanning electron microscopy (SEM); microstructure, morphology and grain size were studied using
The authors are thankful to the Head, Department of Physics and Principal, Pratap College, Amalner, for providing laboratory facilities for this paper. The nancial support for this paper from the Department of Information Technology, Government of India, New Delhi, is gratefully acknowledged. The authors are also thankful to N.P. Lalla and Satish Potdar IUC, Indore, for providing TEM images of the powder samples.

Sensor Review 30/4 (2010) 290 296 q Emerald Group Publishing Limited [ISSN 0260-2288] [DOI 10.1108/02602281011072161]

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Nanocrystalline ZnO powder-based thick lm sensor L.A. Patil, A.R. Bari, M.D. Shinde and Vinita Deo

Sensor Review Volume 30 Number 4 2010 290 296

transmission electron microscopy (TEM) and optical properties were studied using ultraviolet visible spectroscopy. This nanocrystalline ZnO powder was used to fabricate the sensor element in the form of thick lms by screen printing technique and tested for different conventional gases. Nanocrystalline ZnO-based thick lm sensors were observed to be sensitive to NH3.

Experimental
Preparation of nanocrystalline ZnO powder To synthesize ZnO nanopowder, we have developed costeffective USP technique. The setup was composed of three major components: 1 ultrasonic atomizer (2.1-2.3 MHz Gapusol 9001 RBI Meylan, France) with three transducers to transform initial salt solution into aerosol; 2 two-zone reaction furnace to pyrolyze the aerosol; and 3 glass traps to collect nanostructure powder (Figure 1). About 0.5 M aqueous solution of zinc nitrate (Zn(NO)3 6H2O, Merck extra pure) was prepared in double distilled water. The stock solution was stored in cylindrical vessel, which was connected to ultrasonic generator through tube. When solution was allowed to pass to the generator, it was converted into aerosol with the rate of 18 ml/s. The aerosol generated from the generator was pushed forward through quartz reactor. Quartz reactor was placed in tubular doublezone furnace. The temperature of drying zone (rst zone) was kept at 573 K and pyrolysis zone (second zone) was at 1,073 K. The carrier airow rate was optimized as 20 kg/cm2 to prevent compositional segregation so as to obtain uniform and direct droplets of starting solution and to control decomposition of these droplets. Generally, the density of droplets in the aerosol is constant at same solution Figure 1 System for the preparation of ZnO nanopowders by USP technique
Thermocouple

characteristics and ultrasound frequency. An aerosol would pass through the process of heating, solvent evaporation, pyrolysis, reaction with compressed air and nally formation of the ne particles. The residence time of the mist particles is about 5-7 s. The glass traps were used to collect the powder. This powder was then ltered with the ceramic lter. The surface tension of the solution was measured by Quinckes method which was found to be 71.50 dyne/cm. The density was determined by specic gravity bottle. It was 1.1087 g/cm3. The mean droplet diameter (Ddrop) of aerosol was determined (Chapron et al., 2007) by the following relation:   8pgs 1=3 1 Ddrop 0:34 rs f 2 where gs and rs are the surface tension and the density of solution, respectively, and f is the frequency of ultrasonic transducer. The drop diameter was estimated to be 2.4194 mm. Characterizations The crystalline structure, of as-prepared nanopowder, was analysed with X-ray diffractogram (Rigaku DMAX 2500) using CuKa radiation with a wavelength 1.5418 A. The surface topography and elemental composition of the nanopowder were analysed by SEM (JOEL JED 2300) coupled with an energy dispersive spectrometer (6360 LA). The microstructure of nanopowder was studied using transmission electron microscope (Tecnai 20 G2 (FEI make)). UV-visible spectrophotometer (Simadzu 2450 UV-VIS) was used to study the optical properties of nanopowder. Thickness measurements were carried out using Tolensky technique in the laboratory. Thermoelectric power (TEP) measurements were carried out in the laboratory. Electrical and gas-sensing properties were measured using a static gas-sensing system.

Quartz reactor

Furnace 1 Liquid tank

Furnace 2

Themocouple 2

MKS mass flow controller 1

MKS mass flow controller 2

1 Ultrasonic generator Water tank

Oxygen Air cyllinder cyllinder Ultrasonic spray pyrolysis system

Beaker Trap 1 Trap 2 Trap 3 Powder collectors Trap 4

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Results and discussion

Characterizations of as-prepared nanopowder Structural analysis Figure 2 shows the X-ray diffractogram of the as-prepared ZnO nanopowder. The observed peaks are matching well with the standard Joint Committee on Powder Diffraction Standards (JCPDS) data of ZnO (JCPDS data card number 5-664). The broad peaks are due to nanocrystalline nature of ZnO. The average grain size calculated from Scherers formula was found to be 19.25 nm. Surface topography using SEM SEM micrograph is showing topography of the lm surface. The average particle size was found to be 29.75 nm. The morphology of the particles was roughly spherical in shape. Larger particles may be due to agglomeration of smaller crystallites as shown in Figure 3. TEM for grain size determination TEM technique was used to know exact grain size, shape and distribution of the crystallites associated with the powder. It is clear from TEM image (Figure 4) that there are uniformly distributed spherical-shaped grains with the average grain size of 20.10 nm. Additional structural characterization of ZnO nanopowder was carried out by electron diffraction shown Figure 2 X-ray diffractogram of as-prepared ZnO nanopowder
14,000 12,000 Intensity (cps) (100) (002) 10,000 8,000 6,000 4,000 2,000 0 20 30 40 50 2 (deg.) 60 70 80 (101)

Figure 4 TEM image of as-prepared nanocrystalline ZnO powder

100 nm

(200) (112) (201)

(102)

in inset. Spherical rings in electron diffraction patterns suggest that the nanopowder has good crystallinity. The images clearly show the spotty fringes corresponding to the (100), (002) and (101) lattice planes of ZnO. It is clear from TEM images that basically there are nanocrystallites. Aggregates of these crystallites give nanoparticles having larger diameters as indicated in SEM (Figure 3). The lattice parameters of ZnO nanopowder were calculated (Singh et al., 2007) using the equation:     1 4 1 1 2 2 2 3 a2 c d 101 where d is the interplanner distance, and a and c are the lattice p parameters (being hexagonal structure c=a 3=8). The lattice parameters a and c of nanopowder calculated from the above equation are represented in Table I. To calculate the number of unit cells, let us consider a particle p of diameter r. The particle p can be changed into n smaller identical unit cells of edges, a and c without changing its volume: 4  r 3 nV 3 3p 2 where: pp V 3 3 2a2 c i.e.: n 4  r 3 3p 2V 4 for hexagonal structure

(110)

(103)

Figure 3 SEM image of the nanocrystalline ZnO powder

(004)

(202)

Table I d-values, lattice parameters and volume of unit cell of nanocrystalline ZnO powder
Lattice parameter (nm) Volume of unit cell (nm3) 0.1595

d-value
2.5645

a 0.3357

c 0.5472

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Table II represents a number of unit cells calculated by using values of r obtained from XRD and TEM data. Energy dispersive analysis of X-rays for elemental analysis Theoretically, mass percentage of Zn and O in stoichiometric ZnO is expected to be 80.3 and 19.7 and atomic percentage of Zn and O in ZnO is 50 and 50, respectively. The observed values of mass % and atomic % of Zn and O are represented in Table III. As-prepared ZnO powder was observed to be oxygen decient. This deciency is responsible for the semiconducting nature of ZnO. Optical absorption Figure 5 shows the absorption spectra of the as-prepared nanocrystalline ZnO powder. The formula for absorbance is as follows: where: I0 I

AbsorbanceA

log I0 I

initial intensity of the light passed through the sample. intensity of the light after it has passed through the sample.

Table II Unit cells of nanocrystalline ZnO powder from XRD and TEM
Technique XRD TEM Observations Grain size Grain size Size (nm) 19.25 20.10 No. of unit cells (n) 917,477 1,044,246

The unit of absorbance is absorbance unit. The sharp absorption edge suggests a single phase. The band gap energy calculated from the absorption spectra is 3.3713 eV which is exactly matching with the reported band gap energy (3.37 eV) of ZnO. It is interesting to note that nanocrystalline nature do not have a signicant effect on the band gap of the nanocrystalline ZnO powder. No effect on band gap may be due to the particle size far more than the size of ZnO quantum dots and there is no effect of quantum connement. The variation in the band gap of nanoparticles can also be evaluated from the effective mass model expression (Cullity, 1978) as follows: Eg Ebulk g
*

h2 1:8e2 2 2 8mr 1r

For the strong connement limit (i.e. r p aB) of quantum size effect in nanomaterial. For weak connement limit (i.e. r q aB): Eg Ebulk g
*

Table III Elemental compositions of nanocrystalline ZnO powder

Element Zn O ZnO Mass % 86.50 13.50 100.00 Atomic % 59.46 38.94 100.00

h2 8mr2

Figure 5 The absorption spectra of as-prepared nanocrystalline ZnO powder

1.8 1.6 1.4 1.2 Absorbance (AU) 1 0.8 0.6

where Ebulk is the energy band gap for the bulk material and r g is the radius of the nanoparticle calculated from XRD, TEM and SEM. 1/m (1/me) (1/mh) (me and mh being the electron and hole effective masses, respectively). Here, the reduced mass of the exciton is 0.242 m0 (Singh et al., 2007). Thus, we obtain: E* Ebulk g g 1:545 r2 nm 7

The values calculated from the above given formula for all samples are represented in Table IV. Fabrication of sensor element using lab-prepared nanocrystalline ZnO powder The thixotropic pastes were formulated by mixing lab-prepared nanocrystalline zinc oxide powder with the solution of ethyl cellulose (a temporary binder) in mixture of organic solvents such as butyl cellulose, butyl carbitol acetate and terpineol. The ratio of inorganic and organic part was kept at 75:25 in formulating the paste. These pastes were screen printed on glass substrate in the desired pattern of sensors. These sensors were sintered at 5008C for half-anhour to remove the binder permanently. Table IV Calculated band gap energy

0.4 0.2 0 300 400 500 Wavelength (nm) 600 700

Estimated from Reported Absorption spectra SEM TEM XRD

Eg (eV) 3.3700 3.3713 3.3769 3.3840 3.3866

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Thickness measurements The thickness of the lms was observed to be in the range from 12 to 15 mm. The reproducibility of the lm thickness was achieved by maintaining the proper rheology and thixotropy of the paste. TEP measurements The n-type semiconductivity of the thick lms of ZnO was conrmed by measuring thermo-electromotive force of thick lm sensor. Electrical properties of the sensor I-V characteristics I-V characteristics of nanocrystalline ZnO thick lm are observed to be symmetrical in nature indicating the ohmic contact as shown in Figure 6. Electrical conductivity Figure 7 shows the variation of log(conductivity) with reciprocal of operating temperature. The electrical conductivity of sensor element varied linearly with operating temperature. The increase in conductivity with an increase in temperature could be attributed to semiconducting nature and negative temperature coefcient of resistance. The semiconductivity of ZnO must be due to oxygen deciency in the material. This deciency would then promote an adsorption of oxygen on ZnO surface at higher operating temperature as represented by the following chemical reactions: O2 e2 O2 2 and O2 e2 2O2 2

Figure 7 Electrical conductivity of the sensor element

3.5

Log (conductivity) ohm/m

4.5

5 1.45

1.55

1.65 1.75 1,000/ T

1.85

1.95

Gas-sensing performance of thick lm sensor fabricated from nanocrystalline ZnO powder Gas response (S) is dened as the ratio of the change in conductance of the sensor on exposure to the target gas to the original conductance in air and is given by the following relation: S Gg 2 Ga Ga

where Ga is the conductance of sensor on air and Gg is the conductance of sensor in a target gas. Figure 6 I-V characteristics of the sensor element
5,000 4,000 Current (pA) 3,000 2,000

Gas response with operating temperature of sensor Figure 8 shows the variation of gas response with operating temperature of nanocrystalline ZnO sensor (thick lm) for 1,000 ppm LPG, H2, CO2, NH3, C2H5OH and Cl2. It is clear from the gure that nanocrystalline ZnO showed largest response to NH3 at 3008C as compared to responses of C2H5OH and Cl2 at 4008C, LPG and H2 at 3508C and CO2 at 3008C. It is reported that the optimum operating temperature of NH3 sensor prepared from pure ZnO as is 5008C (Choi and Choi, 2000) which is rather high. Also, the sensitivity of the sensor operated at 3008C is poor (Wagh et al., 2006). Sensors of commercial standards should be highly sensitive at relatively lower operating temperature. The sensors reported in the paper are showing reasonably better sensitivity at lower operating temperatures. Enhancement of sensitivity at relatively lower operating temperature may be due to nanocrystalline nature of ZnO powder employed to fabricate the sensors. Figure 8 Variation of gas response with operating temperature of nanocrystalline ZnO
18 16 14 LPG CO2 H2 NH3 C2H5OH Cl2

1,000 Gas response 0 30 20 10 1,000 2,000 0 10 20 Voltage (V) 30

12 10 8 6 4

3,000 4,000 5,000

2 0 250 300 350 Operating temp (C) 400

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Selectivity of thick lm sensor Selectivity is dened as the ability of a sensor to respond to certain gas in the presence of other gases. Figure 9 shows the selectivity of nanocrystalline ZnO for different gases at 3008C. It is observed from Figure 9 that the sensor is highly selective to NH3 gas against LPG, H2, CO2, NH3, C2H5OH and Cl2. Response and recovery time of thick lm sensor Response time and recovery time The time taken for the sensor to attain 90 per cent of the maximum increase in conductance on exposure of the target gas is known as response time. The time taken by the sensor to get back the 90 per cent of the maximum conductance when the ow of gas is switched off is known as recovery time. Figure 10 shows the response and recovery of the nanocrystalline ZnO thick lm sensor at an operating temperature 3008C. The response was quick (,17 s) and the recovery was fast (,37 s). The negligible quantity of the surface reaction products and their high volatility explain the quick response and fast recovery to NH3.

Discussion
The nanocrystalline ZnO is oxygen decient. Owing to oxygen vacancies, the excess zinc ions act as electron donors (Laidler, 1965; Windichmann and Mark, 1979). The interstitial zinc atoms in such cases are ionized via the following reversible reaction: Zni 2 , Zni e2 These electrons are captured by oxygen ions to get themselves adsorbed on the ZnO surface. When reducing gas molecules like NH3 reacts with these negatively charged oxygen ions, the trapped electrons are given back to conduction band of ZnO. The energy released during decomposition of ammonia molecules would be sufcient for electrons to jump up into the conduction of zinc oxide, causing an increase in the conductivity of the sensor. The possible reaction is: 2NH3 3O2 ! 3H2 O N2 3e2 ZnO For this reaction to complete, some amount of activation energy has to be provided thermally. Sensor operating temperature provides this energy. With an increase in operating temperature, thermal energy also increases which stimulates the oxidation of NH3. Response of sensors depends on two factors, namely: 1 the speed of chemical reaction on the surface of the grains; and 2 the speed of the diffusion of gas molecules to that surface. These are activation processes, and the activation energy of chemical reactions is higher. At low temperatures, the sensor response is restricted by the speed of chemical reactions. At higher temperature, the sensor response is restricted by the speed of the diffusion of gas molecules to that surface. At some intermediate temperature, the speed values of two processes become equal and at that point, the sensor response reaches its maximum. According to this mechanism, for every gas, there is a specic temperature at which the sensor sensitivity attains its peak value.

Figure 9 Selectivity of nanocrystalline ZnO for different gases

18 16 14 Gas response 12 10 8 6 4 2 0 LPG Response 0.3 CO2 0.94 H2 0.7 NH3 17.13 C2H5OH 3.84 Cl2 0.37 At 300C

Conclusions
We have developed USP technique to prepare ZnO nanocrystalline powder. The technique is simple and inexpensive and it may be useful for the production of metal oxide nanopowders. XRD analysis conrmed that the powder to be of ZnO with wurtzite structure. SEM image showed roughly spherical particles with an average size of 29.75 nm. Average grain size calculated from XRD was 19.25 nm and from TEM was 20.10 nm. The band gap energy was calculated from absorption spectrum. It is 3.37 eV. This value is exactly matching with the reported value. The response of nanocrystalline ZnO-based sensor was observed to be the largest to NH3. The sensor showed good selectivity to NH3 gas against LPG, H2, CO2, C2H5OH and Cl2 gases. The sensor showed very quick response (17 s) and fast recovery time (37 s) to NH3 gas.

Figure 10 Response and recovery of nanocrystalline ZnO thick lm sensor

18 16 14 Gas response 12 10 8 6 4 2 0 0 Gas on 10 20 30 40 50 Time (s) 60 70 Gas on 80 Gas on At 300C

References
Bari, A.R., Shinde, M.D., Deo, V. and Patil, L.A. (2009), Effect of solvents on the particle morphology of nanostructured ZnO, Indian Journal of Pure and Applied Physics, Vol. 47, pp. 24-7. 295

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` Carotta, M.C., Giberti, A., Guidi, V., Malagu , C., Vendemiati, B. and Martinelli, G. (2005), Gas sensors based on semiconductor oxides: basic aspects of materials and working principles, Materials Research Society Symposium Proceedings, Warrendale, PA, Vol. 828, pp. 173-84. Chapron, D., Girtan, M., Le Pommelec, J.Y. and Bouteville, A. (2007), Droplet dispersion calculations for ultrasonic spray pyrolysis depositions, Journal of Optoelectronics and Advanced Materials, Vol. 9, pp. 902-6. Chawla, A.K., Kaur, D. and Chandra, R. (2007), Structural and optical characterization of ZnO nanocrystalline lms deposited by sputtering, Optical Materials, Vol. 29 No. 8, pp. 995-8. Choi, J.D. and Choi, G.M. (2000), Electrical and CO gas sensing properties of layered ZnO-CuO sensor, Sensors and Actuators B: Chemical, Vol. 69 Nos 1/2, pp. 120-6. Chou, S.M., Teoh, L.G., Lai, W.H., Su, Y.H. and Hon, M.H. (2006), ZnO:Al thin lm gas sensor for detection of ethanol vapor, Sensors, Vol. 6, pp. 1420-7. Close, L.G., Catlin, F.I. and Cohn, A.M. (1980), Acute and chronic effects of ammonia burns on the respiratory tract, Archives of Otolaryngology, Vol. 106 No. 3, pp. 151-8. Cullity, B.D. (1978), Elements of X-ray Diffractions, 2nd ed., Addison-Wesley, Reading, MA, p. 102. Gandhi, A.S., Jayaram, V. and Chokshi, A.H. (2001), Low temperature densication behaviour of metastable phases in ZrO 2-Al2O 3 powders produced by spray pyrolysis, Materials Science & Engineering A, Vol. 304, pp. 785-9. Hoz, R.E., Schlueter, D.P. and Rom, W.N. (1996), Chronic lung disease secondary to ammonia inhalation injury: a report on three cases, American Journal of Industrial Medicine, Vol. 29 No. 2, pp. 209-14. Hsueh, T.J. and Hsu, C.L. (2008), Fabrication of gas sensing devices with ZnO nanostructure by the low-temperature oxidation of zinc particles, Sensors and Actuators B: Chemical, Vol. 131 No. 2, pp. 572-6. Huang, Y., Deng, K., Ai, Z. and Zhang, L. (2009), Ultrasonic spray pyrolysis synthesis and visible light activity of carbon-doped Ti0.91Zr0.09O2 solid solution photocatalysts, Materials Chemistry and Physics, Vol. 114 No. 1, pp. 235-41. Kim, Y.M., Yoon, M., Park, I.W., Park, Y.J. and Lyou, J.H. (2004), Synthesis and magnetic properties of Zn1-xMnxO lms prepared by the sol-gel method, Solid State Communications, Vol. 129 No. 3, pp. 175-8.

Laidler, K.J. (1965), Chemical Kinetics, 2nd ed., McGrawHill, New York, NY, pp. 310-11, TMG, Ch. 6. Michaels, R.A. (1999), Emergency planning and the acute toxic potency of inhaled ammonia, Environ. Health Perspect., Vol. 107, pp. 617-27. Narasimhan, L.R., Goodman, W., Kumar, C. and Patel, N. (2001), Correlation of breath ammonia with blood urea nitrogen and creatinine during hemodialysis, Proceedings of the National Academy of Sciences, Vol. 98 No. 8, pp. 4617-21. Ohya, Y., Niwa, T., Ban, T. and Takahashi, Y. (2001), Thin lm transistor of ZnO fabricated by chemical solution deposition, Japanese Journal of Applied Physics, Vol. 40, pp. 297-8. Rao, B.B. (2000), Zinc oxide ceramic semi-conductor gas sensor for ethanol vapour, Materials Chemistry and Physics, Vol. 64 No. 1, pp. 62-5. Ryu, H.W., Park, B.S., Akbar, S.A., Lee, W.S., Hong, K.J., Seo, Y.J., Shin, D.C., Park, J.S. and Choi, G.P. (2003), ZnO sol-gel derived porous lm for CO gas sensing, Sensors and Actuators B: Chemical, Vol. 96 No. 3, pp. 717-22. Shinde, V.R., Gujar, T.P. and Lokhande, C.D. (2007), LPG sensing properties of ZnO lms prepared by spray pyrolysis method: effect of molarity of precursor solution, Sensors Actuators B: Chemical, Vol. 120 No. 2, pp. 551-9. Singh, P., Kumar, A. and Kaur, D. (2007), Growth and characterization of ZnO nanocrystalline thin lms and nanopowder via low-cost ultrasonic spray pyrolysis, Journal of Crystal Growth, Vol. 306, pp. 303-10. Singh, P., Chawla, A.K., Kaur, D. and Chandra, R. (2007), Effect of oxygen partial pressure on the structural and optical properties of sputter deposited ZnO nanocrystalline thin lms, Materials Letters, Vol. 61 No. 10, pp. 2050-3. Suh, W.H. and Suslick, K.S. (2005), Magnetic and porous nanospheres from ultrasonic spray pyrolysis, Journal of American Chemical Society, Vol. 127 No. 34, pp. 12007-10. Wagh, M.S., Jain, G.H., Patil, D.R., Patil, S.A. and Patil, L.A. (2006), Modied zinc oxide thick lm resistors as NH3 gas sensor, Sensors and Actuators B: Chemical, Vol. 115 No. 1, pp. 128-33. Windichmann, H. and Mark, P. (1979), A model for the operation of a thin lms SnO2 conductance modulation carbon dioxide sensor, Journal of Electrochemical Society, Vol. 126, pp. 627-33.

Corresponding author
L.A. Patil can be contacted at: plalachand_phy_aml@yahoo. co.in

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