Sensors and Actuators B 77 (2001) 421426

An amorphous-like xa-Fe2O3(1 x)ZrO2 solid solution system for low temperature resistive-type oxygen sensing
W. Cao, O.K. Tan*, W. Zhu, B. Jiang, C.V. Gopal Reddy
Microelectronics Centre, School of EEE, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore

Abstract An amorphous-like solid solution of xa-Fe2O3(1 x)ZrO2 powders has been prepared using the high-energy ball milling technique, and their physical and structural properties have been systematically characterised using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The oxygen gas sensing properties of the screen-printed thick lm gas sensors fabricated from such mechanically alloyed materials have been characterised using an automatic gas sensing measurement system. Experimental results show that the particle size of the powders is drastically milled down to 8 nm after 120 h of high-energy ball milling. The TEM result has also revealed an amorphous-like structure agglomerating the sparing nanocrystalline grains together. The resistive-type sensors demonstrate good oxygen gas sensitivity at a very low operating temperature of 3208C. It is believed that the extraordinary high concentration of oxygen vacancies is the critical factor. This sensing mechanism will be discussed. # 2001 Elsevier Science B.V. All rights reserved.
Keywords: Oxygen sensor; Zirconia; Sensitisation mechanism; High energy ball milling; Solid solution

1. Introduction Oxygen gas sensors are playing an increasingly important role in monitoring and control applications for combustion, waste gases, atmospheric and the chemical processes (such as in semiconductor process, steel manufacturing). No single material or method can be employed over such a wide variety of oxygen-sensing environments, which range from the interior of living tissues to liquid steel melt [1]. Currently, most commercial oxygen gas sensors are electrochemical ZrO2-based and are operated at high temperatures (7009008C). Several attempts have been made to lower its operating temperature. Mainly, three approaches are proposed to improve the low temperature performance of oxygen gas sensors [2]. One is surface treatment: treating the ZrO2 electrolyte by HF solution as proposed by Obayashi and Okamoto. They demonstrated that the HF treatment greatly improved the ZrO2 sensor performance below 5008C. The second approach is to use a thin solid electrolyte to reduce the overall impedance of the cell. Electrochemical vapour deposition and RF sputtering have been employed to prepare gas tight ZrO2 solid electrolyte for fuel cell applications. The third possible way of improving sensor performance is to nd alternative materials having high oxygen ion
* Corresponding author. Tel.: 65-790-5411; fax: 65-791-2687. E-mail address: eoktan@ntu.edu.sg (O.K. Tan).

conductivity at low temperatures. Takahashi and Iwahara have shown that the sintered Bi2O3 with second oxide such as Y2O3 and WO3 give conductivity one order of magnitude higher than that of stabilised ZrO2 at corresponding temperatures around 6008C. Even though many attempts have been carried out, none of the electrolyte oxygen gas sensors has achieved satisfactory oxygen sensing at sufciently low operating temperature. Besides the electrolyte oxygen gas sensor, the resistive oxygen gas sensor is another direction. Without the need for the reference gas, the construction of this type of sensor is much more simple. Recently, Nb and Cr doped TiO2 semiconducting oxide-based thick lm oxygen gas sensors were investigated by Sharma and coworkers [35]. The operating temperature is between 400 and 6008C depending on the dopant and its concentration. In order to further lower the operating temperature, we have systematically investigated the gas sensing properties of ZrO2, added with a-Fe2O3, as a semiconducting oxide-based oxygen gas sensor. The results of a low operating temperature of 3208C and the quick response time of 15 s are very encouraging. 2. Experimental For the preparation of samples, powders zirconia, mZrO2, (99% purity, 325 mesh) were mixed with the nominal

0925-4005/01/$ see front matter # 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 5 - 4 0 0 5 ( 0 1 ) 0 0 7 4 8 - 1

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compositions, 5, 10, 15, 20, 25 mol% of hematite, a-Fe2O3, (99.9% purity; particle size < 5 mm). The mixing was carried out using the planetary ball mill (Fritsch Pulverisette 5). An open container with tungsten carbide (93 wt.% WC and 6 wt.% Co) vials and balls were chosen. The milling speed was set at 200 rpm and the ball-to-powder weight ratio was 20:1 [6]. At selected intervals, 2, 20, 60, 120, 200 h, a certain amount of the milled powder was taken out from the vial for analysis and preparation for thick lm paste. The microstructure of the powders was characterised using X-ray diffraction (XRD) and transmission electron microscopy (TEM). A Rigaku RINT 2000 X-ray diffractometer with Cu Ka1 radiation was used at room temperature. The diffractometer range, 2y, was from 20 to 608. The scan speed was set at 18/min. A JEOL JEM2010 transmission electron microscope was employed to observe the microstructure of powders. The thermal stability of these milled powders had been studied in detailed in previous paper [7]. The thick lm screen printing process was employed to fabricate the oxygen gas sensor. The powder samples were formed into paste and screen-printed onto ceramic substrate with inter-digital Au electrodes. The prepared samples were then annealed at the temperatures of 4008008C for 1 h in air at 1 slm ow rate. The gas sensing properties were characterised using a Keithley 236 source measurement unit in the custom designed gas sensing characterisation system programmed using the National Instruments Labview, Version 5.0 [6]. The carrier gas was nitrogen and test gas was oxygen. 3. Results and discussion 3.1. Powder characterisation Fig. 1 shows the XRD patterns of the typical composition powder, 0.2a-Fe2O30.8ZrO2, milled for different hours.

As a reference, the pattern of the unmilled 0.2a-Fe2O3 0.8ZrO2 powder mixed thoroughly in an agate bowl is also attached. It presents the peaks of crystalline monoclinic ZrO2 and corundum a-Fe2O3. For samples with 2-h milling, the basic structure remains unchanged, only the reduction of the grain size has occurred during the rst 2-h of milling. After a milling time of 20 h, the three main peaks of cubic ZrO2 (1 1 1), (2 0 0) and (2 2 0), in 2y range from 20 to 608, can be observed. After a milling time of 60 h, the peaks of monoclinic ZrO2 and corundum a-Fe2O3 disappear completely. There is no signicant change in the XRD peaks with further milling. With prolonged milling, the impact energies derived are more than sufcient to form the substitution of Zr4 by Fe3 and transform the phase from monoclinic to cubic. The alloying process is further investigated using TEM. The details were presented in our previous paper [7]. As a result of high energy ball milling of 60 h, the monoclinic zirconia transforms to cubic zirconia stabilised by Fe3. With the increase of the milling time to 120 h, the powder forms into amorphous-like conglomerates. Fig. 2 shows the TEM dark-eld image and selected area diffraction (SAD) pattern of the sample milled for 120 h. The amorphous rings and powder conglomerates are observed. From the dark-eld images of the powders milled for different hours, the variation of the average particle sizes is depicted in Fig. 3. The thermal stability of the powder is important factor for gas sensing materials. As described in reference [7], an amorphous-like solid solution can be obtained using high-energy ball milling process. ZrO2 is stabilised by the substitution of Zr4 ions with Fe3 ions. When this solid solution undergoes annealing at the temperature above 6508C, it starts to decompose. This thermal decomposition affects the sensing property seriously, which will be discussed in the subsequent section. 3.2. Sensing properties The sensing properties of the ZrO2-based sensors to oxygen gas were studied systematically in terms of mole percent of the mixed a-Fe2O3 powders, annealing temperatures, powder grain size (milling hours), response time and oxygen gas concentrations. 3.2.1. Effect of mole percent of Fe2O3 The effect on the gas sensitivity to 20% of oxygen gas for the different mole percents (mol%) of Fe2O3, 5, 10, 15, 20 and 25, was investigated. All the samples were annealed in air at 6008C for 1 h. The variation of sensitivity with the composition of a-Fe2O3 is depicted in Fig. 4. The concentration of the oxygen vacancies [VO ] increases with the mole percent of Fe2O3. The maximum solubility of iron in sZrO2 is found to be approximately 18.5 mol% [8]. Hence, this composition possesses the highest [VO ], and it is understandable that the maximum sensitivity occurs for the 20 mol% of Fe2O3 among the compositions investigated.

Fig. 1. X-ray diffraction (XRD) patterns for samples milled for different hours.

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Fig. 2. TEM dark-field image and SAD image of the sample milled for 120 h.

3.2.2. Effect of annealing temperature The effect on the gas sensitivity to 20% of oxygen for the different annealing temperatures was characterised. The thick lm devices of 0.2a-Fe2O30.8ZrO2 were annealed for 1 h in air at 400, 500, 600, 700 and 8008C, respectively. The sensitivities of these samples at different operating temperatures are plotted in Fig. 5. The optimal sensitivity of 82 is obtained from the sample annealed at 6008C and operating at 3208C. The samples annealed at different temperatures have a same optimal operating temperature at 3208C. This optimum operating temperature is much lower than those

reported in [2]. At the operating temperature of 3208C, the variation of sensitivity with the annealing temperature is depicted in Fig. 6. The sensitivity increases with the increase of annealing temperatures between 400 and 6008C. After that, the sensitivity decreases with increasing annealing temperatures. According to the substitution and decomposition model [7] Fe2 O3 ?2FeHZr VO  3OO VO decreases with increasing annealing temperatures above 6008C because of the decomposition above 6508C.

Fig. 3. Variation of the average grain size with the milling time.

Fig. 4. Gas sensitivity to 20% oxygen for the samples with different mole percent a-Fe2O3.

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Fig. 7. Relationship between gas sensitivity and grain size with milling time. Fig. 5. Sensitivity of 0.2a-Fe2O30.8ZrO2 for different annealing temperatures.

Hence, the sensitivity decreases for annealing temperature above 6508C. The reason why the sensitivity increases with increasing annealing temperature between 400 and 6008C needs further clarification. 3.2.3. Relationship between grain size and gas sensitivity The effect of grain size on the sensitivity was investigated. The samples from the powder milled for different hours were annealed at 6008C in air for 1 h. Fig. 7 shows the variation of gas sensitivity and grain size with the milling hours. The sensitivity to 1000 ppm of oxygen was characterised at the operating temperature of 3208C. The grain size was taken from the TEM images directly. The two curves in Fig. 7 indicate that the gas sensing properties are strongly related to particle size. As the grain size decreases with increasing milling time, the surface area and hence surface activity increases. This in turns gives rise to an increase in gas

sensitivity because the sensitivity is believed to link to the surface activity directly. The increase in surface defects with increasing milling hours has given rise to the increase in gas sensitivity. When the grain size remains fairly the same after long hours of milling, the gas sensitivity also saturates at about the value of 11. Therefore, the gas sensitivity increases with decreasing particle grain size of the powder. 3.2.4. Response time When an input signal which goes through a well-dened change, the output response is dened by the time interval between the 10 and 90% of the stationary value [9]. To investigate the response time and sensing reversibility, the sensor of 0.2a-Fe2O30.8ZrO2 annealed at 6008C in air for 1 h was characterised. Fig. 8 depicts the response of the sensor in relative scale of the conductance to 20% oxygen in the carry gas of N2. The response time is 15 s. This response time is considered good for low operating temperature resistive oxygen gas sensor. Fig. 9 depicts three response

Fig. 6. Gas sensitivity to 20% oxygen operating at 3208C vs. the annealing temperature.

Fig. 8. Response time of 0.2a-Fe2O30.8ZrO2 sample annealed at 6008C.

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The iron solubility of 18.5 mol% can be obtained using highenergy ball milling process [8]. This solubility is much higher than that of 5 mol% reported in literature [10]. On the other hand, electrons can subsequently be trapped by VO in the case of oxygen deficiency. It can be expressed as VO  eH ?VO  VO  eH ?VO (3) (4)

Reversible processes (3) and (4) are the functions of temperature. Another important reversible reaction involving oxygen sensing directly is VO  2eH 1 O2 g?OO 2
Fig. 9. Reversibility of 0.2a-Fe2O30.8ZrO2 sample annealed at 6008C.

(5)

and recovery cycles. It indicates that this oxygen gas sensor exhibits good repeatability. 3.2.5. The variation of sensitivity with gas concentration The gas sensitivity for the 120 h milled 0.2a-Fe2O3 0.8ZrO2 thick lm samples annealed at 6008C for 1 h in air and operating at 3208C was measured for different concentrations from 50 ppm to pure oxygen. Fig. 10 shows the variation of the sensitivity with different ppm. At a low concentration of oxygen of 30 ppm, the sensitivity is 5. 3.3. Sensing mechanism The dissolution of the Fe2O3 in the cubic ZrO2 phase can be explained by the substitution [3,8,10] Fe2 O3 3 2FeHZr VO  3OO (1) where FeHZr represents the Fe3 ions at Zr lattice site, VO , the oxygen vacancy and OO is the oxygen ion at the oxygen lattice site. Taking into account the decomposition above 6508C, Eq. (1) can be modified as [7] Fe2 O3 ?2FeHZr VO  3OO (2)

This reversible process (5) is a function of temperature and oxygen partial pressure. xa-Fe2O3(1 x)ZrO2 solid solution has mixed conduction (ionic conduction plus electronic conduction). The sensing properties of a sensing material depend substantially on its electrical transport properties in both the carry gas and the detected gas. The oxygen vacancies [VO ] in the solid solution is a critical factor to oxygen sensing. When the concentration of oxygen in the ambient increases, [VO ] decreases because of the forward equilibrium shift of Eq. (5). When the annealing temperature is higher than 6508C, [VO ] decreases sharply due to the decomposition of the solid solution [7]. The variation of mole percentage of Fe2O3 causes the change of [VO ] with a maximum of 18.5 mol% Fe2O3. According to the conduction characterised, there are two different slopes in the plot of Arrhenius-type temperature characteristics. Our result conrms with the ndings reported by Wilhelm and Howarth [10]. They found that the transition from predominantly electronic to ionic conduction occurs at 3008C for ZrO2 containing 3.4 mol% Fe2O3. Above this transitional temperature, the conduction is contributed mainly by oxygen deciency [VO ], and below this transitional temperature, the conduction is dominated by electrons. In our case, the transitional point is about at 3208C which corresponds to the operating temperature. At lower temperature, oxygen molecules cannot derive sufcient energy to break the chemical bonding and form chemical adsorption. While at temperatures above 3208C, the adsorption rate becomes lower than desorption rate of oxygen molecules. Thus, the dissociation of oxygen molecules is reduced in both the cases. In the nal analysis, the equilibrium constant K for reaction (5) is maximum at the temperature of 3208C. Hence, the sensor shows a lower sensitivity at temperatures other than the optimum operating of 3208C. 4. Conclusions

Fig. 10. Sensitivity vs. oxygen concentration.

Nano-sized solid solution has been prepared using the high-energy ball milling technique for low temperature

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W. Cao et al. / Sensors and Actuators B 77 (2001) 421426 on Sensors (ESS'94), Castro Marina, Leee, Italy, 1217 September 1994, pp. 313. [10] R.V. Wilhelm Jr., D.S. Howarth, Iron oxide-doped yttria-stabilised zirconia ceramic: iron solubility and electrical conductivity, Ceram. Bull. 58 (1979) 228232.

oxygen sensor. As a result of mechanical alloying of 60 h, the monoclinic zirconia transforms to cubic zirconia stabilised by Fe3. With the increase of the milling time to 120 h, the powder becomes amorphous-like conglomerates. When this metastable cubic zirconia is subjected to heat-treat, Fe3 ions precipitates as a-Fe2O3 from the cubic ZrO2 above 6508C. Comparing with the electrolyte oxygen gas sensor, the thick lm resistive oxygen gas sensors that we developed have the features of simple construction and low operating temperature of 3208C. The oxygen gas sensing properties of ZrO2 based with a-Fe2O3 thick lm gas sensors have been investigated systematically. The optimal conditions for this oxygen gas sensor is (a) 6008C annealing temperature, (b) 3208C operating temperature and, (c) 0.2a-Fe2O30.8ZrO2 composition. The sensitivity of our optimal sensor to 20% O2 is 82. Even for very low concentration of 30 ppm, the sensitivity is about 5. The response time for the sensor is 15 s. As a low operating temperature oxygen gas sensing material, the sensing properties are encouraging. References
[1] J.W. Schwank, M. DiBattista, Oxygen sensors materials and applications, MRS Bull. 24 (6) (1999) 4448. [2] T. Suzuki, K. Kaku, S. Ukawa, Y. Dansui, Low-temperature performance of thin solid electrolyte cell based on MoO3-doped Bi2O3, Solid State Ion. 13 (1984) 237239. [3] R.K. Sharma, M.C. Bhatnagar, G.L. Sharma, Mechanism of highly sensitive and fast response Cr doped TiO2 oxygen gas sensor, Sens. Actuators B 45 (1997) 209215. [4] R.K. Sharma, M.C. Bhatnagar, Improvement of the oxygen gas sensitivity in doped TiO2 thick films, Sens. Actuators B 56 (1999) 215219. [5] R.K. Sharma, M.C. Bhatnagar, G.L. Sharma, Mechanism in Nb doped titania oxygen gas sensor, Sens. Actuators B 46 (1998) 194201. [6] O.K. Tan, Ferroelectric and semiconductor film gas sensors, Ph.D. Thesis, Nanyang Technological University for Doctor of Philosophy, 1998, pp. 1152. [7] W. Cao, O.K. Tan, W. Zhu, B. Jian, Mechanical alloying and thermal decomposition of (ZrO2)0.8((-Fe2O3)0.2 powder for gas sensing applications, J. Solid State Chem. 155 (2000) 320325. [8] J.Z. Jiang, F.W. Poulsen, S. Mrup, Structure and thermal stability of nano-structured iron-doped zirconia prepared by high-energy ball milling, J. Mater. Res. 14 (4) (1999) 13431352. [9] A. D'amico, C. Di Natale, A. Taroni, Sensors parameters, in: Sensors for Domestic Applications: Proceedings of the First European School

Biographies
Cao Wenqing received his BEng and MEng from Xi'dian University, China. He is currently doing his PhD on semiconductor oxide-based gas sensors with the Sensors and Actuators Group, Microelectronics Centre, Nanyang Technological University (NTU). His research interests are oxide semiconductor thick film gas sensors, microelectronics, and hybrid microcircuit process. Tan Ooi Kiang received his BEng (1st Class Hons.) from the NU Singapore, MSc from the University of Edinburgh, UK, and PhD from NTU. He is currently an Associate Professor at NTU. His areas of research interest include silicon IC designs, thick and thin films, especially semiconductor and ferroelectric films for gas sensor applications and integration on silicon. Dr. Tan is a member of American Ceramic Society and IEEE. Zhu Weiguang received his BSc and MSc from Shanghai Jiaotong University, China, and PhD from Purdue University, USA. He was a PostDoctoral Research Associate at Purdue University, Research Fellow at NTU, and currently an Associate Professor at NTU. Dr. Zhu is a member of American Physical Society, American Ceramic Society, IEEE, Materials Research Society, and the New York Academy of Sciences. He has published widely in electronics materials, thin films, ferroelectric materials and memory applications, gas sensors, intelligent/smart materials integrated with silicon devices, diamond films and applications, etc. Jiang Bin received his PhD degree in Condensed Matter Physics from University of Melbourne, Australia, in January 1999. His research was mainly in high resolution TEM to study of the fundamental questions of nano-structure and size effect on physical properties of ferroelectric materials. Dr. Jiang joined the School of EEE in February 1999 as a NSTB Post-Doctoral research fellow. His research interest is in TEM and EELS to study the microstructure of ferroelectric thin films for IR detectors and gas sensor materials. He is now at the Department of Physics and Astronomy of Arizona State University. C.V. Gopal Reddy received his PhD from Osmania University, India. His research interest is mainly direct towards the development of gas sensors based on semiconducting oxide thick films with different structures like perovskites, spinels, mixed oxides and synthesis of nano-structured metal oxides for gas sensor applications. Dr. Reddy joined in the School of EEE in December 1999 as a Research Fellow.