Journal of the Korean Physical Society, Vol. 51, No. 6, December 2007, pp.

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Design, Fabrication and Characterization of a Low-Power Gas Sensor with High Sensitivity to CO Gas

Si-Dong

Kim, Bum-Joon Kim, Jin-Ho Yoon and Jung-Sik Kim

(Received 3 September 2007)

Department of Material Science Engineering, University of Seoul, Seoul 151-742

Co-planar type micro gas sensors of high sensitivity and fast response were prepared by using a micro electro mechanical systems (MEMS) process and a sol-gel method. The MEMS devices were designed and fabricated for low power consumption and high eciency by adjusting the heater pattern and line width of the micro-heater. A nite element method (FEM) analysis was conducted for predicting the thermal eciency and the temperature distribution, and the maximum value of the thermal eciency was conrmed at a 60-m width of the cap type mono line micro heater. The particle sizes of the SnO2 , the sensing material prepared by using a sol-gel process, was about 40 nm 50 nm, and the maximum gas sensitivity of the fabricated sensor was RS = 0.312 to 50 ppm CO gas at a 1.8-V heater voltage. The high sensitivity of the fabricated sensor for CO gas resulted from a reduction of the potential barrier, which was due to the overlapping of the depletion layer on the surfaces of the nano-sized SnO2 particles. PACS numbers: 85.80.Dg Keywords: Gas sensor, MEMS, Tin oxide, Carbon monoxide


I. INTRODUCTION

Carbon monoxide gas generated by various combustion facilities and automobiles is known to be extremely harmful to the human body [1, 2]. A metal-oxide semiconductor-based tin oxide (SnO2 ) gas sensors are suitable for detection of reducing gases such as CO, CH4 and H2 due to their special properties, such as chemical and thermal stability, natural non-stoichiometry, and stable rutile phase [3]. However, the gas sensing properties of pure tin oxide suer from problems such as high operating temperature and poor selectivity towards similar reducing gases. Therefore, the addition of noble metals such as Pd and Pt as catalytic additives is often needed in order to improve the selectivity and the sensitivity of SnO2 sensing lms [4{7]. Besides, the reduction of particle sizes to nano scales allows high sensitivity because the specic ratio of volume to surface is increased. Much environmental research has been actively conducted to develop new gas sensors that can monitor CO gas exhausted by using advanced technology such as nano materials and MEMS [8{10]. MEMS based gas sensors with semiconducting materials, such as SnO2 , ZnO and WO3 , have many advantages, which are high sensitivity to toxic gases, short response time, and low power consumption [11, 12]. Especially, the synthesis of gas sensing materials by using the sol-gel method is available
E-mail: jskim@uos.ac.kr; Fax: +82-2-2210-2758

for miniaturized gas sensors because of the high specic surface area and the low-temperature heat treatment. In this study, the design, fabrication, and characterization of co-planar-type micro gas sensors were conducted by using MEMS technology and sol-gel method to synthesize the sensing materials. The electro-thermal properties of the MEMS gas sensor devices with the Pt micro heaters were investigated. SnO2 based sensing materials for CO gas detection were synthesized by using the solgel method and were deposited on MEMS devices. The gas-sensing behaviors for CO gas at specic operation temperatures were analyzed using the sensing characteristics of the fabricated gas sensors.

II. EXPERIMENTS

1. Heaters

Design of the MEMS Devices and Micro

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A schematic diagram of the micro gas sensors is shown in Figure 1. The chip and the membrane sizes are 2 mm 2 mm and 0.6 mm 0.6 mm, respectively. Sensing materials based on SnO2 nanoparticles were deposited in the middle of the device, and a Pt thin-lm layer was patterned for the sensing electrode and the micro heater. The micro heaters of two types, a cap type and a circular type, were designed as shown in Figure 2. Here, the heater pattern of each type was designed with two

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Journal of the Korean Physical Society, Vol. 51, No. 6, December 2007 Table 1. Target resistance of dierent types of the designed models. Heater Resistance Model Name Line Width (m) (
, after annealing) A1 40 16.35 A2 50 13.06 A3 60 10.84 B1 40 28.90 B2 50 23.63 B3 60 20.01 C1 40 17.76 C2 50 13.14 C3 60 10.45 D1 40 38.68 D2 50 29.71 D3 60 23.38

Fig. 1. Schematic drawing of the co-planar-type micro gas sensor.

Fig. 2. Designed micro heaters with dierent Pt patterns: (a) cap-type A1 (mono line), (b) cap-type B1 (dual line), (c) circular-type C1 (mono line) and (d) circular-type D1 (dual line) models.
models: mono and double line patterns (A, B, C and D types). The line widths of the designed micro heaters were varied, 40 m, 50 m and 60 m, for analysis of the thermal eciency and the thermal distribution, after the heater voltage was applied. Table 1 presents the design variables for each model and the heater resistance.

Fig. 3. Flow chart for fabrication of MEMS devices.

consists on a nal membrane structure, the thickness and the thermal dissipation factors were considered during the fabrication process. Then, the Pt layer was deposited by sputtering (2) and was patterned by RIE (reactive ion etching) to form a micro heater and sensing electrode (3). SiOX thin lms deposited by using PECVD (plasma-enhanced CVD) were patterned to form a passivation layer preventing the Pt layer from oxidation and achieving a high thermal eciency (4). The backside silicon wafer substrate was etched by using a KOH wet chemical solution to reduce the power consumption of the gas sensor (5). Finally, the MEMS device was fabricated through wafer dicing and silicon micromachining [13]. Three photo masks were used for the fabrications and it

2. Fabrication of the MEMS Devices

Figure 3 shows the ow chart for fabrication of a MEMS devices. The SiNX insulating layer was deposited by using LPCVD (low pressure chemical vapor deposition) on an n-type (100) Si wafer for membrane formation and backside Si etch stop (1). Since this thin lm layer

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Fig. 4. Fabricated MEMS devices (chip size = 2 mm mm, model name: A1).

2 Fig. 6. X-ray diraction data for SnO2 nano particles with dierent heat treatment temperatures.

Fig. 7. SEM images of Pd-doped SnO2 sensing materials. Fig. 5. Flow chart for synthesis of sensing materials.
was possible to reduce the number of process steps and to obtain higher eciency than for multi-layer type gas sensors [14,15]. The fabricated MEMS device is shown in Figure 4.
3. Synthesis of Sensing Materials and Sensor

Fabrication

Figure 5 shows the ow chart for synthesis of the SnO2 based material by using the sol-gel process. Tin isopropoxide (Sn[Oi C3 H7 ]4 C3 H7 OH, 98 %, Alfa Asar) and poly ethylene-glycol (Mv = 2000, PEG2000) were mixed and agitated in 2 methoxy-ethanol (2ME) at 50  C for 1 hour to synthesize a Sn sol [16]. For better gas sensitivity to CO gas, 1 wt% Pd powder (Aldrich, 99 %) was added to the Sn sol. Using a micro dispenser, we dropped the

Sn sol several times on the MEMS device. Then, the deposited sensing materials were heated at 350  C, 450  C and 550  C. The XRD data conrmed that SnO2 crystallization had occurred a temperatures above 450  C, as shown in Figure 6. Thus, the nal heat treatment temperature was xed at 550  C because that provided a sucient increase in the (110) peaks, which are due to the preferred plane for CO gas adsorption [17,18]. The average diameter of the SnO2 nanoparticles was calculated as 40 nm by using the Scherrer equation [19]; the average particle size contained by using the SEM image (in Figure 7) was approximately 10 nm  50 nm, which was almost the same as the calculated one. Pd particles were not found in the SEM image, but were conrmed by using an EDS mapping, as shown in Figure 8. TO39 packages were used for wire-bonding of the fabricated gas sensor, as shown in Figure 9, and the aging of the sensor was carried out for 48 hours to obtain accurate gas sensing characteristics after initial sensor resistance stabilization.

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Fig. 8. EDS surface mapping images of the Pd-doped SnO2 nano particles: (a) tin, (b) oxygen and (c) palladium. Yellow colored parts show of each element. Table 2. Material properties used for the simulation. Elements Pt Si Si3 N4 Thermal Conductivity 71.6 163 20 (W/m K) Density (kg/m3 ) 21450 2330 3100 Heat Capacity (J/kg K) 133 703 700 Electrical Conductivity 8.9 1012 1.0 1012 (S/m) Convection Film 700 920 Coecient (W/m K)

Fig. 9. The fabricated micro gas sensors: (a) after deposition of the gas sensing material and (b) after wire bonding.
III. RESULTS AND DISCUSSION

1. MEMS Device Simulations by Using a Finite Element Method

A FEM analysis for the designed MEMS devices and imbeded micro heater was carried out using a FEM simulator (COMSOL Multiphysics 3.3). The material properties for the nite element model were inputted as shown in Table 2. The convection heat coecients for the passivation layer (SiNX ) and for the bulk silicon were used to consider the conventional heat loss. The ambient temperature for the simulation was set as 27  C. The eect of the sensing electrode on the heat conduction in the MEMS devices was assumed to be negligible. Figure 10 shows the temperature distribution in the MEMS device at a 2.0-V heater voltage. The membrane region was heated locally so that the temperature of the bulk sili-

con region couldn't increase. The formed micro hot plate structure made it possible to lower the power consumption of the gas sensor. The maximum temperatures in the membrane region obtained by using the A1, B1, C1 and D1 models were 706.669  C, 541.716  C, 627.094  C and 456.197  C at a 2.0-V heater voltage, respectively. The temperature of a cap-type sensor was higher than that of a circulartype because of the heat generation at the heater is edge. On the other hand, the temperature distribution in the membrane region of a circular-type heater was more uniform than that of a cap-type one due to the smaller region of heat emission. However, after deposition of the sensing material, the temperature distribution inside the membrane region was more uniform than that before deposition. As a result, a cap-type heater is considered to be more ecient because of its higher temperature inside membrane region.

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Fig. 10. FEM simulation results for the temperature distribution of the designed MEMS device at Vheater = 2.0 V: (a) A1, (b) B1, (c) C1 and (d) D1 models.

Fig. 11. Temperature distribution measurements for each model obtained by using IR thermovision: (a) A3, (b) B3, (c) C3 and (d) D3 models. The graphs below the gures show scannings of the A-A' lines.
The maximum temperature in the same type heaters (A, B, C and D types) occurred at a 60-m heater line width. Especially, the mono line heater showed a higher temperature than that of the double line heater when the heater pattern was the same. The lower the heater resistance was, the higher the heat eciency at the same heater voltage.

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Fig. 12. Temperatures as a function of applied voltages for each model.

2. Thermal Analysis of Micro Heaters

Fig. 13. Comparison of the Temperature as a function of applied voltage between simulations and IR measurements.

The maximum temperature and temperature distribution inside the membrane of the MEMS device were characterized by using a IR thermometer (IR thermovision). The thermal characterization was conducted on four types of patterns (12 models). The applied heater voltage was in the range of 0 V  3.0 V. The temperature distribution inside the membrane agreed well with the FEM simulation data, as shown in Figure 11. The temperature distributions of all the models with dierent heater voltages are shown in Figure 12. The temperature of the micro heater increased linearly as the heater voltage was increased in the order of A > C > B > D; that is, the smaller the heater resistance was, the higher the thermal eciency was. Figure 13 compare the measured data with the simulated data for the third model of each type of heater (60-m heater line width). At the same heater voltage, the maximum value of the temperature inside membrane was in the order of A3 > C3 > B3 > D3.

Fig. 14. CO gas sensitivities, the average values of the measured 10 sensors with dierent heater voltages.
depended on the applied heater voltage, and the maximum value appeared at a 1.8-V heater voltage. Especially, the maximum value of RS , 0.312, to 50-ppm CO was higher than the responses in previous reports [21{ 23]. Figure 15 shows the gas response of the fabricated sensor to CO gas injection. The fast response and recovery times of a few seconds occurred after gas injection and purge, as shown in Figure 15(a). The average values of the gas sensitivity (RS ) was 0.789, 0.662 and 0.344 at 10 ppm, 20 ppm and 50 ppm of CO, respectively, indicating that gas sensitivity decreased as the CO concentration increased, as shown in Figure 15(b). The sensing mechanism of SnO2 -based semiconductor gas sensors was explained by using the variation of the electron depletion layers on the surfaces of the SnO2 particles by adsorption of the gas molecules in the atmosphere [24]. In the case of catalytic metal particles doped in SnO2 , spillover eect occurs between the surfaces of

3. Characteristics of Gas Responses

The response of the fabricated gas sensor to CO gas was examined with dierent operating temperatures and gas concentrations. The gas sensitivity (RS ) was dened as shown in Eq. (1) for quantication of the measured gas sensing properties [20]:

R (1) RS = g ; Ra where Ra is the sensor resistance in air and Rg is the sensor resistance after CO gas injection. Figure 14 shows the RS values of micro gas sensors with various heater voltages for a 50-ppm CO gas injection. CO gas responses

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Fig. 16. Variation of the depletion layers with nano-sized SnO2 particles: (a) Zn > 2Zo and (b) Zn < 2LD .
Three sequences are possible because of dierent physical and chemical reaction that might occur CO gas molecules are adsorbed on the SnO2 surface: (a) electron exchange between Pd additives and SnO2 layers, (b) migration of gas molecules absorbed on Pd additive surface, (c) chemical reaction by combustion of gas molecules (conversion of CO to CO2 ) [27]. Each of the above three sequences can have dierent energy states. The activation energy of sequence (a) is so small that the reaction can occur easily because of the small mass of the electrons. Sequence (b) is a movement of molecules and sequence (c) is a chemical reaction; that is, the activation energy for physical and chemical reactions can be (a) < (b) < (c) in the three sequences. At around 200  C, the available energies are so decient that sequence (a) cannot occur, but the available energies increase as the temperature increases (near 300  C). Above 350  C, sucient energy for all three sequences are available, but sequence (a) has no in uence on the sensitivity because of the increase in the energy for sequence (a) and the increase in the energy for the opposite reaction. Therefore, the maximum sensitivity occurred at 270  C  300  C, which was caused by ecient electron exchanges between the additives and the sensing materials.

Fig. 15. CO gas responses of the fabricated gas sensors: (a) transient responses to CO gas and (b) sensitivity with dierent concentrations. (b) is the average value of 10 sensors at Vheater = 2.0 V.
the catalyst and the sensing material, changing the band structure of SnO2 dur to electron exchanges between the catalyst and the SnO2 [25,26]. If SnO2 particles decrease to a nano size, the gas sensitivity will increase due to the change in the depletion layer by the adsorption of gas molecules. For SnO2 nano particles, it is possible to form a large amount of metal oxide necks as shown in Figure 16. The length of the metal oxide necks (Zn ) is so much larger than the Debye length (LD ) due to the charges at the surface of the SnO2 particle that the depletion layer can overlap at the SnO2 grain boundaries (Figure 16(b)). Then, the overlapped SnO2 energy band may reduce the potential barrier to the migration of charges (electrons) at the SnO2 grain boundaries. Therefore, the reduced potential barriers can in uence the electrical conductivity of SnO2 particles as follows:

IV. CONCLUSIONS

S = o exp(qVs =kT );

(2)

where S is the electrical conductivity at the surface, o is a constant, and {q VS is the potential barrier to migration of charges. The sensor resistance can drastically decrease because the reduced potential barrier increases the electrical conductivity at the SnO2 surface.

In this study, co-planar-type micro gas sensors with high sensitivity and fast response were fabricated by using a MEMS and sol-gel processes. A MEMS device with a low power consumption and a high eciency was fabricated by modifying the design of a micro heater, a heater pattern, and the line width. A FEM analysis was conducted for the thermal eciency and the temperature distribution, and the maximum value of the ther-

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Journal of the Korean Physical Society, Vol. 51, No. 6, December 2007 [11] E.-K. Kim, H. Y. Lee, J. Park, S. J. Park, J. H. Kwak, S. E. Moon, S. Moeng, K. H. Park, S. W. Kim, H. J. Ji and G. T. Kim, J. Korean Phys. Soc. 51, S170 (2007). [12] I. S. Hwang, Y. J. Choi, J. H. Park, J. G. Park, K. W. Kim and J. H. Lee, J. Korean Phys. Soc. 49, 1229 (2006). [13] J. W. Gardner, V. K. Varadan and O. O. Awadelkarim, Microsensors, MEMS and Smart Devices (J. Wiley, New York, 2001), p. 227. [14] S.-H. Lee, J.-H. Choi, W.-S. Choi, J.-Y. Ahn, H.-S. Park and S.-D. Kim, Kor. Patent, 10-0710864 (2007). [15] N.-J. Choi, J.-H. Kwak and D.-D. Lee, J. Korean Phys. Soc. 45, 1205 (2004). [16] M. Shoyama and N. Hashimoto, Sens. and Actuators B 93, 585 (2003). [17] Z. A. Ansari, S. G. Ansari, T. Ko and J.-H. Oh, Sens and Actuators B 87, 105 (2002). [18] A. Ahmad, J. Walsh and T. A. Wheat, Sens. and Actuators B 93, 538 (2003). [19] The calculation of the peak line broadening of the XRD data for SnO2 nano particles by using the Scherrer equation. [20] For detection of exhaust gas generated by automobiles, the fabricated single sensor can detect both reducing (CO) and oxidizing (NOX ) gases at the same time. As dened in RS = Ra /Rg , quantication of measured data is possible (RS < 1 for CO gas and RS >1 for NOX gas). Also, linearly decreasing behaviors of RS work increasing CO gas concentrations, as shown in Figure 15(b) and conveniently available for the circuit design of the output signals. [21] P. M enini, F. Parret, M. Guerrero, K. Soulantica, L. Erades, A. Maisonna and B. Chaudret, Sens. and Actuators B 103, 111 (2004). [22] O. Wurzinger and G. Reinhardt, Sens. and Actuators B 103, 104 (2004). [23] B. Mirkelamoglu and G. Karakas, Applied Catalysis A 299, 84 (2006). [24] S. Roy Morrison, Sens. and Actuators 12, 425 (1987). [25] S. Matsushima, Y. Teraoka, N. Miura and N. Yamazoe, Jpn. J. Appl. Phys. 27, 1798 (1988). [26] N. Barsan, D. Koziej and U. Weimar, Sens. and Actuators B 121, 18 (2007). [27] A. V. Tadeev, G. Delabouglise and M. Labeau, Mat. Sci. Eng. B 57, 76 (1998).

mal eciency was conrmed at a 60-m width of a captype mono-line micro heater. The particle size of the SnO2 -based sensing material prepared by using a sol-gel method was about 40 nm  50 nm. The maximum gas sensitivity of the fabricated sensor was RS = 0.312 to 50 ppm of CO gas at a 1.8-V heater voltage. The high sensitivity of the fabricated sensor to CO gas was due to the potential barrier beeing reduced by overlapping of depletion layers on the surfaces of nano-sized SnO2 particles. The fabricated micro gas sensors are expected to be useful for applications in detecting exhaust gases of automobiles because of the advantages, such as simple fabrication and low fabrication cost, due to the reduced number of photo-lithography process steps, their power consumption being lower than that of multi-layer-type micro gas sensors, and their very high sensitivity to CO gas.

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