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Sensors and Actuators B 128 (2007) 173178

Inuence of annealing on microstructure and NO2-sensing properties of sputtered WO3 thin lms
Zhifu Liu , Toshinai Yamazaki, Yanbai Shen, Toshio Kikuta, Noriyuki Nakatani
School of Engineering, University of Toyama, Toyama 930-8555, Japan Received 27 February 2007; received in revised form 1 June 2007; accepted 1 June 2007 Available online 12 June 2007

Abstract The inuences of thermal annealing on the microstructure and NO2 -sensing properties of sputtered WO3 thin lms were investigated. The WO3 lms as-deposited at room temperature were amorphous and would crystallize to monoclinic structure when annealed at 350 C or above. The grains and pores in the WO3 lms grew larger with an increase in annealing temperature. The effective surface area and pore volume changed nonmonotonously with increasing the annealing temperature. The lm annealed at 350 C showed the largest effective surface area. The lm annealed at 500 C had the largest pore volume. Among the lms investigated in this study, the WO3 thin lm annealed at 500 C showed the quickest response/recovery and the highest response to 10 ppm NO2 . These results indicate the importance of achieving porous structure on improving the gas sensing performance. 2007 Elsevier B.V. All rights reserved.
Keywords: WO3 thin lm; Annealing; Surface area; Pore size; NO2 sensor

1. Introduction Oxide semiconductors have been of widespread interest as gas sensor materials since early 1960s owing to their remarkable gas sensing performance when exposed to reductive or oxidative gases [1]. Different materials such as SnO2 , WO3 , ZnO, MoO3 , TiO2 , InOx , and mixed oxides have been studied and show promising applications for detecting target gases such as NOx , O3 , NH3 , CO, CO2 , H2 S, and SOx [25]. Although some gas sensors made using semiconductor oxides have been commercialized for years, many problems still need to be solved to enlarge the market share [6] and, thus, efforts are being made to improve the sensitivity, selectivity, rate of gas response, and reliability of oxide semiconductor gas sensors [79]. The microstructure factors such as grain size, grain boundary, lm thickness, porosity, phase, dopants, and area of active surface are the main factors determining the gas sensing performance of oxide semiconductor lms. So the control of microstructure and the fundamental mechanism of microstruc-

Corresponding author. Tel.: +81 76 445 6882; fax: +81 76 445 6882. E-mail address: Zhifu liu@yahoo.com (Z. Liu).

ture effects are two of the main themes of the research on oxide semiconductor gas sensors. Researchers have demonstrated that gas sensitivity increases steeply when the grain size decreases to the size comparable with or smaller than the thickness of space charge layer [10]. The effect of lm thickness on the sensitivity has been studied from both experimental and theoretical aspects, and it was deduced that thinner lms show higher sensitivity [11]. Yamazaki et al. [12] investigated the dependence of the sensitivity on the lm density. Korotcenkov et al. [13] even put forward a structure engineering concept to consider all the microstructure factors together. However, the complexity of the microstructure effects makes it still an open subject to be discussed. Among various metal oxide semiconductors, WO3 is a promising material for the detection of toxic gases since it is highly sensitive to NOx , H2 S, and NH3 . Preparation techniques such as magnetron sputtering [14], thermal evaporation [15], chemical vapor deposition [16], pulsed laser deposition [17], and solgel process [18] have been used to deposit WO3 thin lms. Most of these methods required a post-annealing process to stabilize or improve the operation performance of gas sensors. However, thermal annealing leads to the change not only of crystallinity but also of the grain size, pore size, density of

0925-4005/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.snb.2007.06.001

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adsorption sites, and even the composition of the lm. Therefore, it is necessary to have a comprehensive understanding of the effects of thermal annealing. In this study, WO3 thin lms with different microstructure parameters, such as grain size, crystallinity, effective surface area, and pore size, were obtained by annealing the lms sputtered at RT. The effects of annealing on the microstructure and NO2 -sensing properties of the WO3 thin lms were investigated. 2. Experimental WO3 lms were deposited on oxidized Si substrates at room temperature (RT) by reactive dc magnetron sputtering. A circular tungsten target of 100 mm in diameter with a purity of 99.99% supplied by Furuuchi Chemical was used. The discharge gas was an argonoxygen mixture with a ratio of Ar/O2 = 1:1. The chamber was rst evacuated to 4 104 Pa and then was kept at 20 Pa during lm deposition by lling the discharge gas. The discharge current was xed at 100 mA, and the discharge voltage showed a value of about 500 V. The lm thickness was approximately 100 nm. In order to investigate the annealing effects, the lms were annealed at 200650 C for 4 h in air with a heating and cooling rate of 2 C/min. For the measurement of gas sensing properties, Pt interdigital electrodes with gaps of 0.04 mm were formed on Si substrates before WO3 lm deposition. The crystallographic structure of sputtered WO3 lms was investigated by X-ray diffraction (XRD) using an X-ray diffractometer (Shimadzu XRD-6100) with Cu K radiation. The morphologies were measured by a eld emission scanning electron microscope (FE-SEM) (JEOL JSM-6700F) and an atomic force microscope (AFM) (Shimadzu SPM-9500J). A mechanical surface roughness tester (Tokyo Seimitsu SURFCOM 1500DX) was used to measure the lm thickness. Effective surface area and pore size distribution were determined using the method described in Ref. [19] by physical adsorption of Kr or Ar on a Quantachrome AUTOSORB-1-MP facility. The NO2 gas-sensing measurements were carried out in a quartz tube furnace. Dry synthetic air was used as a reference gas. To obtain NO2 at a concentration of 10 ppm, dry synthetic air containing NO2 at a concentration of 200 ppm was added to the reference gas. The gas ow was controlled with mass ow controllers and the total ow rate was kept at 200 ml/min. The resistance of the WO3 lms was determined by measuring the electric current which owed when a voltage of 10 V was applied between Pt interdigital electrodes. For this measurement, a computerized Agilent 34970A multimeter was used. The sensor response was dened by S = (Rg Ra )/Ra , where Ra was the electrical resistance before introduction of NO2 and Rg was the maximum resistance after introduction of NO2 . 3. Results and discussion 3.1. Structural characterization Fig. 1 illustrates the XRD patterns for WO3 thin lms annealed at 200, 350, 500, and 650 C. The structure of the lms remains amorphous at an annealing temperature of 200 C, while

Fig. 1. XRD patterns of WO3 lms deposited at 20 Pa, RT and annealed at 200, 350, 500, and 650 C.

the lms crystallize to a monoclinic structure (JCPDS No. 431035) after annealed at a temperature of 350 C or above. It can also be seen that the crystallized lms tend to be (2 0 0) plane oriented. The annealing-induced oriented crystallization was also observed by Sun et al. [20] when they annealed amorphous WO3 lms sputtered on a sapphire substrate. They suggested that the WO3 crystallized preferentially along the (2 0 0) direction to reduce the mismatch with sapphire lattice. However, the substrates used in our experiments were oxidized Si covered with a layer of amorphous SiO2 of 500 nm in thickness. There must be embedded some different mechanism. One possibility is that the WO3 species have a column like accumulation during the sputtering process at a pressure as high as 20 Pa [21]. The (2 0 0) plane oriented crystallites may form in situ along the column during annealing process. The full width at half maximum (FWHM) of the XRD (2 0 0) peak is 1.5 , 1.1 , 0.8 for the lms annealed at 350, 500, and 650 C, respectively. The decrease of FWHM indicates an improvement of crystallinity with the increase of annealing temperature. The AFM images of the WO3 thin lms annealed at different temperatures are shown in Fig. 2. All the lms are composed of nano-sized grains. The grains of the lms annealed at low temperatures of 200 and 350 C are small. The average grain size is 2030 nm. The grains grow up when the annealing temperatures is above 350 C. The grain size is about 40 nm for the lm annealed at 500 C and is about 7090 nm for the lm annealed at 650 C. It should also be noted that microcracks and even cavity appeared when the lms were annealed at high temperatures of 500 and 650 C. The formation of microcracks and cavities is owing to the porosity or the low density of the as-deposited lms. It has been demonstrated that the density of a sputtered lm decreases with increasing discharge pressure and decreasing substrate temperature [21]. All the WO3 lms used in this study were deposited at a 20 Pa discharge pressure and the lms are porous [22]. At a high annealing temperature, the lm with a low density shrinks. This generates tensile stress in the lms, causing microcracks and cavities.

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Fig. 2. AFM images (500 nm 500 nm) of WO3 lms deposited at 20 Pa, RT and annealed at 200, 350, 500, and 650 C.

3.2. Physical adsorptiondesorption measurements To examine the effect of annealing on the porous structure of the WO3 lms, the pore size distribution and effective surface area of the lms are determined by the physical adsorptiondesorption measurements at liquid nitrogen temperature. For pore size distribution determination, isothermal adsorptiondesorption of Ar gas was carried out. Fig. 3 shows the pore size distribution of the as-deposited WO3 thin lm and the lms annealed at 200, 350, 500, and 650 C. It can be seen that the as-deposited WO3 lm has a pore size distribution peaked at about 1.8 nm. The pore size distribution shifts to larger size with an increase in annealing temperature. The pore size distribution peaks at about 2.2 and 2.8 nm for the lms annealed at 200 and 350 C. For the lms annealed at 500 and 650 C, the pore size distribution has a peak at about 3 nm. These results indicate that a pore growth process has occurred during the annealing process. We can also see that the lm annealed at 500 C shows a pore size distribution in the range 1217 nm, which are considered to be related to the microcracks in the lm observed from AFM images. The effective surface area of WO3 lms annealed at different temperatures was obtained by isothermal Kr gas physical

adsorption measurements and is shown in Fig. 4. The total pore volume of the corresponding lms is also presented. The effective surface area of the WO3 lms increases rst with an increase in annealing temperature and there is a maximum value

Fig. 3. Pore size distribution of as-deposited WO3 lm and those annealed at 200, 350, 500, and 650 C. The inset is the pore size distribution in the range 817 nm.

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Fig. 4. Total pore volume and effective surface area of as-deposited WO3 lm and those annealed at 200, 350, 500, and 650 C.

of 11 m2 /g annealed at 350 C. When annealed at high temperatures of 500 and 650 C, the WO3 lms lost their effective surface area quickly to less than half of the initial value. The increase of the effective surface area of the lms annealed at temperatures lower than 350 C should be caused by the reorganization of the lm crystallites, which may leads to the opening of some closed pore inside the lms. This is accordant with the fact that the total pore volume also increases in the low annealing temperature range as shown in Fig. 4. The decrease of effective surface area of the lms annealed at 500 and 650 C is the result of pore size growth and some small pores combined to form large pores, microcracks or cavities. The high pore volume of the lm annealed at 500 C may be because the microcracks, as shown in the AFM image, were treated as pores. The formation of large cavities leads to the decrease of total pore volume of the lm annealed at 650 C. 3.3. Gas sensing properties Gas sensing of the annealed WO3 lm-based sensors towards 10 ppm NO2 was measured at operating temperatures ranging from 50 to 300 C. Fig. 5 shows the dynamic response of the WO3 lms annealed at different temperatures at an operating temperature of 150 C. The resistance in air is about 430, 85, 50, and 62 k for the 200, 350, 500, and 650 C annealed lms, respectively. The lower resistance at higher annealing temperature is the result of the improvement of crystallinity. It can also be seen that the annealed WO3 lms have a two steps response/recovery. Upon exposure to NO2 gas, a quick and thereafter slow resistance increase occurs and, during the recovery period, the resistance decreases quickly rst, followed by a slow decrease. Fig. 6 illustrates the response and recovery times of sensors based on the annealed WO3 lms. tres90 and trec90 represents the time for 90% of the total resistance increase and the time for 90% recovery of the resistance change, respectively. tres50 and trec50 are the times for 50% of these changes. We consider here tres50 and trec50 as the initial response and recovery time of the lms. For the lms annealed at different temperatures, the difference of the initial response or recovery time is

Fig. 5. Dynamic response of WO3 thin lms annealed at 200, 350, 500, and 650 C to 10 ppm NO2 gas at an operating temperature of 150 C.

small, while there is a large difference at the slow part of the response and recovery. The response and recovery of semiconductor oxide gas sensors underlie complicated physicalchemistry processes such as surface adsorption/desorption, oxygen inter-crystallite diffusion, gas diffusion inside porous structure, and bulk oxygen diffusion [23]. Surface adsorption/desorption is the rst step of gas response/recovery and it causes surface potential change correlated to the initial response/recovery of a sensor. The small difference of the initial response/recovery time implies that annealing does not have large effect on the adsorption/desorption speed of the WO3 lms. In other words, the reported active sites created by annealing [24] do not have large effect on the initial response/recovery. So the diffusion process, either oxygen or gas species, is the controlling step of sensor response/recovery. The pore size and pore volume increase, with increasing the annealing temperature, accelerates the gas diffusion in porous structure, resulting in quicker response/recovery of the lms annealed at higher temperatures. For the lm annealed at 650 C, the long

Fig. 6. The response and recovery times of sensors based on the annealed WO3 lms.

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decreases when the WO3 lms were annealed at temperatures higher than 350 C. These changes are harmful for gas sensing. But the highest response is obtained with the lm annealed at 500 C. The result implies that some other factor dominates the gas sensing performance. We found that the most signicant character of the lm annealed at 500 C is its large pore volume. It is possible that the cross-linked pores or microcracks acting as diffusion channels dominate the high response [25], although the annealing caused increase in active surface sites density, if it is true, can also compensate some response decrease resulted from losing the surface area. 4. Conclusions In this study, XRD, AFM, physical adsorptiondesorption, and NO2 gas sensing measurements have been carried out to investigate sputtered WO3 thin lms annealed at different temperatures. The lm crystallinity improved and the grain size grew larger with increasing the annealing temperature. The WO3 lm annealed at 350 C showed the largest effective surface area. The lm annealed at 500 C had the largest total pore volume and also showed the quickest response/recovery and the highest response value. These results highlight the importance of achieving porous structure on improving the gas sensing performance. By taking advantage of the annealing process, the microstructural parameters of sputtered lms can be controlled to t the request for gas sensor application. Acknowledgement The authors would like to thank for the support of Venture Business Laboratory of the University of Toyama. References
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Fig. 7. Response to 10 ppm NO2 vs. operating temperature of the WO3 lms annealed at 200, 350, 500, and 650 C.

diffusion distance in large grains may be the main reason of the increase in recovery time. Fig. 7 illustrates the relation between the response values and operating temperature of the WO3 thin lms annealed at temperatures of 200650 C. Each lm has an operating temperature at which it shows the maximum response. The maximum responses of the lms as a function of annealing temperature are plotted in Fig. 8. The maximum response of the lm annealed at 200 C is as low as 6.7 at an operating temperature of 200 C. As the annealing temperature increases from 200 to 500 C, the maximum operating temperature shifts to 100 C and the maximum response increases to 73. However, the maximum response decreases to 25 when the lm was annealed at 650 C. Obviously, the annealing-caused microstructure change contributes to the variation of the sensing properties of WO3 lms. It is known that large surface area, small grain size, large pore size, good crystallinity, and more active surface sites are favorable for high sensitivity. However, the annealing process has both favorite and infavorite effects on the microstructure factors. We can see that the grain size increases and the surface area

Fig. 8. Dependence of the response to 10 ppm NO2 of WO3 thin lms on the annealing temperature.

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Z. Liu et al. / Sensors and Actuators B 128 (2007) 173178 [23] G. Korotcenkov, Gas response control through structural and chemical modication of metal oxide lms: state of the art and approaches, Sens. Actuators B 107 (2005) 209232. [24] M. Stankova, X. Vilanova, J. Calderer, E. Llobet, J. Brezmes, I. Gracia, C. Cane, X. Correig, Inuence of the annealing and operating temperatures on the gas sensing properties of rf sputtered WO3 thin-lm sensors, Sens. Actuators B 105 (2005) 271277. [25] G. Lee, S. Kang, Formation of large pores and their effect on electrical properties of SnO2 gas sensors, Sens. Actuators B 107 (2005) 392396.

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Biographies
Zhifu Liu is a postdoctoral research fellow at University of Toyama. He received his PhD degree from Shanghai Institute of Ceramics, Chinese Academy of Science, in 2004. His research interests include oxide semiconductor gas sensors, nanomaterials, electrical and optical properties of semiconductor thin lms, and combinatorial material science. Toshinai Yamazaki received his PhD degree from Nagoya University, Nagoya, Japan, in 1983. He is currently an associate professor at University of Toyama. His research interests are in the areas of semiconducting oxide gas sensors and the deposition process of sputtered lms. Yanbai Shen is a PhD student at University of Toyama, Japan. He received his MS degree at Northeastern University, China, in 2004. His current research is focused on the microstructural, electrical and gas sensing properties of oxide semiconductor thin lms. Toshio Kikuta is an assistant professor at University of Toyama, Toyama, Japan. He received his PhD degree from Hokkaido University, Sapporo, Japan, in 1998. His research interests include X-ray crystal structure analysis, ferroelectrics, ferroic domain engineering. Noriyuki Nakatani received his PhD degree from Hiroshima University, Hiroshima, Japan, in 1978. He is currently a professor at University of Toyama. His research interests are in the area of solid-state physics, especially the structural phase transition of ferroelectric crystal.